A photochromic masterbatch and its preparation method and application

Abstract

The invention discloses a photochromic masterbatch and a preparation method and application thereof. Naphthalene diimide compounds are used as dyes to construct photochromic polyester fibers, which synergize with polyester to achieve color change, and the silk-like color change performance is improved by grafting preferred electron-donating groups. The photochromic masterbatch prepared by the invention has good thermal stability, which is different from the prior art in which photochromic fibers are prepared, which has the disadvantages of poor heat resistance, poor fatigue resistance, poor friction resistance, poor air permeability, and complex process. The process is simple and easy to promote.

Description

Technical Field

[0001] The invention belongs to the technical field of polymer materials, and in particular relates to a photochromic masterbatch and a preparation method and application thereof. Background Art

[0002] Photochromic materials can self-identify light sources of specific wavelengths in the environment and respond in the form of color changes, accompanied by significant changes in the physical and chemical properties of the materials. Among them, smart fiber materials based on photochromic molecules have excellent stealth, camouflage, anti-counterfeiting and fluorescent indication functions, and are widely used in aerospace, military equipment, flexible displays, special process monitoring, product anti-counterfeiting identification and other fields.

[0003] At present, inorganic color-changing materials are mainly based on WO 3 The color-changing glass and film of the color-changing unit have achieved certain commercial applications. Its photochromicity comes from WO 3 The advantages of charge migration between (and within) the crystal lattices are high thermal and mechanical stability, but the color-changing performance is greatly affected by the crystal form, morphology, lattice defects, and processing methods. At the same time, it has poor photosensitivity and reversibility, a high fading temperature, slow fading, and high processing difficulty.

[0004] Commercial organic color-changing powders include spiropyran derivatives, fulgide, diarylethene derivatives, etc. Their photochromicity comes from the structural changes of the molecules undergoing ring opening / closing after exposure to light, which changes the degree of conjugation of the molecules and thus achieves color change. The advantages of this type of color-changing material are: fast single-molecule light response speed, color development and color elimination processes in the case of single-molecule dispersion are at the picosecond level, but there is photodegradation in the color state, poor thermal stability and oxidation resistance, poor durability, and it cannot change color in the solid state itself, requiring a good dispersion process to achieve the color change effect.

[0005] At present, the mainstream market adopts micro-nano capsule coating process and adds appropriate amount of antioxidants, heat stabilizers and ultraviolet absorbers, which can improve its stability and service life to a certain extent. It can be processed and used normally at 220 ℃. It has certain applications in fiber carriers processed by low temperature, no shear or weak shear processing technology, but the thermal stability still does not meet the processing requirements of polyester fiber melt spinning. Diarylethene molecules have high thermal stability, but they are rare P-type photochromic materials. They usually change color under ultraviolet light and fade under visible light. They are complex to synthesize and expensive, and have obvious limitations in use.

[0006] Therefore, most of the existing photochromic polyester fiber fabrics use low-temperature manufacturing processes such as composite spinning or coating to circumvent the above problems. The overall process is complex, the restrictions on the subsequent process are high, and the scope of use is limited. Chinese patent CN216507216U discloses a photosensitive polyester cloth with a nano-coating structure. In the embodiment, the polyester cloth base layer is coated with a pure cotton moisture absorption layer, a bamboo charcoal fiber antibacterial layer, a natural fiber skin-friendly layer, a photochromic fiber layer, and a wear-resistant layer. The process is complicated, and the fiber carrier of the color-changing layer is not polyester, which fails to substantially solve the above problems. Chinese patent CN113957716A discloses a color-changing fiber and its manufacturing process. In the embodiment, a core-spun yarn process is used. The color-changing fiber core layer uses scandium disilicate / cobalt diselenide nanopowder dispersed in polymethyl methacrylate and glycidyl methacrylate carriers to melt-spin to obtain a structural color color-changing fiber. The outer layer is a polyester fiber layer, and the color-changing matrix cannot be composited in the polyester carrier. Chinese patent CN110591303 A discloses a photochromic masterbatch with polyester fiber as carrier for the core layer of the fiber with skin-core structure. In the embodiment, the core layer is a color-changing fiber layer, and the skin layer is a heat stabilizer and antioxidant layer to extend the service life of the color-changing element. The carrier used is modified PBT with a melting point of 220-225°C, which still cannot meet the process requirements of traditional PET spinning. Chinese patent CN114318604 A discloses a color-changing fiber with skin-core structure. In the embodiment, Schiff base complex type color-changing molecules and polyester polymers are used as spinning stock solutions, and the core layer of the color-changing fiber is prepared by electrospinning. This method cannot be used for spinning processing of polyesters such as poly(dimethyl terephthalate) and poly(dibutyl terephthalate), and the photochromic mechanism of Schiff base molecules is proton transfer, and the heat resistance is not high. At the same time, the electrospinning speed is lower than that of the melt spinning method.

[0007] In summary, there is no color-changing masterbatch that is easy to use and can meet the needs of traditional polyester fiber spinning. It is a blank in the industry. The main technical indicators are that the color-changing element can have good dispersibility in polyester fiber, have certain mechanical stability, and can remain stable in the high-temperature process of masterbatch preparation and melt spinning. Naphthalene diimide materials are widely used in the preparation of optoelectronic devices due to their electron-deficient properties. Their large conjugated structure ensures the good thermal and mechanical stability of such molecules. Therefore, the electron donor-acceptor system formed by them and polyester in the present invention can solve the above-mentioned processing problems and effectively prepare color-changing polyester fibers using photoinduced electron transfer. Summary of the invention

[0008] The purpose of this section is to summarize some aspects of embodiments of the present invention and briefly introduce some preferred embodiments. Some simplifications or omissions may be made in this section and the specification abstract and the invention title of this application to avoid blurring the purpose of this section, the specification abstract and the invention title, and such simplifications or omissions cannot be used to limit the scope of the present invention.

[0009] In view of the above problems and / or the problems existing in the prior art, the present invention is proposed.

[0010] Therefore, the purpose of the present invention is to overcome the deficiencies in the prior art and provide a photochromic masterbatch.

[0011] In order to solve the above technical problems, the present invention provides the following technical solution: by weight, comprising:

[0012] 60~99 parts of carrier, 1~40 parts of electrostatic dye and 0~1 parts of auxiliary agent;

[0013] Wherein, the electrical-deficient dye is a naphthalene diimide compound.

[0014] As a preferred embodiment of the photochromic masterbatch of the present invention, the carrier comprises one or more of polyethylene terephthalate, polybutylene terephthalate, polyisosorbide terephthalate and copolymers thereof.

[0015] As a preferred embodiment of the photochromic masterbatch of the present invention, the naphthalene diimide compound is prepared by dissolving naphthalene tetracarboxylic anhydride and an amino derivative in an organic solvent.

[0016] As a preferred embodiment of the photochromic masterbatch of the present invention, the additives include one or more of ethylene bisstearamide, titanate coupling agent, silane coupling agent, silicone additive, stearic acid lubricant, AC® wax powder, Chimassorb® light stabilizer, and Fusabond® toughening agent.

[0017] Another object of the present invention is to overcome the deficiencies in the prior art and provide a method for preparing a photochromic masterbatch.

[0018] In order to solve the above technical problems, the present invention provides the following technical solution: comprising: mixing the carrier, the electric-deficient dye and the auxiliary agent and then drying them, and then granulating and extruding them with a twin-screw granulator to obtain the polyester fiber photochromic masterbatch.

[0019] As a preferred embodiment of the preparation method of the photochromic masterbatch of the present invention, the preparation method of the electric-deficient dye comprises placing naphthalene tetracarboxylic anhydride and an amino derivative in an organic solvent, heating and refluxing, reacting for 4 to 12 hours, and obtaining naphthalene diimide after recrystallization, which is the electric-deficient dye;

[0020] Wherein, the naphthalene tetracarboxylic anhydride is 1,4,5,8-naphthalene tetracarboxylic anhydride.

[0021] As a preferred embodiment of the method for preparing the photochromic masterbatch of the present invention, the drying step comprises: drying for 4 to 8 hours at a drying temperature of 110 to 130°C.

[0022] As a preferred embodiment of the method for preparing the photochromic masterbatch of the present invention, the granulation extrusion comprises the following steps: the rotation speed of the granulator is 100-300 r / min, and the granulation temperature is 250-285°C.

[0023] Another object of the present invention is to overcome the deficiencies in the prior art and provide an application of a photochromic masterbatch.

[0024] In order to solve the above technical problems, the present invention provides the following technical solutions: including melt-spinning the color-changing masterbatch to obtain photochromic polyester fiber; and also including twisting the photochromic polyester fiber on a twisting machine to obtain photochromic fabric.

[0025] As a preferred application scheme of the photochromic masterbatch of the present invention, the temperature of the melt spinning is 260-290°C.

[0026] Beneficial effects of the present invention:

[0027] (1) The photochromic masterbatch prepared by the present invention has good thermal stability, which is different from the prior art that has the disadvantages of poor heat resistance, poor fatigue resistance, poor friction resistance, poor air permeability, and complex process in preparing photochromic fibers. The process is simple and easy to promote.

[0028] (2) The naphthalene diimide compounds selected in the present invention have a large aromatic conjugated structure and have a π-π stacking effect with commonly used polyester fibers such as polyethylene terephthalate and polybutylene terephthalate, and have good compatibility and dispersibility. At the same time, through the CH...π interaction between naphthalene diimide and polyester, a synergistic effect can occur to produce photoinduced electron transfer behavior, so that the fiber can achieve a color change effect. BRIEF DESCRIPTION OF THE DRAWINGS

[0029] In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the following briefly introduces the drawings required for describing the embodiments. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without creative labor. Among them:

[0030] Figure 1 The infrared spectrum of the naphthalene diimide dye A prepared in Example 1 of the present invention;

[0031] Figure 2 These are photos of the naphthalene diimide dye A prepared in Example 1 of the present invention before and after illumination after recrystallization;

[0032] Figure 3 The actual pictures of the photochromic masterbatch A prepared in Example 1 of the present invention before and after color change;

[0033] Figure 4 The infrared spectrum of the naphthalene diimide dye B prepared in Example 2 of the present invention;

[0034] Figure 5 These are photos of the naphthalene diimide dye B prepared in Example 2 of the present invention before and after illumination after recrystallization;

[0035] Figure 6 The infrared spectrum of the naphthalene diimide dye C prepared in Example 3 of the present invention;

[0036] Figure 7 The infrared spectrum of the naphthalene diimide dye D prepared in Example 4 of the present invention;

[0037] Figure 8 This is the infrared spectrum of the naphthalene diimide dye E prepared in Example 5 of the present invention;

[0038] Fig. 9 Thermogravimetric analysis diagrams of naphthalene diimide dyes prepared in Examples 1 to 5 of the present invention;

[0039] Fig.10 This is a colorimetric result diagram of the optically variable fiber prepared in Example 6 of the present invention;

[0040] Fig.11 This is a diagram of the extinction process of the optically variable fiber prepared in Example 6 of the present invention;

[0041] Fig.12 This is a schematic diagram of the photochromic masterbatch constructed in collaboration with the naphthylidene diamine dye and PET of the present invention; DETAILED DESCRIPTION

[0042] In order to make the above-mentioned objects, features and advantages of the present invention more obvious and easy to understand, the specific implementation methods of the present invention are described in detail below in conjunction with the embodiments of the specification.

[0043] In the following description, many specific details are set forth to facilitate a full understanding of the present invention, but the present invention may also be implemented in other ways different from those described herein, and those skilled in the art may make similar generalizations without violating the connotation of the present invention. Therefore, the present invention is not limited to the specific embodiments disclosed below.

[0044] Secondly, the term "one embodiment" or "embodiment" as used herein refers to a specific feature, structure, or characteristic that may be included in at least one implementation of the present invention. The term "in one embodiment" that appears in different places in this specification does not necessarily refer to the same embodiment, nor does it refer to a separate or selective embodiment that is mutually exclusive with other embodiments.

[0045] The slices used in the present invention are produced by Sinopec Yizheng Chemical Fiber Co., Ltd., with the brand name: FC510.

[0046] The auxiliary agent used in the present invention is a mixed auxiliary agent, which is obtained by mixing 20 parts of light stabilizer Chimassorb®944, 20 parts of PE wax AC®6A and 60 parts of dispersant TEGOMER®P121, and then placing the mixture in a high-speed mixer and dispersing it for 6 minutes.

[0047] Example 1

[0048] This embodiment provides a method for preparing a photochromic masterbatch.

[0049] Preparation of naphthylidene diamine dye A, the reaction formula is shown in formula A:

[0050] (Formula A).

[0051] 50 g of 1,4,5,8-naphthalenetetracarboxylic anhydride (0.19 mol), 61 g of 6-aminocaproic acid (0.47 mol) and 1 L of N,N'-dimethylformamide were mixed, ultrasonically dispersed for 5 min, and refluxed at 100 °C for 2 h. During this period, the suspension gradually became clear and the color of the solution changed from transparent to brown-yellow. After the reaction was completed, 2 L of ice water was added, mixed evenly and filtered to obtain a yellow crude product that did not change color under light.

[0052] The crude product cake was dried and recrystallized with N,N'-dimethylformamide, and dried at 160°C to obtain 74.6 g of light yellow dye, namely, naphthylidene dye A, with a yield of 81%.

[0053] Figure 1 is the infrared spectrum of the naphthylidene diamine dye A prepared in this embodiment, and the characterization data are 1 H NMR (300MHz, DMSO- d 6): δ 1.60 (m, 8H), 1.68 (m, 8H), 2.27 (t, 4H), 4.06 (t, 4H);8.66 (s, 4H) FT-IR: (νC=O) 1695 cm -1 .

[0054] Figure 2 After recrystallization, the naphthylidene diamine dye A prepared in this example changes from yellow to green under light.

[0055] Preparation of photochromic masterbatch A:

[0056] 79.3 parts of polyester chips, 20 parts of naphthalene diamine dye A and 0.7 parts of premixed auxiliary agent were mixed, and dried at 110°C for 6 h. The raw materials were put into a twin-screw extruder, and the temperatures of each zone were set to 260°C, 275°C, 275°C, 275°C, 270°C, 270°C, and 260°C. The rotation speed was 300r / min, and the raw materials were extruded through a circular orifice die, cooled in a water trough, and pulled to a pelletizer to be cut into cylindrical masterbatches with a length of 3 mm±1 mm and a diameter of 2 mm±1 mm, thereby obtaining photochromic masterbatch A.

[0057] Figure 3 The actual pictures of the photochromic masterbatch prepared by the present invention before and after color change show that the present invention successfully prepared the masterbatch with photochromic effect.

[0058] Example 2

[0059] This embodiment provides a method for preparing a photochromic masterbatch.

[0060] Preparation of naphthylidene diamine dye B, the reaction formula is shown in formula B:

[0061] (Formula B).

[0062] 50 g of 1,4,5,8-naphthalenetetracarboxylic anhydride (0.19 mol), 61 g of 6-aminobutyric acid (0.47 mol) and 1 L of N,N'-dimethylformamide were mixed, ultrasonically dispersed for 5 min, and refluxed at 120 °C for 6 h. During this period, the suspension gradually became clear and the color of the solution changed from transparent to brown. After the reaction, 2 L of ice water was added, mixed evenly and filtered to obtain a brown crude product that did not change color under light.

[0063] The crude product cake was dried and recrystallized with N,N'-dimethylformamide, and dried at 160°C to obtain 69.2 g of brownish yellow dye, namely naphthylidene diamine dye B, with a yield of 85%.

[0064] Figure 4 is the infrared spectrum of the naphthylidene diamine dye B prepared in this example, and the characterization data are 1 H NMR (300MHz, DMSO- d 6): δ 1.92 (m, 4H), 2.35 (t, J = 7.3 Hz 4H), 4.10 (t, J = 6.8 Hz,4H), 8.64 (s, 4H) FT-IR: (νC=O) 1695 cm -1 .

[0065] Figure 5After recrystallization, the naphthylidene diamine dye B prepared in this example changes from brown to brown under light.

[0066] Preparation of photochromic masterbatch B:

[0067] 79.3 parts of polyester chips, 20 parts of naphthalene diamine dye B and 0.7 parts of premixed auxiliary agent were mixed, and dried at 110°C for 6 h. The raw materials were put into a twin-screw extruder, and the temperatures of each zone were set to 260°C, 275°C, 275°C, 275°C, 270°C, 270°C, and 260°C. The rotation speed was 300r / min, and the raw materials were extruded through a circular orifice die, cooled in a water trough, and pulled to a pelletizer to be cut into cylindrical masterbatches with a length of 3 mm±1 mm and a diameter of 2 mm±1 mm to obtain photochromic masterbatch B.

[0068] Example 3

[0069] This embodiment provides a method for preparing a photochromic masterbatch.

[0070] Preparation of naphthalene diimide dye C, the reaction formula is shown in formula C:

[0071] (Formula C).

[0072] 80.5 g of 1,4,5,8-naphthalenetetracarboxylic anhydride (0.3 mol) was mixed with 1 L of N,N'-dimethylformamide and ultrasonically dispersed for 5 min. 60 ml of aniline (0.66 mol) was added to the suspension and nitrogen was bubbled for 5 min. The mixture was refluxed and stirred at 160 °C in a nitrogen atmosphere for 2 h. The mixture was filtered and the filter cake was washed with ethanol and dried to obtain 68.7 g of fluorescent yellow needle-shaped photochromic powder, i.e., naphthalene diamine dye C, with a yield of 82%.

[0073] Figure 6 is the infrared spectrum of the naphthylidene diamine dye C prepared in this example, and the characterization data are 1 H NMR (300 MHz, CDCl 3 ): δ 7.35 (d, J = 5.58 Hz, 4H), 7.60 (m, 6H), 8.96 (s, 4H) FT-IR: (νC=O) 1659 cm -1 .

[0074] Preparation of photochromic masterbatch C:

[0075] 69 parts of polyester chips, 30 parts of naphthylidene dye C and 1 part of premixed auxiliary agent were mixed, and dried at 110°C for 6 h. The raw materials were put into a twin-screw extruder, and the temperatures of each zone were set to 260°C, 275°C, 275°C, 275°C, 270°C, 270°C, 260°C, and the rotation speed was 300r / min. The raw materials were extruded through a circular orifice die, cooled in a water trough, and pulled into a pelletizer to be cut into cylindrical masterbatches with a length of 3 mm±1 mm and a diameter of 2 mm±1 mm to obtain photochromic masterbatch C.

[0076] Example 4

[0077] This embodiment provides a method for preparing a photochromic masterbatch.

[0078] Preparation of naphthylidene diamine dye D, the reaction formula is shown in formula D:

[0079] (Formula D).

[0080] 26.8 g of 1,4,5,8-naphthalenetetracarboxylic anhydride (0.1 mol), 20.7 g of 4-aminohexanoic acid (0.22 mol) and 1 L of N,N'-dimethylformamide were mixed and nitrogen was bubbled for 5 min. The mixture was refluxed and stirred at 160 °C for 4 h in a nitrogen atmosphere. During this period, the solution gradually turned brown. After cooling, the solution was filtered and washed with N,N'-dimethylformamide until the washing liquid was colorless to obtain 34.5 g of off-white powder crystals, which was naphthylidene diamine dye D, with a yield of 82%.

[0081] Figure 7 is the infrared spectrum of the naphthylidene diamine dye D prepared in this example, and its characterization data are 1 H NMR (300MHz, DMSO- d 6): δ 7.58 (d, J = 4.5 Hz, 4H), 8.75 (s, 4H), 8.81 (d, J = 3.0 Hz,4H) FT-IR: (νC=O) 1670 cm -1 .

[0082] Preparation of photochromic masterbatch D:

[0083] 69 parts of polyester chips, 30 parts of naphthalene diamine dye D and 1 part of premixed auxiliary agent were mixed, and dried at 110°C for 6 h. The raw materials were put into a twin-screw extruder, and the temperatures of each zone were set to 260°C, 275°C, 275°C, 275°C, 270°C, 270°C, and 260°C. The rotation speed was 300r / min, and the raw materials were extruded through a circular orifice die, cooled in a water trough, and pulled to a pelletizer to be cut into cylindrical masterbatches with a length of 3 mm±1 mm and a diameter of 2 mm±1 mm to obtain photochromic masterbatch D.

[0084] Example 5

[0085] This embodiment provides a method for preparing a photochromic masterbatch.

[0086] Preparation of naphthylidene diamine dye E, the reaction formula is shown in Formula E:

[0087] (Formula E).

[0088] 26.8 g 1,4,5,8-naphthalenetetracarboxylic anhydride (0.1 mol), 45.3 g 5-aminoisopic acid (0.25 mol) and 500 mL acetic acid were mixed and refluxed at 120 °C for 8 h under nitrogen atmosphere. During this period, the color of the solid in the suspension changed from yellow to white. After filtering, it was washed with water until there was no obvious sour smell, and a white crude product was obtained, which did not change color under light.

[0089] The crude product cake was dried and recrystallized with N,N'-dimethylformamide to obtain 41.6 g of yellow crystalline dye, namely naphthylidene diamine dye E, with a yield of 70%. The dye changed from yellow to yellow-green under light.

[0090] Figure 8 is the infrared spectrum of the naphthylidene diamine dye E obtained in this example, 1 H NMR (300MHz, DMSO- d 6): δ 8.26 (s, 4H), 8.58 (s, 2H), 8.73 (s, 4H) FT-IR: (νC=O) 1658 cm -1 .

[0091] Preparation of photochromic masterbatch E:

[0092] 69 parts of polyester chips, 30 parts of naphthylidene dye E and 1 part of premixed auxiliary agent were mixed, and dried at 110°C for 6 h. The raw materials were put into a twin-screw extruder, and the temperatures of each zone were set to 260°C, 275°C, 275°C, 275°C, 270°C, 270°C, and 260°C. The rotation speed was 300r / min, and the raw materials were extruded through a circular orifice die, cooled in a water trough, and pulled to a pelletizer to be cut into cylindrical masterbatches with a length of 3 mm±1 mm and a diameter of 2 mm±1 mm to obtain photochromic masterbatch E.

[0093] Fig. 9 Thermogravimetric analysis diagrams of the naphthalene diimide dyes prepared in Examples 1 to 5 of the present invention are shown.

[0094] Example 6

[0095] This embodiment provides a method for preparing optically variable polyester POY yarn.

[0096] The optically variable masterbatch prepared in Examples 1 to 5 and the polyester chips were weighed in proportion so that the naphthalene diimide dye content in the terminal yarn sample was 1%. After blending, they were put into a melt spinning machine, and the melt was extruded from the spinneret hole, air-cooled, oiled, and wound. The temperature during the spinning process was set to 285°C, the fineness was 150d / 48f, and the winding speed was 2800r / min, thereby obtaining an optically variable polyester POY yarn.

[0097] Optical variable performance test and evaluation

[0098] The POY yarn sample spun in Example 6 was placed on an X-rite Ci7800 colorimeter for testing and rated according to the Datacolor built-in color change color chart. The results are shown in Table 1.

[0099] Table 1 Optical performance grades of polyester POY yarns spun from different photochromic masterbatches

[0100]

[0101] Fig.10 , Fig.11 They are the color measurement result diagram and the extinction process diagram of the POY yarn spun by the masterbatch A in Example 6, respectively. Fig.10 It can be seen that the POY silk-like card obtained from the photochromic masterbatch A in Example 1 changes color (from white to yellow-green) after 20 s of ultraviolet irradiation, the color difference value of the obtained silk-like card is 32.12, and the GS color change grade is 1. Its photosensitivity and color difference are better than those currently reported.

[0102] The color change color of the masterbatch and silk sample obtained in Examples 1, 2, and 5 of the present invention is inconsistent with that of the recrystallized dye, indicating that the electron transfer pathways of the dye monomer and the silk sample are different, that is, the color change of the pure crystalline dye comes from the transfer of electron donors within / between molecules to the charge-deficient center of naphthalimide, while the silk sample is transferred from the ester group, terminal carboxyl group and other electron donors in the polyester to the charge-deficient center of naphthalimide. At the same time, after the color change of Examples 1 to 5, there is a typical naphthalene diimide free radical absorption peak near 600nm, and the obtained masterbatch and silk sample are all changed from white / yellow to yellow-green, indicating that the color change mainly comes from the coordinated electron transfer between the dye and the polyester.

[0103] The masterbatch and silk-like color-changing performance obtained in Examples 3 and 4 of the present invention are inferior to those in Examples 1 and 2, indicating that the present invention can improve the silk-like color-changing performance by preferably grafting electron-donating groups. Furthermore, after the dyes prepared in Examples 1, 2, and 5 are grafted with electron-donating groups, their crystallized products can achieve electron transfer and change color. This is because the order is high after recrystallization, and there are electron-donating groups inside the molecules and the electron transfer channels are regular. The grafted groups of the dyes prepared in Examples 3 and 4 do not have electron-donating properties, so the resulting crystalline dyes themselves do not change color.

[0104] In summary, if Fig.12 As shown, it is a schematic diagram of the photochromic masterbatch constructed in cooperation with the naphthylimide dye and PET of the present invention. The present invention uses naphthalene diimide compounds as dyes to construct photochromic polyester fibers, which synergize with polyester to achieve color change, and enhances the silk-like color change performance by grafting preferred electron-donating groups.

[0105] The present invention avoids the spiropyran and spirooxazine optically variable dyes used in existing common optically variable fibers, and selects electron transfer optically variable molecules as the core material of the optically variable fibers, which is more convenient than inorganic electron transfer optically variable materials (WO 3 ), naphthaleneimide can achieve group modification through a simple organic reaction of dehydration, and the efficiency of electron transfer in the fiber can be regulated by changing the electron donor and acceptor groups in the dye molecule, so that the optically variable dye still maintains excellent color-changing properties in the fiber dispersion system;

[0106] At the same time, naphthaleneimide has a planar large conjugated structure, and its temperature resistance and mechanical shear resistance are stronger than spiropyran materials. The color change principle is electron transfer. The color change process does not cause changes in the molecular structure and is not limited by the space of the rigid chain segments in polyester. The prepared photochromic masterbatch has good thermal stability. This is different from the existing technology for preparing photochromic fibers, which has the disadvantages of poor heat resistance, poor fatigue resistance, poor friction resistance, poor air permeability, and complex process. The process is simple and easy to promote.

[0107] It should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention rather than to limit it. Although the present invention has been described in detail with reference to the preferred embodiments, those skilled in the art should understand that the technical solutions of the present invention may be modified or replaced by equivalents without departing from the spirit and scope of the technical solutions of the present invention, which should all be included in the scope of the claims of the present invention.

Claims

1. A photochromic masterbatch, Features: In parts by mass, including: 60 ~ 99 parts of carrier, 1 ~ 40 parts of electrostatic dye and 0 ~ 1 part of auxiliary agent; Wherein, the electrical-deficient dye is a naphthalene diimide compound; The naphthalene diimide compound is prepared by dissolving naphthalene tetracarboxylic anhydride and an amino derivative containing an electron-donating group in an organic solvent; the amino derivative containing an electron-donating group includes one of 6-aminocaproic acid, 6-aminobutyric acid, and 5-aminoisobutyric acid; The preparation method of the photochromic masterbatch is characterized by comprising: mixing a carrier, an electric-deficient dye and an auxiliary agent, drying the mixture, and extruding the mixture using a twin-screw granulator to obtain a polyester fiber photochromic masterbatch; Among them, the granulator speed is 100 ~ 300r / min, and the granulation temperature is 250 ~ 285℃; The carrier includes one or more of polyethylene terephthalate, polybutylene terephthalate, polyisosorbide terephthalate and copolymers thereof; The naphthalene diimide compound is an aromatic conjugated structure.

2. The photochromic masterbatch according to claim 1, Features: The auxiliary agent includes one or more of ethylene bis stearamide, titanate coupling agent, silane coupling agent, silicone auxiliary agent, stearic acid lubricant, AC ® wax powder, Chimassorb ® light stabilizer, and Fusabond ® toughening agent.

3. The photochromic masterbatch according to claim 1, Features: The preparation method of the electric-deficient dye comprises placing naphthalene tetracarboxylic anhydride and an amino derivative in an organic solvent, heating and refluxing, reacting for 4 to 12 hours, and obtaining naphthalene diimide after recrystallization, which is the electric-deficient dye; Wherein, the naphthalenetetracarboxylic anhydride is 1, 4, 5, 8-naphthalenetetracarboxylic anhydride.

4. The photochromic masterbatch according to claim 1, Features: The drying process comprises a drying time of 4 to 8 hours and a drying temperature of 110 to 130°C.

5. An application of the photochromic masterbatch according to any one of claims 1 to 2, Features: include, The photochromic masterbatch is melt-spun to obtain photosensitive color-changing polyester fiber; wherein the melt spinning temperature is 260-290°C.

6. Use of the photochromic masterbatch as claimed in claim 5, Features: The photochromic polyester fiber is twisted on a twisting machine to obtain a photochromic fabric.

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