CN114923895B - A method for realizing anti-counterfeiting identification of textiles dyed with non-aqueous medium - Google Patents

Abstract

The invention discloses a method for realizing textile anti-counterfeiting identification by non-aqueous medium dyeing, which comprises the steps of simultaneously adding a specific amount of certain water-soluble rare earth metal salt into a dyeing agent when the textile is dyed by the non-aqueous medium; when anti-counterfeiting identification is needed, firstly, digestion is carried out on the textile, and then an inductively coupled plasma emission spectrometer is adopted to detect and analyze the quality of the rare earth metal ions contained in the textile sample under the emission wavelength of the added rare earth metal ions; if the detected content value is less than 75% of the theoretical added value or greater than the theoretical added value, the detection result is judged to be false, and if the detected content value is between 75% and 95% of the theoretical added value, the detection result is judged to be true; the theoretical addition value refers to the mass of rare earth metal ions added when 1kg of textile fabric is dyed. Experiments prove that: by adopting the method provided by the invention, the effective anti-counterfeiting identification and traceability identification of the textile dyed by the nonaqueous medium can be realized.

Description

A method for realizing anti-counterfeiting identification of textiles dyed with non-aqueous medium

Technical Field

The invention relates to a method for realizing anti-counterfeiting identification of textiles dyed with non-aqueous media, and belongs to the technical field of textile anti-counterfeiting.

Background Art

Because the traditional water-dying method of textiles consumes a lot of water, dyeing 1 ton of finished products requires about 100 tons of water, and a large amount of alkali and salt are added during the dyeing process, making it difficult to treat the dyeing wastewater. At the same time, more auxiliaries are added during the soaping process, and it contains more surfactants and toxic substances that are harmful to microorganisms. The COD and BOD are not coordinated, which greatly increases the difficulty of treating the wastewater after dyeing and cannot meet the modern textile industry's needs for clean production and water and energy conservation.

The non-aqueous medium dyeing technology uses the dyeing-promoting effect of non-aqueous media on water-soluble dyes during the dyeing process, which not only greatly improves the dye uptake rate (close to 100%), but also reduces the hydrolysis rate of the dye and improves the fixation rate of water-soluble dyes. In addition, the entire dyeing process is carried out in a waterless state, achieving zero wastewater discharge, breaking the constraints of wastewater indicators on the development of the printing and dyeing industry, and the brightness and other quality indicators of the dyed products obtained are comparable to those of water-bath dyeing. Therefore, this non-aqueous medium dyeing technology is a successful attempt at technological innovation in the textile dyeing and finishing industry, and is the mainstream of future industry development, and is expected to replace traditional processes and achieve large-scale application.

However, when the non-aqueous dyeing technology is industrialized on a large scale in the future, how to effectively identify and distinguish the authenticity of such products will become an urgent problem to be solved in this field. If the traceability of textiles dyed with non-aqueous media can be achieved, it can not only effectively protect the innovative development of non-aqueous dyeing technology, but also ensure that the brand of such products and the interests of consumers are not infringed. However, the existing anti-counterfeiting technologies in this industry, such as anti-counterfeiting of hanging tags and anti-counterfeiting of query labels, have the defect of being easily imitated. Therefore, this field urgently needs to develop a method for realizing anti-counterfeiting identification of textiles dyed with non-aqueous media, so as to achieve effective identification and distinction of textiles dyed with non-aqueous media.

Summary of the invention

In view of the above problems and needs in the prior art, an object of the present invention is to provide a method for anti-counterfeiting identification of textiles dyed with non-aqueous media, so as to achieve effective recognition and identification of textiles dyed with non-aqueous media.

In order to achieve the above-mentioned invention object, the technical solution adopted by the present invention is as follows:

A method for realizing anti-counterfeiting identification of textiles dyed with non-aqueous media comprises the following steps: when dyeing the textiles with non-aqueous media, a specific amount of a certain water-soluble rare earth metal salt is simultaneously added to a dye; when anti-counterfeiting identification is required, the textiles are firstly digested, and then an inductively coupled plasma optical emission spectrometer (ICP-OES) is used to detect and analyze the mass of the rare earth metal ions contained in the textile sample at the emission wavelength of the added rare earth metal ions; if the detected content value is less than 75% of a theoretical added value or greater than the theoretical added value, it is judged to be false, and if the detected content value is between 75% and 95% of the theoretical added value, it is judged to be true; the theoretical added value refers to the mass of the rare earth metal ions added when dyeing 1 kg of textiles.

In a preferred embodiment, the theoretical addition value is 1-20 mg/dyed 1 kg of textile.

In a preferred embodiment, the non-aqueous medium is selected from any one or more of alkanes, ethers, sulfolane, dimethyl sulfoxide and siloxanes, and the alkane is selected from isooctane or paraffin.

In a preferred embodiment, during dyeing, the mass ratio of the textile to the non-aqueous medium is (1:3) to (1:30).

In a preferred embodiment, the water-soluble rare earth metal salt is a chloride salt of a rare earth metal.

In a further preferred embodiment, the rare earth metal is any one of lanthanum (La), cerium (Ce), neodymium (Nd), europium (Eu) and samarium (Sm).

In one embodiment, the digestion may be performed by microwave digestion or wet digestion.

In a preferred embodiment, the digestion is carried out by wet digestion, and nitric acid is used as the digestion agent.

In one embodiment, the conditions for detection and analysis using an inductively coupled plasma optical emission spectrometer (ICP-OES) are:

The flow rate of the plasma gas (preferably argon) is 8 to 10 L/min; the flow rate of the nebulizer is 0.5 to 1.0 L/min; the flow rate of the auxiliary gas is 0.1 to 0.5 L/min; the power of the RF generator is 1200 to 1500 W; the injection volume is 1.0 to 2.0 mL/min; the pump peristaltic rate is 1.0 to 2.0 mL/min; the detection wavelength range is 160 to 800 nm, and the integration time is 0.5 to 2 s.

A preferred solution is that the flow rate of the plasma gas (preferably argon) is 8 L/min, the power of the RF generator is 1400 W, the flow rate of the auxiliary gas is 0.3 L/min, the flow rate of the nebulizer is 0.7 L/min, the injection volume is 1.2 mL/min, the pump peristaltic rate is 1.5 mL/min, and the integration time is 0.5 to 2 s.

It should be noted that the textile described in the present application can be a textile in any form such as fiber, yarn or cloth.

Compared with the prior art, the present invention has the following significant beneficial effects:

Experiments have proved that the method described in the present invention can not only realize effective anti-counterfeiting identification and authentication of textiles dyed with non-aqueous media, but also has no obvious adverse effect on the basic properties of the final textiles. It can realize anti-counterfeiting identification and traceability identification of textiles dyed with non-aqueous media, and thus has significant application prospects and practical value.

DETAILED DESCRIPTION

The technical solution of the present invention is further described in detail and completely below in conjunction with specific embodiments. It should be understood that the following embodiments are only used to illustrate the present invention and are not intended to limit the scope of the present invention. The experimental methods in the following embodiments that do not specify specific conditions are usually performed under conventional conditions or according to the conditions recommended by the manufacturer. The textiles described in the following embodiments can be textiles in any form such as fibers, yarns or cloths.

Example 1

In this embodiment, cotton fiber is selected for experiment, and the specific steps are as follows:

1. Staining and labeling

Cotton fiber is added to liquid paraffin (the mass ratio of cotton fiber to non-aqueous medium is 1:20), and then a dye (such as reactive red 120, the added mass of the dye is 2% of the mass of the cotton fiber) and a specific amount (three addition amounts are tested in this embodiment: a) 1 mg/1 kg fiber for dyeing; b) 10 mg/1 kg fiber for dyeing; c) 20 mg/1 kg fiber for dyeing) of a water-soluble rare earth metal salt (in this embodiment, chloride salts of any one of the rare earth metals La, Ce, Nd, Eu, and Sm are selected), are added at room temperature, and then the temperature is kept at room temperature for 10 minutes, and then the dyeing temperature is raised from room temperature (which can be any temperature between 15 and 40°C) to 90°C at a heating rate of 2°C/min, and then kept warm for 30 minutes.

2. Anti-counterfeiting identification and testing

When anti-counterfeiting identification is required, the textile sample is first digested. The digestion can be performed by microwave digestion or wet digestion. This embodiment adopts wet digestion, that is, the textile sample is cut into pieces, 0.2 g is weighed and placed in a digestion tube, and then 3 ml of nitric acid is added to digest at 120° C. for 2 hours;

After the sample digestion is complete, take out the digestion tube and adjust the volume to 25 ml, then transfer it to a 50 ml centrifuge tube and centrifuge at 10000 r/min for 15 minutes;

The emission wavelength of the added rare earth metal ions using an inductively coupled plasma optical emission spectrometer (ICP-OES) is (in nm):

La: 379.478, 398.852, 408.672;

Ce: 413.380, 418.660, 456.336;

Nd: 406.109, 401.225, 430.358;

Eu: 381.967, 412.970;

Sm: 359.260, 442.434;

The mass of the corresponding rare earth metal ions in the textile samples was detected and analyzed. The specific analysis conditions of ICP-OES are as follows:

The flow rate of plasma gas (argon gas) was 8 L/min, the power of RF generator was 1400 W, the flow rate of auxiliary gas was 0.3 L/min, the flow rate of nebulizer was 0.7 L/min, the injection volume was 1.2 mL/min, the pump peristaltic rate was 1.5 mL/min, and the integration time was 0.5 to 2 s;

The specific test results are shown in Tables 1 to 3.

Example 2

In this embodiment, polyester fiber is selected for experiment, and the specific steps are as follows:

1. Staining and labeling

Add polyester fiber to silicone (the mass ratio of polyester fiber to non-aqueous medium is 1:20), then add a dye (such as Disperse Red 73, the added mass of the dye is 0.5% of the mass of the polyester fiber) and a specific amount (three addition amounts are tested in this embodiment: a) 1 mg/dyed 1 kg fiber; b) 10 mg/dyed 1 kg fiber; c) 20 mg/dyed 1 kg fiber) of a certain water-soluble rare earth metal salt (in this embodiment, chloride salts of any one of the rare earth metals La, Ce, Nd, Eu, and Sm are selected), and after the addition, first increase the dyeing temperature to 80°C at a heating rate of 6°C/min, then increase the temperature to 140°C at a heating rate of 3°C/min, and then keep warm for 60 minutes.

2. Anti-counterfeiting identification and testing

Please refer to Example 1 for details.

The specific test results are shown in Tables 1 to 3.

Table 1. Measured content of rare earth metal ions in samples with 1 mg added/1 kg of dyed fiber (mg/kg)

Table 2. Measured content of rare earth metal ions in samples with 10 mg/dyed 1 kg fiber (mg/kg)

Table 3. Measured content of rare earth metal ions in samples with 20 mg/dyed 1 kg fiber (mg/kg)

Combining the test results shown in Tables 1 to 3, it can be seen that: first, when dyeing with a non-aqueous medium, it is feasible to perform tracer labeling on textiles by adding 1 to 20 mg of rare earth metal ions per 1 kg of fiber to be dyed, and the test values of the labeled sample and the blank sample (i.e., the homogeneous textile sample without rare earth labeling) can be clearly distinguished; secondly, because the rare earth metal ions added during dyeing cannot be completely adsorbed into the textile, the actually measured content value is not the theoretical added value, but it can be seen from the test results in the above table that: if the detected content value is between 75% and 95% of the theoretical added value, it can be judged to be true, and if the detected content value is less than 75% of the theoretical added value or greater than the theoretical added value, it can be judged to be false.

Example 3

In this embodiment, homogeneous dyed textiles with or without rare earth metal ions added (two series of experiments on cotton fiber and polyester fiber were carried out in this embodiment) were stacked into 4 layers, and then the K/S value and L, a, b values of the dyed fibers were tested and compared using a computer colorimeter. The specific results are shown in Table 4.

Table 4 K/S value and L, a, b value of dyed fiber test

From the results shown in Table 4, it can be seen that the K/S value and L, a, and b values of the dyed textiles with added rare earth metal ions are not much different from those of the dyed textiles without added rare earth metal ions within the error range, indicating that adding 1 to 20 mg/kg of rare earth metal ions during non-aqueous medium dyeing has no obvious adverse effect on the color depth and color shade of the textile dyeing.

Example 4

In this embodiment, the washing fastness test was performed on cotton fibers and polyester fibers dyed with non-aqueous media without rare earth metal ions and with 1 mg/kg, 10 mg/kg, and 20 mg/kg of rare earth metal ions added according to GB/T 3921-2008 "Textiles - Tests for Color Fastness - Color Fastness to Soaping"; and the rubbing fastness test was performed on cotton fibers and polyester fibers dyed with non-aqueous media without rare earth metal ions and with 1 mg/kg, 10 mg/kg, and 20 mg/kg of rare earth metal ions added according to GB/T 3920-2008 "Textiles - Tests for Color Fastness - Color Fastness to Rubbing"; and according to GB/T 3923.1-2013 "Tensile Properties of Textiles - Part 1: Determination of Breaking Strength and Elongation at Break", an electronic textile strength tester was used to test the breaking strength of the dyed textiles, the tensile rate was 200 mm/min, and the test time was 1 min. The detailed test results are shown in Tables 5 to 7:

Table 5 Effect of rare earth marking on rubbing fastness and strength of dyed textiles

Table 6 Effect of rare earth labeling on washing fastness of dyed cotton fibers

Table 7 Effect of rare earth labeling on washing fastness of dyed polyester fibers

From the results shown in Tables 5 to 7, it can be seen that no matter cotton fiber or polyester fiber, when dyeing with a non-aqueous medium, adding 1 to 20 mg of rare earth metal ions per 1 kg of textile dyed has no adverse effect on the dry and wet friction fastness, breaking strength and washing fastness of the dyed textile, indicating that the method of the present invention can be used for tracing and marking textiles dyed with a non-aqueous medium, and can achieve effective anti-counterfeiting identification and traceability identification of textiles dyed with a non-aqueous medium, and has obvious practical value and application prospects.

Finally, it should be pointed out that the above are only some preferred embodiments of the present invention and should not be construed as limiting the scope of protection of the present invention. Some non-essential improvements and adjustments made by those skilled in the art based on the above contents of the present invention all fall within the scope of protection of the present invention.

Claims (10)

1. A method for realizing anti-counterfeiting identification of textiles dyed with non-aqueous media, characterized in that: when the textiles are dyed with non-aqueous media, a specific amount of a certain water-soluble rare earth metal salt is simultaneously added to the dye; when anti-counterfeiting identification is required, the textiles are first digested, and then an inductively coupled plasma emission spectrometer is used to detect and analyze the mass of the rare earth metal ions contained in the textile sample at the emission wavelength of the added rare earth metal ions; if the detected content value is less than 75% of the theoretical added value or greater than the theoretical added value, it is judged to be false, and if the detected content value is between 75% and 95% of the theoretical added value, it is judged to be true; the theoretical added value refers to the mass of the rare earth metal ions added when dyeing 1 kg of textiles. 2. The method according to claim 1, characterized in that the theoretical added value is 1-20 mg/dyed 1 kg of textile. 3. The method according to claim 1, characterized in that the non-aqueous medium is selected from any one or more of alkanes, ethers, sulfolane, dimethyl sulfoxide and siloxanes, and the alkane is selected from isooctane or liquid paraffin. 4. The method according to claim 1, characterized in that during dyeing, the mass ratio of the textile to the non-aqueous medium is (1:3) to (1:30). 5. The method according to claim 1, characterized in that the water-soluble rare earth metal salt is a chloride of a rare earth metal. 6. The method according to claim 5, characterized in that the rare earth metal is any one of lanthanum (La), cerium (Ce), neodymium (Nd), europium (Eu) and samarium (Sm). 7. The method according to claim 1, characterized in that the digestion is carried out by microwave digestion or wet digestion. 8. The method according to claim 7 is characterized in that: the digestion adopts wet digestion, and the digestion agent is nitric acid. 9. The method according to claim 1, characterized in that the conditions for detection and analysis using inductively coupled plasma emission spectrometer are: The flow rate of plasma gas is 8-10 L/min; the flow rate of nebulizer is 0.5-1.0 L/min; the flow rate of auxiliary gas is 0.1-0.5 L/min; the power of RF generator is 1200-1500 W; the injection volume is 1.0-2.0 mL/min; the peristaltic rate of pump is 1.0-2.0 mL/min; the detection wavelength range is 160-800 nm, and the integration time is 0.5-2 s. 10. The method according to claim 9, characterized in that: the flow rate of plasma gas is 8 L/min, the power of RF generator is 1400 W, the flow rate of auxiliary gas is 0.3 L/min, the flow rate of nebulizer is 0.7 L/min, the injection volume is 1.2 mL/min, the pump peristaltic rate is 1.5 mL/min, and the integration time is 0.5 to 2 s.