Color stabilizer composition for polyamide and application thereof

Abstract

The invention relates to the field of fine chemical engineering, and particularly discloses a color stabilizer composition for polyamide and application thereof.The color stabilizer composition comprises a component A and a component B according to the mass ratio of (0.5-3): (3-10), the component A comprises a hindered amine light stabilizer and an ultraviolet light absorber, and the component B comprises a monodentate ligand compound and multivalent metal salt; wherein a monodentate ligand in the monodentate ligand compound is selected from one or more of acetonitrile, pyridine, triphenylphosphine or negatively charged iodide ions, bromide ions, sulfur ions, thiocyanate ions, chloride ions, nitrate ions, hydroxyl ions, isothiocyanate ions, cyanide ions and nitrite ions, and the negatively charged ions appear in the form of a metal ion compound; the invention also discloses an application of the color stabilizer composition in preparation of polyamide products. The color stability of the polyamide material is improved, the quality and performance of the material are improved, and the service life of the material is prolonged.

Description

Technical Field

[0001] The present application relates to the field of fine chemicals, and more specifically, to a color stabilizer composition for polyamide and application thereof. Background Art

[0002] Polyamide (PA), commonly known as nylon, is a type of thermoplastic resin with excellent physical and chemical properties, including high mechanical strength, low friction coefficient, wear resistance, resistance to oil, weak acid, alkali and general solvents, good electrical insulation and self-extinguishing properties, non-toxic, odorless and good weather resistance. It is widely used in fiber materials such as meltblown non-woven fabrics, spunbond non-woven fabrics, engineering plastics, 3D printing materials and coatings.

[0003] Polyamide materials are mainly colored by dyes or pigments. The colored polyamide materials have a wide range of applications, such as automotive parts, mechanical parts, electronic and electrical products, engineering accessories, furniture, medical equipment, etc. By selecting suitable colorants and coloring methods, polyamide products with different colors and performance requirements can be produced to meet the needs of various industries.

[0004] However, the color stability of polyamide materials is poor for the following reasons:

[0005] First, the melt processing temperature of polyamide resin materials is relatively high, and the active hydrogen in the amide functional group has extremely strong reducing properties when melted, as shown in the following formula:

[0006]

[0007] The strong reducing property of polyamide melt makes many organic pigments and dyes unsuitable for use in polyamide. For example, azo pigments will fade and darken during the polyamide melt processing, and perylene pigments will undergo a reversible reduction reaction in nylon melt, which are not suitable for coloring nylon.

[0008] Secondly, polyamide materials are widely used in various complex and diverse scenarios due to their excellent performance. Environmental factors such as temperature, light, and humidity in these scenarios may affect the color stability of polyamide materials. Especially in outdoor environments, long-term ultraviolet radiation and climate change will accelerate the fading and aging of polyamide materials.

[0009] Finally, the migration of colorants in polyamide materials is also an important factor leading to color instability. In summary, for polyamide materials with high processing temperatures and reducing properties in the molten state, there are fewer pigments or pigments that can be used for polyamide coloring, which has a certain limiting effect, and especially the properties of colorant migration lead to poor color stability of polyamide materials, especially in application scenarios such as heat resistance, hot and cold alternation, light resistance, weather resistance and boiling stability, color instability, fading, discoloration and other problems usually occur. With the continuous development of the polyamide industry, the performance requirements for colorants are getting higher and higher, and it is of great significance to improve the color stability of polyamide materials, improve the quality and performance of materials, and extend the service life of materials. Summary of the invention

[0010] In order to improve the color stability of polyamide materials, enhance the quality, performance and service life of the materials, the present application provides a color stabilizer composition for polyamide and application thereof.

[0011] In a first aspect, the present application provides a color stabilizer composition for polyamide, which adopts the following technical solution:

[0012] A color stabilizer composition for polyamide, comprising a component A and a component B in a mass ratio of (0.5-3):(3-10), wherein the component A comprises 40-60wt% of a hindered amine light stabilizer and the balance is an ultraviolet absorber, and the component B comprises 60-90wt% of a monodentate ligand compound and the balance is a multivalent metal salt;

[0013] The monodentate ligand in the monodentate ligand compound is selected from one or more of acetonitrile, pyridine, triphenylphosphine or negatively charged iodide ion, bromide ion, sulfide ion, thiocyanate, chloride ion, nitrate ion, hydroxide ion, isothiocyanate ion, cyanide ion and nitrite ion, and the above negatively charged ions appear in the form of metal ion compounds.

[0014] By adopting the above technical scheme, the A component of the present application adopts a hindered amine light stabilizer and an ultraviolet absorber to cooperate, which can not only dynamically exchange free radicals with the amide functional groups, tertiary hydrocarbons, and end groups of polyamide, but also dynamically combine with the functional groups in toners such as organic pigments and dyes to protect the structural stability of the toner. In particular, the hindered amine light stabilizer is a colorless product and will not color the polyamide. Moreover, the hindered amine light stabilizer includes stabilization mechanisms such as capturing free radicals, decomposing hydroperoxides, capturing heavy metals, and quenching singlet oxygen, so that it has the functions of a light stabilizer and a thermal oxygen stabilizer at the same time. More importantly, the hindered amine light stabilizer HALS has intrinsic compatibility with polyamide. The molecular structure of the polyamide resin containing an amide bond and the hindered amine light stabilizer having a piperidine ring or other nitrogen-containing heterocyclic structure has certain similarities and interaction mechanisms, so that when the polyamide material is mainly made of polyamide resin and the polyamide resin content is the highest, the hindered amine light stabilizer can be stably stationed in the polyamide material, is not easy to migrate and precipitate, and can better play the role of thermal stability and light stability.

[0015] More importantly, the stabilizer composition in the present application uses a combination of component A and component B. The addition of polyvalent metal fatty acid salt and monodentate ligand in component B allows the polyvalent metal fatty acid salt-amide bond-monodentate ligand to rapidly exchange between fatty acid radicals and monodentate ligands during melt processing, and a dynamic stable melt gel state is formed between the monodentate ligand and the polyvalent metal and amide bond. More specifically, the possible spatial configurations formed by the monodentate ligand include: two-coordination to form a linear type; four-coordination to form a regular tetrahedron or a planar square; six-coordination (no lone electron pair) to form a triangular bipyramid; eight-coordination (no lone electron pair) to form an octahedral configuration; and the dynamic microscopic network formed:

[0016]

[0017] During the melt processing of polyamide materials, the monodentate ligand and the metal ion form a dynamic coordination network, and the dynamic coordination state is reversible, that is, the coordination bond between the ligand and the metal ion is constantly broken and re-formed during the processing, forming a dynamic buffer system during the melt processing, which effectively reduces the strong reducing and alkalinity of the amide bond during the melt processing; and the formation of the dynamic coordination network produces a shielding effect in the polyamide system, and the ligand molecules form a protective layer around the metal ions. This protective layer can block the direct attack of external factors such as oxygen, moisture, and light on the amide bond. Through this shielding effect, the amide bond is more stable and not easy to be destroyed during the melt processing, and due to the reversibility of the coordination bond, When external conditions such as temperature and shear force change, the coordination bond between the ligand and the metal ion will break and reform. This dynamic change enables the coordination network to continuously adapt to environmental changes during the processing process, thereby maintaining a stable protective effect on the amide bond. In addition, the chemical environment of the polyamide system may be adjusted due to the coordination effect between the monodentate ligand and the metal ion, making the amide bond more stable during the processing process, which helps to reduce the degradation and color change of the polyamide resin. In addition, the coordination effect between the ligand molecule and the metal ion allows more cross-linking points to be formed between the polymer chain segments, increasing the cohesion of the molecular chain and making it more stable. The stable molecular chain structure helps to resist the damage to the amide bond by external factors, thereby improving the color stability of the polyamide.

[0018] Finally, the addition of component B in this application forms a reversible dynamic coordination network structure, which protects the amide bond from attack and effectively reduces the strong reducibility and alkalinity of the amide bond during the melt processing through dynamic buffering, stabilization of metal ions, shielding effect, adjustment of chemical environment, enhancement of interaction between molecular chains, and promotion of free radical quenching, thereby improving the color stability of the polyamide material, ensuring the color consistency during the processing of the polyamide material, and significantly improving the thermochromic effect during the molding process of the polyamide material. During the melting process, component A continuously generates and transfers free radicals, and a large number of free radicals are dynamically combined with monodentate ligands, effectively protecting the coordination of the monodentate ligand of component B, so that component B is not oxidatively cross-linked during the melt processing, and plays a role, thereby improving the color stability of the polyamide material.

[0019] Optionally, the added mass ratio of component A to component B is (1-2): (5-8), component A includes 50-65wt% of a hindered amine light stabilizer and the balance is an ultraviolet light absorber, and component B includes 75-90wt% of a monodentate ligand compound and the balance is a polymetallic fatty acid salt.

[0020] By adopting the above technical scheme, when selecting the above ratio, especially the ratio of component A to component B, it is ensured that there is enough component B in the polyamide processing melt, which can play a better buffering role and improve its color stability. In addition, too much component A will also make the acidity and alkalinity of the processing melt difficult to control, thereby losing the buffering effect. The stabilizer composition obtained by the above ratio of component A and component B in the present application is used in the preparation process of polyamide materials to achieve better color stability.

[0021] Optionally, the monodentate ligand in the monodentate ligand compound is selected from at least one of iodide ion, bromide ion, chloride ion, hydroxide ion, isothiocyanate ion and cyanide ion, and the monodentate ligand is added in the form of a metal ion compound.

[0022] By adopting the above technical solution, when the above-mentioned anion is selected as a monodentate ligand compound in the form of a metal ion compound, the color stabilization effect of polyamide is better.

[0023] Optionally, the polyvalent metal salt is selected from one or more of polyvalent metal fatty acid salts, polyvalent metal sulfates, halogen polyvalent metal salts and long carbon chain saturated fatty acid polyvalent salts, wherein the polyvalent metal is selected from Zn 2+ Mg 2+ , Ca 2+ 、Al 3+ , Ba 2 + , Cu 2+ , Fe 3+ , Mn 3+ One of;

[0024] More preferred are one or more of long-chain saturated fatty acid multivalent salts and halogen-based multivalent metal salts, wherein the carbon chain length of the long-chain saturated fatty acid multivalent salt ranges from C10 to C18.

[0025] By adopting the above technical scheme, the above-mentioned multivalent metal fatty salt in component B of the present application and the amide bond and monodentate ligand of the polyamide are rapidly exchanged between the fatty acid radical and the monodentate ligand during the melt processing, so that a dynamic stable molten gel state is formed between the monodentate ligand, the multivalent metal and the amide bond, forming a dynamic buffer system, thereby effectively reducing the strong reducing and alkalinity of the amide bond during the melt processing, thereby improving the color stability of the polyamide material, and the long-chain saturated fatty acid multivalent salt forms good compatibility with the polyamide molecules, and the long-chain fatty acid radical ions can form stable chelates with metal ions, which can effectively resist the influence of external conditions such as ultraviolet rays and temperature, and further play a role in color stabilization.

[0026] Optionally, the ultraviolet absorber is selected from one or more of benzophenone, benzotriazole and triazine ultraviolet absorbers, more preferably benzotriazole.

[0027] By adopting the above technical solution, the above type of ultraviolet absorber is selected to have the characteristics of high efficiency, high temperature resistance, light color and good compatibility.

[0028] Optionally, the benzophenone ultraviolet absorber is selected from one or more of Chimassorb 81, CYASORB UV-531, UV-9 (BP-3), UV-1009, UV-981, UV-2126, Mark LA-51, UV-209, Permasorb A, Permasorb MA, and UV-950; more preferably, UV-1009, UV-981, UV-2126, and Mark LA-51;

[0029] The benzotriazole ultraviolet absorber is selected from one or more of Tinuvin 326, Tinuvin 329, Tinuvin P, Tinuvin 234, Tinuvin 360, Cyasorb 2337, Cyasor 5411, JAST-500, and Norbloc 7966;

[0030] The triazine ultraviolet absorber is selected from UV-1577, UV-1164, UV-400 UV-460, One or more of UV-405 and triazine-5.

[0031] Optionally, the hindered amine light stabilizer is selected from at least one of S-EED, Tinuvin 123, Tinuvin 770, Tinuvin 144, Tinuvin 744, Tinuvin 791, Tinuvin 622, Chimassorb 119, Chimassorb 944, Chimassorb 2020, 788, Cyasorb UV3346, Cyasorb UV3853, CYASORB UV-3529, MarK LA-57, MarK LA-52, MarK LA-68, MarK LA-63, ADK STAB LA-87, ADK STAB LA-81, ADK STAB LA-63P, GW-540, and PDS, and more preferably Chimassorb 944, Chimassorb 2020, Cyasorb UV3346, Cyasorb UV3853, CYASORB UV-3529, ADK STAB At least one of LA-63P, GW-540, and PDS.

[0032] Optionally, the stabilizer composition further comprises a heat stabilizer, and the heat stabilizer is selected from one or more of hindered phenol antioxidants, phosphite antioxidants, thioester antioxidants, free radical scavengers, and epoxy resins.

[0033] Optionally, the stabilizer composition further comprises a flow modifier, and the flow modifier is selected from one or more of long carbon chain fatty acid salts and their complexes, hyperbranched compounds, silicones, SAN oligomers, and low molecular weight polyamide oligomers.

[0034] Optionally, the stabilizer composition further comprises a dispersant, and the dispersant is selected from one or more of polyethylene wax, polypropylene wax, ethylene-acrylic acid oligomer copolymer, ionomer, amphiphilic polymer and hyperdispersant.

[0035] Optionally, the amount of the flow modifier added is 1-3wt% of the amount of component A added, the amount of the heat stabilizer added is 8-12wt% of the amount of component A added, and the amount of the dispersant added is 1-3wt% of the amount of component A added.

[0036] Optionally, the heat stabilizer is a mixture of a hindered phenol antioxidant, a thioester stabilizer and an epoxy resin in a mass ratio of 1:(0.6-0.8):(0.3-0.5).

[0037] By adopting the above technical scheme, hindered phenol antioxidants can effectively capture free radicals generated during the processing of polyamide, prevent them from initiating chain reactions, and maintain color stability. Thioester antioxidants mainly react with active hydrogen in polyamide molecules to generate stable thioether bonds, thereby inhibiting the oxidative degradation of polyamide, and have high processing performance and color stability. The addition of epoxy resin can form a blending system with polyamide resin, which helps to improve the overall thermal stability of the material. Epoxy resin acts as a protective barrier to reduce thermal degradation of polyamide molecular chains and maintain color stability. In addition, the addition of epoxy resin has a certain improvement effect on the melt fluidity of polyamide, which helps its processing and molding.

[0038] Optionally, the epoxy resin is added after being subjected to the following modification treatment:

[0039] 1) Using acrylic acid and hydroxyl-containing acrylic acid ester as monomers and benzyl (6-ethynylpyridin-2-yl) carbamate as a modifier, an acrylic acid-acrylic acid ester copolymer is prepared under the action of an initiator;

[0040] 2) Dissolve the acrylic acid-acrylate copolymer prepared in step 1) in ethyl acetate to obtain a first mixture, react at 45-55° C. for 20-30 minutes, then add aluminum chloride and epoxy resin, and then react at 50-60° C. for 2-3 hours, heat to 70-80° C., keep warm for 10-20 minutes, and then cool to obtain a modified epoxy resin.

[0041] By adopting the above technical scheme, the epoxy resin in the present application is modified by acrylic acid-acrylate copolymer, so that the cross-linking structure of polyamide and epoxy resin is constructed with acrylic acid-acrylate copolymer as an intermediate, thereby forming an interpenetrating macromolecular network structure, forming a tighter cross-linking structure, effectively reducing the electron transfer and reducibility of polyamide, and also restricting the movement of polyamide molecules, improving thermal stability, and further improving the color stability of polyamide.

[0042] In the present application, monomers are acrylic acid and hydroxyl-containing acrylate, carboxyl and hydroxyl functional groups are introduced into the copolymer chain, and under the action of a catalyst, the epoxy resin forms a chemical bond with the hydroxyl and carboxyl functional groups on the copolymer, thereby realizing crosslinking of the copolymer and the epoxy resin, and in the process of preparing the copolymer, benzyl (6-ethynylpyridin-2-yl) carbamate is added as a crosslinking agent, which contains an acetylene group as an unsaturated functional group to participate in the copolymerization of acrylic acid and acrylate monomers, thereby introducing amino and benzyl groups into the copolymer, and the carboxylic acid acid functional group in the copolymer can form a stable chemical bond with the nitrogen atom in the amide bond, thereby reducing the reducibility of the amide bond, and benzyl (6-ethynylpyridin-2-yl) carbamate can also act with the nitrogen atom or carbonyl carbon atom in the amide bond, reducing the difference in electron cloud density between the nitrogen atom and the carbonyl carbon atom in the polyamide, reducing the possibility of electron transfer, and alleviating the color instability caused by the electron transfer reduction effect, thereby improving the color stability of the polyamide during melt processing.

[0043] Optionally, during the epoxy resin modification process, the hydroxyl-containing acrylate monomer is selected from one or both of hydroxyethyl methacrylate and hydroxypropyl methacrylate;

[0044] The initiator is selected from one or both of benzoyl peroxide and diisopropylphenyl peroxide.

[0045] Optionally, during the epoxy resin modification process, the mass ratio of acrylic acid to hydroxyl-containing acrylate monomer added is 1:(1.2-1.5);

[0046] The addition amount of benzyl (6-ethynylpyridin-2-yl) carbamate is 8-15wt% of the addition amount of acrylic acid, and the addition amount of initiator is 0.5-2wt% of the addition amount of acrylic acid;

[0047] The mass ratio of acrylic acid-acrylate copolymer to ethyl acetate is 1:(3-4);

[0048] The amount of aluminum trichloride added is 0.5-1wt% of the amount of acrylic acid-acrylate copolymer added, and the amount of acrylic acid-acrylate copolymer added to epoxy resin is 1:(3-5).

[0049] By adopting the above technical solution and adding in the above ratio, the modified epoxy resin is prepared as a stabilizer for polyamide melt processing, which has better color stability.

[0050] In a second aspect, the present application provides an application of a color stabilizer composition for polyamide, using the following technical solution:

[0051] A use of the color stabilizer composition for polyamide in preparing polyamide products.

[0052] By adopting the above technical solution, the color stabilizer composition for polyamide in the present application can significantly improve the color stability of the polyamide product material when preparing the polyamide product.

[0053] In summary, this application has the following beneficial effects:

[0054] The stabilizer composition in the present application adopts the combination of component A and component B. The addition of polyvalent metal fatty acid salt and monodentate ligand in component B allows the polyvalent metal fatty acid salt-amide bond-monodentate ligand to quickly exchange between fatty acid radical and monodentate ligand during melt processing, and a dynamic stable melt gel state is formed between the monodentate ligand and the polyvalent metal and amide bond. During the melt processing of the polyamide material, the monodentate ligand and the metal ion form a dynamic coordination network to constitute a dynamic buffer system during the melt processing, which effectively reduces the strong reducing and alkalinity of the amide bond during the melt processing, thereby improving the color stability of the polyamide material, ensuring the color consistency before and after the processing of the polyamide material, and significantly improving the thermochromic effect during the molding process of the polyamide material. BRIEF DESCRIPTION OF THE DRAWINGS

[0055] Figure 1 It is a diagram of the dynamic buffer system formed by component A, component B and polyamide in this application;

[0056] Figure 2 This is the polyamide color plate diagram obtained in Example 1 of the present application;

[0057] Figure 3 It is the polyamide color plate diagram prepared in control group 1 of the present application;

[0058] Figure 4 This is the polyamide color plate diagram obtained in Example 2 of the present application;

[0059] Figure 5 It is the polyamide color plate diagram obtained in control group 2 of the present application;

[0060] Figure 6 This is the polyamide color plate diagram obtained in Example 3 of the present application;

[0061] Figure 7 It is the polyamide color plate diagram obtained in control group 3 of the present application;

[0062] Figure 8 This is the polyamide color plate diagram obtained in Example 4 of the present application;

[0063] Fig. 9 This is a polyamide color plate diagram obtained in control group 4 of the present application. DETAILED DESCRIPTION

[0064] The present application is further described in detail below in conjunction with the examples. It is particularly noted that if no specific conditions are specified in the following examples, the experiments are carried out according to conventional conditions or the conditions recommended by the manufacturer. Unless otherwise specified, the raw materials used in the following examples can be obtained from common commercial sources.

[0065] At present, the colorants for nylon (PA) materials mainly include dyes and pigments. Dye colorants are bright in color, eye-catching in color, and have a complete color spectrum, but their disadvantages are poor in heat resistance, weather resistance, and solvent resistance. They are easy to decompose and discolor at plastic processing temperatures or during use at higher temperatures. Dyes have high tinting strength in PA materials and have little effect on the mechanical properties (such as impact toughness, tensile strength, bending modulus, etc.) and molding processing properties of PA materials. However, dye colorants have a greater effect on the light resistance and weather resistance of PA materials, and are easy to fade and discolor under light, especially when used in outdoor environments. Commonly used dyes for PA materials include solvent red 135, solvent red 179, solvent red 122, solvent red 214, solvent yellow 21, solvent yellow 98, solvent yellow 145, solvent orange 60, solvent orange 63, solvent orange 116, solvent blue 104, solvent blue 97, solvent blue 70, solvent blue 132, solvent black 7, etc.

[0066] Pigments are divided into inorganic pigments and organic pigments. Inorganic pigments are superior to organic pigments in terms of light resistance, weather resistance, migration resistance and chemical resistance, but inorganic pigments have poor color strength and brightness, and inorganic pigments have a high reflectivity index and are often used in opaque products. Compared with inorganic pigments, organic pigments show high tinting strength and brightness, but the tinting strength of organic pigment colorants in PA materials is not as good as dyes, and they will affect the crystallization rate, crystallinity and crystal form of nylon, thereby affecting the heat resistance, light resistance and weather resistance of PA materials.

[0067] The organic pigments available for PA materials include pigment 148, pigment yellow 187, pigment yellow 192, pigment yellow 150, pigment red 149, pigment red 177, pigment red 122, pigment red 202, pigment red 177, pigment orange 68, pigment violet 23, pigment blue 15:3, pigment green 7, etc.; the inorganic pigments available for PA resin substrates include pigment yellow 184, pigment blue 29, pigment violet 15, pigment blue 28, pigment green 50, pigment black 28, pigment brown 24, pigment yellow 53, pigment white 6, carbon black, etc.

[0068] In response to the problem of poor coloring stability of polyamide materials, the present application provides a color stabilizer composition for polyamide, comprising component A and component B in a mass ratio of (0.5-3): (3-10), wherein component A comprises 40-60wt% of a hindered amine light stabilizer and the remainder an ultraviolet absorber, and component B comprises 60-90wt% of a monodentate ligand compound and the remainder a multivalent metal salt.

[0069] Among them, the hindered amine (HALS) light stabilizer in component A has the following general structural formula:

[0070]

[0071] Where: R is CH3, R1 is various groups, R2 is H, O·, CH3, OR, etc.

[0072] Specifically, it includes at least one of the trade names S-EED, Tinuvin 123, Tinuvin 770, Tinuvin 144, Tinuvin 744, Tinuvin 791, Tinuvin 622, Chimassorb 119, Chimassorb 944, Chimassorb 2020, 788, Cyasorb UV3346, Cyasorb UV3853, CYASORB UV-3529, MarK LA-57, MarK LA-52, MarK LA-68, MarK LA-63, ADK STAB LA-87, ADK STAB LA-81, ADK STAB LA-63P, GW-540, PDS, etc., and more preferably high molecular weight Chimassorb 944, Chimassorb 2020, Cyasorb UV3346, Cyasorb UV3853, CYASORB UV-3529, ADK STAB At least one of LA-63P, GW-540, PDS, etc.

[0073] The ultraviolet absorber in component B is selected from at least one of benzophenone, benzotriazole and triazine, and more preferably a benzotriazole ultraviolet absorber.

[0074] Among them, the benzophenone ultraviolet absorber has at least one of the following general structural formulas:

[0075]

[0076] Specific trade names include Chimassorb 81, CYASORB UV-531, UV-9 (BP-3), high molecular weight benzophenones such as UV-1009, UV-981, UV-2126, Mark LA-51, and reactive benzophenone products including at least one of UV-209, Permasorb A, Permasorb MA, UV-950, etc., and high molecular weight benzophenone ultraviolet absorbers are more preferred.

[0077] The general structural formula of benzotriazole UV absorber is:

[0078]

[0079] Specific trade names include at least one of Tinuvin 326, Tinuvin 329, Tinuvin P, Tinuvin 234, Tinuvin 360, Cyasorb 2337, Cyasor 5411, JAST-500, Norbloc 7966, etc.

[0080] Triazine UV absorbers include 2-(2'-hydroxyphenyl)-1,3,5-triazine UV absorbers, and also include UV-1577, UV-1164, UV-400 UV-460, At least one of UV-405 and triazine-5.

[0081] In the present application, by controlling the components A and B, a dynamic buffer system is formed with the polyamide during the melt processing, such as Figure 1 shown.

[0082] In addition, one of the ways to use the color stabilizer in this application is to directly pre-treat it with the colorant to obtain a pre-treated color powder, which can then be used in the same way as ordinary colorants for color matching or toning. The specific method of use is:

[0083] The colorant is mixed with the remaining raw materials (specifically component A, heat stabilizer, dispersant and flow modifier) ​​in the color stabilizer composition of the present application except component B, and treated at 50-70°C for 10-15 minutes to obtain a preliminary mixture, which is then cooled to below 30°C and then component B is added, and then mixed at 30-40°C for 20-30 minutes to obtain a pre-treated colorant for treatment. The added mass ratio of the color stabilizer composition to the colorant is (1:9)-(9:1), and more preferably 4:1-(1:4).

[0084] Another method is to package component A and component B separately, and when using, mix component A with component B and then feed them together with other additives through the main feed.

[0085] The following is an explanation in conjunction with specific embodiments. The polyamide resin in the following embodiments is PA6 resin, specifically Yueyang Petrochemical YH800, which is pre-dried at 105°C for 4 hours before use;

[0086] The diffusion oil in the following embodiments is a modified silicone diffusion oil of model HS-S125 produced by Dongguan Huasen New Materials Co., Ltd.

[0087] Example 1

[0088] A color stabilizer composition for polyamide comprises component A and component B, wherein component A is obtained by mixing 3g of a hindered amine light stabilizer (specifically Tinuvin 770) and 2g of an ultraviolet absorber (specifically UV329), and component B is obtained by mixing 0.5g of cuprous iodide, 2.5g of magnesium sulfate and 22g of potassium iodide.

[0089] The polyamide color plate product using the polyamide color stabilizer composition comprises the following raw materials:

[0090] 1kg polyamide raw material, 5g A component and 25g B component, wherein, based on the polyamide raw material, the polyamide raw material includes 2.5g solvent blue 104, 0.2mL diffusion oil and 5kg PA6 resin.

[0091] The specific method of applying the polyamide color stabilizer composition to the preparation of polyamide color plate products comprises the following steps:

[0092] S1, 2.5g solvent blue 104, 0.2mL diffusion oil and 5kg PA6 resin were mixed to prepare a polyamide raw material;

[0093] S2, mixing 3 g of a hindered amine light stabilizer (specifically Tinuvin 770) and 2 g of an ultraviolet absorber (specifically UV329) to obtain component A;

[0094] Mix 0.5 g of cuprous iodide, 1.5 g of magnesium sulfate and 22 g of potassium iodide to obtain component B;

[0095] S3, taking 1 kg of the polyamide raw material prepared in step S1, and mixing it with 5 g of component A and 25 g of component B prepared in step S2, and injection molding to prepare a colored polyamide color plate.

[0096] The injection molding temperatures are 250°C, 270°C and 300°C, respectively, and the injection molding residence time is 5 minutes. The color plates obtained by injection molding at 250°C, 270°C and 300°C using the method in Example 1 are shown in FIG. Figure 2 shown.

[0097] Control group 1

[0098] In the control group 1, the color stabilizer composition prepared in Example 1 of the present application was not added. After 2.5 g of solvent blue 104, 0.2 mL of diffusion oil and 5 kg of PA6 resin were mixed to prepare a polyamide raw material, the polyamide raw material was directly injection molded to obtain a colored polyamide color plate. The injection molding temperatures were also selected to be 250° C., 270° C. and 300° C., respectively. The injection molding residence time was 5 minutes. In the control group 1, the polyamide raw material was directly injection molded at 250° C., 270° C. and 300° C. to obtain a color plate as shown in the figure. Figure 3 shown.

[0099] Reference Figure 2 and Figure 3 It can be seen that with the increase of injection molding temperature, the brightness of solvent blue 104 in PA6 decreases, the tinting strength decreases, and the color light moves towards the green port. Figure 1 In Example 1, as the injection molding temperature increases, the tinting strength of the color plate is not large, and the color light remains reddish. The color plate after adding the color stabilizer composition in Example 1 can withstand higher processing temperatures and has better heat resistance than that of the control group 1.

[0100] In addition, in order to evaluate the color stability and durability of the polyamide color plate under light conditions, so as to consider whether it can maintain good color appearance performance in practical applications, the colored polyamide color plates obtained at an injection temperature of 260° C. in the above Example 1 and Control Group 1 were tested for light resistance and weather resistance, wherein the testing method is:

[0101] Lightfastness test: The polyamide color plate was placed in an artificial aging instrument (temperature of 45°C, relative humidity of 70%, and wavelength of ultraviolet light of 380nm) for 7 days. 50 groups of professionals rated each of the embodiment and the control group. The evaluation levels were divided into 1-8 levels. The higher the level, the better the lightfastness of the color plate. The lightfastness levels are shown in Table 1 below.

[0102] Table 1:

[0103] Level 8 Level 7 Level 6 Level 5 Level 4 Level 3 Level 2 Level 1 Excellent excellent very good good better generally Difference Very bad

[0104] Weathering test: Combined with GB / T 16585, the xenon arc lamp aging method is used to test weathering, observe the color difference, cracks, shedding, deformation and other indicators, and use the gray scale to evaluate the color change during the color fastness test (compare the tested sample with the original sample that has not been tested, observe the color change, and then compare the color change with the gray card in the gray scale, find the gray card level that is closest to the sample color change, and use it as the color fastness level of the sample). The weathering grades are shown in Table 2 below.

[0105] Table 2:

[0106] Level 5 Level 4 Level 3 Level 2 Level 1 good good better generally Difference

[0107] The results of the light resistance grade and weather resistance grade of the polyamide color plates in the above Example 1 and the control group 1 are shown in the following Table 3.

[0108] Table 3: Comparison of lightfastness and weather resistance of solvent blue 104

[0109] sample Light resistance level Weather resistance grade Control group 1 Level 4 2 Example 1 Level 7 4

[0110] Combined with the test results in Table 3 above, when the color stabilizer composition of the present application is added during the preparation of the polyamide color plate, the light resistance and weather resistance level can be improved by more than 2 levels.

[0111] Example 2

[0112] In this embodiment, the color stabilizer composition for polyamide includes component A and component B, wherein component A is obtained by mixing 3g of hindered amine light stabilizer (specifically Chimassorb 2020) and 2g of ultraviolet absorber (specifically Mark LA-51), and component B is obtained by mixing 4g of long-chain saturated fatty acid zinc salt, specifically zinc stearate, and 18g of potassium thiocyanate KSCN.

[0113] The polyamide color plate product used in the color stabilizer composition in this embodiment includes the following raw materials:

[0114] 1kg polyamide raw material, 3g A component and 24g B component, wherein, based on the polyamide raw material, the polyamide raw material includes 2g Pigment Yellow 150, 0.2g Magnesium stearate and 2kg PA6 resin.

[0115] The specific method of applying the color stabilizer composition for polyamide to the preparation of polyamide color plate products is the same as that in Example 1.

[0116] Similarly, the injection molding temperatures in Example 2 were selected as 260°C, 280°C and 310°C, respectively, and the injection molding residence time was 5 minutes. The color plates obtained by injection molding at 260°C, 280°C and 310°C using the method in Example 2 are shown in FIG. Figure 4 shown.

[0117] Control group 2

[0118] In control group 2, the color stabilizer composition prepared in Example 2 was not added. After 2 g of Pigment Yellow 150, 0.2 g of magnesium stearate and 2 kg of PA6 resin were mixed to prepare a polyamide raw material, the polyamide raw material was directly injection molded to obtain a colored polyamide color plate. The injection molding temperatures were also selected to be 260° C., 280° C. and 310° C., respectively, and the injection molding residence time was 5 minutes. In this control group 2, the polyamide raw material was directly injection molded at 260° C., 280° C. and 310° C. to obtain a color plate as shown in the figure. Figure 5 shown.

[0119] Reference Figure 4 and Figure 5 It can be seen that with the increase of injection molding temperature, the color of Pigment Yellow 150 in PA6 becomes darker. Compared with Control Group 2, after adding the color stabilizer composition of the present application in Example 2, the hue and tinting strength of the polyamide color plate obtained in Example 2 are almost unchanged. The color plate in Example 2 can maintain the color unchanged at a higher processing temperature, and the heat resistance in Example 2 is better.

[0120] Similarly, the light resistance grade and weather resistance grade of the polyamide color plates obtained at an injection molding temperature of 280° C. in Example 2 and Control Group 2 were tested in the same manner as in Example 1. The test results are shown in Table 4 below.

[0121] Table 4:

[0122]

[0123]

[0124] Example 3

[0125] In this embodiment, the color stabilizer composition for polyamide includes component A and component B, wherein component A is obtained by mixing 2g of hindered amine light stabilizer (specifically Cyasorb UV3346) and 2g of ultraviolet absorber (specifically UV-400), and component B is obtained by mixing 3g of long-chain saturated fatty acid aluminum salt, specifically aluminum stearate, and 22g of potassium iodide.

[0126] The polyamide color plate product used in the color stabilizer composition in this embodiment includes the following raw materials:

[0127] 1kg polyamide raw material, 4g A component and 25g B component, wherein, based on the polyamide raw material, the polyamide raw material includes 2.5g solvent orange 60, 0.2ml diffusion oil and 5kg PA6 resin.

[0128] The specific method of applying the color stabilizer composition for polyamide to the preparation of polyamide color plate products is the same as that in Example 1.

[0129] Similarly, the injection molding temperatures in Example 3 are 250°C, 270°C and 300°C, respectively, and the injection molding residence time is 5 minutes. The color plates obtained by injection molding at 250°C, 270°C and 300°C using the method in Example 3 are shown in FIG. Figure 6 shown.

[0130] Control group 3

[0131] In control group 3, the color stabilizer composition prepared in Example 3 was not added. After 2.5 g of solvent orange 60, 0.2 ml of diffusion oil and 5 kg of PA6 resin were mixed to prepare a polyamide raw material, the polyamide raw material was directly injection molded to obtain a colored polyamide color plate. The injection molding temperatures were also selected to be 250° C., 270° C. and 300° C., respectively, and the injection molding residence time was 5 minutes. In this control group 3, the polyamide raw material was directly injection molded at 250° C., 270° C. and 300° C. to obtain a color plate as shown in the figure. Figure 7 shown.

[0132] Reference Figure 6 and Figure 7 It can be seen that with the increase of injection molding temperature, the color of solvent orange 60 in PA6 becomes darker. Compared with control group 3, after adding the color stabilizer composition of the present application in Example 3, the color tone and tinting strength of the polyamide color plate obtained in Example 3 are almost unchanged. The color plate in Example 3 can keep the color unchanged at a higher processing temperature, and the heat resistance in Example 3 is better.

[0133] Similarly, the light resistance grade and weather resistance grade of the polyamide color plates obtained at an injection molding temperature of 270° C. in Example 3 and Control Group 3 were tested in the same manner as in Example 1. The test results are shown in Table 5 below.

[0134] Table 5: Comparison of lightfastness and weather resistance of Solvent Orange 60 coloring

[0135] sample Light resistance level Weather resistance grade Control group 3 Level 4 3 Example 3 Level 7 Level 4

[0136] Example 4

[0137] In this embodiment, the color stabilizer composition for polyamide includes component A and component B, wherein component A is obtained by mixing 2g of hindered amine light stabilizer (specifically MarK LA-63) and 2g of ultraviolet absorber (specifically UV 234), and component B is obtained by mixing 4g of long-chain saturated fatty acid zinc salt, specifically zinc stearate, and 18g of potassium thiocyanate KSCN.

[0138] The polyamide color plate product used in the color stabilizer composition in this embodiment includes the following raw materials:

[0139] 1kg polyamide raw material, 4g A component and 24g B component, wherein, based on the polyamide raw material, the polyamide raw material includes 2g Pigment Red 122, 0.2g Magnesium stearate and 2kg PA6 resin.

[0140] The specific method of applying the color stabilizer composition for polyamide to the preparation of polyamide color plate products is the same as that in Example 1.

[0141] Similarly, the injection molding temperatures in Example 4 were selected as 260°C, 280°C and 310°C, respectively, and the injection molding residence time was 5 minutes. The color plates obtained by injection molding at 260°C, 280°C and 310°C using the method in Example 4 are shown in FIG. Figure 8 shown.

[0142] Control group 4

[0143] In control group 4, the color stabilizer composition prepared in Example 4 was not added. After 2 g of Pigment Red 122, 0.2 g of magnesium stearate and 2 kg of PA6 resin were mixed to prepare a polyamide raw material, the polyamide raw material was directly injection molded to obtain a colored polyamide color plate. The injection molding temperatures were also selected to be 260° C., 280° C. and 310° C., respectively, and the injection molding residence time was 5 minutes. In this control group 4, the polyamide raw material was directly injection molded at 260° C., 280° C. and 310° C. to obtain a color plate as shown in the figure. Fig. 9 shown.

[0144] Reference Figure 8 and Fig. 9 It can be seen that with the increase of injection molding temperature, the color of Pigment Red 122 in PA6 becomes darker. Compared with Control Group 4, after adding the color stabilizer composition of the present application in Example 4, the color tone and tinting strength of the polyamide color plate obtained in Example 4 are almost unchanged. The color plate in Example 4 can maintain the color unchanged at a higher processing temperature, and the heat resistance in Example 4 is better.

[0145] Similarly, the light resistance grade and weather resistance grade of the polyamide color plates obtained at an injection molding temperature of 280° C. in Example 4 and Control Group 4 were tested in the same manner as in Example 1. The test results are shown in Table 6 below.

[0146] Table 6: Comparison of lightfastness and weather resistance of Pigment Red 122

[0147] sample Light resistance level Weather resistance grade Control group 4 Level 6 3 Example 4 Level 8 5

[0148] In summary, through the injection molding method of the color plates in the above-mentioned Examples 1-4 and Control Group 4, the color thermal stability, light resistance and weather resistance of the color plates during the injection molding melt processing of polyamide are evaluated from the color change of the color plates, and the color stabilizer composition in the present application is excellent in improving the color stability of the colored polyamide material.

[0149] Example 5

[0150] The color stabilizer composition for polyamide in this embodiment includes component A, component B, a heat stabilizer, a flow modifier and a dispersant, wherein component A is obtained by mixing 3g of a hindered amine light stabilizer (specifically Tinuvin 770) and 2g of an ultraviolet absorber (specifically UV329), component B is obtained by mixing 3g of cuprous iodide, 10g of magnesium sulfate and 22g of potassium iodide, the heat stabilizer is a mixture of a hindered phenol antioxidant (specifically antioxidant 1010), a thioester stabilizer (specifically DSTP) and an epoxy resin E-44 in a mass ratio of 1:0.7:0.4, the dispersant is polyethylene wax, and the flow modifier is zinc stearate;

[0151] The polyamide color plate product using the polyamide color stabilizer composition comprises the following raw materials:

[0152] 1kg polyamide raw material, 7g component A and 23g component B and heat stabilizer, flow modifier and dispersant, the flow modifier is added in an amount of 2wt% of component A, the heat stabilizer is added in an amount of 10wt% of component A, and the dispersant is added in an amount of 2wt% of component A;

[0153] Among them, taking polyamide raw material as a basis, the polyamide raw material includes 2.5g solvent blue 104, 0.2mL diffusion oil and 5kg PA6 resin.

[0154] The specific method of applying the color stabilizer composition for polyamide to prepare the polyamide color plate product is the same as that in Example 1, the difference is that in step S3, a heat stabilizer, a flow modifier and a dispersant are added together with component A.

[0155] Example 6

[0156] The color stabilizer composition for polyamide in this embodiment includes component A, component B, a heat stabilizer, a flow modifier and a dispersant, wherein component A is obtained by mixing 2.75g of a hindered amine light stabilizer (specifically Tinuvin 770) and 2.25g of an ultraviolet absorber (specifically UV329), component B is obtained by mixing 2.75g of cuprous iodide, 6.25g of magnesium sulfate and 16g of potassium iodide, the heat stabilizer is a mixture of a hindered phenol antioxidant (specifically antioxidant 1010), a thioester stabilizer (specifically DSTP) and an epoxy resin E-44 in a mass ratio of 1:0.6:0.3, the dispersant is polyethylene wax, and the flow modifier is zinc stearate;

[0157] The polyamide color plate product using the polyamide color stabilizer composition comprises the following raw materials:

[0158] 1kg polyamide raw material, 6.5g component A and 23.5g component B and heat stabilizer, flow modifier and dispersant, the flow modifier added in an amount of 1wt% of component A, the heat stabilizer added in an amount of 8wt% of component A, and the dispersant added in an amount of 1wt% of component A;

[0159] Among them, taking polyamide raw material as a basis, the polyamide raw material includes 2.5g solvent blue 104, 0.2mL diffusion oil and 5kg PA6 resin.

[0160] The specific method of applying the color stabilizer composition for polyamide to prepare the polyamide color plate product is the same as that in Example 1, the difference is that in step S3, a heat stabilizer, a flow modifier and a dispersant are added together with component A.

[0161] Example 7

[0162] The color stabilizer composition for polyamide in this embodiment includes component A, component B, a heat stabilizer, a flow modifier and a dispersant, wherein component A is obtained by mixing 2g of a hindered amine light stabilizer (specifically Tinuvin 770) and 3g of an ultraviolet absorber (specifically UV329), component B is obtained by mixing 0.5g of cuprous iodide, 2.5g of magnesium sulfate and 22g of potassium iodide, the heat stabilizer is a mixture of a hindered phenol antioxidant (specifically antioxidant 1010), a thioester stabilizer (specifically DSTP) and an epoxy resin E-44 in a mass ratio of 1:0.8:0.5, the dispersant is polyethylene wax, and the flow modifier is zinc stearate;

[0163] The polyamide color plate product using the polyamide color stabilizer composition comprises the following raw materials:

[0164] 1kg polyamide raw material, 5g component A and 25g component B and heat stabilizer, flow modifier and dispersant, the flow modifier added is 3wt% of the amount of component A, the heat stabilizer added is 12wt% of the amount of component A, and the dispersant added is 3wt% of the amount of component A;

[0165] Among them, taking polyamide raw material as a basis, the polyamide raw material includes 2.5g solvent blue 104, 0.2mL diffusion oil and 5kg PA6 resin.

[0166] The specific method of applying the color stabilizer composition for polyamide to prepare the polyamide color plate product is the same as that in Example 1, the difference is that in step S3, a heat stabilizer, a flow modifier and a dispersant are added together with component A.

[0167] Example 8

[0168] The color stabilizer composition for polyamide and its application in this embodiment are the same as those in Example 5, except that the epoxy resin is added after the following modification treatment:

[0169] 1) Using acrylic acid and hydroxyl-containing acrylic acid ester as monomers and benzyl (6-ethynylpyridin-2-yl) carbamate as a modifier, an acrylic acid-acrylic acid ester copolymer is prepared under the action of an initiator;

[0170] The mass ratio of acrylic acid to hydroxyl-containing acrylic acid ester monomer is 1:1.3, the amount of benzyl (6-ethynylpyridin-2-yl) carbamate added is 12wt% of the amount of acrylic acid added, and the amount of initiator added is 1wt% of the amount of acrylic acid added;

[0171] 2) dissolving the acrylic acid-acrylate copolymer prepared in step 1) in ethyl acetate to obtain a first mixture, reacting at 50° C. for 25 minutes, then adding aluminum chloride and epoxy resin, and then reacting at 55° C. for 2.5 hours, heating to 75° C. and keeping warm for 15 minutes before cooling to obtain a modified epoxy resin, wherein the mass ratio of acrylic acid-acrylate copolymer to ethyl acetate is 1:3.5; the amount of aluminum chloride added is 0.8wt% of the amount of acrylic acid-acrylate copolymer added, and the amount of acrylic acid-acrylate copolymer to epoxy resin added is 1:4.

[0172] The hydroxyl-containing acrylate monomer is hydroxyethyl methacrylate, and the initiator is benzoyl peroxide.

[0173] Example 9

[0174] The color stabilizer composition for polyamide and its application in this embodiment are the same as those in Example 5, except that the epoxy resin is added after the following modification treatment:

[0175] 1) Using acrylic acid and hydroxyl-containing acrylic acid ester as monomers and benzyl (6-ethynylpyridin-2-yl) carbamate as a modifier, an acrylic acid-acrylic acid ester copolymer is prepared under the action of an initiator;

[0176] The mass ratio of acrylic acid to hydroxyl-containing acrylate monomer is 1:1.2, the amount of benzyl (6-ethynylpyridin-2-yl) carbamate is 8wt% of the amount of acrylic acid, and the amount of initiator is 0.5wt% of the amount of acrylic acid.

[0177] 2) dissolving the acrylic acid-acrylate copolymer prepared in step 1) in ethyl acetate to obtain a first mixture, reacting at 45° C. for 30 minutes, then adding aluminum chloride and epoxy resin, and then reacting at 50° C. for 3 hours, heating to 70° C. and keeping warm for 20 minutes before cooling to obtain a modified epoxy resin, wherein the mass ratio of acrylic acid-acrylate copolymer to ethyl acetate is 1:3; the amount of aluminum chloride added is 0.5wt% of the amount of acrylic acid-acrylate copolymer added, and the amount of acrylic acid-acrylate copolymer to epoxy resin added is 1:3.

[0178] The hydroxyl-containing acrylate monomer is hydroxypropyl methacrylate, and the initiator is diisopropylphenyl peroxide.

[0179] Example 10

[0180] The color stabilizer composition for polyamide and its application in this embodiment are the same as those in Example 5, except that the epoxy resin is added after the following modification treatment:

[0181] 1) Using acrylic acid and hydroxyl-containing acrylic acid ester as monomers and benzyl (6-ethynylpyridin-2-yl) carbamate as a modifier, an acrylic acid-acrylic acid ester copolymer is prepared under the action of an initiator;

[0182] The mass ratio of acrylic acid to hydroxyl-containing acrylate monomer is 1:1.5, the amount of benzyl (6-ethynylpyridin-2-yl) carbamate is 15wt% of the amount of acrylic acid, and the amount of initiator is 2wt% of the amount of acrylic acid.

[0183] 2) dissolving the acrylic acid-acrylate copolymer prepared in step 1) in ethyl acetate to obtain a first mixture, reacting at 55° C. for 20 minutes, then adding aluminum chloride and epoxy resin, and then reacting at 60° C. for 2 hours, heating to 80° C. and keeping warm for 10 minutes before cooling to obtain a modified epoxy resin, wherein the mass ratio of acrylic acid-acrylate copolymer to ethyl acetate is 1:4; the amount of aluminum chloride added is 1wt% of the amount of acrylic acid-acrylate copolymer added, and the amount of acrylic acid-acrylate copolymer added to epoxy resin is 1:5.

[0184] The hydroxyl-containing acrylate monomer is hydroxyethyl methacrylate, and the initiator is benzoyl peroxide.

[0185] Comparative Example 1

[0186] A color stabilizer composition for polyamide and its application are different from those in Example 1 in that the color stabilizer composition only includes component A but not component B, and when the color stabilizer composition is applied to polyamide color board paperboard, component B is not added.

[0187] Comparative Example 2

[0188] A color stabilizer composition for polyamide and its application are different from those in Example 1 in that the color stabilizer composition only includes component A but not component B. When the color stabilizer composition is applied to polyamide color board paperboard, component B is replaced by component A in equal amount.

[0189] Comparative Example 3

[0190] A color stabilizer composition for polyamide and its application are different from those in Example 1 in that only magnesium sulfate is added to component B of the color stabilizer composition, and no monodentate ligand compound is added.

[0191] Comparative Example 4

[0192] A color stabilizer composition for polyamide and its application are different from those in Example 1 in that only aluminum stearate is added to component B of the color stabilizer composition, and no monodentate ligand compound is added.

[0193] Comparative Example 5

[0194] A color stabilizer composition for polyamide and its application are different from Example 1 in that only cuprous iodide and potassium iodide are added to component B of the color stabilizer composition, and magnesium sulfate is replaced by cuprous iodide and potassium iodide in equal amounts according to the addition ratio of cuprous iodide and potassium iodide.

[0195] Comparative Example 6

[0196] A color stabilizer composition for polyamide and its application are different from those in Example 1 in that only cuprous iodide and potassium iodide are added to component B of the color stabilizer composition, and an equal amount of magnesium sulfate is replaced by potassium thiocyanate KSCN.

[0197] Performance Testing

[0198] The polyamide color plates prepared in the above embodiments and comparative examples were subjected to color difference detection, wherein embodiments 1, 3, 5-10 and comparative examples all selected polyamide color plates prepared at an injection molding temperature of 250°C as reference color plates, and comparative examples 2 and 4 selected polyamide color plates prepared at an injection molding temperature of 260°C as reference color plates, and then embodiments 1, 3, 5-10 and comparative examples all selected polyamide color plates prepared at an injection molding temperature of 300°C as comparison color plates, and comparative examples 2 and 4 selected polyamide color plates prepared at an injection molding temperature of 260°C as reference color plates. The color plate is used as a comparison color plate. The color values ​​of the five different positions of the above-mentioned reference color plate are measured by a colorimeter, and the average value is recorded. Then, the color values ​​of the five different positions of the comparison color plate are calculated by a colorimeter, and the average value is recorded. The color data of the color plate obtained at the above-mentioned different temperatures are measured by a colorimeter to calculate the color difference value, which is expressed as ΔE. For example, ΔE in Example 1 is the difference between the color values ​​of the reference color plate obtained at an injection molding temperature of 250°C and the comparison color plate obtained at an injection molding temperature of 300°C in Example 1. The rest are similar. The statistical results are shown in Table 7 below.

[0199] Table 7:

[0200]

[0201] Referring to the test results in Table 7 above, the smaller the ΔE value, the closer the two colors are. When the color stabilizer composition is added in the preparation process of the polyamide color plate, the color difference of the color plate obtained by injection molding at different temperatures of low temperature and high temperature is small. When the B component is not added to the stabilizer composition in Comparative Example 1, the color difference is large, and the stability of the colorant during the melt processing is reduced. When the B component in Comparative Example 2 is replaced by the A component in equal amounts, its stability is still low, and even too much A component has a worse stability effect, and a dynamic buffer system cannot be formed; and when only a polyvalent metal fatty acid salt is added to the B component in Comparative Examples 3 and 4 without adding a monodentate ligand compound, its color stability is also significantly reduced. Combined with the test results in Comparative Examples 5 and 6, when only a monodentate ligand compound is added, its stability is low.

[0202] This specific embodiment is merely an explanation of the present application and is not a limitation of the present application. After reading this specification, those skilled in the art may make modifications to the present embodiment without any creative contribution as needed, but such modifications are protected by the patent law as long as they are within the scope of the claims of the present application.

Claims

1. A color stabilizer composition for polyamide, characterized in that: The invention comprises a component A and a component B in a mass ratio of (0.5-3):(3-10), wherein the component A comprises a hindered amine light stabilizer in an amount of 40-60 wt% and a UV absorber in an amount of the remainder, and the component B comprises a monodentate ligand compound in an amount of 60-90 wt% and a multivalent metal salt in an amount of the remainder; The monodentate ligand in the monodentate ligand compound is selected from one or more of acetonitrile, pyridine, triphenylphosphine or negatively charged iodide ion, bromide ion, sulfide ion, thiocyanate, chloride ion, nitrate ion, hydroxide ion, isothiocyanate ion, cyanide ion and nitrite ion, and the above negatively charged ions appear in the form of metal ion compounds.

2. A color stabilizer composition for polyamide according to claim 1, characterized in that: The added mass ratio of component A to component B is (1-2): (5-8), component A includes 50-65wt% of a hindered amine light stabilizer and the balance of an ultraviolet light absorber, and component B includes 75-90wt% of a monodentate ligand compound and the balance of a polymetallic fatty acid salt.

3. A color stabilizer composition for polyamide according to claim 1, characterized in that: The monodentate ligand in the monodentate ligand compound is selected from at least one of iodide ion, bromide ion, chloride ion, hydroxide ion, isothiocyanate ion and cyanide ion, and the monodentate ligand is added in the form of a metal ion compound.

4. A color stabilizer composition for polyamide according to claim 1, characterized in that: The polyvalent metal salt is selected from one or more of polyvalent metal fatty acid salts, polyvalent metal sulfates, halogen polyvalent metal salts and long carbon chain saturated fatty acid polyvalent salts, wherein the polyvalent metal is selected from Zn 2+ Mg 2+ , Ca 2+ 、Al 3+ , Ba 2+ , Cu 2+ , Fe 3+ , Mn 3+ One of them.

5. The color stabilizer composition for polyamide according to claim 1, characterized in that: The ultraviolet absorber is selected from one or more of benzophenone, benzotriazole and triazine ultraviolet absorbers.

6. A color stabilizer composition for polyamide according to claim 5, characterized in that: The benzophenone ultraviolet absorber is selected from one or more of Chimassorb 81, CYASORB UV-531, UV-9 (BP-3), UV-1009, UV-981, UV-2126, Mark LA-51, UV-209, Permasorb A, Permasorb MA, and UV-950; more preferably, UV-1009, UV-981, UV-2126, and Mark LA-51; The benzotriazole ultraviolet absorber is selected from one or more of Tinuvin 326, Tinuvin 329, Tinuvin P, Tinuvin 234, Tinuvin 360, Cyasorb 2337, Cyasor 5411, JAST-500, and Norbloc 7966; The triazine ultraviolet absorber is selected from UV-1577, UV-1164, UV-400 UV-460, One or more of UV-405 and triazine-5; The hindered amine light stabilizer is selected from at least one of S-EED, Tinuvin 123, Tinuvin 770, Tinuvin 144, Tinuvin 744, Tinuvin 791, Tinuvin 622, Chimassorb 119, Chimassorb 944, Chimassorb 2020, 788, Cyasorb UV3346, Cyasorb UV3853, CYASORB UV-3529, MarK LA-57, MarK LA-52, MarK LA-68, MarK LA-63, ADK STAB LA-87, ADK STAB LA-81, ADK STAB LA-63P, GW-540, and PDS.

7. A color stabilizer composition for polyamide according to claim 1, characterized in that: The stabilizer composition further comprises a heat stabilizer, wherein the heat stabilizer is selected from one or more of a hindered phenol antioxidant, a phosphite antioxidant, a thioester antioxidant, a free radical scavenger, and an epoxy resin; The stabilizer composition also includes a dispersant, and the dispersant is selected from one or more of polyethylene wax, polypropylene wax, ethylene-acrylic acid oligomer copolymer, ionomer, amphiphilic polymer and superdispersant.

8. A color stabilizer composition for polyamide according to claim 7, characterized in that: The heat stabilizer is a mixture of hindered phenol antioxidant, thioester stabilizer and epoxy resin in a mass ratio of 1: (0.6-0.8): (0.3-0.5).

9. A color stabilizer composition for polyamide according to claim 7, characterized in that: The epoxy resin is added after the following modification treatment: 1) Using acrylic acid and hydroxyl-containing acrylic acid ester as monomers and benzyl (6-ethynylpyridin-2-yl) carbamate as a modifier, an acrylic acid-acrylic acid ester copolymer is prepared under the action of an initiator; 2) Dissolve the acrylic acid-acrylate copolymer prepared in step 1) in ethyl acetate to obtain a first mixture, react at 45-55° C. for 20-30 minutes, then add aluminum chloride and epoxy resin, and then react at 50-60° C. for 2-3 hours, heat to 70-80° C., keep warm for 10-20 minutes, and then cool to obtain a modified epoxy resin.

10. Use of the color stabilizer composition for polyamide according to any one of claims 1 to 9 in the preparation of polyamide products.

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