CN1600535B - Composite membrane possessing diplex functional characteristice and preparation method - Google Patents
Composite membrane possessing diplex functional characteristice and preparation method Download PDFInfo
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- CN1600535B CN1600535B CN 200410066448 CN200410066448A CN1600535B CN 1600535 B CN1600535 B CN 1600535B CN 200410066448 CN200410066448 CN 200410066448 CN 200410066448 A CN200410066448 A CN 200410066448A CN 1600535 B CN1600535 B CN 1600535B
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Abstract
A composite film with double functions is prepared by binding functional layers of colour changing information following to light angle and reflecting information of regression together with media layer. The prepared film has unique visual result and concealed properties of two-line falseproof.
Description
Technical field
The invention belongs to false-proof film material technology field, be specifically related to a kind of laminated film and preparation method thereof with angular color change and retroreflecting information dual function nature.
Background technology
Growing along with economy, many famous-brand and high-quality commodity, marketable securities under the driving of interests, even important identity document all copied, and brings massive losses for individual, businessman and country.Therefore, effectively the anti-false true-guaranteeing technology more and more is subject to people's attention, and develops also more and more faster.
Angular photochromic material is with its strong visual impact, unique physical property, and characteristic such as bore hole is easy to identify once the attention that people occur causing, is widely used in false proof field, and is wherein the widest with the research of angular color change pigment.
The optic angle effect material of early development mainly is an interference pigment, based on inorganic material, best results wherein, have practical value most when number multi-coated interference film pigment, it is that ultra-thin inteferometer coating by the inorganic material vacuum moulding machine preparation of the different reflection efficiencies of multilayer forms through pulverizing.Early introduced the preparation method of this kind material as U.S.Pat.No.4930866 (Phillips et.al), have this Patent right U.S. good fortune come Ces Co.,Ltd afterwards Development and Production go out a series of chameleon pigment, the revolutionary technology that is called as pigment industry, registration mark trade mark jade-like stone agate phenanthrene (ChromaFlair).It is a kind of film ultra-thin, opaque, that be made up of the multi-coated interference film, formed the minimum pigment of particle diameter after crushed, it is by the physics interference of light technology that applies unerringly, control thickness of thin layer and structure and interference light by the time wavelength, thereby produce special reflecting effect, gloss that obtain moving, illusion-colour is along with the difference of viewing angle presents different colors.Be widely used in the false proof of various marketable securities, as the bank note (numeral 100 on Chinese hundred yuan notes) of various countries.This kind pigment has good light resistance and weatherability, and shortcoming is the manufacturing process complexity, and cost is too high, to the alkali instability, does not have desirable acid resistance, and pigment itself is opaque, and the occasion that does not hide end literary composition for needs is inapplicable.
Progress along with science and technology; the organic polymer angular photochromic material begins to enter people's sight; the method that the black type liquid crystal of courage trunk polymer is made in the condensation reaction of wherein German Clariant company exploitation is well used; U.S.Pat.No.005834072A (Erwin et.al) has introduced the principle and the method for melt condensation reaction manufacturing organic polymer angular color change coating; be with chiral component; the hydroxyl hydroxy acid; the mixture of dihydroxy acid or glycol is by the black type trunk polymer of melt condensation prepared in reaction courage of acetic anhydride; through being extruded into wire rod or web; with pelleter or comminutor product is crushed to certain granules again; re-use various types of milling apparatus and suitably further pulverize, obtain practical thermal spraying angular color change coating.This kind coating melts to be coated on through elevated temperature heat to be used on the pretreated flexible substrates of antiplastering aid, and through high temperature blade coating orientation, the sub-cooled fixation can be prepared the film that has with the viewing angle discoloration effect, forms pigment through pulverizing and flexible grinding again.Its principle is to utilize the spiral super-grade structure of the black type liquid crystal polymer of courage, optionally reflects incident ray, it seems on the macroscopic view that the different materials with viewing angle presents different tones.Be widely used in the false proof field of important certificate, as some national passports, driving license, government official's certificate, important competitive sports admission ticket (98 years world cup admission tickets).This kind pigment has preferably weather resisteant, hardness, anti-stroke, anti-solvent and resistance to acids and bases, shortcoming is the complex process of preparation pigment, the operating temperature height, the difficult control of the major diameter of pigment flakes, cause color changeable effect to be had a greatly reduced quality, the pigment molecule thin slice can not form continuous phase, and the saturation degree of color and lightness reduce.
Raising along with the counterfeit level of fraud molecule; single anti-counterfeiting technology has been difficult to reach the purpose of effective protection; so anti-counterfeiting technology is also towards multiple; multi-thread high-end professional complex technique direction develops. and several different professional techniques organically combine the counterfeit difficulty that one increases anti-counterfeiting technology; the particularly ingenious combination of a line (bore hole identification) technology and two wires (by equipment or other conditions) technology; existing characteristic easy to identify; secret information increases counterfeit difficulty again simultaneously. and the high-end anti-counterfeiting technology in comparatively ideal two wires is based on the recessive information recognition technology of retroreflecting base material; information reading need be realized by certain instrument or external condition. introduced a kind of anti-counterfeiting technology of the dual evident characteristics based on the retroreflecting base material as U.S.Pat.No.5169707 (Faykish et.al); main information picture and text are under the home light and all be that bore hole is visible under the retroreflecting light; and retroreflecting information only under special retroreflecting light as seen; and this technology also has certain transparency; the most of visible characteristics of lining information; false proof applicable to high-grade goods and important certificate field; as passport; driving license, vital document etc.Shortcoming is that a line anti-counterfeiting technology content is lower, and anti-counterfeiting information film itself is not transparent fully, and protected portions information is covered, can't satisfy the duplicating requirement.
Summary of the invention
The objective of the invention is to propose a kind of two line anti-counterfeiting technologies that constitute by dual high-end professional technique organic assembling, particularly provide a kind of laminated film and preparation method thereof, to improve the counterfeit difficulty of anti-counterfeiting technology with angular color change and retroreflecting information dual function nature.
Laminated film with angular color change and retroreflecting information dual function nature provided by the invention, constitute through the dielectric layer bonding by angular color change information functional layer and retroreflecting informational function layer, wherein, the angular color change information functional layer comprises by chiral molecules and aligns the angular color change graph text information function film that forms, retroreflecting informational function layer comprises common reflecting film layer, the information recording layer of making by photosensitive material and strengthen the anti-layer of returning of reflection efficiency, described reflecting film comprises the implant that reflects usefulness, be used to embed the adhesive layer of implant, described information recording layer is coated in the adhesive layer bottom of implant below in the described reflecting film, goes back to the top of anti-layer.
In the above-mentioned reflecting film, described implant can be to be ball-shaped structure, pyramidal structure, polygonal structure or other solid geometry structure, and described implant can adopt macromolecule resin to make, and have transparent, even, refractive index is high and characteristics clearly; Described adhesive layer can adopt macromolecule resin material to make, and has the high characteristics of light transmittance height, good weatherability and toughness; Described time anti-layer adopts the material of high reflectance to make, and sputters on the bottom surface of information recording layer.
Above-mentioned preparation method with laminated film of dual function nature is: prepare described angular color change information film and described retroreflecting information film earlier respectively separately, between described angular color change information film and described retroreflecting information film, one deck is set then and is used to connect both dielectric layers, by this dielectric layer described angular color change film and described retroreflecting information film bonding are combined with each other at last.
Further, described dielectric layer material comprises pressure-sensitive adhesive, as acrylic ester type and organosilicon type etc.; Comprise that also heat melts the type binding agent, as polyester-type, polyurethane-type and polyethylene etc.
Further, pressure-sensitive adhesive normal temperature applies certain pressure and uses, and heat is melted the type binding agent and looked particular type and select suitable temperature, is generally 90～110 ℃ for best.
Further, the angular color change information picture and text of described angular color change information film are to utilize field drives, chiral molecules is aligned and obtain.Be a kind of superhelix, have the characteristic that optionally reflects incident ray, thereby present the angular color change effect.The advantage of this method is that angular color change picture and text form and aspect are continuous, and colourity is full beautiful; Transparency is good, does not influence the reading and the duplicating of protected information; Control the tone of optic angle material, easy operating by the ratio of adjusting magnetic field intensity and chiral material; Active component is crosslinked by cured with ultraviolet radiation, forms high molecular polymer, and is acidproof, alkali resistance good, and weatherability is good.
Further, the component of described angular color change information picture and text functional material is as follows:
Cellulose derivative: 20～60wt%,
Can gather monomer: 40～80wt%.
Light trigger: be 0.5～8wt% of above-mentioned two kinds of compositions,
Solvent: be 10～40wt%. of above-mentioned two kinds of compositions
Described cellulose derivative is a kind of cellulose derivative of modification, and its part or all hydroxyl is substituted, and substituting group can be ether, alkyl carbamate etc.; The described monomer that gathers is an acrylate, methacrylate, vinyl ethers, epoxides, maleate etc. a kind of; Described photoinitiator can be general commercial photoinitiator, as the isobutyl group benzoin ether, and 2,4,6-trimethylbenzene formyl hexichol phosphine oxide, 1-hydroxy cyclohexyl phenylketone, 2,2-dimethyl-2-phenyl acetophenone etc. a kind of.
The preparation process of described angular color change information film is: with cellulose derivative, can gather monomer, light trigger and solvent and stir by above-mentioned part by weight, be deployed into and be fit to printing or coating function ink material, material is printed or applied on the transparent functional basement membrane again, pass through the magnetic field of 0.5～5.0T under the room temperature, use the uviol lamp radiation curing again, can obtain required angular color change information film.
Further, the component of described retroreflecting information film is as follows:
Binder polymer: 15～55wt%
Initator: 5～8wt%
Photo polymerization monomer: 20～60wt%
Solvent: 8～20wt%
Total amount satisfies 100%.
Described binder polymer comprises acrylic acid, methacrylic acid, methymethacrylate and acrylic acid 2-ethylhexyl fat; Described initator comprises benzophenone, diethylamino benzophenone, LCV, toluenesulfonic acid-hydrate and diamond green GH, described photo polymerization monomer comprises isobornyl methacrylate, 2-phenoxyethyl acrylate, tripropylene glycol diacrylate, 1,6-hexanediyl ester; Described solvent comprises methyl ethyl ketone.
The preparation process of described retroreflecting information film is: earlier common reflecting film is carried out sided corona treatment, on the reflective membrane of sided corona treatment, be coated with the light-sensitive material that is used for recorded information of one deck 50～100nm thickness then at this, be exposed to this reflective membrane under the ultraviolet light of linear polarization by a template again, through action of ultraviolet light, monomer molecule carries out polymerization along the polarization direction of ultraviolet light, thereby on reflective information film, form the setting graph text information consistent, then time anti-layer material of vacuum evaporation thereon or sputter one deck high reflectance with the ultraviolet light polarization direction.
Further, the outer side covers matcoveredn of described angular color change information layer.
Further; the protective layer of described angular color change information layer outer side covers adopts friable material to make; the reflective membrane of described retroreflecting Information Level adopts friable material to make, and the dielectric layer between described connection angular color change information functional layer and the retroreflecting informational function layer adopts cohesive force to be easy to the binding material of breaking for a short time.
Further, described protective layer friable material adopts the polyurethane-type photopolymer film of Shanghai sky minister company of Fudan University exploitation.
Further, be provided with in the outside of described retroreflecting Information Level and be used for laminated film is compound to tack coat on the object securely, and cover the barrier paper on this tack coat outer surface.
Further, be provided with regular exposed layer with specific physics rule schema literary composition in the outside of described retroreflecting Information Level, and between described retroreflecting Information Level and described exposed layer, one deck is set and is used to be connected both dielectric layers, be provided with in the outside of this rule exposed layer and be used for laminated film is securely adhered to adhesive linkage on the object, and cover the barrier paper on this adhesive linkage outer surface.
The above-mentioned laminated film that the present invention proposes with angular color change and retroreflecting information dual function nature, under normal surround lighting, the transparent optic angle color-changing image-text information of setting on the film is along with the viewing angle difference presents different colors, as the most responsive redness of human eye is arrived emerald green conversion; Under directed retroreflecting light, same viewing angle, transparent optic angle color-changing image-text converts complementary color under the ambient light (become as redness emerald green) to, change viewing angle, picture and text are by emerald green pulverize redness, simultaneously, if the retroreflecting Information Level is handled through special process, also can be observed predefined retroreflecting information picture and text on the laminated film, i.e. mercury shape picture and text of Liu Donging, picture and text disappear behind the rotational angle.
Laminated film technology of the present invention is by making full use of the mutual aid of two-layer functional material characteristic, create the organic combination of the two wires recognition technology of line recognition technology with exquisite outward appearance picture and text and secret information picture and text, really accomplished mutual supplement with each other's advantages, the class and the whole technology content of anti-fake product have been improved, overcome in the past that a line technology is the drawback of purpose with ornamental in the not enough and complex technique of monotechnics product protection dynamics, the visual effect uniqueness, be easy to identification, have very strong antiforge function.Especially laminated film of the present invention can be combined into the transparent body under the ordinary ambient light, does not influence the reading of the information of being capped and duplicating etc., therefore is specially adapted to the false proof of important certificate and document, as passport, file etc.
Description of drawings
Fig. 1 is the structural representation of the first, the 3rd embodiment of the present invention;
Fig. 2 is the structural representation of the second, the 5th embodiment of the present invention;
Fig. 3 is the structural representation of the fourth embodiment of the present invention;
Fig. 4 is the structural representation of the sixth embodiment of the present invention;
Number in the figure: 1 is protective layer, and 2 is the angular color change graph text information, and 3 is dielectric layer, and 4 is adhesive layer, and 5 is implant, and 6 are back anti-layer, and 7 is information recording layer, and 8 is dielectric layer, and 9 is exposed layer, and 10 is tack coat, and 11 is barrier paper, and A is a reflecting film.
The specific embodiment
The invention is further illustrated by the following examples.
Embodiment 1
As shown in Figure 1, described false-proof film comprises angular color change information layer and retroreflecting Information Level, described angular color change information layer comprises by chiral molecules and aligns the angular color change graph text information 2 that forms that described retroreflecting Information Level comprises common reflecting film A and returns anti-layer 6.
Described reflecting film A comprises implant 5 that reflects usefulness and the adhesive layer 4 that is used to embed implant 5, described implant 5 is a ball-shaped, adopt macromolecule resin to make (for a kind of glass microballoon), and have that circularity is good, transparent, even, refractive index is high and characteristics clearly; Described adhesive layer 4 adopts macromolecule resin material to make, and has the high characteristics of light transmittance height, good weatherability and toughness.
The anti-layer 6 that returns of described reflective usefulness adopts the AL material of high reflectance to make, and is coated in the lower surface of glass microballoon below focus layer.
Be provided with the dielectric layer 3 that one deck is used to be connected angular color change information layer and retroreflecting Information Level between described angular color change information layer 2 and described adhesive layer 4, described dielectric layer 3 adopts PU resins or EVA heat-sensitive glue to make.
The outer side covers matcoveredn 1 of described angular color change information layer, described protective layer 1 are made by polyester material.
Be provided with in the outside of described retroreflecting Information Level and be used for the present invention is compound to tack coat 10 on the object securely, and cover the barrier paper 11. on these tack coat 10 outer surfaces
The preparation method of described false-proof film is: prepare described angular color change information film and described retroreflecting information film earlier respectively separately, between described angular color change information rete and described retroreflecting information film, one deck is set then and is used to connect both dielectric layers 3, by this dielectric layer 3 described angular color change information layer and the hot pressing of described retroreflecting Information Level are combined with each other at last.Wherein, this dielectric layer 3 is the EVA heat-sensitive glue, and its hot pressing combined temp is 95 ℃.
The preparation method of described angular color change information film 2 is: with cellulose derivative, trimethylol-propane trimethacrylate mixed in 4: 6 by weight proportion, add 2 of the former two's gross weight 4%, 2-methyl-2-phenyl acetophenone, composition is dissolved in the proper amount of acetone, add an amount of slow curing solvent and levelling agent again, fully stirring is uniformly dispersed it, be deployed into and be fit to printing or coating function ink material, material is printed or applied on the transparent functional basement membrane again, magnetic field by 1.0T under the room temperature, use the uviol lamp radiation curing again, can obtain frontlighting observation redness under the conventional environment, backlight is observed the angular color change information function film of emerald green conversion.
The preparation method of described retroreflecting information film A is: time anti-layer material AL of vacuum evaporation or sputter one deck high reflectance below the focus layer of common reflecting film makes the plant film light tight fully.
False-proof film as shown in Figure 1 is opaque, and the transparent optic angle color-changing image-text information of setting on the film 2 is along with the viewing angle difference presents different colors.Under normal surround lighting, present the color changeable effect of angular photochromic material itself, promptly frontlighting is observed, the picture and text shiny red, backlight is observed, and picture and text become emerald green; Because the strong reflection light action of aluminum plating reflective membrane, embody the effect of retroreflecting film again, adjust viewing angle, frontlighting is observed, can see that picture and text 2 convert the complementary color under the ambient light to---emerald green, slowly change viewing angle, again to pink, tone is continuous by the emerald green bluish violet that changes into for picture and text 2, be in bright colors, certainly, by light emitting tool, under orienting reflex light, also can be observed same effect.
False-proof film as shown in Figure 1 is opaque under ordinary ambient light, but has exquisite outward appearance, and color changeable effect as the magic can be used as safety label, is used to protect commodity, in case false Jianzhen.
Embodiment 2
As shown in Figure 2, described false-proof film comprises angular color change information layer and retroreflecting Information Level, described angular color change information layer comprises by chiral molecules and aligns the angular color change graph text information 2 that forms, and described retroreflecting Information Level comprises common reflecting film A and the information recording layer 7 that records the reflection graph text information made by photosensitive material and return anti-layer 6
Described reflecting film A comprises implant 5 that reflects usefulness and the adhesive layer 4 that is used to embed implant 5, described implant 5 is a ball-shaped, described implant 5 adopts macromolecule resins to make, and has that circularity is good, transparent, even, refractive index is high and characteristics clearly; Described adhesive layer 4 adopts macromolecule resin material to make, and has the high characteristics of light transmittance height, good weatherability and toughness.
Described information recording layer 7 adopts acrylic monomer to make, and applies into the thick coating of 10～60nm in the bottom of described reflecting film.
The anti-layer 6 that returns of described reflective usefulness adopts the ZnS material of high reflectance to make, and is coated in the lower surface of information recording layer.
Be provided with the dielectric layer 3 that one deck is used to be connected angular color change information layer and retroreflecting Information Level between described angular color change information layer 2 and described adhesive layer 4, described dielectric layer 3 adopts PU resins or EVA heat-sensitive glue to make.
The outer side covers matcoveredn 1 of described angular color change information layer, described protective layer 1 are made by polyester material.
Be provided with in the outside of described retroreflecting Information Level and be used for the present invention is compound to tack coat 10 on the object securely, and cover the barrier paper 11 on these tack coat 10 outer surfaces.
The preparation method of described false-proof film is: prepare described angular color change information film and described retroreflecting information film earlier respectively separately, between described angular color change information rete and described retroreflecting information film, one deck is set then and is used to connect both dielectric layers 3, by this dielectric layer 3 described angular color change information layer and the hot pressing of described retroreflecting Information Level are combined with each other at last.Wherein, this dielectric layer 3 is the EVA heat-sensitive glue, and its hot pressing combined temp is 95 ℃.
The preparation method of described angular color change information film 2 is: with cellulose derivative, trimethylol-propane trimethacrylate mixed in 4: 6 by weight proportion, add 2 of the former two's weight 4%, 2-methyl-2-phenyl acetophenone, composition is dissolved in the proper amount of acetone, add an amount of slow curing solvent and levelling agent again, fully stirring is uniformly dispersed it, be deployed into and be fit to printing or coating function ink material, material is printed or applied on the transparent functional basement membrane again, magnetic field by 1.0T under the room temperature, use the uviol lamp radiation curing again, can obtain frontlighting observation redness under the conventional environment, backlight is observed the angular color change information function film of emerald green conversion.
The preparation method of described retroreflecting information film A is: earlier common reflecting film is carried out sided corona treatment, on the reflective membrane of sided corona treatment, be coated with the light-sensitive material that is used for recorded information of one deck 50～100nm thickness then at this, be exposed to this reflective membrane under the ultraviolet light of linear polarization by a template again, through action of ultraviolet light, monomer molecule carries out polymerization along the polarization direction of ultraviolet light, thereby on reflective information film, form the setting graph text information consistent, then time anti-layer material of vacuum evaporation thereon or sputter one deck high reflectance with the ultraviolet light polarization direction.
False-proof film as shown in Figure 2 is transparent, and the transparent optic angle color-changing image-text information of setting on the film 2 is along with the viewing angle difference presents different colors.Under normal surround lighting, present the color changeable effect of angular photochromic material itself, promptly frontlighting is observed, the picture and text shiny red, backlight is observed, and picture and text become emerald green; Under directed retroreflecting light, embody the effect of retroreflecting film again, right-angle view, can see that picture and text 2 convert the complementary color under the ambient light to---emerald green, film is turned an angle, picture and text 2 are by the emerald green pink that changes into, tone is continuous, is in bright colors; Simultaneously, also can be observed predefined retroreflecting information picture and text 7 on the laminated film, i.e. mercury shape picture and text of Liu Donging, picture and text 7 disappear behind the rotational angle.
False-proof film as shown in Figure 2 is transparent under ordinary ambient light, does not influence the reading of the information of being capped and duplicating etc., therefore is specially adapted to the false proof of important certificate and document; as passport, file etc.; also can be used as safety label, be used to protect commodity, in case false Jianzhen.
Embodiment 3
As shown in Figure 1, described false-proof film comprises angular color change information layer and retroreflecting Information Level, described angular color change information layer comprises by chiral molecules and aligns the angular color change graph text information 2 that forms, and described retroreflecting Information Level comprises that common reflecting film A and multilayer return anti-layer 6.
Described multilayer return anti-layer 6 adopt Metal Cr and MgF respectively sputter make.And respectively on the bottom surface of the adhesive layer below the implant sputter become 15nm and the thick coating of 50nm.
Described reflecting film A comprises the implant 5 that reflects usefulness, the adhesive layer 4 that is used to embed implant 5, described implant 5 is a ball-shaped, described implant 5 adopts macromolecule resins to make, and has that circularity is good, transparent, even, refractive index is high and characteristics clearly; Described adhesive layer 4 adopts macromolecule resin material to make, and has the high characteristics of light transmittance height, good weatherability and toughness.
Be provided with the dielectric layer 3 that one deck is used to be connected angular color change information layer and retroreflecting Information Level between described angular color change information layer 2 and described adhesive layer 4, described dielectric layer 3 adopts PU resins or EVA heat-sensitive glue to make.
The outer side covers matcoveredn 1 of described angular color change information layer, described protective layer 1 are made by polyester material.
Be provided with in the outside of described retroreflecting Information Level and be used for the present invention is compound to tack coat 10 on the object securely, and cover the barrier paper 11 on these tack coat 10 outer surfaces.
The preparation method of described false-proof film is: prepare described angular color change information film and described retroreflecting information film earlier respectively separately, between described angular color change information rete and described retroreflecting information film, one deck is set then and is used to connect both dielectric layers 3, by this dielectric layer 3 described angular color change information layer and the hot pressing of described retroreflecting Information Level are combined with each other at last.Wherein, this dielectric layer 3 is the EVA heat-sensitive glue, and its hot pressing combined temp is 95 ℃.
The preparation method of described angular color change information film 2 is: with cellulose derivative, trimethylol-propane trimethacrylate mixed in 5.5: 4.5 by weight proportion, add the former two's weight 5% 2,2-methyl-2-phenyl acetophenone, composition is dissolved in the proper amount of acetone, add an amount of slow curing solvent and levelling agent again, fully stirring is uniformly dispersed it, be deployed into and be fit to printing or coating function ink material, material is printed or applied on the transparent functional basement membrane again, magnetic field by 2.0T under the room temperature, use the uviol lamp radiation curing again, can obtain frontlighting observation green under the conventional environment, backlight is observed the angular color change information function film of blue conversion.
The preparation method of described retroreflecting information film A is: time anti-layer material MgF of vacuum evaporation or the thick high reflectance of sputter one deck 50nm below the focus layer of common reflecting film, the thick Cr of evaporation one deck 15nm again, the light transmittance of plant film is probably about 20%.
The false-proof film that this example proposes is opaque substantially, and the transparent optic angle color-changing image-text information of setting on the film 2 is along with the viewing angle difference presents different colors.Under normal surround lighting, present the color changeable effect of angular photochromic material itself, promptly frontlighting is observed, and picture and text are emerald green, and backlight is observed, and picture and text become blueness; Under directed retroreflecting light, embody the effect of retroreflecting film again, right-angle view, can see that picture and text 2 convert the complementary color under the ambient light---pink to, film is turned an angle, picture and text 2 change orange colour into by pink, tone is continuous, be in bright colors, simultaneously, also can be observed on the laminated film and to return reflective information picture and text 7 and become mauve background by emerald green background transitions, overall look and feel are that vertical angle is observed, the pink individual character picture and text that on emerald green background, are dotted with, rotational angle, the orange colour that is dotted with on aubergine background individual character picture and text.
This routine false-proof film can be used as safety label, is used to protect commodity, in case false Jianzhen.
As shown in Figure 3, described false-proof film comprises angular color change information layer and retroreflecting Information Level, described angular color change information layer comprises by chiral molecules and aligns the angular color change graph text information 2 that forms, and described retroreflecting Information Level comprises common reflecting film A and the information recording layer 7 that records the reflection graph text information made by photosensitive material and return anti-layer 6
Described reflecting film A comprises implant 5 that reflects usefulness and the adhesive layer 4 that is used to embed implant 5, described implant 5 is a ball-shaped, described implant 5 adopts macromolecule resins to make, and has that circularity is good, transparent, even, refractive index is high and characteristics clearly; Described adhesive layer 4 adopts macromolecule resin material to make, and has the high characteristics of light transmittance height, good weatherability and toughness.
Described information recording layer 7 adopts acrylic monomer to make, and applies into the thick coating of 10～60nm in the bottom of described reflecting film.
The anti-layer 6 that returns of described reflective usefulness adopts the ZnS material of high reflectance to make, and is coated in the lower surface of information recording layer.
Be provided with the dielectric layer 3 that one deck is used to be connected angular color change information layer and retroreflecting Information Level between described angular color change information layer 2 and described adhesive layer 4, described dielectric layer 3 adopts PU resins or EVA heat-sensitive glue to make.
The outer side covers matcoveredn 1 of described angular color change information layer, described protective layer 1 are made by polyester material.
The outside of described time anti-layer 6 is provided with the regular exposed layer 9 with specific physics rule schema literary composition, and between described time anti-layer 6 and described exposed layer 9, one deck is set and is used to be connected both dielectric layers 8, be provided with in the outside of this rule exposed layer and be used for the present invention is securely adhered to tack coat 10 on the object, and cover the barrier paper 11 on this adhesive linkage outer surface; Wherein, described regular exposed layer 9 is made up of top layer with yin yang complementarity picture and text and sublevel, because this rule exposed layer 9 is prior arts, is not described in detail in this.
The preparation method of described false-proof film is: prepare described angular color change information film and described retroreflecting information film earlier respectively separately, between described angular color change information rete and described retroreflecting information film, one deck is set then and is used to connect both dielectric layers 3, by this dielectric layer 3 described angular color change information layer and the hot pressing of described retroreflecting Information Level are combined with each other at last.Wherein, this dielectric layer 3 is the EVA heat-sensitive glue, and its hot pressing combined temp is 95 ℃.
The preparation method of described angular color change information film 2 is: with cellulose derivative, trimethylol-propane trimethacrylate mixed in 4: 6 by weight proportion, add 2 of the former two's weight 4%, 2-methyl-2-phenyl acetophenone, composition is dissolved in the proper amount of acetone, add an amount of slow curing solvent and levelling agent again, fully stirring is uniformly dispersed it, be deployed into and be fit to printing or coating function ink material, material is printed or applied on the transparent functional basement membrane again, magnetic field by 1.0T under the room temperature, use the uviol lamp radiation curing again, can obtain frontlighting observation redness under the conventional environment, backlight is observed the angular color change information function film of emerald green conversion.
The preparation method of described retroreflecting information film A is: earlier common reflecting film is carried out sided corona treatment, on the reflective membrane of sided corona treatment, be coated with the light-sensitive material that is used for recorded information of one deck 50～100nm thickness then at this, be exposed to this reflective membrane under the ultraviolet light of linear polarization by a template again, through action of ultraviolet light, monomer molecule carries out polymerization along the polarization direction of ultraviolet light, thereby on reflective information film, form the setting graph text information consistent, then time anti-layer material of vacuum evaporation thereon or sputter one deck high reflectance with the ultraviolet light polarization direction.
False-proof film as shown in Figure 3 is transparent, and the transparent optic angle color-changing image-text information of setting on the film 2 is along with the viewing angle difference presents different colors.Under normal surround lighting, present the color changeable effect of angular photochromic material itself, promptly frontlighting is observed, the picture and text shiny red, backlight is observed, and picture and text become emerald green; Under directed retroreflecting light, embody the effect of retroreflecting film again, right-angle view, can see that picture and text 2 convert the complementary color under the ambient light to---emerald green, film is turned an angle, picture and text 2 are by the emerald green pink that changes into, tone is continuous, is in bright colors; Simultaneously, can be observed predefined retroreflecting information picture and text 7 on the laminated film, i.e. mercury shape picture and text of Liu Donging, picture and text 7 disappear behind the rotational angle.
False-proof film as shown in Figure 3, behind the barrier paper of peelling off on this false-proof film 11, this false-proof film is sticked on the commodity, during use, this false-proof film is opened fast, separate with sublevel on the top layer of described regular exposed layer 9, can stay the characters cut in relief that designs in advance on the regular exposed layer 9 on the commodity, on the false-proof film part of taking off, can stay the characters cut in intaglio of design in advance on the regular exposed layer 9, illustrate that false-proof film was used, guarantee disposable use.
False-proof film in this example, during use, peel off the barrier paper 11 on this false-proof film earlier, then this false-proof film is sticked on the commodity, adhesive be stuck the commodity effect after 2 hours, when attempting when commodity are opened this false-proof film, whole false-proof film can be damaged fully, can't shift, so just guarantee that this false-proof film can not be utilized once more.
As Fig. 4 is the structural representation of embodiments of the invention 6, structure and the preparation method of itself and embodiment 4 shown in Figure 3 are basic identical, the implant 5 that different is among Fig. 4 is for there being the angle pyramid, and the implant 5 among Fig. 3 is a ball-shaped, and being among Fig. 4 has the implant 5 of angle pyramid shape to adopt macromolecule resins to make, and have transparent, even, refractive index is high and characteristics clearly; The label of the remainder of the 6th embodiment shown in Figure 4 and preparation method and the 4th embodiment shown in Figure 3 are identical, are not described in detail in this.
Above-mentioned only is preferred embodiment of the present invention; be not to be used for limiting protection scope of the present invention; the professional in present technique field can carry out various modifications to embodiment under the prerequisite that does not depart from the scope of the present invention with spirit, this modification all belongs in the scope of the present invention.
Claims (8)
1. laminated film with angular color change and retroreflecting information dual function nature, it is characterized in that constituting through the dielectric layer bonding by angular color change information functional layer and retroreflecting informational function layer, wherein, the angular color change information functional layer comprises by chiral molecules and aligns the angular color change graph text information function film that forms, retroreflecting informational function layer comprises common reflecting film layer, the information recording layer of making by photosensitive material and strengthen the anti-layer of returning of reflection efficiency, described reflecting film comprises the implant that reflects usefulness, be used to embed the adhesive layer of implant, described information recording layer is coated in the adhesive layer bottom of implant below in the described reflecting film, goes back to the top of anti-layer; Wherein:
The angular color change information picture and text of described angular color change information film utilize field drives, make chiral molecules align acquisition; Active constituent is crosslinked by cured with ultraviolet radiation, forms high molecular polymer; The component of described angular color change information picture and text functional material is as follows:
Cellulose derivative: 20～60wt%,
Can gather monomer: 40～80wt%.
Light trigger: be 0.5～8wt% of above-mentioned two kinds of compositions,
Solvent: be 10～40wt% of above-mentioned two kinds of compositions;
Described cellulose derivative is a kind of cellulose derivative of modification, and its part or all hydroxyl is substituted, and substituting group is ether or alkyl carbamate; The described monomer that gathers is an acrylate, methacrylate, vinyl ethers, epoxides, maleate a kind of; Described photoinitiator is the isobutyl group benzoin ether, 2,4, and 6-trimethylbenzene formyl hexichol phosphine oxide, 1-hydroxy cyclohexyl phenylketone, 2,2-dimethyl-2-phenyl acetophenone a kind of;
The preparation process of described angular color change information film is: with cellulose derivative, can gather monomer, light trigger and solvent and stir by above-mentioned part by weight, be deployed into and be fit to printing or coating function ink material, material is printed or applied on the transparent functional basement membrane again, pass through the magnetic field of 0.5～5.0T under the room temperature, use the uviol lamp radiation curing again, can obtain required angular color change information film;
The component of described retroreflecting information film is as follows:
Binder polymer: 15～55wt%
Initator: 5～8wt%
Photo polymerization monomer: 20～60wt%
Solvent: 8～20wt%
Total amount satisfies 100%;
Described binder polymer is a kind of in acrylic acid, methacrylic acid, methyl methacrylate and the acrylic acid 2-ethylhexyl ester, described initator is a kind of among benzophenone, diethylamino benzophenone, LCV, toluenesulfonic acid-hydrate and the diamond green GH, described photo polymerization monomer is isobornyl methacrylate, 2-phenoxyethyl acrylate, tripropylene glycol diacrylate or 1,6-hexanediyl ester, described solvent are methyl ethyl ketone;
The preparation process of described retroreflecting information film is: earlier common reflecting film is carried out sided corona treatment, on the reflective membrane of sided corona treatment, be coated with the light-sensitive material that is used for recorded information of one deck 50～100nm thickness then at this, be exposed to this reflective membrane under the ultraviolet light of linear polarization by a template again, through action of ultraviolet light, monomer molecule carries out polymerization along the polarization direction of ultraviolet light, thereby on reflective information film, form the setting graph text information consistent, then time anti-layer material of vacuum evaporation thereon or sputter one deck high reflectance with the ultraviolet light polarization direction.
2. according to the described laminated film of claim 1, it is characterized in that the implant in the described reflecting film is ball-shaped structure or pyramidal structure, the employing macromolecule resin is made, and described adhesive layer adopts the light transmittance height, weather resisteant is good and macromolecule resin that toughness is high is made.
3. according to the described laminated film of claim 1, it is characterized in that described angular color change information layer outer side covers matcoveredn.
4. according to the described laminated film of claim 3; the protective layer that it is characterized in that described angular color change information layer outer side covers adopts friable material to make; the reflective membrane of described retroreflecting Information Level adopts friable material to make, and the dielectric layer between described connection angular color change information functional layer and the retroreflecting informational function layer adopts cohesive force to be easy to the binding material of breaking for a short time.
5. according to the described laminated film of claim 1, it is characterized in that the described retroreflecting Information Level outside is provided with tack coat, this tack coat outer surface is coated with barrier paper.
6. according to the described laminated film of claim 1, it is characterized in that being provided with regular exposed layer with specific physics rule schema literary composition in the outside of described retroreflecting Information Level, and between described retroreflecting Information Level and described exposed layer, one deck is set and is used to be connected both dielectric layers, be provided with in the outside of this rule exposed layer and be used for laminated film is securely adhered to adhesive linkage on the object, and cover the barrier paper on this adhesive linkage outer surface.
7. preparation method of laminated film according to claim 1, it is characterized in that preparing separately respectively earlier described angular color change information film and described retroreflecting information film, between described angular color change information film and described retroreflecting information film, one deck is set then and is used to connect both dielectric layers, by this dielectric layer described angular color change film and described retroreflecting information film bonding are combined with each other at last.
8. the preparation method of laminated film according to claim 7 is characterized in that described dielectric layer is that pressure-sensitive adhesive or heat are melted the type binding agent.
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| CN 200410066448 CN1600535B (en) | 2004-09-16 | 2004-09-16 | Composite membrane possessing diplex functional characteristice and preparation method |
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| CN 200410066448 CN1600535B (en) | 2004-09-16 | 2004-09-16 | Composite membrane possessing diplex functional characteristice and preparation method |
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| CN100586740C (en) * | 2008-07-24 | 2010-02-03 | 上海复旦天臣新技术有限公司 | False proof thin film and preparation thereof |
| CN104882064B (en) * | 2015-06-24 | 2017-05-17 | 山东泰宝防伪技术产品有限公司 | Positioning hollowed-out etching lift-up mark and method for preparing positioning hollowed-out etching lift-up mark through environment-friendly flexible paint |
| CN114604019B (en) * | 2020-12-04 | 2023-09-05 | 中钞特种防伪科技有限公司 | Safety line or strip and preparation method thereof |
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| US5169707A (en) * | 1991-05-08 | 1992-12-08 | Minnesota Mining And Manufacturing Company | Retroreflective security laminates with dual level verification |
| US5834072A (en) * | 1996-04-01 | 1998-11-10 | Clariant Gmbh | Powder coatings whose perceived color depends on the viewing angle |
| CN1283840A (en) * | 1999-03-26 | 2001-02-14 | 株式会社资生堂 | Counterfeit-proof binding mark and its making method |
| CN1408801A (en) * | 2002-09-13 | 2003-04-09 | 上海复旦天臣感光材料有限公司 | Angular photochromic material and its preparing method |
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2004
- 2004-09-16 CN CN 200410066448 patent/CN1600535B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5169707A (en) * | 1991-05-08 | 1992-12-08 | Minnesota Mining And Manufacturing Company | Retroreflective security laminates with dual level verification |
| US5834072A (en) * | 1996-04-01 | 1998-11-10 | Clariant Gmbh | Powder coatings whose perceived color depends on the viewing angle |
| CN1283840A (en) * | 1999-03-26 | 2001-02-14 | 株式会社资生堂 | Counterfeit-proof binding mark and its making method |
| CN1408801A (en) * | 2002-09-13 | 2003-04-09 | 上海复旦天臣感光材料有限公司 | Angular photochromic material and its preparing method |
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