Movatterモバイル変換


[0]ホーム

URL:


CN101059654B - Photolithagraphic diffractive image false-proof film and its preparation method - Google Patents

Photolithagraphic diffractive image false-proof film and its preparation method
Download PDF

Info

Publication number
CN101059654B
CN101059654BCN200710039679ACN200710039679ACN101059654BCN 101059654 BCN101059654 BCN 101059654BCN 200710039679 ACN200710039679 ACN 200710039679ACN 200710039679 ACN200710039679 ACN 200710039679ACN 101059654 BCN101059654 BCN 101059654B
Authority
CN
China
Prior art keywords
film
coating
photoetching
photo
false
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN200710039679A
Other languages
Chinese (zh)
Other versions
CN101059654A (en
Inventor
徐良衡
沈杨
高芸
游仁顺
肖海明
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shanghai Tianchen micro nano technology Co., Ltd
Original Assignee
Tianchen New Technology Co Ltd Fudan Univ Shanghai
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Tianchen New Technology Co Ltd Fudan Univ ShanghaifiledCriticalTianchen New Technology Co Ltd Fudan Univ Shanghai
Priority to CN200710039679ApriorityCriticalpatent/CN101059654B/en
Publication of CN101059654ApublicationCriticalpatent/CN101059654A/en
Application grantedgrantedCritical
Publication of CN101059654BpublicationCriticalpatent/CN101059654B/en
Activelegal-statusCriticalCurrent
Anticipated expirationlegal-statusCritical

Links

Images

Landscapes

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

A kind of photoetching diffraction image false-proof film and preparation method thereof
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
Figure G2007100396795D00021
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
Figure G2007100396795D00041
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/cm2, 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 ℃ ofthermal treatments 1~20 minute, placing light intensity then is 100mj/cm2The 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.
Embodiment 1
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
Figure G2007100396795D00071
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 filter2Radiation 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.
Embodiment 2
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 withembodiment 1.
Embodiment 3
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%);
Figure G2007100396795D00081
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 foregoingdescription 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 offdiaphragm 201, compound with the reflection holography thin film D1 ofembodiment 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/cm2, 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 λ1≈ 600nm; λ2≈ 535nm; λ3≈ 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%);
Figure G2007100396795D00091
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 foregoingdescription 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 andtext 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 andtext mask 201, compound with the reflection holography thin film D1 ofembodiment 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/cm2, 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 λ1≈ 600nm; λ2≈ 523nm; λ3≈ 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
Figure F2007100396795C00011
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/cm2The 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.
CN200710039679A2007-04-192007-04-19Photolithagraphic diffractive image false-proof film and its preparation methodActiveCN101059654B (en)

Priority Applications (1)

Application NumberPriority DateFiling DateTitle
CN200710039679ACN101059654B (en)2007-04-192007-04-19Photolithagraphic diffractive image false-proof film and its preparation method

Applications Claiming Priority (1)

Application NumberPriority DateFiling DateTitle
CN200710039679ACN101059654B (en)2007-04-192007-04-19Photolithagraphic diffractive image false-proof film and its preparation method

Publications (2)

Publication NumberPublication Date
CN101059654A CN101059654A (en)2007-10-24
CN101059654Btrue CN101059654B (en)2010-05-19

Family

ID=38865828

Family Applications (1)

Application NumberTitlePriority DateFiling Date
CN200710039679AActiveCN101059654B (en)2007-04-192007-04-19Photolithagraphic diffractive image false-proof film and its preparation method

Country Status (1)

CountryLink
CN (1)CN101059654B (en)

Families Citing this family (12)

* Cited by examiner, † Cited by third party
Publication numberPriority datePublication dateAssigneeTitle
CN101417564B (en)*2008-10-232011-02-02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
CN101706593B (en)*2009-11-092011-08-10中钞特种防伪科技有限公司Method for enhancing optical effect of holographic optical element
WO2011064794A2 (en)*2009-11-242011-06-03Bilcare LimitedAn anti-counterfeit printed packaging material
CN102335619B (en)*2011-07-082013-01-09华东理工大学Solvent thermal method for preparing silver halide photocatalytic materials
CN102676005B (en)*2012-05-252014-03-26江苏金恒新型包装材料有限公司Novel BOPP laser transfer film back coating
US20180043724A1 (en)*2015-03-062018-02-15Ccl Secure Pty LtdDiffractive device producing angle dependent effects
CN107424246B (en)*2017-04-112021-04-20京东方科技集团股份有限公司 Visible light communication password unlocking device and method
CN107341535B (en)*2017-06-082020-11-03太仓市智威智能科技有限公司Scratch-resistant holographic memory card
CN110795962B (en)*2018-08-012023-08-15上海箩箕技术有限公司Optical fingerprint sensor module and forming method thereof
CN112505939A (en)*2019-08-262021-03-16昇印光电(昆山)股份有限公司Imaging optical film and decorative film
JP7600004B2 (en)*2020-03-302024-12-16関西ペイント株式会社 Multi-layer coating method
CN116198160A (en)*2022-12-282023-06-02深圳歌德新创科技有限公司 Woven camouflage net and preparation method thereof

Citations (7)

* Cited by examiner, † Cited by third party
Publication numberPriority datePublication dateAssigneeTitle
CN1050620A (en)*1989-06-221991-04-10纳幕尔杜邦公司In photopolymer, form the holographic optical elements (HOE) of reflection hologram
JP2001056631A (en)*1999-08-202001-02-27Agency Of Ind Science & TechnolComposition for hologram recording material, hologram recording medium and its production
CN1408801A (en)*2002-09-132003-04-09上海复旦天臣感光材料有限公司Angular photochromic material and its preparing method
CN1416013A (en)*2002-10-162003-05-07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)*1999-10-122004-02-19Ryszard BurzynskiHolographic recording material
CN1586917A (en)*2004-09-232005-03-02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)*2004-06-152005-12-15Mclaughlin Michael JHolographic storage medium

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication numberPriority datePublication dateAssigneeTitle
CN1050620A (en)*1989-06-221991-04-10纳幕尔杜邦公司In photopolymer, form the holographic optical elements (HOE) of reflection hologram
JP2001056631A (en)*1999-08-202001-02-27Agency Of Ind Science & TechnolComposition for hologram recording material, hologram recording medium and its production
US20040033423A1 (en)*1999-10-122004-02-19Ryszard BurzynskiHolographic recording material
CN1408801A (en)*2002-09-132003-04-09上海复旦天臣感光材料有限公司Angular photochromic material and its preparing method
CN1416013A (en)*2002-10-162003-05-07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)*2004-06-152005-12-15Mclaughlin Michael JHolographic storage medium
CN1586917A (en)*2004-09-232005-03-02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

Also Published As

Publication numberPublication date
CN101059654A (en)2007-10-24

Similar Documents

PublicationPublication DateTitle
CN101059654B (en)Photolithagraphic diffractive image false-proof film and its preparation method
CN101034257B (en)Photosensitive film used for holographic recording and manufacturing method
CN101320208B (en)Reflection holography thin film and preparation method thereof
CN101324752A (en)Method for preparing polymer LCD photosensitive material capable of recording reflection holography
US6723479B2 (en)Method for providing a surface of an article with a decoration or text
JP2849021B2 (en) Photosensitive composition for volume hologram recording
KR102171416B1 (en)Method of manufacturing a sheet
WO2007029943A1 (en)Method for preparing photochromic film or plate
BRPI1100786A2 (en) Photopolymer for volume hologram engraving and process to produce it
AU2007203817A1 (en)Bragg diffracting security markers
CN103119522A (en)Volume hologram transfer foil
CN101988974A (en)Method of producing patterned birefringent product and birefringent pattern building material
JP4365494B2 (en) Photosensitive composition for volume hologram recording and hologram obtained therefrom
CN104059402A (en)Photopolymerizaiton-typed photosensitive high-molecular material, preparation method and application thereof
CN117666282B (en) Photopolymer and film thereof, film preparation method, and printing substrate
CN1737881B (en)False-proof thin film and its preparing method
KR101504089B1 (en)Transparent hologram film and method of manufacturing the same
CN113527929B (en)Photopolymer composition and optical grating
CN113534607B (en)Photopolymer composition, diffraction grating and preparation method thereof
CN100487498C (en)A variable optical thin film material and its preparing method
JP2007034334A (en)Photosensitive composition for volume hologram recording, and recording medium and method for forming volume hologram using the same
CN2574152Y (en)Antiforging polymer material film structure
CN113527930B (en)Photopolymer composition, grating and preparation method thereof
CN1186692C (en)Method for preparing hologram light sensitive material of high polymer
Toxqui-López et al.PVA glue as a recording holographic medium

Legal Events

DateCodeTitleDescription
C06Publication
PB01Publication
C10Entry into substantive examination
SE01Entry into force of request for substantive examination
C14Grant of patent or utility model
GR01Patent grant
C56Change in the name or address of the patentee

Owner name:SHANGHAI TECHSUN ANTI-COUNTERFEITING TECHNOLOGY CO

Free format text:FORMER NAME: TIANCHEN NEW TECHNOLOGY CO LTD, FUDAN UNIV, SHANGHAI

CP01Change in the name or title of a patent holder

Address after:5, building 1, building 127, Lane 200433, Cathay Road, Yangpu District, Shanghai

Patentee after:Shanghai Tiancheng Anticounterfeit Technology Co.,Ltd.

Address before:5, building 1, building 127, Lane 200433, Cathay Road, Yangpu District, Shanghai

Patentee before:Tianchen New Technology Co., Ltd., Fudan Univ, Shanghai

CP03Change of name, title or address

Address after:Room 201, building 3, No. 518, shenzhuan Road, Songjiang District, Shanghai

Patentee after:Shanghai Tianchen micro nano technology Co., Ltd

Address before:5, building 1, building 127, Lane 200433, Cathay Road, Yangpu District, Shanghai

Patentee before:Shanghai Techsun Anti-Counterfeiting Technology Holding Co.,Ltd.

CP03Change of name, title or address

[8]ページ先頭

©2009-2025 Movatter.jp