Reactive composite light stabilizer and its use, and light-stable modified polymeric materials

Abstract

The present invention provides a reactive composite light stabilizer and its use, and light-stable modified polymeric material.The reactive composite light stabilizer comprises a reactive ultraviolet absorber and a reactive hindered amine light stabilizer, and the reactive ultraviolet absorber is a reactive triazine ultraviolet absorber.The combination of reactive triazine ultraviolet absorber and reactive hindered amine light stabilizer can increase absorption rate, improve combined effect, reduce volatility, and increase photodegradation resistance stability, and since they are all reactive components, they can exist in the form of chemical bond in polymeric material, and thus have better long-term effective properties.

Description

[Technical field]

[0001] This application claims priority to CN Application No. 202210176909.7 (filed February 24, 2022), the disclosure of which is hereby incorporated by reference in its entirety.

[0002] The present invention relates to the technical field of polymeric material modification, in particular to a reactive composite light stabilizer and its use, as well as to light-stable modified polymeric materials. [Background technology]

[0003] With the progress of material technology, the unique and excellent properties brought by various polymer materials have opened up a huge development space in modern society. Polymer materials play an important role in various fields of national economy and people's lives, but their aging characteristics have become a very serious restrictive factor. Polymer aging will inevitably affect its performance, resulting in shortened life and waste of resources. The main factors that cause polymer aging are light and heat, among which the ultraviolet rays contained in natural sunlight have a particularly significant effect on the long-term effective properties of polymers. At present, outdoor light aging prevention is mainly solved by adding light stabilizers. Such light stabilizers include ultraviolet absorbers and hindered amine light stabilizers. Ultraviolet absorbers can absorb or block ultraviolet rays that can cause damage to polymers, and hindered amine light stabilizers can eliminate free radicals that lead to polymer degradation. Hindered amine light stabilizers can significantly reduce the aging process of polymer materials and have become an important product category in the field of polymer anti-aging.

[0004] Ultraviolet absorbers (referred to as UVA) and hindered amine light stabilizers (referred to as HALS) exhibit synergistic effects, thus significantly improving the anti-aging effect of polymers. Therefore, the combination of UVA and HALS has been successfully applied in many fields of polymer materials. The current traditional combination of UVA and HALS may encounter the following problems:

[0005] 1. Material applicability problems: manifested in two ways. One is a problem caused by the alkalinity of HALS. This alkalinity is directly determined by the group attached to the nitrogen atom of the piperidine ring. The general rule is (in the order of strong to weak alkalinity): NH>NR>N-OR>N-COR. Highly alkaline HALS interacts with undesirable substances (e.g. acid catalysts, desiccants, etc.) contained in the raw material system, leading to a decrease in the expected performance of the final product. Therefore, low alkaline HALS is a more resistant use scenario and a trend for future development. The other is a problem brought about by the compatibility of materials and light stability products. According to the principle of "similar compatibility", the polarity of the material system can affect the compatibility of additive products (including HALS), leading to problems such as precipitation. (Note: compatibility here refers to the compatibility phenomenon that occurs immediately during the production process of polymer materials, which is distinguished from the slow transition described below.)

[0006] 2. The problem of long-term effective properties: HALS can reduce aging by scavenging free radicals and ultimately protect materials, so it can function normally under general use conditions. However, in the case of high temperature and environmental erosion, traditional HALS will cause losses through physical means (volatilization, migration, dissolution), and ultimately fail to achieve the protective effect of materials. A typical application scenario is plastic coating. When a polymer coating is applied to the surface of a plastic product, small molecules (e.g., light stabilizers) in the coating will slowly migrate to the same polymer plastic substrate. With time, the concentration of light stabilizers in the coating will gradually decrease, making it impossible to achieve the protective effect, leading to premature aging and decomposition of the polymer substrate in the coating.

[0007] If ultraviolet absorbers (referred to as UVA) or hindered amine light stabilizers (referred to as HALS) are designed to be reactive, the light stabilizers can be connected to the above-mentioned polymer chains by chemical crosslinking, which can solve the above-mentioned material applicability problems and even achieve long-term protection effects. However, although reactive UVA (e.g. UV-400 (liquid)) and reactive HALS (e.g. Tinuvin 152 (powder)) that are reactive alone have been developed, there are few products that combine reactive UVA with reactive HALS to achieve better anti-aging effects. On the one hand, this is due to the fact that the available reactive UVA and reactive HALS cannot form a stable homogeneous complex. On the other hand, the problems of applicability and long-term effective properties faced by materials have not yet attracted enough attention, as they arise along with the progress of the material itself and the upgrade of the product. In addition, most of the reactive UVA and reactive HALS compositions do not have a significantly improved effect, and there are also problems such as volatility. Summary of the Invention

[0008] The main object of the present invention is to provide a reactive composite light stabilizer and its use, and a light-stable modified polymer material, in order to solve the problems of high volatility and poor long-term effective properties of light stabilizers contained in polymer materials in the prior art.

[0009] In order to achieve the above object, according to one embodiment of the present invention, there is provided a reactive composite light stabilizer, comprising a reactive ultraviolet absorber and a reactive hindered amine light stabilizer, wherein the reactive ultraviolet absorber is a reactive triazine ultraviolet absorber.

[0010] Further, the reactive UV absorber is selected from a mixture of 2-[4-[2-hydroxy-3-tridecyloxypropyl]oxy-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and 2-[4-[2-hydroxy-3-dodecyloxypropyl]oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, and / or 2-[2-hydroxy-4-[3-(2-ethylhexyloxy)-2-hydroxypropoxy]phenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, and the reactive hindered amine light stabilizer is [ka] and / or 2,4-bis[N-butyl-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)amino]-6-(2-hydroxyethylamine)-1,3,5-triazine, preferably, the reactive ultraviolet absorber and the reactive hindered amine light stabilizer are both liquid or both solid at room temperature of 20°C to 30°C.

[0011] Further, the reactive UV absorber is a mixture of 2-[4-[2-hydroxy-3-tridecyloxypropyl]oxy-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and 2-[4-[2-hydroxy-3-dodecyloxypropyl]oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, and the reactive hindered amine light stabilizer is [ka] or the reactive UV absorber is 2-[2-hydroxy-4-[3-(2-ethylhexyloxy)-2-hydroxypropoxy]phenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and the reactive hindered amine light stabilizer is 2,4-bis[N-butyl-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)amino]-6-(2-hydroxyethylamine)-1,3,5-triazine.

[0012] Furthermore, the weight ratio of the reactive ultraviolet absorber:reactive hindered amine light stabilizer is (0.1-10):1, preferably (1-5):1, and more preferably 2:1.

[0013] According to another aspect of the present invention there is further provided the use of a reactive complex light stabilizer in a polymeric material.

[0014] According to another aspect of the present invention, there is further provided a use of a reactive hindered amine light stabilizer in a polymeric material, the reactive hindered amine light stabilizer being [ka] and preferably the polymeric material is a coating.

[0015] According to yet another aspect of the present invention, there is further provided a light-stable modified polymeric material comprising a polymeric material and a light stabilizer, wherein the light stabilizer is the reactive composite light stabilizer described above.

[0016] Further, the polymeric material is one or more of a polyurethane material, an amino resin material, an acrylic resin material, and an epoxy resin material, and preferably, the polymeric material is a coating, an adhesive, a foam material, or an elastomer.

[0017] Further, the polymeric material is an amino acrylic resin coating, an acrylic polyurethane varnish, or a polyurethane powder coating.

[0018] Furthermore, when the polymer material is an aminoacrylic resin coating or an acrylic polyurethane varnish, the reactive ultraviolet absorber in the reactive composite light stabilizer is a mixture of 2-[4-[2-hydroxy-3-tridecyloxypropyl]oxy-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and 2-[4-[2-hydroxy-3-dodecyloxypropyl]oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, and the reactive hindered amine light stabilizer is [ka] and when the polymer material is a polyurethane powder coating, the reactive ultraviolet absorber in the reactive composite light stabilizer is 2-[2-hydroxy-4-[3-(2-ethylhexyloxy)-2-hydroxypropoxy]phenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, and the reactive hindered amine light stabilizer is 2,4-bis[N-butyl-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)amino]-6-(2-hydroxyethylamine)-1,3,5-triazine.

[0019] Furthermore, the reactive complex light stabilizer is incorporated into the polymeric material in an amount of 0.1-5 wt %, preferably 1-2%.

[0020] Compared with other types of reactive UV absorbers (e.g., reactive benzotriazole UV absorbers), the combination of reactive triazine UV absorbers and reactive hindered amine light stabilizers can increase the absorption rate, have good combined effect, reduce volatility, and increase the stability of resistance to photodegradation; and since they are all reactive components, they can exist in the form of chemical bonds in polymer materials, and thus have better long-term effective properties.

[0021] The drawings are included to facilitate a better understanding of the present invention and constitute a part of this application. The exemplary embodiments of the present invention, together with the detailed description of the invention, serve to explain the present invention and are not intended to impose undue limitations on the present invention. The description of the drawings is as follows: [Brief description of the drawings]

[0022] [Figure 1] 1 shows photographs of cured coatings of coatings of Example A-1 of the present invention and Comparative Example A-1, where a shows Comparative Example A-1 and b shows Example A-1. [Diagram 2] Photographs of the cured coatings of Inventive Example A-2, Comparative Example A-2, and Comparative Example A-3 are shown, where a shows Comparative Example A-2, b shows Comparative Example A-3, and c shows Example A-2. [Diagram 3] 1 shows the change curves of chromatic aberration during a QUV aging test for the coatings of Example B-1 and Comparative Examples B-1 to B-3. [Figure 4] 1 shows the change curves of chromatic aberration during a QUV aging test for the coatings of Examples B-2 to B-3 and Comparative Examples B-4 to B-7. [Diagram 5] 1 shows the change curves of chromatic aberration during a QUV aging test for the coatings of Example B-4, Comparative Example B-8, and Comparative Example B-9. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0023] It should be noted that the embodiments and features in the embodiments of the present application can be combined with each other without inconsistency.The present invention will be described in detail below with examples.

[0024] The present invention provides a reactive composite light stabilizer comprising a reactive ultraviolet absorber and a reactive hindered amine light stabilizer, wherein the reactive ultraviolet absorber is a reactive triazine ultraviolet absorber.

[0025] The reactive composite light stabilizer provided according to the present invention comprises reactive ultraviolet absorber and reactive hindered amine light stabilizer, and reactive ultraviolet absorber is reactive triazine ultraviolet absorber.Compared with other types of reactive ultraviolet absorber (such as reactive benzotriazole ultraviolet absorber), the combination of reactive triazine ultraviolet absorber and reactive hindered amine light stabilizer can increase absorption rate, have good combined effect, reduce volatility, and increase the stability of resistance to photodegradation; and because they are all reactive components, they can exist in the form of chemical bond in polymer material, and therefore have better long-term effective properties.

[0026] More preferably, the reactive UV absorber is selected from a mixture of 2-[4-[2-hydroxy-3-tridecyloxypropyl]oxy-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and 2-[4-[2-hydroxy-3-dodecyloxypropyl]oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine (e.g. UV-400), and / or 2-[2-hydroxy-4-[3-(2-ethylhexyloxy)-2-hydroxypropoxy]phenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine (e.g. UV-405), and the reactive hindered amine light stabilizer is [ka] and / or 2,4-bis[N-butyl-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)amino]-6-(2-hydroxyethylamine)-1,3,5-triazine, preferably, both the reactive ultraviolet absorber and the reactive hindered amine light stabilizer are liquid or solid at room temperature of 20°C to 30°C.

[0027] Both reactive UV absorbers and reactive hindered amine light stabilizers are liquid or both solid at room temperature of 20℃ to 30℃. Based on the same form, reactive UV absorbers and reactive hindered amine light stabilizers can form a better combination with better compatibility in polymer materials, for example, in some polymer materials that are highly polar, highly acidic, and require the addition of a large amount of light stabilizer, the compatibility is significantly improved. And since they are both reactive components, they can exist in the form of chemical bonds in polymer materials, and the loss of light stabilizers caused by physical methods (volatilization, migration, dissolution, etc.) can be significantly reduced. Therefore, they have better long-term effective properties and can provide long-term effective protection for polymer materials.

[0028] In one preferred embodiment, the reactive UV absorber is a mixture of 2-[4-[2-hydroxy-3-tridecyloxypropyl]oxy-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and 2-[4-[2-hydroxy-3-dodecyloxypropyl]oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine (e.g., UV-400), and the reactive hindered amine light stabilizer is [ka] or the reactive UV absorber is 2-[2-hydroxy-4-[3-(2-ethylhexyloxy)-2-hydroxypropoxy]phenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine (UV-405), and the reactive hindered amine light stabilizer is 2,4-bis[N-butyl-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)amino]-6-(2-hydroxyethylamine)-1,3,5-triazine (UV-152). RLHA is in liquid form at room temperature, which is convenient for operation and can form a more homogeneous and stable complex with liquid UV absorbers such as UV-400. Its structure retains the low alkaline N-OR body and introduces a hydroxyl group that can participate in the reaction at the other end. The hydroxyl group can chemically crosslink with functional groups in polymeric materials (e.g., isocyanate groups in polyurethane materials, free amine or ether bonds on amino resins, and epoxy groups in epoxy materials). Finally, the small molecules of the hindered amine light stabilizer are bonded to the chains of the polymer substrate. These RLHA properties are utilized to achieve a wide range of compatibility. Combined with reactive UV-400, more excellent long-term anti-aging performance can be achieved. UV-405 and UV-152 are both reactive agents in powder form, which also have excellent combined effects and excellent compatibility with polymeric materials. The composite light stabilizer formed by UV-405 and UV-152 can also exhibit better long-term anti-aging performance.

[0029] More preferably, the weight ratio of the reactive ultraviolet absorber to the reactive hindered amine light stabilizer is (0.1-10): 1, preferably (1-5): 1, more preferably 2: 1. By controlling the weight ratio of these two within the above range, when applied to a polymer material, a more remarkable synergistic effect can be achieved in addition to a more excellent combined effect.

[0030] According to another aspect of the present invention, the use of the above-mentioned reactive composite light stabilizer in polymeric materials is further provided. The reactive composite light stabilizer comprises a reactive ultraviolet absorber and a reactive hindered amine light stabilizer, and the reactive ultraviolet absorber is a reactive triazine ultraviolet absorber. Compared with other types of reactive ultraviolet absorbers (such as reactive benzotriazole), the combination of reactive triazine ultraviolet absorber and reactive hindered amine light stabilizer can increase the absorption rate, have a good combined effect, reduce volatility, and increase the stability of resistance to photodegradation. And since they are all reactive components, they can exist in the form of chemical bonds in polymeric materials, and thus have better long-term effective properties.

[0031] In addition, in the prior art, [ka] In view of the fact that there is no implementation using as an anti-aging modifier in polymeric materials, the present invention provides a method for the preparation of a reactive hindered amine light stabilizer in polymeric materials. [ka] In addition to the beneficial effects of the combination with the reactive UV absorbers mentioned above in the polymeric material, [ka] The single use of can also play an anti-aging role.Although it is inferior to the above-mentioned reactive composite light stabilizer of the present invention, in terms of long-term effective properties, its effect is significantly improved compared with the hindered amine light stabilizer currently used conventionally.In particular, the hindered amine light stabilizer also provides superior compatibility to conventional products in terms of compatibility and coating curability.

[0032] According to yet another aspect of the present invention, there is further provided a light-stable modified polymeric material comprising a polymeric material and a light stabilizer, wherein the light stabilizer is the reactive composite light stabilizer described above.

[0033] In a preferred embodiment, the polymeric material is one or more of polyurethane material, amino resin material, acrylic resin material, and epoxy resin material. In the above-mentioned types of polymeric materials, functional groups, such as isocyanic acid group, amino group, ether bond, and epoxy group, exist in the polymer chain. When applied to polymeric materials, the reactive composite light stabilizer can, on the one hand, have better compatibility with these materials, and on the other hand, crosslink with these groups to better bond to the polymer chain in the form of chemical bond. Therefore, the reactive composite light stabilizer can be maintained for a longer period in the polymeric material product, with less physical loss and longer effectiveness.

[0034] There is no particular restriction on the product form of the above polymer material, and examples of the form include, but are not limited to, a coating, an adhesive, a foam material, or an elastomer. The elastomer is preferably a polyurethane elastomer.

[0035] In some polymeric materials that have high polarity, high acidity, and require a large amount of light stabilizer, the application effect of the reactive composite light stabilizer of the present invention is more prominent. Preferably, the polymeric material is an amino acrylic resin coating, an acrylic polyurethane varnish, or a polyurethane powder coating. The specific solid content of the coating can be the solid content commonly used in this field, for example, 20-100%, the solid content of the liquid coating is typically 20-70wt%, and the solid content of the powder coating is 100%. In particular, in high solid content coatings (for example, solid content of 45-70wt%), the reactive composite light stabilizer according to the present invention still provides a better effect.

[0036] In order to promote good compatibility between the light stabilizer and the polymer material and further improve the anti-aging performance of the material, in one preferred embodiment, when the polymer material is an amino acrylic resin coating or an acrylic polyurethane varnish, the reactive ultraviolet absorber in the reactive composite light stabilizer is a mixture of 2-[4-[2-hydroxy-3-tridecyloxypropyl]oxy-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and 2-[4-[2-hydroxy-3-dodecyloxypropyl]oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine (UV-400), and the reactive hindered amine light stabilizer is [ka] and when the polymer material is a polyurethane powder coating, the reactive ultraviolet absorber in the reactive composite light stabilizer is 2-[2-hydroxy-4-[3-(2-ethylhexoxy)-2-hydroxypropyl]phenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine (UV405), and the reactive hindered amine light stabilizer is 2,4-bis[N-butyl-(1-cyclohexoxy-2,2,6,6-tetramethylpiperidin-4-yl)amino]-6-(2-hydroxyethylamine)-1,3,5-triazine (UV-152).

[0037] More preferably, the reactive composite light stabilizer is incorporated into the polymeric material in an amount of 0.1-5 wt %, even more preferably 1-2%.

[0038] In summary, the present invention combines reactive ultraviolet absorber and reactive hindered amine light stabilizer in the same form to obtain a homogeneous and stable composite light stabilizer that is convenient to add and simplifies the procedure of use.The reactive composite light stabilizer can meet the application of traditional polymer materials, and also meet the compatibility of ultraviolet absorber and hindered amine light stabilizer with special polymer systems, even at high loading levels.It has the widest range of currently available material applications.Compared with traditional non-reactive composite light stabilizer or those that only contain a single type of reactive composite light stabilizer, this reactive composite light stabilizer has excellent long-term anti-aging performance.

[0039] The following examples are presented to illustrate the present application in more detail and cannot be construed as limiting the scope of the present application. EXAMPLES

[0040] Material Applicability Verification Test (1) Improved compatibility of combination products with reactive hindered amine light stabilizers and UV absorbers in highly polar systems High solids coating systems tend to be more polar and are catalyzed by strong acids. Such coating systems require the addition of both an ultraviolet light absorber and a hindered amine light stabilizer. Conventional hindered amine light stabilizers are UV-292 and UV-123, which are liquids at room temperature. These two hindered amine light stabilizers are used as references, and the reactive hindered amine light stabilizer of the present invention is [ka] The suitability of is tested in high solids coating systems. [ka]

[0041] A typical single component high solids coating is selected, the composition formulation of which is shown in Table 1 below (62 wt% solids). [Table 1]

[0042] Example A-1 Test coating samples were formulated by adding 3 wt% of RLHA to the single component high solids coating described above.

[0043] Example A-2 Test coating samples were formulated by adding 2 wt% RLHA and 5 wt% UV-400 (Note: the active content of UV-400 is 85%, the remainder is 15% propylene glycol monomethyl ether solvent. Same below) to the above single component high solids coating without stabilizer.

[0044] Comparative example A-1 Test coating samples were formulated by adding 1% UV-123 (non-reactive, liquid at room temperature) to the above single component high solids coating without stabilizer.

[0045] Comparative example A-2 Test coating samples were formulated by adding 1 wt% UV-123 and 4.25% UV-1164 (non-reactive, solid at room temperature) to the above single component high solids coating without stabilizer.

[0046] Comparative example A-3 Test coating samples were formulated by adding 1 wt% UV-152 (purchased from BASF, Tinuvin 152) and 4.25% UV-1164 (non-reactive, solid at room temperature) to the above single component high solids coating without stabilizer.

[0047] Detection steps: The above coatings were sprayed onto an iron plate, leveled for 10 minutes, and the surface was observed for any precipitates.

[0048] The iron plate was placed in an oven and baked and cured under the conditions of 140°C for 30 minutes. The cured film thickness was 30 microns. After baking was completed, the surface was observed for any precipitation and wiped with a finger to confirm the precipitation.

[0049] The results of Example A-1 and Comparative Example A-1 are shown in Table 2. [Table 2]

[0050] The compatibility of light stabilizers in high solids coatings is a prominent problem in the industry. In Figure 1, a and b show the photographs of the cured coatings of Comparative Example A-1 and Example A-1, respectively. The photographs show that there is a layer of oily precipitate (white area around the image) on the surface of the coating of Comparative Example A-1. The central area is the original color that appears after wiping with a finger. The coating system of Example A-1 was homogeneous without precipitate. This shows that the above light stabilizers of the present invention have better compatibility with the coating system. The oily precipitate of Comparative Example 1 was analyzed to be UV-123.

[0051] The results of Example A-2, Comparative Example A-2, and Comparative Example A-3 are shown in Table 3. [Table 3]

[0052] In Figure 2, a, b, and c show the photographs of the cured coatings of Comparative Example A-2, Comparative Example A-3, and Example A-2, respectively. The photographs also show that Comparative Example A-2 had a layer of oily precipitate on the surface of the coating, and some obvious particulate precipitate (whitish areas and dots around the image). The oily precipitate was analyzed to be UV123, and the particulate precipitate was analyzed to be UV-1164. The coating system of Example A-2 was homogeneous without precipitate. This shows that the above composite light stabilizer of the present invention has better compatibility with the coating system.

[0053] (2) Improving the curability of coatings for composite products with reactive light stabilizers and UV absorbers: This test was also based on the high solids coating shown in Table 1 above. Under insufficient baking conditions, the effect of alkalinity on the formation of the cured film of the coating was particularly significant. Under slightly lower than normal baking conditions (baking at 130°C for 20 minutes), the resin reaction in the coating was affected, and the final hardness was also significantly changed, even failing to meet the requirements for use. The effect of different light stabilizers on the cured performance of the coating was investigated in the following examples and comparative examples.

[0054] Example A-3 Test coating samples were formulated by adding 1 wt% of RLHA to the above single component high solids coating without stabilizer.

[0055] Example A-4 Test coating samples were formulated by adding 1 wt% RLHA and 2 wt% UV-400 to the above single component high solids coating without stabilizer.

[0056] Comparative example A-3 Test coating samples were formulated by adding 1% UV-292 to the above single component high solids coating without stabilizer.

[0057] Comparative example A-4 Test coating samples were formulated by adding 1 wt% UV-292 (non-reactive) and 2 wt% UV-400 to the above single component high solids coating without stabilizer.

[0058] Comparative example A-5 The above single component high solids coating without any light stabilizer was used as a blank reference material.

[0059] Detection steps: The above coating was sprayed onto an iron plate, leveled for 10 minutes, and then baked in an oven to cure. The normal curing condition was baked at 140°C for 30 minutes, and the insufficient condition was baked at 130°C for 20 minutes. The film thickness after curing was 30 microns.

[0060] After baking, they were left at room temperature for 3 days. The hardness of the cured coatings was then measured. The K-Pendulum tester was a BYK Pendulum Hardness Tester (Model 5861). The Martens Hardness Tester was a FISCHERSCOPE® HM2000 Series Micro-Nano Hardness Tester.

[0061] The results are shown in Table 4. [Table 4]

[0062] The hardness data in the table show that the use of the reactive composite light stabilizer of the present invention does not affect the curing performance of the coating under insufficient bake conditions, and the hardness value does not change substantially compared to that of the blank reference coating. However, the comparative light stabilizer has a serious effect on the curing performance of the coating under insufficient bake conditions, resulting in a significant decrease in the hardness of the coating.

[0063] In summary, based on the compatibility data above, it can be seen that the conventional composite products seem to have the following major limitations in high solid coatings: (1) Conventional HALS (UV-123) precipitates in high solid coatings even at very low loadings, making it impossible to composite; (2) Conventional HALS (UV-292) affects the curing of high solid coatings, especially in the case of insufficient baking, which may occur in practice; (3) Conventional UVA (UV-1164) precipitates in polar high solids when loaded too high. When the reactive composite light stabilizer of the present invention is used in high solid coatings, the change in chromatic aberration of the coating is significantly reduced, ensuring the long-term anti-aging performance of the coating.

[0064] Long-term weather resistance evaluation test (1) Improved weatherability of reactive composite light stabilizers in high solids coatings Based on the above high solids coating system, traditional HALS cannot achieve effective compatibility. The composite light stabilizer product can meet this requirement and has better anti-aging effect in long-term use. The test was carried out as follows. Different types of light stabilizers were added to obtain the following four groups of test coating samples:

[0065] Example B-1 Test coating samples were formulated by adding 1 wt% UV-400 and 0.5% RLHA to the high solids coating described above without stabilizers.

[0066] Comparative example B-1 Test coating samples were formulated by adding 1.5 wt% UV-400 to the high solids coating described above without stabilizer.

[0067] Comparative example B-2 Test coating samples were formulated by adding 0.85 wt% UV-1164 and 0.5 wt% UV-292 to the above high solids coating without stabilizer.

[0068] Comparative example B-3 The above high solids coating without light stabilizer was used as a blank reference material.

[0069] Coating test sample plates were prepared by spraying the plates to a film thickness of 30 microns, leveling at room temperature for 10 minutes, and baking in an oven at 140° C. for 30 minutes. QUV testing was performed 3 days after surface conditioning.

[0070] The QUV test conditions were as follows: The test plate was placed in a QUV ultraviolet aging lamp box (model: Q-Lab QUV / Spray UV fluorescence aging test box). The test standard referred to ASTM G154-06 cycle 1. The test plate was taken out at certain intervals to measure the chromatic aberration value. The colorimeter was an X-rite MA5 spectrophotometer.

[0071] The test results are shown in Figure 3, which shows the change curves of chromatic aberration during QUV aging test of the coatings of Example B-1 and Comparative Examples B-1 to B-3. From the curves in this figure, it can be seen that the combination of UV-400 and RLHA provided according to the present invention, when applied to high solid content coating, has better anti-aging performance and significantly longer effective properties.

[0072] (2) Migration resistance in plastic coatings The surface of a plastic substrate may be coated with a layer of coating to achieve beautification and protection. In some outdoor applications, the coating may age due to light and heat. Adding a hindered amine light stabilizer can slow down this process. However, many plastic substrates have good plasticity themselves, which provides some "free space" for the migration of small molecules of the hindered amine light stabilizer within the substrate. TPO, a typical material with good plasticity, was selected for this test.

[0073] A 2K acrylic polyurethane varnish was selected as the additive, the components of which are shown in Table 5. [Table 5]

[0074] The above was a two-component (2K) acrylic polyurethane varnish coating system based on isocyanate curing. The formulation of the A component is shown in Table 5. The B component was Desmodur N3300 (Covestro) with a weight ratio of A:B=100:20.45.

[0075] Material Note: Desmodur N3300: an aliphatic polyisocyanate based on hexamethylene diisocyanate (HDI) (purchased from Covestro Polymer (China) Co., Ltd.). Setalux 1274 BA-70: hydroxyacrylic resin (purchased from Allnex Resins (China) Co., Ltd.). BYK 378: organosilicon leveling agent (purchased from BYK Additives (Shanghai) Co., Ltd.). DBTDL: dibutyltin dilaurate, catalyst (purchased from HEOWNS (Tianjin) Biotechnology Co., Ltd.).

[0076] Example B-2 Test coating samples were formulated by adding 1 wt % UV-400 and 0.5% RLHA to the above 2K acrylic polyurethane varnish without light stabilizers.

[0077] Example B-3 Test coating samples were formulated by adding 0.85 wt% UV-405 and 0.5 wt% UV-RLHA to the above 2K acrylic polyurethane varnish without light stabilizers.

[0078] Comparative example B-4 Test coating samples were formulated by adding 1 wt% UV-400 and 0.5 wt% UV-123 to the above 2K acrylic polyurethane varnish without light stabilizers.

[0079] Comparative example B-5 Test coating samples were formulated by adding 0.85 wt% UV-1164 and 0.5 wt% RLHA to the above 2K acrylic polyurethane varnish without light stabilizers (Note: since the effective content of UV-400 was 85%, an equal effective weight of the solid non-reactive ultraviolet absorber UV-1164 was added).

[0080] Comparative example B-6 The test coating sample was formulated by adding 0.85 wt% of solid reactive UVA (abbreviated as RUV; the structure is shown in the formula below: the source can refer to CN112552250A) and 0.5 wt% of RLHA to the above 2K acrylic polyurethane varnish without light stabilizer. [ka]

[0081] Comparative example B-7 The above 2K acrylic polyurethane varnish without light stabilizer was used as a blank reference material.

[0082] Coating test sample plates were prepared by spraying as follows: TPO (PP:SEBS=1:1) was selected as the substrate, sprayed with blue metal base paint, and leveled at room temperature for 10 minutes; the test coating sample was sprayed with blue metal base paint, controlled the film thickness to 30 microns, leveled at room temperature for 10 minutes, and baked in an oven at 80°C for 30 minutes; QUV test was carried out 7 days after surface conditioning.

[0083] The QUV test conditions were as follows: the test sample plate was placed in a QUV ultraviolet aging lamp box (model: Q-Lab QUV / Spray UV fluorescence aging test box), and the test standard referred to ASTM G154-06 cycle 1. The test plate was taken out at certain intervals to measure the chromatic aberration value. The colorimeter was an X-rite MA5 spectrophotometer.

[0084] The test results are shown in Figure 4, which shows the change curves of chromatic aberration during a QUV aging test for the coatings of Examples B-2 to B-3 and Comparative Examples B-4 to B-7.

[0085] Other solid reactive products (e.g., RUV and UV-405) must be dissolved prior to addition. Two negative consequences were observed: UV-400 and RLHA, both of which are in liquid form, are not easily added in the same way, and the introduction of solvent increases VOC emissions, which is especially unacceptable in high solids systems.

[0086] In particular, the curves in FIG. 4 show that the combination of UV-400 and RLHA of the present invention significantly improves the long-term anti-aging performance of the coating.

[0087] Furthermore, the curves in Figure 4 show that the efficacy of the reactive triazine complexes (UV-400 and RLHA) is superior to that of the reactive benzotriazole complexes (RUV and RLHA), and that the long-term anti-aging efficacy of the reactive solid HALS complexes (UV-405 and UV-RLHA) is superior to that of the reactive benzotriazole complexes (RUV and RLHA). The efficacy of the solid reactive HALS complexes (UV-405 and UV-RLHA) was substantially equivalent to that of the liquid reactive HALS complexes (UV-400 and RLHA), but with the two negative results mentioned above.

[0088] (3) Long-term weather resistance of powder coating Powder coatings are completely free of volatile organic compounds (VOCs) and have excellent environmental properties. Therefore, the attention and use of powder coatings has become more and more widespread in recent years. Early powder coatings were generally used in relatively low-end and mid-end applications, and little emphasis was placed on weather resistance, especially long-term weather resistance. Liquid reactive complex light stabilizers have excellent long-term weather resistance performance in liquid coatings, but the addition form that can be used in powder coatings is preferably powder rather than liquid. The combination of the reactive ultraviolet absorber UV-405 and the reactive hindered amine light stabilizer UV-152 of the present invention forms a powder reactive complex light stabilizer, which has been successfully applied in polyurethane type powder coatings, which have gradually matured in recent years. A long-term light aging test was carried out by comparing the conventional non-reactive ultraviolet absorber UV-1164 and the reactive hindered amine light stabilizer UV-622.

[0089] The formulations of the polyurethane powder coatings used are shown in Table 6. [Table 6]

[0090] Example B-4 In the formulations of Table 6, the hindered amine light stabilizer was UV-152 and the ultraviolet light absorber was UV-405.

[0091] Comparative example B-8 In the formulations of Table 6, the hindered amine light stabilizer was UV-622 and the ultraviolet light absorber was UV-1164.

[0092] Comparative example B-9 In the formulations in Table 6, no hindered amine light stabilizer and no UV absorber were added as a blank reference material.

[0093] Coating test sample plates were prepared by spraying the powder coating of the above formulation to a film thickness of 50 microns and baked in an oven at 200° C. for 15 minutes. QUV testing was performed 3 days after surface conditioning.

[0094] The QUV test conditions were as follows: the test sample plate was placed in a QUV ultraviolet aging lamp box (model: Q-Lab QUV / Spray UV fluorescence aging test box), and the test standard referred to ASTM G154-06 cycle 1. The test plate was taken out at regular intervals to measure the chromatic aberration value. The colorimeter was an X-rite MA5 spectrophotometer.

[0095] The test results are shown in Figure 5. This shows the change curves of chromatic aberration during QUV aging tests for the coatings of Example B-4 and Comparative Examples B-8 to B-9. The curves in Figure 5 also show that the combination of UV-405 and UV-152 of the present invention significantly improved the long-term anti-aging performance of the coating.

[0096] The above description is merely some preferred embodiments of the present invention, and is not intended to limit the present invention. Those skilled in the art can make various modifications and variations of the present invention. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principle of the present invention shall be included in the scope of protection of the present invention.

Claims

1. A reactive composite light stabilizer comprising a reactive ultraviolet absorber and a reactive hindered amine light stabilizer, wherein the reactive ultraviolet absorber is a reactive triazine ultraviolet absorber, said reactive composite light stabilizer.

2. The reactive ultraviolet absorber is selected from the mixture of 2-[4-[2-hydroxy-3-tridecyloxypropyl]oxy-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and 2-[4-[2-hydroxy-3-dodecyloxypropyl]oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, and / or 2-[2-hydroxy-4-[3-(2-ethylhexyloxy)-2-hydroxypropoxy]phenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, and the reactive hindered amine light stabilizer is 【Chemical 1】 and / or selected from 2,4-bis[N-butyl-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)amino]-6-(2-hydroxyethylamine)-1,3,5-triazine. Preferably, both the reactive ultraviolet absorber and the reactive hindered amine light stabilizer are liquid or solid at room temperature of 20 °C to 30 °C. The reactive composite light stabilizer according to Claim 1.

3. The reactive ultraviolet absorber is a mixture of 2-[4-[2-hydroxy-3-tridecyloxypropyl]oxy-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and 2-[4-[2-hydroxy-3-dodecyloxypropyl]oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, and the reactive hindered amine light stabilizer is 【Chemical 2】 or the reactive ultraviolet absorber is 2-[2-hydroxy-4-[3-(2-ethylhexyloxy)-2-hydroxypropoxy]phenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, and the reactive hindered amine light stabilizer is 2,4-bis[N-butyl-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)amino]-6-(2-hydroxyethylamine)-1,3,5-triazine, Preferably, the weight ratio of the reactive ultraviolet absorber to the reactive hindered amine light stabilizer is (0.1 to 10):1, preferably (1 to 5):

1. The reactive composite light stabilizer according to claim 2.

4. A polymer material containing the reactive composite light stabilizer according to any one of claims 1 to 3.

5. A polymer material containing a reactive hindered amine light stabilizer, wherein the reactive hindered amine light stabilizer is 【Chemical Formula 3】 and preferably, the polymer material is a coating. The polymer material.

6. A light stability-modified polymer material containing a polymer material and a light stabilizer, wherein the light stabilizer is the reactive composite light stabilizer according to any one of claims 1 to 3. The light stability-modified polymer material.

7. The polymer material is one or more of a polyurethane material, an amino resin material, an acrylic resin material, and an epoxy resin material. Preferably, the polymer material is a coating, an adhesive, a foamed material, or an elastomer. The light stability-modified polymer material according to claim 5.

8. The polymer material is an aminoacrylic resin coating, an acrylic polyurethane varnish, or a polyurethane powder coating. The light stability-modified polymer material according to claim 5.

9. When the polymer material is the aminoacrylic resin coating or the acrylic polyurethane varnish, the reactive ultraviolet absorber in the reactive composite light stabilizer is a mixture of 2-[4-[2-hydroxy-3-tridecyloxypropyl]oxy-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and 2-[4-[2-hydroxy-3-dodecyloxypropyl]oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, and the reactive hindered amine light stabilizer is 【Chemical Formula 4】 and when the polymer material is the polyurethane powder coating, the reactive ultraviolet absorber in the reactive composite light stabilizer is 2-[2-hydroxy-4-[3-(2-ethylhexyloxy)-2-hydroxypropoxy]phenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, and the reactive hindered amine light stabilizer is 2,4-bis[N-butyl-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)amino]-6-(2-hydroxyethylamine)-1,3,5-triazine, the light stability-modified polymer material according to claim 8.

10. The light stability-modified polymer material according to claim 6, wherein the reactive composite light stabilizer is incorporated into the polymer material in an amount of 0.1 to 5 wt%, preferably 1 to 2 wt%.

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