阅读说明：本技术 一种羽绒纤维红外溯源防伪方法 (Infrared traceability anti-counterfeiting method for down fibers ) 是由 徐阳 金前鹏 于 2019-10-09 设计创作，主要内容包括：本发明公开了一种羽绒纤维溯源防伪方法,属于红外防伪认证技术领域,具体的包括羽绒纤维的防伪方法、防伪材料和检测装置。所述的羽绒纤维防伪方法是首先对单掺Yb(镱)或共掺含Yb(镱)等多种稀土离子的具有特征红外发射的纳米无机非金属材料进行γ-巯丙基三甲基氧基硅烷(MPTMS)包覆并氧化改性,得到纳米磺酸化防伪材料；将洗涤后的羽绒纤维浸入pH＝3～4的含防伪材料整理液中,利用羽绒蛋白质纤维等电点特性,显正电性的羽绒纤维吸附带负电的改性防伪材料,二者利用库仑力和氢键作用力结合,得到具有特征红外发射的可溯源羽绒纤维；并利用具有对应发射和接收二极管的检测装置,对羽绒纤维红外特征光谱检测,实现溯源认证。(The invention discloses a down fiber tracing anti-counterfeiting method, belongs to the technical field of infrared anti-counterfeiting authentication, and particularly comprises an anti-counterfeiting method, an anti-counterfeiting material and a detection device of down fibers. Firstly, carrying out gamma-mercaptopropyltrimethoxysilane (MPTMS) coating and oxidation modification on a nano inorganic non-metallic material which is singly doped with Yb (ytterbium) or co-doped with various rare earth ions containing Yb (ytterbium) and the like and has characteristic infrared emission to obtain a nano sulfonated anti-counterfeiting material; soaking the washed down feather fibers into finishing liquid containing the anti-counterfeiting material, wherein the pH value of the finishing liquid is 3-4, adsorbing the negatively charged modified anti-counterfeiting material by the positively charged down feather fibers by utilizing the isoelectric point characteristics of down feather protein fibers, and combining the negatively charged modified anti-counterfeiting material and the negatively charged modified anti-counterfeiting material by utilizing coulomb force and hydrogen bond acting force to obtain the traceable down feather fibers with characteristic infrared emission; and the infrared characteristic spectrum of the down feather fibers is detected by using a detection device with corresponding transmitting and receiving diodes, so that the tracing authentication is realized.)

1. The preparation method of the anti-counterfeiting down fiber is characterized in that the down fiber with the anti-counterfeiting function is prepared by combining a modified infrared anti-counterfeiting material and the down fiber in an environment without an added adhesive; the bonding is by coulomb and hydrogen bonding forces.

2. The method according to claim 1, wherein the modified infrared anti-counterfeiting material is prepared by taking nano-scale inorganic non-metallic particles of single-doped or co-doped rare earth Yb as anti-counterfeiting traceable markers; the co-doped rare earth comprises Y, Tm.

3. The method according to claim 2, wherein the modified infrared anti-counterfeiting material is prepared by the following steps:

(1) coating: coating and modifying the nano-particles of the single-doped or co-doped rare earth Yb by using a gamma-mercaptopropyltrimethoxysilane coupling agent;

(2) oxidizing by an oxidizing agent: and (2) oxidizing sulfydryl introduced to the surface of the nano-particles obtained after coating modification in the step (1) by using an oxidant into sulfonic acid groups to obtain the modified infrared anti-counterfeiting material.

4. The method according to claim 2, wherein the specific steps of the preparation method comprise:

(1) coating: coating and modifying the nano-particles of the single-doped or co-doped rare earth Yb by using a gamma-mercaptopropyltrimethoxysilane coupling agent; the specific reaction conditions of the coating modification are as follows: reacting every 1g of nano material with 90-99% mercaptosilane coupling agent in a volume of 15-25 mL under the catalysis of 5-10 mL of 20-30% ammonia water at the room temperature of 20-25 ℃ for 4-6 hours; the alcohol-water ratio is (3-9): 1;

(2) oxidizing by an oxidizing agent: oxidizing sulfydryl introduced to the surface of the nano-particles obtained after coating modification in the step (1) by using an oxidant into sulfonic acid groups to obtain a modified infrared anti-counterfeiting material; the specific reaction conditions for oxidizing the oxidant are as follows: the dosage of the oxidant of 90-99% mercaptosilane coupling agent per 1mL is 1-5 mL; the reaction condition is that the reaction is carried out in water dispersion liquid for 2 to 5 hours at the room temperature of 20 to 25 ℃;

(3) pre-finishing down feather: cleaning grease and cell membranes on the surfaces of the down fibers by using a detergent;

(4) preparing the anti-counterfeiting traceable down feather: preparing the modified infrared anti-counterfeiting material into an aqueous solution with the concentration of 2-5 g/L, and adjusting the pH of the solution to 3-4 by using hydrochloric acid to prepare a finishing liquid; soaking the down feather fibers pre-finished in the step (3) in finishing liquid, placing the down feather fibers in a constant-temperature shaking box, preserving heat for 2-4 hours at 50-70 ℃, and filtering and drying to obtain anti-counterfeiting traceable down feather; the bath ratio of the down fibers to the finishing liquid is 1: (20-100).

5. A method for preparing anti-counterfeiting fiber, which is characterized in that the down fiber in the preparation method of any one of claims 1 to 3 is replaced by wool fiber or silk fiber.

6. An anti-counterfeiting fiber prepared by the preparation method of any one of claims 1 to 5.

7. A product containing the security fiber of claim 6, wherein the product comprises composite fibers, yarns, powders and fabrics.

8. Use of the security fiber of claim 6 in clothing, bedding and the like.

9. The use according to claim 8, wherein the use is in anti-counterfeiting of clothing and bedding.

10. The use of the security aspect of claim 9, wherein the use is for identification and authentication of security fibers and articles thereof using a detection device; the detection device comprises a multi-interface infrared light emitting-receiving module; the infrared transmitting-receiving module selects different wavelengths according to the characteristic spectrum of Yb and the co-doped elements thereof.

Technical Field

The invention relates to an infrared tracing anti-counterfeiting method for down feather fibers, and belongs to the technical field of textile anti-counterfeiting.

Background

Down feather fibers are protein fibers composed mainly of amphoteric amino acids, which are light, thin, warm-keeping, and called breathable fibers. China is the biggest down feather and the production, export and consumption countries of products thereof in the world, occupies 70-80% of the market share of the down feather trade in the world, and is a genuine big down feather country. However, the existing domestic market generally has the quality inconclusive effect on domestic down feather and products thereof due to the overwhelming counterfeiting of counterfeit products, the weak protection consciousness of enterprise brands and the lack of effective product anti-counterfeiting authentication technology.

The anti-fake technology applied to the textile at present comprises bar code anti-fake technology, telephone anti-fake technology, photochromic anti-fake technology and the like. The combination of bar code and telephone anti-fake technology is a common technical means, but the anti-fake technology has low threshold and is easy to imitate. Meanwhile, the anti-counterfeiting system taking the two-dimensional code or the bar code as the core is not suitable for anti-counterfeiting of fiber raw materials of high-grade textiles, and traceability authentication of high-value and high-quality fiber raw materials is difficult to realize.

In recent years, photochromic anti-counterfeiting technologies are applied to textile anti-counterfeiting, the anti-counterfeiting technologies are based on up-conversion and down-conversion materials, and anti-counterfeiting is carried out by observing the luminescent color of the fiber after being irradiated by ultraviolet light or infrared light, the technology for distinguishing true from false by perception seems to be simple and easy to implement, but is actually unreliable, because the color is distinguished by human eyes in fact, even lawless persons analyze the color through instruments, the imitated products which are similar in color and cannot be distinguished by human eyes are easily created.

The existing photochromic anti-counterfeiting technology comprises anti-counterfeiting fiber, anti-counterfeiting film and fluorescent anti-counterfeiting ink. The anti-counterfeiting fiber and the anti-counterfeiting film are obtained by adding anti-counterfeiting particles into a polymer spinning solution and spinning to form a film, so that the anti-counterfeiting fiber and the anti-counterfeiting film cannot be used for anti-counterfeiting of natural down fibers. The existing fluorescent anti-counterfeiting ink has stable properties, and is mainly cured on the surface of a material by the adhesion of an adhesion auxiliary agent in the ink to an object to be printed, such as polyurethane adhesives, polyacrylic adhesives and other adhesives. Therefore, the fluorescent ink anti-counterfeiting method can bond the down feather fibers into a cluster, seriously damage the filling power and the heat retention of the fibers and influence the wearability of the down feather fibers.

The anti-counterfeiting technology applied to the existing down products is a single textile taking down fibers as fillers, such as down jackets, down quilts and the like, and the anti-counterfeiting technology can not effectively prevent counterfeit products made of inferior or even synthetic down, so that the anti-counterfeiting technology taking the down fibers as the application objects is urgently needed to be developed.

Disclosure of Invention

The invention aims to overcome the defects of the anti-counterfeiting authentication technology of the existing down fiber and the down fiber product, provides an infrared anti-counterfeiting technology and an infrared anti-counterfeiting method, and realizes the traceability authentication of the down fiber raw material. The invention avoids the problems that the filling power and the heat retention of down feather fibers are reduced by an adhesive auxiliary agent and the wearability is influenced, hydrogen bonds are formed between the modified infrared anti-counterfeiting material and the fibers by a method without the adhesive to obtain the down feather with the characteristic infrared spectrum, and special equipment is designed and used for detection and authentication, so that the anti-counterfeiting system has the advantages of high confidentiality and objective accuracy of an authentication result.

The invention aims to provide a preparation method of anti-counterfeiting down fibers, which combines modified infrared anti-counterfeiting materials with down fibers through coulomb force and hydrogen bond acting force, and can obtain the down fibers with anti-counterfeiting function without adding adhesives.

In one embodiment of the invention, the modified infrared anti-counterfeiting material takes singly-doped or co-doped rare earth Yb (ytterbium) nano-scale inorganic non-metallic particles as anti-counterfeiting traceability markers; the co-doped rare earth comprises Y (yttrium) and Tm (thulium).

In one embodiment of the present invention, the preparation process of the modified infrared anti-counterfeiting material is as follows:

(1) coating: coating and modifying the nano-particles of the Yb (ytterbium) which is singly doped or co-doped with the rare earth by using a gamma-mercaptopropyltrimethoxysilane coupling agent (MPTMS);

(2) oxidizing by an oxidizing agent: oxidizing sulfydryl introduced to the surface of the nano-particles obtained after coating modification in the step (1) by using an oxidant into sulfonic acid groups to obtain a modified infrared anti-counterfeiting material;

in one embodiment of the invention, the preparation method of the anti-counterfeiting down feather fiber comprises the following specific steps:

(1) coating: coating and modifying the nano-particles of the Yb (ytterbium) which is singly doped or co-doped with the rare earth by using a gamma-mercaptopropyltrimethoxysilane coupling agent (MPTMS); the specific reaction conditions of the coating modification are as follows: every 1g of nano material and 15-25 mL of hydrosulphonyl silane coupling agent with the volume and the concentration of 90-99 percent react for 4-6 hours at the room temperature of 20-25 ℃ in a mixed system of alcohol and water (the ratio of alcohol to water is 3-9: 1) under the catalysis of 5-10 mL of ammonia water with the concentration of 27 percent;

(2) oxidizing by an oxidizing agent: oxidizing sulfydryl introduced to the surface of the nano-particles obtained after coating modification in the step (1) by using an oxidant into sulfonic acid groups to obtain a modified infrared anti-counterfeiting material; the specific reaction conditions for oxidizing the oxidant are as follows: the dosage of the oxidant of 90-99% mercaptosilane coupling agent per 1mL is 1-5 mL; the reaction condition is that the reaction is carried out in water dispersion liquid for 2 to 5 hours at the room temperature of 20 to 25 ℃;

(3) pre-finishing down feather: cleaning grease and cell membranes on the surfaces of the down fibers by using a detergent;

(4) preparing the anti-counterfeiting traceable down feather: preparing the modified infrared anti-counterfeiting material into an aqueous solution with the concentration of 2-5 g/L, and adjusting the pH of the solution to 3-4 by using hydrochloric acid to prepare a finishing liquid; soaking the down feather fibers pre-finished in the step (3) in finishing liquid, placing the down feather fibers in a constant-temperature shaking box, preserving heat for 2-4 hours at 50-70 ℃, and filtering and drying to obtain anti-counterfeiting traceable down feather; the bath ratio of the down fibers to the finishing liquid is 1: (20-100).

The second purpose of the invention is to provide a preparation method of the anti-counterfeiting fiber, which is to replace the down feather fiber with wool fiber or silk fiber.

The third purpose of the invention is to provide the anti-counterfeiting fiber prepared by the preparation method.

The fourth purpose of the invention is to provide a product containing the anti-counterfeiting fiber, which comprises composite fiber, yarn, powder and fabric.

The fifth purpose of the invention is to provide the application of the anti-counterfeiting fiber in the aspects of clothes, bedding and the like.

In one embodiment of the invention, the application is in the anti-counterfeiting aspect of the clothing and bedding.

In one embodiment of the invention, the anti-counterfeiting application is to use a detection device to identify and authenticate anti-counterfeiting fibers and products thereof; the detection device is cuboid, and a display screen, a switch, a signal lamp and a user identification lock module are arranged on the front side of the detection device; the upper part is provided with a transmitting diode and a receiving diode; the inside of the device is provided with a multi-interface infrared light emitting and receiving module, a light-electric signal processing and judging module and a reusable power supply module; one end of the multi-interface infrared light emitting and receiving module is connected with the emitting diode and the receiving diode, and the other end of the multi-interface infrared light emitting and receiving module is connected with the light-electric signal processing and judging module; the optical-electrical signal processing and judging module is also connected with a signal lamp and a display screen; the user identification lock module is connected with the reusable power supply module; the detection device has the function of a user identification lock to improve the confidentiality of the detection device, and the user identification lock can be one or more of a digital coded lock, a figure identification lock, fingerprint identification, face identification, voice identification and the like. The computer programs such as line connection among the modules, module operation and the like belong to the prior art. The invention only improves the design of selecting infrared transmitting-receiving modules with different wavelengths according to the characteristic spectrum combination of Yb and co-doped elements thereof on the basis of the prior art; the infrared transmitting and receiving modules of the device are aligned to fibers and textiles needing to be identified and authenticated, a switch of the corresponding detection device is pressed, and a corresponding result is displayed on a screen of the detection device.

The invention has the beneficial effects that:

the invention avoids the problems that the filling power and the heat retention of down feather fibers are reduced by an adhesive auxiliary agent and the wearability is influenced, hydrogen bonds are formed between the modified infrared anti-counterfeiting material and the fibers by a method without the adhesive to obtain the down feather with the characteristic infrared spectrum, and special equipment is designed and used for detection and authentication, so that the anti-counterfeiting system has the advantages of high confidentiality and objective accuracy of an authentication result. In addition, after the down fiber prepared by the invention is washed for 10 times by GB/T5713-1997 textile color fastness test, the traceable anti-counterfeiting down still has the characteristic infrared emission performance, and the test shows that the traceable anti-counterfeiting down fiber has good bonding fastness; the down feather fibers are placed in a pH 4-7 solution for soaking, so that the anti-counterfeiting material is not easy to fall off and has certain acid and alkali resistance.

Drawings

FIG. 1 is a schematic view of an infrared tracing anti-counterfeiting method for down feather fibers. Wherein 1 is down fiber after washing pretreatment; 2 is the anti-counterfeiting material after coating and modifying; 3 is anti-counterfeiting traceable down feather fiber loaded with anti-counterfeiting material; 4 is an anti-counterfeiting tracing down feather identification and authentication detector, and 5 is anti-counterfeiting nano particles; 6 is a mercaptosilane coupling agent.

Fig. 2 is a detection device used in the down fiber infrared tracing anti-counterfeiting method. Wherein, 7 is a multi-interface infrared light emitting and receiving module, 8 is a transmitting diode 9 is a receiving diode; 10 is an optical-electric signal processing and judging module; 11 is a display screen; 12 is a signal lamp; 13 is a switch; 14 is a reusable power supply module; the user identification lock module is indicated at 15.

FIG. 3 is a transmission electron microscope image of the nano anti-counterfeit substance.

FIG. 4 shows the rare earth Yb³⁺Coating of doped inorganic materials and modified fourier infrared spectra.

FIG. 5 is a drawing of rare earth Yb³⁺Infrared emission spectrum (900nm excitation) of doped inorganic materials.

FIG. 6 is a drawing of rare earth Yb³⁺Infrared emission schematic of doped inorganic materials (900nm excitation).

Fig. 7 is an anti-counterfeiting traceable down and its infrared emission spectrum (900nm excitation) after being washed 10 times with water.

Detailed Description

The following description of the preferred embodiments of the present invention is provided for the purpose of better illustrating the invention and is not intended to limit the invention thereto.

And (3) testing the water washing resistance:

the washing method refers to the color fastness to water of a GB/T5713-; one part of the down feather fiber is clamped between a piece of 40mm multiplied by 100mm multi-fiber attached fabric and a piece of 40mm multiplied by 100mm non-dyed fabric, the four sides are sewed (according to GB/T6151-1997, 9.3.3.4) to form a washing sample, and the washing sample is washed 10 times according to the washing procedure stated in GB/T5713-1997 standard (after being soaked in the solution and wetted to 100 percent of the weight of the down feather fiber, the pressure is 12.5 kPa); and taking the washed anti-counterfeiting traceable down feather and the unwashed anti-counterfeiting traceable down feather, and testing the infrared down-conversion emission spectra of the washed anti-counterfeiting traceable down feather and the unwashed anti-counterfeiting traceable down feather.

Conversion emission spectrum experiment: the emission spectra of the samples were tested using an FLS-980 steady state transient fluorescence spectrometer from Edinburgh Instruments, UK, with an excitation light source of 900nm semiconductor laser light provided by the New Catharan industry, and the testing was performed at room temperature.