ANTI-COUNTERFEITING MODAL FIBER, PREPARATION METHOD AND ANTI-COUNTERFEITING METHOD

Abstract

The invention relates to a method for preparing an anti-counterfeiting modal fiber, including: mixing a pulp stock solution with a cellulose catalyst, alkalizing, aging, sulfonating, and then dissolving the pulp stock solution in an alkaline solution to obtain a treatment solution; mixing the treatment solution with multiple amino acid-metal chelates, filtering, defoaming and ripening to obtain a spinning stock solution; and mixing the spinning stock solution with a spinning bath additive, and wet spinning, followed by drafting, defoaming, desulfurizing, water washing, and other post-treatments, to obtain an anti-counterfeiting modal fiber, wherein the amino acid metal-chelates account for 0.5%-1.5% by weight of the spinning stock solution. Amino acid-metal chelates are used to anti-counterfeit and encrypt the modal fibers, and the anti-counterfeiting and encrypting is involved in the spinning stock solution of modal fibers. The fiber source can be tracked and identified by detecting the species of metal elements and amino acids.

Claims

1. Use of amino acid-metal chelates as an anti-counterfeiting tracer in an anti-counterfeiting modal fiber.

2. A method for preparing an anti-counterfeiting modal fiber, comprising steps of: (1) mixing a pulp stock solution with a cellulose catalyst, alkalizing, aging, sulfonating, and then dissolving the pulp stock solution in an alkaline solution to obtain a treatment solution; and (2) mixing the treatment solution uniformly with a plurality of amino acid-metal chelates, filtering, defoaming and ripening to obtain a spinning stock solution; and mixing the spinning stock solution uniformly with a spinning bath additive, and wet spinning, followed by post-treatments, to obtain the anti-counterfeiting modal fiber, wherein the amino acid metal-chelates account for 0.5%-1.5% by weight of the spinning stock solution.

3. The preparation method according to claim 2, wherein in Step (1), the cellulose catalyst is JL-EBZ; and the cellulose catalyst accounts for 0.3%-1.8% by weight of the pulp stock solution.

4. The preparation method according to claim 2, wherein in Step (1), the pulp stock solution has a degree of polymerization of ≥850, and a methylcellulose content of ≥92%.

5. The preparation method according to claim 2, wherein in Step (2), the amino acid-metal chelates comprise an amino acid and a metal ion chelated with the amino acid, and the molar ratio of the amino acid to the metal ion is 2-3:1.

6. The preparation method according to claim 5, wherein the amino acid is selected from the group consisting of tyrosine, lysine, leucine, valine, phenylalanine and any combination thereof and the metal ion is selected from a copper ion, a calcium ion, a iron ion and any combination thereof.

7. The preparation method according to claim 2, wherein in Step (2), the spinning bath additive is JL-FS; and the spinning bath additive accounts for 0.1%-0.25% by weight of the spinning stock solution.

8. The preparation method according to claim 2, wherein in Step (2), the wet spinning is low-speed spinning, and the spinning speed is 28-33 m/min; high drafting is performed in a coagulation bath, with a total drafting rate of 75%-85%; and low drafting is performed in post-treatment, with a total drafting rate of 20%-30%.

9. An anti-counterfeiting modal fiber prepared by the method according to claim 2, comprising modal fibers and multiple amino acid-metal chelates distributed in the modal fibers, wherein the amino acid-metal chelates account for 0.5%-1.5% by weight of the anti-counterfeiting modal fiber.

10. An anti-counterfeiting method using the anti-counterfeiting modal fiber according to claim 9, comprising an encryption step, and a decryption and identification step, wherein the encryption step comprises encoding the anti-counterfeiting modal fiber according to the species and amounts of the amino acid-metal chelates, and sending encrypted information; and the decryption and identification step comprises obtaining the encrypted information, and testing the species and amounts of amino acids and metal ions in the modal fiber; and then comparing with the obtained encrypted information to identify the authenticity of the modal fiber.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0044] FIG. 1 is a flow chart of a method for preparing an anti-counterfeiting modal fiber.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0045] The specific embodiments of the present invention will be described in further detail with reference to embodiments. The following embodiments are intended to illustrate the present invention, instead of limiting the scope of the present invention.

Example 1

[0046] This example provides a method for preparing an anti-counterfeiting modal fiber, and a preparation method thereof. FIG. 1 shows a flow chart of the method, and the specific steps are as follows.

[0047] (1) The auxiliary agent JL-EBZ was added to a pulp stock solution, where JL-EBZ accounted for 0.6% by weight of the pulp stock solution. Then it was alkalized with sodium hydroxide. The pulp stock solution after alkalization was aged in an aging device. The aged pulp stock solution was sulfonated with CS.sub.2, and the cellulose sulfonate after sulfonation was dissolved in a sodium hydroxide solution, to obtain a spinning viscose. Specific conditions for the alkalization, aging and sulfonation were as follows.

[0048] The alkalization was performed for 3 hrs with sodium hydroxide having a concentration of 18 g/L at 15° C., where the bath ratio was 1:7. The aging was performed in an aging device for 4 hrs at a temperature of 18° C. The sulfonation was to treat the pulp stock solution with CS.sub.2 at 65° C. for 2 hrs, where the weight ratio of CS.sub.2 to the pulp stock solution was 1:140.

[0049] (2) Amino acid-metal chelates were prepared. A compound amino acid and copper sulfate pentahydrate were mixed at a molar ratio of 3:1, and chelated for 30 min at pH 11 and a temperature of 60° C. The compound amino acid includes tyrosine, lysine, leucine, and valine, at a molar ratio of 4:3:2:1. The mixed solution obtained after the reaction was centrifuged, and the supernatant was collected to obtain an amino acid-copper chelate solution.

[0050] (3) The amino acid-copper chelate solution was added to the treated spinning viscose in Step (1) and mixed evenly, where the amino acid-copper chelate accounted for 0.5% by weight of the spinning viscose. Then after filtration and rapid continuous defoaming treatment, the spinning viscose was ripened in a ripening barrel to prepare a spinning stock solution. The ripening time was 7 hrs, and the treatment temperature was 15° C.

[0051] (4) The auxiliary agent JL-FS was added to the spinning stock solution, mixed well and wet spun to prepare a modal fiber, where JL-FS accounted for 0.15% by weight of the spinning stock solution. The spinning process was low-speed spinning, and the spinning speed was 28 m/min. High drafting is performed in a coagulation bath, with a total drafting rate of 80%; and low drafting is performed in the post-treatment with a total drafting rate of 25%. The spinning nozzle had a specification of Φ0.05 mm×36000 holes. The new fiber was defoamed, desulfurized and washed with water. The fiber was dried at 75° C., to obtained an encrypted modal fiber containing the amino acid-metal chelates. The temperature of the coagulation bath required for the drafting was 45° C., the coagulation bath included 90 g/L of sulfuric acid, 80 g/L of zinc sulfate, and 130 g/L of sodium sulfate, and the immersion time was 2 sec. The defoaming was performed for 0.5 hr by immersing the new fibers in a defoaming agent with a concentration of 0.8%, where the bath ratio was 1:15. The desulfurization was performed for 3 hrs in a 2 g/L sodium hydroxide solution at a temperature of 80° C., where the bath ratio was 1:12. The water washing was performed for 2 hrs with hot water at 85° C., where the bath ratio was 1:18.

Example 2

[0052] This example provides a method for preparing an anti-counterfeiting modal fiber, the specific steps are as follows.

[0053] (1) Following the same steps as those in Step (1) of Example 1, a spinning viscose was obtained.

[0054] (2) The amino acid-metal chelate was a chelate of tyrosine and copper sulfate pentahydrate. Tyrosine and copper sulfate pentahydrate were mixed at a molar ratio of 3:1, and chelated for 30 min at pH 10 and a temperature of 60° C. The mixed solution obtained after the reaction was centrifuged, and the supernatant was collected to obtain an amino acid-copper chelate solution.

[0055] (3) The amino acid-copper chelate solution obtained in Step (2) was added to the spinning viscose, where the amino acid-copper chelate accounted for 0.8% by weight of the spinning viscose. The rest of the steps were the same as those in Step (3) of Example 1.

[0056] (4) Following the same steps as those in Step (4) of Example 1, an anti-counterfeiting modal fiber was obtained.

Example 3

[0057] This example provides a method for preparing an anti-counterfeiting modal fiber. The specific steps are as follows.

[0058] (1) Following the same steps as those in Step (1) of Example 1, a spinning viscose was obtained.

[0059] (2) Two types of amino acid-metal chelate were prepared. A compound amino acid and iron chloride were mixed at a molar ratio of 2:1, and chelated for 30 min at pH 6 and a temperature of 25° C. The mixed solution obtained after the reaction was centrifuged, and the supernatant was collected to obtain an amino acid-iron chelate solution. A compound amino acid and copper sulfate pentahydrate were mixed at a molar ratio of 3:1, and chelated for 30 min at pH 11 and a temperature of 60° C. The compound amino acid includes tyrosine, lysine, leucine, and valine, at a molar ratio of 4:3:2:1. The mixed solution obtained after the reaction was centrifuged, and the supernatant was collected to obtain an amino acid-copper chelate solution.

[0060] (3) The amino acid-copper chelate solution and the amino acid-iron chelate solution obtained in Step (2) were added to the spinning viscose, and the amino acid-copper chelate and the amino acid-iron chelate accounted for 0.5% by weight of the spinning viscose respectively. The rest of the steps were the same as those in Step (3) of Example 1.

[0061] (4) Following the same steps as those in Step (4) of Example 1, an anti-counterfeiting modal fiber was obtained.

[0062] The anti-counterfeiting modal fiber prepared in Examples 1 to 3 was cut into pieces, and treated for 16 hrs by hydrolysis with a 40 g/L sodium hydroxide solution at a bath ratio of 1:4. The modal fiber solution was detected and tested by inductively coupled plasma spectroscopy, to determine the contents of metal elements. The species and contents of amino acids in the modal fiber solution were determined by capillary electrophoresis/mass spectrometry technology. The results are shown in Table 1. The contents of various substances in Table 1 refer to their percentages relative to the total weight of the modal fiber.

TABLE-US-00001 TABLE 1 Content of amino acids and metal elements (%) Example 1 Embodiment 2 Example 3 Determined Determined Determined Before value after Before value after Before value after spinning spinning spinning spinning spinning spinning Cu.sup.2+ 0.120 0.103 0.200 0.179 0.120 0.101 Fe.sup.3+ — — — — 0.170 0.152 Tyrosine 0.150 0.132 0.600 0.459 0.282 0.255 Lysine 0.115 0.102 — — 0.212 0.197 Leucine 0.075 0.056 — — 0.141 0.128 Valine 0.038 0.025 — — 0.705 0.573

[0063] The anti-counterfeiting method of the present invention is described with Example 3 as an example.

[0064] Before the anti-counterfeiting modal fiber is prepared, the amino acids and metal elements are encoded in advance according to the designed composition, where Cu.sup.2+ is represented by the letter C, Fe.sup.3+ is represented by the letter F, and tyrosine, lysine, leucine and valine are respectively represented by the numerals 1, 2, 3, and 4. The codes for the metal elements are arranged ahead of the codes for amino acids; and at the same time, they are ranked according to the content, and the one with a larger amount is in the front. Therefore, an anti-counterfeiting modal fiber having a target code of FC4123 is prepared in Example 3.

[0065] The target code of a modal fiber product and fiber is obtained by a user, and the obtained modal fiber is decrypted. When decrypted, the species and contents of amino acids and metal elements are detected following the above detection methods. According to the determined value after spinning in Table 1, it can be concluded that the anti-counterfeiting code detected in Example 3 is FC4123, which is compared with the target code, and found to be the same as the target code, suggesting that the user has obtained the desired target fiber. According to the above principle, the accuracy of the anti-counterfeiting codes of Examples 1 and 2 is verified. It is found that the anti-counterfeiting codes of Examples 1 and 2 both have extremely high accuracy, as Example 3 does.

[0066] Since the anti-counterfeiting modal fiber prepared in Example 1 contains the same metal ion and different amino acids, the encryption code has high encryption and anti-counterfeiting power and is easy to distinguish. The fiber source can be traced according to the anti-counterfeiting code. The anti-counterfeiting modal fiber produced in Example 2 is a modal fiber encrypted with an amino acid-metal chelate prepared with a single amino acid. There is an encryption effect, but the encryption power is insufficient. The cryptogram is simple and easy to be copied, so the tracking performance is greatly reduced, and the error probability is large. In Example 3, the spinning stock solution of modal fibers is encrypted by adding amino acid-metal chelates of two metal ions with multiple amino acids. In this manner, an anti-counterfeiting code that is difficult to decrypt is obtained. Compared with the encryption with a single metal element in Example 1, the encryption and anti-counterfeiting effect with multiple metal elements is greatly enhanced.

[0067] In addition, the effect of the method of the present invention on the mechanical performance of the modal fibers is tested, and the results are shown in Table 2.

TABLE-US-00002 TABLE 2 Breaking strength and breaking elongation of modal fibers Conventional Example Example Example modal fiber 1 2 3 Dry breaking 3.43 3.49 3.42 3.45 strength (cN/dtex) Dry breaking 13.1 13.3 13.2 13.3 elongation (%) Wet breaking 2.36 2.41 2.35 2.38 strength (cN/dtex) Wet breaking 14.4 14.7 14.3 14.5 elongation (%)

[0068] According to the GB/T 14337-2008 Performance Test Methods for Chemical staple fiber stretch, the breaking strength and breaking elongation of the modal fibers prepared in Examples 1, 2, and 3 and the conventional modal fibers were tested using a fiber tension strength tester. The test results of various examples are compared. It is found that changes in the contents and species of amino acids and metal elements have little influence on the mechanical performance of modal fibers, and do not cause huge fluctuations in the mechanical performance of modal fibers.

[0069] While preferred embodiments of the present invention have been described above, the present invention is not limited thereto. It should be appreciated that some improvements and variations can be made by those skilled in the art without departing from the technical principles of the present invention, which are also contemplated to be within the scope of the present invention.