WO2020147632A1 - 一种多重响应型荧光油墨及制备方法 - Google Patents

一种多重响应型荧光油墨及制备方法 Download PDF

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WO2020147632A1
WO2020147632A1 PCT/CN2020/071038 CN2020071038W WO2020147632A1 WO 2020147632 A1 WO2020147632 A1 WO 2020147632A1 CN 2020071038 W CN2020071038 W CN 2020071038W WO 2020147632 A1 WO2020147632 A1 WO 2020147632A1
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parts
weight
imprint
agent
fluorescent ink
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PCT/CN2020/071038
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English (en)
French (fr)
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向华
唐瑜
覃月敏
苏丽婵
林木雄
唐晖然
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广东轻工职业技术学院
兰州大学
惠州市随和科技有限公司
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Publication of WO2020147632A1 publication Critical patent/WO2020147632A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/102—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/106—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C09D11/107—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from unsaturated acids or derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/106—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C09D11/108—Hydrocarbon resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/50—Sympathetic, colour changing or similar inks

Definitions

  • the invention relates to a fluorescent ink and a preparation method, in particular to a multi-response fluorescent ink and a preparation method.
  • Fluorescent ink is one of the most important branches of anti-counterfeiting ink, and it is also the ivy in the field of anti-counterfeiting ink technology.
  • the fluorescent inks on the existing market can be divided into three categories: ultraviolet excitation, infrared excitation and visible light excitation according to the excitation light.
  • the main technical feature is that when the excitation light is irradiated on the graphic imprint printed by the fluorescent ink, the imprint emits visible light.
  • the main radiation this technology is quite mature, and the anti-counterfeiting level is relatively low.
  • the market needs new fluorescent ink products with relatively high anti-counterfeiting strength, but there are relatively few products and technologies in this area.
  • the invention provides a multi-response fluorescent ink and a preparation method to at least solve the problem of low anti-counterfeiting level of fluorescent ink in the prior art.
  • the present invention provides a multi-response fluorescent ink, which is characterized in that the multi-response fluorescent ink is composed of the following components in parts by weight: 0.5-5 parts by weight of rare earth metal salts, 1-5 parts by weight of organic ligands , 50-70 parts by weight of organic solvent, 20-30 parts by weight of polymer resin, 0.1-2 parts by weight of additives, the rare earth metal salt is selected from one or two of europium salt and terbium salt, and the polymer
  • the resin is selected from one or more of polyamide resin, acrylic resin, epoxy resin, vinyl resin, and polyurethane resin, and the auxiliary agent is selected from medium slip agent, adhesion enhancer, drier, diluting agent, One or more of viscosity reducing agent, thinner, antioxidant, degelling agent, defoaming agent, surfactant, anti-pinhole agent, and plasticizer, the organic ligand is ⁇ -diketone ligand , The molecular formula of the ⁇ -
  • R 1 is selected from -CH 3 , -CF 3 , -CR 3 , -C 6 H 5 , R 2 is selected from
  • the rare earth metal salt is composed of 0.3-2 parts by weight of europium salt and 0.3-2 parts by weight of terbium salt.
  • the europium salt is selected from one or more of nitrate or chloride salt, and the terbium salt One or more selected from nitrate or chloride salt.
  • organic ligand is N-(pyridin-2-yl)-benzoylacetamide.
  • organic solvent is selected from one or more of industrial alcohol, propanol and butanol.
  • the organic solvent is composed of 30-40 parts by weight of industrial alcohol and 30-40 parts by weight of butanol.
  • the present invention also provides a method for preparing the above fluorescent ink, which includes the following steps:
  • Step 1 Take the rare earth metal salt and organic ligand in a part of the organic solvent (the amount of organic solvent added is subject to the complete dissolution of the organic ligand, mostly 5-30 parts by weight of the organic solvent), and stir to dissolve it. Stir for 1-4 hours at °C;
  • Step 2 Mix the polymer resin, auxiliary agent, grinding aid, and remaining organic solvent into the mixed solution obtained in Step 1, and shake and disperse for 60-240 min under airtight conditions;
  • Step 3 Filter the mixed liquid obtained in Step 2 to remove the grinding aids, and collect the filtrate to be the fluorescent ink;
  • the grinding aid is selected from one or more of glass beads, quartz sand, and metal balls.
  • the present invention also provides a method for identifying the anti-counterfeiting features of the fluorescent ink, which includes the following steps:
  • Step 1 Use ink to apply an imprint on the surface of the medium, and after the imprint is cured, use a 250-300nm ultraviolet shortwave lamp to irradiate the imprint, and the imprint emits orange-red fluorescence;
  • Step 2 Take the key substance key1 to fumigate the imprint for 1-20 minutes, and irradiate the imprint with a 250-300nm ultraviolet shortwave lamp, and the imprint emits green fluorescence;
  • the key substance key1 is a volatile acid.
  • step 3 Further, the method further includes step 3 and step 4 as follows:
  • Step 3 Take the key substance key2 to fumigate the imprint for 1-20 minutes, and irradiate the imprint with a 250-300nm ultraviolet shortwave lamp, and the imprint emits red fluorescence;
  • Step 4 Remove the key material key2, and irradiate the imprint with a 250-300nm ultraviolet shortwave lamp, and the imprint emits orange-red fluorescence;
  • the key material key2 is a volatile base, and the volatile base is an organic amine.
  • the key substance key1 is concentrated hydrochloric acid
  • the key substance key2 is triethylamine
  • the present invention also provides another anti-counterfeiting feature identification method of the fluorescent ink, which includes the following steps: the ink is detected by the first ultraviolet light and the second ultraviolet light respectively, and the wavelength of the first ultraviolet light is 270-290 nm, so The wavelength of the second ultraviolet light is 350-380 nm, the ink emits orange-red fluorescence under the irradiation of the first ultraviolet light, and the ink emits green fluorescence under the irradiation of the second ultraviolet light.
  • the present invention uses rare earth metal salts to prepare fluorescent inks, which makes the fluorescent inks present different fluorescent colors under ultraviolet conditions of different wavelengths, improves the anti-counterfeiting effect, and has the advantages of high anti-counterfeiting level and strong anti-counterfeiting ability.
  • the fluorescent ink of the present invention can use multiple stimuli to make the fluorescent ink have different fluorescent color responses, realize the fluorescent anti-counterfeiting effect, make the detection step complicated and concealed, greatly increase the difficulty of counterfeiting, and improve the anti-counterfeiting level.
  • the fluorescent ink of the present invention has simple preparation process, low cost, low promotion resistance, and has broad application prospects.
  • FIG. 1 is a diagram of the result of using the first anti-counterfeiting feature identification method in Embodiment 1 of the present invention
  • FIG. 2 is a diagram of the result of using the second anti-counterfeiting feature identification method in Embodiment 1 of the present invention.
  • the fluorescent ink of the embodiment of the present invention is composed of the following components in parts by weight: 0.38 parts by weight of europium nitrate, 0.37 parts by weight of terbium nitrate, 1.2 parts by weight of N-(pyridin-2-yl)-benzoylacetamide, and 38.05 parts by weight of industrial alcohol.
  • the rare earth metal salt is selected from one or two of europium salt and terbium salt
  • the organic ligand is ⁇ -Diketone molecules
  • the polymer resin is a polyamide resin
  • the auxiliary agent is a slip agent and an adhesion enhancer are mixed in a mass ratio of 1:1.
  • Step 1 Mix industrial alcohol and n-butanol evenly, and configure organic solvent
  • Step 2 Take europium nitrate, terbium nitrate, and N-(pyridin-2-yl)-benzoylacetamide in 10 parts by weight of an organic solvent, stir to dissolve, and stir at 55-60°C for 2 hours;
  • Step 3 Mix the polymer resin, additives, glass beads, and the remaining organic solvent into the mixed solution obtained in step 2, and shake and disperse for 120 min under airtight conditions;
  • Step 4 Filter the mixed liquid obtained in Step 3 to remove the glass beads, and collect the filtrate to be the fluorescent ink of the embodiment of the present invention
  • the fluorescent ink of the embodiment of the present invention is composed of the following components in parts by weight: 0.76 parts by weight of europium nitrate, 0.74 parts by weight of terbium nitrate, 2.4 parts by weight of N-(quinolin-2-yl)-benzoylacetamide, and industrial alcohol 36.10 parts by weight, 30 parts by weight of n-butanol, 29 parts by weight of polymer resin, 1 part by weight of additives, the rare earth metal salt is selected from one or two of europium salt and terbium salt, and the organic ligand is ⁇ -diketone molecules, the polymer resin is selected from epoxy resin, and the auxiliary agent is a slip agent and an adhesion enhancer mixed in a mass ratio of 1:1.
  • Step 1 Mix industrial alcohol and n-butanol evenly, and configure organic solvent
  • Step 2 Take europium nitrate, terbium nitrate, and N-(pyridin-2-yl)-benzoylacetamide in 5 parts by weight of an organic solvent, stir to dissolve, and stir at 40-50°C for 4 hours;
  • Step 3 Mix the polymer resin, additives, metal balls, and the remaining organic solvent into the mixed solution obtained in step 2, and shake and disperse for 120 minutes under airtight conditions;
  • Step 4 Filter the mixed liquid obtained in Step 3 to remove the metal balls, and collect the filtrate to be the fluorescent ink of the embodiment of the present invention
  • the fluorescent ink of the embodiment of the present invention is composed of the following components in parts by weight: 1.13 parts by weight of europium nitrate, 1.12 parts by weight of terbium nitrate, 0.5-5 parts by weight, and 3.6 parts by weight of N-(indol-2-yl)-benzoylacetamide Parts by weight, 34.15 parts by weight of industrial alcohol, 30 parts by weight of n-butanol, 29 parts by weight of polymer resin, 1 part by weight of additives, the rare earth metal salt is selected from one or two of europium salt and terbium salt, so
  • the organic ligand is a ⁇ -diketone molecule
  • the polymer resin is selected from vinyl resin
  • the auxiliary agent is a slip agent and an adhesion enhancer are mixed in a mass ratio of 1:1.
  • Step 1 Mix industrial alcohol and n-butanol evenly, and configure organic solvent
  • Step 2 Take europium nitrate, terbium nitrate, and N-(pyridin-2-yl)-benzoylacetamide in 20 parts by weight of an organic solvent, stir to dissolve, and stir at 55-60°C for 2 hours;
  • Step 3 Mix the polymer resin, additives, glass beads, and the remaining organic solvent into the mixed solution obtained in step 2, and shake and disperse for 120 min under airtight conditions;
  • Step 4 Filter the mixed liquid obtained in Step 3 to remove the glass beads, and collect the filtrate to be the fluorescent ink of the embodiment of the present invention
  • the fluorescent ink of the embodiment of the present invention is composed of the following components in parts by weight: 1.51 parts by weight of europium nitrate, 1.49 parts by weight of terbium nitrate, 4.8 parts by weight of N-(2-benzimidazole)-benzoylacetamide, and 32.20 parts by weight of industrial alcohol. Parts by weight, 30 parts by weight of n-butanol, 20-30 parts by weight of polymer resin, 0.1-2 parts by weight of auxiliary agent, the organic ligand is ⁇ -diketone molecule, and the polymer resin is selected from polyurethane resin,
  • the auxiliary agent is a slip agent and an adhesion enhancer mixed in a mass ratio of 1:1.
  • the steps of the first anti-counterfeiting feature identification method are as follows:
  • Step 1 Use ink to apply an imprint on the surface of the medium (plastic or paper), and after the imprint is cured, use a 250-300nm ultraviolet shortwave lamp to irradiate the imprint, and the imprint emits orange-red fluorescence;
  • Step 2 Take concentrated hydrochloric acid (key1) in a closed container, place the medium with the mark in the container, and make the acidic substance volatilized by the concentrated hydrochloric acid fumigate the mark for 1-20min (usually 2-5min is enough) ), and use a 250-300nm ultraviolet shortwave lamp to irradiate the fumigated imprint, and the imprint emits green fluorescence;
  • Step 3 Take triethylamine (key 2) to fumigate the imprint treated with concentrated hydrochloric acid for 1-20 minutes, and irradiate the imprint with a 250-300nm ultraviolet shortwave lamp, and the imprint emits red fluorescence;
  • Step 4 Use a hair dryer to remove the triethylamine on the imprint, and again use a 250-300nm ultraviolet shortwave lamp to irradiate the imprint, and the imprint emits orange-red fluorescence.
  • the steps of the second anti-counterfeiting feature identification method are as follows: use ink to smear an imprint on the surface of the medium (plastic or paper), and after the imprint is cured, use the first ultraviolet light and the second ultraviolet light to detect the ink, the first The wavelength of the ultraviolet light is 280 nm, the wavelength of the second ultraviolet light is 365 nm, the ink emits orange-red fluorescence under the irradiation of the first ultraviolet light, and the ink emits green fluorescence under the irradiation of the second ultraviolet light.
  • the color development state of the fluorescent ink of embodiment 1 of the present invention during the first anti-counterfeiting feature identification method is shown in Figure 1, which is printed in concentrated hydrochloric acid ( The key substance key1) and triethylamine (key substance key2) will show fluorescent green and fluorescent red respectively after fumigation treatment, and show orange-red fluorescence after removing triethylamine.
  • the color development state of the fluorescent ink in the second anti-counterfeiting feature identification method of Example 2 of the present invention is shown in Figure 2.
  • the luminous position of the imprint under the irradiation of 280nm ultraviolet light falls in the orange-red fluorescent area of the CIE1931 diagram, and the imprint is The light-emitting position under the irradiation of 365nm ultraviolet light falls in the green fluorescent area of CIE1931.
  • the ink imprint can be stimulated by using different conjugate acids (key material key1) and different conjugate bases (key material key2) to achieve fluorescence.
  • the color change, soaking or fumigation, etc. can be used to stimulate the ink imprint, but the ink imprint is easy to recover after the fumigation method is stimulated, and multiple anti-counterfeiting inspections can be carried out.
  • the soaking method will damage the ink and affect the ink imprint. Reuse and anti-counterfeiting inspection.
  • Examples 1-4 of the present invention europium salt and terbium salt are mixed and combined with N-(pyridin-2-yl)-benzoylacetamide to prepare the complex, so that the fluorescent ink with the complex is displayed under different wavelengths of ultraviolet conditions Different fluorescent colors improve the anti-counterfeiting effect, and have the advantages of high anti-counterfeiting level and strong anti-counterfeiting ability.
  • the fluorescent inks of Examples 1-4 of the present invention have different fluorescent color response effects under the stimulation of acid and alkali conditions, and have strong anti-counterfeiting performance.
  • the detection steps are complicated and concealed, which greatly increases the difficulty of fraud.
  • the existing fluorescent ink can only display monochromatic fluorescence, and under the stimulation of acid and alkali conditions, the fluorescent color will not change, resulting in limited anti-counterfeiting inspection methods of fluorescent ink and poor anti-counterfeiting performance. Therefore, the fluorescent ink of the embodiment of the present invention Compared with the existing fluorescent ink, the anti-counterfeiting level is improved. In addition, the fluorescent ink of the embodiment of the present invention has a simple preparation process, low cost, low promotion resistance, and has broad application prospects.

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Abstract

一种多重响应型荧光油墨及制备方法，由下列重量份比的组分组成：稀土金属盐0.5-5重量份、有机配体1-5重量份、有机溶剂50-70重量份、高分子树脂20-30重量份、助剂0.1-2重量份，所述稀土金属盐选自铕盐、铽盐中的一种或两种，所述有机配体为β-二酮类分子，所述高分子树脂选自丙烯酸树脂、环氧树脂、乙烯树脂、聚氨酯中的一种或多种，所述助剂选自催干剂、冲淡剂、减粘剂、稀薄剂、抗氧化剂、反胶化剂、消泡剂、表面活性剂、防针孔剂、爽滑剂、增塑剂中的一种或多种。本发明的荧光油墨在不同波长的紫外条件下呈现不同的荧光颜色，经不同物质刺激可以呈现多种颜色荧光，具有防伪级别高、防伪能力强的优点。

Description

一种多重响应型荧光油墨及制备方法 技术领域
本发明涉及一种荧光油墨及制备方法，特别是涉及一种多重响应型荧光油墨及制备方法。
背景技术
荧光油墨是防伪油墨最重要的分支之一，同时也是防伪油墨技术领域的常青藤。现有市场上的荧光油墨按照激发光可分为紫外激发、红外激发和可见光激发三大类，主要技术特征为当激发光照射到由荧光油墨印刷的图文印记上时，印记发出以可见光为主的辐射，这个技术已经相当成熟，防伪级别比较低。市场需要防伪力度比较高的荧光油墨新产品，而这方面的产品和技术比较少。
发明内容
本发明提供了一种多重响应型荧光油墨及制备方法，以至少解决现有技术中荧光油墨防伪级别低的问题。
本发明提供了一种多重响应型荧光油墨，其特征在于，所述多重响应型荧光油墨由下列重量份比的组分组成：稀土金属盐0.5-5重量份、有机配体1-5重量份、有机溶剂50-70重量份、高分子树脂20-30重量份、助剂0.1-2重量份，所述稀土金属盐选自铕盐、铽盐中的一种或两种，所述高分子树脂选自聚酰胺树脂、丙烯酸树脂、环氧树脂、乙烯树脂、聚氨酯树脂中的一种或多种，所述助剂选自中爽滑剂、附着力增强剂、催干剂、冲淡剂、减粘剂、稀薄剂、抗氧化剂、反胶化剂、消泡剂、表面活性剂、防针孔剂、增塑剂的一种或多种，所述有机配体为β-二酮配体，所述β-二酮配体分子式如下：
Figure PCTCN2020071038-appb-000001
其中R 1选自-CH 3、-CF 3、-CR 3、-C 6H 5、R 2选自
Figure PCTCN2020071038-appb-000002
Figure PCTCN2020071038-appb-000003
Figure PCTCN2020071038-appb-000004
或其它N杂环化合物。
进一步地，所述稀土金属盐由0.3-2重量份铕盐和0.3-2重量份的铽盐组成，所述铕盐选自硝酸盐或氯盐中的一种或多种，所述铽盐选自硝酸盐或氯盐中的一种或多种。
进一步地，所述有机配体为N-(吡啶-2-基)-苯甲酰乙酰胺。
进一步地，所述有机溶剂选自工业酒精、丙醇、丁醇的一种或多种。
更进一步地，所述有机溶剂由30-40重量份的工业酒精和30-40重量份的丁醇组成。
本发明还提供了一种上述荧光油墨的制备方法，包括步骤如下：
步骤1：取稀土金属盐、有机配体于部分有机溶剂(有机溶剂的加入量以有机配体完全溶解为准，多为5-30重量份有机溶剂)中，并搅拌溶解，在40-80℃下搅拌1-4小时；
步骤2：将高分子树脂、助剂、助磨剂、剩余有机溶剂混合加入步骤1所得混合液中，并在密闭条件下震荡分散60-240min；
步骤3：将步骤2所得混合液过滤，除去助磨剂，收集滤液即为荧光油墨；
所述助磨剂选自玻璃珠、石英砂、金属球中一种或多种。
本发明还提供了一种上述荧光油墨的防伪特征鉴别方法，包括步骤如下：
步骤1：使用油墨在介质表面涂抹印记，并待印记固化后，使用250-300nm紫外短波灯对印记进行照射，所述印记发橘红色荧光；
步骤2：取密匙物质key1对印记进行熏蒸1-20min，并使用250-300nm紫外短波灯对印记进行照射，所述印记发绿色荧光；
所述密匙物质key1为挥发性酸。
进一步地，所述方法还包括步骤3、步骤4如下：
步骤3：取密匙物质key2对印记进行熏蒸1-20min，并使用250-300nm紫外短波灯对印记进行照射，所述印记发红色荧光；
步骤4：去除密匙物质key2，使用250-300nm紫外短波灯对印记进行照射，所述印记发橘红色荧光；
所述密匙物质key2为挥发性碱，所述挥发性碱为有机胺。
更进一步地，所述密匙物质key1为浓盐酸，所述密匙物质key2为三乙胺。
本发明还提供了另一种上述荧光油墨的防伪特征鉴别方法，包括步骤如下：分别使用第一紫外光、第二紫外光对油墨进行检测，所述第一紫外光波长为270-290nm，所述第二紫外光波长为350-380nm，所述油墨在第一紫外光照射下发橘红色荧光，所述油墨在第二紫外光照射下发绿色荧光。
本发明相对于现有技术，采用稀土金属盐制备荧光油墨，使荧光油墨在不同波长的紫外条件下呈现不同的荧光颜色，提高防伪效果，具有防伪级别高、防伪能力强的优点。同时，本发明的荧光油墨可利用多重刺激使荧光油墨具有不同的荧光颜色响应，实现荧光防伪效果，使检测步骤具有繁杂性及隐蔽性，极大增强了造假的难度，提高了防伪级别。此外，本发明的荧光油墨制备工艺简单，成本低，推广阻力小，具有广阔的应用前景。
附图说明
图1为本发明实施例1使用第一种防伪特征鉴别方法的结果图；
图2为本发明实施例1使用第二种防伪特征鉴别方法的结果图。
具体实施方式
为了使本技术领域的人员更好地理解本发明方案，下面将对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本发明一部分的实施例，而不是全部的实施例。
实施例1
本发明实施例荧光油墨由下列重量份比的组分组成：硝酸铕0.38重量份、硝酸铽0.37重量份、N-(吡啶-2-基)-苯甲酰乙酰胺1.2重量份、工业酒精38.05重量份、正丁醇30重量份、高分子树脂29重量份、助剂1重量份，所述稀土金属盐选自铕盐、铽盐中的一种或两种，所述有机 配体为β-二酮类分子，所述高分子树脂为聚酰胺树脂，所述助剂为爽滑剂、附着力增强剂按照质量比1：1混合。
本发明实施例荧光油墨的制备方法，包括步骤如下：
步骤1：将工业酒精、正丁醇混合均匀，配置有机溶剂；
步骤2：取硝酸铕、硝酸铽、N-(吡啶-2-基)-苯甲酰乙酰胺于10重量份有机溶剂中，并搅拌溶解，在55-60℃下搅拌2小时；
步骤3：将高分子树脂、助剂、玻璃珠、剩余有机溶剂混合加入步骤2所得混合液中，并在密闭条件下震荡分散120min；
步骤4：将步骤3所得混合液过滤，除去玻璃珠，收集滤液即为本发明实施例荧光油墨；
实施例2
本发明实施例荧光油墨由下列重量份比的组分组成：硝酸铕0.76重量份、硝酸铽0.74重量份、N-(喹啉-2-基)-苯甲酰乙酰胺2.4重量份、工业酒精36.10重量份、正丁醇30重量份、高分子树脂29重量份、助剂1重量份，所述稀土金属盐选自铕盐、铽盐中的一种或两种，所述有机配体为β-二酮类分子，所述高分子树脂选自环氧树脂，所述助剂为爽滑剂、附着力增强剂按照质量比1：1混合。
本发明实施例荧光油墨的制备方法，包括步骤如下：
步骤1：将工业酒精、正丁醇混合均匀，配置有机溶剂；
步骤2：取硝酸铕、硝酸铽、N-(吡啶-2-基)-苯甲酰乙酰胺于5重量份有机溶剂中，并搅拌溶解，在40-50℃下搅拌4小时；
步骤3：将高分子树脂、助剂、金属球、剩余有机溶剂混合加入步骤2所得混合液中，并在密闭条件下震荡分散120min；
步骤4：将步骤3所得混合液过滤，除去金属球，收集滤液即为本发明实施例荧光油墨；
实施例3
本发明实施例荧光油墨由下列重量份比的组分组成：硝酸铕1.13重量份、硝酸铽1.12重量份0.5-5重量份、N-(吲哚-2-基)-苯甲酰乙酰胺3.6重量份、工业酒精34.15重量份、正丁醇30重量份、高分子树脂29重量份、助剂1重量份，所述稀土金属盐选自铕盐、铽盐中的一种或两种，所述有机配体为β-二酮类分子，所述高分子树脂选自乙烯树脂，所述助剂为爽滑剂、附着力增强剂按照质量比1：1混合。
本发明实施例荧光油墨的制备方法，包括步骤如下：
步骤1：将工业酒精、正丁醇混合均匀，配置有机溶剂；
步骤2：取硝酸铕、硝酸铽、N-(吡啶-2-基)-苯甲酰乙酰胺于20重量份有机溶剂中，并搅拌 溶解，在55-60℃下搅拌2小时；
步骤3：将高分子树脂、助剂、玻璃珠、剩余有机溶剂混合加入步骤2所得混合液中，并在密闭条件下震荡分散120min；
步骤4：将步骤3所得混合液过滤，除去玻璃珠，收集滤液即为本发明实施例荧光油墨；
实施例4
本发明实施例荧光油墨由下列重量份比的组分组成：硝酸铕1.51重量份、硝酸铽1.49重量份、N-(2-苯并咪唑)-苯甲酰乙酰胺4.8重量份、工业酒精32.20重量份、正丁醇30重量份、高分子树脂20-30重量份、助剂0.1-2重量份，所述有机配体为β-二酮类分子，所述高分子树脂选自聚氨酯树脂，所述助剂为爽滑剂、附着力增强剂按照质量比1：1混合。
荧光油墨的防伪特征鉴别方法
本发明实施例荧光油墨的防伪特征鉴别方法主要有两种。
第一种防伪特征鉴别方法的步骤如下：
步骤1：使用油墨在介质(塑料或纸)表面涂抹印记，并待印记固化后，使用250-300nm紫外短波灯对印记进行照射，所述印记发橘红色荧光；
步骤2：取浓盐酸(密匙物质key1)于密闭的容器中，将具有印记的介质放置于容器中，使浓盐酸挥发的酸性物质对印记进行熏蒸1-20min(一般为2-5min即可)，并使用250-300nm紫外短波灯对熏蒸后印记进行照射，所述印记发绿色荧光；
步骤3：取三乙胺(密匙物质key2)对浓盐酸处理后的印记进行熏蒸1-20min，并使用250-300nm紫外短波灯对印记进行照射，所述印记发红色荧光；
步骤4：使用电吹风去除印记上的三乙胺，并再次使用250-300nm紫外短波灯对印记进行照射，所述印记发橘红色荧光。
第二种防伪特征鉴别方法的步骤如下：使用油墨在介质(塑料或纸)表面涂抹印记，并待印记固化后，分别使用第一紫外光、第二紫外光对油墨进行检测，所述第一紫外光波长为280nm，所述第二紫外光波长为365nm，所述油墨在第一紫外光照射下发橘红色荧光，所述油墨在第二紫外光照射下发绿色荧光。
其中，以本发明实施例1荧光油墨的防伪特征鉴别过程为例，本发明实施例1荧光油墨在第一种防伪特征鉴别方法过程中的显色状态如图1所示，印记在浓盐酸(密匙物质key1)、三乙胺(密匙物质key2)熏蒸处理后分别显示荧光绿色、荧光红色，在去除三乙胺后显示橘红色荧光。本发明实施例2荧光油墨在第二种防伪特征鉴别方法过程中的显色状态如图2所示，印记在280nm紫外光的照射下的发光位置落于CIE1931图的橘红色荧光区域，印记在365nm紫外光的照射下的发光位置落于CIE1931图的绿色荧光区域。
应当注意的是，在第一种防伪特征鉴别过程中，通过采用不同的共轭酸(密匙物质key1)、不同的共轭碱(密匙物质key2)对油墨印记进行刺激，均能实现荧光颜色的变换，采用浸泡或熏蒸等方式均可实现对油墨印记的刺激，但使用熏蒸方式刺激后油墨印记易于恢复，可进行多次防伪检验，而浸泡方式会对油墨产生破坏，影响油墨印记的再次使用及防伪检验。
本发明实施例1-4采用铕盐、铽盐混合并与N-(吡啶-2-基)-苯甲酰乙酰胺制备配合物，使具有配合物的荧光油墨在不同波长的紫外条件下呈现不同的荧光颜色，提高防伪效果，具有防伪级别高、防伪能力强的优点。同时，本发明实施例1-4的荧光油墨在酸碱条件的刺激下具有不同的荧光颜色响应效果，防伪性能强，同时使检测步骤具有繁杂性及隐蔽性，极大增强了造假的难度，而现有的荧光油墨只能显示单色荧光，且在酸碱条件刺激下，并不会发生荧光颜色变化，导致荧光油墨的防伪检验手段有限，防伪性能差，因此本发明实施例的荧光油墨与现有的荧光油墨相比，提高了防伪级别。此外，本发明实施例的荧光油墨制备工艺简单，成本低，推广阻力小，具有广阔的应用前景。
最后应当说明的是，以上实施例仅用以说明本发明的技术方案而非对其限制，尽管参照上述实施例对本发明进行了详细的说明，所属领域的普通技术人员应当理解，技术人员阅读本申请说明书后依然可以对本发明的具体实施方式进行修改或者等同替换，但这些修改或变更均未脱离本发明申请待批权利要求保护范围之内。

Claims (10)

  1. 一种多重响应型荧光油墨，其特征在于，所述多重响应型荧光油墨由下列重量份比的组分组成：稀土金属盐0.5-5重量份、有机配体1-5重量份、有机溶剂50-70重量份、高分子树脂20-30重量份、助剂0.1-2重量份，所述稀土金属盐选自铕盐、铽盐中的一种或两种，所述高分子树脂选自聚酰胺树脂、丙烯酸树脂、环氧树脂、乙烯树脂、聚氨酯树脂中的一种或多种，所述助剂选自中爽滑剂、附着力增强剂、催干剂、冲淡剂、减粘剂、稀薄剂、抗氧化剂、反胶化剂、消泡剂、表面活性剂、防针孔剂、增塑剂的一种或多种，所述有机配体为β-二酮配体，所述β-二酮配体分子式如下：
    Figure PCTCN2020071038-appb-100001
    其中R 1选自-CH 3、-CF 3、-CR 3、-C 6H 5、R 2选自
    Figure PCTCN2020071038-appb-100002
    Figure PCTCN2020071038-appb-100003
    或其它N杂环化合物。
  2. 根据权利要求1所述的多重响应型荧光油墨，其特征在于，所述稀土金属盐由0.3-2重量份铕盐和0.3-2重量份的铽盐组成，所述铕盐选自硝酸盐或氯盐中的一种或多种，所述铽盐选自硝酸盐或氯盐中的一种或多种。
  3. 根据权利要求1所述的多重响应型荧光油墨，其特征在于，所述有机配体为N-(吡啶-2-基)-苯甲酰乙酰胺。
  4. 根据权利要求1所述的多重响应型荧光油墨，其特征在于，所述有机溶剂选自工业酒精、丙醇、丁醇的一种或多种。
  5. 根据权利要求4所述的多重响应型荧光油墨，其特征在于，所述有机溶剂由30-40重量份的工业酒精和30-40重量份的丁醇组成。
  6. 一种如权利要求1-5任一所述荧光油墨的制备方法，其特征在于，包括步骤如下：
    步骤1：取稀土金属盐、有机配体于部分有机溶剂中，并搅拌溶解，在40-80℃下搅拌1-4小时；
    步骤2：将高分子树脂、助剂、助磨剂、剩余有机溶剂混合加入步骤1所得混合液中，并在密闭条件下震荡分散60-240min；
    步骤3：将步骤2所得混合液过滤，除去助磨剂，收集滤液即为荧光油墨；
    所述助磨剂选自玻璃珠、石英砂、金属球中一种或多种。
  7. 一种如权利要求1-5任一所述荧光油墨的防伪特征鉴别方法，其特征在于，包括步骤如下：
    步骤1：使用油墨在介质表面涂抹印记，并待印记固化后，使用250-300nm紫外短波灯对印记进行照射，所述印记发橘红色荧光；
    步骤2：取密匙物质key1对印记进行熏蒸1-20min，并使用250-300nm紫外短波灯对印记进行照射，所述印记发绿色荧光；
    所述密匙物质key1为挥发性酸。
  8. 根据权利要求7所述的使用方法，其特征在于，所述方法还包括步骤3、步骤4如下：
    步骤3：取密匙物质key2对印记进行熏蒸1-20min，并使用250-300nm紫外短波灯对印记进行照射，所述印记发红色荧光；
    步骤4：去除密匙物质key2，使用250-300nm紫外短波灯对印记进行照射，所述印记发橘红 色荧光；
    所述密匙物质key2为挥发性碱，所述挥发性碱为有机胺。
  9. 根据权利要求8所述的使用方法，其特征在于，所述密匙物质key1为浓盐酸，所述密匙物质key2为三乙胺。
  10. 一种如权利要求1-5任一所述荧光油墨的防伪特征鉴别方法，其特征在于，包括步骤如下：分别使用第一紫外光、第二紫外光对油墨进行检测，所述第一紫外光波长为270-290nm，所述第二紫外光波长为350-380nm，所述油墨在第一紫外光照射下发橘红色荧光，所述油墨在第二紫外光照射下发绿色荧光。
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