A fabric capable of anti-counterfeiting detection and its preparation method and application

Abstract

The present invention discloses a preparation method of an anti-counterfeiting and detectable fabric, comprising the following steps: mixing nanoparticles Au with a dye evenly and printing the mixture on a transfer substrate to form a transfer printing paper with a pattern; preparing a fabric, the surface of the fabric containing CeO2 and CeZrO x ; laminating the transfer printing paper with the fabric and heating to transfer the pattern on the transfer printing paper to the fabric, obtaining the anti-counterfeiting and detectable fabric; during the heating process, the nanoparticles Au in the dye combine with CeZrO x to form Au / CeZrO x , and the nanoparticles Au combine with CeO2 to form Au / CeO2. The preparation method of the anti-counterfeiting and detectable fabric of the present invention, through the distribution of CeO2 in the polyester substrate layer and the distribution of the polyurethane foam with CeZrOx, utilizes the transfer printing heating process, the dye containing nanoparticles Au sublimes, combines with CeZrO x to form Au / CeZrO x , combines with CeO2 to form Au / CeO2, can achieve differential dual Raman detection, endow the fabric with unique anti-counterfeiting information, and realize efficient anti-counterfeiting detection.

Description

Technical Field

[0001] The present invention relates to the technical field of textiles, and in particular to a method for preparing a fabric capable of anti-counterfeiting detection, the fabric capable of anti-counterfeiting detection prepared by the preparation method, and application of the preparation method in textiles such as fabrics. Background Art

[0002] Fabrics with anti-counterfeiting detection protect brands and supply chains, and can meet customers' needs for establishing traceable supply chains and sustainable brand development, ensuring that customers are provided with high-quality products. Fabrics with anti-counterfeiting detection prepared by transfer printing can meet customer needs while achieving brand protection. However, the existing processes lack relevant preparation processes that can be industrialized. Summary of the invention

[0003] In view of this, in order to overcome the defects of the prior art, one of the objectives of the present invention is to provide a method for preparing fabric that can be anti-counterfeiting detected.

[0004] In order to achieve the above object, the present invention adopts the following technical solutions:

[0005] A method for preparing a fabric capable of anti-counterfeiting detection comprises the following steps:

[0006] The nanoparticles Au and dye are mixed evenly and then printed on a transfer substrate to form a transfer printing paper with a pattern;

[0007] Preparation of a cloth having CeO2 and CeZrO on its surface x ;

[0008] The transfer printing paper is attached to the cloth and heated to transfer the pattern on the transfer printing paper to the cloth, thereby obtaining the anti-counterfeiting detectable cloth; during the heating process, the nanoparticles Au in the dye and CeZrO x Combined to form Au / CeZrO x , nanoparticles Au combine with CeO2 to form Au / CeO2;

[0009] The CeO2 is located at the first part of the surface of the fabric, and the CeZrO x The second part located on the surface of the fabric, the first part and the second part do not overlap at all, can form complementary patterns, and can avoid material waste. If the first part and the second part partially overlap or completely overlap, not only will it waste materials and cause an increase in production costs, but it will also lead to insignificant full-pull detection effects.

[0010] According to some preferred embodiments of the present invention, the fabric comprises a substrate layer and a foaming printing layer, the CeO2 is located in the substrate layer, the CeZrO xLocated in the foaming print layer, the CeO2 is located on the surface of the first part of the substrate layer, and the foaming print layer covers the surface of the second part of the substrate layer.

[0011] According to some preferred embodiments of the present invention, when preparing the fabric, the surface of the first part of the CeO2 substrate layer is firstly coated with CeZrO x The foaming printing layer covers the surface of the second part of the substrate layer. CeO2 must be embedded in the surface of the textile polyester substrate layer first, and then the foaming printing layer is prepared to cover another part of the surface of the textile polyester substrate layer. If the foaming printing layer is prepared first, and then CeO2 is embedded in the surface of the textile polyester substrate layer; because the foaming printing layer is prepared first, the raised foaming is not convenient for the subsequent blowing and spraying technology to spray the CeO2 / ethanol solution on part of the surface of the textile polyester substrate layer. In addition, the foaming printing layer is prepared first, and the subsequent blowing and spraying of the CeO2 / ethanol solution will cause CeO2 to enter the polyurethane of the foaming printing layer. The CeO2 entering the polyurethane hinders the CeZrO x Combined with Au nanoparticles, it affects the subsequent Raman detection effect.

[0012] According to some preferred embodiments of the present invention, CeO2 is uniformly dispersed in an ethanol-water solution to form a CeO2 / ethanol solution, and CeO2 is embedded in a partial or entire area of ​​the surface of the substrate layer by a spraying method. The ambient temperature of the spraying is 210-220°C. If the temperature is lower than 210°C, ethanol and water cannot be effectively volatilized; if the temperature is higher than 210°C, the polyester softens, and CeO2 penetrates into the interior of the polyester, making it impossible to combine CeO2 with nanoparticles Au during transfer printing. Preferably, the average particle size of the CeO2 particles is 50nm.

[0013] According to some preferred embodiments of the present invention, in the CeO2 / ethanol solution, the mass percentage of CeO2 is 8.0-10.0%, the mass percentage of ethanol is 60-70%, and the balance is water.

[0014] According to some preferred embodiments of the present invention, CeZrO x Dispersed in polyurethane foaming agent, and tetrahydrofuran and / or N,N-dimethylformamide are added to dissolve to obtain foaming printing paste, and the foaming printing paste is covered on the surface of the second part of the substrate layer to form a foaming printing layer. The ambient temperature of the spraying is 180-210℃. If the temperature is lower than 180℃, THF and DMF cannot be effectively volatilized; if the temperature is higher than 210℃, polyester softens, and polyurethane (CeZrO x ) penetrates into the polyester and cannot achieve transfer printing. x Combined with nanoparticle Au. CeZrO is preferred x The average particle size of the particles is 50 nm.

[0015] Preferably, the mass concentration of the polyurethane foaming agent is 50-80%. If the concentration of the polyurethane foaming agent is greater than 80%, the pores produced by the polyurethane foaming are too large, and a small amount of small CeZrOx particles will fall from the pores, affecting the subsequent Raman detection effect. If the concentration of the polyurethane foaming agent is less than 50%, the pores produced by the polyurethane foaming are too small, and the gold nanoparticles in the dye cannot enter the polyurethane and combine with CeZrOx.

[0016] According to some preferred embodiments of the present invention, polyurethane (CeZrO x ) CeZrO in the mixed solution x The mass ratio to the polyurethane foaming agent is 1:6-9.

[0017] In some embodiments, by weight, the polyurethane foaming agent is 60-70 parts, CeZrO x 5-10 parts, configured into polyurethane (CeZrO x ) mixture. Tetrahydrofuran (THF) and N,N-dimethylformamide (DMF) were used as solvents at a mass ratio of 0.45-0.55:1, and polyurethane (CeZrO x ) The mixed liquid is configured into a solution with a mass fraction of 8-12%, namely, a foaming printing slurry. The foaming printing slurry is sprayed onto the polyester substrate layer by a blowing spraying technology to form a foaming printing layer, which covers another part of the surface of the polyester substrate layer of the textile.

[0018] According to some preferred embodiments of the present invention, the dye includes, by weight: 10-20 parts of disperse dye, 10-15 parts of dispersant, 5-6 parts of high temperature resistant resin, 1-2 parts of nano gold particles, 1-2 parts of leveling agent, 0.5-1 part of defoaming agent, and 60-80 parts of deionized water.

[0019] Preferably, the disperse dye is 8111 red FFG, 8601 green FB, 8301 blue FFG; the dispersant is SN-5040 polycarboxylic acid sodium salt dispersant; the high temperature resistant resin is a mixture of one or more of acrylic resin and polyurethane resin; the leveling agent is fatty alcohol polyoxyethylene ether; the defoamer is a general-purpose water-based defoamer. The nano-gold particles are spherical gold nano-particles, preferably with a particle size of 10-20nm, compared with gold nanorods and asymmetric gold nano-particles, and CeO2, CeZrO x The combination has better Raman enhancement effect.

[0020] According to some preferred implementation aspects of the present invention, the anti-counterfeiting detection is performed using surface enhanced Raman technology with a scanning range of 100 to 1000 cm -1 .

[0021] According to some preferred embodiments of the present invention, the heating temperature during transfer printing is 180-240°C. If the temperature is lower than 180°C, the dye cannot be sublimated efficiently; if the temperature is higher than 240°C, the polyester changes from a highly elastic state to a viscous flow state, and transfer printing cannot be achieved. At the same time, the temperature is too high, the foaming time is short, the foaming is uneven, and the process is difficult to control. During transfer printing, the dye containing nano-gold particles sublimates and transfers from the kraft paper to the base material layer and the foaming printing layer of the fabric to form a pattern. At the same time, a complementary shape is formed by the design of the pattern (the pattern of the first part of the fabric containing CeO2 and the pattern of the first part of the fabric containing CeZrO2 are complementary to each other). x The pattern of the second part of the fabric is complementary to that of the second part of the fabric), which can avoid material waste.

[0022] Another object of the present invention is to provide a fabric with anti-counterfeiting detection prepared by the preparation method as described above or the application of the preparation method in textiles.

[0023] Due to the adoption of the above technical scheme, compared with the prior art, the present invention is beneficial in that: the preparation method of the fabric capable of anti-counterfeiting detection of the present invention, through the distribution of CeO2 in the polyester substrate layer and the distribution of polyurethane foaming with CeZrOx, utilizes the transfer printing heating process, the dye containing nanoparticles Au sublimates, and CeZrO x Combined to form Au / CeZrO x , combined with CeO2 to form Au / CeO2, can realize differentiated dual Raman detection, give the fabric unique anti-counterfeiting information, and achieve efficient anti-counterfeiting detection. BRIEF DESCRIPTION OF THE DRAWINGS

[0024] In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the following briefly introduces the drawings required for use in the description of the embodiments. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without creative work.

[0025] Figure 1 It is a schematic diagram of the structure of the cloth and the transfer printing paper in the preferred embodiment of the present invention;

[0026] Figure 2 It is a schematic diagram of the transfer printing of the cloth and the transfer printing paper when they are attached together in the preferred embodiment of the present invention;

[0027] Figure 3 This is a schematic diagram after transfer printing is completed in a preferred embodiment of the present invention;

[0028] Figure 4 This is a schematic diagram of a clothing sample prepared in a preferred embodiment of the present invention;

[0029] Figure 5 The schematic diagram and the physical diagram of the pattern in the preferred embodiment of the present invention;

[0030] Figure 6 This is a Raman detection effect diagram of anti-counterfeiting detection fabric in a preferred embodiment of the present invention;

[0031] Figure 7 This is a Raman detection effect diagram of the fabric in Comparative Example 3 of the present invention;

[0032] Among them: 1. kraft paper; 2. dye; 3. nano gold particles; 4. foaming printing paste; 5. granular CeZrOx; 6. granular CeO2; 7. polyester fabric substrate layer; 8. CeZrOx / Au particles; 9. CeO2 / Au particles. DETAILED DESCRIPTION

[0033] In order to enable those skilled in the art to better understand the technical solution of the present invention, the technical solution in the embodiments of the present invention will be clearly and completely described below in conjunction with the drawings in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work should fall within the scope of protection of the present invention.

[0034] In the following examples and comparative examples, the experimental methods used are conventional methods unless otherwise specified, and the materials, reagents, etc. used are all commercially available unless otherwise specified.

[0035] Polyester thermoplastic polyurethane (TPU), purchased from Yuyao Bangchao Plastic Chemical Co., Ltd., hardness 65-95; tetrahydrofuran (THF), average Mn2000, purchased from McLean Reagent Direct Sales Store; N,N-dimethylformamide (DMF), content ≥99.0%, purchased from Tianqing Experimental Reagent; kraft paper, purchased from Yiwu Qiaoguan Paper Products Co., Ltd., 300g; nanoparticle gold, purchased from Nanjing Xianfeng Nanomaterials Technology, particle size 10-20nm; polyethylene glycol (molecular weight 8000), purchased from Hefei Qiansheng Biotechnology, purity >98%; cerium oxide, zirconium oxide, purchased from Zhongyanhang Barium Metal Materials, Average particle size 50nm, purity 99%; polyester, purchased from Yongsheng Cotton Mill, white, shrinkage 10%; disperse dyes 8111 red FFG, 8601 green FB, 8301 blue FFG, high concentration water-based dyes, concentration 3%-8%, purchased from Deliou Screen Printing Mall; SN-5040 polycarboxylic acid sodium salt type dispersant, pH 7.5, solid content (mass %): 43, ionicity: anionic, purchased from Shenzhen Yoshida Chemical; acrylic resin is E0503, slightly yellow translucent emulsion, pH 6-7, solid content 35%, purchased from Shenzhen Yoshida Chemical; polyurethane resin density 1.55-1.65g / cm 3 , viscosity 11000-15000mPa.s, purchased from Suzhou Xiongcai International Trade; fatty alcohol polyoxyethylene ether, AEO-5, purchased from Meikeyin Daily Chemical; the defoaming agent is a general-purpose water-based defoaming agent, J0401, pH7-8, active matter content 15%, purchased from Shenzhen Yoshida Chemical.

[0036] like Figure 1-6 As shown, the method for preparing the anti-counterfeiting detectable fabric of the present invention comprises the following steps:

[0037] Step 1) Preparation of CeO2 / ethanol solution

[0038] CeO2 is uniformly dispersed in an ethanol-water solution to form a CeO2 / ethanol solution. In terms of mass percentage, the mass proportion of CeO2 in the CeO2 / ethanol solution is 8.0-10.0%, the mass proportion of ethanol is 60-70%, and the balance is water. The average particle size of CeO2 particles is 50nm.

[0039] Step 2) preparing foaming printing paste

[0040] Polyurethane foaming agent 60-70 parts, CeZrO x 5-10 parts, configured into polyurethane (CeZrO x ) mixed solution; tetrahydrofuran (THF) and N,N-dimethylformamide (DMF) were used as solvents in a mass ratio of 0.45-0.55:1, and polyurethane (CeZrO x) mixed liquid is prepared into a solution with a mass fraction of 8-12%, which is the foaming printing paste 4. CeZrO x The average particle size of the particles is 50 nm.

[0041] Step 3) Preparation of fabric substrate layer and foaming printing layer

[0042] Prepare a cloth, the cloth includes a substrate layer 7 and a foaming printing layer, CeO2 is located in the substrate layer 7, CeZrO x Located in the foaming printing layer, CeO2 is located on the surface of the first part of the substrate layer 7, and the foaming printing layer covers the surface of the second part of the substrate layer 7, and the first part and the second part do not overlap at all.

[0043] Specifically, CeO2 is first embedded in a part or all of the surface of the substrate layer 7 by blowing a CeO2 / ethanol solution through a blowing method. Then the foaming printing slurry 4 is covered on the surface of the substrate layer 7 to form a foaming printing layer. CeO2 must first be embedded in the surface of the textile polyester substrate layer 7, and then the foaming printing layer is prepared to cover another part of the surface of the textile polyester substrate layer 7. If the foaming printing layer is prepared first, and then CeO2 is embedded in the surface of the textile polyester substrate layer 7. Because the foaming printing layer is prepared first, the raised foaming is not convenient for the subsequent blowing technology to spray the CeO2 / ethanol solution on a part of the surface of the textile polyester substrate layer 7. In addition, the foaming printing layer is prepared first, and the subsequent blowing of the CeO2 / ethanol solution will cause CeO2 to enter the polyurethane of the foaming printing layer. The CeO2 entering the polyurethane hinders the CeZrO x Combined with Au nanoparticles, it affects the subsequent Raman detection effect.

[0044] Step 4) Preparation of transfer printing paper

[0045] The nanoparticles Au and the dye 2 are evenly mixed and then printed on the kraft paper 1 to form a transfer printing paper with a pattern.

[0046] In parts by weight, dye 2 includes: 10-20 parts of disperse dye, 10-15 parts of dispersant, 5-6 parts of high temperature resistant resin, 1-2 parts of nano gold particles, 1-2 parts of leveling agent, 0.5-1 parts of defoaming agent, and 60-80 parts of deionized water.

[0047] The disperse dyes are 8111 red FFG, 8601 green FB, and 8301 blue FFG; the dispersant is SN-5040 polycarboxylic acid sodium salt dispersant; the high temperature resistant resin is a mixture of one or more of acrylic resin and polyurethane resin; the nano-gold particles 3 are spherical gold nano-particles; the leveling agent is fatty alcohol polyoxyethylene ether; and the defoamer is a general-purpose water-based defoamer. The gold nanosphere particles are spherical gold nano-particles with a particle size of 10-20 nm. Compared with gold nanorods and asymmetric gold nanoparticles, they are similar to CeO2, CeZrO xThe combination has better Raman enhancement effect.

[0048] Step 5) Transfer printing

[0049] The transfer printing paper is attached to the fabric and heated to transfer the pattern on the transfer printing paper to the fabric, thereby obtaining fabric that can be detected for anti-counterfeiting.

[0050] During the heating process, the foaming printing layer foams, and the dye 2 is transferred from the kraft paper 1 to the polyester substrate layer 7 of the cloth and the porous polyurethane foaming printing layer to form a pattern. The dye containing nanoparticles Au sublimates, penetrates into the polyurethane pores and reacts with CeZrO x 5 combined to form Au / CeZrO x 8. Nanoparticle Au 3 combines with CeO26 on the surface of polyester substrate layer 7 to form Au / CeO29.

[0051] The heating temperature during transfer printing is 180-240°C. If the temperature is lower than 180°C, the dye 2 cannot be sublimated efficiently; if the temperature is higher than 240°C, the polyester changes from a highly elastic state to a viscous flow state, and transfer printing cannot be achieved. At the same time, the temperature is too high, the foaming time is short, the foaming is uneven, and the process is difficult to control. During transfer printing, the dye 2 sublimates and transfers from the kraft paper 1 to the base material layer 7 of the cloth and the foaming printing layer to form a pattern. At the same time, the complementary shapes are formed by the design of the pattern, which can avoid material waste.

[0052] Step 6) Anti-counterfeiting detection

[0053] Through surface enhanced Raman technology detection, the porous polyurethane foam printing layer pattern and the polyester substrate layer 7 surface pattern achieve Raman enhancement differentiation effect, realizing anti-counterfeiting detection. The scanning range of surface enhanced Raman detection is 100~1000cm -1 .

[0054] For the convenience of description and understanding, the above steps are numbered and described separately, but this is not limiting. In actual situations, at least some of the above steps can be performed simultaneously or in no particular order.

[0055] The anti-counterfeiting detectable fabric prepared by the above preparation method comprises two layers, a substrate layer 7 and a foaming printing layer. The dye 2 containing the nanoparticles Au is sublimated by transfer printing, and Au and CeZrO in the foaming printing layer are x Au is combined with CeO2 on the surface of the substrate layer 7. Through Raman detection, this fabric can achieve dual Raman anti-counterfeiting detection. The anti-counterfeiting detectable fabric prepared by transfer printing realizes the combination of the functionality and color of the dye 2, and utilizes the characteristics of transfer printing to realize the combination of Au with CeO2 and CeZrOx, producing a dual Raman effect with strong Raman effect in some parts and weak Raman effect in some parts, thereby realizing anti-counterfeiting detection.

[0056] Embodiment 1:

[0057] like Figure 1-5 As shown, the method for preparing the anti-counterfeiting detectable fabric in this embodiment specifically includes the following steps:

[0058] Step 1) Preparation of fabric substrate layer and foaming printing layer

[0059] The cloth comprises two layers, a polyester base material layer and a porous polyurethane foam printing layer. The porous polyurethane foam printing layer is located above the polyester base material layer, and the porous polyurethane foam printing layer covers a part of the polyester base material layer.

[0060] A CeO2 / ethanol solution was prepared, and CeO2 was embedded in the surface area of ​​the first part of the polyester substrate layer of the textile by a blowing method. The mass fraction of CeO2 in the CeO2 / ethanol solution was 8.5%, the mass fraction of ethanol was 60%, and the balance was water. The blowing environment temperature was 210°C. The average particle size of CeO2 particles was 50nm.

[0061] Preparation of tetrahydrofuran (THF) and N,N-dimethylformamide (DMF) / polyurethane (CeZrO x ) solution, i.e., foaming printing paste, is formed into a porous polyurethane foaming printing layer by a blowing method, which covers the surface area of ​​the second part of the textile polyester substrate layer. The first part and the second part do not overlap at all. CeZrO x The average particle size of the particles is 50 nm.

[0062] During preparation, 60 parts of polyurethane foaming agent, CeZrO x 8 parts, configured as polyurethane (CeZrO x ) mixed solution. The concentration of polyurethane foaming agent is 65%. Tetrahydrofuran (THF) and N,N-dimethylformamide (DMF) are used as solvents in a mass ratio of 0.5:1, and polyurethane (CeZrO x ) mixed liquid is prepared into a solution with a mass fraction of 10%, which is the foaming printing paste. The blowing environment temperature is 215℃.

[0063] Step 2) Preparation of transfer printing paper

[0064] The transfer printing paper substrate is kraft paper. Nanoparticle gold is mixed into the dye and printed on the kraft paper according to a predetermined pattern. The dye contains 15 parts of disperse dye, 12 parts of dispersant, 5 parts of high temperature resistant resin, 1 part of nano gold particles, 1 part of leveling agent, 1 part of defoaming agent, and 70 parts of deionized water. The gold nanosphere particles are spherical gold nanoparticles with a particle size of 10-20nm.

[0065] The disperse dyes are 8111 bright red FFG, 8601 green FB, and 8301 blue FFG; the dispersant is SN-5040 polycarboxylate sodium salt type dispersant; the high temperature resistant resin is acrylic resin; the nano gold particles are spherical gold nano particles; the leveling agent is fatty alcohol polyoxyethylene ether; and the defoaming agent is a general-purpose water-based defoaming agent.

[0066] Step 3) Transfer printing

[0067] Heated to 190℃, the foaming printing layer produces foam. The dye sublimates and transfers from the kraft paper to the base layer of the cloth and the foaming printing layer to form a pattern. The nanoparticles Au in the dye penetrate into the polyurethane pores and react with CeZrO x Combined to form Au / CeZrO x , the nanoparticles Au combine with the CeO2 on the surface of the polyester substrate layer to form Au / CeO2.

[0068] Step 4) Anti-counterfeiting detection

[0069] Finally, the surface enhanced Raman technique was used for detection, with a scanning range of 100 to 1000 cm -1 The porous polyurethane foam printing layer pattern and the polyester substrate layer surface pattern achieve the effect of Raman enhancement differentiation and realize anti-counterfeiting detection.

[0070] Embodiment 2:

[0071] like Figure 1-5 As shown, the method for preparing the anti-counterfeiting detectable fabric in this embodiment specifically includes the following steps:

[0072] Step 1) Preparation of fabric substrate layer and foaming printing layer

[0073] The cloth comprises two layers, a polyester base material layer and a porous polyurethane foam printing layer. The porous polyurethane foam printing layer is located above the polyester base material layer, and the porous polyurethane foam printing layer covers a part of the polyester base material layer.

[0074] A CeO2 / ethanol solution was prepared, and CeO2 was embedded in a part of the surface area of ​​the polyester substrate layer of the textile by a spraying method. The mass fraction of CeO2 in the CeO2 / ethanol solution was 9.8%, the mass fraction of ethanol was 70%, and the balance was water. The spraying environment temperature was 210°C.

[0075] Preparation of tetrahydrofuran (THF) and N,N-dimethylformamide (DMF) / polyurethane (CeZrO x ) solution, i.e., foaming printing paste, is formed into a porous polyurethane foaming printing layer by a blowing method, which covers another part of the surface of the polyester substrate layer of the textile.

[0076] During preparation, 70 parts of polyurethane foaming agent, CeZrO x9 parts, configured as polyurethane (CeZrO x ) mixed solution. The concentration of polyurethane foaming agent is 80%. Tetrahydrofuran (THF) and N,N-dimethylformamide (DMF) are used as solvents in a mass ratio of 0.5:1, and polyurethane (CeZrO x ) mixed liquid is prepared into a solution with a mass fraction of 12%, which is the foaming printing paste. The spraying environment temperature is 215℃.

[0077] Step 2) Preparation of transfer printing paper

[0078] The transfer printing paper is kraft paper, nanoparticle gold is mixed into the dye, and printed on the kraft paper according to a predetermined pattern. The dye contains 20 parts of disperse dye, 10 parts of dispersant, 6 parts of high temperature resistant resin, 2 parts of nano gold particles, 1 part of leveling agent, 0.5 parts of defoaming agent, and 75 parts of deionized water.

[0079] The disperse dyes are 8111 bright red FFG, 8601 green FB, and 8301 blue FFG; the dispersant is SN-5040 polycarboxylate sodium salt type dispersant; the high temperature resistant resin is acrylic resin; the nano gold particles are spherical gold nano particles; the leveling agent is fatty alcohol polyoxyethylene ether; and the defoaming agent is a general-purpose water-based defoaming agent.

[0080] Step 3) Transfer printing

[0081] Heated to 190℃, the foaming printing layer produces foaming. The dye sublimates and transfers from the kraft paper to the base layer of the cloth and the foaming printing layer to form a pattern, which complements each other. The nanoparticles Au in the dye penetrate into the pores of the polyurethane and react with CeZrO x Combined to form Au / CeZrO x , the nanoparticles Au combine with the CeO2 on the surface of the polyester substrate layer to form Au / CeO2.

[0082] Step 4) Anti-counterfeiting detection

[0083] Finally, the surface enhanced Raman technique was used for detection, with a scanning range of 100 to 1000 cm -1 The porous polyurethane foam printing layer pattern and the polyester substrate layer surface pattern achieve Raman enhancement differentiation effect and realize anti-counterfeiting detection.

[0084] Comparative Example 1

[0085] The difference between this comparative example and Example 1 is that the foaming printing layer is eliminated in this comparative example, that is, only CeO2 exists on the fabric, and no CeZrO x , and the corresponding Au / CeZrO is not generated later. x The remaining steps and parameters are basically the same as those in Example 1.

[0086] Comparative Example 2

[0087] The difference between this comparative example and Example 1 is that the fabric substrate layer of this comparative example does not contain CeO2, and the corresponding Au / CeO2 is not generated subsequently. The remaining steps and parameters are basically the same as Example 1.

[0088] Comparative Example 3

[0089] The difference between this comparative example and Example 1 is that the CeO2 in the substrate layer is eliminated in this comparative example, and 8 parts of CeZrO2 in the preparation of the foaming printing paste are replaced by 8 parts of CeZrO2. x Replaced with 4 parts CeO2 and 4 parts CeZrO x , that is, CeO2 and CeZrO x Together integrated in the foaming printing layer, the subsequent foaming printing layer contains Au / CeZrO x The remaining steps and parameters are basically the same as those in Example 1.

[0090] Comparative Example 4

[0091] The difference between this comparative example and Example 1 is that, in this comparative example, the mass proportion of CeO2 in the CeO2 / ethanol solution is 15%. At the same time, the preparation of the foaming printing layer is cancelled and CeZrO is prepared instead. x / ethanol solution, CeZrO x CeZrO / ethanol solution x The mass proportion of CeZrO is also 15%. x The CeZrO x Together with CeO2, it is embedded on the surface of the polyester substrate layer of the textile, so that Au / CeZrO is subsequently formed in the substrate layer. x The remaining steps and parameters are basically the same as those in Example 1.

[0092] Test Example 1

[0093] The fabrics prepared in the above-mentioned Example 1 and Comparative Examples 1-3 were subjected to Raman testing according to the following standards: Raman testing index: SNT 3236-2012 "Test method for identification of textile fibers - Raman spectroscopy".

[0094] In Example 1, a fabric with anti-counterfeiting detection prepared by transfer printing has a double Raman effect, and the detection effect is more obvious. The results are as follows: Figure 6 shown.

[0095] The fabrics prepared in Comparative Examples 1 and 2 only have a single Raman effect, and the detection effect is not obvious.

[0096] The fabric in Comparative Example 3 has Au / CeZrO xMixed with Au / CeO2, there is only a single Raman effect, such as Figure 7 shown.

[0097] Test Example 2

[0098] The fabrics prepared in the above-mentioned Example 1 and Comparative Example 4 were subjected to friction testing according to the following standards: Pilling test index: GB / T 4802.2-2008 "Textiles. Determination of pilling properties of fabrics. Part 2: Modified Martindale method".

[0099] The samples prepared in the above-mentioned Example 1 and Comparative Example 4 were washed 20 times. The specific operation was as follows: the washing temperature was 45°C, the sample was placed flat on the washing plane, the two ends were fixed with a clamping mechanism, the friction head fell to contact the sample, the running direction of the friction head was consistent with the longitudinal direction of the sample, the running speed was 1 reciprocating friction cycle per second, the single-way friction stroke was 10 cm, the downward pressure was 10 N, a total of 20 reciprocating friction cycles, and then dried at 120°C. The mechanical properties of the dried samples were measured. The test results of the performance after the water washing test are shown in Table 2 below:

[0100] Table 2 Test results From the results in Table 2, it can be seen that Example 1 does not need to add more CeZrO x and CeO2, and at the same time have better friction performance. Comparative Example 4 not only needs to add more CeZrO x and CeO2, which costs money and is more prone to pilling due to the addition of more particles.

[0101] The Example 1 and the Comparative Example 4 rubbed 10,000 times were subjected to Raman detection according to the following standards: Raman detection index: SNT 3236-2012 "Test method for identification of textile fibers - Raman spectroscopy". The Example 1 and the Comparative Example 4 still have a dual Raman effect.

[0102] The Example 1 and the Comparative Example 4 rubbed 100,000 times were subjected to Raman detection according to the following standards: Raman detection index: SNT 3236-2012 "Textile fiber identification test method - Raman spectroscopy". The Example 1 still has a double Raman effect, while the Comparative Example 4 has no Raman effect.

[0103] The test results show that the foaming of the foaming printing layer in Example 1 has a significant effect on the Au / CeZrO x and Au / CeO2 in the substrate layer played a protective role, while the Au / CeZrO x Au / CeO2 is in direct contact with the friction head. When the friction times reach 100,000 times, Au / CeZrOx Au / CeO2 is basically depleted and the Raman effect disappears.

[0104] In summary, compared with Comparative Example 4, Example 1 does not need to add more CeZrO x and CeO2, and has better friction performance. In addition, the fabric can still maintain a good dual Raman detection effect after multiple wears in actual use. Compared with comparative example 4, embodiment 1 not only has good friction resistance, anti-pilling, cost saving, economic and environmental protection, but also can meet the sustainable dual Raman detection, and has good practical significance.

[0105] The present invention combines the color and functionality of the dye by combining the nanoparticle Au with the dye. The dye containing the nanoparticle Au sublimates and combines with CeZrO x Combined to form Au / CeZrO x , combined with CeO2 to form Au / CeO2, can achieve dual Raman detection effect; combine transfer printing with anti-counterfeiting detection to effectively protect the brand. The beneficial effects of the present invention are as follows:

[0106] 1. The dye is combined with functional gold nanoparticles to achieve the combination of color and functionality of the dye.

[0107] 2. Taking advantage of the characteristics of transfer printing, the nanoparticles Au are combined with CeO2 of the polyester substrate layer and CeZrOx of the foaming printing layer respectively, realizing the differentiation of functional particles in different pattern layers, and then realizing the dual Raman detection effect, achieving the purpose of anti-counterfeiting detection.

[0108] 3. With the help of the foaming process, the fabric obtains a three-dimensional flower pattern, and the foaming printing layer also has functional particles. The foaming printing layer and the polyester substrate layer have the characteristics of strong Raman effect in some parts and weak Raman effect in others, realizing differentiated dual Raman detection.

[0109] 4. Different patterns can be designed by utilizing the characteristics of transfer printing. By changing the distribution of dyes combined with nanoparticle Au on kraft paper, the distribution of CeO2 in the polyester substrate layer, and the distribution of polyurethane foam with CeZrOx, and using differentiated dual Raman detection, unique anti-counterfeiting information can be given to the fabric, achieving efficient anti-counterfeiting detection;

[0110] 5. The method of the present application uses a transfer printing process to combine nanoparticle Au with a dye, thereby achieving a combination of the color and functionality of the dye; there is no need to combine Au with Ceo2 and CeZrOx at the beginning, and the heat of transfer printing is fully utilized to combine the three substances in pairs to achieve a dual Raman detection effect.

[0111] The above embodiments prepared by the method of the present invention are only for illustrating the technical concept and features of the present invention, and their purpose is to enable people familiar with the technology to understand the content of the present invention and implement it accordingly, and they cannot be used to limit the protection scope of the present invention. Any equivalent changes or modifications made according to the spirit and essence of the present invention should be included in the protection scope of the present invention.

Claims

1. A method for preparing anti-counterfeiting detectable fabric, characterized in that: The steps include: The nanoparticles Au and dye are mixed evenly and then printed on a transfer substrate to form a transfer printing paper with a pattern; Preparation of a cloth containing CeO2 and CeZrO x ; Laminating the transfer printing paper with the cloth and heating the paper so that the pattern on the transfer printing paper is transferred to the cloth, thereby obtaining the anti-counterfeiting detectable cloth; During the heating process, the Au nanoparticles in the dye and CeZrO x Combined to form Au / CeZrO x , nanoparticles Au combine with CeO2 to form Au / CeO2; The CeO2 is located in the first part of the fabric, the CeZrO x Located at a second portion of the fabric, the first portion and the second portion do not overlap at all; The fabric comprises a substrate layer and a foaming printing layer, wherein the CeO2 is located in the substrate layer, and the CeZrO x Located in the foaming printing layer, the CeO2 is located on the surface of the first part of the substrate layer, and the foaming printing layer covers the surface of the second part of the substrate layer; When preparing the fabric, CeO2 is first applied to cover the surface of the first portion of the substrate layer; Then CeZrO x The foaming printing layer covers the surface of the second part of the substrate layer; Evenly dispersing CeO2 in an ethanol aqueous solution to form a CeO2 / ethanol solution, and embedding CeO2 on the surface of the first portion of the substrate layer by a spraying method; CeZrO x The polyurethane foam is dispersed in a polyurethane foaming agent, and tetrahydrofuran and / or N,N-dimethylformamide are added for dissolution to obtain a foaming printing paste, and the foaming printing paste is covered on the surface of the second part of the substrate layer to form a foaming printing layer.

2. The preparation method according to claim 1, characterized in that: The CeZrO x The mass ratio of polyurethane foaming agent to polyurethane foaming agent is 1:6-9.

3. The preparation method according to claim 1, characterized in that The anti-counterfeiting detection is carried out using surface enhanced Raman technology with a scanning range of 100~1000 cm -1 .

4. A fabric with anti-counterfeiting detectability prepared by the preparation method according to any one of claims 1 to 3.

5. Use of the preparation method according to any one of claims 1 to 3 in textiles.

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