Masterbatch additives and the use of masterbatch additives.

Abstract

DEPCT68 Additive pigments and the use of additive pigments, including raw materials for additive pigments and resins, have been provided. Substances, high melting point additives, and low melting point additives, where the melting point of... High melting point additives (above 40 degrees Celsius) and low melting point additives. Equal to or less than 40 degrees Celsius, pigment additives correct low melting point pigment additives that tend to Sticking and clumping, difficult preparation process, difficult to mold, etc. The formulated pigment additives, which are not prone to clumping, can be prepared. Easily prepared using a combined process for pigment preparation, it is easy to mold and can be prepared as follows: Pigments with different particle sizes;

Description

A kind of auxiliary agent masterbatch and its application

[0001] This application is based on the Chinese application with CN application number 202210940265.4 and application date August 5, 2022, and claims its priority. The disclosed content of the CN application is again introduced as a whole into this application. Technical Field

[0002] The present application relates to the technical field of polymer materials, and in particular to an additive masterbatch and its application. Background Art

[0003] When polymer materials are exposed to sunlight for a long time, they absorb ultraviolet energy and age and degrade, resulting in discoloration, cracking, decreased mechanical and electrical properties, and other aging phenomena in the materials, making them unusable. This process is called photoaging.

[0004] Adding light stabilizers during the production of polymer materials can effectively slow down the above-mentioned light aging reactions.

[0005] Currently, light stabilizers primarily include UV absorbers and hindered amine light stabilizers. UV absorbers include benzophenones, benzotriazoles, and triazines. UV absorbers function as light stabilizers by absorbing harmful ultraviolet light and converting it into heat. Hindered amine light stabilizers function by first forming reactive free radicals, which then capture free radicals generated by aging and degradation. Hindered amine light stabilizers represent a significant advancement in polymer light stabilization and are widely used in general-purpose plastics, engineering plastics, coatings, adhesives, rubber, and other fields.

[0006] While hindered amine light stabilizers (HALSs) offer excellent performance, some have low melting points, making them difficult to dose during use. The solution is to prepare these low-melting-point HALSs into additive masterbatches to facilitate mixing and processing with polymer materials. However, these additive masterbatches, due to their low-melting-point additive components, can agglomerate during storage, transportation, and subsequent use, impacting downstream customers' ability to use them. For example, 2,2,6,6-tetramethyl-4-piperidinyl stearate (UV-3853) has a melting point of only around 28°C and appears white to light yellow, waxy, or oily at room temperature. As mentioned above, this product is typically prepared as a masterbatch for customer use, but these masterbatches can experience agglomeration during storage, transportation, and subsequent use.

[0007] In response to the technical problems of the above-mentioned low-melting-point additive masterbatch, taking UV-3853 as an example, the current mainstream solutions in the anti-aging additive industry are mainly the following: (1) Use some other processing aids, such as foaming agents and adsorbents, to improve the coating performance of the PP carrier for the light stabilizer UV-3853, thereby achieving the purpose of inhibiting the precipitation of the light stabilizer UV-3853; however, due to the introduction of a certain proportion of adsorbents and foaming agents in this method, some adverse effects may be produced in the processing of polymer materials, such as compatibility issues. (2) Use foamed polypropylene as a carrier, and absorb the 3853 liquid through the foamed polypropylene, thereby achieving the purpose of improving the precipitation of the light stabilizer 3853. This method has high production costs, low production efficiency, and high requirements for processing technology, and does not have cost advantages. (3) Adding a protective layer to the surface. For example, patent CN108137863A discloses 3853PP5 produced by multi-stage extruder co-extrusion technology. The wrapping effect is achieved by extruding another layer of sheath on the surface. However, since the cutter cutting surface cannot be protected, precipitation and agglomeration will still occur in actual application.

[0008] In addition to UV-3853, other low-melting-point additive masterbatches also have the above-mentioned preparation difficulties and the problem of high masterbatch adhesion.

[0009] In view of this, this application is hereby filed.

[0010] Summary of the Invention

[0011] The main purpose of the present application is to provide an additive masterbatch and its application, so as to solve the problems of easy agglomeration and complex process of low-melting-point additive masterbatch in the prior art.

[0012] In order to achieve the above-mentioned purpose, according to one aspect of the present application, an additive masterbatch is provided, the raw materials of which include a resin base material, a high melting point additive and a low melting point additive; wherein the melting point of the high melting point additive is greater than 40°C, and the melting point of the low melting point additive is ≤40°C.

[0013] Furthermore, the low melting point adjuvant is a liquid or paste at room temperature, or a solid with a melting point ≤ 40°C; preferably, the high melting point adjuvant has a melting point greater than 80°C, more preferably greater than 100°C, further preferably greater than 150°C, further preferably greater than 200°C.

[0014] Furthermore, the low melting point additive is a weathering additive with a melting point ≤ 40°C, preferably a light stabilizer with a melting point ≤ 40°C; preferably, the light stabilizer is a hindered amine light stabilizer and / or an ultraviolet absorber, more preferably a hindered amine light stabilizer or a combination thereof.

[0015] Furthermore, the hindered amine light stabilizer or its composition is selected from one or more of the following: the reaction product of bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate, tert-butyl hydroperoxide and octane, 2,2,6,6-tetramethyl-4-piperidinyl stearate, a mixture of bis(1,2,2,6,6,-pentamethyl-4-piperidinyl) sebacate and mono(1,2,2,6,6,-pentamethyl-4-piperidinyl) sebacate, and a mixture of bis(2,2,6,6-tetramethyl-1-undecyloxy-4-yl)-carbonate 2,2,6,6-tetramethyl-4-piperidinyl stearate and 3,5-di-tert-butyl-4-hydroxybenzoic acid n-hexadecyl.

[0016] Further, the ultraviolet absorber is selected from one or more of benzotriazole ultraviolet absorbers, cyanoacrylate ultraviolet absorbers, benzamidine ultraviolet absorbers, benzophenone ultraviolet absorbers, hydroxyphenyltriazine ultraviolet absorbers, oxalic acid anilide ultraviolet absorbers or salicylate ultraviolet absorbers; more preferably, the ultraviolet absorber is selected from the reaction product of 3-(3-(2H-benzotriazole-2-yl)-5-tert-butyl-4-hydroxyphenyl) methyl propionate and PEG 300, 3,5-di-tert-butyl-4-hydroxybenzoic acid hexadecyl ester, 2-cyano-3,3-diphenylacrylate-2'-ethylhexyl ester, N-(ethoxycarbonylphenyl)-N'-methyl-N'-phenylformamidine and one or more.

[0017] Furthermore, the high melting point additive is an organic and / or inorganic substance, preferably a high melting point additive is a polymer material additive; more preferably, the high melting point additive is a polymer material organic additive with a relative molecular mass greater than 500, further preferably a polymer material organic additive with a relative molecular mass greater than 600; further preferably, the high melting point additive is selected from one or more of tris[2.4-di-tert-butylphenyl]phosphite, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, and polyethylene wax; preferably, the resin matrix is Thermoplastic resin; more preferably, the thermoplastic resin is selected from one or more of polyolefin, polyester, polyether, polyketone, polyamide, polyurethane, polystyrene, high impact styrene, polyacrylate, polymethacrylate, polyacetal, polyacrylonitrile, polybutadiene, acrylonitrile-butadiene-benzenetriene terpolymer, styrene-acrylonitrile copolymer, acrylate-styrene-acrylonitrile terpolymer, cellulose acetate butyrate, cellulose polymer, polyimide, polyamideimide, polyetherimide, polyphenylene sulfide, polyphenylene oxide, polysulfone, polyethersulfone, polyvinyl chloride, polycarbonate, polyoxymethylene, and ethylene-vinyl acetate polymer; more preferably, the resin matrix is ​​polyolefin; further preferably, the polyolefin is selected from polypropylene and / or polyethylene.

[0018] Furthermore, in parts by weight, the raw materials of the polymer material additive masterbatch include 30 to 70 parts of a resin base material, 0.1 to 30 parts of a high melting point additive and 30 to 70 parts of a low melting point additive; more preferably, in parts by weight, the raw materials of the polymer material additive masterbatch include 30 to 70 parts of a resin base material, 1 to 25 parts of a high melting point additive and 30 to 70 parts of a low melting point additive; further preferably, in parts by weight, the raw materials of the polymer material additive masterbatch include 40 to 60 parts of a resin base material, 1 to 20 parts of a high melting point additive and 40 to 60 parts of a low melting point additive; further preferably, the weight ratio of the high melting point additive to the low melting point additive is 1:3 to 15, and most preferably 1:5 to 15.

[0019] Furthermore, the low melting point auxiliary agent is one or more of 2,2,6,6-tetramethyl-4-piperidinyl stearate, a mixture of 2,2,6,6-tetramethyl-4-piperidinyl stearate and 3,5-di-tert-butyl-4-hydroxybenzoic acid hexadecyl, the resin base material is polyethylene or polypropylene, and the high melting point auxiliary agent is one or more of tris[2,4-di-tert-butylphenyl]phosphite, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, and polyethylene wax;

[0020] Preferably, the auxiliary agent masterbatch comprises: 1 to 20 parts of tris[2,4-di-tert-butylphenyl]phosphite, 30 to 50 parts of 2,2,6,6-tetramethyl-4-piperidinyl stearate and 30 to 50 parts of polypropylene resin; or 1 to 20 parts of 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 30 to 50 parts of 2,2,6,6-tetramethyl-4-piperidinyl stearate and 30 to 5 0 parts of polypropylene resin; or 1 to 20 parts of 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, 30 to 50 parts of 2,2,6,6-tetramethyl-4-piperidinyl stearate and 30 to 50 parts of polypropylene resin; or 0.1 to 10 parts of tris[2,4-di-tert-butylphenyl]phosphite, 0.1 to 10 parts of 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, 30 to 50 parts of 2,2,6,6-tetramethyl-4-piperidinyl stearate and 30-50 parts of polypropylene resin; or 0.1-10 parts of tris[2,4-di-tert-butylphenyl]phosphite, 0.1-10 parts of 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 30-50 parts of 2,2,6,6-tetramethyl-4-piperidinyl stearate and 30-50 parts of polypropylene resin; or 0.1-1 0 parts of polyethylene wax, 0.1-10 parts of 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione and / or tris[2,4-di-tert-butylphenyl]phosphite and / or 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, 30-50 parts of 2,2,6,6-tetramethyl-4-piperidinyl stearate and 30-50 parts of polypropylene resin.

[0021] Furthermore, the polymer material additive masterbatch is formed by screw extrusion, granulation, drying and cooling of the raw materials in sequence. Preferably, underwater pelletizing is used for granulation, and the operating temperature is 190-230°C.

[0022] Furthermore, the particle size of the polymer material additive masterbatch is 1 to 5 mm.

[0023] According to another aspect of the present application, there is also provided an application of the above-mentioned additive masterbatch in polymer materials.

[0024] The present application effectively solves the problems of easy adhesion and agglomeration of low-melting-point additive masterbatches and complex preparation processes. The additive masterbatches prepared in the present application are not easy to agglomerate and can be produced using commonly used equipment and processes for preparing masterbatches. The operation is simple and additive masterbatch products of different particle sizes can be prepared. BRIEF DESCRIPTION OF THE DRAWINGS

[0025] The drawings that constitute part of this application are used to provide a further understanding of this application. The illustrative embodiments of this application and their descriptions are used to explain this application and do not constitute an improper limitation on this application. In the drawings:

[0026] FIG1 shows a product photo of a large-particle additive masterbatch prepared according to one embodiment of the present application;

[0027] FIG2 shows a product photo of a small particle additive masterbatch prepared according to one embodiment of the present application;

[0028] Figure 3 shows photos of the additive masterbatch prepared in Example 1 of the present application, wherein (a) is a photo before the test and (b) is a photo after the test;

[0029] Figure 4 shows photos of the additive masterbatch prepared in Example 2 of the present application, wherein (a) is a photo before the test and (b) is a photo after the test;

[0030] Figure 5 shows photos of the additive masterbatch prepared in Example 3 of the present application, wherein (a) is a photo before the test and (b) is a photo after the test;

[0031] Figure 6 shows photos of the additive masterbatch prepared in Example 4 of the present application, wherein (a) is a photo before the test and (b) is a photo after the test;

[0032] FIG7 shows photos of the additive masterbatch prepared in Example 5 of the present application, wherein (a) is a photo before the test and (b) is a photo after the test;

[0033] FIG8 shows photos of the additive masterbatch prepared in Example 6 of the present application, wherein (a) is a photo before the test and (b) is a photo after the test;

[0034] Figure 9 shows photos of the additive masterbatch prepared in Example 7 of the present application, wherein (a) is a photo before the test and (b) is a photo after the test;

[0035] Figure 10 shows photos of the additive masterbatch prepared in Example 8 of the present application, wherein (a) is a photo before the test, and (b) is a photo after the test;

[0036] Figure 11 shows photos of the additive masterbatch prepared in Example 9 of the present application, wherein (a) is a photo before the test, and (b) is a photo after the test;

[0037] Figure 12 shows photos of the additive masterbatch prepared in Example 10 of the present application, wherein (a) is a photo before the test, and (b) is a photo after the test;

[0038] Figure 13 shows photos of the additive masterbatch prepared in Example 11 of the present application, wherein (a) is a photo before the test, and (b) is a photo after the test;

[0039] Figure 14 shows photos of the additive masterbatch prepared in Example 12 of the present application, wherein (a) is a photo before the test, and (b) is a photo after the test;

[0040] Figure 15 shows photos of the additive masterbatch prepared in Example 13 of the present application, wherein (a) is a photo before the test, and (b) is a photo after the test;

[0041] Figure 16 shows a photo of the additive masterbatch after testing in Comparative Example 1;

[0042] Figure 17 shows a photo of the additive masterbatch after testing in Comparative Example 2;

[0043] FIG18 shows photographs of the auxiliary agent masterbatch in Comparative Example 3, wherein (a) is the product at the beginning of production, (b) is the product 5 minutes after production, and (c) is an untested product. DETAILED DESCRIPTION

[0044] It should be noted that, in the absence of conflict, the embodiments and features of the embodiments in this application can be combined with each other. The present application will be described in detail below with reference to the accompanying drawings and in combination with the embodiments.

[0045] As described in the background technology section, low-melting-point additive masterbatches are prone to sticking and agglomerating. The existing technical solutions include introducing components that can adsorb low-melting-point additives to reduce the precipitation of additives and thus reduce the risk of masterbatch sticking and agglomeration, or achieving an anti-sticking and agglomeration effect by squeezing a layer of sheath on the surface of the masterbatch. Existing solutions either introduce unconventional adsorbents or have complex preparation processes and are difficult to implement. Against this background, the present application provides a simpler and more effective solution, which completely solves the problem of easy sticking and agglomeration of additive masterbatches, and at the same time, the preparation process of the additive masterbatch provided is simple.

[0046] In a typical embodiment of the present application, an additive masterbatch is provided, the raw materials of which include a resin base material, a high melting point additive and a low melting point additive; wherein the melting point of the high melting point additive is greater than 40°C, and the melting point of the low melting point additive is ≤40°C.

[0047] Low-melting-point additives are easy to precipitate in the masterbatch resin matrix. In addition to their low melting point, it is also related to the poor compatibility between the two. It is difficult for the resin matrix to fully wrap around the surface of the low-melting-point additive. When the temperature rises, the low-melting-point additive melts or the fluidity increases, causing precipitation problems, especially near the surface of the masterbatch, where the precipitation problem is more obvious. The additive masterbatch provided in this application, in addition to the resin matrix and the low-melting-point additive, also introduces a high-melting-point additive with a melting point greater than 40°C. In the preparation process of the masterbatch, the raw materials usually undergo screw extrusion, granulation, drying, cooling and other steps. The above-mentioned high-melting-point additive introduced in this application can be uniformly melted and dispersed in the resin matrix together with the low-melting-point additive during the screw extrusion and granulation stages of the masterbatch. Subsequently, due to the decrease in processing temperature, the high-melting-point additive will first solidify and wrap around the surface of the low-melting-point additive, forming a protective barrier, thereby effectively suppressing the adhesion and agglomeration problem of the additive masterbatch during subsequent transportation and use.

[0048] In addition, the additive masterbatch provided in this application can be made using a conventional granulation process. It should be noted that the inventors of this application have found through research that masterbatch granulation also has certain requirements for particle size. Generally, it is necessary to prepare large or small particles to meet the needs of different downstream material additions. The particle size of small particle masterbatch is usually (2±1)×(2±1)mm, and the particle size of large particle masterbatch is usually (4±1)×(4±1)mm. The raw materials of this application have a large melt pressure during the granulation process because the material melt has a large strength, which ensures that it can smoothly pass through the small hole die head to form small-sized masterbatch particles, and the masterbatch shape is round and full, with good fluidity. Therefore, the particle size range of the polymer material additive masterbatch of this application is adjustable, relatively wide, and has good molding performance. The large particle masterbatch and small particle masterbatch formed are shown in Figures 1 and 2 respectively.

[0049] The greater the difference in melting points between the high-melting-point additive and the low-melting-point additive, the more favorable it is for the high-melting-point additive to form a protective film on the surface of the low-melting-point additive, which further promotes the anti-caking and adhesion of the masterbatch. In a preferred embodiment, the low-melting-point additive of this application is a liquid or paste at room temperature, or a solid with a melting point of 40°C or less. The melting point of the high-melting-point additive is greater than 80°C, more preferably greater than 100°C, even more preferably greater than 150°C, and even more preferably greater than 200°C.

[0050] Preferably, the low-melting-point additive is a weathering additive with a melting point of 40°C or less, preferably a light stabilizer with a melting point of 40°C or less. This application is more suitable for such low-melting-point additives, as they are more effective in improving problems such as masterbatch agglomeration. Preferably, the light stabilizer is a hindered amine light stabilizer and / or a UV absorber, more preferably a hindered amine light stabilizer or a combination thereof.

[0051] For example, hindered amine light stabilizers include, but are not limited to, the reaction product of bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate, tert-butyl hydroperoxide and octane (UV-123), 2,2,6,6-tetramethyl-4-piperidinyl stearate (UV-3853), a mixture of bis(1,2,2,6,6,-pentamethyl-4-piperidinyl) sebacate and mono(1,2,2,6,6,-pentamethyl-4-piperidinyl) sebacate (UV-292), bis(2,2,6,6-tetramethyl-1- The UV absorber includes, but is not limited to, one or more of benzotriazole UV absorbers, cyanoacrylate UV absorbers, benzamidine UV absorbers, benzophenone UV absorbers, hydroxyphenyltriazine UV absorbers, oxalic acid anilide UV absorbers or salicylate UV absorbers; more preferably, the UV absorber is selected from the reaction product of methyl 3-(3-(2H-benzotriazol-2-yl)-5-tert-butyl-4-hydroxyphenyl) propionate and PEG 300 (UV-1130), hexadecyl 3,5-di-tert-butyl-4-hydroxybenzoate (UV-2908), 2-cyano-3,3-diphenylacrylate-2′-ethylhexyl ester (UV-3039), N-(ethoxycarbonylphenyl)-N′-methyl-N′-phenylformamidine (UV-1). The combination of the hindered amine light stabilizer and the ultraviolet absorber is a mixture (UV-3808) of 2,2,6,6-tetramethyl-4-piperidinyl stearate (UV-3853) and 3,5-di-tert-butyl-4-hydroxybenzoic acid hexadecyl (UV2908).

[0052] In a preferred embodiment, the high melting point additive is an organic and / or inorganic substance, and preferably the high melting point additive is a polymer material additive. The use of polymer material additives can have better dispersibility and compatibility in the resin matrix, and can form a better coating for the low melting point additive on the basis of a lower dosage, so that the anti-caking ability of the masterbatch is better. More preferably, the high melting point additive is a polymer material organic additive with a relative molecular mass greater than 500. The above-mentioned polymer material organic additive is selected so that it can precipitate to the surface of the masterbatch together with the melted low melting point additive in the granulation process during the masterbatch preparation process. It is worth noting that the present application even utilizes such precipitation properties of the high melting point additive, so that it can fully precipitate the high melting point additive in the granulation process of the masterbatch preparation process, so that it can more fully condense and coat the surrounding low melting point additive precipitated in the subsequent cooling process, so as to better inhibit agglomeration after the masterbatch is formed. The use of a high melting point additive with a relative molecular weight greater than 500 has a better promoting effect on preventing the final masterbatch product from sticking and agglomerating. More preferably, the high melting point additive is a polymer material organic additive with a relative molecular weight greater than 600.

[0053] In a preferred embodiment, the high melting point additive is selected from one or more of tris[2,4-di-tert-butylphenyl]phosphite (antioxidant 168, melting point 183-187°C), 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione (antioxidant 3114, melting point 218-223°C), 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene (antioxidant 330, melting point 240-245°C), and polyethylene wax (melting point 90-120°C). In addition to better exerting the above-mentioned precipitation and encapsulation effects, these high melting point additives can form a masterbatch together with the above-mentioned low melting point additives without affecting the subsequent application of the masterbatch and can even exert a better anti-aging effect. In particular, the use of functional additives such as Antioxidant 168, Antioxidant 330, and Antioxidant 3114 not only prevents the precipitation of low-melting-point additives but also provides an anti-aging effect when used on resin substrates. Furthermore, the addition of these high-melting-point additives does not need to be excessive to effectively resolve the masterbatch agglomeration problem.

[0054] The resin matrix described in this application can be adjusted according to the use environment of the additive masterbatch. For example, if the additive masterbatch needs to be added to a polypropylene resin system, the resin matrix can be polypropylene resin; if the additive masterbatch needs to be added to a polyethylene resin system, the resin matrix can be polyethylene resin. Preferably, the resin matrix is ​​a thermoplastic resin. On the one hand, the thermoplastic resin can be directly used as a component of the plastic product during subsequent processing (even if it is different from the product composition, since the amount of additive masterbatch added is often small, it will not cause other effects on the performance of the plastic product). On the other hand, it can also serve as a better first-layer barrier to the melted low-melting-point additive.

[0055] More preferably, the resin matrix is ​​a thermoplastic resin; further preferably, the thermoplastic resin is selected from one or more of polyolefins, polyesters, polyethers, polyketones, polyamides, polyurethanes, polystyrenes, high-impact styrenes, polyacrylates, polymethacrylates, polyacetals, polyacrylonitrile, polybutadiene, acrylonitrile-butadiene-benzenetriene terpolymers, styrene-acrylonitrile copolymers, acrylate-styrene-acrylonitrile terpolymers, cellulose acetate butyrate, cellulose polymers, polyimides, polyamide-imides, polyetherimides, polyphenylene sulfide, polyphenylene oxide, polysulfones, polyethersulfones, polyvinyl chloride, polycarbonates, polyoxymethylene, and ethylene-vinyl acetate polymers.

[0056] More preferably, the resin matrix is ​​a polyolefin. Using a polyolefin as a resin matrix offers greater versatility, and the high-melting-point additives mentioned above can further improve the overall performance of the masterbatch. Further preferably, the polyolefin is selected from polypropylene and / or polyethylene.

[0057] In a preferred embodiment, the raw materials of the additive masterbatch include 30 to 70 parts of resin base material (for example, 30 parts, 32 parts, 35 parts, 40 parts, 42 parts, 44 parts, 45 parts, 46 parts, 48 ​​parts, 50 parts, 52 parts, 55 parts, 58 parts, 60 parts, 65 parts, 70 parts), 0.1 to 30 parts of high melting point additive (for example, 0.1 parts, 0.2 parts, 0.5 parts, 0.8 parts, 1 part, 2 parts, 3 parts, 5 parts, 6 parts, 8 parts, 10 ... More preferably, the raw materials of the additive masterbatch include 30 to 70 parts of resin base material, 1 to 25 parts of high melting point additive and 30 to 70 parts of low melting point additive in parts by weight. Further preferably, the raw materials of the polymer material additive masterbatch include 40 to 60 parts of resin base material, 1 to 20 parts of high melting point additive and 40 to 60 parts of low melting point additive in parts by weight. More preferably, the weight ratio of the high melting point additive to the low melting point additive is 1:3 to 15, and most preferably 1:5 to 15. By controlling the amount of each component within the above range, the amount of low melting point additive added can be increased as much as possible while effectively suppressing problems such as agglomeration.

[0058] In a preferred embodiment, the low melting point auxiliary agent is one or more of 2,2,6,6-tetramethyl-4-piperidinyl stearate, a mixture of 2,2,6,6-tetramethyl-4-piperidinyl stearate and 3,5-di-tert-butyl-4-hydroxybenzoic acid hexadecyl ester, the resin substrate is polyethylene or polypropylene, and the high melting point auxiliary agent is one or more of tris[2.4-di-tert-butylphenyl]phosphite (antioxidant 168), 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione (antioxidant 3114), 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene (antioxidant 330), and polyethylene wax. By compounding the high melting point additive with the low melting point additive and the resin base material in the above manner, the resulting masterbatch has better anti-blocking performance, and the additive itself also has better anti-aging performance.

[0059] Exemplarily, the additive masterbatch includes:

[0060] 1 to 20 parts of tris[2,4-di-tert-butylphenyl]phosphite, 30 to 50 parts of 2,2,6,6-tetramethyl-4-piperidinyl stearate and 30 to 50 parts of polypropylene resin; or

[0061] 1-20 parts of 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 30-50 parts of 2,2,6,6-tetramethyl-4-piperidinyl stearate and 30-50 parts of polypropylene resin; or

[0062] 1 to 20 parts of 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, 30 to 50 parts of 2,2,6,6-tetramethyl-4-piperidinyl stearate and 30 to 50 parts of polypropylene resin; or

[0063] 0.1-10 parts of tris[2,4-di-tert-butylphenyl]phosphite, 0.1-10 parts of 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, 30-50 parts of 2,2,6,6-tetramethyl-4-piperidinyl stearate and 30-50 parts of polypropylene resin; or

[0064] 0.1-10 parts of tris[2,4-di-tert-butylphenyl]phosphite, 0.1-10 parts of 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 30-50 parts of 2,2,6,6-tetramethyl-4-piperidinyl stearate and 30-50 parts of polypropylene resin; or

[0065] 0.1-10 parts of polyethylene wax, 0.1-10 parts of 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione and / or tris[2,4-di-tert-butylphenyl]phosphite and / or 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, 30-50 parts of 2,2,6,6-tetramethyl-4-piperidinyl stearate, and 30-50 parts of polypropylene resin.

[0066] As previously mentioned, the masterbatch pelletizing process in this application can be conventionally used in the art. For example, the additive masterbatch is formed by screw extrusion, pelletizing, drying, and cooling the raw materials. Preferably, the pelletizing process is performed by underwater pelletizing at an operating temperature of 190-230°C.

[0067] The particle size of the polymer material additive masterbatch of the present application can be adjusted according to needs, and preferably the particle size is 1 to 5 mm.

[0068] In addition, this application also provides the use of the above-mentioned additive masterbatch in polymer materials. Due to its excellent anti-caking properties, the additive masterbatch also facilitates the dispersion and compatibility of the masterbatch during polymer material processing. Specifically, the polymer material substrate includes but is not limited to polyolefins, polyvinyl chloride, polyacetal, polyamide, styrene polymers, polyurethane, ABS resin, etc. Specific polymer material products include but are not limited to plastic products, thermoplastic elastomer products, rubber products, coatings, adhesives, etc.

[0069] In summary, this application has a simple operation process, a wide range of equipment applications, stable production, and product quality and appearance compared to others have the following advantages:

[0070] (1) The additive masterbatch of the present application has a high melting point additive as a protective layer, and the prepared additive masterbatch does not agglomerate at all even in a storage or transportation environment with high temperature or alternating high and low temperatures;

[0071] (2) The preparation process of the additive masterbatch of the present application is simple, easy to industrialize and mass-produce, and has high stability; and does not affect the processing of downstream materials;

[0072] (3) The present application can prepare products with large and small particles. After a 24-hour, 50°C beaker with a 500G weight fluidity level test, the agglomerate fluidity of the additive masterbatch of the present application is level 1-2, meeting the diverse needs of downstream material processing.

[0073] The present application is further described in detail below with reference to specific embodiments. These embodiments should not be construed as limiting the scope of protection claimed in this application.

[0074] Example 1

[0075] In this example, an automatic metering loss-in-weight scale was used to add PP resin and antioxidant 168 to a twin-screw extruder according to the proportions in Table 1 below. UV-3853 liquid was added to the twin-screw extruder using a liquid metering pump. After screw extrusion (extrusion process see Table 2), water-cooled pelletizing, drying, and cooling were performed to obtain masterbatches with a particle size of 3.5 to 5 mm.

[0076] Table 1

[0077] Table 2

[0078] The masterbatch product was subjected to a 24-hour, 50°C beaker with a 500G weight fluidity test. The results are shown in the table below. Photos before and after the test are shown in Figure 3 below, where (a) is the photo before the test and (b) is the photo after the test.

[0079] Example 2

[0080] The only difference between this embodiment and embodiment 1 is that the component ratio is shown in Table 3, a small-diameter die head is used in the extrusion process (the extrusion process is shown in Table 4), and the particle size of the prepared masterbatch is 1.0 to 2.5 mm.

[0081] Table 3

[0082] Table 4

[0083] The masterbatch product was subjected to a 24-hour, 50°C beaker with a 500G weight flowability test. The results are shown in the table below. Photos before and after the test are shown in Figure 4 below, where (a) is the photo before the test and (b) is the photo after the test.

[0084] Example 3

[0085] The only difference between this embodiment and embodiment 1 is that the component ratio is shown in Table 5, the extrusion process is shown in Table 6, and the particle size of the prepared masterbatch is 3.5 to 5 mm.

[0086] Table 5

[0087] Table 6

[0088] The masterbatch product was subjected to a 24-hour, 50°C beaker with a 500G weight fluidity test. The results are shown in the table below. Photos before and after the test are shown in Figure 5 below, where (a) is the photo before the test and (b) is the photo after the test.

[0089] Example 4

[0090] The only difference between this embodiment and embodiment 1 is that the component ratio is shown in Table 7, the extrusion process is shown in Table 8, and the particle size of the prepared masterbatch is 3.5 to 5 mm.

[0091] Table 7

[0092] Table 8

[0093] The masterbatch product was tested for fluidity level at 50°C for 24 hours using a 500G weight in a beaker. The results are shown in the table below. Photos before and after the test are shown in Figure 6 below, where (a) is the photo before the test and (b) is the photo after the test.

[0094] Example 5

[0095] The only difference between this embodiment and embodiment 1 is that the component ratio is shown in Table 9, the extrusion process is shown in Table 10, and the particle size of the prepared masterbatch is 1.0 to 2.5 mm.

[0096] Table 9

[0097] Table 10

[0098] The masterbatch product was subjected to a 24-hour, 50°C beaker with a 500G weight fluidity test. The results are shown in the table below. Photos before and after the test are shown in Figure 7 below, where (a) is the photo before the test and (b) is the photo after the test.

[0099] Example 6

[0100] The only difference between this embodiment and embodiment 1 is that the component ratio is shown in Table 11, the extrusion process is shown in Table 12, and the particle size of the prepared masterbatch is 1.0 to 2.5 mm.

[0101] Table 11

[0102] Table 12

[0103] The masterbatch product was tested for fluidity level at 50°C for 24 hours using a 500G weight in a beaker. The results are shown in the table below. Photos before and after the test are shown in Figure 8 below, where (a) is the photo before the test and (b) is the photo after the test.

[0104] Example 7

[0105] The only difference between this embodiment and embodiment 1 is that the component ratio is shown in Table 13, the extrusion process is shown in Table 14, and the particle size of the prepared masterbatch is 1.0 to 2.5 mm.

[0106] Table 13

[0107] Table 14

[0108] The masterbatch product was subjected to a 24-hour, 50°C beaker with a 500G weight fluidity test. The results are shown in the table below. Photos before and after the test are shown in Figure 9 below, where (a) is the photo before the test and (b) is the photo after the test.

[0109] Example 8

[0110] The only difference between this embodiment and embodiment 1 is that the component ratio is shown in Table 15, the extrusion process is shown in Table 16, and the particle size of the prepared masterbatch is 3.5 to 5 mm.

[0111] Table 15

[0112] Table 16

[0113] The masterbatch product was subjected to a 24-hour, 50°C beaker with a 500G weight flowability test. The results are shown in the table below. Photos before and after the test are shown in Figure 10 below, where (a) is the photo before the test and (b) is the photo after the test.

[0114] Example 9

[0115] The only difference between this embodiment and embodiment 1 is that the component ratio is shown in Table 17, the extrusion process is shown in Table 18, and the particle size of the prepared masterbatch is 3.5 to 5 mm.

[0116] Table 17

[0117] Table 18

[0118] The masterbatch product was subjected to a 24-hour, 50°C beaker with a 500G weight fluidity test. The results are shown in the table below. Photos before and after the test are shown in Figure 11 below, where (a) is the photo before the test and (b) is the photo after the test.

[0119] Example 10

[0120] The only difference between this embodiment and embodiment 1 is that the component proportions are shown in Table 19, the extrusion process is shown in Table 20, and the particle size of the prepared masterbatch is 1.0 to 2.5 mm.

[0121] Table 19

[0122] Table 20

[0123] The masterbatch product was tested for fluidity level at 50°C for 24 hours using a 500G weight in a beaker. The results are shown in the table below. Photos before and after the test are shown in Figure 12 below, where (a) is the photo before the test and (b) is the photo after the test.

[0124] Example 11

[0125] The only difference between this embodiment and embodiment 1 is that the component proportions are shown in Table 21, the extrusion process is shown in Table 22, and the particle size of the prepared masterbatch is 1.0 to 2.5 mm.

[0126] Table 21

[0127] Table 22

[0128] The masterbatch product was subjected to a 24-hour, 50°C beaker with a 500G weight fluidity test. The results are shown in the table below. Photos before and after the test are shown in Figure 13 below, where (a) is the photo before the test and (b) is the photo after the test.

[0129] Example 12

[0130] The only difference between this embodiment and embodiment 1 is that the component ratio is shown in Table 23, the extrusion process is shown in Table 24, and the particle size of the prepared masterbatch is 1.0 to 2.5 mm.

[0131] Table 23

[0132] Table 24

[0133] The masterbatch product was subjected to a 24-hour, 50°C beaker with a 500G weight flowability test. The results are shown in the table below. Photos before and after the test are shown in Figure 14 below, where (a) is the photo before the test and (b) is the photo after the test.

[0134] Example 13

[0135] The only difference between this embodiment and embodiment 1 is that the component proportions are shown in Table 25, the extrusion process is shown in Table 26, and the particle size of the prepared masterbatch is 1.0 to 2.5 mm.

[0136] Table 25

[0137] Table 26

[0138] The masterbatch product was subjected to a 24-hour, 50°C beaker with a 500G weight flowability test. The results are shown in the table below. Photos before and after the test are shown in Figure 15 below, where (a) is the photo before the test and (b) is the photo after the test.

[0139] Comparative Example 1

[0140] Commercially available UV-3853 PP masterbatch product 1 (UV-3853 weight content 50%) was subjected to a 24-hour, 50°C beaker with a 500G weight flowability test, as shown in FIG16 .

[0141] The above-mentioned product uses co-extrusion technology to form a protective cover on the surface of ordinary masterbatch products. However, the cut surface is not protected by the cover when the cutter cuts the pellets, and the color is very dark yellow and there will still be agglomeration.

[0142] Comparative Example 2

[0143] The commercially available UV-3853 PP masterbatch product 2 (UV-3853 weight content 50%) has a fluidity level of 4 after foaming. The masterbatch product was subjected to a 24-hour, 50°C beaker with a 500G weight fluidity level test. The photo is shown in Figure 17 and shows severe agglomeration.

[0144] Comparative Example 3

[0145] The product (UV-3853 weight content 50%) produced according to the method of CN 113462079 A was found to be difficult to form a pressure differential during granulation due to the dilute material and low melt pressure. This ensured relatively normal granulation only for the first five minutes, after which flaky particles with severe tailing appeared. Furthermore, due to the dilute material, it was prone to overflow and die clogging, resulting in low material utilization and a low yield rate. Figure 18 shows photos of the product at the start of production, the product produced five minutes later, and the product after testing, where Figure (a) shows the product at the start of production, Figure (b) shows the product produced five minutes later, and Figure (c) shows the untested product.

[0146] While the product produced with this formula does not agglomerate, the material's fluidity is similar to that of melted pure wax. The extremely low resin content results in a masterbatch with low strength, severe tailing, poor regularity, and low density. This makes the masterbatch difficult to process and lacks machine adaptability, making stable batch production challenging. Furthermore, the processing and use of this masterbatch carries the risk of low strength and cracking. Due to the material's characteristics, this process cannot produce small particles.

[0147] After the masterbatch of the above embodiments and comparative examples was prepared, its appearance was observed and the yield (qualified product amount / feeding amount) was calculated. The results are shown in Table 27.

[0148] The masterbatch products of the above embodiments and comparative examples were subjected to a 24h, 50°C beaker with a 500G weight fluidity grade test, and the specific operation is as follows:

[0149] 1. Place 50g of masterbatch in a beaker, place a jar (round stainless steel sheet) on the powder or granules, and place a 500g weight on the jar;

[0150] 2. Place the beaker in a forced air oven at 50°C for 24 hours (use a new sample for each temperature exposure);

[0151] 3. Take it out and cool it to room temperature for two hours;

[0152] 4. Use the following grading system to rank the sample for caking, blocking, brittleness, and flow characteristics:

[0153] Level 1 - Free flow;

[0154] Level 2 - some lumps, easily broken (brittle);

[0155] Level 3 - Mostly lumpy, can be broken down with some effort (relatively brittle);

[0156] Level 4 - Most blocks do not split;

[0157] Grade 5 - molten solid;

[0158] The results are shown in Table 27:

[0159] Table 27

[0160] The above results show that the low melting point additive masterbatch produced in this application has a good anti-caking effect. It is baked in a forced air convection oven at 50°C for 24 hours without any adhesion or agglomeration.

[0161] The production method of the additive masterbatch of the present application is simple, the process is stable, the output is high, the equipment is widely applicable, the cost is low, and there is no use risk for back-end customers. It has extremely high market competitiveness in the domestic and foreign markets.

[0162] The above description is merely a preferred embodiment of the present application and is not intended to limit the present application. Various modifications and variations are possible for those skilled in the art. Any modifications, equivalent substitutions, or improvements made within the spirit and principles of the present application shall be included within the scope of protection of the present application.

Claims

DEPCT681. Additive Pigments, whereby the raw materials of the additive pigment consist of a resin substrate, high melting point additives and low melting point additives, where the melting point of the high melting point additives is greater than 40°C and the melting point of the low melting point additives is equal to or less than 40°C.

2. Additive Pigments under Patent 1, whereby the low melting point additives are liquids or viscous substances at room temperature or solids with a melting point equal to or less than 40°C and, in the desired form, the melting point of the high melting point additives is greater than 80°C, in the desired form greater than 100°C, in the desired form greater than 150°C, and in the desired form greater than 200°C.

3. Additive Pigments under Patent 1 or 2,Where low melting point additives are weather-resistant additives with a melting point equal to or less than 40°C as desired, are photostabilizers with a melting point equal to or less than 40°C as desired, and the photostabilizer is composed of an amine-blocking photostabilizer and / or an ultraviolet absorber as desired; moreover, the amine-blocking photostabilizer or its components 4. Pigment additives pursuant to claim 3, where A light-stabilizing amine or other constituent compound is selected from one or more of the reaction products of bis(2,2,6,6-tetramethyl-4-piperidinyl) zebacate with butyl hydroperoxide and octane, 2,2,6,6-tetramethyl-4-piperidinyl stearate, a mixture of bis(1,2,2,6,6-pentamethyl-4-piperidinyl) zebacate and mono(1,2,2,6,6-pentamethyl-4-piperidinyl) zebacate, bis(2,2,6,6-tetramethyl-1-undecanoxy-4-yl)-carbonate, and a mixture of 2,2,6,6-tetramethyl-4-piperidinyl stearate and hexadecil3.5-Bistert-Butyl-4-Hydroxybenzoate 5. Pigment additive pursuant to Patent 3, whereby a UV adsorbent is selected from one or more of the following UV adsorbents: benzotriazole UV adsorbent, cyanoacrylate UV adsorbent, benzamidine UV adsorbent, benzophenone UV adsorbent, hydroxyphenyltriazine UV adsorbent, oxanilide UV adsorbent or salicylate UV adsorbent and in lux. For more advanced properties, the ultraviolet adsorbent was selected from one or more of the reaction products of methyl3-(3-(2H-benzotriazole-2-yl)-5-tert-butyl-4-hydroxyphenyl)propionate and PEG300, hexadezyl3,5-di-tert-butyl-4-hydroxybenzoate, 2'-ethylhexyl2-cyano-3,3-diphenylacrylate and N-(ethoxycarbonylphenyl)-N'-methyl-N'-phenylformamidine.

6. Pigment additives as per one of claims 1 through 4.Where high melting point additives are composed of organic and / or inorganic compounds and, in a manner desired, high melting point additives are polymer additives; more specifically, high melting point additives are organic polymer additives with a relative molecular weight greater than 500; further specifically, high melting point additives are organic polymer additives with a relative molecular weight greater than 600; further specifically, high melting point additives are selected from one or more of the tri[2,4-di-tert-b]. [Butylphenyl phosphite, 1,3,5-tri(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 1,3,5-trimethyl-2,4,6-tri(3,5-di-tert-butyl-4-hydroxybenzyl)benzene and polyethylene wax in the desired manner, the substrate resin is a thermoplastic resin in the desired manner, more specifically, the thermoplastic resin is selected from one or more of the following: polyolefin, polyester, polyether, polyketone, polyamide, polyurethane, polystyrene, high-impact styrene, polyacrylate, polymethacrylate, polyacetal, polyacrylonitrile,Polybutadiene, acrylonitrile-butadiene-phenyltriene trimmer, styrene-acrylonitrile copolymer, acrylate-styrene-acrylonitrile trimmer, cellulose acetate butyrate, cellulose polymer, polyimide, polyamide imide, polyether imide, polyphenylene sulfide, polyphenyl ether, polysulfone, polyether sulfone, polyvinyl chloride, polycarbonate, polyformaldehyde and ethylene-vinyl acetate polymer in more desired forms, the resin substrate is polyolephite. Furthermore, in the manner required, polyolefins are selected from polypropylene and / or polyethylene.

7. Pigment additives as per one of claims 1 through 6, where by weight the raw material of the pigment additive consists of 30-70 parts resin substrate, 0.1-30 parts high melting point additives and 30-70 parts low melting point additives; in the manner required, by weight the raw material of the pigment additive consists of 30-70 parts resin substrate,1-25 parts of high melting point additives and 30-70 parts of low melting point additives, in the desired manner, according to the weight ratio of raw material, the pigment additive consists of 40-60 parts of resin substrate, 1-20 parts of high melting point additives and 40-60 parts of low melting point additives, and in the desired manner, the weight ratio of high melting point additives to low melting point additives is 1:3-15, in the most desired manner 1:5-15.

8. Pigment additives according to one of the claims in Patents 1 to 7, Low melting point additives consist of one or more of 2,2,6,6-tetramethyl-4-piperidinyl stearate and a mixture of 2,2,6,6-tetramethyl-4-piperidinyl stearate and hexadezil 3,5-bis-tert-butyl-4-hydroxybenzoate resin substrates composed of polyethylene or polypropylene. High melting point additives consist of one or more of tri[2,4-di-tert-butylphenyl]phosphite, 1,3,5-tri(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 1,3,5-trimethyl-2,4,6-tri(3,5-di-tert-butyl-4-hydroxybenzyl)benzene and polyethylene wax, and in the desired form, the pigment additive consists of 1-20 parts of tri[2,4-di-tert-butylphenyl]phosphite, 30-50 parts of 2,2,6,6-tetramethyl-4-piperidinyl stearate and 30-50 parts of polypropylene resin or 1 -20 parts of 1,3,5-tri(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 30-50 parts of 2,2,6,6-tetramethyl-4-piperidinylstearate and 30-50 parts of polypropylene resin or 1-20 parts of 1,3,5-trimethyl-2,4,6-tri(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione 1,3,5-trimethyl-2,4,6-tri(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, 30-50 parts of 2,2,6,6-tetramethyl-4-piperidinyl stearate and 30-50 parts of polypropylene resin or 0.1-10 parts of tri[2,4-di-tert-butylphenyl]phosphite, 0.1-10 parts of 1,3,5-trimethyl-2,4,6-tri(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, 30-50 parts A mixture of 2,2,6,6-tetramethyl-4-piperidinyl stearate and 30-50 part of polypropylene resin or 0.1-10 part of tri[2,4-di-tert-butylphenyl]phosphite, 0.1-10 part of 1,3,5-tri(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 30-50 part of 2,2,6,6-tetramethyl-4-piperidinyl stearate and 30-50 part of polypropylene resin or 0.1-10 part of polyethylene wax, 0.1-10 part of 1,3,5-tri(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione and / or tri[2,4-di-tert-butylphenyl]phosphite and / or 1,3,5-trimethyl-2,4,6-tri(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, 30-50 part of 2,2,6,6-tetramethyl-4-piperidinyl stearate and 30-50 part of polypropylene resin.

9. Tablets.

10. Use of any of the color additives in Patents 1-9 in polymer materials; where the color additives are formed by screw extrusion, pelletizing, drying and cooling of the raw materials, respectively, and in the desired manner, pelletizing is carried out by underwater pelletizing at an operating temperature of 190-230°C and in the desired manner, the particle size of the polymer material is 1-5 mm.

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