Thermochromic luminous master batch for hot working as well as preparation method and application of thermochromic luminous master batch

Abstract

The invention discloses a thermochromic luminous master batch for hot working as well as a preparation method and application of the thermochromic luminous master batch. The preparation method comprises the following steps: uniformly mixing the dried thermoplastic polymer, the dried long afterglow material, the dried reversible thermochromic microcapsule, the chain extender, the oxidation stabilizer, the dispersing agent, the coupling agent and the lubricant, performing melt extrusion, and pelletizing to obtain the thermochromic luminous master batch for hot processing. The thermochromic luminescent master batch for thermal processing is used as a raw material or a filler to prepare thermochromic luminescent fibers, thermochromic luminescent melt-blown non-woven fabrics, thermochromic luminescent biaxially oriented films and thermochromic luminescent 3D printing wires. The thermoplastic polymer, the long afterglow material and the reversible thermochromic microcapsule are used as main raw materials, the master batch with the thermochromic light-emitting function is prepared through a thermal method, the process is simple, no solvent is needed, environment friendliness is achieved, the production efficiency is high, and the cost is low.

Description

Technical Field

[0001] The invention relates to the field of polymer luminescent materials, in particular to a thermochromic luminescent masterbatch for thermal processing and a preparation method and application thereof. Background Art

[0002] With the progress and development of society, people's consumption needs are constantly changing, and textiles with a single function can no longer meet people's diverse needs. In addition to meeting the basic needs of daily wear, textiles are also required to have more and more novel functions. Textiles with luminous and color-changing functions are one of the most anticipated functional textiles. This product can not only greatly meet people's requirements for the novelty of the appearance of textiles, but also can keenly perceive changes in ambient temperature and have a warning effect of luminous at night, which greatly ensures the personal safety of night travelers. It can be widely used in clothing fabrics, building decoration, fire emergency, night warning, anti-counterfeiting, temperature monitoring, thermal labeling and other fields.

[0003] Thermochromic luminescent materials are luminescent materials that can change color according to temperature changes. The key to the preparation technology of thermochromic luminescent masterbatch is to effectively combine the thermochromic material and the luminescent material and form a uniform distribution in the polymer matrix to prepare a product with excellent temperature-sensitive color change and luminescence functions.

[0004] The document with application number 201810229374.9 discloses a thermochromic luminous fiber and its preparation method. The luminescent material is used as the raw material, and the luminescent fiber with thermochromic characteristics is prepared through a solution spinning process. After absorbing ultraviolet light or natural light, the thermochromic luminescent fiber can emit blue light in a dark environment at room temperature; the fiber can emit white light at a temperature of 40°C or above, and can be widely used in the manufacture of anti-counterfeiting and functional fibers, fabrics, textiles and clothing. However, the solution spinning process consumes a large amount of solvents, and toxic and hazardous substances are difficult to recycle. The production cost is high, the output is low, the mechanical properties are poor, and it pollutes the environment.

[0005] Compared with the solution spinning process, the melt spinning process is a thermal processing process, which has no solvent consumption, is green and environmentally friendly, has high production efficiency, and has few process parameters. It can prepare a variety of special-shaped cross-section fibers with excellent mechanical properties, which is of great significance to the industrialization and large-scale application of thermochromic luminescent fibers. At present, there is no thermal processing process to prepare a composite material combining reversible thermochromic microcapsules and polymer matrix. Summary of the invention

[0006] In view of the deficiencies in the prior art, the technical problem to be solved by the present invention is to provide a thermochromic luminescent masterbatch for thermal processing and a preparation method and application thereof.

[0007] The technical solution of the present invention to solve the technical problem of masterbatch is to provide a method for preparing thermochromic luminescent masterbatch for thermal processing, characterized in that the method comprises the following steps: Step 1, drying raw materials: drying the thermoplastic polymer, the long afterglow material and the reversible thermochromic microcapsules to remove moisture from the raw materials of each component; Step 2, preparation of thermochromic luminescent masterbatch for thermal processing: after uniformly mixing the dried thermoplastic polymer, the dried long afterglow material, the dried reversible thermochromic microcapsules, the chain extender, the oxidative stabilizer, the dispersant, the coupling agent and the lubricant, the mixture is melt-extruded and pelletized to obtain the thermochromic luminescent masterbatch for thermal processing.

[0008] The technical solution of the present invention to solve the above-mentioned application technical problems is to provide an application of thermochromic luminescent masterbatch for thermal processing, which is characterized in that the thermochromic luminescent masterbatch for thermal processing is used as a raw material or filler, and a thermochromic luminescent fiber is prepared by a melt spinning process, or a skin-core structured thermochromic luminescent fiber is prepared by a melt spinning process, or a thermochromic luminescent melt-blown nonwoven fabric is prepared by a melt blowing process, or a thermochromic luminescent biaxially stretched film is prepared by a biaxial stretching method, or a thermochromic luminescent 3D printing wire is prepared by a melt wire extrusion process.

[0009] Compared with the prior art, the present invention has the following beneficial effects: (1) The present invention uses thermoplastic polymers, long afterglow materials and reversible thermochromic microcapsules as main raw materials, and prepares masterbatches with thermochromic luminescent function by thermal method. The process is simple, solvent-free, green and environmentally friendly, with high production efficiency and low cost. It meets the requirements of various thermal forming processes such as melt spinning, melt blowing, and biaxial stretching, and can prepare thermochromic luminescent materials with excellent mechanical properties and good afterglow brightness on a large scale and efficiently. It can be widely used in multiple fields including thermochromic luminescent fibers, thermochromic luminescent composite fibers, thermochromic luminescent melt-blown nonwoven fabrics, thermochromic luminescent biaxially stretched films, 3D printing wires, etc.

[0010] (2) The present invention uses an appropriate amount of chain extender and coupling agent to cross-link the thermochromic microcapsules, thereby improving the dispersion uniformity, thermodynamic stability and compatibility between the microcapsules and the polymer, and increasing the heat resistance temperature to above 250°C, thereby expanding the application range of the reversible thermochromic microcapsules. BRIEF DESCRIPTION OF THE DRAWINGS

[0011] Figure 1 This is a SEM image of a cross section of the thermochromic luminescent fiber of Example 1 of the present invention; Figure 2 This is a SEM image of the surface of the thermochromic luminescent fiber of Example 1 of the present invention; Figure 3This is a diagram of the mechanical properties of the thermochromic luminescent fiber after stretching according to Example 1 of the present invention; Figure 4 This is a schematic diagram of the color-changing light emission of the thermochromic light-emitting fiber according to Example 1 of the present invention. DETAILED DESCRIPTION

[0012] The specific embodiments of the present invention are given below. The specific embodiments are only used to further illustrate the present invention in detail and do not limit the protection scope of the present invention.

[0013] The present invention provides a method for preparing a thermochromic luminescent masterbatch for thermal processing (hereinafter referred to as the method), characterized in that the method comprises the following steps: Step 1, drying the raw materials: fully drying the thermoplastic polymer, the long afterglow material and the reversible thermochromic microcapsules to remove the moisture in the raw materials of each component; Preferably, in step 1, the thermoplastic polymer includes polyester, liquid crystal polyester, polyurethane, polylactic acid, polypropylene, polyethylene, polyamide and meltable polyacrylonitrile.

[0014] Preferably, in step 1, the long afterglow material comprises rare earth aluminates, rare earth silicates, rare earth titanates, rare earth gallates and rare earth vanadates, specifically SrAl 2 O 4 :(Eu 2+ ,Dy 3+ )、SrAl 14 O 25 :(Eu 2+ ,Dy 3+ )、SrMgSi 2 O 7 :(Eu 2+ ,Dy 3+ ) at least one of the following: the particle size of the long afterglow material is 1~15μm (preferably 5~10μm).

[0015] Preferably, in step 1, the average particle size of the reversible thermochromic microcapsules is 1-8 μm; the colors of the reversible thermochromic microcapsules include red, yellow, blue, vermilion, aqua blue and royal blue; the color change temperatures of the reversible thermochromic microcapsules include 22°C, 25°C, 28°C, 31°C, 33°C, 35°C, 38°C, 45°C and 65°C.

[0016] Preferably, in step 1, the moisture content of each component raw material after drying is less than 50 ppm.

[0017] Step 2, preparation of thermochromic masterbatch for thermal processing: after uniformly mixing the dried thermoplastic polymer, the dried long afterglow material, the dried reversible thermochromic microcapsules, the chain extender, the oxidative stabilizer, the dispersant, the coupling agent and the lubricant, the mixture is melt-extruded and pelletized to prepare the thermochromic masterbatch for thermal processing.

[0018] Preferably, in step 2, the thermoplastic polymer is 50-95wt.% (preferably 60-90wt.%), the long afterglow material is 4-40wt.% (preferably 5-30wt.%), the reversible thermochromic microcapsule is 0.5-10wt.% (preferably 1-5wt.%), the chain extender is 0.1-2wt.% (preferably 0.5-1.5wt.%), the oxidation stabilizer is 0.01-0.5wt.% (preferably 0.02-0.4wt.%), the dispersant is 0.01-0.5wt.% (preferably 0.1-0.4wt.%), the coupling agent is 0.5-2.5wt.% (preferably 0.8-2wt.%), and the lubricant is 0.01-0.5wt.% (preferably 0.05-0.3wt.%), and the sum of the weights of each component is 100%; Preferably, in step 2, the chain extender includes at least one of chain extender 3700 (copolymer of styrene (ST), methyl methacrylate (MMA) and glycidyl methacrylate (GMA)), HQEE-L (4-hydroxyethyloxyethyl-1-hydroxyethylphenylene ether), resorcinol-bis(β-hydroxyethyl) ether, hydroquinone dihydroxyethyl ether, 3,3'-dihydroxybenzidine, p-hydroxybenzyl alcohol, (p-hydroxyphenyl) aminoacetic acid and p-hydroxyphenylpropionic acid.

[0019] Preferably, in step 2, the oxidation stabilizer includes at least one of antioxidant 1010, antioxidant 1076 and antioxidant 264.

[0020] Preferably, in step 2, the dispersant includes at least one of methyl cellulose, calcium stearate, zinc stearate, magnesium stearate, polyethylene wax, copper stearate, methyl stearate, butyl stearate and liquid paraffin; Preferably, in step 2, the coupling agent is a silane coupling agent, specifically at least one of vinyltrimethoxysilane, KH550, KH560, KH570 and KH572.

[0021] Preferably, in step 2, the lubricant includes at least one of white mineral oil, stearic acid amide, methyl stearate, polyethylene wax and hexenyl bisstearamide.

[0022] Preferably, in step 2, mechanical stirring is used for uniform mixing; melt extrusion is carried out in a twin-screw extruder at a melt extrusion temperature of 160-295° C.; and pelletizing is carried out in the pelletizer after cooling and pulling.

[0023] The present invention also provides a thermochromic luminescent masterbatch for thermal processing prepared by the preparation method of the thermochromic luminescent masterbatch for thermal processing.

[0024] The present invention also provides an application of the thermochromic luminescent masterbatch for hot processing, which is characterized in that the thermochromic luminescent masterbatch for hot processing is used as a raw material or filler (when used as a filler, the thermochromic luminescent masterbatch for hot processing needs to be evenly mixed with a thermoplastic polymer and then subjected to secondary granulation), and a thermochromic luminescent fiber is prepared by a melt spinning process, or a skin-core structured thermochromic luminescent fiber is prepared by a melt spinning process, or a thermochromic luminescent melt-blown nonwoven fabric is prepared by a melt blowing process, or a thermochromic luminescent biaxially stretched film is prepared by a biaxial stretching method, or a thermochromic luminescent 3D printing wire is prepared by a melt wire extrusion process.

[0025] Preferably, the preparation method of the thermochromic luminescent fiber is: after the dried thermochromic luminescent masterbatch for heat processing and the thermoplastic polymer are mixed evenly by mechanical stirring, the mixture is sent into a twin-screw extruder for secondary granulation to obtain the mixture pelletized; the mixture pelletized is then melt-spun to obtain the thermochromic luminescent primary fiber; and then the thermochromic luminescent fiber is obtained after drawing, winding and heat setting; The thermoplastic polymer includes polyester, liquid crystal polyester, polyurethane, polylactic acid, polypropylene, polyethylene, polyamide and meltable polyacrylonitrile; The mass fraction of the thermochromic masterbatch for thermal processing is 10~100wt.%, the mass fraction of the thermoplastic polymer is 0~90wt.%, and the sum of the masses of the two is 100%; The melt spinning temperature is 160~290℃.

[0026] Preferably, the preparation method of the thermochromic luminescent fiber with a skin-core structure is as follows: after the dried thermochromic luminescent masterbatch for heat processing and the thermoplastic polymer are mixed evenly by mechanical stirring, they are sent into a twin-screw extruder for secondary granulation to obtain mixed material pellets; then the mixed material pellets and the thermoplastic polymer are respectively sent into the melt spinning system of the skin layer and the core layer for melt extrusion, and the mixed material melt and the thermoplastic polymer melt are passed through a skin-core composite spinning box for skin-core coaxial composite spinning to obtain the thermochromic luminescent fiber with a skin-core structure; wherein the skin layer of the thermochromic luminescent fiber with a skin-core structure is a mixture of the thermochromic luminescent masterbatch for heat processing and the thermoplastic polymer, and the core layer is a thermoplastic polymer; The thermoplastic polymer includes polyester, liquid crystal polyester, polyurethane, polylactic acid, polypropylene, polyethylene, polyamide and meltable polyacrylonitrile; Melt extrusion temperature is 160~290℃; In the cortex, the mass fraction of the thermochromic masterbatch for thermal processing is 50-100wt.%, the mass fraction of the thermoplastic polymer is 0-50wt.%, and the sum of the masses of the two is 100%; In the skin-core structure thermochromic luminescent fiber, the mass ratio of the skin layer to the core layer is 1~9:1; The cross section of the skin-core structure thermochromic luminescent fiber is circular, triangular or polygonal; the polygon is five-star, five-leaf, hexagonal and branch-shaped.

[0027] Preferably, the preparation method of the thermochromic luminescent melt-blown nonwoven fabric is: after the dried thermochromic luminescent masterbatch for hot processing is evenly mixed with the melt-blown grade thermoplastic polymer, the mixture is sent into a twin-screw extruder for secondary granulation to obtain mixed material pellets; then the mixed material pellets are sent into a melt-blown spinning machine for melt-blowing to obtain the thermochromic luminescent melt-blown nonwoven fabric; The meltblown grade thermoplastic polymers include polyester, polyurethane, polylactic acid, polypropylene, polyethylene, polyamide and meltable polyacrylonitrile; The mass ratio of thermochromic masterbatch for thermal processing to melt-blown grade thermoplastic polymer is 1~9:1; The melting temperature is 100~290℃, the receiving distance is 100~500mm, the hot air pressure is 0.3~0.9MPa, and the winding speed is 3~8m / min.

[0028] Preferably, the preparation method of the thermochromic luminescent biaxially stretched film is as follows: after the dried thermochromic luminescent masterbatch for hot processing is evenly mixed with the thermoplastic polymer, the mixture is sent into a twin-screw extruder for secondary granulation to obtain mixed material pellets; the mixed material pellets are then sent into a single-screw extruder with a wide film die head, and the mixed material melt is made into a thick film through a narrow and long die head; then, in a biaxial stretching machine, synchronous biaxial stretching is performed in both the horizontal and vertical directions at the same time or separately, and the mixture is cooled or heat-treated through a heat setting process, and rolled up to obtain a thermochromic luminescent biaxially stretched film; The meltblown grade thermoplastic polymers include polyester, polyurethane, polylactic acid, polypropylene, polyethylene, polyamide and meltable polyacrylonitrile; The mass ratio of thermochromic masterbatch to thermoplastic polymer for thermal processing is 1~9:1; The stretching process is: stretching speed of 5-15 mm / s, temperature of 100-280°C, longitudinal stretching ratio of 3-10 times (preferably 4-6 times), transverse stretching ratio of 3-10 times (preferably 6-10 times); The temperature of the heat setting process is 90~250℃.

[0029] Preferably, the preparation method of the thermochromic luminescent 3D printing wire is: after the dried thermochromic luminescent masterbatch for hot processing and the thermoplastic polymer are mixed evenly by mechanical stirring, the mixture is sent into a twin-screw extruder for secondary granulation to obtain mixed material pellets; then the mixed material pellets are sent into the twin-screw extruder and melt-extruded through the die head of the 3D wire forming machine, and then cooled in a water bath and wound into a roller to obtain the thermochromic luminescent 3D printing wire; The thermoplastic polymer includes polyester, liquid crystal polyester, polyurethane, polylactic acid, polypropylene, polyethylene, polyamide and meltable polyacrylonitrile; The mass fraction of the thermochromic masterbatch for thermal processing is 10-100wt.%, the mass fraction of the thermoplastic polymer is 0-90wt.%, and the sum of the masses of the two is 100wt.%; The melt extrusion temperature is 150~290℃.

[0030] Example 1 (1) Drying of raw materials: The thermoplastic polymer, long afterglow material and reversible thermochromic microcapsules are fully dried to make the moisture content of each component raw material less than 50 ppm; (2) Preparation of thermochromic masterbatch for thermal processing: 500g of PET pellets and 100g of SrAl 2 O 4 :(Eu 2+ ,Dy 3+ ), 40g reversible thermochromic microcapsules, 5g chain extender 3700, 0.5g antioxidant 1010, 4.5g calcium stearate, 4.5g coupling agent KH570 and 0.5g white mineral oil are mixed evenly by mechanical stirring and then sent into a twin-screw extruder for melt extrusion. The temperatures of each zone are set to 255°C, 275°C, 285°C and 295°C. After cooling, they are sent to a pelletizer for pelletizing to make thermochromic luminescent masterbatch for hot processing.

[0031] Application: Preparation of thermochromic luminescent fiber: Dry 200g of thermochromic luminescent masterbatch for hot processing and 300g of PET pellets at 120℃ for 20h to make the moisture content of each component raw material less than 50ppm; then mix the dried raw materials evenly by mechanical stirring, and send them into a twin-screw spinning machine for secondary granulation to obtain mixed material pellets; then send the mixed material pellets into a twin-screw spinning machine for melt spinning, and the temperature of each zone is set to 250℃, 275℃, 285℃, and 295℃. Cool and solidify to obtain thermochromic luminescent primary fibers, and then make thermochromic luminescent fibers after drawing, winding, and heat setting.

[0032] The color change temperature of the thermochromic luminescent fiber is 31°C. When the temperature is below 31°C, the fiber is blue, and when the temperature is above 31°C, the fiber turns white. After being excited by a 200lx fluorescent lamp for 15 minutes, it can emit blue-green light in a dark environment at 25°C and 50°C. The breaking strength of the thermochromic luminescent PET fiber is 2.84cN / dtex, and the elongation at break is 11.5%. It can continuously emit strong light for 5 hours in dark conditions.

[0033] Figure 1 and Figure 2 It can be seen that the melt-blended long afterglow material and reversible thermochromic microcapsules are randomly distributed and relatively uniform inside the fiber, which ensures the uniformity of the luminescence and color-changing properties of the thermochromic luminescent fiber.

[0034] Depend on Figure 3 It can be seen that the mechanical strength of thermochromic luminescent fibers can meet the requirements of textiles.

[0035] Depend on Figure 4 It can be seen that the luminous properties and color-changing effect of the thermochromic luminescent fiber. At room temperature of 20°C, the thermochromic luminescent fiber is pink. When the temperature rises to 50°C, the fiber turns white, and in a lightless environment, the fiber can continue to emit yellow-green light.

[0036] Example 2 (1) Raw material drying: the same as in Example 1; (2) Preparation of thermochromic masterbatch for thermal processing: 500g of PET pellets and 80g of SrAl 14 O 25 :(Eu 2+ ,Dy 3+ ), 40g reversible thermochromic microcapsules, 2.5g chain extender p-hydroxyphenylpropionic acid, 0.5g antioxidant 1010, 4.5g calcium stearate, 4.5g coupling agent KH550 and 0.5g white mineral oil are mixed evenly by mechanical stirring and then sent into a twin-screw extruder for melt extrusion. The temperatures of each zone are set to 255°C, 275°C, 285°C and 295°C. After cooling, they are sent to a pelletizer for pelletizing to make thermochromic luminescent masterbatch for hot processing.

[0037] Application: Preparation of thermochromic luminescent fiber with skin-core structure: The dried thermochromic luminescent masterbatch for hot processing and PET pellets are respectively fed into the twin-screw extruder system of the skin layer and the core layer for melt extrusion. The temperature of each zone is set to 255℃, 275℃, 285℃ and 295℃. The melt of thermochromic luminescent masterbatch for hot processing and the melt of PET are fed into the skin-core composite spinning box for skin-core coaxial composite spinning to obtain the skin-core structured thermochromic luminescent PET fiber with a mass ratio of skin to core of 7:3.

[0038] The color change temperature of the thermochromic luminescent PET fiber is 33℃. When the temperature is below 33℃, the fiber is red, and when the temperature is above 33℃, the fiber turns white. After being excited by a 200lx fluorescent lamp for 15 minutes, it can emit bright blue-green light in a dark environment of 25℃ and 50℃. The breaking strength of the thermochromic luminescent PET fiber with a skin-core structure is 2.35cN / dtex, and the elongation at break is 15.3%. It can continuously emit strong light for 4 hours in dark conditions.

[0039] Example 3 (1) Raw material drying: the same as in Example 1; (2) Preparation of thermochromic masterbatch for thermal processing: 500g of melt-blown polypropylene pellets and 100g of SrAl 2 O 4 :(Eu 2+ ,Dy 3+ ), 40g reversible thermochromic microcapsules, 7.5g chain extender hydroquinone dihydroxyethyl ether, 0.5g antioxidant 1076, 5g zinc stearate, 5g coupling agent KH570 and 0.5g stearic acid amide, after mechanical stirring and mixing evenly, sent into a twin-screw extruder for melt extrusion, the temperature of each zone was set to 155℃, 165℃, 180℃, and 190℃, and after cooling, it was sent to a pelletizer for pelletizing to make thermochromic luminescent masterbatch for hot processing.

[0040] Application: Preparation of thermochromic luminescent melt-blown nonwoven fabric: After drying, 900g of thermochromic luminescent masterbatch for hot processing and 100g of polypropylene pellets for melt-blown are mixed evenly, and then sent to a twin-screw extruder for secondary granulation to obtain mixed pellets; then the mixed pellets are sent to a twin-screw extruder, and the temperature of each zone is set to 155℃, 165℃, 185℃, and 200℃, extruded through a spinneret, stretched by high-pressure and high-temperature airflow on both sides, gathered on the collecting device below (i.e., the roller curtain), and formed into a thermochromic polypropylene melt-blown nonwoven fabric after cooling and solidification; the receiving distance is 100mm, the hot air pressure is 0.3MPa, the winding speed is 5m / min, and the product weight is 60~120g / m 2 Thermochromic luminous meltblown nonwoven fabric.

[0041] The color change temperature of the thermochromic luminescent nonwoven fabric is 28℃. When the temperature is below 28℃, the fiber is yellow, and when the temperature is above 28℃, the fiber turns white. After being excited by a 200lx fluorescent lamp for 15 minutes, it can emit bright blue-green light in a dark environment at 25℃ and 50℃, and can emit light stably for more than 3 hours. The longitudinal breaking strength of the thermochromic luminescent polypropylene nonwoven fabric is 16.4N, the breaking elongation is 59.5%, the transverse breaking strength is 10.7N, and the breaking elongation is 54.2%.

[0042] Example 4 (1) Raw material drying: the same as in Example 1; (2) Preparation of thermochromic masterbatch for thermal processing: 500g of PE pellets and 80g of SrMgSi 2 O 7 :(Eu 2+ ,Dy 3+ ), 40g reversible thermochromic microcapsules, 4g chain extender resorcinol-bis(β-hydroxyethyl) ether, 0.5g antioxidant 1010, 4.5g calcium stearate, 4.5g coupling agent KH570 and 0.5g white mineral oil are mixed evenly by mechanical stirring and then sent into a twin-screw extruder for melt extrusion. The temperatures of each zone of the twin-screw are set to 100°C, 115°C, 145°C and 165°C respectively. After cooling, they are sent to a pelletizer for pelletizing to make thermochromic luminescent masterbatch for hot processing.

[0043] Application: Preparation of thermochromic luminescent biaxially stretched film: After the dried thermochromic luminescent masterbatch for hot processing is mixed evenly with PE pellets (the ratio of thermochromic luminescent masterbatch to PE pellets is 4:1), it is sent to a twin-screw spinning machine for secondary granulation to obtain mixed material pellets; then the mixed material pellets are sent to the casting equipment, and the temperature of each zone of the twin-screw extruder is set to 100℃, 115℃, 145℃, and 165℃. The mixed material melt is extruded through a narrow and long die to form a cast thick sheet with a thickness of 300μm; an initial film of 150mm×150mm is cut out, and a biaxial stretching machine is used to preheat at 120℃ for 3min, and synchronous biaxial stretching is performed at a stretching speed of 8mm / s, with a longitudinal stretching ratio of 3 times and a transverse stretching ratio of 3 times. After cooling or heat treatment through a heat setting process at 110℃, it is rolled up to form a thermochromic luminescent biaxially stretched film.

[0044] The color change temperature of the thermochromic luminescent PE film is 33℃. When the temperature is lower than 33℃, the fiber is red. When the temperature is higher than 33℃, the biaxially stretched film turns white. After being excited by a 200lx fluorescent lamp for 15 minutes, it can emit bright blue-green light in a dark environment of 25℃ and 50℃, and can emit light stably for 3 hours. The breaking strength of the thermochromic luminescent PE biaxially stretched film in the transverse and longitudinal directions is about 40MPa, and the modulus is about 800Mpa.

[0045] Example 5 (1) Drying of raw materials: The thermoplastic polymer, long afterglow material and reversible thermochromic microcapsules are fully dried to make the moisture content of each component raw material less than 50 ppm; (2) Preparation of thermochromic masterbatch for thermal processing: 500g polyurethane slices, 100g SrMgSi 2 O 7 :(Eu 2+ ,Dy 3+), 40g reversible thermochromic microcapsules, 7g chain extender 3,3'-dihydroxybenzidine, 0.5g antioxidant 1010, 4.5g calcium stearate, 4.5g coupling agent KH570 and 0.5g white mineral oil are mixed evenly by mechanical stirring and then sent into a twin-screw extruder for melt extrusion. The temperature of each zone is set to 200℃, 215℃, 225℃ and 245℃. After cooling, the mixture is sent to a pelletizer for pelletizing to make thermochromic luminescent masterbatch for hot processing.

[0046] Application: Preparation of thermochromic luminescent fiber: Dry 200g of thermochromic luminescent masterbatch for hot processing and 300g of polyurethane chips at 120℃ for 20h to make the moisture content of each component raw material less than 50ppm; then the dried raw materials are mixed evenly by mechanical stirring, and then sent to a twin-screw spinning machine for secondary granulation to obtain mixed material pellets; then the mixed material pellets are sent to a twin-screw spinning machine for melt spinning, and the temperature of each zone is set to 200℃, 215℃, 225℃, and 245℃ to obtain thermochromic luminescent primary polyurethane fiber, which is obtained by drawing, winding, and heat setting to obtain thermochromic luminescent polyurethane fiber.

[0047] The color change temperature of the thermochromic luminescent polyurethane fiber is 35℃. When the temperature is below 35℃, the polyurethane fiber is royal blue, and when the temperature is above 35℃, the polyurethane fiber turns white. After being excited by a 200lx fluorescent lamp for 15 minutes, it can emit bright blue-green light in a dark environment of 25℃ and 50℃, and can continue to emit strong light for more than 4 hours. The breaking strength of the thermochromic luminescent polyurethane fiber is 1.15cN / dtex, and the breaking elongation is 550%.

[0048] Example 6 (1) Raw material drying: the same as in Example 1; (2) Preparation of thermochromic masterbatch for thermal processing: 500 g of meltable polyacrylonitrile pelletized and 80 g of SrAl 14 O 25 :(Eu 2+ ,Dy 3+ ), 40g reversible thermochromic microcapsules, 6.5g chain extender p-hydroxybenzyl alcohol, 0.5g antioxidant 1010, 4.5g calcium stearate, 4.5g coupling agent KH550 and 0.5g white mineral oil are mixed evenly by mechanical stirring and then sent into a twin-screw extruder for melt extrusion. The temperatures of each zone are set to 175°C, 195°C, 205°C and 225°C. After cooling, they are sent to a pelletizer for pelletizing to make thermochromic luminescent masterbatch for hot processing.

[0049] Application: Preparation of thermochromic luminescent fiber with skin-core structure: The dried thermochromic luminescent masterbatch for hot processing and meltable polyacrylonitrile pellets (the ratio of thermochromic luminescent masterbatch to polyacrylonitrile pellets is 3:1) are mixed evenly by mechanical stirring, and then secondary granulation is carried out to obtain mixed material pellets; then the mixed material pellets and low-melting point PET pellets (melting point temperature is about 180°C) are respectively sent to the twin-screw extruder system of the skin layer and the core layer for melt extrusion. The temperature of each zone is set to 175°C, 185°C, 205°C, and 220°C. The mixed material melt and the PET melt are passed through a skin-core composite spinning box for skin-core coaxial composite spinning to obtain a skin-core structured thermochromic luminescent fiber with a mass ratio of skin to core layer of 7:3.

[0050] The color change temperature of the thermochromic luminescent fiber is 35℃. When the temperature is below 35℃, the fiber is yellow, and when the temperature is above 35℃, the fiber turns white. After being excited by a 200lx fluorescent lamp for 15 minutes, it can continuously emit bright blue-green light for more than 4 hours in a dark environment of 25℃ and 50℃. The breaking strength of the thermochromic polyacrylonitrile fiber with a skin-core structure is 2.0cN / dtex, and the breaking elongation is 12.6%.

[0051] Example 7 (1) Raw material drying: the same as in Example 1; (2) Preparation of thermochromic masterbatch for thermal processing: same as Example 3.

[0052] Application: Preparation of thermochromic luminescent 3D printing filaments: Dry 150g of thermochromic luminescent masterbatch for hot processing and 350g of PET pellets at 120°C for 20h to make the moisture content of each component raw material less than 50ppm; then the dried raw materials are mixed evenly by mechanical stirring, and then sent to a twin-screw extruder for secondary granulation to obtain mixed material pellets; then the mixed material pellets are sent to a twin-screw extruder and melt-extruded through the die head of a 3D wire forming machine. The temperatures of each zone are set to 250°C, 275°C, 280°C, and 290°C, and then cooled in a water bath and wound into a roller to obtain the thermochromic luminescent 3D printing filament.

[0053] The color change temperature of the thermochromic luminescent wire is 33℃. When the temperature is lower than 33℃, the fiber is scarlet, and when the temperature is higher than 33℃, the 3D wire turns white. After being excited by a 200lx fluorescent lamp for 15 minutes, it can continuously emit bright blue-green light for more than 3 hours in a dark environment of 25℃ and 50℃.

[0054] Example 8 (1) Raw material drying: the same as in Example 1; (2) Preparation of thermochromic masterbatch for thermal processing: 500g of PET pellets and 80g of SrAl 14 O 25:(Eu 2+ ,Dy 3+ ), 50g reversible thermochromic microcapsules, 5.6g chain extender 3,3'-dihydroxybenzidine, 0.5g antioxidant 1010, 4.5g calcium stearate, 4.5g coupling agent KH570 and 0.5g white mineral oil are mixed evenly by mechanical stirring and then sent into a twin-screw extruder for melt extrusion. The temperatures of each zone are set to 255°C, 275°C, 280°C and 290°C. After cooling, they are sent to a pelletizer for pelletizing to make thermochromic luminescent masterbatch for hot processing.

[0055] Application: Preparation of thermochromic luminescent PET fiber with skin-core structure: The dried thermochromic luminescent masterbatch for hot processing and PET pellets are mixed evenly by mechanical stirring (the ratio of thermochromic luminescent masterbatch to PET pellets is 1:1), and then sent to a twin-screw extruder for secondary granulation to obtain mixed pellets; then the mixed pellets and PET pellets are respectively sent to the twin-screw extruder system of the skin layer and the core layer for melt extrusion, and the temperature of each zone is set to 255℃, 275℃, 280℃, and 290℃. The mixed material melt and the PET melt are passed through a skin-core composite spinning box for skin-core coaxial composite spinning to obtain a skin-core structured thermochromic luminescent PET fiber with a skin-to-core mass ratio of 75:25.

[0056] The color change temperature of the thermochromic luminescent fiber is 33℃. When the temperature is below 33℃, the fiber is red, and when the temperature is above 33℃, the fiber turns white. After being excited by a 200lx fluorescent lamp for 15 minutes, it can continuously emit bright blue-green light for more than 5 hours in a dark environment of 25℃ and 50℃. The breaking strength of the thermochromic PET primary fiber with skin-core structure is 2.35cN / dtex, and the breaking elongation is 15.3%.

[0057] Any matters not described in the present invention are applicable to the prior art.

Claims

1. A method for preparing a thermochromic masterbatch for thermal processing, characterized in that: The method comprises the following steps: Step 1, drying raw materials: drying the thermoplastic polymer, the long afterglow material and the reversible thermochromic microcapsules to remove moisture from the raw materials of each component; Step 2, preparation of thermochromic luminescent masterbatch for thermal processing: after uniformly mixing the dried thermoplastic polymer, the dried long afterglow material, the dried reversible thermochromic microcapsules, the chain extender, the oxidative stabilizer, the dispersant, the coupling agent and the lubricant, the mixture is melt-extruded and pelletized to obtain the thermochromic luminescent masterbatch for thermal processing.

2. The method for preparing thermochromic masterbatch for hot processing according to claim 1, characterized in that: In step 1, the thermoplastic polymer includes polyester, liquid crystal polyester, polyurethane, polylactic acid, polypropylene, polyethylene, polyamide and meltable polyacrylonitrile; The long afterglow material includes rare earth aluminates, rare earth silicates, rare earth titanates, rare earth gallates and rare earth vanadates, specifically SrAl2O4:(Eu 2+ ,Dy 3+ )、SrAl 14 O 25 :(Eu 2+ ,Dy 3+ )、SrMgSi2O7:(Eu 2+ ,Dy 3+ ) at least one of the following; the particle size is 1 to 15 μm; The average particle size of the reversible thermochromic microcapsules is 1-8 μm; the colors of the reversible thermochromic microcapsules include red, yellow, blue, vermilion, aqua blue and royal blue; the color change temperatures of the reversible thermochromic microcapsules include 22°C, 25°C, 28°C, 31°C, 33°C, 35°C, 38°C, 45°C and 65°C; The moisture content of each component raw material after drying is less than 50ppm.

3. The method for preparing thermochromic masterbatch for hot processing according to claim 1, characterized in that: In step 2, the sum of the weight of the thermoplastic polymer 50-95wt.%, the long afterglow material 4-40wt.%, the reversible thermochromic microcapsule 0.5-10wt.%, the chain extender 0.1-2wt.%, the oxidation stabilizer 0.01-0.5wt.%, the dispersant 0.01-0.5wt.%, the coupling agent 0.5-2.5wt.%, and the lubricant 0.01-0.5wt.% is 100%; The chain extender includes at least one of chain extender 3700, HQEE-L, resorcinol-bis(β-hydroxyethyl) ether, hydroquinone dihydroxyethyl ether, 3,3'-dihydroxybenzidine, p-hydroxybenzyl alcohol, (p-hydroxyphenyl) aminoacetic acid and p-hydroxyphenylpropionic acid; The oxidation stabilizer includes at least one of antioxidant 1010, antioxidant 1076 and antioxidant 264; The dispersant comprises at least one of methyl cellulose, calcium stearate, zinc stearate, magnesium stearate, polyethylene wax, copper stearate, methyl stearate, butyl stearate and liquid paraffin; The coupling agent is a silane coupling agent, specifically at least one of vinyltrimethoxysilane, KH550, KH560, KH570 and KH572; The lubricant comprises at least one of white mineral oil, stearic acid amide, methyl stearate, polyethylene wax and hexenyl bisstearamide; The mixing is carried out by mechanical stirring; the melt extrusion is carried out in a twin-screw extruder, and the melt extrusion temperature is 160-295°C; the pelletizing process is carried out in a pelletizer after cooling and pulling.

4. A thermochromic luminescent masterbatch for thermal processing prepared by the method for preparing the thermochromic luminescent masterbatch for thermal processing according to any one of claims 1 to 3.

5. An application of the thermochromic luminescent masterbatch for thermal processing according to claim 4, characterized in that: Using thermochromic luminescent masterbatch for thermal processing as raw material or filler, thermochromic luminescent fiber is prepared by melt spinning process, or skin-core structure thermochromic luminescent fiber is prepared by melt spinning process, or thermochromic luminescent melt-blown nonwoven fabric is prepared by melt blowing process, or thermochromic luminescent biaxially stretched film is prepared by biaxial stretching method, or thermochromic luminescent 3D printing wire is prepared by melt wire extrusion process.

6. The use of the thermochromic masterbatch for hot processing according to claim 5, characterized in that: The preparation method of the thermochromic luminescent fiber is as follows: after the dried thermochromic luminescent masterbatch for heat processing is mixed evenly with the thermoplastic polymer, secondary granulation is performed to obtain the mixed material pellets; the mixed material pellets are then melt-spun to obtain the thermochromic luminescent primary fiber; and then the thermochromic luminescent fiber is obtained after drawing, winding and heat setting; The mass fraction of the thermochromic masterbatch for thermal processing is 10~100wt.%, the mass fraction of the thermoplastic polymer is 0~90wt.%, and the sum of the masses of the two is 100%; The melt spinning temperature is 160~290℃.

7. The use of the thermochromic masterbatch for hot processing according to claim 5, characterized in that: The preparation method of the thermochromic luminescent fiber with a skin-core structure is as follows: after the dried thermochromic luminescent masterbatch for heat processing is evenly mixed with the thermoplastic polymer, secondary granulation is performed to obtain the mixed material pellets; then the mixed material pellets and the thermoplastic polymer are respectively sent to the melt spinning system of the skin layer and the core layer for melt extrusion, and the mixed material melt and the thermoplastic polymer melt are subjected to skin-core coaxial composite spinning through a skin-core composite spinning box to obtain the thermochromic luminescent fiber with a skin-core structure; wherein the skin layer of the thermochromic luminescent fiber with a skin-core structure is a mixture of the thermochromic luminescent masterbatch for heat processing and the thermoplastic polymer, and the core layer is the thermoplastic polymer; Melt extrusion temperature is 160~290℃; In the cortex, the mass fraction of the thermochromic masterbatch for thermal processing is 50-100wt.%, the mass fraction of the thermoplastic polymer is 0-50wt.%, and the sum of the masses of the two is 100%; In the skin-core structure thermochromic luminescent fiber, the mass ratio of the skin layer to the core layer is 1~9:1; The cross section of the skin-core structure thermochromic luminescent fiber is circular, triangular or polygonal; the polygon is five-star, five-leaf, hexagonal and branch-shaped.

8. The use of the thermochromic masterbatch for hot processing according to claim 5, characterized in that: The preparation method of the thermochromic luminescent melt-blown nonwoven fabric is as follows: after the dried thermochromic luminescent masterbatch for heat processing is evenly mixed with the melt-blown grade thermoplastic polymer, secondary granulation is performed to obtain the mixed material pellets; then the mixed material pellets are sent to a melt-blown spinning machine for melt-blowing to obtain the thermochromic luminescent melt-blown nonwoven fabric; The meltblown grade thermoplastic polymers include polyester, polyurethane, polylactic acid, polypropylene, polyethylene, polyamide and meltable polyacrylonitrile; The mass ratio of thermochromic masterbatch for thermal processing to melt-blown grade thermoplastic polymer is 1~9:1; The melting temperature is 100~290℃, the receiving distance is 100~500mm, the hot air pressure is 0.3~0.9MPa, and the winding speed is 3~8m / min.

9. The use of the thermochromic masterbatch for hot processing according to claim 5, characterized in that: The preparation method of the thermochromic luminescent biaxially stretched film is as follows: after the dried thermochromic luminescent masterbatch for hot processing is mixed evenly with the thermoplastic polymer, secondary granulation is performed to obtain mixed material pellets; then the mixed material pellets are fed into a single screw extruder with a wide film die head, and the mixed material melt is formed into a thick film through a narrow and long die head; then in a biaxial stretching machine, synchronous biaxial stretching is performed in both the horizontal and vertical directions at the same time or separately, and cooling or heat treatment is performed through a heat setting process, and then the thermochromic luminescent biaxially stretched film is obtained after winding; The mass ratio of thermochromic masterbatch to thermoplastic polymer for thermal processing is 1~9:1; The stretching process is: stretching speed of 5~15mm / s, temperature of 100~280℃, longitudinal stretching ratio of 3~10 times, transverse stretching ratio of 3~10 times; The temperature of the heat setting process is 90~250℃.

10. The use of the thermochromic masterbatch for hot processing according to claim 5, characterized in that: The preparation method of the thermochromic luminescent 3D printing wire is as follows: after the dried thermochromic luminescent masterbatch for hot processing is mixed evenly with the thermoplastic polymer, secondary granulation is performed to obtain the mixed material pellets; then the mixed material pellets are sent to a twin-screw extruder to be melt-extruded through the die head of a 3D wire forming machine, and then cooled in a water bath and wound into a roll to obtain the thermochromic luminescent 3D printing wire; The mass fraction of the thermochromic masterbatch for thermal processing is 10-100wt.%, the mass fraction of the thermoplastic polymer is 0-90wt.%, and the sum of the masses of the two is 100wt.%; The melt extrusion temperature is 150~290℃.

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