阅读说明：本技术 近红外发光材料在编码中的应用 (Application of near-infrared luminescent material in coding ) 是由 周晶 翟雪娇 于 2018-06-21 设计创作，主要内容包括：本发明公开了一种近红外发光材料在编码中的应用。本发明提供的编码材料为在可见及近红外激光的激发下能够发射出近红外光的材料。可通过对不同波段的近红外光和不同材料所被激发的近红外光的强度不同进行编码,用于隐形防伪。此种防伪方法所制成的防伪标识具有信息容量大,隐蔽性好的特点,具有重要的应用价值。(The invention discloses an application of a near-infrared luminescent material in coding. The coding material provided by the invention is a material capable of emitting near infrared light under the excitation of visible and near infrared laser. The invisible anti-counterfeiting code can be used for invisible anti-counterfeiting by encoding near infrared light of different wave bands and near infrared light excited by different materials in different intensities. The anti-counterfeiting mark manufactured by the anti-counterfeiting method has the characteristics of large information capacity and good concealment, and has important application value.)

1. The application of near infrared luminescent material in coding.

2. Use according to claim 1, characterized in that: the near-infrared luminescent material is selected from at least one of rare earth materials, semiconductor materials, high molecular polymers, high molecular coordination polymers, small molecular organic matters, small molecular complexes and fluorescent protein;

the light-emitting wavelength range of the near-infrared light-emitting material is 700-2500 nm; the excitation light wavelength is 400nm-1700 nm.

3. Use according to claim 1 or 2, characterized in that: the rare earth element in the rare earth material is selected from at least one of lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, scandium and yttrium;

the rare earth material is selected from at least one of rare earth halides, rare earth-doped halides, rare earth oxides, rare earth-doped oxides, rare earth phosphates, rare earth-doped phosphates, rare earth sulfides, rare earth-doped sulfides, rare earth tellurides, rare earth silicates, rare earth carbonates, rare earth molybdates, rare earth vanadates, and rare earth borates;

the semiconductor material is at least one of metal sulfide, doped sulfide, metal selenide, doped selenide, metal phosphide, doped phosphide, metal arsenide, doped arsenide, metal telluride, doped telluride and carbon nano tube;

wherein, the metal element in the metal sulfide is at least one of silver, cadmium, zinc, lead, indium and copper; in the doped sulfide, doped selenide, doped phosphide, doped arsenide and doped telluride, the doping element is at least one of copper, silver, lead, bismuth, indium, gallium, iridium and tin;

the high molecular polymer is an organic conjugated polymer; specifically at least one selected from polythiophene, polypyrrole, poly (p-phenylene vinylene), polydopamine and polyoxadiazole;

the high molecular coordination polymer is a metal organic framework material; specifically, the metal oxide is at least one selected from europium-triphenylacid polymer, ytterbium-triphenylacid polymer, neodymium-triphenylacid polymer, zirconium tetracarboxylic acid porphyrin polymer and hafnium tetracarboxylic acid porphyrin polymer;

the micromolecular organic matter is selected from at least one of dyes Cy3, Cy3.5, Cy5, Cy5.5, Cy7, IR783, IR820, ICG and BODIPY;

the small molecule complex is at least one selected from zinc phthalocyanine, platinum phthalocyanine, zinc porphyrin and platinum porphyrin.

4. Use according to any one of claims 1 to 3, characterized in that: in the coding, the coding type is selected from at least one of paper, ink, printing, physics, biology, numbers, English characters, colors, seals and structures;

in the coding of the printing ink, the realization form of the coding is selected from at least one of photoluminescence printing ink, chemical encryption printing ink, multiple encryption printing ink, infrared anti-counterfeiting printing ink and anti-counterfeiting inkpad; the photoluminescent ink code is implemented in a form selected from at least one of letters, languages, pictures, numbers, logos, grayscale images, and color images;

in the codes of the numbers, the English characters and the colors, the background material of the codes is selected from at least one of paper, wood, glass, metal, plastic, marble, film material and electronic display material; the code realization form is selected from at least one of handwriting code, ink-jet printing, laser printing and seal;

specifically, the encoding includes: spatially distributing the near-infrared luminescent materials having the same or different emission spectra.

5. Use according to any one of claims 1 to 4, characterized in that: the code is an anti-counterfeiting code.

6. Use according to claim 5, characterized in that: the anti-counterfeiting code is realized in the form of at least one of a one-dimensional bar code, an invisible one-dimensional bar code, a two-dimensional matrix code, an invisible two-dimensional code, a digital sequence, an invisible digital sequence, a character sequence and an invisible character sequence.

7. The product encoded with the near-infrared luminescent material of any one of claims 1 to 6.

8. Use of the product of claim 7 for at least one of information encryption, article security, and biometric marking and imaging.

9. Use according to claim 8, characterized in that: the information encryption is at least one selected from digital encryption, character encryption and invisible encryption;

the article anti-counterfeiting is at least one selected from one-dimensional codes, monochromatic two-dimensional codes, color two-dimensional codes and invisible anti-counterfeiting.

Technical Field

The invention belongs to the field of materials, and relates to an application of a near-infrared luminescent material in coding.

Background

The code is an encryption means for information, wherein the optical code has a series of advantages of high identification speed, simple manufacture, large information capacity and the like, and the optical code comprises a space code, a time code, a frequency code and the like, and is used in the fields of secret communication, information encryption, article anti-counterfeiting, biological marking, imaging and the like, such as a one-dimensional bar code and a two-dimensional code which are already commercialized. The near infrared light refers to light with the wavelength of 700-2500nm, the light in the wavelength band has many novel physical properties, and compared with visible light (400-700nm), the near infrared light has the outstanding advantages of wide wavelength band range, invisible to human eyes, excellent stealth performance, good biological tissue penetrability and the like. The wide near infrared spectrum range endows the near infrared code with larger information capacity, the invisible near infrared code endows the near infrared code with special invisible advantages and can be used for invisible anti-counterfeiting codes, the near infrared code has excellent biological mark and imaging performance due to good biological tissue penetrability, and the excellent performance can enable the near infrared code to have huge potential application in the fields of information encryption, invisible anti-counterfeiting, biological mark and imaging and the like.

Disclosure of Invention

The invention aims to provide an application of a near-infrared luminescent material in coding.

The invention claims an application of a near-infrared luminescent material in coding.

In the application, the near-infrared luminescent material is selected from at least one of rare earth materials, semiconductor materials, high molecular polymers, high molecular coordination polymers, small molecular organic matters, small molecular complexes and fluorescent proteins;

in the near-infrared luminescent material, the luminescent wavelength range of the material is 700-2500nm, and the excitation wavelength of the material is 400-1700 nm.

The exciting light is a single-wavelength light source or a single-wavelength light source in a waveband from 400nm to 1700nm, and particularly is a single-wavelength light source.

The single-wavelength light source is one of a pulse laser, a continuous laser, a high-pressure mercury lamp, a low-pressure mercury lamp, a xenon lamp and an LED lamp, and is specifically a continuous laser;

the wavelength of the continuous laser is at least one of 405nm, 532nm, 650nm, 660nm, 740nm, 800nm, 808nm, 974nm, 980nm, 1210nm, 1470nm, 1490nm and 1550nm, specifically 808 nm.

Specifically, the rare earth element in the rare earth material is selected from at least one of lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, scandium, and yttrium;

the rare earth material may be specifically selected from at least one of rare earth halides, rare earth-doped halides, rare earth oxides, rare earth-doped oxides, rare earth phosphates, rare earth-doped phosphates, rare earth sulfides, rare earth-doped sulfides, rare earth tellurides, rare earth silicates, rare earth carbonates, rare earth molybdates, rare earth vanadates, and rare earth borates;

in the rare earth halide and the rare earth doped halide, the halide is fluoride, chloride or iodide;

the apparent size of the rare earth fluoride material is not limited, and the rare earth fluoride material can be at least one of a bulk level, a micron level, a nanometer level or a small molecular level; the dimension can be zero, one, two or three dimensional;

the nano-scale rare earth fluoride material can be a single-core rare earth nano material, a single-shell rare earth nano material or a multi-shell rare earth nano material;

the semiconductor material can be at least one of metal sulfide, doped sulfide, metal selenide, doped selenide, metal phosphide, doped phosphide, metal arsenide, doped arsenide, metal telluride, doped telluride and carbon nano tube;

wherein, the metal element in the metal sulfide is at least one of silver, cadmium, zinc, lead, indium and copper; in the doped sulfide, doped selenide, doped phosphide, doped arsenide and doped telluride, the doping element is at least one of copper, silver, lead, bismuth, indium, gallium, iridium and tin; the metal sulfide can be a single-core metal sulfide, a single-shell sulfide or a multi-shell sulfide;

the high molecular polymer can be specifically an organic conjugated polymer; specifically at least one selected from polythiophene, polypyrrole, poly (p-phenylene vinylene), polydopamine and polyoxadiazole;

the high-molecular coordination polymer can be specifically metal organic framework Materials (MOFs); specifically, the metal oxide is at least one selected from europium-triphenylacid polymer, ytterbium-triphenylacid polymer, neodymium-triphenylacid polymer, zirconium tetracarboxylic acid porphyrin polymer and hafnium tetracarboxylic acid porphyrin polymer;

the small molecule organic matter can be selected from at least one of dyes Cy3, Cy3.5, Cy5, Cy5.5, Cy7, IR783, IR820, ICG and BODIPY;

the small molecule complex is at least one selected from zinc phthalocyanine, platinum phthalocyanine, zinc porphyrin and platinum porphyrin.

In the coding, the coding type is selected from at least one of paper, ink, printing, physics, biology, numbers, English characters, colors, seals and structures;

in the coding of the printing ink, the realization form of the coding is selected from at least one of photoluminescence printing ink, chemical encryption printing ink, multiple encryption printing ink, infrared anti-counterfeiting printing ink and anti-counterfeiting inkpad; in particular photoluminescent ink codes.

The photoluminescence ink codes are realized in at least one of letters, languages, pictures, numbers, marks, gray images and color images;

in the codes of the numbers, the English characters and the colors, the background material of the codes is selected from at least one of paper, wood, glass, metal, plastic, marble, film material and electronic display material; the code realization form is selected from at least one of handwriting code, ink-jet printing, laser printing and stamp.

Specifically, the encoding includes: spatially distributing the near-infrared luminescent materials having the same or different emission spectra;

the near-infrared luminescent material is spatially distributed, so that the spatial coding of near-infrared light can be obtained, and the method can be used for information encryption, invisible anti-counterfeiting and the like; the near-infrared light coding method has the advantages that the frequency coding of near-infrared light can be obtained by coding materials with different emission spectrums, and the obtained near-infrared light coding has the double characteristics of simultaneous space and frequency coding, has larger information encryption capacity, and is better in invisible performance and anti-counterfeiting effect.

The code may specifically be an anti-counterfeiting code.

The anti-counterfeiting code is realized in the form of at least one of a one-dimensional bar code, an invisible one-dimensional bar code, a two-dimensional matrix code, an invisible two-dimensional code, a digital sequence, an invisible digital sequence, a character sequence and an invisible character sequence.

In addition, the product obtained by the near-infrared luminescent material coding and the application of the product in at least one of information encryption, article anti-counterfeiting, biological marking and imaging also belong to the protection scope of the invention. Wherein the information encryption is selected from at least one of number encryption, character encryption and stealth encryption;

the article anti-counterfeiting is at least one selected from one-dimensional codes, monochromatic two-dimensional codes, color two-dimensional codes and invisible anti-counterfeiting.

The instrument for collecting the information of the invisible encryption and the invisible anti-counterfeiting is one of a photomultiplier tube and a Charge Coupled Device (CCD), in particular to a charge coupled device.

The coding material provided by the invention is a material capable of emitting near infrared light under the excitation of visible and near infrared laser. The anti-counterfeiting code can be used for various anti-counterfeiting, especially invisible anti-counterfeiting by encoding different near-infrared light with different wave bands and different intensities of the near-infrared light excited by different materials. The anti-counterfeiting mark manufactured by the anti-counterfeiting method has the characteristics of large information capacity and good concealment, and has important application value.

Drawings

FIG. 1 is a photograph showing a cyclohexane dispersion used for a photoluminescent coding material. The left picture is NaYF₄:[email protected]₄Material diagram dispersed in cyclohexane, right panel NaErF₄@NaLuF₄Physical pattern dispersed in cyclohexane at a concentration of 10mg ml^-1。

FIG. 2 shows a NaYF dispersion₄:[email protected]₄The material is taken as a coding material to be handwritten on paper for printing numerical values, the handwritten contents are Arabic numbers 1, 2 and 3 and Roman numbers I, II and X, and the written printing paper photos are shot under a fluorescent lamp.

Fig. 3 is a near-infrared emission photograph of the printing paper of fig. 2 collected with a charge-coupled device under the excitation of a 808nm laser.

FIG. 4 shows NaYF to be dispersed₄:[email protected]₄The material is used as a coding material to be handwritten on paper printed with English characters, the handwritten content is English letters CNU, and the written printing paper photos are shot under a fluorescent lamp.

Fig. 5 is a near-infrared emission photograph of the printing paper of fig. 4 collected with a charge coupled device under 808nm laser excitation.

FIG. 6 shows NaYF to be dispersed₄:[email protected]₄The material is used as coding material to be handwritten on the paper of English character, the handwritten content is Capital Normal University, and the book is photographed under the daylight lampThe printed paper after writing is photographed.

Fig. 7 is a near-infrared emission photograph of the printing paper of fig. 6 collected with a charge coupled device under 808nm laser excitation.

FIG. 8 shows the use of dispersed NaErF₄@NaLuF₄After the material is sucked into the capillary, a near-infrared luminous false color photo is collected by a charge coupling device excited by laser at 808 nm.

FIG. 9 is Ag for photoluminescence near-infrared coding₂A real photograph of the cyclohexane dispersion of S.

FIG. 10 shows Ag in example 1₂Photo-induced near-infrared emission photograph of S cyclohexane dispersion.

FIG. 11 shows Ag to be dispersed₂S material is used as coding material to be handwritten on black paperboard, and the handwritten content is English letters Ag₂And S, shooting a written paperboard picture under a fluorescent lamp.

FIG. 12 is a photograph of the cardboard of FIG. 11 in the near infrared emission collected with a charge coupled device under 808nm laser excitation.

FIG. 13 is a photograph of a jam paper of FIG. 11 in the form of a near infrared luminescence false color collected at 808nm laser excitation using a charge coupled device.

Detailed Description

The present invention will be further illustrated with reference to the following specific examples, but the present invention is not limited to the following examples. The method is a conventional method unless otherwise specified. The starting materials are commercially available from the open literature unless otherwise specified. NaYF used in the following examples₄:[email protected]₄Among the materials, NaYF₄Nd is rare earth fluoride doped with rare earth, and the doping rate is 5 percent; NaYF₄:[email protected]₄The material is shown that the core is NaYF₄Nd, shell of NaLuF₄。