Preparation method for improving water resistance and dyeing stability of noctilucent fiber and application thereof

Abstract

The application discloses a preparation method for improving water resistance and dyeing stability of a noctilucent fiber and application thereof, and relates to the following steps: modifying rare earth luminescent material SAOED, carrying out dehydration condensation reaction of hydroxyl groups on the chain of the modified SAOED and hydroxyl groups generated by hydrolysis of HDTMS under heating, effectively solving the problem that the luminescent powder is prone to hydrolysis in water and improving water resistance of the luminescent powder; considering subsequent processing and application of the prepared noctilucent fiber, carrying out inorganic coating of the modified SAOED with SiO2 which has good light transmittance, and the inorganic coating has little influence on residual brightness of the SAOED and plays a good role in protecting the luminescent master batch and is beneficial to dyeing of the noctilucent fiber. The application adopts a low-temperature carrier dyeing method, utilizes plastic swelling of the carrier to diffuse dyes onto the fiber, the dyed noctilucent fiber has high residual brightness intensity and good dyeing fastness, and the method has the advantages of simple process, low cost and high safety.

Description

Technical Field

[0001] This invention belongs to the field of luminescent fiber materials, specifically relating to a preparation method for improving the water resistance and dyeing stability of luminescent fibers and its application. Background Technology

[0002] Rare earth luminescent fiber is a functional and environmentally friendly fiber made from rare earth luminescent materials. It features high added value and sustainable self-luminescence, and is widely used in transportation, aviation, marine, and entertainment apparel industries. SrAl2O4:Eu 2+ Dy 3+ SAOED (Synthetic Alkyl ...

[0003] Current dyeing processes generally use water as a solvent and require a certain dyeing time, which poses a challenge to the dyeing of luminescent fibers. Currently, a liquid phase deposition method is used to coat the surface of SAOED powder with an amorphous CaF2 coating layer, and it has been found that SAOED with a coating amount of 8% exhibits both good water resistance and luminescence properties. Secondly, excessively high temperatures can cause thermal annihilation of the luminescent particles inside the luminescent fiber, reducing its afterglow performance. Under the same dyeing time, high-temperature and high-pressure dyeing methods cause more severe damage to the luminescence properties of luminescent fibers than low-temperature dyeing. Therefore, low-temperature dyeing is a key factor in obtaining good luminescence properties after dyeing luminescent fibers. Therefore, to solve the problems of long dyeing time, high-temperature damage to the luminescent masterbatch, and reduced brightness and shortened luminescence time caused by contact, reaction, and friction in the dyeing environment, it is urgent to develop a luminescent fiber with good water resistance, high stability, and excellent luminescence performance, as well as a low-temperature and environmentally friendly dyeing process. Summary of the Invention

[0004] The purpose of this section is to outline some aspects of embodiments of the present invention and to briefly describe some preferred embodiments. Simplifications or omissions may be made in this section, as well as in the abstract and title of this application, to avoid obscuring the purpose of these documents; however, such simplifications or omissions should not be construed as limiting the scope of the invention.

[0005] In view of the problems existing in the above and / or prior art, the present invention is proposed.

[0006] Therefore, the purpose of this invention is to overcome the shortcomings of the prior art and provide a preparation method and its application for improving the water resistance and dyeing stability of luminescent fibers.

[0007] To solve the above-mentioned technical problems, the present invention provides the following technical solution: a method for preparing luminescent fibers with improved water resistance and dyeing stability, and its application, characterized in that it includes:

[0008] SAOED, a rare-earth luminescent material for luminescent fibers, was prepared by a high-temperature consolidation method. Modified SAOED was obtained by dehydration condensation reaction of SAOED with hexadecyltrimethoxysilane.

[0009] The modified SAOED was inorganically coated with SiO2 using the sol-gel method, and then luminescent fibers were prepared by melt spinning using polyethylene terephthalate as the substrate.

[0010] Ethyl benzoate was selected as the dyeing carrier, and the luminescent fibers were dyed at low temperature using the carrier dyeing method.

[0011] As a preferred embodiment of the preparation method described in this invention, the method for preparing rare-earth luminescent material SAOED for luminescent fibers using a high-temperature consolidation method includes,

[0012] The raw materials SrCO3, Al2O3, Eu2O3, Dy2O3 and H3BO3 were mixed evenly in a mortar and ultrasonically dispersed for 30 min with anhydrous ethanol as solvent. After drying, the mixture was placed in a tube-type high-temperature sintering furnace for full reaction. Under a weak reducing atmosphere, the mixture was calcined at 1400℃ for 4 h. The sample obtained after natural cooling is the rare earth luminescent material SAOED.

[0013] In a preferred embodiment of the preparation method described in this invention, the molar ratio of Sr:Al:Eu:Dy in SrCO3, Al2O3, Eu2O3, and Dy2O3 is 1:2:0.025:0.025; and H3BO3 accounts for 5% of the total.

[0014] As a preferred embodiment of the preparation method described in this invention, the method for preparing the modified SAOED includes,

[0015] SAOED was mixed with HDTMS and then added to a mixed solution of anhydrous ethanol and deionized water. The mixture was heated and stirred in a water bath at 70°C to ensure a complete reaction. Acetic acid was added dropwise to adjust the pH of the solution during the reaction. After the reaction, the mixture was washed, filtered, and dried to obtain modified SAOED.

[0016] In a preferred embodiment of the preparation method described in this invention, the mass ratio of SAOED to HDTMS is 1:0.8-3, the mass ratio of anhydrous ethanol to deionized water is 1:5, the concentration of acetic acid is 2 mol / L, and the pH is adjusted to a stable value of 3.

[0017] As a preferred embodiment of the preparation method described in this invention, the luminescent fiber is prepared by dissolving tetraethyl orthosilicate in a mixed solution of ethanol and deionized water, stirring evenly, and then placing it in a 60°C water bath for reflux reaction for 4 hours. The pH is adjusted to 2-3 with dilute sulfuric acid, and the mixture is continuously heated and stirred to ensure complete hydrolysis until a uniform and transparent sol is formed.

[0018] Modified ASOED was added to the above sol, and the mixture was heated and stirred to make the modified ASOED expand and loosen, forming a flocculent gel. The gel was then placed in a room temperature sealed environment for aging and drying for 24 hours. After that, it was placed in a tube-type high-temperature sintering furnace for calcination. The sample after being filtered with deionized water and dried is SiO2 / modified ASOED.

[0019] PET masterbatch is mixed with SiO2 / modified ASOED and spinning aids are added to form luminescent masterbatch through melting. The masterbatch is then extruded through a twin-screw extruder and then drawn and wound to produce luminescent fibers with good water resistance.

[0020] As a preferred embodiment of the preparation method described in this invention, the mass ratio of TEOS, ethanol and deionized water is 1:10:15, the SiO2 coating amount of modified ASOED is 3%-8%, the calcination temperature is 200℃~400℃, the calcination time is 4h, and the mass ratio of PET masterbatch to SiO2 / modified ASOED is 8~15:1.

[0021] As a preferred embodiment of the preparation method described in this invention, the preparation process of the carrier solution includes dissolving ethyl benzoate and Pingpingjia O-25 in deionized water, heating and stirring in a water bath to fully emulsify the ethyl benzoate, and obtaining a colorless and transparent solution, which is the carrier solution.

[0022] As a preferred embodiment of the preparation method described in this invention, the concentration of ethyl benzoate is 5 g / L, the concentration of Pingpingjia O-25 is 0.6 g / L, the water bath temperature is 70°C, and the time is 150 min.

[0023] As a preferred embodiment of the preparation method described in this invention, the low-temperature dyeing of luminescent fibers by carrier dyeing involves dissolving disperse dye in deionized water to prepare a dye solution, adding an appropriate amount of carrier solution to the dye solution, heating in a water bath, adding the luminescent fibers after reaching a certain temperature, maintaining the temperature for dyeing, and finally washing and drying. The concentration of the dye solution is 0.1 g / L to 0.3 g / L, the mass of ethyl benzoate solution in the dye solution is 3 g / L to 10 g / L, the water bath heating temperature is 90°C, and the holding time is 10 to 30 minutes.

[0024] Beneficial effects of this invention:

[0025] This invention modifies and then coats the rare earth luminescent material ASOED, which not only improves the water resistance and organic compatibility of the ASOED powder, but also provides excellent protection and enhances stability in subsequent applications. By using a carrier dyeing method, the luminescent fibers still have good luminescence performance after low-temperature dyeing. Moreover, this dyeing process is green and environmentally friendly, and has high economic benefits. The process is simple, low-cost, and highly safe. Attached Figure Description

[0026] To more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings used in the description of the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort. Wherein:

[0027] Figure 1 Images of the undyed and dyed luminescent fibers prepared in Example 1.

[0028] Figure 2 The images show the luminescence of the luminescent fibers prepared in Example 1, both dyed and undyed, in a dark environment. Detailed Implementation

[0029] To make the above-mentioned objects, features and advantages of the present invention more apparent and understandable, the specific embodiments of the present invention will be described in detail below with reference to the examples in the specification.

[0030] Many specific details are set forth in the following description in order to provide a full understanding of the invention. However, the invention may also be practiced in other ways different from those described herein, and those skilled in the art can make similar extensions without departing from the spirit of the invention. Therefore, the invention is not limited to the specific embodiments disclosed below.

[0031] 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 phrase "in one embodiment" appearing in different places in this specification does not necessarily refer to the same embodiment, nor is it a single or selective embodiment that is mutually exclusive with other embodiments.

[0032] Unless otherwise specified, all raw materials used in the embodiments of this invention are commercially available. See Table 1 for details.

[0033] Table 1

[0034]

[0035]

[0036] Example 1

[0037] (1) Preparation of modified SAOED: The raw materials SrCO3, Al2O3, Eu2O3, Dy2O3 and H3BO3 were mixed evenly in a mortar at a ratio of n(Sr):n(Al):n(Eu):n(Dy) of 1:2:0.025:0.025, with H3BO3 accounting for 5% (molar amount) of the total matrix. The mixture was ultrasonically dispersed for 30 min with anhydrous ethanol as solvent. After drying, the mixture was placed in a tubular high-temperature sintering furnace for full reaction. Under a weak reducing atmosphere, the mixture was calcined at 1400℃ for 4 h. After natural cooling, the obtained sample was the rare earth luminescent material SrAl2O4:Eu 2+ Dy 3 + (SAOED). SAOED and HDTMS were mixed at a mass ratio of 1:1.6, and then added to an anhydrous ethanol / deionized water mixed solution prepared at a mass ratio of 1:5. The mixture was heated and stirred in a 70°C water bath to ensure a complete reaction. During the reaction, 2 mol / L acetic acid was added dropwise to adjust the pH of the solution to 3. After the reaction, the mixture was washed, filtered, and dried to obtain modified SAOED.

[0038] (2) Tetraethyl orthosilicate (TEOS) was dissolved in a mixed solution of ethanol and deionized water and stirred evenly to form a reaction solution with a mass ratio of 1:10:15. The solution was then placed in a 60°C water bath for reflux reaction for 4 hours. The pH was adjusted to 2-3 with dilute sulfuric acid and heated and stirred continuously to ensure complete hydrolysis until a uniform and transparent sol was formed. Modified ASOED was added to the sol at a 5% coating ratio and heated and stirred continuously to make the modified ASOED expand and loosen, forming a flocculent gel. The gel was then placed in a sealed environment at room temperature for aging and drying for 24 hours. After that, it was placed in a tubular high-temperature sintering furnace at 300°C for 4 hours. The sample after filtration and drying was SiO2 / modified ASOED. PET masterbatch and SiO2 / modified ASOED were mixed at a mass ratio of 10:1 and a spinning aid was added to melt and form a luminous masterbatch. The masterbatch was then extruded by a twin-screw extruder and then drawn and wound to produce a water-resistant luminous fiber.

[0039] (3) Dissolve 0.5g of ethyl benzoate and 0.06g of Pingpingjia O-25 in 100mL of deionized water, and heat and stir in a 70℃ water bath for 150min to fully emulsify the ethyl benzoate and obtain a colorless and transparent carrier solution; weigh 0.02g of disperse dye and dissolve it in 100mL of deionized water to prepare a dye solution with a concentration of 0.2g / L, and add 0.5g of carrier solution to the dye solution so that the mass of the carrier solution in the dye solution is 5g / L. Heat in a water bath until it reaches 90℃, then add the luminous fiber, keep it warm for 15min, and finally wash and dry.

[0040] Example 2

[0041] The difference from Example 1 is that the mass ratio of SAOED to HDTMS in step (1) is 1:0.8.

[0042] Example 3

[0043] The difference from Example 1 is that the mass ratio of SAOED to HDTMS in step (1) is 1:3.

[0044] Example 4

[0045] The difference from Example 1 is that in step (2), modified ASOED is added to the sol at a coating ratio of 3%.

[0046] Example 5

[0047] The difference from Example 1 is that in step (2), modified ASOED is added to the sol at an 8% coating ratio.

[0048] Example 6

[0049] The difference from Example 1 is that the calcination temperature in step (2) is 200°C.

[0050] Example 7

[0051] The difference from Example 1 is that the calcination temperature in step (2) is 400°C.

[0052] Example 8

[0053] The difference from Example 1 is that in step (2), the mass ratio of PET masterbatch to SiO2 / modified ASOED is 8:1.

[0054] Example 9

[0055] The difference from Example 1 is that the mass ratio of PET masterbatch to SiO2 / modified ASOED in step (2) is 15:1.

[0056] Example 10

[0057] The difference from Example 1 is that the mass of ethyl benzoate solution in the dye solution in step (3) is 3 g / L.

[0058] Example 11

[0059] The difference from Example 1 is that the mass of ethyl benzoate solution in the dye solution in step (3) is 10 g / L.

[0060] Example 12

[0061] The difference from Example 1 is that the concentration of the dye solution in step (3) is 0.1 g / L.

[0062] Example 13

[0063] The difference from Example 1 is that the concentration of the dye solution in step (3) is 0.3 g / L.

[0064] Example 14

[0065] The difference from Example 1 is that the heat preservation and dyeing time in step (3) is 10 min.

[0066] Example 15

[0067] The difference from Example 1 is that the heat preservation and dyeing time in step (3) is 30 min.

[0068] Example 16

[0069] The hydrophobic and water-resistant properties, afterglow properties, and color fastness properties of Examples 1 to 15 were tested respectively, and the water resistance, luminescence, and color fastness of the prepared luminescent fibers were observed.

[0070] (1) The method for detecting hydrophobic properties is as follows: The static water contact angle of SiO2 / modified ASOED powder is detected by a water contact angle analyzer (WCA). The sample is pressed evenly on a glass slide to make its surface flat. Deionized water is added to the instrument for measurement. The wettability of the liquid to the solid is determined by measuring the size of the hydrophilic contact angle formed between the liquid and the solid.

[0071] (2) The method for testing water resistance is as follows: equal masses of SiO2 / modified ASOED powder were placed in equal volumes of deionized water and stirred. After 20 minutes, the pH of the hydrolysate was measured. Since the initial pH of the solution was 7, the water resistance of the sample can be characterized by the change in solution pH. The higher the pH, the faster the hydrolysis rate of the sample and the worse the water resistance.

[0072] (3) The method for detecting afterglow brightness is as follows: The afterglow characteristics of the sample are tested using a fluorescence afterglow brightness tester. Before the test, the sample should be placed in the dark for 24 hours. Conditions: Excite with 1000 lx for 15 min, wait for 10 s and then start sampling, with a time of 1200 s.

[0073] (4) The test of color fastness performance includes: according to the national standards GB / T3921-2008 and GB / T3920-2008, the color fastness to soap washing and color fastness to rubbing are tested on the prepared luminous fiber respectively.

[0074] As shown in Examples 1 to 3, changing the mass ratio of ASOED to HDTMS affects the hydrolysis resistance and luminescence properties of the SiO2 / modified ASOED powder. This is because HDTMS undergoes hydrolysis during heating to generate silanol. The hydroxyl groups on the silanol simultaneously undergo dehydration condensation with a large number of hydroxyl groups on the surface of the ASOED powder, ultimately forming a low surface energy siloxane. This results in the grafting of dense organic hydrophobic long chains onto the surface, achieving a hydrophobic effect and enhancing organic compatibility. When the mass ratio of ASOED to HDTMS is 1:0.8, the afterglow brightness of the luminescent powder decreases to 5.087 cd / m². 2 The reason is that HDTMS is insufficient to completely react the hydroxyl groups on the surface of ASOED, and unmodified ASOED will still undergo hydrolysis; when the mass ratio of ASOED to HDTMS is 1:3, the contact angle of the luminescent material is 120°, and the afterglow brightness is 5.201 cd / m². 2 The luminescence rate was also lower than that of Example 1, possibly due to the self-condensation effect of excess HDTMS hydrolysis products leading to a reduction in the grafting rate on the ASOED surface. In summary, the hydrolysis resistance and luminescence performance were optimal when SAOED and HDTMS were mixed at a mass ratio of 1:1.6 as in Example 1.

[0075] As can be seen from Examples 1 to 3 and Examples 4 to 7, changing the experimental conditions for inorganic coating of modified ASOED affects the coating effect. When the SiO2 coating amount is 8%, although the high-temperature oxidation resistance of the modified ASOED is improved, thus enhancing its protective effect on the luminescent material and achieving a contact angle of 139°, it reduces the excitation and emission efficiency of the phosphor, lowering the luminescence performance to 5.704 cd / m². 2 However, if the coating amount is too low, it will not achieve the desired effect of resisting hydrolysis and protecting the internal powder. Similarly, when the calcination temperature is as low as 200℃, the activity of silicon dioxide is relatively low, the resulting coating layer is relatively loose, and the afterglow brightness of the luminescent powder is 5.367 cd / m². 2 At excessively high temperatures, the high reactivity of silicon dioxide makes it difficult to control the reaction rate and prevents the formation of a dense, uniform coating layer on the powder surface. The afterglow brightness of the luminescent powder is 4.945 cd / m². 2 In conclusion, the experimental conditions of Example 1 yielded the best experimental results.

[0076] Table 2 Performance of SiO2 / Modified ASOED Luminescent Powder

[0077]

[0078] Based on Examples 1 and 8-9, it is evident that the mixing mass ratio of PET masterbatch to SiO2 / modified ASOED is a key factor in the spinning of luminescent fibers. When the mass ratio reaches 8:1, although the afterglow brightness of the dyed luminescent fiber reaches 1.131 cd / m², the overall effect is different. 2 However, the flowability of the two deteriorates during blending, resulting in a high breakage rate and affecting the normal spinning process. Furthermore, when the SiO2 / modified ASOED content is low, a good luminescence effect is not achieved, with an afterglow brightness of 0.998 cd / m². 2 Therefore, the best results are achieved when the mass ratio of PET masterbatch to SiO2 / modified ASOED is 10:1.

[0079] Table 3 Luminescent properties of dyed phosphorescent fibers

[0080]

[0081] As can be seen from Examples 1 and 10 to 15, the amount of carrier, the concentration of the dye bath, and the dyeing time all affect the dyeing and luminescence properties of the luminescent fiber. The ideal amount of carrier is just enough to saturate the dye bath without forming a third phase. Excessive carrier will lead to the formation of a third phase, resulting in more dye residue in the dye bath and reducing the dye uptake. When the carrier solution concentration in the dye bath reaches 10 g / L, the luminescent fiber exhibits a washing fastness of 3 and a light fastness of 4, respectively, with an afterglow brightness of 1.009 cd / m². 2 .

[0082] The dyeing process doesn't just occur on the surface of the luminescent fiber; it also penetrates into the fiber's interior. Therefore, the dye can easily coat the luminescent masterbatch and affect its luminescence properties. When the dye concentration reaches 0.3 g / L, although both the colorfastness to washing and the lightfastness reach grade 4, the fiber's afterglow brightness is only 0.898 cd / m². 2 The dyeing time is related to the water resistance of the luminescent fiber and the dye uptake rate. Therefore, selecting appropriate dye concentration, dyeing temperature, and time is key to ensuring that the dyed luminescent fiber exhibits both excellent luminescence properties and good colorfastness. In summary, the optimal experimental conditions were achieved when the concentration of ethyl benzoate carrier was 5 g / L, the dye concentration was 0.2 g / L, and the dyeing time was 15 min, as described in Example 1.

[0083] Comparative Example 1

[0084] The difference from Example 1 is that the ASOED was not inorganically coated, and the afterglow brightness of the final luminescent powder was 4.878 cd / m². 2 .

[0085] Comparative Example 2

[0086] The difference from Example 1 is that no modification was performed on ASOED, and the final afterglow brightness of the luminescent powder was 4.774 cd / m². 2 .

[0087] Comparative Example 3

[0088] The difference from Example 1 is that the mass ratio of PET masterbatch to SiO2 / modified ASOED is 1:1, and the afterglow brightness of the final dyed luminescent fiber is 0.467 cd / m. 2 .

[0089] Comparative Example 4

[0090] The difference from Example 1 is that the concentration of the dye solution was 1 g / L, and the afterglow brightness of the luminescent fiber after dyeing was 0.321 cd / m. 2 .

[0091] Comparative Example 5

[0092] The difference from Example 1 is that ethyl benzoate carrier was not added during the dyeing of the luminescent fibers, and the afterglow brightness of the final dyed luminescent fibers was 0.931 cd / m². 2 The color fastness to soap washing and the color fastness to sunlight are both grade 2.

[0093] To address the drawback of SAOED powder's susceptibility to hydrolysis in water, this invention first modifies it by undergoing a dehydration condensation reaction of its surface hydroxyl groups to form a low-surface-energy siloxane. The modified SAOED is then coated with SiO2, achieving a hydrophobic and water-resistant effect. If the powder surface is not modified and only coated with SiO2, the SAOED will hydrolyze upon contact with water or moisture during subsequent use due to the rupture of the SiO2 coating, resulting in reduced luminescence performance. Conversely, if modification is performed without coating, the powder's resistance to high-temperature oxidation during spinning deteriorates, leading to poor spinnability and dyeing performance, both of which limit subsequent processing and dyeing of the luminescent fiber. In the dyeing process of luminescent fibers, dye concentration and carrier are key factors. Since the luminescence of the fiber is blocked by the dye, excessively high dye concentration results in more dye being applied to the fiber, further blocking the luminescence and reducing its luminescence performance. The addition of a carrier can not only improve the dyeing rate, but also enable low-temperature dyeing, which plays a positive role in the luminescence performance of luminescent fibers. This is because the small molecules of the carrier can enter the fiber interior and bind with the fiber through hydrogen bonds or van der Waals forces, increasing the probability of large holes being generated and allowing the dye to be dyed smoothly. Compared with high-temperature and high-pressure dyeing, low-temperature dyeing not only reduces the damage to the luminescent masterbatch, but also reduces energy consumption and improves economic efficiency.

[0094] Table 4 Performance of Luminescent Powders

[0095]

[0096] Table 5 Properties of the dyed luminescent fibers

[0097]

[0098] Figure 1 The prepared luminescent fibers, undyed (left) and dyed (right); Figure 2 The luminescence of the prepared luminescent fibers, with and without dyeing (left) in a dark environment.

[0099] It should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and are not intended to limit it. Although the present invention has been described in detail with reference to preferred embodiments, those skilled in the art should understand that modifications or equivalent substitutions can be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, and all such modifications or substitutions should be covered within the scope of the present invention.

Claims

1. A method for preparing luminescent fibers with improved water resistance and dyeing stability, characterized in that: include, SAOED, a rare-earth luminescent material for luminescent fibers, was prepared by a high-temperature consolidation method. Modified SAOED was obtained by dehydration condensation reaction of SAOED with hexadecyltrimethoxysilane. The modified SAOED was inorganically coated with SiO2 using the sol-gel method, and then luminescent fibers were prepared by melt spinning using polyethylene terephthalate as the substrate. Ethyl benzoate was selected as the dyeing carrier, and the luminescent fibers were dyed at low temperature using the carrier dyeing method.

2. The preparation method according to claim 1, characterized in that: The method for preparing rare-earth luminescent material SAOED for luminescent fibers using a high-temperature consolidation method includes the following steps: The raw materials SrCO3, Al2O3, Eu2O3, Dy2O3 and H3BO3 were mixed evenly in a mortar and ultrasonically dispersed for 30 min with anhydrous ethanol as solvent. After drying, the mixture was placed in a tube-type high-temperature sintering furnace for full reaction. Under a weak reducing atmosphere, the mixture was calcined at 1400℃ for 4 h. The sample obtained after natural cooling is the rare earth luminescent material SAOED.

3. The preparation method according to claim 2, characterized in that: The molar ratio of Sr:Al:Eu:Dy in the SrCO3, Al2O3, Eu2O3, and Dy2O3 is 1:2:0.025:0.025; H3BO3 accounts for 5% of the total.

4. The preparation method according to claim 1, characterized in that: The preparation method of the modified SAOED includes, SAOED was mixed with HDTMS and then added to a mixed solution of anhydrous ethanol and deionized water. The mixture was heated and stirred in a water bath at 70°C to ensure a complete reaction. Acetic acid was added dropwise to adjust the pH of the solution during the reaction. After the reaction, the mixture was washed, filtered, and dried to obtain modified SAOED.

5. The preparation method according to claim 4, characterized in that: The mass ratio of SAOED to HDTMS is 1:0.8~3, the mass ratio of anhydrous ethanol to deionized water is 1:5, the concentration of acetic acid is 2 mol / L, and the pH is adjusted to a stable value of 3.

6. The preparation method according to claim 1, characterized in that: The preparation of the luminous fiber involves dissolving tetraethyl orthosilicate in a mixed solution of ethanol and deionized water, stirring until homogeneous, and then placing the solution in a 60°C water bath for reflux for 4 hours. The pH is adjusted to 2-3 with dilute sulfuric acid, and the solution is continuously heated and stirred to ensure complete hydrolysis until a uniform and transparent sol is formed. Modified SAOED was added to the above sol, and the mixture was heated and stirred to make the modified SAOED expand and loosen, forming a flocculent gel. The gel was then placed in a room temperature sealed environment for aging and drying for 24 hours. After that, it was placed in a tube-type high-temperature sintering furnace for calcination. The sample after being filtered with deionized water and dried is SiO2 / modified SAOED. PET masterbatch is thoroughly mixed with SiO2 / modified SAOED, and spinning aids are added to melt and form luminescent masterbatch. The masterbatch is then extruded through a twin-screw extruder, and then drawn and wound to produce luminescent fibers with good water resistance.

7. The preparation method according to claim 6, characterized in that: The mass ratio of tetraethyl orthosilicate, ethanol and deionized water is 1:10:15, the SiO2 coating amount of modified SAOED is 3%~8%, the calcination temperature is 200℃~400℃, the calcination time is 4h, and the mass ratio of PET masterbatch to SiO2 / modified SAOED is 8~15:

1.

8. The preparation method according to claim 1, characterized in that: The method of low-temperature dyeing of luminescent fibers by carrier dyeing involves dissolving disperse dye in deionized water to prepare a dye solution, adding an appropriate amount of carrier solution to the dye solution, heating in a water bath, adding the luminescent fibers after reaching a certain temperature, maintaining the temperature for dyeing, and finally washing and drying. The concentration of the dye solution is 0.1 g / L to 0.3 g / L, the mass of ethyl benzoate solution in the dye solution is 3 g / L to 10 g / L, the water bath heating temperature is 90℃, and the holding time is 10 to 30 minutes.

9. The preparation method according to claim 8, characterized in that: The preparation process of the carrier solution includes dissolving ethyl benzoate and Pingpingjia O-25 in deionized water, heating and stirring in a water bath to fully emulsify the ethyl benzoate, and obtaining a colorless and transparent solution, which is the carrier solution.

10. The preparation method according to claim 9, characterized in that: The concentration of ethyl benzoate was 5 g / L, the concentration of Pingpingjia O-25 was 0.6 g / L, the water bath temperature was 70℃, and the time was 150 min.

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