Nano color paste for PVC (polyvinyl chloride) gloves and preparation method of nano color paste

Abstract

The invention discloses nano color paste for PVC (polyvinyl chloride) gloves and a preparation method of the nano color paste. The nano color paste comprises the following components in parts by mass: 45-55 parts of modified titanium dioxide; 10 to 20 parts by mass of water-based acrylic resin; 1.5 to 2.5 parts by mass of rare earth phosphate; 1.5 to 2.5 parts by mass of silicon dioxide aerosol; 6-8 parts by mass of a dispersant; 1-2 parts by mass of a wetting agent; 0.5 to 1.5 parts by mass of a bactericide; 45 to 55 parts by mass of deionized water; the modified titanium dioxide is obtained by sequentially coating cerium dioxide, zirconium dioxide and aluminum phosphate on the surface of titanium dioxide. The modified titanium dioxide is compounded with the rare earth phosphate, the silicon dioxide aerosol and other components to prepare the nano color paste, and the obtained nano color paste is used as color paste for preparing the PVC glove material, so that the weather resistance and the corrosion resistance of PVC gloves can be effectively enhanced.

Description

Technical Field

[0001] This invention relates to a nano-color paste for PVC gloves and its preparation method, belonging to the field of nano-color paste technology. Background Technology

[0002] PVC gloves (polyvinyl chloride gloves) are widely used in the medical, food, and electronics industries due to their low price, chemical resistance, and antistatic properties. The main raw materials for PVC gloves include PVC paste resin, plasticizers, colorants, and solvents. Among these, colorants play a crucial role in PVC glove raw materials, their function extending beyond basic coloring to significantly impact the performance of the PVC gloves.

[0003] The coloring function of color pastes is mainly manifested by the pigments within them. Titanium dioxide, with its excellent chemical stability and optical properties, is a commonly used pigment in color pastes for PVC gloves. However, titanium dioxide suffers from photochemical reactivity. Under ultraviolet radiation from sunlight, oxygen ions in titanium dioxide lose electrons to become single atomic oxygen atoms. These atomic oxygen atoms, due to their high reactivity, easily oxidize organic matter in the organic system containing titanium dioxide. Simultaneously, under ultraviolet irradiation, titanium dioxide readily reacts with water and oxygen adsorbed on its surface to generate substances with highly chemically active groups, which in turn oxidize organic matter in the application medium. Therefore, PVC gloves using titanium dioxide as a color paste pigment exhibit poor weather resistance and are prone to fading, cracking, and other aging phenomena during long-term outdoor use, severely impacting their lifespan. Furthermore, when PVC gloves are used in medical, chemical, and laboratory settings, high corrosion resistance is required, and existing color pastes do not adequately meet these requirements. Summary of the Invention

[0004] To address the aforementioned problems in the existing technology, the purpose of this invention is to provide a nano-color paste for PVC gloves and its preparation method.

[0005] To achieve the above-mentioned objectives, the technical solution adopted by the present invention is as follows: A nano-pigment paste for PVC gloves has the following composition and proportions: Modified titanium dioxide: 45~55 parts by weight; Water-based acrylic resin: 10~20 parts by weight; Rare earth phosphates: 1.5~2.5 parts by weight; Silica aerosol: 1.5~2.5 parts by weight; Dispersant: 6-8 parts by weight; Wetting agent: 1-2 parts by weight; Fungicide: 0.5~1.5 parts by weight; Deionized water: 45-55 parts by weight; The modified titanium dioxide is obtained by sequentially coating the surface of titanium dioxide with cerium dioxide (CeO2), zirconium dioxide (ZrO2), and aluminum phosphate (AlPO4).

[0006] One embodiment of the modified titanium dioxide preparation includes the following steps: a) Disperse nano-titanium dioxide in water to obtain a titanium dioxide slurry; b) At room temperature, polyvinylpyrrolidone (PVP) is added to an aqueous solution of cerium nitrate and stirred at room temperature for 25-35 minutes. Then, ammonia is added dropwise while stirring, and the mixture is stirred at room temperature for 50-70 minutes to obtain cerium oxide sol. c) Heat the titanium dioxide slurry to 55~65℃, then add polycarboxylate and adjust the pH of the slurry to 8~9. Slowly add cerium oxide sol to the titanium dioxide slurry while maintaining the pH at 8~9. After the addition is complete, age for 30~90 minutes, filter, wash, dry and grind to obtain cerium dioxide-coated titanium dioxide composite material, denoted as: CeO2 / TiO2; d) Disperse CeO2 / TiO2 in water, heat the resulting slurry to 55~65℃, then add polycarboxylate and adjust the pH of the slurry to 8.5~9.5. Then slowly add zirconium oxychloride aqueous solution, maintaining the pH of the slurry at 8.5~9.5 during this process. After the addition is complete, age for 30~90 minutes, filter, wash, dry, and grind to obtain zirconium dioxide / cerium dioxide coated titanium dioxide composite material, denoted as: ZrO2 / CeO2 / TiO2; e) Disperse ZrO2 / CeO2 / TiO2 in water, heat the resulting slurry to 80~85℃, then add polycarboxylate and adjust the pH of the slurry to 9~10. Then, slowly add aluminum sulfate aqueous solution and sodium hexametaphosphate aqueous solution at the same time, maintaining the pH of the slurry at 9~10 during this process. After the addition is complete, age for 30~90 minutes, filter, wash, dry and grind to obtain aluminum phosphate / zirconium dioxide / cerium dioxide coated titanium dioxide composite material, denoted as: AlPO4 / ZrO2 / CeO2 / TiO2.

[0007] In a preferred embodiment, in step a), the particle size of the nano-titanium dioxide is 10~20nm, and the concentration of the titanium dioxide slurry is 200~300g / L.

[0008] In a preferred embodiment, in step b), the concentration of the cerium nitrate aqueous solution is 0.05M, the concentration of the ammonia solution is 2M, and the ratio of polyvinylpyrrolidone:cerium nitrate aqueous solution:ammonia solution is (1.5~2.5)g:(150~250)mL:(4.5~5.5)mL.

[0009] In a preferred embodiment, in step c), the coating amount of cerium dioxide is 0.1~0.3wt% based on titanium dioxide.

[0010] In a preferred embodiment, in step d), the coating amount of zirconium dioxide is 0.5~1.5wt% based on titanium dioxide.

[0011] In a preferred embodiment, in step e), the coating amount of aluminum phosphate is 2-3 wt% based on titanium dioxide.

[0012] In one embodiment, the waterborne acrylic resin is Joncryl 678 (BASF).

[0013] In one embodiment, the rare earth phosphate is gadolinium phosphate (GdPO4).

[0014] In one embodiment, the dispersant is Tego Dispers 755W.

[0015] In one embodiment, the wetting agent is Tego Wet 270.

[0016] In one embodiment, the bactericide is Acticide MBS.

[0017] A method for preparing the nano-pigment for PVC gloves according to the present invention includes the following steps: First, add the specified amounts of water-based acrylic resin, wetting agent, and bactericide to deionized water and stir until they are evenly mixed. Then, add the specified amounts of modified titanium dioxide, rare earth phosphate, silica aerosol, and dispersant and stir until they are evenly mixed. Next, grind the resulting mixture using a three-roll mill to obtain nano-color paste for PVC gloves.

[0018] Compared with the prior art, the present invention has the following significant advantages: This invention sequentially coats titanium dioxide with cerium dioxide, zirconium dioxide, and aluminum phosphate to obtain modified titanium dioxide. The modified titanium dioxide is then compounded with rare earth phosphates, silica aerosol, and other components to obtain nano-color paste. The obtained nano-color paste is used as a color paste to prepare PVC glove material, which can effectively enhance the weather resistance and corrosion resistance of PVC gloves and has extremely high industrial application value. Detailed Implementation

[0019] The technical solution of the present invention will be further described in detail and completely below with reference to the embodiments. It should be understood that these embodiments are only used to illustrate the present invention and are not intended to limit the scope of the present invention. Experimental methods in the following embodiments that do not specify specific conditions are generally performed under conventional conditions or as recommended by the manufacturer. Example 1

[0020] I. Preparation of Modified Titanium Dioxide (AlPO4 / ZrO2 / CeO2 / TiO2) a) Disperse nano-titanium dioxide in water to obtain a titanium dioxide slurry of 250 g / L; b) At room temperature, polyvinylpyrrolidone (PVP) was added to a 0.05M cerium nitrate aqueous solution and stirred at room temperature for 30 minutes. Then, 2M ammonia was added dropwise while stirring. The ratio of polyvinylpyrrolidone:cerium nitrate aqueous solution:ammonia was 2g:200mL:5mL. The mixture was stirred at room temperature for 60 minutes to obtain cerium oxide sol. c) Heat the titanium dioxide slurry to 60°C, then add polycarboxylate, wherein the mass ratio of titanium dioxide slurry to polycarboxylate is 35:0.1. Adjust the pH of the slurry to 8.5. Slowly add cerium oxide sol to the titanium dioxide slurry using a peristaltic pump (addition rate of 0.5 mL / min) while maintaining the pH at 8.5. After addition, age for 60 minutes, filter, wash, dry, and grind to obtain a cerium dioxide-coated titanium dioxide composite material, denoted as CeO2 / TiO2, where the coating amount of CeO2 is 0.1 wt% of TiO2. d) CeO2 / TiO2 was dispersed in water, and the resulting slurry (concentration 250 g / L) was heated to 60°C. Then, polycarboxylate was added, with a slurry:polycarboxylate mass ratio of 35:0.1. The pH of the slurry was adjusted to 9, and then 3M zirconium chloride aqueous solution was slowly added dropwise while maintaining the pH of the slurry at 9. After the addition was complete, the mixture was aged for 60 minutes, filtered, washed, dried, and ground to obtain a zirconium dioxide / cerium dioxide-coated titanium dioxide composite material, denoted as ZrO2 / CeO2 / TiO2, with the ZrO2 coating amount being 0.5 wt% of TiO2. e) Disperse ZrO2 / CeO2 / TiO2 in water, heat the resulting slurry (slurry concentration of 250 g / L) to 80°C, then add polycarboxylate, the mass ratio of slurry to polycarboxylate is 35:0.1, and adjust the pH of the slurry to 9. Then, slowly add 0.3 M aluminum sulfate aqueous solution and 0.15 M sodium hexametaphosphate aqueous solution dropwise, maintaining the pH of the slurry at 9 during this process. After the addition is complete, age for 60 minutes, filter, wash, dry, and grind to obtain aluminum phosphate / zirconium dioxide / cerium dioxide coated titanium dioxide composite material, denoted as: AlPO4 / ZrO2 / CeO2 / TiO2, the coating amount of AlPO4 is 2 wt% of TiO2.

[0021] II. Preparation of Nano Pigments First, add 15 parts by weight of water-based acrylic resin, 1.5 parts by weight of wetting agent, and 1 part by weight of bactericide to 50 parts by weight of deionized water and stir until they are evenly mixed (stirring speed is 300 rpm, stirring for 20 minutes). Then, add 50 parts by weight of modified titanium dioxide, 2 parts by weight of gadolinium phosphate, 2 parts by weight of silica aerosol, and 7 parts by weight of dispersant and stir until they are evenly mixed (stirring speed is 400 rpm, stirring for 30 minutes). Next, grind the resulting mixture through a three-roll mill (grinding speed is 800 rpm, grinding for 30 minutes) to obtain nano-color paste for PVC gloves.

[0022] Example 2 The difference between this comparative example and Example 1 is that, in the preparation of modified titanium dioxide, the coating amount of CeO2 is 0.2wt% of TiO2, the coating amount of ZrO2 is 1wt% of TiO2, and the coating amount of AlPO4 is 2.5wt% of TiO2.

[0023] Example 3

[0024] The difference between this comparative example and Example 1 is that, in the preparation of modified titanium dioxide, the coating amount of CeO2 is 0.3wt% of TiO2, the coating amount of ZrO2 is 1wt% of TiO2, and the coating amount of AlPO4 is 3wt% of TiO2.

[0025] Comparative Example 1 The difference between this comparative example and Example 2 is that the modified titanium dioxide used in the color paste is CeO2 / TiO2.

[0026] Comparative Example 2 The difference between this comparative example and Example 2 is that the modified titanium dioxide used in the color paste is ZrO2 / TiO2, and the preparation method of ZrO2 / TiO2 is as follows: TiO2 was dispersed in water, and the resulting slurry (concentration 250 g / L) was heated to 60°C. Then, polycarboxylate was added, with a slurry:polycarboxylate mass ratio of 35:0.1. The pH of the slurry was adjusted to 9, and then 3M zirconium chloride aqueous solution was slowly added dropwise while maintaining the pH of the slurry at 9. After the addition was complete, the mixture was aged for 60 minutes, filtered, washed, dried, and ground to obtain a zirconium dioxide-coated titanium dioxide composite material, denoted as ZrO2 / TiO2.

[0027] Comparative Example 3 The difference between this comparative example and Example 2 is that the modified titanium dioxide used in the color paste is AlPO4 / TiO2, and the preparation method of AlPO4 / TiO2 is as follows: TiO2 was dispersed in water, and the resulting slurry (concentration 250 g / L) was heated to 80°C. Then, polycarboxylate was added, with a slurry:polycarboxylate mass ratio of 35:0.1. The pH of the slurry was adjusted to 9. Then, 0.3 M aluminum sulfate aqueous solution and 0.15 M sodium hexametaphosphate aqueous solution were slowly added dropwise, maintaining the pH of the slurry at 9 throughout the process. After the addition was complete, the mixture was aged for 60 minutes, filtered, washed, dried, and ground to obtain aluminum phosphate-coated titanium dioxide composite material, denoted as AlPO4 / TiO2.

[0028] Comparative Example 4 The difference between this comparative example and Example 2 is that the modified titanium dioxide used in the color paste is AlPO4 / ZrO2 / SiO2 / TiO2, and the method of coating SiO2 is as follows: Titanium dioxide slurry was heated to 80°C, and then polycarboxylate was added. The mass ratio of titanium dioxide slurry to polycarboxylate was 35:0.1. The pH of the slurry was adjusted to 10, and then water glass solution was slowly added dropwise while maintaining the pH of the slurry at 10. After the addition was complete, the mixture was aged for 60 minutes, filtered, washed, dried, and ground to obtain a silicon dioxide-coated titanium dioxide composite material, denoted as SiO2 / TiO2, with the coating amount of SiO2 being 0.5 wt% of TiO2.

[0029] Comparative Example 5 The difference between this comparative example and Example 2 is that the modified titanium dioxide used in the color paste is Al2O3 / ZrO2 / CeO2 / TiO2, and the method of coating Al2O3 is as follows: ZrO2 / CeO2 / TiO2 was dispersed in water, and the resulting slurry (concentration 250 g / L) was heated to 80°C. Then, polycarboxylate was added, with a slurry:polycarboxylate mass ratio of 35:0.1. The pH of the slurry was adjusted to 5, and then 100 g / L sodium aluminate solution was slowly added dropwise while maintaining the pH of the slurry at 5. After the addition was complete, the mixture was aged for 60 minutes, filtered, washed, dried, and ground to obtain an alumina / zirconium dioxide / cerium dioxide-coated titanium dioxide composite material, denoted as Al2O3 / ZrO2 / CeO2 / TiO2, where the coating amount of Al2O3 was 2 wt% of TiO2.

[0030] Comparative Example 6 The difference between this comparative example and Example 2 is that the pigment does not contain gadolinium phosphate and fumed silica.

[0031] Comparative Example 7 The difference between this comparative example and Example 2 is that the titanium dioxide in the color paste is unmodified titanium dioxide and does not contain gadolinium phosphate or fumed silica.

[0032] The color pastes from Examples 1-3 and Comparative Examples 1-7 were applied to PVC glove material according to the following PVC glove material formulation: 35 parts by weight of PVC paste resin (P-450), 45 parts by weight of plasticizer, 2 parts by weight of calcium-zinc stabilizer, 3 parts by weight of color paste, 0.5 parts by weight of lubricant (stearic acid), and 14.5 parts by weight of water. PVC gloves were produced using existing processes. The weather resistance of the prepared PVC gloves was tested, specifically: UV aging test according to ASTM G154 standard and damp heat aging test according to ISO 6270-2 standard. The weather resistance of the PVC gloves was evaluated based on the color difference and tensile strength retention rate of the PVC gloves.

[0033] The PVC gloves were subjected to salt spray resistance test according to GB / T 1771-2007 standard to evaluate their corrosion resistance performance.

[0034] Table 1

[0035] As shown in Table 1, under the same conditions, the PVC gloves (AlPO4 / ZrO2 / CeO2 / TiO2+gadolinium phosphate+fumed silica) prepared using the pigments from Examples 1-3 exhibit significantly higher weather resistance and corrosion resistance than those prepared using Comparative Examples 1 (CeO2 / TiO2+gadolinium phosphate+fumed silica), 2 (ZrO2 / TiO2+gadolinium phosphate+fumed silica), 3 (AlPO4 / TiO2+gadolinium phosphate+fumed silica), and 4 (AlPO4 / ZrO2 / SiO2 / TiO2+gadolinium phosphate+fumed silica). The PVC gloves prepared from the color pastes of Comparative Example 5 (Al2O3 / ZrO2 / CeO2 / TiO2 + Gadolinium Phosphate + Fumed Silica), Comparative Example 6 (AlPO4 / ZrO2 / CeO2 / TiO2), and Comparative Example 7 (TiO2) demonstrate that there is a synergistic effect between modified titanium dioxide, gadolinium phosphate, and fumed silica. Furthermore, there is a synergistic effect among AlPO4, ZrO2, and CeO2 in the modified titanium dioxide. This synergistic effect significantly improves the weather resistance and corrosion resistance of PVC gloves, thereby significantly extending their service life.

[0036] Finally, it should be noted that the above are only some preferred embodiments of the present invention and should not be construed as limiting the scope of protection of the present invention. Any non-essential improvements and adjustments made by those skilled in the art based on the above content of the present invention shall fall within the scope of protection of the present invention.

Claims

1. A nano-color paste for PVC gloves, characterized in that, It has the following composition and proportions: Modified titanium dioxide: 45~55 parts by weight; Water-based acrylic resin: 10~20 parts by weight; Rare earth phosphates: 1.5~2.5 parts by weight; Silica aerosol: 1.5~2.5 parts by weight; Dispersant: 6-8 parts by weight; Wetting agent: 1-2 parts by weight; Fungicide: 0.5~1.5 parts by weight; Deionized water: 45-55 parts by weight; The modified titanium dioxide is obtained by sequentially coating the surface of titanium dioxide with cerium dioxide, zirconium dioxide and aluminum phosphate.

2. The nano-color paste for PVC gloves according to claim 1, characterized in that: The preparation of the modified titanium dioxide includes the following steps: a) Disperse nano-titanium dioxide in water to obtain a titanium dioxide slurry; b) At room temperature, polyvinylpyrrolidone was added to an aqueous solution of cerium nitrate and stirred for 25-35 minutes. Then, ammonia was added dropwise while stirring and stirred for 50-70 minutes at room temperature to obtain cerium oxide sol. c) Heat the titanium dioxide slurry to 55~65℃, then add polycarboxylate and adjust the pH of the slurry to 8~9. Slowly add cerium oxide sol to the titanium dioxide slurry while maintaining the pH at 8~9. After the addition is complete, age for 30~90 minutes, filter, wash, dry and grind to obtain cerium dioxide-coated titanium dioxide composite material, denoted as: CeO2 / TiO2; d) Disperse CeO2 / TiO2 in water, heat the resulting slurry to 55~65℃, then add polycarboxylate and adjust the pH of the slurry to 8.5~9.

5. Then slowly add zirconium oxychloride aqueous solution, maintaining the pH of the slurry at 8.5~9.5 during this process. After the addition is complete, age for 30~90 minutes, filter, wash, dry, and grind to obtain zirconium dioxide / cerium dioxide coated titanium dioxide composite material, denoted as: ZrO2 / CeO2 / TiO2; e) Disperse ZrO2 / CeO2 / TiO2 in water, heat the resulting slurry to 80~85℃, then add polycarboxylate and adjust the pH of the slurry to 9~10. Then, slowly add aluminum sulfate aqueous solution and sodium hexametaphosphate aqueous solution at the same time, maintaining the pH of the slurry at 9~10 during this process. After the addition is complete, age for 30~90 minutes, filter, wash, dry and grind to obtain aluminum phosphate / zirconium dioxide / cerium dioxide coated titanium dioxide composite material, denoted as: AlPO4 / ZrO2 / CeO2 / TiO2.

3. The nano-pigment for PVC gloves according to claim 2, characterized in that: In step a), the particle size of nano-titanium dioxide is 10~20nm, and the concentration of titanium dioxide slurry is 200~300g / L.

4. The nano-color paste for PVC gloves according to claim 2, characterized in that, In step b), the concentration of the cerium nitrate aqueous solution is 0.05M, the concentration of the ammonia solution is 2M, and the ratio of polyvinylpyrrolidone:cerium nitrate aqueous solution:ammonia solution is (1.5~2.5)g:(150~250)mL:(4.5~5.5)mL.

5. The nano-color paste for PVC gloves according to claim 2, characterized in that: In step c), the coating amount of cerium dioxide is 0.1~0.3wt% based on titanium dioxide.

6. The nano-color paste for PVC gloves according to claim 2, characterized in that: In step d), the coating amount of zirconium dioxide is 0.5~1.5wt% based on titanium dioxide.

7. The nano-pigment for PVC gloves according to claim 2, characterized in that: In step e), the coating amount of aluminum phosphate is 2-3 wt% based on titanium dioxide.

8. The nano-color paste for PVC gloves according to claim 1, characterized in that: The rare earth phosphate is gadolinium phosphate.

9. A method for preparing the nano-pigment for PVC gloves according to claim 1, characterized in that, The process includes the following steps: First, add the specified amounts of water-based acrylic resin, wetting agent, and bactericide to deionized water and stir to mix evenly. Then, add the specified amounts of modified titanium dioxide, rare earth phosphate, silica aerosol, and dispersant and stir to mix evenly. Next, grind the resulting mixture using a three-roll mill to obtain nano-color paste for PVC gloves.

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