A highly color-stable orange masterbatch specially used for nylon materials and its preparation method and application

Abstract

The invention relates to a highly color-stable orange masterbatch for nylon materials and a preparation method and application thereof, and belongs to the technical field of polymer materials. The masterbatch comprises the following components: PA6 resin, an orange powder compound (a mixture of solvent orange 116 and solvent orange 60 formed in a certain mass ratio), a plasticizer, titanium dioxide, a heat stabilizing agent and a processing lubricant. By adding two orange pigments whose ΔL, Δa and Δb change oppositely under hygroscopic conditions to the masterbatch, and combining the synergistic effect of adding a plasticizer, when the masterbatch is added to the nylon material, the value of the color difference ΔE of the nylon material after hygroscopicity is greatly reduced, and the color can be kept stable under long-term hygroscopic conditions, thereby solving the problem of serious discoloration of the orange nylon material due to hygroscopicity. The preparation method has simple operation steps and can realize large-scale industrial production.

Description

Technical Field

[0001] The invention belongs to the technical field of polymer materials and relates to a highly color-stable orange masterbatch special for nylon materials and a preparation method and application thereof. Background Art

[0002] Nylon materials are widely used as engineering plastics in various industries due to their excellent comprehensive properties. While people pursue the mechanical properties of nylon materials, they also gradually put forward requirements for their appearance and color. In order to obtain a variety of colors, nylon materials need to be dyed. A common method is to add color powder or masterbatch to the nylon matrix. However, nylon materials are prone to serious discoloration problems under light, high temperature or humid conditions, especially bright colors such as orange, yellow and red. Therefore, in order to ensure the stability of color, people have proposed a series of solutions from the perspective of modification and optimization of the pigment itself.

[0003] CN112029269A discloses a color masterbatch for nylon with heat aging resistance and stable color. The color masterbatch is composed of polyamide carrier resin, modified color powder, dispersant and antioxidant. The color masterbatch in the invention is a bright red series masterbatch, which solves the problem of poor heat aging color stability of traditional color masterbatch in nylon products while maintaining the original color brightness. CN103756294A discloses a color masterbatch formula for UV-resistant nylon. The color masterbatch is composed of the following components: brown colorant, polyamide resin, composite stabilizer, infrared reflective pigment, cis-cypermethrin, dispersant; the composite stabilizer includes at least two of hindered phenol antioxidants, phosphite antioxidants, copper halide stabilizers, hindered amine light stabilizers, anti-hydrolysis agents, benzophenones, and benzotriazole ultraviolet absorbers. This invention mainly adopts the compound of multiple stabilizers to make various stabilizers produce synergistic effects, ensuring the stability of the material during the processing and long-term outdoor use. The mechanical properties of the material are better and it is suitable for the design and application of high-end nylon products with long-term weather resistance requirements.

[0004] However, there is no report in the prior art on how to obtain a color-stable orange nylon masterbatch under hygroscopic conditions. Therefore, it is necessary to develop an orange masterbatch that can maintain the color stability of nylon materials under humid conditions, thereby providing a new idea for the preparation of highly color-stable orange nylon materials. Summary of the invention

[0005] In view of this, one of the objects of the present invention is to provide a highly color-stable orange masterbatch dedicated to nylon materials; a second object of the present invention is to provide a method for preparing a highly color-stable orange masterbatch dedicated to nylon materials; a third object of the present invention is to provide an application of a highly color-stable orange masterbatch dedicated to nylon materials in preparing highly color-stable orange nylon materials.

[0006] In order to achieve the above object, the present invention provides the following technical solutions:

[0007] 1. A highly color-stable orange masterbatch for nylon material, comprising the following components by weight: 44-58.5 parts of PA6 resin, 5-8 parts of orange powder compound, 25-30 parts of plasticizer, 10-15 parts of titanium dioxide, 0.5-1 parts of heat stabilizing agent, and 1-2 parts of processing lubricant;

[0008] The orange powder compound is a mixture of solvent orange 116 and solvent orange 60; the mass ratio of solvent orange 116 to solvent orange 60 is 1.5-2:1.

[0009] Preferably, the plasticizer is any one of N-butylbenzenesulfonamide or N-ethylbenzenesulfonamide.

[0010] Preferably, the heat stabilizing agent is any one or more of antioxidant 1010, antioxidant 168, antioxidant 1098, antioxidant 1076, antioxidant H10 or antioxidant H161.

[0011] Preferably, the processing lubricant is any one or more of silicone wax, silicone or pentaerythritol stearate.

[0012] 2. The preparation method of the masterbatch is as follows: PA6 resin, orange powder compound, titanium dioxide, heat stabilizing agent and processing lubricant are mixed evenly and added to the extruder from the main feed port, and the plasticizer is added to the extruder from the liquid feed port, and the mixture is melted, extruded and granulated.

[0013] Preferably, the extrusion temperature is 220-240°C.

[0014] 3. Application of the masterbatch in preparing orange nylon material with high color stability.

[0015] The beneficial effect of the present invention is that the present invention provides a highly color-stable orange masterbatch specially used for nylon materials. The masterbatch comprises the following components: PA6 resin, orange powder compound (a mixture of solvent orange 116 and solvent orange 60 formed in a certain mass ratio), plasticizer, titanium dioxide, heat stabilizing additive and processing lubricant. By adding two orange pigments (solvent orange 116 and solvent orange 60) whose ΔL, Δa and Δb change oppositely under hygroscopic conditions to the masterbatch, and combining the synergistic effect of adding plasticizer, when the masterbatch is added to the nylon material, the serious problem of orange nylon material discoloration due to hygroscopicity is solved, so that the color of the orange nylon material can be kept stable under long-term hygroscopic conditions, and the color difference ΔE is less than 0.3.

[0016] The invention also provides a method for preparing a highly color-stable orange masterbatch specially used for nylon materials. The preparation method has simple operation steps and can realize large-scale industrial production.

[0017] Other advantages, objectives and features of the present invention will be described in the following description to some extent, and to some extent, will be obvious to those skilled in the art based on the following examination and study, or can be taught from the practice of the present invention. The objectives and other advantages of the present invention can be realized and obtained through the following description. BRIEF DESCRIPTION OF THE DRAWINGS

[0018] In order to make the purpose, technical solutions and advantages of the present invention more clear, the present invention will be described in detail below in conjunction with the accompanying drawings, wherein:

[0019] Figure 1 Schematic diagram of the color difference change of the highly color-stable orange masterbatch specially used for the nylon material in this application when applied to the nylon material under moisture absorption conditions. DETAILED DESCRIPTION

[0020] The following describes the embodiments of the present invention by specific examples, and those skilled in the art can easily understand other advantages and effects of the present invention from the contents disclosed in this specification. The present invention can also be implemented or applied through other different specific embodiments, and the details in this specification can also be modified or changed in various ways based on different viewpoints and applications without departing from the spirit of the present invention. It should be noted that the illustrations provided in the following embodiments only illustrate the basic concept of the present invention in a schematic manner, and the following embodiments and features in the embodiments can be combined with each other without conflict.

[0021] Embodiments 1 to 5

[0022] The components of the highly color-stable orange masterbatch specially used for nylon materials in Examples 1 to 5 are as follows, and the proportions of the components are shown in Table 1:

[0023] PA6 resin: brand M2400;

[0024] Orange powder compound: a mixture of solvent orange 116 and solvent orange 60;

[0025] Plasticizer: N-butylbenzenesulfonamide;

[0026] Titanium dioxide: titanium dioxide;

[0027] Antioxidant: H161;

[0028] Processing lubricant: silicone wax, brand E525;

[0029] Table 1 Ratio of components in the highly color-stable orange masterbatch for nylon materials in Examples 1 to 5

[0030]

[0031] The specific preparation method of each color masterbatch in Examples 1 to 5 is as follows: PA6 resin, orange powder compound, titanium dioxide, heat stabilizing agent and processing lubricant are mixed evenly according to the ratio of each component in Table 1, and then added to the extruder from the main feed port, and the plasticizer is added to the extruder from the liquid feed port, and then melted, extruded and granulated (the extrusion temperature is 240°C).

[0032] Comparative Examples 1 to 6

[0033] The difference from Examples 1 to 5 is that the composition or ratio of each component in the orange masterbatch is different, as shown in Table 2:

[0034] Ratios of the components in the orange masterbatch in Comparative Examples 1 to 6

[0035]

[0036] The specific preparation method of each color masterbatch in Comparative Examples 1 to 6 is as follows: PA6 resin, orange powder compound, titanium dioxide, heat stabilizing agent and processing lubricant are mixed evenly according to the ratio in Table 2, and then added to the extruder from the main feed port, and the plasticizer is added to the extruder from the liquid feed port, and then melted, extruded and granulated (the extrusion temperature is 240°C).

[0037] Figure 1 Schematic diagram of the color difference change of the highly color-stable orange masterbatch specially used for the nylon material in this application when applied to the nylon material under moisture absorption conditions. Figure 1 △L is the black-white deviation, positive value becomes white, negative value becomes black; △a is the red-green deviation, positive value becomes red, negative value becomes green; △b is the yellow-blue deviation, positive value becomes yellow, negative value becomes blue. Figure 1It can be seen that when solvent orange 116 is added to the orange masterbatch for nylon, the changes of △L, △a, and △b of the nylon material added with the masterbatch under hygroscopic conditions are positive and negative; when solvent orange 60 is added to the orange masterbatch for nylon, the changes of △L, △a, and △b of the nylon material added with the masterbatch under hygroscopic conditions are negative and positive; and when a mixture of solvent orange 116 and solvent orange 60 compounded in a specific proportion is added to the orange masterbatch for nylon, the nylon material added with the masterbatch under hygroscopic conditions has opposite changes in △L, △a, and △b of solvent orange 116 and solvent orange 60, which can offset each other. According to the calculation formula of color difference △E, △E=(△L 2 +△a 2 +△b 2 ) 1 / 2 It can be seen that the ΔE value of the orange nylon material finally prepared is very small, that is, the color change is very small, thereby achieving high color stability of the orange nylon material under long-term moisture absorption conditions.

[0038] Performance Testing

[0039] In order to verify the performance of the highly color-stable orange masterbatch for nylon materials obtained in the present invention, the masterbatch obtained in Examples 1 to 5 and Comparative Examples 1 to 6 was added to PA6 resin to perform moisture absorption discoloration and moisture absorption rate tests, and the test results are shown in Table 3. The specific test method is as follows:

[0040] The masterbatches obtained in Examples 1 to 5 and Comparative Examples 1 to 6 were added to PA6 resin in an amount of 4 wt.%, mixed evenly, placed in a vacuum oven, dried at 100° C. for 3 h, and then injection molded into color plates with a size of 60 mm×60 mm×2 mm and a smooth surface using an injection molding machine; after cooling each color plate in an environment of 23° C. and 55% humidity, the L, a, b and weight of each color plate at 0 day (reference standard), 1 day, 7 days, 30 days, and 60 days were tested using a colorimeter (D65 light source) and a balance, and the corresponding ΔL, Δa, Δb, ΔE and moisture absorption rate were calculated. The experimental results are shown in Table 3.

[0041] Table 3 Comparison of the corresponding hygroscopic discoloration and moisture absorption rate when the corresponding masterbatch is added to the nylon material in Examples 1 to 5 and Comparative Examples 1 to 6

[0042]

[0043] It can be seen from Table 3 that the ratio of solvent orange 116 and solvent orange 60 and the content of plasticizer have a crucial influence on the discoloration effect of the nylon material added with the masterbatch after moisture absorption. When the ratio of solvent orange 116 and solvent orange 60 in the masterbatch is 1.8:1 and the plasticizer is 30 parts, the discoloration of the corresponding nylon material after moisture absorption can be significantly improved.

[0044] As for the proportion of solvent orange 116 and solvent orange 60, it can be found by comparing examples 1 to 3 and comparative examples 1 to 4 that when the orange powder compound in the masterbatch is only solvent orange 116 or solvent orange 60, the △E value of the corresponding nylon material increases rapidly, indicating that its hygroscopic discoloration is very serious; and when the orange powder compound in the masterbatch contains both solvent orange 116 and solvent orange 60, since the change directions of △L, △a, and △b of solvent orange 116 and solvent orange 60 are opposite during the hygroscopic process, the △E value of the corresponding nylon material is reduced, and the discoloration is small. Among them, when the ratio of solvent orange 116 to solvent orange 60 is 1.8:1, the △E value of the corresponding nylon material is the smallest, the hygroscopic discoloration is relatively light, and the nylon material obtained by adding the orange masterbatch is color-stable under long-term hygroscopic conditions.

[0045] As for the plasticizer, by comparing Examples 4-5 and Comparative Examples 5-6, it can be found that when no plasticizer is added to the masterbatch, the corresponding nylon material has serious hygroscopic discoloration, and the △L, △a, △b and △E values ​​fluctuate greatly; when 30 parts of plasticizer are added to the masterbatch, the corresponding nylon material has a lighter hygroscopic discoloration. That is, the masterbatch with the addition of plasticizer can improve the discoloration of the corresponding nylon material after hygroscopic discoloration, but if the amount of plasticizer added is insufficient, the effect of improving hygroscopic discoloration is not obvious; if the amount of plasticizer added is too much, the masterbatch cannot be processed.

[0046] In summary, the present invention provides a highly color-stable orange masterbatch for nylon materials. By adding two orange pigments (Solvent Orange 116 and Solvent Orange 60) whose ΔL, Δa, and Δb change oppositely under hygroscopic conditions to the masterbatch, and combining the synergistic effect of adding a plasticizer, when the masterbatch is added to the nylon material, the serious problem of nylon material discoloration due to hygroscopicity is solved, and the color can maintain high stability under long-term hygroscopic conditions.

[0047] The invention also provides a method for preparing a highly color-stable orange masterbatch specially used for nylon materials. The preparation method has simple operation steps and can realize large-scale industrial production.

[0048] Finally, it should be noted that the above embodiments are only used to illustrate the technical solution of the present invention rather than to limit it. Although the present invention has been described in detail with reference to the preferred embodiments, those skilled in the art should understand that the technical solution of the present invention can be modified or replaced by equivalents without departing from the purpose and scope of the technical solution, which should be included in the scope of the claims of the present invention.

Claims

1. A highly color-stable orange masterbatch for nylon material, characterized by: The masterbatch comprises the following components by weight: 44-58.5 parts of PA6 resin, 5-8 parts of orange powder compound, 25-30 parts of plasticizer, 10-15 parts of titanium dioxide, 0.5-1 parts of heat stabilizing agent, and 1-2 parts of processing lubricant; The orange powder compound is a mixture of solvent orange 116 and solvent orange 60; the mass ratio of solvent orange 116 to solvent orange 60 is 1.5-2:1; and the plasticizer is any one of N-butylbenzenesulfonamide and N-ethylbenzenesulfonamide.

2. The masterbatch according to claim 1, characterized in that: The heat stabilizing agent is any one or more of antioxidant 1010, antioxidant 168, antioxidant 1098, antioxidant 1076, antioxidant H10 or antioxidant H161.

3. The masterbatch according to claim 1, characterized in that: The processing lubricant is any one or more of silicone wax, silicone or pentaerythritol stearate.

4. The method for preparing a masterbatch according to any one of claims 1 to 3, characterized in that: The preparation method is as follows: PA6 resin, orange powder compound, titanium dioxide, heat stabilizing agent and processing lubricant are mixed evenly and then added into the extruder from the main feeding port, and the plasticizer is added into the extruder from the liquid feeding port, and then melted, extruded and granulated.

5. The preparation method according to claim 4, characterized in that: The extrusion temperature is 220-240°C.

6. Use of the masterbatch according to any one of claims 1 to 3 in the preparation of orange nylon materials with high color stability.

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