Non-polar resin composite material, preparation method and application thereof

Abstract

The application belongs to the technical field of high polymer materials, and particularly relates to a non-polar resin composite material and a preparation method and application thereof, and specifically discloses a non-polar resin composite material, which comprises the following components in parts by weight: non-polar resin 90-110 parts; organic pigment green 0.1-2 parts; organic pigment yellow 0.5-3 parts; light stabilizer 0.1-0.5 parts; and water 0.5-3 parts. The application provides a non-polar resin composite material without using color-forming color master batches, the material has high saturation of yellow-green color, and yellow-green organic pigments can be prevented from obviously changing color under light conditions, the application can realize good dispersion of pigments in the system without pretreating the pigments in the early stage, and the material prepared has few toner points on the surface. The application can be applied to preparation of food contact products and household appliances.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of high polymer materials, and particularly relates to a non-polar resin composite material and a preparation method and application thereof. BACKGROUND

[0002] Non-polar resin refers to resin made by polymerization of monomers with small dipole moment and without any functional groups. They do not contain or contain very few functional groups that can form hydrogen bonds, such as hydroxyl groups, carboxyl groups, etc., so they do not have polar characteristics. Common non-polar resins include polyethylene and polypropylene. Polyethylene is a high molecular compound formed by polymerization of ethylene monomers. Polypropylene is a thermoplastic resin formed by polymerization of propylene monomers, and is one of the five general-purpose plastics.

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

[0004] In recent years, high-saturation color products have become increasingly popular in various fields. In the design of food contact products, high-saturation colors are gradually favored by designers and consumers because of their strong visual impact and appeal. However, the non-polar resin composite material provided by the prior art has the following difficulties in preparing high-saturation yellow-green color products under the premise of ensuring safety in contact with food:

[0005] First, high-saturation color products, especially those using yellow-green organic pigments, are significantly discolored under light conditions.

[0006] Second, achieving high-saturation color requires increasing the amount of organic pigment added, which may result in color powder points due to uneven dispersion of the pigment during actual production, affecting the appearance of the product.

[0007] The existing technology solves this problem by using a master batch method, i.e., first making a color master batch by pre-dispersing the organic pigment. However, on the one hand, this method reduces efficiency and increases cost; on the other hand, it is also difficult to disperse the organic pigment sufficiently in the master batch. It is a difficult point in the field to maintain high-saturation yellow-green color in products without using color master batches, avoid significant discoloration of yellow-green organic pigments under light conditions, and have good product appearance with few color powder points. SUMMARY

[0008] The object of the present invention is to overcome the existing technical problems and provide a non-polar resin composite material. The material can avoid obvious discoloration of yellow-green organic pigments under light conditions while ensuring contact with food, and can achieve good dispersion of the pigments in the system without the need for pre-treatment of the pigments in the early stage. The non-polar resin composite material prepared by the present invention has a small number of color powder spots on the surface.

[0009] Another object of the present invention is to provide a method for preparing the above-mentioned non-polar resin composite material.

[0010] Another object of the present invention is to provide an application of the non-polar resin composite material.

[0011] The present invention is achieved through the following technical solutions:

[0012] A non-polar resin composite material, comprising the following components in parts by weight:

[0013] 90-110 parts of non-polar resin;

[0014] 0.1-2 parts of organic pigment green;

[0015] Organic pigment yellow 0.5-3 parts;

[0016] Light stabilizer 0.1-0.5 parts

[0017] 0.5-3 parts water.

[0018] Preferably, the amount of water added is 1-2 parts.

[0019] Preferably, the non-polar resin is selected from at least one of polypropylene resin and polyethylene resin, and the non-polar resin is selected from at least one of polypropylene resin and polyethylene resin, and the polypropylene has a melt mass flow rate of 0.01g-110g / 10min at 230°C and a load of 2.16kg.

[0020] Further preferably, the polypropylene has a melt mass flow rate of 0.01 g to 50 g / 10 min at 230° C. and a load of 2.16 kg.

[0021] More preferably, the polypropylene has a melt mass flow rate of 0.01 g to 30 g / 10 min at 230° C. and a load of 2.16 kg.

[0022] The lower the melt mass flow rate of polypropylene, the fewer the number of toner dots. It is speculated that the reason is that the low melt index helps to reduce toner aggregation, making the toner better dispersed, thereby reducing the number of toner dots.

[0023] Preferably, the organic pigment green is selected from at least one of polychloro copper phthalocyanine or yellow light phthalocyanine.

[0024] Further preferably, the organic pigment green is selected from yellow light phthalocyanine.

[0025] Preferably, the organic pigment yellow is selected from at least one of benzimidazolone disazo, tetrachloro isoindolinone, benzimidazolone, monoazo calcium salt lake or isoindolinone.

[0026] Further preferably, the organic pigment yellow is selected from benzimidazolone.

[0027] Preferably, the light stabilizer is selected from at least one of salicylate ultraviolet absorber, benzophenone ultraviolet absorber, benzotriazole ultraviolet absorber or triazine ultraviolet absorber.

[0028] Further preferably, the light stabilizer is selected from benzotriazole ultraviolet absorber.

[0029] Specifically, the salicylate ultraviolet absorber is selected from at least one of phenyl salicylate, p-octyl phenyl salicylate or p-tert-butyl phenyl salicylate.

[0030] Specifically, the benzophenone ultraviolet absorber is selected from at least one of 2,4-dihydroxyxylene ketone, 2-hydroxy-4-methoxy benzophenone, 2.2'-dihydroxy-4-methoxy benzophenone, 2-hydroxy-4-methoxy-2'-carboxy benzophenone, 2-hydroxy-4-dodecyloxy benzophenone or 2.2'-dihydroxy-4,4'-dimethoxy benzophenone.

[0031] Specifically, the benzotriazole ultraviolet absorber is selected from at least one of 2-(2'-hydroxy-3'-5'-dihydroxy tert-butyl phenyl) benzotriazole, 2-(2'-hydroxy-5'-methyl phenyl) benzotriazole or 2-(2'-hydroxy-5'-tert-octyl phenyl) benzotriazole.

[0032] Specifically, the triazine ultraviolet absorber is selected from at least one of 2,4-bis(2,4-dihydroxy phenyl)-6-(4-methoxy phenyl)-1,3,5-triazine, 2,4-bis(2,4-dihydroxy phenyl)-6-phenyl-1,3,5-triazine, 2-(2,4-dihydroxy phenyl)-4,6-diphenyl-1,3,5-triazine or 2,4,6-tris(2,4-dihydroxy phenyl)-1,3,5-triazine.

[0033] The processing aid can be added by 0.05-0.5 parts by weight as required by those skilled in the art.

[0034] Preferably, the processing aid is selected from antioxidant.

[0035] Preferably, the antioxidant is selected from at least one of hindered phenolic antioxidant, amine antioxidant or phosphite antioxidant.

[0036] Specifically, the hindered phenolic antioxidant is selected from at least one of tetrakis [3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate] pentaerythritol, N,N'-hexamethylene bis(3,5-di-tert-butyl-4-hydroxyphenylpropionamide), beta-(4-hydroxyphenyl-3,5-di-tert-butyl) propionic acid n-octadecyl or 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione.

[0037] Specifically, the amine antioxidant is selected from at least one of 4,4'-bis(alpha,alpha-dimethylbenzyl) diphenylamine, N-N'-diphenyl ethylenediamine, N-N'-diphenyl propylenediamine or p,p'-dioctyl diphenylamine.

[0038] Specifically, the phosphite antioxidant is at least one of tris(2,4-di-tert-butylphenyl) phosphite, cyclic pentaerythritol tetra(diphenyl-2,6-di-tert-butyl-4-methylphenyl) phosphite or bis(2,4-di-tert-butylphenyl) pentaerythritol diphosphite.

[0039] The application provides a preparation method of the non-polar resin composite material, comprising the following steps:

[0040] After mixing the components, extruding and granulating to obtain the non-polar resin composite material.

[0041] Preferably, the resin is mixed with other components except water first, and then mixed with water to obtain the mixed material.

[0042] The mixing time of the resin with other components except water is preferably 3-5 min, and the stirring speed is 20-40 Hz.

[0043] The mixing time of the resin with other components except water is preferably 3-5 min, and the stirring speed is 20-40 Hz.

[0044] Preferably, the temperature of the extruding and granulating is 200-240 DEG C, and the feeding speed is 800-1200 kg / h.

[0045] The application also provides the application of the non-polar resin composite material, which is characterized by being used for making food contact products and household appliances.

[0046] Compared with the prior art, the application has the following beneficial effects:

[0047] The non-polar resin composite provided by the application can ensure high saturation of yellow-green color under the premise of contacting food, and on the other hand, the non-polar resin composite provided by the application can avoid obvious discoloration of yellow-green organic pigment under light conditions. Water can infiltrate the organic pigment, so that good dispersion of the pigment in the system can be achieved without pretreatment of the pigment in the early stage or special extrusion process, so that the surface of the pigment is free of color powder points.

[0048] The organic pigment green is selected to be yellow in the application, so that the addition amount of organic pigment yellow can be reduced. The organic yellow pigment is obviously discolored in the weather resistance test, and is relatively poor in weather resistance, so that the addition amount of the organic pigment yellow which is relatively poor in weather resistance can be reduced by adopting the scheme of the organic pigment green and the organic pigment yellow, so that the overall weather resistance level is improved.

[0049] In the application, the color powder can be effectively dispersed by adding an appropriate amount of water, the color powder points on the surface of the injection molding color plate can be significantly reduced, and the color saturation C value can be higher and the color can be more bright.

[0050] Meanwhile, the non-polar resin composite provided by the application can realize the above technical effects without adjusting the feeding and extrusion process, so that the production efficiency is improved and the cost is reduced. DETAILED DESCRIPTION

[0051] The application will be described in detail below in combination with specific embodiments. The following embodiments will help those skilled in the art to further understand the application, but do not limit the application in any form. It should be pointed out that those skilled in the art can make several modifications and improvements without departing from the concept of the application. These all belong to the protection scope of the application.

[0052] The raw materials used in the application are as follows:

[0053] Polyethylene: HDPE FL8920, Fujian United Petrochemical Co., Ltd., melt mass flow rate under a load of 190℃ and 2.16kg is 20g / 10min;

[0054] Polypropylene 1: PP SP179, China Petroleum Lanzhou Chemical Industry Co., Ltd., melt mass flow rate under a load of 230℃ and 2.16kg is 10g / 10min;

[0055] Polypropylene 2: PP8285E1, Exxonmobil Chemical Asia, melt mass flow rate under a load of 230℃ and 2.16kg is 26g / 10min;

[0056] Polypropylene 3: PP BX3900, Borealis, melt mass flow rate 60 g / 10 min at 230 °C, 2.16 kg load;

[0057] Polypropylene 4: K7780, Zhenhai Refinery and Chemical Co., Ltd., melt mass flow rate 80 g / 10 min at 230 °C, 2.16 kg load;

[0058] Polypropylene 5: PP K7100, Zhenhai Refinery and Chemical Co., Ltd., melt mass flow rate 110 g / 10 min at 230 °C, 2.16 kg load;

[0059] Polar resin 1: ABS 8391, Beifang Huajin Chemical Industry Co., Ltd., melt mass flow rate 30 g / 10 min at 220 °C, 2.16 kg load;

[0060] Polar resin 2: PMMA IF860, LG MMA, melt mass flow rate 16 g / 10 min at 230 °C, 3.8 kg load;

[0061] Polar resin 3: PS 350K, Guoheng Chemical Co., Ltd., melt mass flow rate 12 g / 10 min at 230 °C, 3.8 kg load

[0062] Polar resin 4: SAN 80HF, Ningbo Lekin Yongxing Chemical Co., Ltd., melt mass flow rate 32 g / 10 min at 220 °C, 10 kg load;

[0063] Pigment G-1: Polychloro copper phthalocyanine, Pigment Green 7, K8730, BASF.

[0064] Pigment G-2: Yellow light phthalocyanine, Pigment Green 36, Green 6Y FW-C, Clariant.

[0065] Pigment B-1: Copper phthalocyanine blue, Pigment Blue 15:4, K7104LW, BASF.

[0066] Pigment Y-1: Benzimidazolone disazo, Pigment Yellow 180, Arrovide Yellow G180, Clariant.

[0067] Pigment Y-2: Tetrachloro isoindolinone pigment, Pigment Yellow 110, Irgazin Yellow K 2060 SQ, BASF.

[0068] Pigment Y-3: Benzimidazolone, Pigment Yellow 151, PV Fast yellow H4G, Clariant.

[0069] Pigment Y-4: Benzimidazolone, Pigment Yellow 214, PV Fast H9G, Clariant.

[0070] Pigment Y-5: Benzimidazolone, Pigment Yellow 175, Hostaperm Yellow H6G, Clariant.

[0071] Pigment Y-6: Monoazo calcium salt lake, Pigment Yellow 191, PV Fast yellow HGR, Clariant.

[0072] Light stabilizer 1: One of the triazine ultraviolet absorbers, UV-460, Tianjin Li'an Long.

[0073] Light stabilizer 2: One of the benzophenone ultraviolet absorbers, UV-531, Tianjin Li'an Long.

[0074] Light stabilizer 3: One of the benzotriazole ultraviolet absorbers, UV-234, Tianjin Li'an Long.

[0075] Antioxidant 1: One of the hindered phenol antioxidants, IRGANOX 1010, BASF.

[0076] Antioxidant 2: One of the amine antioxidants, S-EED FF, Clariant.

[0077] Antioxidant 3: One of the phosphite antioxidants, THANOX 168, Tianjin Li'an Long.

[0078] Test methods:

[0079] Color powder point detection: The color plate with a thickness of 2.0 mm and a size of 50 mm x 80 mm, whether there are color powder points with a particle size greater than 0.1 mm on the surface is observed.

[0080] Color measurement method: Using a spectrophotometer in reflection mode, the L* value, a* value, b* value and C* value of the color plate in the CIELab color space are measured. The spectrophotometer is Color-Eye 7000A spectrophotometer of X-rite. By measuring the spectral reflectance factor or spectral transmittance of an object, the three stimulus 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.

[0081] L* represents lightness, ranging from 0 to 100, indicating the color from dark (black) to light (white).

[0082] a* represents red-green, the value changes from positive to negative, indicating the color from red to green.

[0083] b* represents yellow-blue, the value changes from positive to negative, indicating that the color changes from yellow to blue.

[0084] C* represents saturation, C* = (a*^2+ b*^2)^0.5, the larger C* represents the higher color saturation, the more bright color, the smaller C* represents the lower color saturation, the more light color.

[0085] DL* is the difference of lightness, positive value indicates lighter (white), negative value indicates darker (black).

[0086] Da* is the difference of red-green, positive value indicates redder, negative value indicates greener.

[0087] Db* is the difference of yellow-blue, positive value indicates yellower, negative value indicates bluer.

[0088] DE represents the total color difference. The calculation formula is as follows:

[0089]

[0090] Weathering performance test: xenon lamp aging is determined according to ISO 4892.2:2013 cycle 2 standard. The color difference DE before and after 1000 hours of weathering test of the marking area is measured. The lower the value, the better the weathering performance, and vice versa.

[0091] Preparation method of the inventive examples and comparative examples:

[0092] S1: weigh each component by weight parts, add the weighed non-polar resin into the premixer;

[0093] S2: add other components except non-polar resin and water into the premixer during stirring;

[0094] S3: finally add 0.5-3 parts of water, mix for 5 min, get the mixed material, put the mixed material into the extruder, the extrusion temperature is 220℃, the feeding is 1000kg / h, after melting and homogenization, extrude and granulate, cool, get the non-polar resin composite material.

[0095] Table 1: weight parts of each component of non-polar resin composite material of examples 1-9 and test results

[0096]

[0097] From Example 2 and Example 4, when the organic pigment green is selected as yellow light phthalocyanine, the saturation C can reach more than 60, and the DE change after weather resistance test is only 1.85. It can be seen that yellow light phthalocyanine organic pigment green has better effect than polychloro copper phthalocyanine organic pigment green in the present application. It is speculated that the reason is that yellow light phthalocyanine is biased to yellow phase, which is close to the yellow phase of pigment yellow, and the absorption of yellow light reflected by pigment yellow is less, so that higher saturation can be achieved.

[0098] From Examples 4-9, compared with other organic pigment yellows, when the organic pigment yellow is selected as benzimidazolone, the saturation C can all reach more than 61, the color is more bright, and the weather resistance level is also better.

[0099] Table 2 Weight parts of each component of non-polar resin composite material in Examples 10-17

[0100]

[0101] From Examples 7, 12-13, the amount of water added has a certain effect on the saturation and weather resistance of the non-polar resin composite material.

[0102] From Examples 7, 14-17, the lower the melt mass flow rate of the non-polar resin, the stronger the color powder dispersing ability, the higher the saturation color can be achieved, and the smaller the DE value change after weather resistance test.

[0103] Table 3 Weight parts of each component of resin composite material in Comparative Examples 1-6

[0104]

[0105] Comparative Example 1 uses organic pigment blue instead of organic pigment green, and the saturation value C is less than 50. Compared with Example 7 using organic pigment green, the color is dull, because pigment blue can absorb more yellow light reflected by pigment yellow than pigment green, so it is difficult to have high saturation; and the DE after weather resistance test reaches 4.86, and the discoloration after light is obvious. It can be seen that the organic pigment blue cannot achieve the technical effect of the present application.

[0106] Comparative Example 2 does not add water, and the organic pigment cannot be fully dispersed, and the color powder point is obvious.

[0107] Comparative Examples 3-6 use polar resin material instead of non-polar resin material. Compared with non-polar resin material, the weather resistance of polar resin material after light is poor. Secondly, the product made of polar resin material cannot meet the requirements of food contact materials in various countries and regions.

Claims

1. A non-polar resin composite material, characterized in that: Calculated by weight, it includes the following components: 90-110 parts of non-polar resin; 0.1-2 parts of organic pigment green; Organic pigment yellow 0.5-3 parts; Light stabilizer 0.1-0.5 parts; 0.5-3 parts water; The organic green pigment is selected from at least one of polychlorinated copper phthalocyanine and yellow phthalocyanine; The organic pigment yellow is selected from at least one of benzimidazolone, monoazo calcium salt lake or tetrachloroisoindolinone.

2. A 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 and polyethylene resin, and the melt mass flow rate of the polypropylene at 230° C. and a load of 2.16 kg is 0.01 g-110 g / 10 min.

4. The non-polar resin composite material according to claim 3, characterized in that: The polypropylene has a melt mass flow rate of 0.01 g to 50 g / 10 min at 230° C. and a load of 2.16 kg.

5. The non-polar resin composite material according to claim 1, characterized in that: The organic green pigment is selected from yellow phthalocyanine.

6. The non-polar resin composite material according to claim 1, characterized in that: The benzimidazolone is selected from benzimidazolone disazo.

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

8. The non-polar resin composite material according to claim 7, characterized in that: The light stabilizer is selected from benzotriazole ultraviolet absorbers.

9. The non-polar resin composite material according to claim 7, characterized in that: The salicylate-based UV absorber is selected from at least one of phenyl salicylate, p-octylphenyl salicylate, or p-tert-butylphenyl salicylate; the benzophenone-based UV 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 UV absorber is selected from at least one of 2-(2'-hydroxy-3'-5'-dihydroxy-tert-butylbenzophenone) At least one of 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-(2'-hydroxy-5'-tert-octylphenyl)benzotriazole or 2-(2'-hydroxy-5'-tert-octylphenyl)benzotriazole; the triazine ultraviolet 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.

10. The non-polar resin composite material according to claim 1, characterized in that: Calculated by weight, the invention also includes 0.05-0.5 parts of processing aids.

11. The non-polar resin composite material according to claim 10, characterized in that: The processing aid is selected from antioxidants.

12. The method for preparing a non-polar resin composite material according to any one of claims 1 to 11, characterized in that: The following steps are involved: After mixing the various components, the mixture is extruded and granulated to obtain a non-polar resin composite material.

13. Use of a non-polar resin composite material according to any one of claims 1 to 11, characterized in that: Used in the production of food contact products and appliances.

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