CN112064129A - Anti-counterfeiting chemical fiber and preparation method thereof - Google Patents
Anti-counterfeiting chemical fiber and preparation method thereof Download PDFInfo
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- CN112064129A CN112064129A CN201910501211.6A CN201910501211A CN112064129A CN 112064129 A CN112064129 A CN 112064129A CN 201910501211 A CN201910501211 A CN 201910501211A CN 112064129 A CN112064129 A CN 112064129A
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- 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
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- 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
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
- D01F6/90—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyamides
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- 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
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
- D01F6/92—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyesters
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Abstract
The invention discloses an anti-counterfeiting chemical fiber, which comprises raw materials of fiber-forming high polymer and element mother liquor, wherein the element mother liquor comprises a biological derived oil carrier, an anti-counterfeiting tracking agent and a dispersing agent, the anti-counterfeiting tracking agent is composed of at least two metal oxides, the metal element content of each metal oxide is controlled to have a fixed feeding mass ratio, and the metal oxides are zinc oxide, molybdenum trioxide, zirconium dioxide, aluminum oxide, calcium oxide, strontium oxide, germanium dioxide or vanadium pentoxide; the sum of the metal element contents of the various metal oxides accounts for 5-50% of the element mother liquor by mass percentage, and the sum of the metal element contents of the various metal oxides is controlled to account for 0.1-1 per mill of the anti-counterfeiting chemical fiber; the anti-counterfeiting chemical fiber disclosed by the invention has the advantages of memory tracking property, recognition function, high anti-counterfeiting strength and good anti-counterfeiting concealment property.
Description
Technical Field
The invention belongs to the field of chemical fibers with an anti-counterfeiting function, and particularly relates to an anti-counterfeiting chemical fiber and a preparation method thereof.
Background
As a common anti-counterfeiting technical means, the anti-counterfeiting chemical fiber is widely applied to the fields of securities, banknotes, passports and the like. At present, the anti-counterfeiting chemical fiber mainly takes monochromatic light fluorescent fiber as a main component, and products such as double-waveband fluorescent fiber, multi-waveband dyed fiber, photochromic, infrared absorption anti-counterfeiting and the like also appear in succession, for example, Chinese patents CN2731620Y, CN103850144B and CN 104963241B. With continuous progress of science and technology, the single-color fluorescent fiber and the double-waveband fluorescent fiber have single anti-counterfeiting characteristics and are easy to forge, and the anti-counterfeiting strength of the single-color fluorescent fiber and the double-waveband fluorescent fiber cannot adapt to high-end security fields such as currency notes, passports and the like; the stability of the multi-color section dyed fiber is poor, the fiber is colored fluorescent fiber, the concealment of the anti-counterfeiting characteristic is poor, and the fiber is not suitable for high-end security fields such as bank notes, passports and the like; photochromism and infrared absorption are easy to forge and are easy to be interfered by other substances.
At present, a preparation method of labeled cellulose fiber-CN 101942707B is also proposed, which discloses a dispersion liquid added in the preparation process of cellulose fiber, wherein the dispersion liquid comprises a metal inorganic compound, a dispersant and water, and the dispersant is fatty alcohol polyoxyethylene phosphate, sodium hexametaphosphate, nonylphenol polyoxyethylene ether, sodium polyacrylate or sodium butylnaphthalene sulfonate; comparing the remaining amount and the added amount of the metal inorganic compound in the fiber to judge and distinguish and identify the textile; on one hand, the anti-counterfeiting liquid has the defect of insufficient anti-counterfeiting strength, is easy to imitate and counterfeit and is difficult to have the memory tracing property, and on the other hand, the mentioned dispersion liquid is only suitable for preparing cellulose fibers and is difficult to apply to the anti-counterfeiting of chemical fibers.
Therefore, the development of chemical fibers with higher anti-counterfeiting safety performance has excellent practical significance for the anti-counterfeiting of the chemical fibers and textiles made of the chemical fibers.
Disclosure of Invention
The invention aims to solve the technical problem of overcoming the defects in the prior art and provide the anti-counterfeiting chemical fiber which has both memory tracking property and recognition function and high anti-counterfeiting strength.
The invention also provides a preparation method of the anti-counterfeiting chemical fiber.
In order to solve the technical problems, the invention adopts a technical scheme as follows:
an anti-counterfeiting chemical fiber is prepared from fiber-forming high polymer and element mother liquor, wherein the element mother liquor contains a biologically-derived oil carrier, an anti-counterfeiting tracking agent and a dispersing agent, the anti-counterfeiting tracking agent is composed of at least two metal oxides, the metal element content of each metal oxide is controlled to have a fixed feeding mass ratio, and the metal oxides are zinc oxide, molybdenum trioxide, zirconium dioxide, aluminum oxide, calcium oxide, strontium oxide, germanium dioxide or vanadium pentoxide; the sum of the metal element contents of the metal oxides accounts for 5-50% of the element mother liquor by mass percentage, and the sum of the metal element contents of the metal oxides is controlled to account for 0.1-1% of the anti-counterfeiting chemical fiber.
According to some specific aspects of the present invention, the anti-counterfeiting tracking agent is composed of zinc oxide, zirconium dioxide and aluminum oxide; or the anti-counterfeiting tracking agent consists of zinc oxide, zirconium dioxide, aluminum oxide and calcium oxide; or the anti-counterfeiting tracking agent consists of zinc oxide, zirconium dioxide, vanadium pentoxide and germanium dioxide; or the anti-counterfeiting tracking agent is composed of zinc oxide, molybdenum trioxide, zirconium dioxide and aluminum oxide; or the anti-counterfeiting tracking agent consists of molybdenum trioxide, zirconium dioxide, aluminum oxide and calcium oxide; or the anti-counterfeiting tracking agent consists of zirconium dioxide, aluminum oxide, calcium oxide and strontium oxide; or the anti-counterfeiting tracking agent consists of zirconium dioxide, aluminum oxide, calcium oxide and strontium oxide; or the anti-counterfeiting tracking agent consists of zinc oxide, aluminum oxide and strontium oxide; or the anti-counterfeiting tracking agent is composed of zinc oxide, molybdenum trioxide and strontium oxide; or the anti-counterfeiting tracking agent is composed of zirconium dioxide, aluminum oxide, calcium oxide, strontium oxide and germanium dioxide; or the anti-counterfeiting tracking agent is composed of zinc oxide, molybdenum trioxide, zirconium dioxide, aluminum oxide, calcium oxide, strontium oxide, germanium dioxide and vanadium pentoxide; and so on.
According to some preferred aspects of the present invention, the anti-counterfeiting tracking agent comprises at least one of strontium oxide, aluminum trioxide and zinc oxide, more preferably comprises two of strontium oxide, aluminum trioxide and zinc oxide, and even more preferably comprises at least three metal oxides of strontium oxide, aluminum trioxide and zinc oxide.
According to the invention, the fixed feeding mass ratio in the step of controlling the fixed feeding mass ratio between the metal element contents of the various metal oxides can be any ratio, and only one ratio is determined before preparation, for example, when the anti-counterfeiting tracking agent consists of two kinds, the ratio of the two metal oxides can be 1: 1, 1: 2, 1: 3, 2: 5, 3: 2, 4: 5, 7: 3, 8: 3, 2.3: 7, 1.1: 1 and the like; for example, when the anti-counterfeiting tracking agent is composed of three metal oxides, the ratio of the three metal oxides can be 1: 1, 1: 2: 1, 1: 3: 6, 2: 3: 5, 1: 4: 5, 1: 3: 1, 1: 2, 1: 2.1: 1, etc.; for example, when the anti-counterfeiting tracking agent is composed of four kinds, the ratio of the four metal oxides can be 1: 1, can be 1: 2: 1, can be 1: 3: 1: 5, can be 1: 4: 5, can be 1: 3: 6: 10, and the like; for example, when the anti-counterfeiting tracking agent is composed of five metal oxides, the ratio of the five metal oxides can be 1: 1, can be 1: 2: 1, can be 1: 3: 1: 2: 1, can be 1: 5: 4: 1, can be 1: 4: 2: 3: 5, can be 1: 3: 6: 2: 8, and the like. Furthermore, when the element mother liquor containing the above proportions is applied to the chemical fibers, each chemical fiber can be endowed with a combination sequence for encryption, the combination sequences are enough, different chemical fibers can be coded, and when various metal oxides are contained, when the specific metal elements are unknown, the most appropriate acid is not easy to select for dissolving out all the metal elements contained in the chemical fibers, so that the measurement result is inaccurate, and the imitation is not easy; further, when a plurality of metal oxides exist simultaneously, all metal elements contained in the chemical fiber cannot be well dissolved out by adopting conventional single acid, so that the measurement result is inaccurate, and the content ratio of each element is more difficult to determine, so that counterfeiters are not easy to counterfeit, and the anti-counterfeiting strength and safety are further improved.
According to some specific aspects of the invention, the fiber-forming polymer is a combination of one or more selected from the group consisting of polyethylene terephthalate (PET), polylactic acid (PLA), Polycaprolactone (PCL), recycled PET, polybutylene succinate (PBS), copolymer of 3-hydroxybutyrate and 3-hydroxyvalerate (PHBV), polybutylene terephthalate (PBAT), Polyethylene (PE), polypropylene (PP), Polystyrene (PS), Polyamide (PA), polyvinyl chloride and polyurethane.
According to some preferred aspects of the invention, the bio-derived oil carrier has a flash point of 230-320 ℃.
According to some preferred aspects of the invention, the bio-derived oil carrier has a density of 0.91 to 0.95 g/mL.
According to some specific and preferred aspects of the present invention, the biologically-derived oil carrier is a combination of one or more selected from the group consisting of linseed oil, olive oil, grapeseed oil, corn oil, castor oil, sesame oil, soybean oil and sunflower oil. The biological derived oil carrier selected by the definition can ensure that the metal oxide is dispersed more uniformly, is suitable for the preparation process of chemical fibers, and has better effect compared with other oil carriers.
According to some preferred aspects of the invention, the dispersant is polyacrylamide or polyethylene glycol having a molecular weight of 400-2000 or a mixture of both.
According to some preferred aspects of the invention, the elemental mother liquor comprises at least three metal oxides, and further preferably comprises at least four metal oxides.
According to some preferred aspects of the present invention, the metal oxide has an average particle size of 200-750 nm.
According to some preferred aspects of the present invention, the sum of the contents of the metal elements contained in the respective metal oxides is 10 to 40% by mass of the element mother liquor.
According to some preferred aspects of the present invention, the sum of the metal element contents of the metal oxides is controlled to be 0.5 to 1 per mill of the security chemical fiber.
According to some specific and preferred aspects of the present invention, the bio-derived oil carrier accounts for 30-70% by mass of the element mother liquor.
According to some specific and preferred aspects of the present invention, the dispersant accounts for 1 to 8% by mass of the element mother liquor.
According to some specific aspects of the invention, the element mother liquor further comprises 1-6% of antioxidant and 1-6% of coupling agent by mass percentage, wherein the antioxidant is antioxidant B215 of Swiss soda; the coupling agent is Japanese Beacon KBM 403.
The invention provides another technical scheme that: the preparation method of the anti-counterfeiting chemical fiber comprises the following steps:
(1) preparing an element mother solution: (a) weighing each component in the element mother solution according to the formula amount; (b) mixing the anti-counterfeiting tracking agent weighed in the step (1) with a dispersing agent, adding the mixture into a bio-derived oil carrier, stirring and kneading to prepare the element mother solution;
(2) preparing anti-counterfeiting chemical fiber: and (2) weighing the fiber-forming high polymer and the element mother liquor prepared in the step (1) according to the formula ratio, injecting the element mother liquor with the formula amount into molten liquid of the fiber-forming high polymer in a mixing section, and carrying out melt extrusion and spinning to obtain the anti-counterfeiting chemical fiber.
According to some specific and preferred aspects of the invention, the metal oxide is preferentially added to the bio-derived oil carrier in a lighter weight, i.e. less dense.
In the present invention, the metal oxide to be added is preferably high in purity, and interference of impurities is reduced.
Due to the adoption of the technical scheme, compared with the prior art, the invention has the following advantages:
the anti-counterfeiting chemical fiber adopts the element mother liquor formed by adding a plurality of specific metal elements with fixed feeding proportion into a biological derived oil carrier serving as a dispersion system, and on one hand, the element mother liquor can be added in the melt spinning process of the anti-counterfeiting chemical fiber in the form of the mother liquor, so that the dispersibility, uniformity and compatibility of the metal elements in a high polymer are improved, the processing difficulty and processing cost are reduced, the influence of the added metal elements on the performance of the fiber is avoided, and the problems of difficult dispersion, difficult processing, non-uniformity and the like caused by directly adding oxides of the metal elements in the spinning process of the chemical fiber are also avoided; on the other hand, the element mother liquor adopted by the invention has a plurality of specific metal elements with fixed feeding proportion, can endow the chemical fiber with a sequence combination which is difficult to crack, and increases the anti-counterfeiting strength, and meanwhile, the specific metal elements can not damage the performance of the fiber, thereby increasing the anti-counterfeiting concealment, so that the anti-counterfeiting chemical fiber disclosed by the invention has the advantages of memory tracking property, recognition function, high anti-counterfeiting strength and good anti-counterfeiting concealment.
Detailed Description
The above-described scheme is further illustrated below with reference to specific examples; it is to be understood that these embodiments are provided to illustrate the general principles, essential features and advantages of the present invention, and the present invention is not limited in scope by the following embodiments; the implementation conditions used in the examples can be further adjusted according to specific requirements, and the implementation conditions not indicated are generally the conditions in routine experiments.
In the following, all starting materials are essentially obtained commercially or prepared by conventional methods in the art, unless otherwise specified.
The metal oxide is selected from the following: the average grain diameters of zinc oxide, zirconium dioxide, aluminum oxide, calcium oxide, vanadium pentoxide, germanium dioxide and strontium oxide are respectively 350 +/-30 nm, and the purities are all higher than 99.999%; the antioxidant in the examples below is antioxidant B215 from Ciba, Switzerland and the coupling agent is KBM403 from Nippon.
EXAMPLE 1 preparation of elemental mother liquors suitable for use in security chemical fibres
The embodiment provides an element mother solution suitable for anti-counterfeiting chemical fibers, which comprises, by mass, 41.03 parts of soybean oil, 7.47 parts of zinc oxide (6 parts of zinc element content), 12.15 parts of zirconium dioxide (9 parts of zirconium element content), 28.35 parts of aluminum oxide (15 parts of aluminum element content), 4008 parts of polyethylene glycol and 3 parts of antioxidant; wherein the ratio of zinc element to zirconium element to aluminum element is 6: 9: 15= 2: 3: 5;
the preparation method comprises the following steps:
(1) weighing each component in the element mother solution according to the formula amount;
(2) and (2) mixing the zinc oxide, the zirconium dioxide, the aluminum oxide and the polyethylene glycol 400 weighed in the step (1), adding the mixture into soybean oil, adding an antioxidant, and kneading the mixture in a kneader to obtain the element mother liquor suitable for the anti-counterfeiting chemical fiber.
EXAMPLE 2 preparation of elemental mother liquors suitable for use in security chemical fibres
The embodiment provides an element mother solution suitable for anti-counterfeiting chemical fibers, which comprises 42.02 parts of sunflower seed oil, 4.98 parts of zinc oxide (with the content of 4 zinc elements), 8.10 parts of zirconium dioxide (with the content of 6 zirconium elements), 18.90 parts of aluminum oxide (with the content of 10 aluminum elements), 14 parts of calcium oxide (with the content of 10 calcium elements), 10006 parts of polyethylene glycol, 3 parts of an antioxidant and 3 parts of a coupling agent in parts by mass; wherein, the ratio of zinc element to zirconium element to aluminum element to calcium element is = 4: 6: 10= 2: 3: 5;
the preparation method comprises the following steps:
(1) weighing each component in the element mother solution according to the formula amount;
(2) and (2) mixing the zinc oxide, the zirconium dioxide, the aluminum oxide, the calcium oxide and the polyethylene glycol 1000 weighed in the step (1), adding the mixture into sunflower seed oil, adding an antioxidant and a coupling agent, and kneading the mixture in a kneading machine to obtain the element mother liquor suitable for the anti-counterfeiting chemical fiber.
EXAMPLE 3 preparation of elemental mother liquors suitable for use in security chemical fibres
The embodiment provides an element mother solution suitable for anti-counterfeiting chemical fibers, which comprises, by mass, 63.59 parts of corn oil, 1.24 parts of zinc oxide (zinc element content is 1 part), 4.05 parts of zirconium dioxide (zirconium element content is 3 parts), 10.71 parts of vanadium pentoxide (vanadium element content is 6 parts), 14.41 parts of germanium dioxide (germanium element content is 10 parts), and 10006 parts of polyethylene glycol; wherein the ratio of zinc element content to zirconium element content to vanadium element content to germanium element content is = 1: 3: 6: 10;
the preparation method comprises the following steps:
(1) weighing each component in the element mother solution according to the formula amount;
(2) and (2) mixing the zinc oxide, the zirconium dioxide, the vanadium pentoxide, the germanium dioxide and the polyethylene glycol 1000 weighed in the step (1), adding the mixture into corn oil, and kneading the mixture in a kneader to obtain the element mother liquor suitable for the anti-counterfeiting chemical fibers.
EXAMPLE 4 preparation of elemental mother liquors suitable for use in security chemical fibres
The embodiment provides an element mother solution suitable for anti-counterfeiting chemical fibers, which comprises 46.69 parts of corn oil, 1.24 parts of zinc oxide (with the content of 1 part of zinc element), 9.45 parts of aluminum oxide (with the content of 5 parts of aluminum element), 7.1 parts of strontium oxide (with the content of 6 parts of strontium element), 11.52 parts of germanium dioxide (with the content of 8 parts of germanium element), 6 parts of polyethylene glycol 4006 parts and 4 parts of antioxidant by mass; wherein the ratio of zinc element to aluminum element to strontium element to germanium element is 1: 5: 6: 8;
the preparation method comprises the following steps:
(1) weighing each component in the element mother solution according to the formula amount;
(2) and (2) mixing the zinc oxide, aluminum oxide, strontium oxide, germanium dioxide and polyethylene glycol 400 weighed in the step (1), adding the mixture into corn oil, adding an antioxidant, and kneading the mixture in a kneading machine to obtain the element mother liquor suitable for the anti-counterfeiting chemical fiber.
EXAMPLE 5 preparation of anti-counterfeiting chemical fiber
The embodiment provides an anti-counterfeiting chemical fiber which comprises the following raw materials in parts by mass: 99.7 parts of polyethylene terephthalate and 0.3 part of the element mother liquor prepared in example 1.
The preparation method comprises the following steps: weighing the polyethylene glycol terephthalate and the element mother liquor prepared in the example 1 according to the formula ratio, continuously injecting the element mother liquor with the formula amount into the molten polyethylene glycol terephthalate in a mixing section, and carrying out melt extrusion and spinning to obtain the anti-counterfeiting chemical fiber.
EXAMPLE 6 preparation of anti-counterfeiting chemical fiber
The embodiment provides an anti-counterfeiting chemical fiber which comprises the following raw materials in parts by mass: 99.8 parts of regenerated polyethylene terephthalate and 0.2 part of the element mother liquor prepared in example 2.
The preparation method comprises the following steps: weighing the regenerated polyethylene glycol terephthalate and the element mother liquor prepared in the example 2 according to the formula proportion, continuously injecting the element mother liquor with the formula amount into the molten polyethylene glycol terephthalate in a mixing section, and carrying out melt extrusion and spinning to obtain the anti-counterfeiting chemical fiber.
EXAMPLE 7 preparation of security chemical fibers
The embodiment provides an anti-counterfeiting chemical fiber which comprises the following raw materials in parts by mass: 99.6 parts of polylactic acid and 0.4 part of the element mother liquor prepared in example 3.
The preparation method comprises the following steps: and weighing the polylactic acid and the element mother liquor prepared in the embodiment 3 according to the formula proportion, continuously injecting the element mother liquor with the formula amount into the molten polyethylene in a mixing section, and carrying out melt extrusion and spinning to obtain the anti-counterfeiting chemical fiber.
EXAMPLE 8 preparation of anti-counterfeiting chemical fiber
The embodiment provides an anti-counterfeiting chemical fiber which comprises the following raw materials in parts by mass: 99.5 parts of polyamide and 0.5 part of element mother liquor prepared in example 4.
The preparation method comprises the following steps: and weighing the polyamide and the element mother liquor prepared in the example 4 according to the formula ratio, continuously injecting the element mother liquor with the formula amount into the molten polyethylene in a mixing section, and carrying out melt extrusion and spinning to obtain the anti-counterfeiting chemical fiber.
Comparative example
Basically, the method is the same as the method in example 8, except that: the raw material is not added with element mother liquor.
The various acids used in the following are analytically pure.
EXAMPLE 9 detection of Security chemical fibers
The anti-counterfeiting chemical fiber prepared in the embodiment 5 is detected according to the following method, and the specific detection method comprises the following steps:
(1) sampling at multiple points, and adding 0.1g of the obtained anti-counterfeiting chemical fiber sample into 10mL of mixed acid solution (the volume ratio of hydrochloric acid to hydrofluoric acid to sulfuric acid is 2: 1) to obtain premix;
(2) digesting the premix obtained in the step (1) in a digestion instrument, wherein the digestion temperature is changed by heating the room temperature to 25 ℃ to 150 ℃, heating the room temperature to 200 ℃ again and keeping the room temperature for 30 minutes; evaporating the solution after the digestion at 130 +/-5 ℃ for 3h for acid-expelling treatment, and carrying out constant volume to obtain 10mL of constant volume solution;
(3) and (3) carrying out element quantitative analysis on the constant volume solution obtained in the step (2) by using an inductively coupled plasma spectrometer, and measuring that the content of zinc element is 17.874ppm (g), the content of zirconium element is 26.325ppm (g), the content of aluminum element is 44.550ppm (g), the content of iron element is 0.003ppm (g), and the content of magnesium element is 0.005ppm (g), so that the content of zinc element, the content of zirconium element and the content of aluminum element are = 5.958: 8.775: 14.850.
EXAMPLE 10 detection of Security chemical fibers
The anti-counterfeiting chemical fiber prepared in the embodiment 6 is detected according to the following method, and the specific detection method comprises the following steps:
(1) sampling at multiple points, and adding 0.1g of the obtained anti-counterfeiting chemical fiber sample into 10mL of mixed acid solution (hydrochloric acid, hydrofluoric acid, sulfuric acid and nitric acid in a volume ratio of 2: 1: 2) to obtain premix;
(2) digesting the premix obtained in the step (1) in a digestion instrument, wherein the temperature change process of digestion is that the room temperature is 25 ℃ and the temperature is raised to 150 ℃, the temperature is raised to 190 ℃ again, and the temperature is kept for 30 minutes; evaporating the solution after the digestion at 130 +/-5 ℃ for 3h for acid-expelling treatment, and carrying out constant volume to obtain 10mL of constant volume solution;
(3) and (3) carrying out element quantitative analysis on the constant volume solution obtained in the step (2) by using an inductively coupled plasma spectrometer, and measuring that the content of zinc element is 7.960ppm (g), the content of zirconium element is 11.676ppm (g), the content of aluminum element is 19.880ppm (g), the content of calcium element is 19.600ppm (g), the content of iron element is 0.001ppm (g), the content of iron element is 0.002ppm (g), and the content of sodium element is 0.003ppm (g), so that the content of zinc element, the content of zirconium element, the content of aluminum element and the content of calcium element are = 3.980: 5.838: 9.940: 9.800.
EXAMPLE 11 detection of Security chemical fibers
The anti-counterfeiting chemical fiber prepared in the embodiment 7 is detected according to the following method, and the specific detection method comprises the following steps:
(1) sampling at multiple points, and adding 0.1g of the obtained anti-counterfeiting chemical fiber sample into 10mL of mixed acid solution (hydrochloric acid, fluoroboric acid, sulfuric acid and nitric acid in a volume ratio of 3: 1: 2) to obtain premix;
(2) digesting the premix obtained in the step (1) in a digestion instrument, wherein the digestion temperature is changed by heating the room temperature to 25 ℃ to 150 ℃, heating the room temperature to 200 ℃ again and keeping the room temperature for 30 minutes; evaporating the solution after the digestion at 130 +/-5 ℃ for 3h for acid-expelling treatment, and carrying out constant volume to obtain 10mL of constant volume solution;
(3) and (3) carrying out element quantitative analysis on the constant volume solution obtained in the step (2) by using an inductively coupled plasma spectrometer, and measuring that the content of zinc is 3.968ppm (g), the content of zirconium is 11.664ppm (g), the content of vanadium is 23.256ppm (g), the content of germanium is 39.120ppm (g), the content of iron is 0.004ppm (g), and the content of sodium is 0.003ppm (g), so that the content of zinc, zirconium, vanadium and germanium is = 0.992: 2.916: 5.814: 9.780.
EXAMPLE 12 detection of Security chemical fibers
The anti-counterfeiting chemical fiber prepared in the embodiment 8 is detected according to the following method, and the specific detection method comprises the following steps:
(1) sampling at multiple points, and adding 0.1g of the obtained anti-counterfeiting chemical fiber sample into 10mL of mixed acid solution (hydrochloric acid, hydrofluoric acid, sulfuric acid and nitric acid in a volume ratio of 2: 1: 3) to obtain premix;
(2) digesting the premix obtained in the step (1) in a digestion instrument, wherein the digestion temperature is changed by raising the temperature to 150 ℃ at the room temperature of 25 ℃, raising the temperature to 185 ℃ again and keeping the temperature for 35 minutes; evaporating the solution after the digestion at 130 +/-5 ℃ for 3h for acid-expelling treatment, and carrying out constant volume to obtain 10mL of constant volume solution;
(3) and (3) carrying out element quantitative analysis on the constant volume solution obtained in the step (2) by using an inductively coupled plasma spectrometer, and measuring that the content of zinc element is 4.960ppm (g), the content of aluminum element is 24.825ppm (g), the content of strontium element is 29.790ppm (g), the content of germanium element is 39.080ppm (g), the content of iron element is 0.002ppm (g), the content of magnesium element is 0.003ppm (g), and the content of sodium element is 0.003ppm (g), so that the content of zinc element, the content of aluminum element, the content of strontium element and the content of germanium element are = 0.992: 4.965: 5.958: 7.816.
EXAMPLE 13 detection of chemical fibers
The chemical fiber prepared by the comparative example is detected according to the following method, and the specific detection method comprises the following steps:
(1) sampling at multiple points, and adding 0.1g of the obtained chemical fiber sample into 10mL of mixed acid solution (hydrochloric acid, hydrofluoric acid, sulfuric acid and nitric acid according to the volume ratio of 2: 1: 3) to obtain premix;
(2) digesting the premix obtained in the step (1) in a digestion instrument, wherein the digestion temperature is changed by raising the temperature to 150 ℃ at the room temperature of 25 ℃, raising the temperature to 185 ℃ again and keeping the temperature for 35 minutes; evaporating the solution after the digestion at 130 +/-5 ℃ for 3h for acid-expelling treatment, and carrying out constant volume to obtain 10mL of constant volume solution;
(3) and (3) carrying out element quantitative analysis on the constant volume solution obtained in the step (2) by using an inductively coupled plasma spectrometer, wherein the content of iron element is 0.002ppm (g), the content of magnesium element is 0.003ppm (g), and the content of sodium element is 0.003ppm (g).
The embodiment shows that the metal oxides in the specific combination mode are prepared into the mother solution and added into the preparation of the chemical fiber, the detection result shows that the content ratio of each specific metal oxide is almost the same as the input amount ratio, the detected content phase difference value belongs to the part lost in the experimental error or the preparation process, but the loss amount is very small, and the judgment and identification of the chemical fiber are not influenced, the combination obviously endows the chemical fiber with the sequence combination which is difficult to crack, the anti-counterfeiting force is increased, meanwhile, the specific metal elements do not damage the performance of the fiber, and the anti-counterfeiting concealment is increased, so that the element mother solution can endow the chemical fiber with the advantages of memory tracking property and identification function, high anti-counterfeiting force and good anti-counterfeiting concealment; the detection results of the comparative example further prove that the sequence combination of the invention is not interfered by the conventional textile technology in the prior art, and the anti-counterfeiting performance is reliable.
The above embodiments are merely illustrative of the technical concept and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the content of the present invention and implement the invention, and not to limit the scope of the invention, and all equivalent changes or modifications made according to the spirit of the present invention should be covered by the scope of the present invention.
Claims (10)
1. The anti-counterfeiting chemical fiber is characterized in that raw materials of the anti-counterfeiting chemical fiber comprise a fiber-forming high polymer and an element mother solution, wherein the element mother solution comprises a biological derived oil carrier, an anti-counterfeiting tracking agent and a dispersing agent, the anti-counterfeiting tracking agent is composed of at least two metal oxides, the fixed feeding mass ratio is controlled among the metal element contents of the metal oxides, and the metal oxides are zinc oxide, molybdenum trioxide, zirconium dioxide, aluminum oxide, calcium oxide, strontium oxide, germanium dioxide or vanadium pentoxide; the sum of the metal element contents of the metal oxides accounts for 5-50% of the element mother liquor by mass percentage, and the sum of the metal element contents of the metal oxides is controlled to account for 0.1-1% of the anti-counterfeiting chemical fiber.
2. The chemical fiber of claim 1, wherein the fiber-forming polymer is a combination of one or more selected from the group consisting of polyethylene terephthalate, polylactic acid, polycaprolactone, recycled PET, polybutylene succinate, a copolymer of 3-hydroxybutyrate and 3-hydroxyvalerate, polybutylene terephthalate, polyethylene, polypropylene, polystyrene, polyamide, polyvinyl chloride, and polyurethane.
3. The anti-counterfeiting chemical fiber according to claim 1, wherein the flash point of the bio-derived oil carrier is 230-320 ℃.
4. The anti-counterfeiting chemical fiber according to claim 3, wherein the bio-derived oil carrier has a density of 0.91 to 0.95 g/mL.
5. The anti-counterfeiting chemical fiber according to claim 1, 3 or 4, wherein the biologically-derived oil carrier is a combination of one or more selected from the group consisting of linseed oil, olive oil, grapeseed oil, corn oil, castor oil, sesame oil, soybean oil and sunflower oil.
6. The anti-counterfeiting chemical fiber as claimed in claim 1, wherein the dispersant is polyacrylamide or polyethylene glycol with molecular weight of 400-2000 or a mixture of the two.
7. The security chemical fiber according to claim 1, wherein the elemental mother liquor comprises at least three metal oxides, further preferably at least four metal oxides; and/or the average particle size of the metal oxide is 200-750 nm.
8. The anti-counterfeiting chemical fiber according to claim 1, wherein the sum of the contents of metal elements contained in the metal oxides accounts for 10-40% of the element mother solution in percentage by mass; and/or controlling the sum of the metal element contents of the metal oxides to be 0.5-1 per mill of the anti-counterfeiting chemical fiber in percentage by mass.
9. The anti-counterfeiting chemical fiber according to claim 1, wherein the biological-derived oil carrier accounts for 30-70% of the element mother liquor by mass percent; and/or the dispersant accounts for 1-8% of the element mother liquor by mass percentage.
10. A method for preparing a security chemical fiber according to any one of claims 1 to 9, comprising the steps of:
(1) preparing an element mother solution: (a) weighing each component in the element mother solution according to the formula amount; (b) mixing the anti-counterfeiting tracking agent weighed in the step (1) with a dispersing agent, adding the mixture into a bio-derived oil carrier, stirring and kneading to prepare the element mother solution;
(2) preparing anti-counterfeiting chemical fiber: and (2) weighing the fiber-forming high polymer and the element mother liquor prepared in the step (1) according to the formula ratio, injecting the element mother liquor with the formula amount into molten liquid of the fiber-forming high polymer in a mixing section, and carrying out melt extrusion and spinning to obtain the anti-counterfeiting chemical fiber.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201910501211.6A CN112064129A (en) | 2019-06-11 | 2019-06-11 | Anti-counterfeiting chemical fiber and preparation method thereof |
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| CN201910501211.6A CN112064129A (en) | 2019-06-11 | 2019-06-11 | Anti-counterfeiting chemical fiber and preparation method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113913965A (en) * | 2021-12-03 | 2022-01-11 | 上海纳米技术及应用国家工程研究中心有限公司 | Degradable polyester fiber and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20150377841A1 (en) * | 2014-06-27 | 2015-12-31 | Eastman Chemical Company | Fibers with chemical markers and physical features used for coding |
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2019
- 2019-06-11 CN CN201910501211.6A patent/CN112064129A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20150377841A1 (en) * | 2014-06-27 | 2015-12-31 | Eastman Chemical Company | Fibers with chemical markers and physical features used for coding |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113913965A (en) * | 2021-12-03 | 2022-01-11 | 上海纳米技术及应用国家工程研究中心有限公司 | Degradable polyester fiber and preparation method thereof |
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