WO2010009593A1 - 一种防伪薄膜及其制备方法 - Google Patents

一种防伪薄膜及其制备方法 Download PDF

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Publication number
WO2010009593A1
WO2010009593A1 PCT/CN2008/071794 CN2008071794W WO2010009593A1 WO 2010009593 A1 WO2010009593 A1 WO 2010009593A1 CN 2008071794 W CN2008071794 W CN 2008071794W WO 2010009593 A1 WO2010009593 A1 WO 2010009593A1
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Prior art keywords
layer
film
coating
cellulose
photochromic
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PCT/CN2008/071794
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English (en)
French (fr)
Inventor
徐良衡
杨凯
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上海复旦天臣新技术有限公司
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Priority to US13/055,313 priority Critical patent/US8541095B2/en
Priority to EP08783787A priority patent/EP2329962B1/en
Publication of WO2010009593A1 publication Critical patent/WO2010009593A1/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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B42—BOOKBINDING; ALBUMS; FILES; SPECIAL PRINTED MATTER
    • B42D—BOOKS; BOOK COVERS; LOOSE LEAVES; PRINTED MATTER CHARACTERISED BY IDENTIFICATION OR SECURITY FEATURES; PRINTED MATTER OF SPECIAL FORMAT OR STYLE NOT OTHERWISE PROVIDED FOR; DEVICES FOR USE THEREWITH AND NOT OTHERWISE PROVIDED FOR; MOVABLE-STRIP WRITING OR READING APPARATUS
    • B42D25/00—Information-bearing cards or sheet-like structures characterised by identification or security features; Manufacture thereof
    • B42D25/20—Information-bearing cards or sheet-like structures characterised by identification or security features; Manufacture thereof characterised by a particular use or purpose
    • B42D25/29—Securities; Bank notes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B42—BOOKBINDING; ALBUMS; FILES; SPECIAL PRINTED MATTER
    • B42D—BOOKS; BOOK COVERS; LOOSE LEAVES; PRINTED MATTER CHARACTERISED BY IDENTIFICATION OR SECURITY FEATURES; PRINTED MATTER OF SPECIAL FORMAT OR STYLE NOT OTHERWISE PROVIDED FOR; DEVICES FOR USE THEREWITH AND NOT OTHERWISE PROVIDED FOR; MOVABLE-STRIP WRITING OR READING APPARATUS
    • B42D25/00—Information-bearing cards or sheet-like structures characterised by identification or security features; Manufacture thereof
    • B42D25/40—Manufacture
    • B42D25/45—Associating two or more layers
    • B42D25/465—Associating two or more layers using chemicals or adhesives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B44—DECORATIVE ARTS
    • B44F—SPECIAL DESIGNS OR PICTURES
    • B44F1/00—Designs or pictures characterised by special or unusual light effects
    • B44F1/08—Designs or pictures characterised by special or unusual light effects characterised by colour effects
    • B44F1/10—Changing, amusing, or secret pictures
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/02—Ingredients treated with inorganic substances
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
    • C08L1/08—Cellulose derivatives
    • 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
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/004—Reflecting paints; Signal paints
    • 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
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/29—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for multicolour effects
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/65—Additives macromolecular
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/70—Additives characterised by shape, e.g. fibres, flakes or microspheres
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/12—Reflex reflectors
    • G02B5/126—Reflex reflectors including curved refracting surface
    • G02B5/128—Reflex reflectors including curved refracting surface transparent spheres being embedded in matrix
    • B42D2033/18—
    • B42D2033/20—
    • B42D2033/24—
    • B42D2033/30—
    • B42D2035/24—
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B42—BOOKBINDING; ALBUMS; FILES; SPECIAL PRINTED MATTER
    • B42D—BOOKS; BOOK COVERS; LOOSE LEAVES; PRINTED MATTER CHARACTERISED BY IDENTIFICATION OR SECURITY FEATURES; PRINTED MATTER OF SPECIAL FORMAT OR STYLE NOT OTHERWISE PROVIDED FOR; DEVICES FOR USE THEREWITH AND NOT OTHERWISE PROVIDED FOR; MOVABLE-STRIP WRITING OR READING APPARATUS
    • B42D25/00—Information-bearing cards or sheet-like structures characterised by identification or security features; Manufacture thereof
    • B42D25/40—Manufacture
    • B42D25/45—Associating two or more layers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24802—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.]
    • Y10T428/24835—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.] including developable image or soluble portion in coating or impregnation [e.g., safety paper, etc.]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/28—Web or sheet containing structurally defined element or component and having an adhesive outermost layer
    • Y10T428/2848—Three or more layers

Definitions

  • the present invention relates to a film for use in the field of anti-counterfeiting and a method of producing the same, which has a viewing angle change characteristic under directional retroreflective conditions.
  • the novel photochromic material can selectively reflect light of a specific wavelength by using a spiral structure inside the material, and the macroscopic expression is a photochromic effect, and the photochromic material is a transparent material.
  • photochromic materials have chiral polymer optical angle color changing materials (such as Chinese patents).
  • Directional retroreflective technology is a kind of physical optics technology. It was originally developed by Dr. Dong Yifang, a Chinese American scientist in the 1950s. The main technical principle is: When a parallel beam of light is irradiated from a certain angle on a surface with a special structure, a considerable part of the light is reflected by the parallel beam to the incident direction of the light source. Light passes through the incident-refraction-reflection process to form a regression Directional reflection characteristics produce a unique reflective effect. With the development of the automotive industry and road traffic, a series of reflective materials based on this technical principle have been widely used, and patented technologies related to structural design and production methods of reflective materials have been continuously introduced, such as US Pat. No. 4,721,649.
  • the above-mentioned several kinds of optical angle discoloration anti-counterfeiting technologies have similar effects and lack of technical concealment, and the application of the directional retroreflective technology is currently limited to the fields of road traffic and the like. Therefore, the present invention studies the directional retroreflective technology and the optical angle.
  • the combination of color-changing technology develops new anti-counterfeiting films with unique visual effects to meet the requirements of high-end anti-counterfeiting.
  • the object of the present invention is to provide an anti-counterfeiting film and a preparation method thereof, which overcome the defects of the prior art, such as similar effects and lack of technical concealment, and meet the needs of development in related fields.
  • the anti-counterfeiting film of the present invention comprises a layered retroreflective layer, a photochromic information layer, a reflective layer and a support layer;
  • the support layer is a polymer resin material, and has the characteristics of high light transmittance, good weather resistance and high toughness.
  • the preferred polymer resin material is polyurethane, phenolic resin or polyacrylic resin;
  • the reflective layer is nanometer-scale a material having a high reflectance of thickness (20 to 100 nm), preferably ZnO, SnO, ZnS or Ti0 2 ;
  • the photochromic information layer is a chiral polymer photochromic material or a cellulose photochromic material having a helical structure, and the chiral polymer photochromic material having a helical structure is a chiral compound and a functional group.
  • the compound is polymerized by a condensation polymerization method, and the functional group is a hydroxyl group, a carboxyl group or an amino group;
  • the chiral compound is one or more selected from the group consisting of isosorbide, D-camphoric acid, 2,3-dihydroxybutyric acid or 3-methyladipic acid; and the compound having a functional group is hydroquinone, Triethylene glycol, p-hydroxybenzoic acid, ethylene One or more of alcohol, oxalic acid, terephthalic acid, etc., or one or more of phenol, fatty acid, formaldehyde, and the like;
  • composition of the chiral polymer photochromic material having a helical structure and a preparation method thereof are described in detail in Chinese Patent Application No. 03114913.8;
  • the cellulose photochromic material is composed of a cellulose derivative and a polymerizable monomer
  • the structural formula of the cellulose derivative is:
  • the polymerizable monomer includes one or more of an acrylate, a methacrylate, a vinyl ether, an epoxy resin or a cis butyl succinate;
  • the directional retroreflective layer is a sphere made of a high refractive index optical material, preferably glass or polycarbonate, etc., while the directional retroreflective layer is spherically embedded in the support layer;
  • the refractive index of the material of the retroreflective layer has an important influence on the directional retroreflective properties. Therefore, the refractive index of the material of the retroreflective layer of the present invention is 1.9 to 1.93.
  • the directional retroreflective properties are only exhibited under certain optical conditions, and by combining with the photochromic material, the optical angular discoloration information in the anti-counterfeit film is hidden under the naked eye, only through specific optical conditions. Under the observation, the hidden color angle discoloration information appears. Under the special identifier, the surface of the anti-counterfeit film disappears, and the light-angled image is hidden. When the angle is rotated, the color of the image will change, such as from green to red.
  • the dedicated identifier provides directional retroreflective optical conditions, the structure of which is prior art as described in U.S. Patent No. 6,019,287.
  • the preparation method of the anti-counterfeit film of the invention comprises the following steps:
  • the base film is selected from the group consisting of transparent high molecular polyester film materials, preferably polybutylene terephthalate, polycarbonate, polystyrene or polyvinyl chloride;
  • the release material is preferably liquid paraffin
  • the coating may be applied by coating such as reticulation coating, hot melt coating, blade coating or through gravure Printing/coating the optical angle color changing information layer by printing, flexographic or screen printing.
  • the anti-counterfeit film obtained by the above method due to the special directional retro-reflective optical structure of the anti-counterfeit film, such as the process of coating the anti-counterfeit film with a full-plate coating of the photo-angle discoloring material, when the anti-counterfeit film is bent to form an arc (30 to 360 degrees) Under the condition of directional retroreflective optics, the disappearance of the surface of the film reveals a unique rainbow effect.
  • the full-coated light-angle color-changing material may be a chiral polymer light-angle color-changing material having a spiral structure or a Chinese patent application number 02136974.7 fiber-optic light-angle color-changing material in Chinese Patent Application No. 03114913.8.
  • the invention utilizes the basic principle of directional retroreflection, and a special optical structure combined with a novel photochromic material to obtain a transparent anti-counterfeit film with unique visual effects. Its anti-counterfeiting features are unique, transparent, high technical barriers, and strong anti-counterfeiting. It can be widely used in various high-end goods. In the fields of securities, certificate cards, etc.
  • Figure 1 is a schematic view showing the structure of a security film.
  • Figure 2 is a rendering of the anti-counterfeiting film.
  • Fig. 3 is a rainbow effect when the security film is bent to form a curvature.
  • the security film of the present invention comprises a layered retroreflective layer 1 , a photochromic information layer 2, a reflective layer 3 and a support layer 4;
  • the directional retroreflective layer 1 is a sphere made of a high refractive index optical material, preferably glass or polycarbonate, etc., while the directional retroreflective layer 1 is spherically embedded in the support layer 4, and the diameter of the sphere is 10 ⁇ : L00 micron.
  • PET polyethylene terephthalate
  • the alcohol ester) base film and the release layer expose the oriented retroreflective layer, that is, form a security film having a viewing angle discoloration characteristic under directional retroreflective conditions.
  • the surface is printed with a graphic anti-counterfeiting film 5, in U.S. Patent No. 6,019,287.
  • the special identifier 6 provided provides the observation of the retroreflective optical condition, the surface of the anti-counterfeit film disappears, and the light-angled discolored image is hidden therein.
  • step 7 of rotating the viewing angle the color of the graphic will change. If it turns from green to red.
  • Embodiment 1 of the Chinese Patent No. 02136974.7 is as follows:
  • Color changing information layer then high vacuum vapor deposition reflective layer material ZnS, thickness 50 nm, coating polyurethane support layer material on the re-reflecting layer, drying at 100 ° C for 5 minutes, dialing the surface of PET (poly-p-phenylene)
  • the base film of the butyl glycolate and the release layer expose the oriented retroreflective layer, i.e., form a security film having viewing angle discoloration characteristics under directional retroreflective conditions.
  • the surface of the anti-counterfeiting film 5 is printed on the surface, and the special identifier 6 provided in U.S. Patent No. 6,019,287 provides a fixed observation of the optical condition of the retroreflective film, and the surface of the anti-counterfeit film disappears, revealing the light-angle discoloration pattern hidden therein. , using step 7 of rotating the viewing angle, the figure The color of the text will change, as it turns from green to red.
  • 3-methylhexanoic acid added to the reactor, added 40 ml of acetic anhydride, mechanically stirred, protected with nitrogen, heated to reflux, system temperature was 150 ° C, held for 30 min; started to distill water and acetic acid, the reaction temperature gradually increased to 300 °C, hold for 30min. After no liquid was distilled off, distillation under reduced pressure was started, and the degree of vacuum was continuously increased to 10 mbar for 30 minutes. The viscosity of the system begins to increase, the color becomes darker, the stirring is increased, and after maintaining a high vacuum and high temperature for 30 minutes, the reactants turn blue, slowly cool down, and return to normal pressure. The blue color of the material is slowly fixed and taken out to obtain a product.
  • a spherical glass material with a refractive index of 1.9 having a diameter of 60 ⁇ m was implanted thereon to form a directional retroreflection.
  • the cellulose photochromic material (such as the photochromic material described in Example 1 of Chinese Patent No. 02136974.7) is coated on the oriented retroreflective layer by a textured coating method to form a full version.
  • the photochromic layer then the high vacuum vapor deposition reflective layer material ZnS, having a thickness of 20 nm, is coated with a polyurethane support layer material on the re-reflective layer, and the surface of the PET is removed after drying (poly terephthalic acid has been
  • the base film and the release layer expose the oriented retroreflective layer, i.e., form a security film having viewing angle discoloration characteristics under directional retroreflective conditions.

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Description

一种防伪薄膜及其制备方法
技术领域
本发明涉及一种应用于防伪领域的薄膜及其制备方法， 其具有在定向 回归反射条件下的视角变色特性。
技术背景
九十年代初， 国外出现一种光角变色防伪产品， 即随着观察角度的变 化， 图案会发生显著的色彩变化。 此类产品具有技术领先、 易于辨别、 安 全性高、 鉴别方便等特点， 逐渐成为被全球各国公共安全防伪的权威机构 广泛采用的技术之一。 目前已成功地应用于各国货币、证件等众多领域（如 人民币、 美元、 欧元、 国外护照、 驾驶执照）。 但传统光角变色防伪产品， 如光变油墨 0VI、 光变全息膜等， 其材料的光变效果均通过颜料干涉、 光学 镀膜或激光蚀刻技术实现， 因而产品存在材料不可透视、 工艺路线长、 多 技术复合难度大以及产品价格昂贵等许多缺陷， 大大局限了光角变色防伪 产品的应用范围。
新型光角变色材料利用其材料内部具有的螺旋结构能够选择性地反射 特定波长的光， 宏观表现为光角变色效果， 这类光角变色材料为透明性材 料。 目前该类光角变色材料有手性高分子光角变色材料 （如中国专利
03114913.8)、 纤维素光角变色材料 （如中国专利 02136974.7 ) 等；
定向回归反射技术属一种物理光学技术， 最初由二十世纪五十年代年 美国华裔科学家董祺芳博士研发成功。 主要技术原理为： 当一束平行光线 从一定的角度照射在具有特殊结构的表面上时， 相当大的一部分光线呈平 行光束向光源的入射方向反射。 光线通过入射 -折射 -反射过程， 形成回归 定向反射特性， 产生独特的反光效果。 随着汽车工业与道路交通的发展， 基于该技术原理的系列反光材料得以广泛应用， 有关反光材料的结构设计、 生产方法等方面的专利技术也不断推陈出新， 如美国专利 US4721649。
但是， 上述几种光角变色防伪技术效果比较类同、 缺少技术隐蔽性，而 定向回归反射技术的应用目前也仅局限于道路交通等领域， 因此， 本发明 研究将定向回归反射技术与光角变色技术相结合， 开发具有独特视觉效果 的新型防伪薄膜， 以满足高端防伪领域的要求。
发明内容
本发明的目的是提供一种防伪薄膜及其制备方法， 以克服现有技术所 存在的效果类同、 缺少技术隐蔽性等缺陷， 满足有关领域发展的需要。
本发明所述的防伪薄膜， 包括依次复合的定向回归反射层、 光角变色 信息层、 反射层和支撑层；
所述支撑层为高分子树脂材料， 并具有透光率高、 耐候性好和韧性高 的特点， 优选的高分子树脂材料为聚氨酯、 酚醛树脂或聚丙烯酸树脂等； 所述反射层为纳米级厚度（20〜100纳米）的具有高反射率材料， 优选 的为 ZnO、 SnO、 ZnS或 Ti02等；
所述光角变色信息层为具有螺旋结构的手性高分子光角变色材料或纤 维素光角变色材料， 所述具有螺旋结构的手性高分子光角变色材料是将手 性化合物与具有官能团的化合物通过缩合聚合法聚合而成， 所述的官能团 如羟基、 羧基或氨基；
所述手性化合物为异山梨醇、 D-樟脑酸、 2， 3-二羟基丁垸或 3-甲基 己二酸等中的一种以上； 所述具有官能团的化合物为对苯二酚、 三甘醇、 对羟基苯甲酸、 乙二 醇、 乙二酸、 对苯二甲酸等中的一种或几种， 或为苯酚、 脂肪酸、 甲醛等 中的一种或几种；
所述具有螺旋结构的手性高分子光角变色材料的组成及其制备方法， 在中国专利申请号 03114913.8中有详细的描述；
所述纤维素光角变色材料由纤维素衍生物和可聚单体组成；
所述纤维素衍生物的结构通式为：
0
II
Cell— O— R 或 Cell— 0~C— NH— R 式中 Cell为纤维素， R为 d~C2Q的垸基或苯基的衍生物；
所述可聚单体包括丙烯酸酯、 甲基丙烯酸酯、 乙烯基醚、 环氧树脂或 顺丁基二酸酯中的一种或几种；
所述纤维素光角变色材料及其制备方法在中国专利申请号 02136974.7 中有详细的描述；
所述定向回归反射层为具有高折射率光学材制成的球状物， 优选玻璃 或聚碳酸酯等， 同时所述定向回归反射层呈球状嵌入支撑层中；
发明人经过大量的试验发现， 所述的定向回归反射层材料的折射率， 对定向回归反射特性具有重要的影响， 因此， 本发明的定向回归反射层材 料的折射率为 1.9〜1.93， 使其只有在一定光学条件下才显现定向回归反射 特性， 并通过与所述的光角变色材料相结合， 使得在肉眼观察下所述防伪 薄膜中的光角变色信息被隐藏， 只有通过特定的光学条件下观察才显现其 中隐藏的光角变色信息。 在专用识别器下观察， 防伪薄膜表面图文消失， 显现隐藏其中的光角变色图文， 转动观察角度， 该图文的颜色将发生转变， 如由绿变红。 所述专用识别器提供定向回归反射光学条件， 该专用识别器的结构为 现有技术， 如美国专利 US6019287中所述。
本发明所述防伪薄膜的制备方法包括如下步骤：
( 1 )在基膜上涂布具有粘结力的离型材料， 然后在离型层上植入定向 回归反射层的材料， 100〜130°C烘干， 烘干时间为 2〜3分钟；
所述的基膜选自透明高分子聚酯薄膜材料， 优选的为聚对苯二甲酸已 二醇酯、 聚碳酸酯、 聚苯乙烯或聚氯乙烯等；
所述的离型材料优选液态石蜡；
(2 )然后在定向回归反射层上涂布或印刷光角变色信息层， 然后高真 空气相沉积反射层材料， 再在反射层上涂布支撑层材料， 100〜120°C烘干， 烘干时间为 3〜5分钟， 然后去除基膜和离型层， 获得所说的防伪薄膜； 所说的涂布可选用网紋涂布、 热熔涂布、 刮刀涂布等涂布方式或通过 凹版、 柔版、 丝网等印刷方式印刷 /涂布光角变色信息层。
采用上述方法获得的防伪薄膜， 由于所述防伪薄膜的特殊的定向回归 反射光学结构， 如采用满版涂布光角变色材料的工艺， 将所述防伪薄膜弯 曲形成弧度（30〜360度） 时， 在定向回归反射光学条件下观察， 薄膜表面 图文消失可显现独特的彩虹效果。
所述的满版涂布的光角变色材料可选用中国专利申请号 03114913.8中 具有螺旋结构的手性高分子光角变色材料或中国专利申请号 02136974.7纤 维素光角变色材料。
本发明利用定向回归反射的基本原理， 以及特殊的光学结构结合新型 光角变色材料， 获得一种透明的具有独特视觉效果的防伪薄膜。 其防伪特 征独特、 透明、 技术壁垒高、 防伪力度大， 可被广泛应用于各类高档商品、 有价证券、 证件证卡等领域。
附图说明
图 1为防伪薄膜结构示意图。
图 2为防伪薄膜效果图。
图 3为将所述防伪薄膜弯曲形成弧度时的彩虹效果。
具体实施方式
参见图 1，本发明所述的防伪薄膜，包括依次复合的定向回归反射层 1、 光角变色信息层 2、 反射层 3和支撑层 4;
所述定向回归反射层 1 为具有高折射率光学材制成的球状物， 优选玻 璃或聚碳酸酯等， 同时所述定向回归反射层 1呈球状嵌入支撑层 4中， 球 状物直径为 10〜： L00微米。
实施例 1
以 PET (聚对苯二甲酸已二醇酯） 为基膜， 涂布液态石蜡作为离型层， 然后在其上植入直径为 70微米的折射率为 1.9的球形玻璃材料， 形成定向 回归反射层， 110°C烘干 3分钟， 再在定向回归反射层上通过丝网印刷纤维 素光角变色材料， 其组成及制备方法如中国专利 02136974.7中实施例 1所 述， 以形成光角变色信息层， 然后高真空气相沉积反射层材料 ZnO, 厚度 为 60纳米， 在再反射层上涂布聚氨酯支撑层材料， 120°C烘干 3分钟， 拨 去表面的 PET (聚对苯二甲酸已二醇酯）基膜和离型层， 将定向回归反射层 露出， 即形成具有在定向回归反射条件下的视角变色特性的防伪薄膜。
通过美国专利 US6019287中报道的专用识别器观察， 可见如图 2所示 效果。
由图 2可见， 表面印刷有图文的防伪薄膜 5， 在美国专利 US6019287 提供的专用识别器 6提供定的向回归反射光学条件观察， 防伪薄膜表面图 文消失， 显现隐藏其中的光角变色图文， 采用转动观察角度的步骤 7， 该图 文的颜色将发生转变， 如由绿变红。
所述中国专利 02136974.7中实施例 1中具体描述如下：
将 10g纤维素 （由醋酸纤维素水解得到） 溶于 210ml吡啶中， 升温至 回流， 加入 50ml异氰酸苯酯， 回流 48hr， 减压蒸馏除去大部分吡啶， 加入 0.8L甲醇， 析出固体， 过滤， 将滤饼溶于 600ml丙酮中， 再加入 0.8L甲醇 使产品沉淀析出， 过滤， 洗涤， 真空干燥。 得 20g产品。 经 IR证实， 纤维 素微晶中的羟基基本上已经完全被酯化。
实施例 2
以 PET (聚对苯二甲酸已二醇酯） 为基膜， 涂布液态石蜡作为离型层， 然后在其上植入直径为 100微米的折射率为 1.93的球形玻璃材料， 形成定 向回归反射层， 100°C烘干 3分钟， 再在定向回归反射层上通过柔版印刷手 性高分子光角变色材料， 其组成及制备方法如中国专利 03114913.8中实施 例 1所述， 以形成光角变色信息层， 然后高真空气相沉积反射层材料 ZnS, 厚度为 50纳米，在再反射层上涂布聚氨酯支撑层材料， 100°C烘干 5分钟，， 拨去表面的 PET (聚对苯二甲酸已二醇酯）基膜和离型层将定向回归反射层 露出， 即形成具有在定向回归反射条件下的视角变色特性的防伪薄膜。
通过美国专利 US6019287中报道的专用识别器观察， 可见如图 2所示 效果。
由图 2可见， 表面印刷有图文的防伪薄膜 5， 在美国专利 US6019287 提供的专用识别器 6提供定的向回归反射光学条件观察， 防伪薄膜表面图 文消失， 显现隐藏其中的光角变色图文， 采用转动观察角度的步骤 7， 该图 文的颜色将发生转变， 如由绿变红。
所述中国专利 03114913.8中实施例 1中具体描述如下：
13g对羟基苯甲酸， 4g对苯二甲酸， lg对苯二酚， 2.5g异山梨醇， 4.0g
3-甲基己酸， 加入反应器中， 加入 40ml乙酸酐， 机械搅拌， 氮气保护， 加 热至回流， 体系温度为 150°C， 保持 30min; 开始蒸出水和乙酸， 反应温度 逐渐升高至 300°C， 保持 30min。 没有液体蒸出后， 开始减压蒸馏， 真空度 不断升高至 lOmbar, 保持 30min。 体系粘度开始加大， 颜色变深， 加大搅 拌， 保持高真空、 高温 30min后， 反应物变为蓝色， 缓慢降温， 恢复常压， 材料的蓝色慢慢固定下来， 取出， 获得产物。
实施例 3
以 PET (聚对苯二甲酸已二醇酯） 为基膜， 涂布液态石蜡作为离型层， 然后在其上植入直径为 60微米的折射率为 1.9的球形玻璃材料， 形成定向 回归反射层， 烘干处理后再在定向回归反射层上通过网紋涂布方式， 涂布 纤维素光角变色材料 （如中国专利 02136974.7中实施例 1所述的光角变色 材料）， 以形成满版的光角变色层， 然后高真空气相沉积反射层材料 ZnS , 厚度为 20纳米， 在再反射层上涂布聚氨酯支撑层材料， 经烘干处理后拨去 表面的 PET (聚对苯二甲酸已二醇酯）基膜和离型层将定向回归反射层露出， 即形成具有在定向回归反射条件下的视角变色特性的防伪薄膜。
将上述的防伪薄膜 5弯曲形成 60度弧度时， 在美国专利 US6019287 中报道的专用识别器 6下观察可显现独特的彩虹效果， 如图 3所示。
所述中国专利 02136974.7中实施例 1具体描述如下：
将 10g纤维素 （由醋酸纤维素水解得到） 溶于 210ml吡啶中， 升温至 回流， 加入 50ml异氰酸苯酯， 回流 48hr， 减压蒸馏除去大部分吡啶， 加入 0.8L甲醇， 析出固体， 过滤， 将滤饼溶于 600ml丙酮中， 再加入 0.8L甲醇 使产品沉淀析出， 过滤， 洗涤， 真空干燥。 得 20g产品。 经 IR证实， 纤维 素微晶中的羟基基本上已经完全被酯化。

Claims

权 利 要 求
1. 防伪薄膜， 其特征在于， 包括依次复合的定向回归反射层、 光角变 色信息层、 反射层和支撑层；
所述支撑层为高分子树脂材料；
所述反射层为纳米级厚度的反射率材料；
所述光角变色信息层为具有螺旋结构的手性高分子光角变色材料或纤 维素光角变色材料， 所述具有螺旋结构的手性高分子光角变色材料是将手 性化合物与具有官能团的化合物的缩合产物；
所述纤维素光角变色材料由纤维素衍生物和可聚单体组成；
所述定向回归反射层为光学材制成的球状物， 所述定向回归反射层呈 球状嵌入支撑层中；
定向回归反射层材料的折射率为 1.9〜1.93。
2. 根据权利要求 1所述的防伪薄膜， 其特征在于， 支撑层的高分子树 脂材料为聚氨酯、 酚醛树脂或聚丙烯酸树脂。
3.根据权利要求 1所述的防伪薄膜，其特征在于，所述反射层为 ZnO、
SnO、 ZnS或 Ti02。
4. 根据权利要求 1、 2或 3所述的防伪薄膜， 其特征在于， 所述手性 化合物为异山梨醇、 D-樟脑酸、 2， 3-二羟基丁垸或 3-甲基己二酸中的一种 以上； 所述具有官能团的化合物为对苯二酚、 三甘醇、 对羟基苯甲酸、 乙二 醇、 乙二酸或对苯二甲酸中的一种或几种， 或者为苯酚、 脂肪酸或甲醛中 的一种或几种；
所述纤维素衍生物的结构通式为： o
II
Cell— O— R 或 Cell— 0~C— NH— R . 式中： Cell为纤维素， R为 d~C2Q的垸基或苯基的衍生物；
所述可聚单体为丙烯酸酯、 甲基丙烯酸酯、 乙烯基醚、 环氧树脂或顺 丁基二酸酯中的一种或几种。
5. 制备权利要求 1〜4任一项所述防伪薄膜的方法， 其特征在于， 包 括如下步骤：
( 1 )在基膜上涂布具有粘结力的离型材料， 然后在离型层上植入定向 回归反射层的材料， 烘干；
(2 )然后在定向回归反射层上涂布或印刷光角变色信息层， 然后高真 空气相沉积反射层材料， 再在反射层上涂布支撑层材料， 烘干， 然后去除 基膜和离型层， 获得所说的防伪薄膜。
6. 根据权利要求 5所述的方法， 其特征在于， 所说的涂布选用网紋涂 布、 热熔涂布或刮刀涂布， 或者通过凹版、 柔版或丝网印刷方式。
7. 根据权利要求 5所述的方法， 其特征在于， 所述的基膜选自透明高 分子聚酯薄膜材料，
8. 根据权利要求 7所述的方法， 其特征在于， 所述的基膜选自为聚对 苯二甲酸已二醇酯、 聚碳酸酯、 聚苯乙烯或聚氯乙烯。
9. 根据权利要求 5所述的方法， 其特征在于， 所述的离型材料为液态 石蜡。
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Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2493369B (en) 2011-08-02 2013-09-25 Rue De Int Ltd Improvements in security devices
US9233572B2 (en) 2013-08-30 2016-01-12 International Business Machines Corporation Anti-counterfeiting opto-thermal watermark for electronics
EP3374200B1 (en) * 2015-11-12 2022-08-10 Safestamp Inc. Anti-counterfeiting device and method
KR102700941B1 (ko) 2016-10-21 2024-09-02 삼성디스플레이 주식회사 재귀반사층을 갖는 컬러 기판 및 이를 포함하는 표시 장치
JP6933006B2 (ja) * 2017-06-09 2021-09-08 横浜ゴム株式会社 空気入りタイヤ
KR20200065062A (ko) 2017-10-27 2020-06-08 쓰리엠 이노베이티브 프로퍼티즈 캄파니 1차 반사 층 및 2차 반사 층을 포함하는 재귀반사 요소를 포함하는 재귀반사 물품
CN111263902A (zh) 2017-10-27 2020-06-09 3M创新有限公司 包括嵌入反射层的回射制品
CN109435516A (zh) * 2018-10-25 2019-03-08 宁夏金世纪包装印刷有限公司 一种多级隐含图像防伪工艺
CN110456439B (zh) * 2019-08-01 2020-09-22 武汉大学 同时实现彩色纳米印刷与彩色相位型全息的超表面材料及其设计方法
CN113355085B (zh) * 2021-05-17 2024-03-12 西安交通大学 一种光/声/磁三重防伪特性复合膜及其制备方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6019287A (en) 1993-10-06 2000-02-01 3M Innovative Properties Company Security reader for automatic detection of tampering and alteration
CN1600535A (zh) * 2004-09-16 2005-03-30 上海复旦天臣新技术有限公司 一种具有双重功能特性的复合薄膜及其制备方法
CN101116015A (zh) * 2005-02-10 2008-01-30 日本电石工业株式会社 逆反射片

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1525383A (en) * 1974-08-02 1978-09-20 Portals Ltd Paper for printed sheets
US5169707A (en) * 1991-05-08 1992-12-08 Minnesota Mining And Manufacturing Company Retroreflective security laminates with dual level verification
US5726803A (en) 1994-09-30 1998-03-10 Nippon Carbide Kogyo Kabushiki Kaisha Lens-type retroreflective sheeting
CN2363337Y (zh) * 1998-07-14 2000-02-09 钱宏毅 防伪定向反光膜
JP2002201222A (ja) * 2000-09-19 2002-07-19 Merck Patent Gmbh ポリマービーズ、ポリマービーズの使用方法、反射フィルム、セキュリティマーク、有価証券、セキュリティ装置
DE60230445D1 (de) * 2001-12-20 2009-01-29 Seiko Epson Corp Aufzeichnungsmaterie mit fälschungsschutz
CN1454912A (zh) * 2003-01-15 2003-11-12 上海复旦天臣感光材料有限公司 一种光角变色粉末材料及其制备方法和应用
CN100426012C (zh) * 2004-04-28 2008-10-15 纪和化学工业株式会社 色相可变型逆反射薄片
CN1737881B (zh) * 2004-08-20 2011-07-20 上海复旦天臣新技术有限公司 防伪薄膜及其制备方法
EP1879057B1 (en) * 2005-04-11 2011-03-16 Nippon Carbide Kogyo Kabushiki Kaisha Printed image-set retro-reflection sheet
KR100788215B1 (ko) * 2006-03-31 2007-12-27 주식회사 지.비라이트 수성수지를 이용한 재귀반사 제품의 제조방법

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6019287A (en) 1993-10-06 2000-02-01 3M Innovative Properties Company Security reader for automatic detection of tampering and alteration
CN1600535A (zh) * 2004-09-16 2005-03-30 上海复旦天臣新技术有限公司 一种具有双重功能特性的复合薄膜及其制备方法
CN101116015A (zh) * 2005-02-10 2008-01-30 日本电石工业株式会社 逆反射片

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP2329962A4

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US20110293858A1 (en) 2011-12-01
EP2329962B1 (en) 2012-09-05
US8541095B2 (en) 2013-09-24

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