Preparation method of photochromic anti-counterfeiting master batch and fiber thereof

Abstract

The invention discloses a preparation method of a photochromic anti-counterfeiting master batch. Comprising the following steps: step S11, weighing each component in the anti-counterfeiting master batch according to a formula; step S12, uniformly mixing the components weighed in the step S11, feeding into a screw extruder, and melting to form a melt material strip; and step S13, carrying out water-cooling plasticizing on the material strips extruded in the step S12, and pelletizing to obtain the anti-counterfeiting master batch suitable for the polyamide fibers. The invention further discloses a preparation method of the polyamide fiber with the photochromic anti-counterfeiting function. The color-changing anti-counterfeiting agent is used as a pure inorganic metal cluster compound, has the advantages of high stability, low toxicity and the like, and is more applicable to the field of fibers than an organic color-changing anti-counterfeiting agent. Compared with the prior art, the photochromic anti-counterfeiting fiber prepared by the invention has the advantages that the color changing speed is slightly slow, the color returning speed is higher, the color changing effect is not easily triggered in daily use, and the daily use of the fiber is not excessively influenced.

Description

Technical Field

[0001] The present invention relates to the technical field of nylon masterbatch, and particularly relates to a preparation method of a photochromic anti-counterfeiting masterbatch and its fiber. Background Art

[0002] Nylon fiber is widely used in the production of high-end civilian clothing due to its advantages such as heat resistance, wear resistance, high strength, and high elasticity. With the increasing market demand in recent years, the production capacity of nylon has been increasing year by year, and it is gradually developing towards high-end, differentiated, and functional directions. However, during the rapid development of nylon products, the industry as a whole is relatively chaotic. There are many unscrupulous merchants who pass off inferior goods as good ones and engage in fraud. When quality disputes occur, there will be a phenomenon where upstream and downstream manufacturers shift responsibilities to each other, resulting in difficulties in safeguarding rights. Therefore, in order to maintain the healthy development of the high-end nylon product market, it is of great significance to add a fast and effective anti-counterfeiting method to nylon fiber.

[0003] In the current research results, the photochromic effect, as a relatively common anti-counterfeiting means, has advantages such as convenient and rapid detection, and is often applied to the fields of fiber and textiles. Patent CN103556300B prepared a photochromic fiber with anti-counterfeiting marks by the core-sheath spinning method. However, the process of the core-sheath spinning method is relatively cumbersome, and the natural color of the color-changing anti-counterfeiting agent material is light yellow, which will have a certain impact on the spinning color. Patent CN117106132A discloses an anti-counterfeiting method using polyethylene fluorescent microspheres, and realizes the anti-counterfeiting technology by compounding the prepared polyethylene fluorescent microspheres with fabrics. However, this technology is more suitable for being loaded on fabrics by methods such as impregnation and hot pressing, and it is difficult to be directly compounded with fibers at the spinning stage. Summary of the Invention

[0004] Current color-changing anti-counterfeiting products usually select organic compounds with color-changing properties. Such materials usually have relatively light colors themselves, are difficult to achieve the effect of invisible anti-counterfeiting, and have relatively poor stability, making it difficult to be directly applied to the spinning process to endow fibers with anti-counterfeiting functions. Based on this research status, the purpose of the present invention is to provide a preparation method of a photochromic anti-counterfeiting masterbatch and its fiber, which can meet the requirements of a photochromic material with fast response, invisible appearance, and high stability, and directly add it to the fiber to achieve the anti-counterfeiting effect at the fiber level.

[0005] The technical solution adopted by the present application to solve its technical problems is: a preparation method of a photochromic anti-counterfeiting masterbatch, comprising the following steps:

[0006] Step S11, weighing each component in the anti-counterfeiting masterbatch according to the formula;

[0007] Step S12, mixing the components weighed in step S11 and feeding them into a screw extruder for melting to form a melt strand;

[0008] In step S13, the extruded strip in step S12 is subjected to water-cooled plasticization and pelletizing to obtain an anti-counterfeiting masterbatch applicable to nylon fibers.

[0009] Furthermore, the formula in step S11 includes a dispersant, a color-changing anti-counterfeiting agent, and bright nylon chips. Among them, the proportion of the dispersant, the color-changing anti-counterfeiting agent, and the bright nylon chips by mass is 1:10:89.

[0010] Furthermore, the dispersant is dispersant or JIAWax-100 dispersant.

[0011] Furthermore, the content of the color-changing anti-counterfeiting agent in the anti-counterfeiting masterbatch is 10%.

[0012] Furthermore, the average particle size of the color-changing anti-counterfeiting agent is 300 - 500 nm.

[0013] Furthermore, the extrusion temperature in step S12 is 240 - 270 °C.

[0014] Furthermore, the relative viscosity of the anti-counterfeiting masterbatch described in step S13 is 2.029 - 2.132, and the melting point is 222.8 - 261.2 °C.

[0015] Furthermore, the preparation method of the color-changing anti-counterfeiting agent includes the following steps:

[0016] Step S21: Dissolve Na2WO4·2H2O and Na2SiO3 in water, add HCl solution under stirring, and boil to concentrate the solution;

[0017] Step S22: Filter, add an aqueous solution containing anhydrous sodium carbonate to the clear liquid, and slightly heat the solution under stirring to obtain Na 10 [SiW9O 34 ·18H2O white precipitate.

[0018] Furthermore, in step S21, the mass ratio of Na2SiO3 to Na2WO4·2H2O is 1:12 - 20.

[0019] Among them, step S21 is: Dissolve Na2WO4·2H2O (182 g, 0.55 mol) and Na2SiO3 (11 g, 0.05 mol) in 200 mL of water, add HCl solution (130 mL) under stirring, and boil for 1 h to concentrate the solution to 300 mL; step S22 is: Filter, add 50 mL of an aqueous solution containing 50 g of anhydrous sodium carbonate to the clear liquid, and slightly heat the solution under slow stirring to obtain Na 10 [SiW9O 34 ·18H2O white precipitate, with a yield of about 110 g and a yield rate of about 85%.

[0020] The technical solution adopted by the present application to solve its technical problems is: a preparation method of polyamide fiber with photochromic anti-counterfeiting function, comprising the following steps:

[0021] Step S31, drying the anti-counterfeiting masterbatch and bright nylon chips for later use; wherein, the anti-counterfeiting masterbatch is the anti-counterfeiting masterbatch prepared by the above preparation method;

[0022] Step S32, feeding the dried anti-counterfeiting masterbatch and bright nylon chips into a metering pump and a screw extruder to melt and form a melt;

[0023] Step S33, the melt is extruded through a spinneret to form a tow, and then through slow cooling, monomer suction, side blowing cooling, bundling and oiling, secondary cooling in the duct, stretching and setting, and finally winding and shaping to obtain polyamide fiber with anti-counterfeiting function.

[0024] Further, the drying temperature in step S31 is 90 - 110 °C, and the drying time is 20 - 28 h.

[0025] Further, the drying temperature in step S31 is 102 °C, and the drying time is 24 h.

[0026] Further, the melting temperature in step S22 is 260 - 290 °C.

[0027] Further, in step S22, the polyamide fiber with photochromic function is SD FDY (semi-dull fully drawn yarn), and the specification is one of 105D / 34F and 52D / 34F.

[0028] Further, in step S22, the breaking strength of the polyamide anti-counterfeiting fiber is 2.99 - 3.87 cN / dtex, and the breaking elongation is 28.90 - 41.11%.

[0029] Further, the ratio of the anti-counterfeiting masterbatch to the bright nylon chips by mass is 1:10.

[0030] Compared with the prior art, the beneficial effects of the present application are:

[0031] (1) The color-changing anti-counterfeiting agents used in the existing photochromic anti-counterfeiting technology usually have their own colors, which will cause a certain degree of influence on the color of the fiber when introduced into the fiber. The color-changing anti-counterfeiting agent adopted by the present invention is white in its natural color, does not affect the color of the fiber, and can achieve invisible anti-counterfeiting.

[0032] (2) The present invention realizes the photochromic function by adding a color-changing anti-counterfeiting agent to the nylon masterbatch and applying this masterbatch to spinning to obtain polyamide fiber. The main component of the color-changing anti-counterfeiting agent is an inorganic metal cluster compound, and the molecular formula is Na 10 [Si W9O 34·18H2O. The transition metal W in this color-changing anti-counterfeiting agent has variable valence states. It is white under normal conditions. When irradiated with ultraviolet light, W 6+ turns into W 5+ , and the appearance turns dark blue. It can quickly return to its original color after removing the ultraviolet light source, and can always maintain its original structural framework, with high stability and recyclability. The color-changing anti-counterfeiting agent used in the present invention, as a pure inorganic metal cluster compound, has advantages such as high stability and low toxicity, and is more suitable for the fiber field than organic color-changing anti-counterfeiting agents.

[0033] (3) Compared with the prior art, the photochromic anti-counterfeiting fiber prepared in the present invention has a slightly slower color-changing speed and a faster color-returning speed. The color-changing effect is not easily triggered during daily use and will not cause too much impact on the daily use of the fiber. BRIEF DESCRIPTION OF THE DRAWINGS

[0034] Figure 1 It is a color change diagram of Example 3 of this application after being irradiated with an ultraviolet flashlight and left standing naturally;

[0035] Figure 2 It is a color change diagram of Example 4 of this application after being irradiated with an ultraviolet flashlight and left standing naturally. DETAILED DESCRIPTION OF THE INVENTION

[0036] In order to better explain the present invention for easy understanding, the present invention will be described in detail below with reference to the drawings through specific embodiments.

[0037] A preparation method of a photochromic anti-counterfeiting masterbatch disclosed in the present invention includes the following steps: Step S11, weighing each component in the anti-counterfeiting masterbatch according to the formula; Step S12, mixing the components weighed in Step S11 and feeding them into a screw extruder for melting to form a melt strip; Step S13, subjecting the strip extruded in Step S12 to water cooling and plasticization, and pelletizing to obtain an anti-counterfeiting masterbatch suitable for nylon fibers.

[0038] The color-changing anti-counterfeiting agent used in the present invention is white in its natural color and will not affect the color of the fiber, and can achieve invisible anti-counterfeiting. The present invention realizes the photochromic function by adding a color-changing anti-counterfeiting agent to a nylon masterbatch and applying this masterbatch to spinning to obtain nylon fibers. The main component of the color-changing anti-counterfeiting agent is an inorganic metal cluster compound, with the molecular formula of Na 10 [SiW9O 34 ·18H2O. The transition metal W in this color-changing anti-counterfeiting agent has variable valence states. It is white under normal conditions. When irradiated with ultraviolet light, W 6+ turns into W 5+, the appearance turns dark blue and can quickly return to its original color after removing the ultraviolet light source. At the same time, it can always maintain its original structural framework, with high stability and recyclability. The color-changing anti-counterfeiting agent used in the present invention, as a pure inorganic metal cluster compound, has advantages such as high stability and low toxicity, and is more suitable for the fiber field than organic color-changing anti-counterfeiting agents.

[0039] In this embodiment, the formulation in step S11 includes a dispersant, a color-changing anti-counterfeiting agent, and bright nylon chips. Among them, the ratio of the dispersant, the color-changing anti-counterfeiting agent, and the bright nylon chips, by mass fraction, is 1:10:89. After testing, the nylon masterbatch prepared with this ratio and the nylon fiber made of bright nylon chips have a slightly slower color-changing speed and a faster color-returning speed. The color-changing effect is not easily triggered during daily use and will not cause too much impact on the daily use of the fiber.

[0040] Among them, the dispersant is the dispersant or JIAWax-100 dispersant. The content of the color-changing anti-counterfeiting agent in the anti-counterfeiting masterbatch is 10%, and the average particle size of the color-changing anti-counterfeiting agent is 300 - 500 nm. The extrusion temperature in step S12 is 240 - 270 °C. The relative viscosity of the anti-counterfeiting masterbatch described in step S13 is 2.029 - 2.132, and the melting point is 222.8 - 261.2 °C.

[0041] In this embodiment, the preparation method of the color-changing anti-counterfeiting agent includes the following steps:

[0042] Step S21: Dissolve Na2WO4·2H2O and Na2SiO3 in water, add HCl solution under stirring, and boil to concentrate the solution; Step S22: Filter, add an aqueous solution containing anhydrous sodium carbonate to the clear liquid, and slightly heat the solution under stirring to obtain Na 10 [SiW9O 34 ·18H2O white precipitate. Specifically, step S21 is: Dissolve Na2WO4·2H2O (182 g, 0.55 mol) and Na2SiO3 (11 g, 0.05 mol) in 200 mL of water, add HCl solution (130 mL) under stirring, and boil for 1 h to concentrate the solution to 300 mL; Step S22 is: Filter, add 50 mL of an aqueous solution containing 50 g of anhydrous sodium carbonate to the clear liquid, and slightly heat the solution under slow stirring to obtain Na 10 [SiW9O 34 ·18H2O white precipitate, with a yield of about 110 g and a yield rate of about 85%.

[0043] The color-changing anti-counterfeiting agent used in the present invention is white in its natural color, does not affect the color of the fiber, and can achieve invisible anti-counterfeiting. The color-changing anti-counterfeiting agent used in the present invention, as a pure inorganic metal cluster compound, has advantages such as high stability and low toxicity, and is more suitable for the fiber field than organic color-changing anti-counterfeiting agents.

[0044] The present invention also discloses a preparation method of polyamide fiber with photochromic anti-counterfeiting function, comprising the following steps:

[0045] Step S31: drying the anti-counterfeiting masterbatch and polyamide bright chips for standby; Step S32: feeding the dried anti-counterfeiting masterbatch and polyamide bright chips into a metering pump and a screw extruder to melt and form a melt; Step S33: extruding the melt through a spinneret assembly to form a tow, then through slow cooling, monomer suction, side blowing cooling, bundling and oiling, secondary cooling in the duct, and drawing and setting, and finally winding and forming to obtain the polyamide fiber with anti-counterfeiting function.

[0046] Among them, the drying temperature in step S31 is 90 - 110 °C, and the drying time is 20 - 28 h. Specifically, the drying temperature in step S31 is 102 °C, and the drying time is 24 h. The melting temperature in step S22 is 260 - 290 °C. In step S22, the polyamide fiber with photochromic function is SD FDY (semi-dull fully drawn yarn), and the specification is one of 105D / 34F and 52D / 34F. After testing, in step S22, the breaking strength of the polyamide anti-counterfeiting fiber is 2.99 - 3.87 cN / dtex, and the breaking elongation is 28.90 - 41.11%. The ratio of the anti-counterfeiting masterbatch to the polyamide bright chips is 1:10 by mass.

[0047] Example 1

[0048] This example provides an anti-counterfeiting masterbatch applicable to polyamide 6 fiber, which, by mass, comprises 89 parts of polyamide 6 bright chips, 10 parts of color-changing anti-counterfeiting agent, and 1 part of dispersant. Its preparation method is as follows:

[0049] (1) Weigh each component in the ultraviolet indicator masterbatch according to the formula;

[0050] (2) Mix the components weighed in step (1) and feed them into a screw extruder to melt and form a melt strip, with an extrusion temperature of 240 °C and a main machine speed of 550 r / min.

[0051] (3) Water-cool and plasticize the strip extruded in step (2) and cut it into pellets to obtain the anti-counterfeiting masterbatch 1 applicable to polyamide 6 fiber.

[0052] Example 2

[0053] This example provides an anti-counterfeiting masterbatch applicable to polyamide 66 fiber, which, by mass, comprises 89 parts of polyamide 66 bright chips, 10 parts of color-changing anti-counterfeiting agent, and 1 part of JIAWax-100 dispersant. Its preparation method is as follows:

[0054] (1) Weigh each component in the ultraviolet indicator masterbatch according to the formula;

[0055] (2) Mix the components weighed in step (1), feed them into a screw extruder, and melt them to form a melt strip. The extrusion temperature is 270 °C, and the main machine speed is 550 r / min.

[0056] (3) Water-cool and plasticize the strip extruded in step (2), and pelletize it to obtain the anti-counterfeiting masterbatch 2 applicable to nylon 66 fibers.

[0057] Example 3

[0058] This example provides a nylon 6 fiber with a photochromic anti-counterfeiting function. Calculated by mass, its raw materials include: 90 parts of bright nylon 6 chips and 10 parts of the anti-counterfeiting masterbatch 1. Its preparation method is as follows:

[0059] (1) Dry the anti-counterfeiting masterbatch 1 and bright nylon 6 chips for later use.

[0060] (2) Feed the dried anti-counterfeiting masterbatch 1 and bright nylon 6 chips into a metering pump and a screw extruder to melt and obtain a melt. The melting temperature is 260 °C. The melt is extruded through a spinneret assembly to form a filament bundle, and then through slow cooling, monomer suction, side blowing cooling, bundling and oiling, secondary cooling in the channel, and stretching and setting, and finally winding and forming to obtain the nylon 6 fiber 1 with a photochromic anti-counterfeiting function.

[0061] Example 4

[0062] This example provides a nylon 66 fiber with an ultraviolet intensity indication function. Calculated by mass, its raw materials include: 90 parts of bright nylon 66 chips and 10 parts of the anti-counterfeiting masterbatch 2. Its preparation method is as follows:

[0063] (1) Dry the anti-counterfeiting masterbatch 2 and bright nylon 66 chips for later use.

[0064] (2) Feed the dried anti-counterfeiting masterbatch 2 and bright nylon 66 chips into a metering pump and a screw extruder to melt and obtain a melt. The melting temperature is 290 °C. The melt is extruded through a spinneret assembly to form a filament bundle, and then through slow cooling, monomer suction, side blowing cooling, bundling and oiling, secondary cooling in the channel, and stretching and setting, and finally winding and forming to obtain the nylon 66 fiber 2 with an ultraviolet intensity indication function.

[0065] Comparative Example 1

[0066] Basically the same as Example 3, the only difference is that: the anti-counterfeiting masterbatch is not added to the raw materials.

[0067] Comparative Example 2

[0068] Basically the same as Example 4, the only difference is that: the anti-counterfeiting masterbatch is not added to the raw materials.

[0069] The color cards were wound respectively with Examples 3 - 4 and Comparative Examples 1 - 2, irradiated with an ultraviolet flashlight (365 nm, 5W), and the color changes were recorded. It was found from Table 1 that when the irradiation time was within 10 s, it was difficult to observe the color change with the naked eye. After the irradiation time reached 20 s, an obvious light gray - blue color visible to the naked eye appeared. After removing the ultraviolet light source, Examples 3 - 4 could return to their original colors relatively quickly. After standing still for 5 min, the colors of Example 3 and Example 4 had returned close to the state before being irradiated by the ultraviolet flashlight. After standing still for 30 min, both of them completely returned to their original colors.

[0070] Table 1 Lab values of Examples 3 - 4 after being irradiated by the ultraviolet flashlight and standing still naturally

[0071]

[0072] The test results of Examples 1 - 2 are as follows:

[0073] Item Unit Example 1 Example 2 Relative viscosity - 2.029 2.132 Water content ppm 825.4 808.9 Extractable ％ 0.77 0.71 Terminal amino group mmol / kg 46.27 45.35 Terminal carboxyl group mmol / kg 40.01 41.55 Ash content ％ 8.86 8.91 Particle size g / 100 grains 1.457 1.501 Melting point ℃ 222.8 261.2

[0074] As can be seen from the above table, in Examples 1 - 2, all the indicators of the anti - counterfeiting masterbatch are normal and can be applied to spinning.

[0075] The test results of Examples 3 - 4 are as follows:

[0076]

[0077]

[0078] As can be seen from the above table, in Examples 3 - 4, the indicators of the photochromic anti - counterfeiting fibers of polyamide 6 and polyamide 66 have no obvious difference from those of the corresponding conventional polyamide fibers, indicating that this anti - counterfeiting method will not have an adverse impact on the quality of polyamide fiber products.

[0079] The above are only the embodiments of the present invention, and thus do not limit the patent scope of the present invention. All equivalent transformations made by using the content of the specification and drawings of the present invention, or directly or indirectly applied in related technical fields, are equally included in the patent protection scope of the present invention.

Claims

1. A preparation method of a photochromic anti-counterfeiting masterbatch, characterized in that: It includes the following steps: Step S11: Weigh each component in the anti-counterfeiting masterbatch according to the formula; Step S12: Mix the components weighed in Step S11 and then feed them into a screw extruder to be melted to form a melt strip; Step S13: Water-cool and plasticize the strip extruded in Step S12, and pelletize it to obtain the anti-counterfeiting masterbatch applicable to nylon fibers.

2. The preparation method of the photochromic anti-counterfeiting masterbatch according to claim 1, characterized in that: The formula in Step S11 includes a dispersant, a color-changing anti-counterfeiting agent, and bright nylon chips. Among them, the ratio of the dispersant, the color-changing anti-counterfeiting agent, and the bright nylon chips by mass fraction is 1:10:

89.

3. The preparation method of the photochromic anti-counterfeiting masterbatch according to claim 1, characterized in that: The dispersant is Dispersant 330 or JIAWax-100 dispersant.

4. The preparation method of the photochromic anti-counterfeiting masterbatch according to claim 1, characterized in that: The content of the color-changing anti-counterfeiting agent in the anti-counterfeiting masterbatch is 10%.

5. The preparation method of the photochromic anti-counterfeiting masterbatch according to claim 1, characterized in that: The average particle size of the color-changing anti-counterfeiting agent is 300 - 500 nm.

6. The preparation method of the photochromic anti-counterfeiting masterbatch according to claim 1, characterized in that: The extrusion temperature in Step S12 is 240 - 270 °C; the melting point of the anti-counterfeiting masterbatch described in Step S13 is 222.8 - 261.2 °C.

7. The preparation method of the photochromic anti-counterfeiting masterbatch according to claim 1, characterized in that: The preparation method of the color-changing anti-counterfeiting agent comprises the following steps: Step S21: Dissolve Na2WO4·2H2O and Na2SiO3 in water, add HCl solution under stirring, and boil to concentrate the solution; Step S22: Filter, add an aqueous solution containing anhydrous sodium carbonate to the clear liquid, slightly heat the solution under stirring to obtain a white precipitate of Na 10 [SiW9O 34 ·18H2O.

8. A preparation method of polyamide fiber with photochromic anti-counterfeiting function, characterized in that: It includes the following steps: Step S31: Dry the anti-counterfeiting masterbatch and the bright nylon chips for standby; among them, the anti-counterfeiting masterbatch is the anti-counterfeiting masterbatch prepared by the preparation method described in any one of Claims 1 - 7; Step S32: Put the dried anti-counterfeiting masterbatch and the bright nylon chips into a metering pump and a screw extruder to be melted to form a melt; Step S33: The melt is sprayed through a spinneret to form a tow, and then through slow cooling, monomer suction, side blowing cooling, bundling and oiling, secondary cooling in the duct, and drawing and setting, and finally winding and forming to obtain nylon fibers with anti-counterfeiting function.

9. The preparation method of the polyamide fiber with a photochromic anti-counterfeiting function according to claim 1, characterized in that: The drying temperature in Step S31 is 90 - 110 °C, and the drying time is 20 - 28 h; the melting temperature in Step S22 is 260 - 290 °C.

10. The preparation method of the polyamide fiber with a photochromic anti-counterfeiting function as described in claim 1, characterized in that: The ratio of the anti-counterfeiting masterbatch to the bright nylon chips by mass fraction is 1:10.

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