PVC single leather with improved heat resistance and preparation process

Abstract

The present invention discloses a PVC single leather with improved heat resistance and a preparation process. The raw materials of the PVC single leather with improved heat resistance include: PVC resin powder, compound plasticizer, compound stabilizer, silicate needle fiber, organic wollastonite and nano-mixed titanium oxide. The preparation process includes the following steps: (1) uniformly mixing the PVC resin powder, compound stabilizer and wollastonite needle fiber in a dry powder state; (2) adding the compound plasticizer to the mixed dry powder of step (1), stirring until the compound plasticizer is absorbed by the mixed dry powder to obtain a mixture; (3) pouring the mixture into an internal mixer, adding organic wollastonite and nano-mixed titanium oxide to the internal mixer, and internally mixing to obtain a clinker, which is refined in an open mill and then calendered to form a semi-finished product; (4) surface treating the calendered semi-finished product and then baking it. The present invention improves the stability and heat resistance of the product by formula optimization.

Description

Technical Field

[0001] The invention relates to the technical field of synthetic leather, in particular to a PVC single leather with improved heat resistance and a preparation process. Background Art

[0002] PVC artificial leather is a composite material, which is a mixture of polyvinyl chloride resin, plasticizer, stabilizer and other additives, coated or laminated on a base fabric, and then processed through other processes. There are currently two main production processes for PVC leather used in automobiles: coating and calendering.

[0003] The main material of the coating method is PVC paste resin, which is evenly mixed with other additives, and then scraped on the release paper in the order of surface layer-foaming layer-base fabric layer by scraping. The main material of the calendering method is PVC powder, which is evenly mixed with other additives, and then bonded to the surface of the base fabric by refining-calendering.

[0004] At present, there are four common seat materials used in automotive leather: PVC leather, microfiber leather, PU leather, and real leather. Among them, PVC leather has become the focus of research and development due to its obvious price advantage. Since cars often face high temperatures, strong sunlight and other environments during use, PVC leather is required to have good heat resistance. The traditional PVC leather production process (calendering and scraping) basically adds stabilizers, anti-ultraviolet agents, anti-aging agents and other additives to improve its stability. However, due to the characteristics of PVC itself, when targeting some light-colored products, it often cannot meet the long-term heat resistance and non-discoloration requirements of car companies (test conditions 100°C, 336 hours, gray ≥ 4 levels). This problem is even more prominent, especially at a time when the customer base is getting younger and younger and the requirements for interior decoration are becoming more diversified. Summary of the invention

[0005] The purpose of the present invention is to provide a PVC single leather with improved heat resistance and a preparation process, and to improve the stability and heat resistance of the product by optimizing the formula.

[0006] To achieve this object, the present invention adopts the following technical solutions:

[0007] A PVC single leather with improved heat resistance, the raw materials of which include: PVC resin powder, compound plasticizer, compound stabilizer, silicate needle fiber, organic pentane and nano-grade mixed titanium oxide;

[0008] The components of the compound plasticizer include DPHP, TOTM, di(nonyl / decyl / undecyl)phthalate and epoxidized soybean oil;

[0009] The components of the composite stabilizer include a main calcium zinc stabilizer, an auxiliary organic stabilizer and a perchlorate inorganic stabilizer.

[0010] Furthermore, the raw materials of the PVC single leather with improved heat resistance include, by mass, 100 parts of PVC resin powder, 80-120 parts of compound plasticizer, 4-7 parts of compound stabilizer, 5-15 parts of wollastonite needle-like fiber, 3-15 parts of organic penrunclay and 1-3 parts of nano-mixed titanium oxide.

[0011] Furthermore, the components of the composite plasticizer include: DPHP, TOTM, di(nonyl / decyl / undecyl) phthalate and epoxy soybean oil, and the mass ratio of DPHP, TOTM, di(nonyl / decyl / undecyl) phthalate and epoxy soybean oil is (20-60):(15-30):(15-30):(5-10).

[0012] Furthermore, the components of the composite stabilizer include a main calcium zinc stabilizer, an auxiliary organic stabilizer and a perchlorate inorganic stabilizer, and the mass ratio of the main calcium zinc stabilizer, the auxiliary organic stabilizer and the perchlorate inorganic stabilizer is (3-3.5): (1.5-2): (1.5-2).

[0013] Furthermore, the mass ratio of the components of the composite stabilizer is main calcium zinc stabilizer: auxiliary organic stabilizer: perchlorate inorganic stabilizer = 3:1.5:1.5.

[0014] Furthermore, the organic bentonite is a composite of an organic quaternary ammonium salt and natural bentonite;

[0015] The nano-scale mixed titanium oxide is a mixture of nano-scale rutile titanium oxide and nano-scale anatase titanium oxide.

[0016] Furthermore, the raw materials of the PVC single leather for improving heat resistance include, by weight: 0.5-3 parts of antioxidant, 0.5-3 parts of anti-ultraviolet agent, 0.5-10 parts of foaming agent, 0.5-3 parts of 1# processing aid and 0.5-10 parts of 2# processing aid.

[0017] A preparation process of PVC single leather with improved heat resistance, the preparation process is used to prepare the above-mentioned PVC single leather with improved heat resistance, and the preparation process comprises the following steps:

[0018] (1) PVC resin powder, compound stabilizer and wollastonite needle-shaped fiber are mixed uniformly in a dry powder state;

[0019] (2) adding a compound plasticizer to the mixed dry powder of step (1), stirring until the compound plasticizer is absorbed by the mixed dry powder, to obtain a mixture;

[0020] (3) pouring the mixture into an internal mixer, adding organic benzenetite and nano-mixed titanium oxide into the internal mixer, and internally kneading to obtain clinker, which is then refined in an open mixer and then calendered to form a semi-finished product;

[0021] (4) The calendered semi-finished product is surface treated and then baked.

[0022] Furthermore, the preparation method of the compound plasticizer is:

[0023] Stir TOTM and di(nonyl / decyl / undecyl)phthalate at 30-40°C for 0.2-0.5h;

[0024] Slowly add DPHP to the mixture of TOTM and di(nonyl / decyl / undecyl)phthalate and stir at 30-40°C for 0.2-0.5h;

[0025] Then, the epoxy soybean oil was added in several times and stirred for 0.1-0.3h to obtain the composite plasticizer.

[0026] Furthermore, the preparation method of the compound stabilizer is:

[0027] Mix the main calcium zinc stabilizer and the auxiliary organic stabilizer evenly;

[0028] Then, a perchlorate inorganic stabilizer is added and stirred for 0.1-0.3h to obtain the composite stabilizer;

[0029] The above steps are carried out at room temperature.

[0030] The technical solution provided by the present invention may include the following beneficial effects:

[0031] The PVC single leather with improved heat resistance of the present invention adopts a compound plasticizer to replace a single plasticizer, which makes up for the problem that the single plasticizer in the past has obvious performance defects and cannot take into account the leather performance. A compound stabilizer is used to suppress the degradation of PVC by replacing unstable chlorine atoms, absorbing hydrogen chloride and reacting with unsaturated parts, etc.; at the same time, nano-scale mixed titanium oxide is used to improve the coloring performance and weather resistance of PVC, and organic penrun clay is used to improve its weather resistance. The compound plasticizer, compound stabilizer, nano-scale mixed titanium oxide and organic penrun clay work together to effectively improve the stability of light-colored PVC single leather and improve its heat resistance. DETAILED DESCRIPTION

[0032] The technical solution of the present invention is further explained below in conjunction with specific implementation methods.

[0033] The present invention provides a PVC single leather with improved heat resistance, the raw materials of which include: PVC resin powder, compound plasticizer, compound stabilizer, silicate needle fiber, organic pentane and nano-grade mixed titanium oxide;

[0034] The components of the compound plasticizer include DPHP, TOTM, di(nonyl / decyl / undecyl)phthalate and epoxidized soybean oil;

[0035] The components of the compound stabilizer include a main calcium zinc stabilizer, an auxiliary organic stabilizer and a perchlorate inorganic stabilizer.

[0036] The PVC single leather with improved heat resistance described in the present invention adopts compound plasticizer, compound stabilizer, silicate needle fiber, organic penrunite and nano-mixed titanium oxide through formula optimization, which not only improves the stability and heat resistance of the product, but also meets the technical indicators of automobile leather such as VOC and atomization of automobile companies. At the same time, the compound plasticizer and compound stabilizer are compounded in advance, which can be effectively and evenly dispersed into the product, and the degradation of PVC is inhibited by replacing unstable chlorine atoms, absorbing hydrogen chloride and reacting with unsaturated parts. Nano-mixed titanium oxide can not only improve its weather resistance, but also improve its coloring effect. The addition of organic penrunite and wollastonite needle fiber better improves the weather resistance of the product; thereby improving the stability of the product and improving its heat resistance.

[0037] Among compound plasticizers, DPHP (di(2-propylheptyl)phthalate) is cheap, but has poor weather resistance and high heat loss; TOTM (trioctyl trimellitate) has good weather resistance, low heat loss, and excellent atomization value, but has a high price; and di(nonyl / decyl / undecyl)phthalate and epoxy soybean oil both have excellent heat resistance, but have a disadvantage of obvious precipitation of epoxy soybean oil. The present invention compounds these plasticizers to solve the performance defects of a single plasticizer.

[0038] The compound stabilizer is mainly composed of calcium zinc stabilizer, supplemented by perchlorate inorganic and organic stabilizers, and delays PVC aging by chemical reactions such as substitution, absorption, and addition with the PVC matrix. The main calcium zinc stabilizer and the auxiliary organic stabilizer in the present invention are mainly composed of calcium zinc stabilizer and supplemented by organic stabilizer. Specifically, the auxiliary organic stabilizer is 1,2-diundecyl phthalate, and the perchlorate inorganic stabilizer is selected from one or more of sodium perchlorate, magnesium perchlorate, and calcium perchlorate.

[0039] Wollastonite needle fiber is a triclinic system, thin plate-like crystal, the aggregate is radial needle or fiber-shaped, and is an anti-aging filling material. Wollastonite needle fiber is non-toxic, chemically resistant, and has good thermal stability and dimensional stability. Nano-scale mixed titanium oxide is a mixture of rutile titanium oxide and anatase titanium oxide. It is a white powder that uses light scattering to block UV radiation.

[0040] Further, the raw materials of the PVC single leather for improving heat resistance include: 100 parts of PVC resin powder, 80-120 parts of compound plasticizer, 4-7 parts of compound stabilizer, 5-15 parts of wollastonite needle fiber, 3-15 parts of organic pentane and 1-3 parts of nano-mixed titanium oxide. Within this ratio range, the stability and heat resistance of the product can be greatly improved.

[0041] Further, the components of the compound plasticizer include DPHP, TOTM, di(nonyl / decyl / undecyl)phthalate and epoxidized soybean oil in parts by mass, and the mass ratio of DPHP, TOTM, di(nonyl / decyl / undecyl)phthalate and epoxidized soybean oil is (20-60):(15-30):(15-30):(5-10). By this ratio, the advantages of each plasticizer can be fully utilized to improve the quality of the product.

[0042] Further, the components of the compound stabilizer include a main calcium zinc stabilizer, an auxiliary organic stabilizer and a perchlorate inorganic stabilizer, and the mass ratio of the main calcium zinc stabilizer, the auxiliary organic stabilizer and the perchlorate inorganic stabilizer is (3-3.5): (1.5-2): (1.5-2). The stabilizers within this ratio range cooperate to improve the stability of the product.

[0043] Preferably, the mass ratio of the components of the composite stabilizer is main calcium zinc stabilizer: auxiliary organic stabilizer: perchlorate inorganic stabilizer = 3:1.5:1.5. Under this ratio, the product has the best stability and heat resistance.

[0044] Furthermore, organic bentonite is a composite of organic quaternary ammonium salt and natural bentonite, which can improve the compatibility of natural bentonite with organic matter, and the organic bentonite can be evenly dispersed in the product to achieve stable product performance; the nano-scale mixed titanium oxide is a mixture of nano-scale rutile titanium oxide and nano-scale anatase titanium oxide. The mass ratio of rutile titanium oxide to anatase titanium oxide is (30-80): (20-70). Preferably, the mass ratio is rutile titanium oxide: anatase titanium oxide = 3:1.

[0045] In order to further improve the weather resistance of the product, the raw materials for improving the heat resistance of the PVC single leather also include: 0.5-3 parts of antioxidant, 0.5-3 parts of anti-ultraviolet agent, 0.5-10 parts of foaming agent, 0.5-3 parts of 1# processing aid, and 0.5-10 parts of 2# processing aid.

[0046] Specifically, the antioxidant is selected from at least one of octadecyl propionate, pentaerythritol ester, and phosphite; the anti-ultraviolet agent is selected from at least one of benzotriazole chloride, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, and benzotriazole; the foaming agent is selected from at least one of sodium dodecyl sulfate, sodium lauroyl sarcosinate, and azodicarbonamide; and the 1# processing aid and the 2# processing aid are both selected from at least one of ACR, MBS, and CPE.

[0047] Accordingly, the present invention also provides a preparation process of a PVC single leather with improved heat resistance, the preparation process is used to prepare the above-mentioned PVC single leather with improved heat resistance, and the preparation process comprises the following steps:

[0048] (1) PVC resin powder, compound stabilizer and wollastonite needle-shaped fiber are mixed uniformly in a dry powder state;

[0049] (2) adding a compound plasticizer to the mixed dry powder of step (1), stirring until the compound plasticizer is absorbed by the mixed dry powder, to obtain a mixture;

[0050] (3) pouring the mixture into an internal mixer, adding organic benzenetite and nano-mixed titanium oxide into the internal mixer, and internally kneading to obtain clinker, which is then refined in an open mixer and then calendered to form a semi-finished product;

[0051] (4) The calendered semi-finished product is surface treated and then baked.

[0052] In the above preparation process, compound plasticizer, compound stabilizer, organic pentane, nano-mixed titanium oxide, and wollastonite needle-shaped fiber are added to PVC resin powder in steps, and then stirred by a high-speed agitator, processed by an internal mixer, and refining, and the performance of the produced PVC single leather is significantly improved. In the above process, the raw materials are mixed in steps, which can effectively improve the mixing uniformity of the raw materials.

[0053] It should be noted that when the raw materials of PVC single leather contain antioxidant, anti-ultraviolet agent, foaming agent, 1# processing aid and 2# processing aid, the antioxidant, anti-ultraviolet agent, 1# processing aid and 2# processing aid are added in step (1) and mixed evenly with the PVC resin powder; the foaming agent is added in step (3).

[0054] In order to ensure that the components of the compound plasticizer can be fully mixed, the preparation method of the compound plasticizer is as follows: TOTM and di(nonyl / decyl / undecyl) phthalate are stirred evenly at 30-40°C for 0.2-0.5h; DPHP is slowly added to the mixture of TOTM and di(nonyl / decyl / undecyl) phthalate, and stirred at 30-40°C for 0.2-0.5h; then epoxy soybean oil is added in multiple times and stirred for 0.1-0.3h to obtain the compound plasticizer. It should be noted that the stirring temperature and time need to be controlled during the preparation process to ensure that the plasticizers can be fully mixed evenly to prevent excessive reaction caused by long stirring time or too high stirring temperature.

[0055] Furthermore, the preparation method of the composite stabilizer is: evenly mix the main calcium zinc stabilizer and the auxiliary organic stabilizer; then add the perchlorate inorganic stabilizer and stir for 0.1-0.3h to obtain the composite stabilizer; perform the above steps at room temperature to ensure the chemical stability of each component.

[0056] The present invention is further described below by way of examples and comparative examples.

[0057] Example Group 1

[0058] The preparation process of the PVC single leather with improved heat resistance in this embodiment group is as follows:

[0059] (1-1) Preparing a composite plasticizer: stirring TOTM and di(nonyl / decyl / undecyl) phthalate at 30-40° C. for 0.2-0.5 h; slowly adding DPHP to the mixture of TOTM and di(nonyl / decyl / undecyl) phthalate, stirring at 30-40° C. for 0.2-0.5 h; then adding epoxidized soybean oil in multiple portions, stirring for 0.1-0.3 h, to obtain the composite plasticizer;

[0060] (1-2) preparing a composite stabilizer at room temperature: uniformly mixing a main calcium zinc stabilizer and an auxiliary organic stabilizer; then adding a perchlorate inorganic stabilizer and stirring for 0.1-0.3h to obtain the composite stabilizer;

[0061] (1-3) Preparing nano-scale mixed titanium oxide: uniformly mixing nano-scale rutile titanium oxide and nano-scale anatase titanium oxide at room temperature;

[0062] (2-1) Mixing PVC resin powder, compound stabilizer, wollastonite needle fiber antioxidant, UV inhibitor, 1# processing aid and 2# processing aid in a dry powder state;

[0063] (2-2) adding a compound plasticizer to the mixed dry powder of step (2-1), stirring until the compound plasticizer is absorbed by the mixed dry powder, to obtain a mixture;

[0064] (2-3) pouring the mixture into an internal mixer, adding organic benzenetite, nano-mixed titanium oxide and a foaming agent into the internal mixer, and internally mixing to obtain a clinker, which is then refined twice in an open mixer and then calendered to form a semi-finished product;

[0065] (2-4) The calendered semi-finished product is subjected to surface treatment, coated with a surface treatment agent, and then baked.

[0066] The formula of the PVC single leather with improved heat resistance of Example Group 1 is shown in the following table in parts by mass.

[0067] raw material Mass raw material Mass PVC resin powder 100 Antioxidants 1 Compound plasticizer 90 UV inhibitor 1 Compound stabilizer 5 Foaming agent 3 Wollastonite needle-shaped fiber 10 1# Processing aid (ACR) 1 Organic Benrun Clay 9 2# Processing aid (MBS) 3 Nano-scale mixed titanium oxide 2 - -

[0068] Among them, the formulas of compound stabilizers and compound plasticizers in parts by mass are shown in the following table.

[0069]

[0070] Comparative Example

[0071] The formula of the PVC single leather in this comparative example is: by mass, 100 parts of PVC resin powder, 90 parts of DPHP, 5 parts of calcium zinc stabilizer, 10 parts of wollastonite needle-shaped fiber, 9 parts of organic bermudagrass, 2 parts of nano-mixed titanium oxide, 1 part of antioxidant, 1 part of anti-ultraviolet agent, 3 parts of foaming agent, 1 part of 1# processing aid, and 3 parts of 2# processing aid.

[0072] The preparation process of the PVC single leather formula of this comparative example is:

[0073] (1) PVC resin powder, calcium zinc stabilizer and wollastonite needle-shaped fiber are mixed uniformly in a dry powder state;

[0074] (2) adding DPHP to the mixed dry powder of step (1), stirring until the DPHP is absorbed by the mixed dry powder, to obtain a mixture;

[0075] (3) pouring the mixture into an internal mixer, adding organic benzenetite and nano-mixed titanium oxide into the internal mixer, and internally kneading to obtain clinker, which is then refined in an open mixer and then calendered to form a semi-finished product;

[0076] (4) The calendered semi-finished product is surface treated and then baked.

[0077] It should be noted that, in both the PVC single leather of Example Group 1 and the comparative example, colorants were added during the quilting process to prepare light grey PVC single leather.

[0078] The light stability test was conducted on the PVC single leather of Example Group 1 and the comparative example. Three specimens of each sample were taken and tested at 100° C. and 336 hours. The test results are as follows:

[0079]

[0080] It can be seen from the above table that compared with the comparative example, the color change value △E of Example 1-1 of Example Group 1 is 2.10, the color change values ​​△E of Examples 1-2, 1-3 and 1-4 are around 2.3, and the color change value △E of the comparative example is 4.92. Relative to the color change of PVC, the larger the value, the worse the effect, which proves that the PVC single leather of Example Group 1 has greatly improved stability and heat resistance.

[0081] Example Group 2

[0082] The PVC single leather with improved heat resistance in this embodiment group adopts the compound stabilizer and compound plasticizer of Examples 1-4, and the formula in parts by mass is shown in the following table.

[0083]

[0084] The preparation method of the PVC single leather with improved heat resistance in this example group is the same as that in example group 1. The color change value △E of the PVC single leather obtained in example group 2 is between 2.0 and 2.7, and has good stability and heat resistance.

[0085] The PVC single leather with improved heat resistance of the present invention is used for automobile seats. The product is non-toxic and environmentally friendly, complies with European REACHSVHC201 standards, has good stability, and can effectively improve the heat resistance of light-colored PVC single leather.

[0086] The technical principle of the present invention is described above in conjunction with specific embodiments. These descriptions are only for explaining the principle of the present invention and cannot be interpreted as limiting the scope of protection of the present invention in any way. Based on the explanations herein, those skilled in the art can associate other specific implementations of the present invention without paying creative labor, and these methods will fall within the scope of protection of the present invention.

Claims

1. A PVC single leather with improved heat resistance, characterized in that: Its raw materials include: PVC resin powder, compound plasticizer, compound stabilizer, silicate needle fiber, organic pentane and nano-mixed titanium oxide; The components of the compound plasticizer include DPHP, TOTM, di(nonyl / decyl / undecyl)phthalate and epoxidized soybean oil; The components of the composite stabilizer include a main calcium zinc stabilizer, an auxiliary organic stabilizer and a perchlorate inorganic stabilizer; The organic bentonite is a composite of an organic quaternary ammonium salt and natural bentonite; The nano-scale mixed titanium oxide is a mixture of nano-scale rutile titanium oxide and nano-scale anatase titanium oxide.

2. The PVC single leather with improved heat resistance according to claim 1, characterized in that: The raw materials thereof include, by mass, 100 parts of PVC resin powder, 80-120 parts of compound plasticizer, 4-7 parts of compound stabilizer, 5-15 parts of wollastonite needle-shaped fiber, 3-15 parts of organic penrun clay and 1-3 parts of nano-grade mixed titanium oxide.

3. The PVC single leather with improved heat resistance according to claim 1, characterized in that: The components of the composite plasticizer, measured in parts by mass, include: DPHP, TOTM, di(nonyl / decyl / undecyl) phthalate and epoxy soybean oil, and the mass ratio of DPHP, TOTM, di(nonyl / decyl / undecyl) phthalate and epoxy soybean oil is (20-60): (15-30): (15-30): (5-10).

4. The PVC single leather with improved heat resistance according to claim 1, characterized in that: The components of the composite stabilizer include a main calcium zinc stabilizer, an auxiliary organic stabilizer and a perchlorate inorganic stabilizer, and the mass ratio of the main calcium zinc stabilizer, the auxiliary organic stabilizer and the perchlorate inorganic stabilizer is (3-3.5): (1.5-2): (1.5-2).

5. The PVC single leather with improved heat resistance according to claim 4, characterized in that: The mass ratio of the components of the composite stabilizer is main calcium zinc stabilizer: auxiliary organic stabilizer: perchlorate inorganic stabilizer = 3:1.5:1.

5.

6. The PVC single leather with improved heat resistance according to claim 2, characterized in that: The raw materials thereof further include, by weight: 0.5-3 parts of antioxidant, 0.5-3 parts of anti-ultraviolet agent, 0.5-10 parts of foaming agent, 0.5-3 parts of 1# processing aid and 0.5-10 parts of 2# processing aid.

7. A process for preparing PVC single leather with improved heat resistance, characterized in that: The preparation process is used to prepare the PVC single leather with improved heat resistance according to any one of claims 1 to 6, and the preparation process comprises the following steps: (1) Mix PVC resin powder, compound stabilizer and wollastonite needle-shaped fiber evenly in dry powder state; (2) adding a compound plasticizer to the mixed dry powder of step (1), stirring until the compound plasticizer is absorbed by the mixed dry powder, to obtain a mixture; (3) pouring the mixed material into an internal mixer, adding organic benzenetite and nano-mixed titanium oxide into the internal mixer, and internally kneading to obtain clinker, which is then refined in an open mixer and then rolled into a semi-finished product; (4) The calendered semi-finished product is surface treated and then baked.

8. The preparation process according to claim 7, characterized in that: The preparation method of the compound plasticizer is: Stir TOTM and di(nonyl / decyl / undecyl)phthalate at 30-40°C for 0.2-0.5h; Slowly add DPHP to the mixture of TOTM and di(nonyl / decyl / undecyl)phthalate and stir at 30-40°C for 0.2-0.5h; Then, epoxidized soybean oil was added in several portions and stirred for 0.1-0.3h to obtain the composite plasticizer.

9. The preparation process according to claim 8, characterized in that: The preparation method of the composite stabilizer is: Mix the main calcium zinc stabilizer and the auxiliary organic stabilizer evenly; Then, a perchlorate inorganic stabilizer is added and stirred for 0.1-0.3h to obtain the composite stabilizer; The above steps are carried out at room temperature.

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