WO2022100052A1 - 防伪莫代尔纤维、制备方法及防伪方法 - Google Patents

防伪莫代尔纤维、制备方法及防伪方法 Download PDF

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WO2022100052A1
WO2022100052A1 PCT/CN2021/094789 CN2021094789W WO2022100052A1 WO 2022100052 A1 WO2022100052 A1 WO 2022100052A1 CN 2021094789 W CN2021094789 W CN 2021094789W WO 2022100052 A1 WO2022100052 A1 WO 2022100052A1
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counterfeiting
amino acid
modal fiber
treatment
spinning
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PCT/CN2021/094789
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English (en)
French (fr)
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刘宇清
李琴
李兴兴
张叶轲
王钟
王国和
潘志娟
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苏州大学
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Priority to US17/618,317 priority Critical patent/US11946166B2/en
Publication of WO2022100052A1 publication Critical patent/WO2022100052A1/zh

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    • G—PHYSICS
    • G07—CHECKING-DEVICES
    • G07D—HANDLING OF COINS OR VALUABLE PAPERS, e.g. TESTING, SORTING BY DENOMINATIONS, COUNTING, DISPENSING, CHANGING OR DEPOSITING
    • G07D7/00—Testing specially adapted to determine the identity or genuineness of valuable papers or for segregating those which are unacceptable, e.g. banknotes that are alien to a currency
    • G07D7/02—Testing electrical properties of the materials thereof
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/06—Wet spinning methods
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F2/00—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof
    • D01F2/06—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof from viscose
    • D01F2/08—Composition of the spinning solution or the bath
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F2/00—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof
    • D01F2/06—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof from viscose
    • D01F2/08—Composition of the spinning solution or the bath
    • D01F2/10—Addition to the spinning solution or spinning bath of substances which exert their effect equally well in either
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/71—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light thermally excited
    • G01N21/73—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light thermally excited using plasma burners or torches
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/416—Systems
    • G01N27/447—Systems using electrophoresis
    • G01N27/44704—Details; Accessories
    • G01N27/44717—Arrangements for investigating the separated zones, e.g. localising zones
    • G01N27/4473—Arrangements for investigating the separated zones, e.g. localising zones by electric means
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/62—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating the ionisation of gases, e.g. aerosols; by investigating electric discharges, e.g. emission of cathode
    • G—PHYSICS
    • G07—CHECKING-DEVICES
    • G07D—HANDLING OF COINS OR VALUABLE PAPERS, e.g. TESTING, SORTING BY DENOMINATIONS, COUNTING, DISPENSING, CHANGING OR DEPOSITING
    • G07D7/00—Testing specially adapted to determine the identity or genuineness of valuable papers or for segregating those which are unacceptable, e.g. banknotes that are alien to a currency
    • G07D7/06—Testing specially adapted to determine the identity or genuineness of valuable papers or for segregating those which are unacceptable, e.g. banknotes that are alien to a currency using wave or particle radiation
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D1/00—Treatment of filament-forming or like material
    • D01D1/02—Preparation of spinning solutions
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/10—Other agents for modifying properties
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2201/00—Cellulose-based fibres, e.g. vegetable fibres
    • D10B2201/20—Cellulose-derived artificial fibres
    • D10B2201/22—Cellulose-derived artificial fibres made from cellulose solutions
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2505/00—Industrial

Definitions

  • the invention relates to anti-counterfeiting fibers, in particular to an anti-counterfeiting modal fiber, a preparation method and an anti-counterfeiting method.
  • anti-counterfeiting fibers there are many chemical fibers in the main base material of anti-counterfeiting fibers, and most of the known anti-counterfeiting fibers are anti-counterfeiting by the color of the fibers, and their origin cannot be traced.
  • the anti-counterfeiting fiber in Chinese patent CN207193675U has a specific color structure, and different specific color structures have specific color characteristics that are perceived by the human eye under sunlight.
  • This type of anti-counterfeiting fiber is a sphere or an ellipsoid and is mostly used in paper materials. .
  • the anti-counterfeiting mark is carried out by setting color dots on the fiber to form a specific color pattern, and its application scope is also mainly for paper products.
  • the use of fiber morphological structure and its superposition effect for anti-counterfeiting marking is also the mainstream of anti-counterfeiting fiber applications.
  • a fiber body is formed by a geometric section composed of upper and lower surfaces, forming a concave-convex shielding structure, so that the upper surface or the lower surface is formed. Due to visual differences, two or more characteristic patterns can be observed, or different characteristic patterns can be observed from other angles. Its application range is mainly anti-counterfeiting paper, anti-counterfeiting packaging materials, etc.
  • amino acid metal chelate is mainly in the field of animal feed and plant fertilizer.
  • amino acid chelated copper is added to feed for animal consumption to enhance the activity of enzymes in animals and improve the production of protein, fat and vitamins. utilization, and improve the growth performance of animals.
  • amino acid metal chelates there is currently no technology that discloses the use of amino acid metal chelates in the preparation of anti-counterfeiting materials.
  • the purpose of the present invention is to provide a kind of anti-counterfeiting modal fiber, preparation method and anti-counterfeiting method. And detection and coding of amino acid species for anti-counterfeiting identification.
  • the first object of the present invention is the application of the amino acid metal chelate as an anti-counterfeiting tracking agent for anti-counterfeiting modal fibers.
  • the above application refers to adding an amino acid metal chelate as an anti-counterfeiting tracking agent during the preparation process of modal fibers to prepare anti-counterfeiting modal fibers.
  • the second object of the present invention is to provide a kind of preparation method of anti-counterfeiting modal fiber, comprising the following steps:
  • the cellulose catalyst is JL-EBZ (Shandong Moore Chemical Co., Ltd.); the cellulose catalyst accounts for 0.3%-1.8% of the mass fraction of the pulp stock solution.
  • the pulp stock solution is pulp with a degree of polymerization ⁇ 850 and a methyl cellulose content ⁇ 92%.
  • the pulp stock solution includes cotton pulp, wood pulp or bamboo pulp.
  • step (1) the concentration of the alkali solution used in the alkalization treatment is 15-25g/L, the alkalization treatment is treated at 10-18° C. for 3-4 hours, and the liquor ratio is 1:6-10.
  • step (1) the aging treatment time is 4-5 hours, and the temperature is 14-20°C.
  • step (1) CS 2 is used for sulfonation treatment.
  • the mass ratio of CS 2 to pulp stock solution is 1:120-150.
  • the sulfonation treatment temperature is 55-75°C, and the treatment time is 1-2.5 hours.
  • step (1) after treatment, it is dissolved in 40-100 g/L sodium hydroxide aqueous solution, and the bath ratio is 1:3-5.
  • the amino acid metal chelate comprises amino acid and metal ion chelated with amino acid, and the molar ratio of amino acid to metal ion is 2-3:1.
  • amino acid is selected from one or more of tyrosine, lysine, leucine, valine and phenylalanine.
  • the metal ions are selected from one or more of copper, calcium and iron ions.
  • the metal ions in the multiple amino acid metal chelates are the same, but the amino acids are different.
  • preparation method of amino acid metal chelate comprises the following steps:
  • the amino acid is a compound amino acid
  • the chelation reaction conditions of the compound amino acid and copper ions are pH 10-11, the reaction temperature is 60-65°C, and the reaction time is 30 minutes
  • the chelation reaction conditions of compound amino acids and calcium ions are pH value 6-8, the reaction temperature is 55-65 DEG C, and the reaction time is 30 minutes
  • the chelation reaction conditions of the compound amino acid and iron ions are pH 5-6, the reaction temperature is 25-30 DEG C, and the reaction time is 30 minutes.
  • the spinning bath additive is JL-FS (Shandong Moore Chemical Co., Ltd.); the spinning bath additive accounts for 0.1%-0.25% of the mass fraction of the spinning dope.
  • step (2) the treatment time of the aging treatment is 6-8 hours, and the treatment temperature is 10-20°C.
  • step (2) the wet spinning adopts low-speed spinning, the spinning speed is 28-33 m/min, and the coagulation bath is high-stretched, and the total draft rate is 75%-85%. Low draft, the total draft rate is 20%-30%.
  • step (2) the size of the spinneret for wet spinning is ⁇ 0.05mm ⁇ 36000 holes.
  • the temperature of the coagulation bath required for the drawing treatment is 35-55 ° C, and the coagulation bath is composed of sulfuric acid 80-100g/L, zinc sulfate 70-90g/L, sodium sulfate 130-150g/L , the immersion time is 1-2 seconds.
  • the defoaming treatment is to immerse the new fibers in a defoaming agent with a concentration of 0.5%-1.2% for 0.5-1 hour, and the bath ratio is 1:10-15.
  • step (2) the desulfurization treatment is to treat in 2-3g/L sodium hydroxide solution for 3-4 hours, the temperature is 75-85°C, and the liquor ratio is 1:10-15.
  • step (2) the water washing treatment is treated with hot water at 75-90° C. for 2-3 hours, and the bath ratio is 1:15-25.
  • the post-treatment also includes the step of drying treatment, and the temperature is 70-85°C.
  • the third object of the present invention is to provide an anti-counterfeiting modal fiber prepared by the above-mentioned preparation method, including modal fiber and various amino acid metal chelates distributed in the modal fiber, and the amino acid metal chelate accounts for the total amount of the anti-counterfeiting modal fiber. 0.5%-1.5% of mass.
  • the anti-counterfeiting modal fiber has the advantages of both traceability and high anti-counterfeiting strength: the anti-counterfeiting modal fiber prepared by the present invention has its specific anti-counterfeiting code, and all yarns, fabrics or related textiles prepared from the anti-counterfeiting modal fiber can pass The anti-counterfeiting code can be traced to the source of the raw material and has traceability; the modal fiber anti-counterfeiting code in the present invention is encrypted by mixed encoding of various amino acids and various metal elements, and has extremely high anti-counterfeiting strength.
  • the fourth object of the present invention is to provide a kind of anti-counterfeiting method of above-mentioned anti-counterfeiting modal fiber, comprising encryption step and decryption, identification step:
  • the encryption step includes: coding the anti-counterfeiting modal fiber according to the type and amount of the amino acid metal chelate, and sending encrypted information;
  • the decryption and identification steps include: obtaining encrypted information, and testing the type and amount 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.
  • the encryption step can be carried out at the same time as the preparation process of the anti-counterfeiting modal fiber, and the coding information table is designed at the same time: coding is performed according to the type and amount of amino acids and metal ions contained in the amino acid metal chelate, and different amino acids and different metal ions are coded. Code with different serial numbers, for example, use different English letters to number amino acids, and use different Arabic numerals to number metal ions; when encrypting, they are sorted according to the amount of amino acids and metal ions, such as according to the content from high to low. Combining the two can get a string of true fiber numbers.
  • identification step after testing the type and consumption of amino acid and metal ion in modal fiber, can be contrasted with the encrypted information (comprising true fiber number and coding information table) obtained, if match with true fiber number, It is identified as a true fiber, otherwise it is a false fiber.
  • the encrypted information comprising true fiber number and coding information table
  • capillary electrophoresis/mass spectrometry was used to determine the type and content of amino acids, and the type and content of metal elements were detected by inductively coupled plasma spectroscopy.
  • the present invention has at least the following advantages:
  • the invention discloses an anti-counterfeiting modal fiber and a preparation method thereof.
  • the modal fiber is anti-counterfeited and encrypted by using an amino acid metal chelate compound.
  • the modal fiber can be traced and identified by the detection of metal elements and amino acid types, and its types are numbered with letters or numbers to form a unique block code.
  • the invention uses the type and content of metal elements and amino acids as the anti-counterfeiting marks, and the anti-counterfeiting marks of the anti-counterfeiting modal fibers are inside the fibers without affecting the mechanical properties of the modal fibers, and the anti-counterfeiting marks of the anti-counterfeiting modal fibers are easy to detect and identify, and have a long time period and effective encryption.
  • the fiber source can be traced according to the anti-counterfeiting code. It has the advantages of high anti-counterfeiting strength, difficult to counterfeit, and simple preparation process. It does not increase the complexity of the modal fiber preparation process, and has a good market application prospect.
  • Fig. 1 is the process diagram of the preparation method of anti-counterfeiting modal fiber.
  • the present embodiment provides an anti-counterfeiting modal fiber and a preparation method thereof, the process flow of which is shown in Figure 1, and the specific steps are as follows:
  • auxiliary agent JL-EBZ to the pulp stock solution, and JL-EBZ accounts for 0.6% of the pulp stock solution mass fraction. Then, it is alkalized with sodium hydroxide, and the pulp stock solution after alkalization treatment is aged in aging equipment. The aged pulp stock solution is sulfonated with CS 2 , and the sulfonated cellulose sulfonic acid The ester is dissolved in sodium hydroxide solution to obtain spun viscose.
  • the specific conditions of alkalization treatment, aging treatment and sulfonation treatment are as follows:
  • Alkalization treatment The concentration of sodium hydroxide is 18g/L, treated at 15 °C for 3 hours, the liquor ratio is 1:7; the aging treatment is carried out in the old equipment, the treatment is carried out for 4 hours, and the temperature is 18 °C; The pulp stock solution was treated at a temperature of 65°C for 2 hours, and the mass ratio of CS 2 to pulp stock solution was 1:140.
  • step (3) Add the amino acid chelated copper solution to the spun viscose treated in step (1) and mix it evenly, and the amino acid chelated copper accounts for 0.5% of the mass fraction of the spun viscose; , and then place the spun viscose in an aging barrel for aging treatment to obtain a spinning dope.
  • the aging treatment time was 7 hours, and the treatment temperature was 15°C.
  • JL-FS auxiliary agent
  • the spinning process adopts low-speed spinning, the spinning speed is 28 m/min, the high-stretching in the coagulation bath, and the total drafting rate is 80%. In the post-processing medium and low draft, the total draft rate is 25%.
  • the size of the spinning nozzle is ⁇ 0.05mm ⁇ 36000 holes, and the new silk is defoamed, desulfurized and washed with water. After drying the fiber at 75 °C, the modal fiber containing amino acid chelate metal encryption is obtained.
  • the temperature of the coagulation bath required for the drawing treatment was 45°C
  • the composition of the coagulation bath was 90 g/L of sulfuric acid, 80 g/L of zinc sulfate, 130 g/L of sodium sulfate, and the immersion time was 2 seconds.
  • the defoaming treatment is to immerse the new fibers in a defoaming agent with a concentration of 0.8%? 0.5 hours, the liquor ratio is 1:15.
  • the desulfurization treatment is treated in 2g/L sodium hydroxide solution for 3 hours, the temperature is 80°C, and the liquor ratio is 1:12.
  • the water washing treatment was treated with hot water at 85°C for 2 hours, and the bath ratio was 1:18.
  • the present embodiment provides an anti-counterfeiting modal fiber and a preparation method thereof, and the specific steps are as follows:
  • the amino acid metal chelate is a chelate of tyrosine and copper sulfate pentahydrate. Mix tyrosine and copper sulfate pentahydrate in a molar ratio of 3:1, at a pH of 10 and a temperature of 60°C The chelation reaction was carried out under the same conditions, and the reaction time was 30 minutes. The mixed solution obtained after the reaction is centrifuged, and the supernatant liquid is taken to obtain an amino acid chelated copper solution.
  • step (3) adding the amino acid chelated copper solution obtained in step (2) into the spun viscose, and the amino acid chelated copper accounts for 0.8% of the mass fraction of the spun viscose.
  • the remaining steps are the same as step (3) of the first embodiment.
  • the present embodiment provides an anti-counterfeiting modal fiber and a preparation method thereof, and the specific steps are as follows:
  • the mixed solution obtained after the reaction is centrifuged, and the supernatant is taken to obtain an amino acid chelated iron solution;
  • the compound amino acid is mixed with copper sulfate pentahydrate in a molar ratio of 3:1, at a pH of 11 and a temperature of 60
  • the chelation reaction is carried out under the condition of °C, and the reaction time is 30 minutes, wherein the complex amino acids are tyrosine, lysine, leucine, and valine, and the molar ratio of the four in order is 4:3:2:1.
  • the mixed solution obtained after the reaction is subjected to centrifugation, and the supernatant is taken to obtain an amino acid chelated copper solution.
  • step (3) adding the amino acid chelated copper solution and amino acid chelated iron solution obtained in step (2) into the spun viscose, and the amino acid chelated copper and amino acid chelated iron both account for 0.5% of the mass fraction of the spun viscose.
  • the remaining steps are the same as step (3) of the first embodiment.
  • the anti-counterfeiting modal fibers prepared in Examples 1 to 3 were cut into pieces, and were hydrolyzed with 40 g/L sodium hydroxide solution for 16 hours, and the liquor ratio was 1:4.
  • the modal fiber solution was detected by inductively coupled plasma spectroscopy, and the metal was tested.
  • the content of elements; the type and content of amino acids in the modal fiber solution were determined by capillary electrophoresis/mass spectrometry, and the results are shown in Table 1.
  • the content of each substance in Table 1 refers to its percentage in the total mass of modal fibers.
  • Embodiment 3 as an example to illustrate the anti-counterfeiting method of the present invention:
  • Example 3 is to prepare the anti-counterfeiting modal fiber whose target code is FC4123.
  • the user obtains the target codes of modal fiber products and fibers, and decrypts the obtained modal fibers.
  • decrypting detect amino acid type and content, metal element type and content according to the above detection method, according to the actual measured value after spinning in Table 1, the anti-counterfeiting code detected in Example 3 is FC4123, and it is compared with the target code, If the two codes are the same, it means that the user has obtained the desired target fiber.
  • the anti-counterfeiting coding accuracy of the embodiments 1 and 2 is the same as that of the embodiment 3, and both have extremely high accuracy.
  • the anti-counterfeiting modal fiber prepared in Example 1 contains the same metal ion and different amino acids, its encryption code has high security and strong anti-counterfeiting strength, and is easy to distinguish, and the source of the fiber can be traced according to the anti-counterfeiting code.
  • the anti-counterfeiting modal fiber obtained in Example 2 uses a single type of amino acid to prepare amino acid metal chelate for modal fiber encryption, which has encryption effect but insufficient encryption strength, the password is simple and easy to be copied, the tracking effect is also greatly reduced, and the error probability is large.
  • Example 3 Adding two kinds of amino acid chelates of metal ions to the modal spinning stock solution for encryption, and cooperating with a variety of amino acid codes for encryption, an anti-counterfeiting code that is difficult to decipher can be obtained. Compared with the encryption of a single metal element in Example 1, The encryption and anti-counterfeiting effect of various metal elements is greatly enhanced.

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Abstract

本发明涉及一种防伪莫代尔纤维的制备方法，包括以下步骤：将浆粕原液与纤维素催化剂混合后进行碱化处理、老成处理以及磺化处理，处理后溶于碱溶液，得到处理液；将处理液与多种氨基酸金属螯合物混匀，经过滤、脱泡和熟成处理后制得纺丝原液；然后将纺丝原液与纺丝浴添加剂混匀后进行湿法纺丝，经牵伸、消泡、脱硫、水洗等后加工得到防伪莫代尔纤维；其中，氨基酸金属螯合物占纺丝原液质量分数的0.5％-1.5％。本发明采用氨基酸金属螯合物对莫代尔纤维进行防伪加密，本发明的加密区域为莫代尔纤维纺丝原液，可通过对金属元素和氨基酸种类的检测来追踪识别纤维来源。

Description

防伪莫代尔纤维、制备方法及防伪方法 技术领域
本发明涉及防伪纤维，尤其涉及一种防伪莫代尔纤维、制备方法及防伪方法。
背景技术
目前防伪纤维的主体基材中化学纤维偏多，且现已知的防伪纤维大多通过纤维的颜色进行防伪标识，不可追踪其来源。如中国专利CN207193675U中防伪纤维具有特定颜色结构，不同的特定颜色结构在日光照射下具有被人眼感知的特定颜色特征，该类防伪纤维为圆球体或椭球体，多用于纸质材料中的应用。中国专利CN205557182U中通过在纤维上设置色彩点以形成特定色彩图案来进行防伪标识，其应用范围也以纸类用品为主。此外利用纤维的形态结构及其叠加效应进行防伪标识也是防伪纤维应用的主流，如中国专利CN2716320Y中通过由上、下表面组成的几何截面构成纤维体，形成凹凸遮挡结构，使上表面或下表面因视觉差异可观察到二个及以上的特征图案，或从其他角度观察到不同特征图案，其应用范围主要为防伪纸、防伪包装材料等。
目前氨基酸金属螯合物的开发应用主要在动物饲料和植物肥料领域，如中国专利CN103535521A中氨基酸螯合铜添加到饲料中供动物食用，以加强动物体内酶的活性，提高蛋白质、脂肪和维生素的利用率，提高动物的生长性能。但目前并未有技术公开氨基酸金属螯合物在制备防伪材料中的用途。
发明内容
为解决上述技术问题，本发明的目的是提供一种防伪莫代尔纤维、制备方法及防伪方法，本发明的防伪莫代尔纤维利用多种氨基酸金属螯合物对莫代尔纤维进行防伪加密处理，通过对金属元素和氨基酸种类的检测和编码进行防伪识别。
本发明的第一个目的是氨基酸金属螯合物作为防伪莫代尔纤维的防伪追踪剂的应用。
上述应用指的是，在莫代尔纤维的制备过程中，添加氨基酸金属螯合物作为防伪追踪剂，以制备出防伪莫代尔纤维。
本发明的第二个目的是提供一种防伪莫代尔纤维的制备方法，包括以下步骤：
(1)将浆粕原液与纤维素催化剂混合后进行碱化处理、老成处理以及磺化处理，处理后溶于碱溶液，得到处理液；
(2)将处理液与多种氨基酸金属螯合物混匀，经过滤、脱泡和熟成处理后制得纺丝原液；然后将纺丝原液与纺丝浴添加剂混匀后进行湿法纺丝，经牵伸、消泡、脱硫、水洗等后加工得到防伪莫代尔纤维；其中，氨基酸金属螯合物占纺丝原液质量分数的0.5％-1.5％。
进一步地，在步骤(1)中，纤维素催化剂为JL-EBZ(山东摩尔化工有限公司)；纤维素催化剂占浆粕原液质量分数的0.3％-1.8％。
进一步地，在步骤(1)中，浆粕原液为聚合度≥850，且甲基纤维素含量≥92％的浆粕。优选地，浆粕原液包括棉浆粕、木浆粕或竹浆粕。
进一步地，在步骤(1)中，碱化处理所使用的碱溶液的浓度为15-25g/L，碱化处理在10-18℃下处理3-4小时，浴比1：6-10。
进一步地，在步骤(1)中，老成处理的时间4-5小时，温度为14-20℃。
进一步地，在步骤(1)中，采用CS 2进行磺化处理。CS 2与浆粕原液的质量比为1：120-150。磺化处理温度为55-75℃，处理时间为1-2.5小时。
进一步地，在步骤(1)中，处理后溶于40-100g/L的氢氧化钠水溶液，浴比为1：3-5。
进一步地，在步骤(2)中，氨基酸金属螯合物包括氨基酸以及与氨基酸螯合的金属离子，氨基酸与金属离子的摩尔比为2-3:1。
进一步地，氨基酸选自络氨酸、赖氨酸、亮氨酸、缬氨酸和苯丙氨酸中的一种或几种。
进一步地，金属离子选自铜、钙和铁离子中的一种或几种。
优选地，多种氨基酸金属螯合物中的金属离子相同，但氨基酸不同。
进一步地，氨基酸金属螯合物的制备方法包括以下步骤：
将金属化合物和氨基酸在水中混匀，调节混合液的pH，反应完全后分离出氨基酸金属螯合物。
优选地，氨基酸为复合氨基酸，复合氨基酸与铜离子的螯合反应条件为pH值10-11，反应温度60-65℃，反应时间30分钟；复合氨基酸与钙离子的螯合反应条件为pH值6-8，反应温度55-65℃，反应时间30分钟；复合氨基酸与铁离子的螯合反应条件为pH值5-6，反应温度25-30℃，反应时间30分钟。
进一步地，在步骤(2)中，纺丝浴添加剂为JL-FS(山东摩尔化工有限公司)；纺丝浴添加剂占纺丝原液质量分数的0.1％-0.25％。
进一步地，在步骤(2)中，熟成处理的处理时间为6-8小时，处理温度为10-20℃。
进一步地，在步骤(2)中，湿法纺丝采用低速纺丝，纺丝速度为28-33m/min，凝固浴中高倍牵伸，总牵伸率为75％-85％，后加工中低倍牵伸，总牵伸率为20％-30％。
进一步地，在步骤(2)中，湿法纺丝的纺丝喷头选用规格为Ф0.05mm×36000孔。
进一步地，在步骤(2)中，牵伸处理所需凝固浴温度为35-55℃，凝固浴组成为硫酸80-100g/L，硫酸锌70-90g/L，硫酸钠130-150g/L，浸没时间为1-2秒。
进一步地，在步骤(2)中，消泡处理为将新生纤维浸入浓度为0.5％-1.2％的消泡剂中处理0.5-1小时，浴比1：10-15。
进一步地，在步骤(2)中，脱硫处理为在2-3g/L的氢氧化钠溶液中处理3-4小时，温度75-85℃，浴比1：10-15。
进一步地，在步骤(2)中，水洗处理为用75-90℃的热水处理2-3小时，浴比1：15-25。
进一步地，后处理还包括烘干处理的步骤，温度为70-85℃。
本发明的第三个目的是提供一种采用上述制备方法所制备的防伪莫代尔纤维，包括莫代尔纤维以及分布于莫代尔纤维中的多种氨基酸金属螯合物，氨基酸金属螯合物占防伪莫代尔纤维总质量的0.5％-1.5％。
本发明中，防伪莫代尔纤维兼具可追踪性，防伪力度高的优点：本发明制备的防伪莫代尔纤维具有其特定的防伪编码，所有以防伪莫代尔纤维制备的纱线、织物或相关纺织品均可通过其防伪编码追踪到原料来源，具有可追踪性；本发明中的莫代尔纤维防伪编码由多种氨基酸和多种金属元素混合编码加密，具有极高防伪力度。
本发明的第四个目的是提供一种上述防伪莫代尔纤维的防伪方法，包括加密步骤和解密、鉴别步骤：
加密步骤包括：根据氨基酸金属螯合物的类型和用量，对防伪莫代尔纤维进行编码，发出加密信息；
解密、鉴别步骤包括：获得加密信息，并测试莫代尔纤维中的氨基酸和金属离子的类型和用量；然后与获得的加密信息比较，鉴别莫代尔纤维的真伪。
进一步地，加密步骤可与防伪莫代尔纤维的制备工艺同时进行，同时设计编码信息表：根据氨基酸金属螯合物中包含的氨基酸和金属离子类型和用量进行编码，为不同的氨基酸和不同的金属离子编以不同的序号，如利用不同的英文字母对氨基酸进行编号，利用不同的阿拉伯数字对金属离子进行编号；加密时按照氨基酸和金属离子的用量进行排序，如按照含量由高到低依次排序，二者组合后可获得一串真纤维编号。
进一步地，解密、鉴别步骤中，测试莫代尔纤维中的氨基酸和金属离子的类型和用量后，可与获得的加密信息(包括真纤维编号以及编码信息表)对照，若与真纤维编号相匹配，则鉴定为真纤维，否则为假纤维。
进一步地，对氨基酸种类和含量测定采用毛细管电泳/质谱联用技术，金属元素种类与含量采用电感耦合等离子体光谱法检测。
借由上述方案，本发明至少具有以下优点：
本发明公开了一种防伪莫代尔纤维及其制备方法，采用氨基酸金属螯合物对莫代尔纤维进行防伪加密，本发明的加密区域为莫代尔纤维纺丝原液，使其获得含有特定金属元素和特定氨基酸种类的莫代尔纤维，可通过对金属元素和氨基酸种类的检测来追踪识别纤维来源，以字母或数字对其种类进行编号，形成独特的区块密码。
本发明利用金属元素和氨基酸种类和含量作为防伪标识，且防伪莫代尔纤维的防伪标识在纤维内部，不影响莫代尔纤维的力学性能，且防伪莫代尔纤维的防伪标识易检测识别，时效长，具有有效加密性和可追踪性，可根据防伪编码追踪纤维来源，防伪力度高，难仿造，制备工艺简便等优点，不会增加莫代尔纤维制备工艺的复杂性，具有良好的市场应用前景。
上述说明仅是本发明技术方案的概述，为了能够更清楚了解本发明的技术手段，并可依照说明书的内容予以实施，以下以本发明的较佳实施例并配合详细附图说明如后。
附图说明
图1是防伪莫代尔纤维的制备方法工艺图。
具体实施方式
下面结合实施例，对本发明的具体实施方式作进一步详细描述。以下实施例用于说明本发明，但不用来限制本发明的范围。
实施例1
本实施例提供了一种防伪莫代尔纤维及其制备方法，其工艺流程如图1所示，具体步骤如下：
(1)首先在浆粕原液中添加助剂JL-EBZ，JL-EBZ占浆粕原液质量分数的0.6％。然后用氢氧化钠进行碱化处理，碱化处理后的浆粕原液在老成设备中老成处理，老成处理好的浆粕原液采用CS 2进行磺化处理，将磺化处理后的纤维素磺酸酯加入氢氧化钠溶液中溶解处理，得到纺丝粘胶。其中，碱化处理、老成处理以及磺化处理的具体条件如下：
碱化处理氢氧化钠浓度18g/L，在15℃下处理3小时，浴比1：7；老成处理在老成设备中进行，处理4小时，温度为18℃；磺化处理条件为采用CS 2处理浆粕原液，处理温度为65℃，处理2小时，CS 2与浆粕原液质量比为1：140。
(2)制备氨基酸金属螯合物，将复合氨基酸与五水硫酸铜按摩尔比3：1比例混合，在 pH值为11，温度为60℃的条件下进行螯合反应，反应时间30分钟，其中复合氨基酸为络氨酸、赖氨酸、亮氨酸、缬氨酸，摩尔比为4:3:2:1，将反应后得到的混合溶液进行离心处理，取上层清液，获得氨基酸螯合铜溶液。
(3)向步骤(1)处理好的纺丝粘胶中加入氨基酸螯合铜溶液混合均匀，氨基酸螯合铜占纺丝粘胶的质量分数的0.5％；然后进行过滤、快速连续脱泡处理，再将纺丝粘胶置于熟成桶中进行熟成处理制得纺丝原液。熟成处理的时间为7小时，处理温度为15℃。
(4)在纺丝原液中添加助剂JL-FS，混合均匀后通过湿法纺丝法制备莫代尔纤维，JL-FS占纺丝原液质量分数的0.15％。其中纺丝过程采用低速纺丝，纺丝速度为28m/min，凝固浴中高倍牵伸，总牵伸率为80％。后加工中低倍牵伸，总牵伸率为25％。纺丝喷头选用规格为Ф0.05mm×36000孔，对新生丝进行消泡，脱硫和水洗处理，75℃下烘干纤维后获得含氨基酸螯合金属加密的莫代尔纤维。其中，牵伸处理所需凝固浴温度为45℃，凝固浴组成为硫酸90g/L，硫酸锌80g/L，硫酸钠130g/L，浸没时间为2秒。消泡处理为将新生纤维浸入浓度为0.8％的消泡剂中处理？0.5小时，浴比1：15。脱硫处理为在2g/L的氢氧化钠溶液中处理3小时，温度80℃，浴比1：12。水洗处理为用85℃的热水处理2小时，浴比1：18。
实施例2
本实施例提供了一种防伪莫代尔纤维及其制备方法，具体步骤如下：
(1)按照与实施例一步骤(1)相同的步骤进行，制备得到纺丝粘胶。
(2)氨基酸金属螯合物为络氨酸与五水硫酸铜的螯合物，将络氨酸与五水硫酸铜按摩尔比3：1比例混合，在pH值为10，温度为60℃的条件下进行螯合反应，反应时间30分钟。将反应后得到的混合溶液进行离心处理，取上层清液，获得氨基酸螯合铜溶液。
(3)将步骤(2)得到的氨基酸螯合铜溶液加入纺丝粘胶中，氨基酸螯合铜占纺丝粘胶的质量分数的0.8％。其余步骤与实施例一步骤(3)相同。
(4)按照与实施例一步骤(4)相同的步骤进行，制备得到防伪莫代尔纤维。
实施例3
本实施例提供了一种防伪莫代尔纤维及其制备方法，具体步骤如下：
(1)按照与实施例一步骤(1)相同的步骤进行，制备得到纺丝粘胶。
(2)制备两种氨基酸金属螯合物，将复合氨基酸与氯化铁按摩尔比2：1比例混合，在pH值为6，温度为25℃的条件下进行螯合反应，反应时间30分钟，将反应后得到的混合溶液进行离心处理，取上层清液，获得氨基酸螯合铁溶液；将复合氨基酸与五水硫酸铜按摩尔 比3：1比例混合，在pH值为11，温度为60℃的条件下进行螯合反应，反应时间30分钟，其中复合氨基酸为络氨酸、赖氨酸、亮氨酸、缬氨酸，按顺序四者摩尔比为4:3:2:1，将反应后得到的混合溶液进行离心处理，取上层清液，获得氨基酸螯合铜溶液。
(3)将步骤(2)得到的氨基酸螯合铜溶液和氨基酸螯合铁溶液加入纺丝粘胶中，氨基酸螯合铜与氨基酸螯合铁均占纺丝粘胶的质量分数的0.5％。其余步骤与实施例一步骤(3)相同。
(4)按照与实施例一步骤(4)相同的步骤进行，制备得到防伪莫代尔纤维。
将实施例1至3制备的防伪莫代尔纤维为剪碎，采用40g/L的氢氧化钠溶液水解处理16小时，浴比1：4，采用电感耦合等离子体光谱法对莫代尔纤维溶液检测，测试金属元素的含量；采用毛细管电泳/质谱联用技术对莫代尔纤维溶液中氨基酸种类和含量进行测定，结果如表1所示。表1中各物质的含量均指的是其占莫代尔纤维总质量的百分比。
表1氨基酸与金属元素含量(％)
Figure PCTCN2021094789-appb-000001
以实施例3为例说明本发明的防伪方法：
在防伪莫代尔纤维制备之前，按照配方设计，预先对氨基酸和金属元素进行编码，Cu 2+用字母C代表，Fe 3+用字母F代表，络氨酸、赖氨酸、亮氨酸和缬氨酸分别用数字1、2、3、4代表，将金属元素编码排列于氨基酸编码前面，同时按照含量大小进行排序，量大的排在前列。因此，实施例3为制备目标编码为FC4123的防伪莫代尔纤维。
用户获得莫代尔纤维制品和纤维的目标编码，并对获得的莫代尔纤维进行解密。解密时根据上文检测方法检测氨基酸种类及含量、金属元素种类及含量，根据表1中纺丝后实测值 则可得实施例3中检测出的防伪编码为FC4123，将其与目标编码对比，二者编码相同，则说明用户得到了所需的目标纤维。根据以上原理验证实施例1、2，实施例1、2的防伪编码准确性同实施例3一致，均具有极高准确性。
由于实施例1制得的防伪莫代尔纤维含有同一种金属离子和不同的氨基酸，其加密编码加密性高防伪力度大，易分辨，可根据防伪编码追踪纤维来源。而实施例2制得防伪莫代尔纤维采用单一种类氨基酸制备氨基酸金属螯合物为莫代尔纤维加密，具有加密效果但加密强度不足，密码简单易被复制，追踪效果也会大大降低，误差概率大。实施例3在莫代尔纺丝原液中添加两种金属离子的氨基酸螯合物进行加密，配合多种氨基酸编码加密，可获得难破译的防伪编码，相较与实施例1的单一金属元素的加密，多种金属元素的加密防伪效果大大增强。
另外，测试本发明的方法对莫代尔纤维的力学性能的影响，结果如表2所示。
表2莫代尔纤维断裂强度与断裂伸长率
Figure PCTCN2021094789-appb-000002
根据GB/T 14337-2008化学纤维短纤维拉伸性能试验方法，使用纤维断裂强度试验机对实施例1、2、3所制备的莫代尔纤维以及常规莫代尔纤维进行断裂强度与断裂伸长率进行测试，对比各实施例的测试结果，氨基酸和金属元素的含量与种类变化对莫代尔纤维的力学性能影响微小，不会造成莫代尔纤维力学性能的巨大波动。
以上仅是本发明的优选实施方式，并不用于限制本发明，应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明技术原理的前提下，还可以做出若干改进和变型，这些改进和变型也应视为本发明的保护范围。

Claims (10)

  1. 氨基酸金属螯合物作为防伪莫代尔纤维的防伪追踪剂的应用。
  2. 一种防伪莫代尔纤维的制备方法，其特征在于，包括以下步骤：
    (1)将浆粕原液与纤维素催化剂混合后进行碱化处理、老成处理以及磺化处理，处理后溶于碱溶液，得到处理液；
    (2)将所述处理液与多种氨基酸金属螯合物混匀，经过滤、脱泡和熟成处理后制得纺丝原液；然后将所述纺丝原液与纺丝浴添加剂混匀后进行湿法纺丝，后加工得到所述防伪莫代尔纤维；其中，所述氨基酸金属螯合物占所述纺丝原液质量分数的0.5％-1.5％。
  3. 根据权利要求2所述的制备方法，其特征在于：在步骤(1)中，所述纤维素催化剂为JL-EBZ；所述纤维素催化剂占浆粕原液质量分数的0.3％-1.8％。
  4. 根据权利要求2所述的制备方法，其特征在于：在步骤(1)中，所述浆粕原液为聚合度≥850，且甲基纤维素含量≥92％的浆粕。
  5. 根据权利要求2所述的制备方法，其特征在于：在步骤(2)中，所述氨基酸金属螯合物包括氨基酸以及与所述氨基酸螯合的金属离子，所述氨基酸与金属离子的摩尔比为2-3:1。
  6. 根据权利要求5所述的制备方法，其特征在于：所述氨基酸选自络氨酸、赖氨酸、亮氨酸、缬氨酸和苯丙氨酸中的一种或几种；所述金属离子选自铜、钙和铁离子中的一种或几种。
  7. 根据权利要求2所述的制备方法，其特征在于：在步骤(2)中，所述纺丝浴添加剂为JL-FS；所述纺丝浴添加剂占所述纺丝原液质量分数的0.1％-0.25％。
  8. 根据权利要求2所述的制备方法，其特征在于：在步骤(2)中，湿法纺丝采用低速纺丝，纺丝速度为28-33m/min，凝固浴中高倍牵伸，总牵伸率为75％-85％，后加工中低倍牵伸，总牵伸率为20％-30％。
  9. 一种权利要求2-8中任一项所述的制备方法所制备的防伪莫代尔纤维，其特征在于，包括莫代尔纤维以及分布于所述莫代尔纤维中的多种氨基酸金属螯合物，所述氨基酸金属螯合物占所述防伪莫代尔纤维总质量的0.5％-1.5％。
  10. 一种权利要求9所述的防伪莫代尔纤维的防伪方法，其特征在于，包括加密步骤和解密、鉴别步骤：
    所述加密步骤包括：根据氨基酸金属螯合物的类型和用量，对防伪莫代尔纤维进行编码，发出加密信息；
    所述解密、鉴别步骤包括：获得加密信息，并测试莫代尔纤维中的氨基酸和金属离子的 类型和用量；然后与获得的加密信息比较，鉴别莫代尔纤维的真伪。
PCT/CN2021/094789 2020-11-11 2021-05-20 防伪莫代尔纤维、制备方法及防伪方法 WO2022100052A1 (zh)

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