CN112063122A - Element master batch suitable for anti-counterfeiting chemical fiber and preparation method thereof - Google Patents
Element master batch suitable for anti-counterfeiting chemical fiber and preparation method thereof Download PDFInfo
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- CN112063122A CN112063122A CN201910501205.0A CN201910501205A CN112063122A CN 112063122 A CN112063122 A CN 112063122A CN 201910501205 A CN201910501205 A CN 201910501205A CN 112063122 A CN112063122 A CN 112063122A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
- C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
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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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2423/04—Homopolymers or copolymers of ethene
- C08J2423/06—Polyethene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2467/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
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- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2244—Oxides; Hydroxides of metals of zirconium
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
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Abstract
The invention discloses an element master batch suitable for anti-counterfeiting chemical fibers, which comprises a matrix high polymer, an anti-counterfeiting tracking agent and a polyolefin dispersing agent, wherein 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 proportion, and the metal oxide compound is zinc oxide, molybdenum trioxide, zirconium dioxide, aluminum oxide, calcium oxide, strontium oxide, germanium dioxide or vanadium pentoxide; the sum of the contents of metal elements contained in the various metal oxides accounts for 5-50% of the element master batch by mass percentage; the element master batch disclosed by the invention can endow the chemical fiber with memory tracking property and recognition function, and has the advantages of high anti-counterfeiting strength and good anti-counterfeiting concealment.
Description
Technical Field
The invention belongs to the field of chemical fibers with an anti-counterfeiting function, and particularly relates to an element master batch suitable for anti-counterfeiting chemical fibers 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 defects of insufficient anti-counterfeiting strength, is easy to imitate and counterfeit and is difficult to have the memory tracing property, on the other hand, the mentioned dispersion liquid is only suitable for being used in the preparation of cellulose fibers, and the preparation method of chemical fibers is completely different from the preparation method of the cellulose fibers, so that the chemical fibers can be applied 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.
Disclosure of Invention
The invention aims to solve the technical problem of overcoming the defects in the prior art and provide the element master batch for the anti-counterfeiting chemical fiber, which has the memory tracking property and the recognition function and high anti-counterfeiting strength.
The invention also provides a preparation method of the element master batch.
In order to solve the technical problems, the invention adopts a technical scheme as follows:
an element master batch suitable for anti-counterfeiting chemical fibers comprises a matrix high polymer, an anti-counterfeiting tracking agent and a polyolefin dispersing agent, wherein the anti-counterfeiting tracking agent is composed of at least two metal oxides, the content of metal elements contained in each metal oxide is controlled to have a fixed feeding mass ratio, and the metal oxide compounds are zinc oxide, molybdenum trioxide, zirconium dioxide, aluminum oxide, calcium oxide, strontium oxide, germanium dioxide or vanadium pentoxide; the sum of the contents of metal elements contained in the metal oxides accounts for 5-50% of the element master batch by mass percentage.
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 master batches containing the proportion are 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 and preferred aspects of the present invention, the matrix 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), a copolymer of 3-hydroxybutyrate and 3-hydroxyvalerate (PHBV), polybutylene terephthalate succinate (PBAT), Polyethylene (PE), polypropylene (PP), Polystyrene (PS), Polyamide (PA), polyvinyl chloride, and polyurethane.
According to some specific and preferred aspects of the present invention, the polyolefin dispersant is a polyethylene wax or a polypropylene wax or a mixture of both.
According to some preferred aspects of the invention, the anti-counterfeiting tracking agent is composed of at least three metal oxides, and more preferably 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 20% by mass of the element master batch.
According to some specific and preferred aspects of the present invention, the matrix polymer accounts for 20 to 70% by mass of the element mother particle.
According to some specific and preferred aspects of the present invention, the polyolefin dispersant accounts for 1 to 8% by mass of the element masterbatch.
According to some specific aspects of the invention, the element master batch further comprises 3-6% of an antioxidant and 3-6% of a coupling agent by mass percentage. The antioxidant is antioxidant B215 of Swiss soda; the coupling agent is Japanese Beacon KBM 403.
According to some specific and preferred aspects of the present invention, the element masterbatch is prepared by mixing the components in the formula amounts, extruding, cooling, drying, and granulating.
In the present invention, the metal oxide to be added is preferably high in purity, and interference of impurities is reduced.
The invention provides another technical scheme that: the preparation method of the element master batch suitable for the anti-counterfeiting chemical fiber comprises the following steps:
(1) weighing each component in the element master batch according to the formula amount;
(2) uniformly mixing the components weighed in the step (1), adding the mixture into an extruder, and extruding at the extrusion temperature of 180-300 ℃;
(3) and (3) carrying out water cooling, drying and grain cutting on the material strips extruded in the step (2) to obtain the element master batch suitable for the anti-counterfeiting chemical fiber.
Due to the adoption of the technical scheme, compared with the prior art, the invention has the following advantages:
the element master batch provided by the invention takes chemical fiber raw material high polymer as a dispersion system, and is formed by adding a plurality of specific metal elements with fixed feeding proportion into the dispersion system, on one hand, the element master batch can be added in the preparation process of the anti-counterfeiting chemical fiber in the form of master batch, so that the dispersibility, uniformity and compatibility of the metal elements in the 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 master batch 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, increases the anti-counterfeiting strength, and simultaneously, the specific metal elements can not damage the performance of the fiber, and increases the anti-counterfeiting concealment, so that the element master batch can endow the chemical fiber with the advantages of memory tracking property and 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 masterbatch suitable for anti-counterfeiting chemical fiber
The embodiment provides an element master batch suitable for anti-counterfeiting chemical fibers, which comprises 66.01 parts of polyethylene terephthalate, 2.49 parts of zinc oxide (with the content of 2 zinc elements), 4.05 parts of zirconium dioxide (with the content of 3 zirconium elements), 9.45 parts of aluminum oxide (with the content of 5 aluminum elements), 8 parts of polyethylene wax, 5 parts of antioxidant and 5 parts of coupling agent in parts by mass; wherein the ratio of zinc element to zirconium element to aluminum element is 2: 3: 5;
the preparation method comprises the following steps: (1) weighing each component in the element master batch according to the formula amount; preparing the weighed polyethylene glycol terephthalate into powder with the average particle size of 350 +/-30 nm by using a pulverizer;
(2) uniformly mixing the components weighed in the step (1), adding the mixture into a screw extruder, and extruding at the extrusion temperature of 280 +/-5 ℃ and the screw rotation speed of 300 r/min;
(3) and (3) cooling the extruded material strips in the step (2) by water, drying and granulating to obtain the element master batch suitable for the anti-counterfeiting chemical fiber.
Example 2 preparation of elemental masterbatch suitable for anti-counterfeiting chemical fiber
The embodiment provides an element master batch suitable for anti-counterfeiting chemical fibers, which comprises 61.01 parts of regenerated PET, 2.49 parts of zinc oxide (zinc element content is 2 parts), 4.05 parts of zirconium dioxide (zirconium element content is 3 parts), 9.45 parts of aluminum oxide (aluminum element content is 5 parts), 7 parts of calcium oxide (calcium element content is 5 parts), 8 parts of polyethylene wax, 4 parts of antioxidant and 4 parts of coupling agent by mass; wherein the ratio of zinc element to zirconium element to aluminum element to calcium element is = 2: 3: 5;
the preparation method comprises the following steps: (1) weighing each component in the element master batch according to the formula amount; preparing the weighed regenerated PET into powder with the average particle size of 350 +/-30 nm by using a pulverizer;
(2) uniformly mixing the components weighed in the step (1), adding the mixture into a screw extruder, and extruding at 275 +/-5 ℃ at the screw rotating speed of 300 r/min;
(3) and (3) cooling the extruded material strips in the step (2) by water, drying and granulating to obtain the element master batch suitable for the anti-counterfeiting chemical fiber.
Example 3 preparation of elemental masterbatch suitable for anti-counterfeiting chemical fiber
The embodiment provides an element master batch suitable for anti-counterfeiting chemical fibers, which comprises 55.59 parts of polyamide, 1.24 parts of zinc oxide (1 part of zinc element content), 4.05 parts of zirconium dioxide (3 parts of zirconium element content), 10.71 parts of vanadium pentoxide (6 parts of vanadium element content), 14.41 parts of germanium dioxide (10 parts of germanium element content), 6 parts of polyethylene wax, 4 parts of antioxidant and 4 parts of coupling agent in parts by mass; 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 master batch according to the formula amount; preparing the weighed polyamide into powder with the average particle size of 350 +/-30 nm by using a pulverizer;
(2) uniformly mixing the components weighed in the step (1), adding the mixture into a screw extruder, and extruding at the extrusion temperature of 230 +/-5 ℃ and the screw rotation speed of 350 r/min;
(3) and (3) cooling the extruded material strips in the step (2) by water, drying and granulating to obtain the element master batch suitable for the anti-counterfeiting chemical fiber.
Example 4 preparation of elemental masterbatch suitable for anti-counterfeiting chemical fiber
The embodiment provides an element master batch suitable for anti-counterfeiting chemical fibers, which comprises 56.69 parts of polylactic acid, 1.24 parts of zinc oxide (zinc element content is 1 part), 9.45 parts of aluminum oxide (aluminum element content is 5 parts), 7.1 parts of strontium oxide (strontium element content is 6 parts), 11.52 parts of germanium dioxide (germanium element content is 8 parts), 6 parts of polyethylene wax, 4 parts of antioxidant and 4 parts of coupling agent 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 master batch according to the formula amount; preparing the weighed polylactic acid into powder with the average particle size of 350 +/-30 nm by using a pulverizer;
(2) uniformly mixing the components weighed in the step (1), adding the mixture into a screw extruder, and extruding at the extrusion temperature of 190 +/-5 ℃ and the screw rotation speed of 280 r/min;
(3) and (3) cooling the extruded material strips in the step (2) by water, drying and granulating to obtain the element master batch 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: 99.5 parts of polyethylene terephthalate and 0.5 part of the element master batch prepared in example 1.
The preparation method comprises the following steps: and weighing the polyethylene glycol terephthalate and the element master batch prepared in the example 1 according to the formula proportion, mixing, carrying out melt extrusion, carrying out pre-drafting spinning, and carrying out elasticization 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: 99.6 parts of recycled PET and 0.4 part of the element master batch prepared in example 2.
The preparation method comprises the following steps: and weighing the regenerated PET and the element master batch prepared in the example 2 according to the formula proportion, mixing, carrying out melt extrusion, and carrying out one-step 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 polyamide and 0.4 part of element master batch prepared in example 3.
The preparation method comprises the following steps: and weighing polyamide and the element master batch prepared in the example 3 according to the formula proportion, mixing, carrying out melt extrusion, and carrying out one-step 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 polylactic acid and 0.5 part of the element master batch prepared in example 4.
The preparation method comprises the following steps: and weighing polylactic acid and the element master batch prepared in the example 4 according to the formula proportion, mixing, performing melt extrusion, and performing one-step 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 materials are not added with element master batches.
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 9.900ppm (g), the content of zirconium element is 14.550ppm (g), the content of aluminum element is 24.725ppm (g), the content of iron element is 0.002ppm (g), and the content of magnesium element is 0.001ppm (g), so that the content of zinc element, the content of zirconium element and the content of aluminum element are = 1.98: 2.91: 4.945.
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 7.928ppm (g), the content of zirconium element is 11.652ppm (g), the content of aluminum element is 19.800ppm (g), the content of calcium element is 19.500ppm (g), the content of iron element is 0.001ppm (g), the content of magnesium element is 0.001ppm (g), and the content of sodium element is 0.001ppm (g), so that the content of zinc element, the content of zirconium element, the content of aluminum element and the content of calcium element is = 1.982: 2.913: 4.950: 4.875.
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 11.640ppm (g), the content of vanadium is 23.256ppm (g), the content of germanium is 39.080ppm (g), the content of iron is 0.001ppm (g), and the content of sodium is 0.003ppm (g), so that the content of zinc, zirconium, vanadium and germanium is = 0.992: 2.910: 5.814: 9.770.
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 4.965ppm (g), the content of aluminum element is 24.800ppm (g), the content of strontium element is 29.760ppm (g), the content of germanium element is 39.120ppm (g), the content of iron element is 0.003ppm (g), the content of magnesium 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 aluminum element, the content of strontium element and the content of germanium element are = 0.993: 4.960: 5.952: 7.824.
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 0.003ppm (g), the content of magnesium element is 0.002ppm (g), and the content of sodium element is 0.003ppm (g).
According to the embodiment, the metal oxides in the specific combination mode are prepared into master batches 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 an experimental error or a lost part in the preparation process, but the loss amount is extremely small, and the judgment and identification of the chemical fiber are not influenced, the combination obviously endows the chemical fiber with a 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 master batches 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 element master batch is characterized by comprising a matrix polymer, an anti-counterfeiting tracking agent and a polyolefin dispersing agent, wherein the anti-counterfeiting tracking agent is composed of at least two metal oxides, the content of metal elements contained in 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 contents of metal elements contained in the metal oxides accounts for 5-50% of the element master batch by mass percentage.
2. The elemental masterbatch suitable for anti-counterfeit chemical fiber according to claim 1, wherein the matrix polymer is one or more selected from polyethylene terephthalate, polylactic acid, polycaprolactone, recycled PET, polybutylene succinate, 3-hydroxybutyrate-3-hydroxyvalerate copolymer, polybutylene terephthalate, polyethylene, polypropylene, polystyrene, polyamide, polyvinyl chloride, and polyurethane.
3. The elemental masterbatch suitable for anti-counterfeiting chemical fiber according to claim 1, wherein the polyolefin dispersing agent is polyethylene wax or polypropylene wax or a mixture of the polyethylene wax and the polypropylene wax.
4. The elemental masterbatch suitable for use in security chemical fibers according to claim 1, wherein the security tracking agent is composed of at least three metal oxides, and more preferably at least four metal oxides.
5. The element masterbatch suitable for anti-counterfeiting chemical fiber according to any one of claims 1 to 4, wherein the average particle size of the metal oxide is 200-750 nm.
6. The elemental master batch applicable to the anti-counterfeiting chemical fiber according to claim 1, wherein the sum of the contents of the metal elements contained in the metal oxides accounts for 10-20% of the elemental master batch in terms of mass percentage.
7. The element master batch suitable for the anti-counterfeiting chemical fiber according to claim 1, wherein the matrix polymer accounts for 20-70% of the element master batch by mass percent; and/or the polyolefin dispersant accounts for 1-8% of the element master batch by mass percentage.
8. The elemental masterbatch suitable for anti-counterfeiting chemical fiber according to claim 1, wherein the elemental masterbatch further comprises 3 to 6 mass percent of an antioxidant and 3 to 6 mass percent of a coupling agent.
9. The element masterbatch suitable for anti-counterfeiting chemical fiber according to claim 1, wherein the element masterbatch is prepared by uniformly mixing the components according to the formula amount, extruding, cooling, drying and granulating.
10. The preparation method of the element master batch suitable for the anti-counterfeiting chemical fiber according to any one of claims 1 to 9, wherein the preparation method comprises the following steps:
(1) weighing each component in the element master batch according to the formula amount;
(2) uniformly mixing the components weighed in the step (1), adding the mixture into an extruder, and extruding at the extrusion temperature of 180-300 ℃;
(3) and (3) carrying out water cooling, drying and grain cutting on the material strips extruded in the step (2) to obtain the element master batch suitable for the anti-counterfeiting chemical fiber.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1966785A (en) * | 2006-09-15 | 2007-05-23 | 东华大学 | Infrared anti-false fiber and its production method and use |
| CN101372821A (en) * | 2008-08-15 | 2009-02-25 | 东莞市天盛特种纸制品有限公司 | Element anti-fake paper |
| CN104311945A (en) * | 2014-09-19 | 2015-01-28 | 金发科技股份有限公司 | Polyethylene anti-counterfeiting plastic bag and preparation method thereof |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1966785A (en) * | 2006-09-15 | 2007-05-23 | 东华大学 | Infrared anti-false fiber and its production method and use |
| CN101372821A (en) * | 2008-08-15 | 2009-02-25 | 东莞市天盛特种纸制品有限公司 | Element anti-fake paper |
| CN104311945A (en) * | 2014-09-19 | 2015-01-28 | 金发科技股份有限公司 | Polyethylene anti-counterfeiting plastic bag and preparation method thereof |
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