CN116376271A - A high color stable orange masterbatch for nylon materials and its preparation method and application - Google Patents

Abstract

The invention relates to a high-color-stable orange masterbatch specially used for nylon materials and a preparation method and application thereof, belonging to the technical field of polymer materials. The color masterbatch includes the following components: PA6 resin, orange powder compound (a mixture of solvent orange 116 and solvent orange 60 in a certain mass ratio), plasticizer, titanium dioxide, thermal stability aid and processing lubricant. By adding two kinds of orange pigments whose △L, △a, and △b change oppositely under the condition of moisture absorption to the color masterbatch, and at the same time combining the synergistic effect of adding plasticizers, when the color masterbatch is added to the nylon material Among them, the value of color difference △E after moisture absorption of nylon material is greatly reduced, and the color can remain stable under long-term moisture absorption conditions, which solves the serious problem of orange nylon material discoloration due to moisture absorption. The preparation method has simple operation steps and can realize large-scale industrial production.

Description

A kind of high color stable orange color masterbatch special for nylon material and preparation method thereof and application

technical field

The invention belongs to the technical field of polymer materials, and relates to a high-color-stable orange masterbatch specially used for nylon materials, a preparation method and application thereof.

Background technique

Nylon material is widely used in various industries as engineering plastics because of its excellent comprehensive properties. While pursuing the mechanical properties of nylon materials, people have gradually put forward requirements for its appearance and color. To obtain a wide variety of colors, the nylon material needs to be dyed. A common method is to add toner 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 the color, people have proposed a series of solutions from the perspective of modification and optimization of the pigment itself.

CN112029269A discloses a color masterbatch with heat-resistant aging color stability for nylon. The composition of the color masterbatch includes polyamide carrier resin, modified toner, dispersant and antioxidant. The color masterbatch in this invention is a brightly colored red series masterbatch, which solves the problem of poor color stability of traditional color masterbatches in nylon products due to heat aging resistance while maintaining the original color brilliance. CN103756294A discloses a color masterbatch formula for anti-UV nylon. The 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 hindered phenolic antioxidant, phosphite antioxidant Oxygen agent, copper halide stabilizer, hindered amine light stabilizer, anti-hydrolysis agent, benzophenone and benzotriazole ultraviolet absorber. The invention mainly adopts the compounding of various stabilizers, so that various stabilizers can produce a synergistic effect, ensuring the stability of the material during processing and long-term outdoor use, and the mechanical properties of the material are better, which is suitable for long-term use. Design and application of high-end nylon products with weather resistance requirements.

However, in the prior art, there is no report on how to obtain a stable color masterbatch for orange nylon materials under hygroscopic conditions. Therefore, it is necessary to develop an orange color masterbatch that can maintain the color stability of nylon materials under wet conditions, thereby providing a new idea for the preparation of orange nylon materials with high color stability.

Contents of the invention

In view of this, one of the purposes of the present invention is to provide a high color stable orange masterbatch for nylon materials; the second purpose of the present invention is to provide a high color stable orange masterbatch for nylon materials Preparation method; the third purpose of the present invention is to provide the application of high color stable orange masterbatch for nylon materials in the preparation of high color stable orange nylon materials.

To achieve the above object, the present invention provides the following technical solutions:

1. A high-color-stable orange color masterbatch dedicated to nylon materials. In parts by weight, the color masterbatch comprises the following components: 44 to 58.5 parts of PA6 resin, 5 to 8 parts of orange powder compound, 25-30 parts of plasticizer, 10-15 parts of titanium dioxide, 0.5-1 part of thermal stability additive, 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 and solvent orange 60 is 1.5˜2:1.

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

Preferably, the heat stabilization aid is any one or more of antioxidant 1010, antioxidant 168, antioxidant 1098, antioxidant 1076, antioxidant H10 or antioxidant H161.

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

2. The preparation method of the color masterbatch, the preparation method is as follows: PA6 resin, orange powder compound, titanium dioxide, thermal stability aid and processing lubricant are mixed uniformly and then added to the extruder from the main feeding port In the process, the plasticizer is added into the extruder from the liquid feeding port, and it can be melted, extruded and granulated.

Preferably, the extruding temperature is 220-240°C.

3. The application of the color masterbatch in the preparation of high color stable orange nylon material.

The beneficial effect of the present invention is that: the present invention provides a high color stable orange color masterbatch specially used for nylon materials. The color masterbatch includes the following components: PA6 resin, orange powder compound (a mixture of solvent orange 116 and solvent orange 60 in a certain mass ratio), plasticizer, titanium dioxide, thermal stability aid and processing lubricant. By adding two kinds of orange pigments (Solvent Orange 116 and Solvent Orange 60) whose △L, △a, and △b change oppositely under hygroscopic conditions, combined with the synergistic effect of adding plasticizers, when the The color masterbatch is added to the nylon material to solve the serious problem of orange nylon material discoloration due to moisture absorption, so that the color of the orange nylon material can remain stable under long-term moisture absorption conditions, and the color difference △E<0.3.

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

Other advantages, objects and features of the present invention will be set forth in the following description to some extent, and to some extent, will be obvious to those skilled in the art based on the investigation and research below, or can be obtained from Taught in the practice of the present invention. The objects and other advantages of the invention may be realized and attained by the following specification.

Description of drawings

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

Figure 1 is a schematic diagram of the application of the highly color-stable orange masterbatch for nylon materials in this application to the change in color difference under hygroscopic conditions.

Detailed ways

Embodiments of the present invention are described below through specific examples, and those skilled in the art can easily understand other advantages and effects of the present invention from the content disclosed in this specification. The present invention can also be implemented or applied through other different specific implementation modes, and various modifications or changes can be made to the details in this specification based on different viewpoints and applications without departing from the spirit of the present invention. It should be noted that the diagrams provided in the following embodiments are only schematically illustrating the basic concept of the present invention, and the following embodiments and the features in the embodiments can be combined with each other in the case of no conflict.

Embodiment 1-5

The components included in the highly color-stable orange masterbatch for nylon materials in Examples 1 to 5 are as follows, and the proportioning ratio of each component is shown in Table 1:

PA6 resin: grade M2400;

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

Plasticizer: N-butylbenzenesulfonamide;

Titanium dioxide: titanium dioxide;

Antioxidant: H161;

Processing lubricant: silicone wax, grade E525;

The ratio of each component in the high-color-stable orange masterbatch dedicated to nylon materials in Examples 1 to 5 of Table 1

The specific preparation method of each color masterbatch in Examples 1 to 5 is as follows: mix PA6 resin, orange powder compound, titanium dioxide, thermal stability aid and processing lubricant according to the proportion of each component in Table 1 and then mix them uniformly from The main feeding port is fed into the extruder, and the plasticizer is fed into the extruder from the liquid feeding port, and it can be melted, extruded, and granulated (the extruding temperature is 240°C).

Comparative example 1-6

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

The ratio of each component in the orange color masterbatch in comparative examples 1 to 6

The specific preparation method of each color masterbatch in Comparative Examples 1-6 is as follows: mix PA6 resin, orange powder compound, titanium dioxide, thermal stability additive and processing lubricant according to the ratio in Table 2, and then feed it from the main The plasticizer is fed into the extruder from the liquid feeding port, and it can be melted, extruded, and granulated (the extruding temperature is 240°C).

Figure 1 is a schematic diagram of the application of the highly color-stable orange masterbatch for nylon materials in this application to the change in color difference under hygroscopic conditions. In Figure 1, △L is the deviation of black and white, positive value turns white, and negative value turns black; △a is the deviation of red and green, positive value turns red, and negative value turns green; △b is yellow-blue deviation, positive value turns yellow , negative values turn blue. It can be seen from Figure 1 that when solvent orange 116 is added to the special orange color masterbatch for nylon, the changes of △L, △a, and △b are positive and negative under the condition of moisture absorption for the nylon material to which the color masterbatch is added; When solvent orange 60 is added to the orange color masterbatch for nylon, the changes of △L, △a, and △b of the nylon material added with the color masterbatch are negative and positive under the condition of moisture absorption; When the mixture of solvent orange 116 and solvent orange 60 formed by compounding in a specific ratio is added to the masterbatch, the nylon material to which the masterbatch is added is under hygroscopic conditions, due to the △L, △a, △b changes oppositely and can cancel each other out. According to the calculation formula of color difference △E △E=(△L ² +△a ² +△b ² ) ^1/2 , it can be seen that the △E value of the final orange nylon material is very small, That is, the discoloration is very small, thereby achieving high color stability of the orange nylon material under long-term moisture absorption conditions.

Performance Testing

In order to verify the performance of the high-color-stable orange color masterbatch special for nylon materials obtained in the present invention, the color masterbatches obtained in Examples 1 to 5 and Comparative Examples 1-6 were added to PA6 resin for hygroscopic discoloration and moisture absorption tests. The results are shown in Table 3. The specific test method is as follows:

Add the color masterbatches obtained in Examples 1-5 and Comparative Examples 1-6 to PA6 resin in an amount of 4wt.%, mix evenly, place in a vacuum oven, dry at 100°C for 3 hours, and then use an injection molding machine to inject Make color plates with a size of 60mm×60mm×2mm and a smooth surface; after cooling each color plate in an environment of 23°C and 55% humidity, use a color difference meter (D65 light source) and a balance to test each color plate on day 0 (reference standard) , 1 day, 7 days, 30 days, 60 days L, a, b and weight, and calculate the corresponding △L, △a, △b, △E and moisture absorption rate, the experimental results are shown in Table 3.

Table 3 Comparison of corresponding hygroscopic discoloration and moisture absorption rate when the corresponding color masterbatches in Examples 1-5 and Comparative Examples 1-6 are added to nylon materials

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 proportion of solvent orange 116 and solvent orange 60 is 1.8:1, and the plasticizer is 30 parts, the discoloration of the corresponding nylon material after moisture absorption can be significantly improved.

For the ratio of solvent orange 116 and solvent orange 60, by comparing Examples 1-3 and Comparative Examples 1-4, it can be found that when the component of 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; while the orange powder compound in the masterbatch contains both solvent orange 116 and solvent orange 60 When solvent orange 116 and solvent orange 60 change in the opposite directions of ΔL, Δa, and Δb during the moisture absorption process, the ΔE value of the corresponding nylon material decreases and the discoloration is small. Among them, when the ratio of solvent orange 116 and solvent orange 60 is 1.8:1, the △E value of the corresponding nylon material is the smallest, and the discoloration of moisture absorption is relatively light, and the color of the nylon material obtained by adding the orange color masterbatch is stable under long-term moisture absorption conditions .

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 color masterbatch, the hygroscopic discoloration of the corresponding nylon material is serious, and △L, △ The values of a, △b and △E fluctuate greatly; when 30 parts of plasticizer is added to the masterbatch, the corresponding nylon material has less moisture absorption and discoloration. That is, the color masterbatch with plasticizer can improve the discoloration of the corresponding nylon material after moisture absorption, but if the amount of plasticizer added is insufficient, the effect of improving the color change after moisture absorption is not obvious; if the amount of plasticizer added is too much, it will lead to grains cannot be processed.

In summary, the present invention provides a highly color-stable orange color masterbatch for nylon materials. By adding two kinds of orange pigments (Solvent Orange 116 and Solvent Orange 60) whose △L, △a, and △b change oppositely under hygroscopic conditions, combined with the synergistic effect of adding plasticizers, when the The color masterbatch is added to the nylon material, which solves the serious problem of nylon material discoloration due to moisture absorption, and the color can maintain high stability under long-term moisture absorption conditions.

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

Finally, it is noted that the above embodiments are only used to illustrate the technical solutions of the present invention without limitation. Although the present invention has been described in detail with reference to the preferred embodiments, those of ordinary skill in the art should understand that the technical solutions of the present invention can be carried out Modifications or equivalent replacements, without departing from the spirit and scope of the technical solution, should be included in the scope of the claims of the present invention.

Claims (7)

1. A special orange color master batch with high color stability for nylon materials is characterized in that: the color master batch comprises the following components in parts by weight: 44 to 58.5 parts of PA6 resin, 5 to 8 parts of orange powder compound, 25 to 30 parts of plasticizer, 10 to 15 parts of titanium dioxide, 0.5 to 1 part of heat stabilizing additive and 1 to 2 parts of processing lubricant;

the orange powder compound is a mixture formed by solvent orange 116 and solvent orange 60; the mass ratio of the solvent orange 116 to the solvent orange 60 is 1.5-2:1.

2. The masterbatch according to claim 1, characterized in that: the plasticizer is any one of N-butyl benzene sulfonamide or N-ethyl benzene sulfonamide.

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

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

5. The process for producing a masterbatch according to any one of claims 1 to 4, characterized in that: the preparation method comprises the following steps: uniformly mixing PA6 resin, orange powder compound, titanium pigment, heat stabilizing additive and processing lubricant, adding the mixture into an extruder from a main feeding port, adding a plasticizer into the extruder from a liquid feeding port, and carrying out melting, extrusion and granulation.

6. The method of manufacturing according to claim 5, wherein: the extrusion temperature is 220-240 ℃.

7. Use of the masterbatch according to any one of claims 1-4 for the preparation of a high color stable orange nylon material.

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