CN101059654B - Photolithagraphic diffractive image false-proof film and its preparation method - Google Patents
Photolithagraphic diffractive image false-proof film and its preparation method Download PDFInfo
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- CN101059654B CN101059654B CN200710039679A CN200710039679A CN101059654B CN 101059654 B CN101059654 B CN 101059654B CN 200710039679 A CN200710039679 A CN 200710039679A CN 200710039679 A CN200710039679 A CN 200710039679A CN 101059654 B CN101059654 B CN 101059654B
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Abstract
The invention discloses a photo-etching diffraction image false-proof film and a relative preparation method, comprising composite a photo-etching color-change false-proof film and a reflective holographic light sensing film, wherein the reflective holographic light sensing film comprises a base film, a buffer layer coated on one side of the reflective holographic base film, and a light sensing polymer coat formed by the light sensing polymer paint coated on another side of the buffer layer, and the photo-etching color-change false-proof film comprises a photo-etching base film and a photo-etching layer formed by the photo-etching material B exposed by laser or ultraviolet light coated on one side of the photo-etching base film. The inventive film has clear red and green image in front view, while the image will be changed from red to green and green to blue after changing watching angle. The pattern on the photo-etching diffraction image false-proof film has dual-color-change effect, to apply product false-proof, identification guard, file false-proof and package decoration.
Description
Technical field
The present invention relates to a kind of optic metachromatic film anti-fake material and preparation method thereof, relate in particular to a kind of pair of variable color image false-proof film.
Technical background
In view of the continuous development of commodity economy, the demand of anti-counterfeiting technology is also more and more, and its technological means also emerges in an endless stream.It is one of state-of-the-art false proof means in the world at present that light becomes material, comprises that light-variation film, light become powder and photochromatic printing ink.It is a kind of desirable popular anti-fake product, and the content height that possesses skills can not be replicated with self being difficult to and can be widely used in currency, securities, certificate and various high-level anti-fake product by characteristics such as counterfeit.
Light becomes material with its unique visual identity effect, liked by businessman, and be one of high-end anti-fake material.The image that adopts light to become the material made claims light variation image, and its color is to change with the viewing angle conversion.
Present phototropic material, can have multiple, as: a kind of is to adopt chiral molecules, arranges by oriented molecule to produce specific helical structure and cause color to become with the variation of viewing angle; Another kind is the effect that reaches phototropic by the nano metal microparticle material of oxidation; Another is to produce color transformed according to the conversion that the principle that has interference effect between the multilayer optical film reaches with viewing angle.
But employing aforesaid way, the conversion of its image color can only be to another wavelength from a kind of wavelength conversion, the material of gained is a kind of monotropic look material, and certain defective is all arranged for its stock, as hide shading image or require dark-background, be used for fields such as product false proof, the packing of product, certificate safety, incrustation and optics is reflective and be subjected to certain restriction.
Summary of the invention
The technical issues that need to address of the present invention are to disclose a kind of photoetching coating A, to satisfy the needs of the two variable color image false-proof films of preparation photoetching diffraction;
Another technical matters that the present invention need solve is to disclose a kind of photoetching color-changing anti-counterfeit film C;
Another technical matters that the present invention need solve is to disclose a kind of photoetching diffraction colour image false-proof film D, to overcome the above-mentioned defective that prior art exists;
The invention still further relates to the preparation method of described photoetching diffraction colour image false-proof film D, so that suitability for industrialized production.
A kind of photoetching coating A comprises solvent and the photoetching material B that is dissolved in the said solvent, and the weight solid content of said photoetching coating A is 5%-60%;
Component and the weight percent content of said photoetching material B comprise:
Cementing agent 20～80%;
Monomer 15～75%;
Initiating agent 0.1～3%;
Plastifier 0.01～3%;
Ultraviolet absorber 0.05～1%;
Surfactant 0.15～1%;
Preferably:
Cementing agent 30～65%;
Monomer 30～70%;
Initiating agent 0.8～2%;
Plastifier 0.5～2.5%;
Ultraviolet absorber 0.1～0.5%;
Surfactant 0.3～0.8%
Said cementing agent is selected from the multipolymer of multipolymer, vinyl acetate and butyl acrylate of vinyl acetate and methyl methacrylate or polyvinyl butyral etc.;
Said monomer is two or more and can carries out radical addition polymerization, its boiling point is greater than 100 ℃ monomer, having at least a kind of is ethylenically unsaturated monomers, weight ratio between two or more in diacrylate, single acrylic acid phenol ethoxylate ester or the tristane dimethanol diacrylate etc. of the bisphenol-A of preferred ethoxylation, two kinds of monomers is 0.5～1.2;
Said initiating agent is selected from isobutyl benzoin ether, 1-hydroxy cyclohexyl phenylketone or 2,2-dimethyl-2-phenyl acetophenone etc.;
Said plastifier adds for increase sensitization monomer transfer ability, and plastifier is selected from dibutyl phthalate or separates two dibutyl phthalates etc.;
Said ultraviolet absorber is selected from 2-hydroxyl-4-methoxy benzophenone (CAS:131-57-7) or 2-(2H-benzotriazole-2)-4,6-two (1-methyl isophthalic acid-phenethyl) phenol (CAS:70321-86-7);
Said surfactant is a non-ionic surfactant, is selected from the fluoro aliphatic polymer fat surfactant that polyglycol, methoxy poly (ethylene glycol) or 3M company produce
FC-4430 (CAS No.108-88-3) is in order to regulate paintability.
Said solvent is mixed solvents such as butanone, methylene chloride, ethanol, and part by weight is 5: 0.5～1.5: 0.5～1.5, preferably 5: 1: 1;
Said photoetching color-changing anti-counterfeit film C, comprise the photoetching basement membrane, coated is at the lithography layer that is formed by laser or ultraviolet photoetching by said photoetching material B of photoetching basement membrane one side, lithography layer thickness is 3～50 μ m, the lithography layer glazing is carved with image, and said photoetching basement membrane is selected from PVC, PET or the BOPP film of 20～100 μ m;
Photoetching diffraction colour image false-proof film D involved in the present invention comprises above-mentioned photoetching color-changing anti-counterfeit film C and reflection holography photosensitive film D1;
Said reflection holography photosensitive film D1 comprises reflection holography basement membrane and the coated cushion on reflection holography basement membrane one side, the photopolymer coating that the photopolymer coating B1 of coated on the cushion opposite side forms, the interference fringe of hologram image or two color-changing image-texts is recorded in the photopolymer coating, and the thickness of recording layer is 3～50 μ m.
Said reflection holography basement membrane is selected from PVC, PET, BOPP film;
The lithography layer of said photoetching color-changing anti-counterfeit film D is mutually compound with the photopolymer coating of reflection holography photosensitive film D1;
Said photopolymer B1 coating comprises following components in weight percentage:
Film forming agent 20%～80%
Monomer 10%～70%
Light trigger 0.5%～7%
Chain-transferring agent 0.3%～5%
Photosensitizer 0.05%～2%
Preferred percentage by weight is as follows;
Film forming agent 30%～70%
Monomer 23.0%～60.0%
Light trigger 2.0%～7.0%
Chain-transferring agent 1.0%～～3.0wt%
Photosensitizer 0.5%～2.0%
Said film forming agent is selected from blend, vinyl acetate butyl acrylate acrylic acid terpolymer or the polystyrene vinyl cyanide etc. of multipolymer, polyvinyl butyral and the cellulose acetate of polymethylmethacrylate, poly-cellulose acetate butyl ester, cellulose acetate butyl ester and ethyl vinyl ether, or the composite material of above-mentioned polymkeric substance and fluoropolymer;
Said monomer is selected from two or more in the unsaturated class of thiazolinyl, and the weight ratio between two kinds of monomers is 0.5～1.8;
The unsaturated class of said thiazolinyl contains unsaturated group on the position usually endways, they can carry out radical addition polymerization, boiling point is higher than 100 ℃, be selected from the higher vinylcarbazole of refractive index, multitube can be rolled into a ball rare class unsaturated monomer etc., the preferably diacrylate of the bisphenol-A of simple function group esters of acrylic acid, N-vinylcarbazole class, ethoxylation, 9-(4 phenyl, 2 third rare acyl ethoxys) two fluorenes or tristane dimethanol diacrylate etc.;
Light trigger, chain-transferring agent and photosensitizer constitute light initiation system, initiator system is the key factor of decision luminous sensitivity, initiator system comprises one or more when with the light radiation excitation, can directly produce the compound of free radical, and its free radical can carry out polymerization by trigger monomer;
Preferred light trigger is selected from 2,4,6-triphenyl imidazole radicals doublet;
Preferred photosensitizer be selected from the red B of algae,, lignocaine-benzal cyclopentanone, michaelis ketone or 1,3,3-trimethyl-2-[5-(1,3,3-trimethyl-2-indoles fork)-1,3-pentadiene] indoles salt compounded of iodine etc.;
Preferred chain-transferring agent is selected from 2-mercaptobenzoxazole, lauryl mercaptan, mercaptobenzothiazoler;
Above-mentioned photopolymer B1 comprises that also plastifier is selected from phthalic ester based on the plastifier of photopolymer coating B1 general assembly (TW) 0.5～3%, alkyl acid ester, polyglycol carboxylate, diethyl sebacate etc.;
Above-mentioned photopolymer B1, also comprise ultraviolet absorber based on photopolymer coating B1 general assembly (TW) 0.1～1%, ultraviolet absorber is selected from 2-hydroxyl-4-methoxy benzophenone or 2-(2H-benzotriazole-2)-4,6-two (1-methyl isophthalic acid-phenethyl) phenol;
Above-mentioned photopolymer B1 also comprises the non-ionic surfactant based on photopolymer coating B1 general assembly (TW) 0.1～1%, and non-ionic surfactant is selected from the plain surfactant of fluorine that polyglycol, methoxy poly (ethylene glycol) or 3M company produce
FC-4430 (CAS No.108-88-3) is in order to regulate paintability;
The preparation method of said reflection holography thin film D1 comprises the steps:
(1) preparation of coating material:, in proportion film forming agent, monomer, initiating agent, photosensitizer, plastifier and surfactant are added in the solvent under red light at the lucifuge conditioned disjunction, stirring and dissolving obtains said photosensitive coating A1;
Said solvent is elected the mixed solvent of butanone/methylene chloride as, and its part by weight is 4～6: 0.5～1.5: 0.5～1.5, preferably: 5: 1: 1;
In the solvent, the weight solid content of photopolymer coating B1 is 5%-50%;
(2) preparation of film: on basement membrane, be coated with the vinyl acetate of 1～2 μ m and acrylic acid lipin polymer, vinylidene chloride styrene vinyl acetate co-polymer, as cushion, at the lucifuge conditioned disjunction under red light, photosensitive coating A1 with step, be coated on the basement membrane of existing cushion, thickness was 20～100 μ m, 65-75 ℃ following dry 1～5 minute, obtaining thickness is 20-50 μ m hologram light sensitive material, drying;
(3) preparation of reflection holography thin film D1: with the product of step (2), adopt the reflection holography recording method, record a hologram on the photopolymer coating, on the ultra-violet curing machine, film is carried out ultraviolet and visible light burn-out then, 120 ℃ were heated 2～50 minutes, promptly obtain reflection holography thin film D1,, have certain pliability for a kind of solid transparent film photosensitive material;
The wavelength of said red light should adopt lucifuge conditioned disjunction red light greater than 600nm, its objective is the exposure of avoiding photosensitive coating A;
The wavelength of LASER Light Source is 514.5nm or 532nm, and light intensity is 60～110mw/cm
2, the time shutter, LASER Light Source can adopt Argon ion laser (wavelength is 514nm) or semiconductor solid state laser (wavelength 532nm) at 0.1-1.0s;
Said reflection holography recording method is a kind of prior art, is general holographic optics recording principle, and relevant technologies personnel can be with reference to enforcement.
The preparation method of said photoetching diffraction colour image false-proof film D comprises the steps:
(1) under yellow or red safety lamp, in proportion with cementing agent, monomer, initiating agent, plastifier, ultraviolet absorber and surfactant dissolves in solvent, obtain photoetching coating A; Adopt yellow or red safety lamp, purpose is to prevent exposure;
(2) the photoetching coating A with step (1) is coated on the basement membrane, and the control coating build is 5～30 μ m, at 50～100 ℃ of dryings, covered with protective film;
Said diaphragm is PET film that release coating is arranged, PE film, BOPP film etc., and thickness is 16～40 μ m, also can have image on the diaphragm, is a kind of mask with image;
Said diaphragm, can adopt existing release coating, preferred thickness is PET film, BOPP film, PE or the PVC film of 16～23 μ m, this have PET film, BOPP film, PE or the PVC film of release coating all can purchase on market.
(3) adopt the 457.9nm wave band of Argon ion laser or the light of helium cadmium laser 441nm wave band, carry out the exposure photo-etching processing from the product of diaphragm one pace rapid (2), write down required picture and text, throw off diaphragm then, lithography layer is mutually compound with the photopolymer coating of reflection holography photosensitive film D1;
(4) with the product of step (3) 80～160 ℃ of thermal treatments 1～20 minute, placing light intensity then is 100mj/cm
2The high-pressure mercury mercury lamp under be cured, promptly obtain the two variable color image false-proof films of photoetching diffraction of the present invention.
The two variable color image false-proof films of this photoetching diffraction, top view has red clearly green image, and after changing viewing angle, image can green by red stain, green change indigo plant.The heat-treatment optically variable films obtains product.
Ultimate principle of the present invention is such: photolithography thin film is after optical processing, the monomer of photoetching part is initiated and carries out polymerization, and photoetching does not partly have polymerization, after compound with the photosensitive film that writes down reflective grating, the monomer diffusive migration of photoetching part is not gone into the photopolymer coating of reflection holography thin film D1, grating space is increased, and the picture and text color is to long wavelength's direction transformation.Form red green pair of variable color diffraction image.
By above-mentioned disclosed technical scheme as seen, the two variable color image false-proof films of photoetching diffraction of the present invention, be by a kind of high-resolution high-molecular photosensitive material, through coherent light interference irradiation, form the high brightness reflexed light film, after adopting photolithography thin film to carry out the special light carving technology, with the reflective membrane of high brightness compound after, form contrast colors image with reflexed light film.This image can be realized background picture and text amphichroic effect simultaneously.This optically variable films can cover (or compound) with stock or document, does not have specific (special) requirements, does not also hide burelage, is product false proof, certificate safety, the ideal material that document is false proof and packing is decorated.
Description of drawings
Fig. 1 is a photoetching color-changing anti-counterfeit film C synoptic diagram.
Fig. 2 is a reflection holography photosensitive film D1 synoptic diagram.
Fig. 3 is the two variable color image false-proof film D synoptic diagram of photoetching diffraction.
Fig. 4 is a reflection holography thin film laser log synoptic diagram.
Embodiment
Referring to Fig. 1, said photoetching color-changing anti-counterfeit film C, comprise photoetching basement membrane (11), coated passes through the lithography layer (12) that exposure forms basement membrane (11) one sides by said photoetching material B, lithography layer thickness is 3～50 μ m, the lithography layer glazing is carved with image, and said basement membrane is selected from PVC, PET or the BOPP film of 20～100 μ m;
Referring to Fig. 2, said reflection holography photosensitive film D1 comprises basement membrane (1) and coated at the cushion (2) on basement membrane (1) one side, the photopolymer dope layer (3) of coated on cushion (2) opposite side, the interference fringe of photopolymer dope layer (3) has been gone up imprinting hologram image or two color-changing image-texts.
Referring to Fig. 3, the two variable color image false-proof film D of said photoetching diffraction, comprise photoetching color-changing anti-counterfeit film C and reflection holography photosensitive film D1, the lithography layer (12) of said photoetching color-changing anti-counterfeit film D is mutually compound with the photopolymer coating (3) of reflection holography photosensitive film D1.
The present invention is described by the following examples, but these embodiment are exemplary, the present invention does not limit to this.
The preparation of reflection holography thin film D1:
Under the red safety lamp of wavelength greater than 600nm, with film forming agent polyvinyl acetate (PVA) butyl acrylate acrylic acid terpolymer, 6 grams (67.3wt%), monomer N-vinyl carbazole 1.2 grams (13.5wt%), monomer tristane dimethanol diacrylate 1.0 grams (11.2wt%), light trigger 2,4,6-triphenyl imidazole radicals doublet 0.2 gram (2.2wt%), photosensitizer lignocaine-benzal cyclopentanone 0.05 gram (0.57%), chain-transferring agent 2-mercaptobenzothiazole 0.15 gram (1.68wt%), ultraviolet absorber 2-hydroxyl-4-methoxy benzophenone 0.05 gram (0.56wt%), non-ionic surfactant
FC-44300.06 restrains (0.67wt%), plastifier diethyl sebacate 0.2 gram (2.2wt%) is added to mixed solution (butanone: methylene chloride: methyl alcohol=5: 1: 1, weight ratio) in, the weight solid content is 10%, stirring at room records viscosity 10～12cp (25 ℃) to dissolving, filters, obtain photosensitive coating, stand-by;
The PET film of choosing the 50 μ m high grades of transparency is the reflection holography basement membrane, the preparation weight concentration is 40% vinylidene chloride styrene vinyl acetate co-polymer solution, coats the reflection holography basement membrane with the anilox roll of 120 lines, with 60 ℃ of oven dry, obtain cushion, the thickness of cushion is 1.5 μ m;
The gap of adjusting scraper and dispense tip is 200 μ m, above-mentioned photosensitive coating coated scribble cushion, thickness is on the PET film of 50 μ m, in 75 ℃ convective drying case, dry overlay film, coating thickness is 10 μ m, the existing release coating thickness of covering is 23 microns a PET film, obtains photosensitive polymer film;
The preparation of reflection holography thin film D1:
Adopt the recording method of " at axle " reflection holography; specifically referring to shown in Figure 5; said hologram light sensitive material is cut into the sheet material of 30*30mm; be pasted on catoptron (43) after throwing off surface protection film, Argon ion laser laser (514nm) light beam (300) is 60mw/cm by beam expanding lens (41) and aspheric surface collimation convex lens (42) formation parallel beam (301) light intensity that has pinhole filter
2Radiation is in photosensitive polymer film C, flat pattern light (301) arrives catoptron (43) from basement membrane incident through cushion and photosensitive coating layer, and the time shutter is at 0.1s, thereby record a hologram on the photosensitive polymer film C, on the ultra-violet curing machine film is carried out ultraviolet and visible light burn-out then, 120 ℃ were heated 2 minutes, promptly obtain reflection holography thin film D1, vision is visible as holographic mirror.This film is a kind of solid transparent membraneous material, has certain pliability.
Under the red safety lamp of wavelength greater than 600nm, blend with film forming agent polyvinyl butyral and cellulose acetate, 2.5 gram (30.5wt%), monomer N-vinyl carbazole 2.8 grams (34.1wt%), diacrylate 1.7 grams (20.7wt%) of the bisphenol-A of monomer ethoxylated, light trigger isobutyl benzoin ether 0.54 gram (6.6wt%), photosensitizer michaelis ketone 0.12 gram (1.46wt%), chain-transferring agent 2-mercaptobenzothiazole 0.23 gram (2.8wt%), ultraviolet absorber 2-hydroxyl-4-methoxy benzophenone 0.06 gram (0.73wt%), non-ionic surfactant methoxy poly (ethylene glycol) 0.06 gram (0.73wt%), plastifier diethyl sebacate 0.2 gram (2.4wt%) is added to mixed solution (butanone: methylene chloride: methyl alcohol=5: 1: 1, weight ratio) in, the weight solid content is 32.4%, and stirring at room is to dissolving, record viscosity 28.3cp (25 ℃), filter, obtain photosensitive coating, stand-by;
The PET film of choosing the 36 μ m high grades of transparency is a basement membrane, the preparation weight concentration is the copolymer solution of 30% vinyl acetate and acrylic acid butyl ester, coats basement membrane with the anilox roll of 100 lines, 60 ℃ oven for drying, obtain having the basement membrane of cushion, the thickness of cushion is 2 μ m.
The gap of adjusting scraper and dispense tip is 180 μ m, above-mentioned photosensitive coating A is coated scribble cushion, and thickness is on the PET film of 30 μ m, in 75 ℃ convective drying case, dry overlay film, coating thickness is 10 μ m, and cladding thickness is 16 microns a aluminum plated PET film, obtains photosensitive polymer film; Adopt the method identical, prepare reflection holography thin film D1 with embodiment 1.
The preparation of photoetching coating A:
The preparation of imprinting material not containing the yellow of ultraviolet light or redness safety etc. down, is calibrated the weighing utensil, takes by weighing multipolymer 6.97 grams (62.3%) of vinyl acetate and methyl methacrylate respectively; Diacrylate 2.0 grams (17.9%) of the bisphenol-A of ethoxylation, single acrylic acid phenol ethoxylate ester 1.8 grams (16.1%); 2,2-dimethyl-2-phenyl acetophenone 0.09 gram (0.82%); Separate two dibutyl phthalates, 0.26 gram (2.3%); 2-hydroxyl-4-methoxy benzophenone 0.013 gram (0.12%);
FC-44300.73 restrains (0.65%), at butanone, methylene chloride, alcohol mixed solvent (ratio is 5: 1: 1), and abundant stirring and dissolving, until no solid particle and blob of viscose, being assigned to solid content is 24.6%, filter, static froth breaking, stand-by.
The preparation of photolithography thin film:
On transfer coater; adjust the gap 200 μ m of scraper and dispense tip; the imprinting layer solution that the foregoing description 1 has been prepared; evenly coating thickness is the PET film of 23 μ m; coating thickness is 12 μ m, and the coating precision is controlled at ± 1 μ m, dries in 90 ℃ convective drying case; multiple diaphragm 201, rolling is stand-by.
The wavelength of adjusting Argon ion laser is 457.9nm, forms directional light (400), from 201 irradiations of diaphragm.See Fig. 1; Among the figure, tip is depicted as laser and injects direction.
The preparation of two variable color photoetching diffraction films:
With above-mentioned product, throw off diaphragm 201, compound with the reflection holography thin film D1 of embodiment 1, enter 120 ℃ drying tunnel, heated 10 minutes, to send into the high-pressure mercury mercury lamp and carry out the ultra-violet curing photographic fixing, photographic fixing institute energy requirement is 100mj/cm
2, can observe red green picture and text this moment, and after changing viewing angle, picture and text are blue from green, the green change of red stain again simultaneously.Its reflection wavelength is respectively λ
1≈ 600nm; λ
2≈ 535nm; λ
3≈ 470nm.Reflection efficiency is 85%.
Embodiment 4
The preparation of photoetching coating A:
The preparation of imprinting material not containing the yellow of ultraviolet light or redness safety etc. down, is calibrated the weighing utensil, takes by weighing multipolymer 2.95 grams (31wt%) of vinyl acetate and butyl acrylate respectively; Diacrylate 3.3 grams (34.7%) of the bisphenol-A of ethoxylation, tristane dimethanol diacrylate 2.95 grams (31%); 2,2-dimethyl-2-phenyl acetophenone 0.171 gram (1.8%); Dibutyl phthalate 0.49 gram (0.52%); 2-(2H-benzotriazole-2)-4,6-two (1-methyl isophthalic acid-phenethyl) phenol 0.5 gram (0.53%);
FC-44300.03 restrains (0.32%), at butanone, methylene chloride, alcohol mixed solvent (ratio is 5: 1: 1), and abundant stirring and dissolving, until no solid particle and blob of viscose, being assigned to solid content is 34.8%, filter, static froth breaking, stand-by.
The preparation of photolithography thin film:
On transfer coater, adjust the gap 160 μ m of scraper and dispense tip, the imprinting layer solution that the foregoing description 1 has been prepared, evenly coating thickness is the PET film of 23 μ m, and the coating precision is controlled at ± 1 μ m, dries in 90 ℃ convective drying case, multiple picture and text mask 201, rolling is stand-by.
Coating thickness is 12 μ m.The wavelength of adjusting Argon ion laser is 457.9nm, forms directional light (300), from 201 irradiations of picture and text mask.See Fig. 1;
The preparation of two variable color photoetching diffraction films:
Above-mentioned product is thrown off picture and text mask 201, compound with the reflection holography thin film D1 of embodiment 2, enter 120 ℃ drying tunnel, heated 2～10 minutes, to send into the high-pressure mercury mercury lamp and carry out the ultra-violet curing photographic fixing, photographic fixing institute energy requirement is 100mj/cm
2, can observe red green picture and text this moment, and after changing viewing angle, picture and text are blue from green, the green change of red stain again simultaneously.Its reflection wavelength is respectively λ
1≈ 600nm; λ
2≈ 523nm; λ
3≈ 457nm.Reflection efficiency is 82%.
Claims (2)
1. prepare the method for photoetching diffraction colour image false-proof film D, comprise the steps:
(1) under yellow or red safety lamp, in proportion with cementing agent, monomer, initiating agent, plastifier, ultraviolet absorber and surfactant dissolves in solvent, obtain photoetching coating A;
Described photoetching coating A comprises solvent and the photoetching material B that is dissolved in the solvent, and the weight solid content of said photoetching coating A is 5%-60%;
Component and the weight percent content of said photoetching material B comprise:
Cementing agent 20～80%;
Monomer 15～75%;
Initiating agent 0.1～3%;
Plastifier 0.01～3%;
Ultraviolet absorber 0.05～1%;
Surfactant 0.15～1%;
Said cementing agent is selected from the multipolymer or the polyvinyl butyral of multipolymer, vinyl acetate and the butyl acrylate of vinyl acetate and methyl methacrylate;
Said monomer is two or more in the diacrylate of the bisphenol-A of ethoxylation, single acrylic acid phenol ethoxylate ester or the tristane dimethanol diacrylate, and the weight ratio between two kinds of monomers is 0.5～1.2;
Said initiating agent is selected from isobutyl benzoin ether, 1-hydroxy cyclohexyl phenylketone or 2,2-dimethyl-2-phenyl acetophenone;
Said plastifier is selected from dibutyl phthalate or separates two dibutyl phthalates;
Said ultraviolet absorber is selected from 2-hydroxyl-4-methoxy benzophenone or 2-(2H-benzotriazole-2)-4,6-two (1-methyl isophthalic acid-phenethyl) phenol;
Said surfactant is a non-ionic surfactant, is selected from the fluoro aliphatic polymer fat surfactant that polyglycol, methoxy poly (ethylene glycol) or 3M company produce
FC-4430;
Said solvent is butanone, methylene chloride, alcohol mixed solvent, and part by weight is 5: 0.5～1.5: 0.5～1.5.
(2) the photoetching coating A with step (1) is coated on the basement membrane, and the control coating build is 5～30 μ m, at 50～100 ℃ of dryings, covered with protective film;
(3) adopt the 457.9nm wave band of Argon ion laser or the light of helium cadmium laser 441nm wave band, carry out the exposure photo-etching processing from the product of diaphragm one pace rapid (2), write down required picture and text, throw off diaphragm then, lithography layer is mutually compound with the photopolymer coating of reflection holography photosensitive film D1;
Said reflection holography photosensitive film D1 comprises reflection holography basement membrane and the coated cushion on reflection holography basement membrane one side, the photopolymer coating that the photopolymer coating B1 of coated on the cushion opposite side forms, and the interference fringe of hologram image or two color-changing image-texts is recorded in the photopolymer coating;
Said photopolymer B1 coating comprises following components in weight percentage:
Film forming agent 20%～80%
Monomer 10%～70%
Light trigger 0.5%～7%
Chain-transferring agent 0.3%～5%
Photosensitizer 0.05%～2%;
Said film forming agent is selected from blend, vinyl acetate butyl acrylate acrylic ternary copolymer or the polystyrene vinyl cyanide of multipolymer, polyvinyl butyral and the cellulose acetate of polymethylmethacrylate, poly-cellulose acetate butyl ester, cellulose acetate butyl ester and ethyl vinyl ether, or the composite material of above-mentioned polymkeric substance and fluoropolymer;
Said monomer is selected from two or more in diacrylate, 9-(4 phenyl, 2 acryloyl ethoxys) two fluorenes or the tristane dimethanol diacrylate of the bisphenol-A of simple function group esters of acrylic acid, N-vinylcarbazole class, ethoxylation, and the weight ratio between two kinds of monomers is 0.5～1.8;
Light trigger is selected from 2,4,6-triphenyl imidazole radicals doublet;
Photosensitizer be selected from the red B of algae,, lignocaine-benzal cyclopentanone, michaelis ketone or 1,3,3-trimethyl-2-[5-(1,3,3-trimethyl-2-indoles fork)-1,3-pentadiene] the indoles salt compounded of iodine;
Chain-transferring agent is selected from 2-mercaptobenzoxazole, lauryl mercaptan, mercaptobenzothiazoler;
(4) with the product of step (3) 80～160 ℃ of thermal treatments 1～20 minute, placing light intensity then is 100mj/cm
2The high-pressure mercury mercury lamp under be cured, promptly obtain photoetching diffraction colour image false-proof film.
2. method according to claim 1 is characterized in that, diaphragm is a kind of mask with image.
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| Application Number | Priority Date | Filing Date | Title |
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| CN200710039679A CN101059654B (en) | 2007-04-19 | 2007-04-19 | Photolithagraphic diffractive image false-proof film and its preparation method |
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| CN200710039679A CN101059654B (en) | 2007-04-19 | 2007-04-19 | Photolithagraphic diffractive image false-proof film and its preparation method |
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| CN101417564B (en) * | 2008-10-23 | 2011-02-02 | 上海复旦天臣新技术有限公司 | Anti-counterfeiting film with double color-changing pattern and preparation method thereof |
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| WO2011064794A2 (en) * | 2009-11-24 | 2011-06-03 | Bilcare Limited | An anti-counterfeit printed packaging material |
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| MX2017011436A (en) * | 2015-03-06 | 2018-11-09 | Ccl Secure Pty Ltd | Diffractive device producing angle dependent effects. |
| CN107424246B (en) * | 2017-04-11 | 2021-04-20 | 京东方科技集团股份有限公司 | Visible light communication password unlocking device and method |
| CN107341535B (en) * | 2017-06-08 | 2020-11-03 | 太仓市智威智能科技有限公司 | Scratch-resistant holographic memory card |
| CN110795962B (en) * | 2018-08-01 | 2023-08-15 | 上海箩箕技术有限公司 | Optical fingerprint sensor module and forming method thereof |
| CN112505939A (en) * | 2019-08-26 | 2021-03-16 | 昇印光电（昆山）股份有限公司 | Imaging optical film and decorative film |
| JP2022008010A (en) * | 2020-03-30 | 2022-01-13 | 関西ペイント株式会社 | Multiple-layered coating film forming method |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1050620A (en) * | 1989-06-22 | 1991-04-10 | 纳幕尔杜邦公司 | In photopolymer, form the holographic optical elements (HOE) of reflection hologram |
| JP2001056631A (en) * | 1999-08-20 | 2001-02-27 | Agency Of Ind Science & Technol | Composition for hologram recording material, hologram recording medium and its production |
| 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 |
| CN1416013A (en) * | 2002-10-16 | 2003-05-07 | 上海朗创光电科技发展有限公司 | Method for preparing hologram light sensitive material of high polymer |
| US20040033423A1 (en) * | 1999-10-12 | 2004-02-19 | Ryszard Burzynski | Holographic recording material |
| CN1586917A (en) * | 2004-09-23 | 2005-03-02 | 上海复旦天臣新技术有限公司 | Composite film with reflecting holographic and angular color change information double property |
| US20050277747A1 (en) * | 2004-06-15 | 2005-12-15 | Mclaughlin Michael J | Holographic storage medium |
-
2007
- 2007-04-19 CN CN200710039679A patent/CN101059654B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1050620A (en) * | 1989-06-22 | 1991-04-10 | 纳幕尔杜邦公司 | In photopolymer, form the holographic optical elements (HOE) of reflection hologram |
| JP2001056631A (en) * | 1999-08-20 | 2001-02-27 | Agency Of Ind Science & Technol | Composition for hologram recording material, hologram recording medium and its production |
| US20040033423A1 (en) * | 1999-10-12 | 2004-02-19 | Ryszard Burzynski | Holographic recording material |
| 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 |
| CN1416013A (en) * | 2002-10-16 | 2003-05-07 | 上海朗创光电科技发展有限公司 | Method for preparing hologram light sensitive material of high polymer |
| US20050277747A1 (en) * | 2004-06-15 | 2005-12-15 | Mclaughlin Michael J | Holographic storage medium |
| CN1586917A (en) * | 2004-09-23 | 2005-03-02 | 上海复旦天臣新技术有限公司 | Composite film with reflecting holographic and angular color change information double property |
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