Non-polar resin composite material, preparation method therefor, and use thereof

Abstract

The present invention relates to the technical field of polymer materials, and particularly to a non-polar resin composite material, a preparation method therefor, and a use thereof. Specifically, disclosed in the present invention is a non-polar resin composite material, comprising, in parts by weight, the following components: 90-110 parts of a non-polar resin, 0.1-2 parts of a green organic pigment, 0.5-3 parts of a yellow organic pigment, 0.1-0.5 parts of a light stabilizer, and 0.5-3 parts of water. The present invention provides a non-polar resin composite material in which no pre-colored masterbatch is used. The material has a highly saturated yellow-green color and can avoid significant discoloration of yellow-green organic pigments under light conditions. The present invention can achieve good dispersion of pigments in a system without pretreatment of the pigments in the earlier stage, resulting in few pigment spots on the surface of the prepared material. The present invention can be applied to the manufacturing of food contact products and household appliances.

Description

A nonpolar resin composite material, its preparation method, and its application. Technical Field

[0001] This invention belongs to the field of polymer materials technology, and particularly relates to a non-polar resin composite material, its preparation method, and its application. Background Technology

[0002] Nonpolar resins are resins produced by polymerizing monomers with very small dipole moments and lacking any functional groups. Their molecular structures contain little or no functional groups capable of forming hydrogen bonds, such as hydroxyl and carboxyl groups, and therefore do not possess polar properties. Common nonpolar resins include polyethylene and polypropylene. Polyethylene is a polymer formed by the polymerization of ethylene monomers. Polypropylene is a thermoplastic resin polymerized from propylene monomers and is one of the five major general-purpose plastics.

[0003] The advantages of non-polar materials in food contact applications include non-toxicity, high temperature resistance, good chemical stability, high mechanical strength, good transparency, environmental friendliness, and cost-effectiveness. These characteristics make them an ideal choice for food packaging and contact materials.

[0004] In recent years, products with high-saturation colors have become increasingly popular in various fields. In food contact product design, high-saturation colors are gradually gaining favor with designers and consumers due to their strong visual impact and appeal. However, the preparation of high-saturation yellow-green colored products using existing non-polar resin composite materials, while ensuring food contact safety, presents the following challenges:

[0005] First, highly saturated colored products, especially those made with yellow-green organic pigments, show obvious color changes under light conditions.

[0006] Secondly, achieving highly saturated colors requires increasing the amount of organic pigments added. In actual production, uneven pigment dispersion can lead to pigment specks, affecting the product's appearance.

[0007] Existing technologies address this problem by using a masterbatch method, which involves pre-dispersing organic pigments into masterbatches. However, this approach reduces efficiency and increases costs; furthermore, ensuring adequate dispersion of the organic pigments within the masterbatch remains a challenge. A key challenge in this field is how to maintain a highly saturated yellow-green hue in a product without using a colorant, preventing significant color changes in the yellow-green organic pigments under light, and achieving a good product appearance with minimal pigment specks.

[0008] Summary of the Invention

[0009] The purpose of this invention is to overcome the existing technical problems and provide a non-polar resin composite material that can prevent yellow-green organic pigments from changing significantly under light conditions while ensuring contact with food. Furthermore, it can achieve good pigment dispersion in the system without the need for pretreatment of the pigments in the early stage. The non-polar resin composite material prepared by this invention has a small number of pigment dots on its surface.

[0010] Another object of the present invention is to provide a method for preparing the above-mentioned non-polar resin composite material.

[0011] Another object of the present invention is to provide applications of the above-mentioned non-polar resin composite materials.

[0012] This invention is achieved through the following technical solution:

[0013] A non-polar resin composite material, by weight, contains the following components:

[0014] 90-110 parts of non-polar resin;

[0015] Organic pigment green, 0.1-2 parts;

[0016] Organic pigment yellow 0.5-3 parts;

[0017] Light stabilizer 0.1-0.5 parts

[0018] Water 0.5-3 parts.

[0019] Preferably, the amount of water added is 1-2 parts.

[0020] Preferably, the non-polar resin is selected from at least one of polypropylene resin or polyethylene resin, and the polypropylene has a melt mass flow rate of 0.01g-110g / 10min at 230°C and 2.16kg load.

[0021] More preferably, the polypropylene has a melt flow rate of 0.01g-50g / 10min at 230°C and a load of 2.16kg.

[0022] More preferably, the polypropylene has a melt flow rate of 0.01g-30g / 10min at 230°C and a load of 2.16kg.

[0023] The lower the melt flow rate of polypropylene, the fewer the number of pigment spots. This is presumably because a low melt index helps reduce pigment aggregation, allowing the pigment to disperse better and thus reducing the number of pigment spots.

[0024] Preferably, the organic pigment green is selected from at least one of polychlorinated copper phthalocyanine or yellow phthalocyanine.

[0025] More preferably, the organic pigment green is selected from yellow phthalocyanine.

[0026] Preferably, the organic pigment yellow is selected from at least one of benzimidazolone diazo, tetrachloroisoindolone, benzimidazolone, monoazo calcium salt lake, or isoindolone.

[0027] More preferably, the organic pigment yellow is selected from benzimidazole ketones.

[0028] Preferably, the light stabilizer is selected from at least one of salicylate-based ultraviolet absorbers, benzophenone-based ultraviolet absorbers, benzotriazole-based ultraviolet absorbers, or triazine-based ultraviolet absorbers.

[0029] More preferably, the light stabilizer is selected from benzotriazole ultraviolet absorbers.

[0030] Specifically, the salicylate-based ultraviolet absorber is selected from at least one of phenyl salicylate, p-octylphenyl salicylate, or p-tert-butylphenyl salicylate.

[0031] Specifically, the benzophenone-based ultraviolet absorber is selected from at least one of 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-2'-carboxybenzophenone, 2-hydroxy-4-dodecyloxybenzophenone, or 2,2'-dihydroxy-4,4'-dimethoxybenzophenone.

[0032] Specifically, the benzotriazole ultraviolet absorber is selected from at least one of 2-(2'-hydroxy-3'-5'-dihydroxy-tert-butylphenyl)benzotriazole, 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, or 2-(2'-hydroxy-5'-tert-octylphenyl)benzotriazole.

[0033] Specifically, the triazine UV absorber is selected from at least one of 2,4-bis(2,4-dihydroxyphenyl)-6-(4-methoxyphenyl)-1,3,5-triazine, 2,4-bis(2,4-dihydroxyphenyl)-6-phenyl-1,3,5-triazine, 2-(2,4-dihydroxyphenyl)-4,6-diphenyl-1,3,5-triazine, or 2,4,6-tris(2,4-dihydroxyphenyl)-1,3,5-triazine.

[0034] Those skilled in the art can add 0.05-0.5 parts by weight of processing aids as needed.

[0035] Preferably, the processing aid is selected from antioxidants.

[0036] Preferably, the antioxidant is selected from at least one of hindered phenolic antioxidants, amine antioxidants, or phosphite antioxidants.

[0037] Specifically, the hindered phenolic antioxidant is selected from at least one of pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], N,N'-hexamethylenebis(3,5-di-tert-butyl-4-hydroxyphenylpropionamide), β-(4-hydroxyphenyl-3,5-di-tert-butyl)propionate n-octadecyl alcohol, or 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione.

[0038] Specifically, the amine antioxidant is selected from at least one of 4,4'-bis(α,α-dimethylbenzyl)diphenylamine, N-N'-diphenylethylenediamine, N-N'-diphenylpropylenediamine or p-p-dioctyldiphenylamine.

[0039] Specifically, the phosphite antioxidant is at least one of tris(2,4-di-tert-butylphenyl) phosphite, cyclic pentapentaerythritol di(2,6-di-tert-butyl-4-methylphenyl phosphite), or bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite.

[0040] This invention provides a method for preparing the above-mentioned non-polar resin composite material, comprising the following steps:

[0041] After mixing the components, the mixture is extruded and granulated to obtain a non-polar resin composite material.

[0042] Preferably, the resin is first mixed with other components except water, and then water is added and mixed to obtain a homogeneous material.

[0043] The preferred mixing time for the resin with other components besides water is 3-5 minutes, and the stirring speed is 20 Hz to 40 Hz.

[0044] The preferred mixing time for adding water is 3-5 minutes, and the mixing frequency is 20Hz~40Hz.

[0045] Preferably, the extrusion granulation temperature is 200~240℃, and the feeding speed is 800~1200 kg / h.

[0046] The present invention also provides applications of the above-mentioned non-polar resin composite material, characterized in that it is used to manufacture food contact products and household appliances.

[0047] Compared with the prior art, the present invention has the following advantages:

[0048] The non-polar resin composite material provided by this invention can ensure a highly saturated yellow-green color when in contact with food. Furthermore, it prevents the yellow-green organic pigment from significantly changing color under light. Water can wet the organic pigment, so there is no need for pretreatment or special extrusion processes to achieve good dispersion of the pigment in the system, resulting in a surface free of pigment specks.

[0049] This invention selects organic pigment green, which is yellowish in nature, thus reducing the amount of organic pigment yellow to be added. Organic yellow pigment shows significant color change in weathering tests and has relatively poor weather resistance. Therefore, to achieve a highly saturated yellow-green color, the combination of organic pigment green and organic pigment yellow reduces the amount of organic pigment yellow required for weather resistance, thereby improving the overall weather resistance.

[0050] In this invention, adding an appropriate amount of water can effectively disperse the color powder, significantly reduce the color powder spots on the surface of the injection molded color plate, and also make the color saturation C value higher and the color more vivid.

[0051] Meanwhile, the non-polar resin composite material provided by this invention achieves the above-mentioned technical effects without adjusting the feeding and extrusion processes, thereby improving production efficiency and reducing costs.

[0052] Detailed Implementation

[0053] The present invention will now be described in detail with reference to specific embodiments. These embodiments will help those skilled in the art to further understand the present invention, but do not limit the invention in any way. It should be noted that those skilled in the art can make various modifications and improvements without departing from the concept of the present invention. These all fall within the scope of protection of the present invention.

[0054] Sources of raw materials used in this invention:

[0055] Polyethylene: HDPE FL8920, Fujian United Petrochemical Co., Ltd., melt mass flow rate at 190℃ and 2.16kg load is 20g / 10min;

[0056] Polypropylene 1: PP SP179, Lanzhou Chemical Industry Company of China National Petroleum Corporation, melt mass flow rate at 230℃ and 2.16kg load is 10g / 10min;

[0057] Polypropylene 2: PP8285E1, Exxonmobil Chemical Asia, melt mass flow rate at 230℃ and 2.16kg load is 26g / 10min;

[0058] Polypropylene 3: PP BX3900, SK Tech International Trading (Shanghai) Co., Ltd., melt mass flow rate at 230℃ and 2.16kg load is 60g / 10min;

[0059] Polypropylene 4: K7780, Zhenhai Refining & Chemical Branch of China Petroleum & Chemical Corporation, melt mass flow rate of 80g / 10min at 230℃ and 2.16kg load;

[0060] Polypropylene 5: PP K7100, Zhenhai Refining & Chemical Branch of China Petroleum & Chemical Corporation, melt mass flow rate of 110g / 10min at 230℃ and 2.16kg load;

[0061] Polar resin 1: ABS 8391, North China Huajin Chemical Industry Co., Ltd., melt mass flow rate of 30g / 10min at 220℃ and 2.16kg load;

[0062] Polar resin 2: PMMA IF860, LG MMA, melt mass flow rate of 16 g / 10 min at 230℃ and 3.8 kg load;

[0063] Polar resin 3: PS 350K, Guoheng Chemical Co., Ltd., melt flow rate at 230℃ and 3.8kg load: 12g / 10min

[0064] Polar resin 4: SAN 80HF, Ningbo LG Yongxing Chemical Co., Ltd., melt mass flow rate at 220℃ and 10kg load: 32g / 10min;

[0065] Pigment G-1: Polychlorinated copper phthalocyanine, Pigment Green 7, K8730, BASF.

[0066] Pigment G-2: Yellow Phthalocyanine, Pigment Green 36, Green 6Y FW-C, Clariant.

[0067] Pigment B-1: Copper Phthalocyanine Blue, Pigment Blue 15:4, K7104LW, BASF.

[0068] Pigment Y-1: Benzimidazole bisazo, Pigment Yellow 180, Arrovide Yellow G180, Clariant.

[0069] Pigment Y-2: Tetrachloroisoindolinetone pigment, Pigment Yellow 110, Irgazin Yellow K 2060 SQ, BASF.

[0070] Pigment Y-3: Benzimidazole ketone, Pigment Yellow 151, PV Fast Yellow H4G, Clariant.

[0071] Pigment Y-4: Benzimidazole ketone, Pigment Yellow 214, PV Fast H9G, Clariant.

[0072] Pigment Y-5: Benzimidazole ketone, Pigment Yellow 175, Hostaperm Yellow H6G, Clariant.

[0073] Pigment Y-6: Monoazo calcium salt lake, Pigment Yellow 191, PV Fast Yellow HGR, Clariant.

[0074] Light stabilizer 1: A triazine-based ultraviolet absorber, UV-460, Tianjin Lianlong.

[0075] Light stabilizer 2: Benzophenone is a substance among ultraviolet absorbers, UV-531, Tianjin Lialong.

[0076] Light stabilizer 3: A substance among benzotriazole ultraviolet absorbers, UV-234, Tianjin Lialon.

[0077] Antioxidant 1: A type of hindered phenolic antioxidant, IRGANOX 1010, BASF.

[0078] Antioxidant 2: A substance among amine antioxidants, S-EED FF, Clariant.

[0079] Antioxidant 3: A substance among phosphite antioxidants, THANOX 168, Tianjin Lialong.

[0080] Test methods:

[0081] Pigment speckle detection: Use a 2.0mm thick, 50mm×80mm color plate to observe whether there are pigment specks with a particle size greater than 0.1mm on the surface.

[0082] Color measurement method: Using a spectrophotometer in reflectance mode, the L*, a*, b*, and C* values ​​of the color sample in the CIELab color space are measured. The spectrophotometer used is the X-rite Color-Eye 7000A spectrophotometer. By measuring the spectral reflectance factor or spectral transmittance of the object, the tristimulus values ​​of the sample color are calculated and converted to CIELab. The L*, a*, and b* values ​​represent the lightness, red-green hue, and yellow-blue hue of a color, respectively.

[0083] L* represents lightness, ranging from 0 to 100, indicating colors from dark (black) to light (white).

[0084] a* represents red and green, and the value changes from positive to negative, indicating the color changes from red to green.

[0085] b* represents yellow to blue, and the value changes from positive to negative, indicating a color change from yellow to blue.

[0086] C* represents saturation. C* = (a*^2 + b*^2)^0.5. The larger the C*, the higher the color saturation and the more vivid the color. The smaller the C*, the lower the color saturation and the paler the color.

[0087] DL* represents the difference in brightness; a positive value indicates a lighter (whiter) lightness, while a negative value indicates a darker (blacker) lightness.

[0088] Da* represents the difference between red and green; a positive value indicates more red, and a negative value indicates more green.

[0089] Db* represents the difference between yellow and blue; a positive value indicates more yellow, and a negative value indicates more blue.

[0090] DE represents the total color difference. The calculation formula is as follows:

[0091]

[0092] Weathering resistance test: Xenon lamp aging was determined according to ISO 4892.2:2013 cycle 2 standard. The color difference (DE) of the marked area before and after 1000 hours of weathering test was measured. The lower the value, the better the weathering resistance, and vice versa.

[0093] Preparation methods of the embodiments and comparative examples of the present invention:

[0094] S1: Weigh each component according to the weight parts and add the weighed non-polar resin into the premixer;

[0095] S2: During the mixing process, add the weighed components other than non-polar resin and water into the premixer;

[0096] S3: Finally, add 0.5-3 parts of water, mix for 5 minutes to obtain a homogeneous material, put the homogeneous material into an extruder, extrusion temperature 220℃, feed 1000kg / h, and after melting and homogenization, extrude and granulate, cool to obtain a non-polar resin composite material.

[0097] Table 1. Weight parts of each component and test results of non-polar resin composite materials in Examples 1-9

[0098] Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Polyethylene 90 110 Polypropylene 1100 100 100 100 100 100 Pigment G-1 0.1 12 Pigment G-2 111 111 Pigment Y-1 0.5 3 1.5 3 Pigment Y-2 3 Pigment Y-3 3 Pigment Y-4 3 Pigment Y-5 3 Pigment Y-6 3 Water 0.5 1.5 3 1.5 1.5 1.5 1.5 1.5 1.5 Light Stabilizer 10.3 0.3 0.3 0.3 30.30.30.3 Light stabilizer 20.1 Light stabilizer 30.5 Antioxidant 10.05 Antioxidant 20.25 0.25 0.25 0.25 0.25 0.25 0.25 Antioxidant 30.5 Pigment speckles None None None None None None None None None C50.56 55.90 51.05 60.47 53.53 62.77 61.15 61.68 56.67 Weather resistance test results DE2.73 2.79 2.39 1.85 2.06 1.66 1.88 1.98 2.97

[0099] As shown in Examples 2 and 4, when yellow phthalocyanine is selected as the organic pigment green, the saturation C can reach over 60, and the change in DE after weathering performance testing is small, only 1.85. Therefore, it can be concluded that yellow phthalocyanine-based organic pigment green has a better effect than polychlorinated copper phthalocyanine-based organic pigment green in this invention. It is speculated that this is because yellow phthalocyanine is biased towards the yellow phase, which is close to the yellow phase of pigments, resulting in less absorption of the yellow light reflected from the pigment yellow, thus achieving a higher saturation.

[0100] As shown in Examples 4-9, compared with other organic pigment yellows, when benzimidazole ketones are selected as organic pigment yellows, the saturation C can reach above 61, the color is more vivid, and the weather resistance is also better.

[0101] Table 2. Parts by weight of each component in non-polar resin composite materials of Examples 10-17

[0102] Example 10 Example 11 Example 12 Example 13 Example 14 Example 15 Example 16 Example 17 Polypropylene 1100 100 100 100 Polypropylene 2 100 Polypropylene 3 100 Polypropylene 4 100 Polypropylene 5 100 Pigment G-2 11111111 Pigment Y-4 333333333 Water 1.5 1.5 0.5 3 1.5 1.5 1.5 1.5 Light stabilizer 20.3 Light stabilizer 30.3 0.30.30.30.30.30.3 Antioxidant 20.250.250.250.250.250.250.250.25 Pigment Spots None None None None None Slight Slight C60.9161.8159.3059.8961.1060.3358.9155.76 Weather Resistance Test Results DE2.051.252.232.211.981.892.132.36

[0103] Examples 7 and 12-13 show that the amount of water added has a certain influence on the saturation and weather resistance of non-polar resin composite materials.

[0104] As can be seen from Examples 7 and 14-17, the lower the melt flow rate of the non-polar resin, the stronger its ability to disperse pigments, the higher the saturation of the color can be achieved, and the smaller the change in the DE value after the weather resistance test.

[0105] Table 3. Parts by weight of each component in the resin composites of Comparative Examples 1-6

[0106] Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Polypropylene 100 100 Polar Resin 1 100 Polar Resin 2 100 Polar Resin 3 100 Polar Resin 4 100 Pigment B-11 Pigment G-2 11111 Pigment Y-4 333333 Water 1.5 / 1.5 1.5 1.5 1.5 1.5 1.5 Light Stabilizer 30.30.30.30.30.3 Antioxidant 20.25 0.25 0.25 0.25 0.25 Pigment Spots None None None None C 44.0 149.23 62.70 62.68 60.60 58.84 After Weather Resistance Test DE 4.8 62.5 74.2 23.9 14.1 23.53

[0107] Comparative Example 1 uses organic pigment blue instead of organic pigment green. Its saturation characterization value C is less than 50. Compared with Example 7 which uses organic pigment green, the color is dull. This is because pigment blue can absorb more yellow light reflected by pigment yellow than pigment green, so it is difficult to have a high saturation. Moreover, its DE after weather resistance test is 4.86, and it changes color obviously after being exposed to light. Therefore, it can be seen that organic pigment blue cannot achieve the technical effect to be achieved by the present invention.

[0108] In Comparative Example 2, no water was added, and the organic pigments were not fully dispersed, resulting in noticeable pigment spots.

[0109] Comparative Examples 3-6 used polar resin materials instead of non-polar resin materials. In comparison, the weather resistance of polar resin materials after exposure to light was worse than that of non-polar resin materials. Secondly, products made with polar resin materials could not meet the requirements of various countries and regions for food contact materials.

Claims

1. A non-polar resin composite material, characterized in that, By weight, it includes the following components: 90-110 parts of non-polar resin; Organic pigment green, 0.1-2 parts; Organic pigment yellow 0.5-3 parts; Light stabilizer 0.1-0.5 parts; Water 0.5-3 parts.

2. The non-polar resin composite material according to claim 1, characterized in that, The amount of water added is 1-2 parts by weight.

3. The non-polar resin composite material according to claim 1, characterized in that, The non-polar resin is selected from at least one of polypropylene resin or polyethylene resin, wherein the polypropylene has a melt mass flow rate of 0.01g-110g / 10min at 230°C and 2.16kg load, preferably 0.01g-50g / 10min.

4. The non-polar resin composite material according to claim 1, characterized in that, The organic pigment green is selected from at least one of polychlorinated copper phthalocyanine or yellow phthalocyanine, preferably yellow phthalocyanine.

5. The non-polar resin composite material according to claim 1, characterized in that, The organic pigment yellow is selected from at least one of benzimidazolone diazo, tetrachloroisoindolone, benzimidazolone, monoazo calcium salt, or isoindolone, preferably benzimidazolone.

6. The non-polar resin composite material according to claim 1, characterized in that, The light stabilizer is selected from at least one of salicylate-based ultraviolet absorbers, benzophenone-based ultraviolet absorbers, benzotriazole-based ultraviolet absorbers, or triazine-based ultraviolet absorbers, preferably benzotriazole-based ultraviolet absorbers.

7. The non-polar resin composite material according to claim 6, characterized in that, The salicylate-based ultraviolet absorber is selected from at least one of phenyl salicylate, p-octylphenyl salicylate, or p-tert-butylphenyl salicylate; the benzophenone-based ultraviolet absorber is selected from at least one of 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-2'-carboxybenzophenone, 2-hydroxy-4-dodecyloxybenzophenone, or 2,2'-dihydroxy-4,4'-dimethoxybenzophenone; the benzotriazole-based ultraviolet absorber is selected from at least one of 2-(2'-hydroxy-3'-5'-dihydroxy-tert-butylphenyl) The triazine UV absorber is selected from at least one of butylphenyl)benzotriazole, 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, or 2-(2'-hydroxy-5'-tert-octylphenyl)benzotriazole; 8. The non-polar resin composite material according to claim 1, characterized in that, The product also includes 0.05-0.5 parts by weight of processing aids; preferably, the processing aids are antioxidants.

9. A method for preparing a nonpolar resin composite material according to any one of claims 1-8, characterized in that, Includes the following steps: After mixing the components, the mixture is extruded and granulated to obtain a non-polar resin composite material.

10. The application of the nonpolar resin composite material according to any one of claims 1-8, characterized in that, Used in the manufacture of food contact products and home appliances.

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