CN116814006A - A functional masterbatch and its preparation method and application - Google Patents

Abstract

The invention discloses a functional masterbatch and its preparation method and application. In parts by weight, it includes: 20 to 90 parts of matrix plastic, 5 to 80 parts of powdery colloidal photonic crystal, 1 to 10 parts of compatibilizer, and diffusion agent. 0.5 to 5 parts of agent, 0.3 to 1 part of antioxidant, 0.1 to 0.5 part of ultraviolet absorber, and 0.2-1.0 part of anti-hydrolysis agent; among them, the transmittance of the base plastic at a wavelength of 400nm to 800nm is ≥70%, and the transmittance of the base plastic is ≥70%. The molding temperature is ≤270℃; the powdered colloidal photonic crystal includes nanospheres and carrier resin. Compared with the existing technology, the functional masterbatch of the present invention contains a photonic crystal three-dimensional micro-nano structure, which can selectively regulate light at specific angles and specific wavelengths to form corresponding structural colors, and can also obtain different colors to achieve functions. The masterbatch has different colors depending on the angle and dynamic discoloration function; it also has the advantages of not fading, not containing chemical pigments and good compatibility with plastics.

Description

A functional masterbatch and its preparation method and application

Technical field

The present invention relates to the technical field of polymer materials, and more specifically, to a functional masterbatch and its preparation method and application.

Background technique

Angular heterochromia refers to the phenomenon that different colors can appear when viewed from different angles under light. In other words, when the observer is not moving and the angle of the light source changes, different colors can also appear. This phenomenon is common in nature, such as purple butterflies, peacocks, colorful opals, etc. As human society continues to pursue a better life, researching functional materials with angular and dynamic color changes and developing their applications in various fields has become an emerging hot topic.

Currently, chameleon pigments are commonly used in the plastics industry. Chameleon pigments use a variety of materials as substrates, and coat a variety of metal oxides on the surface of the substrate to obtain pigments of different colors as the viewing angle changes. Generally, the surface is colored with organic or inorganic pigments and contains chemicals. pigment. When chameleon pigments are used in the plastics industry, because it is difficult for chameleon pigment substrates to be arranged in parallel and orderly, plastic products often have problems with different colors depending on the angle and the dynamic discoloration effect is not obvious. In addition, chameleon pigments have poor compatibility with plastics, and plastic products prepared with chameleon pigments have obvious weld marks.

In view of this, how to expand the wide application of functional materials that change color with angle and dynamic color in plastics, it is indeed necessary to provide a technical solution to solve the above technical problems.

Contents of the invention

In order to overcome the shortcomings of the existing technology, one of the purposes of the present invention is to provide a functional masterbatch to solve the problem of poor compatibility of chameleon pigments currently used in plastics, and containing chemical pigments and angular discoloration, and the dynamic discoloration effect is not obvious. question.

The technical solution of the present invention is as follows: a functional masterbatch, including in parts by weight: 20 to 90 parts of matrix plastic, 5 to 80 parts of powdery colloidal photonic crystal, 1 to 10 parts of compatibilizer, and 0.5 parts of diffusing agent ~5 parts, antioxidant 0.3~1 part, ultraviolet absorber 0.1~0.5 part, anti-hydrolysis agent 0.2-1.0 part;

Wherein, the transmittance of the base plastic at a wavelength of 400nm to 800nm is ≥70%, and the molding temperature of the base plastic is ≤270°C; the powdery colloidal photonic crystal includes nanospheres and a carrier resin.

Further, in parts by weight, 40 to 90 parts of base plastic, 8 to 60 parts of powdered colloidal photonic crystal, 1 to 10 parts of compatibilizer, 0.5 to 5 parts of diffusing agent, 0.3 to 1 part of antioxidant, and ultraviolet rays 0.1 to 0.5 parts of absorbent and 0.2 to 1.0 part of anti-hydrolysis agent; the transmittance of the base plastic at a wavelength of 400 nm to 800 nm is ≥90%.

Further, the weight proportion of the nano microspheres in the powdery colloidal photonic crystal is 50% to 80%, and the weight proportion of the carrier resin in the powdery colloidal photonic crystal is 20% to 50%. %; the particle size of the nanospheres is 10 nm to 600 nm.

Further, the powdery colloidal photonic crystal is prepared from a colloidal photonic crystal film by freezing ultrafine crushing or airflow ultrafine pulverization; the thickness of the colloidal photonic crystal film is 10 to 100 μm, and the thickness of the powdery colloidal photonic crystal is The fineness is 50~500 mesh.

Further, the preparation method of the colloidal photonic crystal film is as follows: the nano microspheres are arranged in the carrier resin in an orderly manner through self-assembly to form a three-dimensional micro-nano structure, and after solidification, a colloidal photonic crystal film is obtained; the colloidal photonic crystal film is The thickness of the crystal film is 15-50 μm, the fineness of the powdery colloidal photonic crystal is 100-300 mesh; the nano-microspheres are polymer synthetic microspheres, and the carrier resin is light-curing resin.

Further, the polymer synthetic microspheres are polystyrene microspheres, and the photocurable resin is aqueous photocurable polyacrylate resin.

Further, the base plastic is at least one of PP, PE, ABS, AS, BS, PS, PC, PMMA, TPU, EVA, PET, PA, and TPE; the compatibilizer is a non-reactive compatibilizer. agent; the non-reactive compatibilizer includes at least one of EAA, EEA, EMA, EVA, CPE, and SEBS; the diffusing agent includes pentaerythritol ester, liquid paraffin, polyethylene wax, oxidized polyethylene wax, dimethyl At least one of base silicone oil, stearic acid, stearate, ethylene distearate, and ethylene bisoleamide; the antioxidants include hindered phenols, phosphites, and sulfonates , composites, and at least one of hindered amines; the ultraviolet absorber includes at least one of salicylates, benzophenones, benzotriazoles, substituted acrylonitriles, triazines, and hindered amines. One; the anti-hydrolysis agent includes at least one of an isocyanate compound, an oxazoline compound, an anhydride compound, an epoxy compound, a carbodiimide and a polycarbodiimide.

Further, the base plastic is at least one of PP, EVA, PS, TPU and TPE; the non-reactive compatibilizer is EVA; the diffusing agent is pentaerythritol ester and dimethyl silicone oil; the anti- The oxygen agent is hindered phenols and phosphites; the ultraviolet absorber is benzotriazole; and the anti-hydrolysis agent is carbodiimide and/or polycarbodiimide.

The second object of the present invention is to provide a method for preparing the above-mentioned functional masterbatch, which includes the following steps:

Weigh each component in parts by weight, including 20 to 90 parts of base plastic, 5 to 80 parts of powdered colloidal photonic crystal, 1 to 10 parts of compatibilizer, 0.5 to 5 parts of diffusing agent, 0.3 to 1 part of antioxidant, 0.1-0.5 parts of ultraviolet absorber, 0.2-1.0 parts of anti-hydrolysis agent, and dry the powdery colloidal photonic crystal;

After drying, each component is stirred and mixed, and then extruded and granulated at a temperature of ≤270°C to obtain functional masterbatch.

The third object of the present invention is to provide an application of the above-mentioned functional masterbatch in plastic products.

According to the above-mentioned solution, the present invention has a beneficial effect compared with the prior art: the functional masterbatch provided by the present invention uses nano-microspheres to self-assemble in a carrier resin to construct a three-dimensional micro-nano structure of photonic crystals, and the resulting colloidal photonic crystal It is dispersed in powder form in a matrix plastic with high transmittance. Visible light energy irradiates into and acts on the nano-microspheres. The three-dimensional micro-nano structure forms a photonic band gap, which can selectively regulate light at specific angles and specific wavelengths. Form corresponding structural colors, and obtain different colors through reflection, refraction and diffraction of incident light, realizing the function of functional masterbatch with different colors and dynamic discoloration with angle; in addition, the molding temperature of the base plastic used is ≤270℃, during the preparation process A medium to low molding temperature can avoid thermal degradation of powdered colloidal photonic crystals and damage to the internal three-dimensional micro-nano structure. In addition, the functional masterbatch of the present invention also has the advantages of not fading, containing no chemical pigments, and good compatibility with plastics. It not only effectively reduces environmental pollution and carbon footprint, but also makes the plastic products more beautiful.

Description of the drawings

Figure 1 is a schematic diagram of the visual inspection angle of the color test according to the present invention;

Figure 2 is a schematic diagram of the PP rope puller jacket in Embodiment 1 of the present invention;

Figure 3 is a schematic diagram of the TPU rope slider in Embodiment 7 of the present invention.

Detailed ways

The embodiments of the present invention will be described in further detail below with reference to the accompanying drawings and examples. The detailed description of the following embodiments and the accompanying drawings are used to illustrate the principles of the present invention, but cannot be used to limit the scope of the present invention, that is, the present invention is not limited to the described embodiments.

The first aspect of the present invention aims to provide a functional masterbatch, which includes, in parts by weight: 20 to 90 parts of matrix plastic, 5 to 80 parts of powdery colloidal photonic crystal, 1 to 10 parts of compatibilizer, and 0.5 parts of diffusing agent. ~5 parts, antioxidant 0.3~1 part, ultraviolet absorber 0.1~0.5 part, anti-hydrolysis agent 0.2-1.0 part;

Wherein, the transmittance of the base plastic at a wavelength of 400nm to 800nm is ≥70%, and the molding temperature of the base plastic is ≤270°C; the powdery colloidal photonic crystal includes nanospheres and a carrier resin.

The present invention uses powdered colloidal photonic crystals, matrix plastics and various additives to prepare functional masterbatch through extrusion and granulation. The components have good compatibility, uniform dispersion, good structural color brightness and saturation, and good angle-changing properties. It has strong continuity of heterochromia and dynamic discoloration, high sensitivity and obvious discoloration effect. It effectively solves the current problems of poor compatibility of chameleon pigments used in plastics, and contains chemical pigments and angular discoloration, and the dynamic discoloration effect is not obvious.

Preferably, in parts by weight, 40 to 90 parts of base plastic, 8 to 60 parts of powdered colloidal photonic crystal, 1 to 10 parts of compatibilizer, 0.5 to 5 parts of diffusing agent, 0.3 to 1 part of antioxidant, and ultraviolet rays 0.1-0.5 parts of absorbent and 0.2-1.0 parts of anti-hydrolysis agent.

Among them, the base plastic of the present invention is preferably a thermoplastic plastic, which is softened by heat, can be molded repeatedly and recycled, which expands the application scope of functional masterbatch. At the same time, choosing a thermoplastic with a molding temperature of ≤270°C can avoid the problem of thermal degradation of powdered colloidal photonic crystals at higher molding temperatures, thereby ensuring that the three-dimensional micro-nano structure inside the powdered colloidal photonic crystal is not destroyed. In addition, the matrix plastic should also meet the transmittance of ≥70% at a wavelength of 400nm to 800nm, ensuring transmittance under visible light, which can enhance the intensity of incident light acting on the powdery colloidal photonic crystal and ensure the structure of the powdery colloidal photonic crystal. The brightness and luster of the color are ensured, thereby ensuring the angular and dynamic discoloration effect of the functional masterbatch. Preferably, the transmittance of the matrix plastic at a wavelength of 400nm to 800nm is ≥90%. The higher the transmittance, the greater the intensity of incident light acting on the powdery colloidal photonic crystal, and the powdery colloidal photonic crystal produces structural color brightness, The better the color, the better the functional masterbatch’s angular and dynamic discoloration effects.

In some embodiments, the base plastic may be at least one of PP, PE, ABS, AS, BS, PS, PC, PMMA, TPU, EVA, PET, PA, and TPE. Thermoplastics with transmittance ≥90% can preferably be high-transparent PP, high-transparent EVA, high-transparent PS, or high-transparent TPU.

In some embodiments, the base plastic may be 20 to 30 parts, 30 to 40 parts, 40 to 50 parts, 50 to 60 parts, 60 to 70 parts, 70 to 80 parts or 80 to 90 parts by weight. . Preferably, the base plastic is 40 to 90 parts.

The content of the matrix plastic is adjusted with the content of the powdery colloidal photonic crystal. When the mass content of the matrix plastic is higher (greater than or equal to 70%), that is, when the content of the powdery colloidal photonic crystal is lower, the functional masterbatch of the present invention can be directly As plastic masterbatch, it is used in various molding processes such as injection molding, extrusion, calendering, blow molding, and tape casting to prepare plastic products with angular and dynamic discoloration functions. The plastic products do not fade and do not contain chemical pigments. And if the content of the matrix plastic is low, that is, when the mass content of the powdered colloidal photonic crystal is high (greater than or equal to 15%), the functional masterbatch of the present invention can be added to the corresponding virgin plastic (referring to the functional masterbatch) according to a certain proportion. Mix the same type and model of matrix plastic in the masterbatch to reduce the content of powdery colloidal photonic crystals and increase the content of matrix plastic, and then apply it to injection molding, extrusion, calendering, blow molding, casting, etc. In a variety of molding processes, plastic products with angular and dynamic discoloration functions can be prepared. The plastic products do not fade and do not contain chemical pigments.

In some embodiments, the powdered colloidal photonic crystal may be 5 to 10 parts, 10 to 20 parts, 20 to 30 parts, 30 to 40 parts, 40 to 50 parts, 50 to 60 parts, or 60 parts by weight. ~70 servings or 70-80 servings. Preferably, the powdery colloidal photonic crystal is 8 to 60 parts by weight.

When preparing a highly concentrated functional masterbatch with a mass content of powdery colloidal photonic crystals greater than 50%, it is preferable to use a highly transparent EVA matrix plastic. The EVA highly concentrated functional masterbatch can be added to most plastics for proportioning, reducing the After adjusting the content of powdery colloidal photonic crystals, it is then used in various molding processes such as injection molding, extrusion, calendering, blow molding, and tape casting to prepare plastic products with angular and dynamic discoloration functions. The plastic products do not fade. And no chemical coloring. In addition, preparing EVA highly concentrated functional masterbatch can reduce the cost of functional masterbatch granulation preparation and improve the production efficiency of functional masterbatch.

Among them, the nanospheres included in powdery colloidal photonic crystals refer to small polymer particles with a particle size of nanometers. The raw materials are easy to obtain, the preparation method is simple, the particle size and dispersion control technology is mature, and they self-assemble into orderly The three-dimensional micro-nano structure can form a photonic band gap, which can selectively regulate light at specific angles and specific wavelengths to form corresponding structural colors, and obtain different colors through reflection, refraction and diffraction of incident light to achieve powdery Colloidal photonic crystals have different colors and dynamic color changes with angle. Structural color development does not require chemical pigments. It uses three-dimensional micro-nano structures to develop color. As long as the refractive index and shape of the material remain unchanged, there is no problem of fading, effectively reducing environmental pollution and carbon footprint. Preferably, the nano-microspheres are preferably polymer synthetic microspheres. Polymers are used to synthesize nano-microspheres. The monomers can be arranged in a three-dimensional order in the carrier resin through self-assembly. The internal micro-nano structure constructed is more stable and has a structural color. The color rendering effect is better. More preferably, the nano-microspheres are polystyrene microspheres.

The carrier resin is used as a supporting carrier, and the nano-microspheres are self-assembled in the carrier resin and arranged in an orderly manner to form a three-dimensional micro-nano structure, and then the colloidal photonic crystal film is obtained by solidifying the carrier resin, and then the powdery colloidal photonic crystal is obtained. The carrier resin of the present invention is preferably a photo-curable resin, which has good transparency. Light passes through the carrier resin, and the stereotyped three-dimensional micro-nano structure constructed by the nano-microspheres can show structural colors in all directions and is not limited by specific visual directions. The obtained powdery colloidal photonic crystal is then dispersed in the matrix plastic, without the trouble of secondary orderly arrangement. It can show structural colors in all directions, with obvious different colors and dynamic color changes with angle, which more effectively solves the existing problems. Chameleon pigments are used in plastics that contain chemical pigments and are difficult to arrange in an orderly manner, resulting in different colors with angles and insignificant dynamic color-changing effects. More preferably, the carrier resin is preferably a water-based light-curing polyacrylate resin, a powdery colloidal photonic crystal formed by a water-based light-curing polyacrylate resin and polystyrene microspheres, and a functional masterbatch formed by combining with the matrix plastic. The heterochromatic and dynamic discoloration effects are more obvious.

The particle size of the nanometer microspheres used in the present invention is 10 nm to 600 nm. The macrostructures composed of nanospheres of different sizes will show different colors. For example, the three-dimensional micro-nano structures of nanospheres with particle sizes of 80nm and 200nm appear green and blue respectively. The present invention can adjust the structural color of the powdery colloidal photonic crystal by adjusting the particle size of the nanospheres, and adjust the color change range according to production needs to obtain colors corresponding to different wavelengths in the visible spectrum.

In some embodiments, the powdery colloidal photonic crystal is prepared from a colloidal photonic crystal film by freezing ultrafine crushing or airflow ultrafine pulverization; the thickness of the colloidal photonic crystal film is 10 to 100 μm. Preferably, the thickness of the colloidal photonic crystal film is 15-50 μm.

In some embodiments, the preparation method of the colloidal photonic crystal film is as follows: the nano microspheres are arranged in an orderly manner in the carrier resin through self-assembly to form an internal three-dimensional micro-nano structure, and a colloidal photonic crystal film is obtained after solidification.

After first mixing nanospheres and carrier resin to form a colloidal photonic crystal film, the colloidal photonic crystal film is then ultrafinely broken to obtain a powder state. The volume of the obtained powdery colloidal photonic crystal is controllable, and the powder state is easier to disperse in the matrix. In plastics, the effect of functional masterbatch changing color with angle and dynamic color is guaranteed.

In some embodiments, the fineness of the powdered colloidal photonic crystal is 50 to 500 mesh. Preferably, the fineness of the powdery colloidal photonic crystal is 100-300 mesh. The number of nano-microspheres accommodated by the powdery colloidal photonic crystal is proportional to the volume of the powder. The larger the volume of the powder, the greater the number of nano-microspheres accommodated by the powder. The number of nano-microspheres affects the structural color. The saturation, as well as the continuity and sensitivity of angular heterochromia and dynamic color change, the content and particle size of nanospheres can be selected according to production needs.

In some embodiments, the weight proportion of the nanospheres in the powdery colloidal photonic crystal is 50% to 80%, and the weight proportion of the carrier resin in the powdery colloidal photonic crystal is 20%. %~50%. Specifically, the weight proportion of nano microspheres can be 50%, 55%, 60%, 65%, 70%, 75% or 80%, and the weight proportion of carrier resin can be 50%, 45%, 40%, 35%, 30%, 25% or 20%.

In some embodiments, the compatibilizer may be 1 to 3 parts, 3 to 5 parts, 5 to 7 parts, or 7 to 10 parts by weight.

In some embodiments, the compatibilizer is a non-reactive compatibilizer; the non-reactive compatibilizer includes at least one of EAA, EEA, EMA, EVA, CPE, and SEBS. Of course, the compatibilizer of the present invention can also be a reactive compatibilizer, but in order to better protect the internal structure of the powdered colloidal photonic crystal, a non-reactive compatibilizer is preferred. The compatibilizer can overcome the problem of poor compatibility between powdered colloidal photonic crystals and matrix plastics, and effectively improve the bonding strength of the interface between the two blend systems. Compared with the poor compatibility between conventional chameleon pigments and plastics, which leads to the problem of obvious weld marks in plastic products prepared from chameleon pigments, the present invention adds a compatibilizer, which is matched with the base plastic and powdery colloidal photonic crystals, and the final plastic obtained The product has good appearance and mechanical properties.

Preferably, the non-reactive compatibilizer is EVA. EVA can better match the use of water-based light-curing polyacrylate resin as the carrier resin. After the carrier resin is cured, the molecules present a cross-linked network structure and the surface polarity is weak. Therefore, the powdery colloidal photonic crystal and the matrix plastic The compatibility between them is poor, and the interface bonding strength of the blend system is not high. For this reason, EVA is preferably used in the present invention. The inventor has proved through experimental tests that EVA has good compatibility with powdered colloidal photonic crystals and with most materials in the matrix plastic. Through the compatibilizer EVA, the blend system The interface bonding force between the powdery colloidal photonic crystal and the matrix plastic increases, and the blend structure is stable. The resulting plastic product has no weld marks at all, is more beautiful, and has better mechanical properties.

In addition, if the base plastic is directly made of EVA and other compatibilizers are selected, the plastic products obtained through the functional masterbatch of the present invention will also not have the problem of welding marks.

In some embodiments, the diffusing agent may be 0.5 to 1 part, 1 to 2 parts, 2 to 3 parts, 3 to 4 parts or 4 to 5 parts by weight. Adding a diffusing agent to the functional masterbatch of the present invention can improve the dispersion of the powdery colloidal photonic crystal and avoid agglomeration; in the functional masterbatch of the present invention, the powdery colloidal photonic crystal is a dispersed phase, the matrix plastic is a continuous phase, and the diffusing agent Addition can also effectively improve the processing fluidity of functional masterbatch. During the preparation process of the functional masterbatch, the more uniformly dispersed the powdery colloidal photonic crystals are, the better the continuity of the structural color development, and the more prominent the angular and dynamic discoloration effects of the functional masterbatch.

In some embodiments, the diffusing agent includes pentaerythritol ester (PETS), liquid paraffin, polyethylene wax, oxidized polyethylene wax, dimethicone, stearic acid, stearate, ethylene distearate (EBS), ethylene bisoleamide (EBO). Preferably, the diffusing agent is pentaerythritol ester and dimethyl silicone oil. On the one hand, pentaerythritol ester and dimethyl silicone oil do not affect the transparency of the blend system, and can better ensure the angular and dynamic discoloration effects of the functional masterbatch; on the other hand, the pentaerythritol ester and dimethyl silicone oil do not affect the transparency of the blend system. On the other hand, when the various components are stirred and mixed, dimethyl silicone oil can also promote the adhesion between the powdery colloidal photonic crystal and the matrix plastic, further improving the uniformity of the dispersion of the powdery colloidal photonic crystal in the functional masterbatch. More preferably, the compound mass ratio of pentaerythritol ester and dimethicone is 1:2.

In some embodiments, the antioxidant includes at least one of hindered phenols, phosphites, sulfonates, complexes, and hindered amines. The antioxidant can inhibit, prevent or delay the oxidation reaction of the powdery colloidal photonic crystal and matrix plastic during processing and use, and extend the service life of the functional masterbatch. Preferably, the antioxidants are hindered phenols and phosphites. More preferably, the antioxidant is a compound of hindered phenolic antioxidant 1010 and phosphite antioxidant 168, and the compound mass ratio is 1:1.

In some embodiments, the ultraviolet absorber includes at least one of salicylates, benzophenones, benzotriazoles, substituted acrylonitriles, triazines, and hindered amines. The ultraviolet absorber can prevent the powdery colloidal photonic crystal and matrix plastic from photodecomposition and discoloration under the action of light, thereby avoiding affecting the angular and dynamic discoloration effects of the plastic functional masterbatch. Preferably, the ultraviolet absorber is benzotriazole. More preferably, the ultraviolet absorber is UV-P.

In some embodiments, the anti-hydrolysis agent includes at least one of an isocyanate compound, an epoxy compound, an oxazoline compound, an anhydride compound, a carbodiimide, and a polycarbodiimide. By changing the process of water decomposition or inhibiting the decomposition reaction, the anti-hydrolysis agent can delay or prevent the occurrence of water decomposition during the processing and use of powdered colloidal photonic crystals and matrix plastics, avoid damage to their internal molecular chain structures, and thereby prevent Influence the plastic functional masterbatch's color change with angle and dynamic discoloration effect. In particular, powdered colloidal photonic crystals contain hydrophilic groups and are more prone to water decomposition, so it is particularly important to add the anti-hydrolysis agent. Preferably, the anti-hydrolysis agent is carbodiimide and polycarbodiimide. More preferably, the anti-hydrolysis agent is polycarbodiimide.

The second aspect of the present invention aims to provide a method for preparing the above-mentioned functional masterbatch, which includes the following steps:

Weigh each component in parts by weight, including 20 to 90 parts of base plastic, 5 to 80 parts of powdered colloidal photonic crystal, 1 to 10 parts of compatibilizer, 0.5 to 5 parts of diffusing agent, 0.3 to 1 part of antioxidant, 0.1-0.5 parts of ultraviolet absorber, 0.2-1.0 parts of anti-hydrolysis agent, and dry the powdery colloidal photonic crystal;

After drying, each component is stirred and mixed, and then extruded and granulated at a temperature of ≤270°C to obtain functional masterbatch.

Because the powdered colloidal photonic crystal contains hydrophilic groups and has high water absorption, the preparation method of the present invention requires that the powdered colloidal photonic crystal be fully dried before mixing the components, and then stirred and mixed, thereby avoiding the need for extrusion at high temperatures. The powdery colloidal photonic crystals and matrix plastic in the particles are hydrolyzed. Specifically, a dehumidifying drying device can be used for drying, with a drying temperature of 80 to 100°C and a drying time of ≥ 4 hours. If there is a lot of moisture in other components, they should also be dried before mixing.

The mixing time is ≥10 minutes to mix the components evenly to ensure the continuity of structural color development, the effect of different colors with angle and dynamic color change. For granulation, you can choose a twin-screw extruder for granulation, turn on the vacuum device to exhaust, and then granulate at a processing temperature of ≤270°C to avoid damaging the micro-nano structure inside the powdered colloidal photonic crystal due to excessive granulation temperature.

The third aspect of the present invention aims to provide an application of the above-mentioned functional masterbatch in plastic products.

Specifically, the functional masterbatch of the present invention can be used in various molding processes such as injection molding, extrusion, calendering, blow molding, and tape casting to prepare plastic products with angular and dynamic discoloration functions. If used in the injection molding process, various injection molding products with angular and dynamic color-changing functions can be prepared; if used in the extrusion process, pipes, wires, and rods with angular and dynamic color-changing functions can be prepared. Material-type profile products; if used in the calendering process, plate-like sheet products with angular color change and dynamic discoloration functions can be prepared; if used in the blow molding process, plate-like sheet products with angular change color and dynamic discoloration functions can be prepared Bottle hollow products; if used in the casting process, diaphragm composite products with angular and dynamic discoloration functions can be prepared.

In order to better understand the present invention, the present invention will be further described below in conjunction with the accompanying drawings and specific embodiments, but is not limited to the following embodiments.

Example 1

A functional masterbatch, in parts by weight, including: 85.7 parts of base plastic PP (model: Fupolylene ST868M), 9 parts of powdery colloidal photonic crystal (mass content in the functional masterbatch is 9%), phase Container transparent EVA (model: 150W) 3 parts, diffusing agent (industrial grade pentaerythritol ester + dimethicone compounded at a mass ratio of 1:2) 1.5 parts, antioxidant (industrial grade 1010 and 168 compounded at a mass ratio of 1:1) 0.3 0.2 parts of ultraviolet absorber UV-P, 0.3 parts of anti-hydrolysis agent (industrial grade polycarbodiimide);

Wherein, the powdery colloidal photonic crystal includes nano-microspheres and a carrier resin. The polystyrene microsphere particle size is 70 nm. The carrier resin is a water-based light-curing polyacrylate resin. The thickness of the colloidal photonic crystal film is 15 μm. The fineness of the crystal is 150 mesh, the weight proportion of polystyrene microspheres in the powdery colloidal photonic crystal is 50%, and the weight proportion of the carrier resin in the powdery colloidal photonic crystal is 50%.

The preparation method of powdery colloidal photonic crystal is as follows: first, mix the emulsion of polystyrene microspheres, the first acrylate monomer, the second acrylate monomer, and the acrylate oligomer to obtain a slurry, and then pass the polystyrene microspheres through the polystyrene microspheres. The balls are self-assembled in the carrier resin and arranged in an orderly manner to form a three-dimensional micro-nano structure, and then cured by ultraviolet light to obtain a 15 μm thick colloidal photonic crystal film. The colloidal photonic crystal film is then ultrafinely pulverized by airflow to obtain powdered colloidal photonic crystals. crystal.

The preparation method of this functional masterbatch is:

(1) Weighing: Weigh each component according to the above ratio;

(2) Drying: Dehumidify and dry the powdered colloidal photonic crystal at a drying temperature of 100°C and a drying time of 8 hours; other component materials do not have high water absorption and do not need to be dried;

(3) Mixing: Put the dried powdery colloidal photonic crystal and other component materials into a mixer and mix for 15 minutes;

(4) Extrusion granulation: Put the mixed materials into the twin-screw extruder for granulation. The processing temperature is: 1st stage (blanking port) 120℃, 2nd stage 150℃, 3rd stage 160℃, 4th stage 180℃, 5 Section 180℃, Section 6 (die head) 185℃, turn on the vacuum device to exhaust, extrusion and pelletizing to prepare PP functional masterbatch.

The obtained PP functional masterbatch is directly used in injection molding to produce a cord puller jacket with the function of changing color according to the angle and dynamic color.

Specific injection molding process parameters: The injection molding machine is a 25T vertical injection molding machine. The number of injection mold cavities is 1 and 2. The unit weight of the product is 0.65g. The weight of the runner nozzle is 1.1g. The injection molding temperature is 165°C for the first stage and 165°C for the second stage. 175℃, the third stage is 185℃, the fourth stage is 185℃, and the fifth stage is 195℃. The injection pressure is 50kgf/cm ² , the injection speed is 35%, the injection time is 5s, and the cycle is 20s.

Example 2

The difference from Example 1 is that the content of the base plastic and powdery colloidal photonic crystals, in parts by weight, is 90 parts of the base plastic PP (model: Fupolylene ST868M) and 6 parts of powdery colloidal photonic crystals. (The mass content in the functional masterbatch is 6%).

The obtained PP functional masterbatch is also directly used in injection molding to produce a cord puller jacket with different colors and dynamic discoloration functions.

For the rest, refer to the settings of Embodiment 1, which will not be described again here.

Example 3

The difference from Example 1 is that the content of each component, in parts by weight, is 71.5 parts of the base plastic PP (model: polyethylene ST868M) and 20 parts of powdery colloidal photonic crystal (in the functional masterbatch). The mass content in is 20%), compatibilizer transparent EVA (model is 150W) 5 parts, diffusing agent (industrial grade pentaerythritol ester + dimethicone compounded at a mass ratio of 1:2) 2.2 parts, antioxidant (industrial grade 1010 and 168 compounded at a mass ratio of 1:1) 0.5 0.3 parts of ultraviolet absorber UV-P, 0.5 parts of anti-hydrolysis agent (industrial grade polycarbodiimide).

The obtained PP functional masterbatch and PP raw material (Fupolylene ST868M) are mixed according to the mass ratio of 1:3, and then used for injection molding. At this time, the mass content of the powdery colloidal photonic crystal in the injection molding is 5%. The same product with A cord puller jacket with different colors and dynamic color changing function.

For the rest, refer to the settings of Embodiment 1, which will not be described again here.

Example 4

The difference from Example 1 is that the content of each component, in parts by weight, is 71.5 parts of the base plastic PP (model: polyethylene ST868M) and 20 parts of powdery colloidal photonic crystal (in the functional masterbatch). The mass content in is 20%), compatibilizer transparent EVA (model is 150W) 5 parts, diffusing agent (industrial grade pentaerythritol ester + dimethicone compounded at a mass ratio of 1:2) 2.2 parts, antioxidant (industrial grade 1010 and 168 compounded at a mass ratio of 1:1) 0.5 0.3 parts of ultraviolet absorber UV-P, 0.5 parts of anti-hydrolysis agent (industrial grade polycarbodiimide).

Wherein, the particle size of polystyrene microspheres in the powdery colloidal photonic crystal is 200 nm.

The obtained PP functional masterbatch and PP raw material (Fupolyene ST868M) are mixed according to the mass ratio of 1:1, and then used for injection molding. At this time, the mass content of the powdery colloidal photonic crystal in the injection molding is 10%. The same product with A cord puller jacket with different colors and dynamic color changing function.

For the rest, refer to the settings of Embodiment 1, which will not be described again here.

Example 5

Different from Example 4, this example mixes the PP functional masterbatch obtained in Example 4 with the PP raw material (polyene ST868M) according to a mass ratio of 1:3, and then applies it to injection molding. At this time, the powder in the injection molding The mass content of the colloid photonic crystal is 5%, and the same cord puller jacket with different colors and dynamic color changes according to the angle is produced.

For the rest, refer to the settings of Embodiment 4, which will not be described again here.

Example 6

The difference from Example 4 is that the selection of each component, in terms of parts by weight, is 71.5 parts of the base plastic PP (model: polyethylene ST868M) and 20 parts of powdery colloidal photonic crystal (in the functional masterbatch). The mass content in is 20%), compatibilizer transparent EVA (model is 150W) 5 parts, diffusing agent (industrial grade pentaerythritol ester) 2.2 parts, antioxidant (industrial grade 1010 and 168 compounded in a mass ratio of 1:1) 0.5 parts, ultraviolet absorber UV-P 0.3 parts, anti-hydrolysis agent (Industrial grade polycarbodiimide) 0.5 parts.

The obtained PP functional masterbatch and PP raw material (Fupolyene ST868M) are mixed according to the mass ratio of 1:1, and then used for injection molding. At this time, the mass content of the powdery colloidal photonic crystal in the injection molding is 10%. The same product with A cord puller jacket with different colors and dynamic color changing function.

For the rest, refer to the settings of Embodiment 4, which will not be described again here.

Example 7

A kind of functional masterbatch, in terms of parts by weight, 86.6 parts of the base plastic TPU (model: Covestro 3690AU) in this embodiment and 10 parts of powdery colloidal photonic crystal (the mass content in the functional masterbatch is 10%) , compatibilizer transparent EVA (model: 150W) 1 part, diffusing agent (industrial grade pentaerythritol ester + dimethicone compounded at a mass ratio of 1:2) 1.5 parts, antioxidant (industrial grade 1010 and 168 compounded at a mass ratio of 1:1) 0.3 0.2 parts of ultraviolet absorber UV-P, 0.4 parts of anti-hydrolysis agent (industrial grade polycarbodiimide).

Wherein, the powdery colloidal photonic crystal includes nano-microspheres and a carrier resin. The polystyrene microsphere particle size is 100 nm. The carrier resin is a water-based light-curing polyacrylate resin. The thickness of the colloidal photonic crystal film is 15 μm. The fineness of the crystal is 150 mesh, the weight proportion of polystyrene microspheres in the powdery colloidal photonic crystal is 50%, and the weight proportion of the carrier resin in the powdery colloidal photonic crystal is 50%.

The preparation method of this functional masterbatch is:

(1) Weighing: Weigh each component according to the above ratio;

(2) Drying: Dehumidify and dry the powdered colloidal photonic crystal and matrix plastic TPU at a drying temperature of 100°C and a drying time of 8 hours; other component materials do not have high water absorption and do not need to be dried;

(3) Mixing: Put the dried powdery colloidal photonic crystal, matrix plastic TPU and other component materials into a mixer and mix for 15 minutes;

(4) Extrusion granulation: Put the mixed materials into the twin-screw extruder for granulation. The processing temperature is: 180°C in section 1 (blanking port), 190°C in section 2, 200°C in section 3, 215°C in section 4, 5 Section 220℃, Section 6 (die head) 225℃, turn on the vacuum device to exhaust, extrusion and pelletizing, to obtain TPU functional masterbatch.

The obtained TPU functional masterbatch is directly used in injection molding to produce a rope slider with the function of changing color according to the angle and dynamic color.

Specific injection molding process parameters: The injection molding machine is a 25T vertical injection molding machine. The number of injection mold cavities is 1 and 8 cavities. The unit weight of the product is 0.75g. The weight of the runner nozzle is 3.38g. The injection molding temperature is 190°C for the first stage and 190°C for the second stage. 195℃, the third stage is 210℃, the fourth stage is 220℃, the fifth stage is 230℃, the injection pressure is 80kgf/cm ² , the injection speed is 30%, the injection time is 8s, and the cycle is 35s.

The plastic products obtained in the above-mentioned Examples 1 to 7 were subjected to a color test.

Color test: The test method is visual inspection. For the visual angle, see Figure 1. Assemble the cord puller jacket on the black cord core, adjust it to different directions to observe the color displayed on the cord puller jacket (or turn the cord Adjust the belt slider to different directions and observe the color displayed on the belt slider); when the belt slider jacket (or belt slider) rotates slowly, observe the dynamic changes in the color displayed on the belt slider jacket.

The test results are shown in Table 1 below and Figures 2-3.

Table 1

It can be seen from the comparison of Examples 1 to 7 that different particle sizes of nanospheres can cause plastic products to exhibit different structural colors, as shown in Figures 2 to 3. In addition, from the comparison of Examples 1 and 3 and Examples 4 to 5, it can be seen that within a certain range, the plastic products with a higher content of powdery colloidal photonic crystals have higher color saturation and color continuity. better.

Compared with the angular and dynamic discoloration effects of chameleon pigments in plastic products, the functional masterbatch provided by the present invention produces plastic products with dreamlike colors and has relatively obvious angular and dynamic discoloration effects. It also has no chemical pigments and does not have the problem of fading. Plastic products are also more beautiful and more practical. In particular, when the proportion of each component within the preferred range is used, the effect of different colors with angle and dynamic color change is obvious, the color saturation is high, and the color continuity is good.

It should be understood that those skilled in the art can make improvements or changes based on the above description, and all these improvements and changes should fall within the protection scope of the appended claims of the present invention.

The patent of the present invention has been exemplarily described above in conjunction with the accompanying drawings. It is obvious that the implementation of the patent of the present invention is not limited by the above methods, as long as various improvements of the method concept and technical solution of the patent of the present invention are adopted, or without improvement Direct application of the concepts and technical solutions patented in the present invention to other situations shall fall within the protection scope of the present invention.

Claims (10)

1. The functional master batch is characterized by comprising the following components in parts by weight: 20 to 90 parts of matrix plastic, 5 to 80 parts of powdery colloid photon crystal, 1 to 10 parts of compatilizer, 0.5 to 5 parts of dispersing agent, 0.3 to 1 part of antioxidant, 0.1 to 0.5 part of ultraviolet absorber and 0.2 to 1.0 part of anti-hydrolysis agent;

wherein the transmittance of the matrix plastic at the wavelength of 400-800 nm is more than or equal to 70%, and the molding temperature of the matrix plastic is less than or equal to 270 ℃; the powdery colloid photon crystal comprises nanometer microspheres and carrier resin.

2. The functional master batch according to claim 1, wherein the functional master batch comprises, by weight, 40-90 parts of matrix plastic, 8-60 parts of powdery colloidal photonic crystals, 1-10 parts of compatilizer, 0.5-5 parts of dispersing agent, 0.3-1 part of antioxidant, 0.1-0.5 part of ultraviolet absorber and 0.2-1.0 part of anti-hydrolysis agent; the transmittance of the matrix plastic at the wavelength of 400-800 nm is more than or equal to 90%.

3. A functional masterbatch according to claim 1 or 2 wherein the weight ratio of said nanomicrospheres in said powdered colloidal photonic crystals is 50% to 80% and the weight ratio of said carrier resin in said powdered colloidal photonic crystals is 20% to 50%; the particle size of the nano microsphere is 10 nm-600 nm.

4. The functional masterbatch according to claim 1, wherein the powdery colloidal photonic crystals are prepared by subjecting colloidal photonic crystal films to freeze ultrafine crushing or air flow ultrafine crushing; the thickness of the colloid photon crystal film is 10-100 mu m, and the fineness of the powder colloid photon crystal is 50-500 meshes.

5. The functional masterbatch according to claim 4, wherein the colloidal photonic crystal film is prepared by: the nano microspheres are orderly arranged in the carrier resin through self-assembly to form a three-dimensional micro-nano structure, and a colloid photon crystal film is obtained after solidification; the thickness of the colloid photon crystal film is 15-50 mu m, and the fineness of the powder colloid photon crystal is 100-300 meshes; the nanometer microsphere is a polymer synthetic microsphere, and the carrier resin is a photo-curing resin.

6. The functional masterbatch according to claim 5 wherein said polymeric synthetic microspheres are polystyrene microspheres and said photocurable resin is an aqueous photocurable polyacrylate resin.

7. A functional masterbatch according to claim 1 or 2 wherein the matrix plastic is at least one of PP, PE, ABS, AS, BS, PS, PC, PMMA, TPU, EVA, PET, PA, TPE; the compatilizer is a non-reactive compatilizer; the non-reactive compatibilizing agent comprises at least one of EAA, EEA, EMA, EVA, CPE, SEBS; the dispersing agent comprises at least one of pentaerythritol ester, liquid paraffin, polyethylene wax, oxidized polyethylene wax, dimethyl silicone oil, stearic acid, stearate, ethylene distearate and ethylene dioleate; the antioxidant comprises at least one of hindered phenols, phosphites, thio-groups, composite groups and hindered amines; the ultraviolet absorbent comprises at least one of salicylates, phenones, benzotriazoles, substituted acrylonitriles, triazines and hindered amines; the anti-hydrolysis agent comprises at least one of isocyanate compound, oxazoline compound, anhydride compound, epoxy compound, carbodiimide and polycarbodiimide.

8. The functional masterbatch according to claim 7 wherein said base plastic is at least one of PP, EVA, PS, TPU, TPE; the non-reactive compatilizer is EVA; the dispersing agent is pentaerythritol ester and dimethyl silicone oil; the antioxidant is hindered phenols and phosphites; the ultraviolet absorber is benzotriazole; the anti-hydrolysis agent is carbodiimide and/or polycarbodiimide.

9. A method for preparing the functional masterbatch according to any one of claims 1-8, characterized by the following steps:

weighing 20-90 parts of matrix plastic, 5-80 parts of powdery colloid photon crystal, 1-10 parts of compatilizer, 0.5-5 parts of dispersing agent, 0.3-1 part of antioxidant, 0.1-0.5 part of ultraviolet absorber and 0.2-1.0 part of hydrolysis inhibitor according to parts by weight, and drying the powdery colloid photon crystal;

and (3) stirring and mixing the components after drying, extruding and granulating at the temperature of less than or equal to 270 ℃ to obtain the functional master batch.

10. Use of the functional masterbatch according to any one of claims 1-8 in plastic articles.