CN1032827A - Write or anti-medium and the correlation technique that duplicates of printing type face - Google Patents
Write or anti-medium and the correlation technique that duplicates of printing type face Download PDFInfo
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- CN1032827A CN1032827A CN88109081A CN88109081A CN1032827A CN 1032827 A CN1032827 A CN 1032827A CN 88109081 A CN88109081 A CN 88109081A CN 88109081 A CN88109081 A CN 88109081A CN 1032827 A CN1032827 A CN 1032827A
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
- G03C5/08—Photoprinting; Processes and means for preventing photoprinting
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G21/00—Arrangements not provided for by groups G03G13/00 - G03G19/00, e.g. cleaning, elimination of residual charge
- G03G21/04—Preventing copies being made of an original
- G03G21/043—Preventing copies being made of an original by using an original which is not reproducible or only reproducible with a different appearence, e.g. originals with a photochromic layer or a colour background
Abstract
A kind ofly be used to write or the anti-medium that duplicates of printing type face, it makes, and any copy is different with original document maybe can not be read.This medium comprises a chromic systems, and it is made up of at least a photochromic material and a kind of photosensitizer, is being used for disturbing the contrast between writing on background document and the file during the copying operation.By the method that have nothing in common with each other relevant, introduce this chromic systems with medium.
Description
The present invention relates to protect formal file (secret, that maintain secrecy ...); document of title; transferable or the file of other form, all or part of valuable publication (books, magazine, report ...); or any other file is anti-duplicates, and these duplicating comprise to be used as duplicity duplicating that static or xerox carry out.
Because people have known that to use static or xerox very convenient, and the cost that duplicates is also very low, therefore generally take place with the phenomenon of indiscriminate ground xcopy without permission and be on the rise.This author to file is predictable, for example, makes secret file open or author's legitimate rights and interests are invaded." original document " speech of Shi Yonging refers to any file that can be replicated herein.Such original document by macromolecule medium and the information put down in writing above (literal, figure ...) form, the information of record is applied on the medium by existing any printing technology or in the medium.
Many French Patent (FRP)s and other national patent disclosure some make these unnecessary methods of duplicating minimizing, for example, proposed to use special dark colour paper (Canadian Patent CA-A-118 for original document, 791,4 and U.S. Pat-A-388,774,2), this paper can obtain from market.But the information and the contrast between background color that adopt this method to make to put down in writing on this paper are very little, thereby make original document be difficult to read, and see that eyes are produced is very important or even insupportable tired.
Many other patented methods that do not form at present suitability for industrialized production can also be proposed, incomplete enumerating: reflective original document (paper of handling with metal), luminous original document, special mark, photochromic file ...The invention particularly relates to the photochromic file made from photochromic material.
As everyone knows, photochromic material (or be abbreviated as " Photochromes ") has such character: (wavelength is generally under 200～800nm) the effect, gives medium with reversible variable color in visible light or ultraviolet electromagnetic radiation.
Reversible photochromic action can be summarized as: under the effect of reactive electro magnetic radiation, color, is not having under the situation of described radiation to the B attitude from the A attitude, gets back to the change procedure of A attitude again from the B attitude.The A attitude has very different in nature characteristics with the B attitude, for example: the A attitude may be colourless and also absorb comprise photochromic action the ultraviolet ray of specific active wavelength, when being subjected to ultraviolet source and exciting, variation from the A attitude to the B attitude just takes place, and the B attitude may be coloured and therefore absorb visible light.By using this material, might under normal illumination, make information and the background put down in writing on the original document that enough contrasts visually be arranged, but penetrate down in suitable illumination, background wherein just obtains fairly obvious colour developing effect.Can be with reference to following patent specification: GB-A-122,720,1, US-A-359,708,2 and DE-A-241,927,8, these patents relate to the use of duplicator, and these duplicators are equipped with special lamp, and these lamps are suitable for ultraviolet ray excited and absorb this ultraviolet photochromic material.
Japan Patent JP605, in 398,1 and 607,999,2 itemizing some embodiment, wherein specify and use spiropyran compounds.With the duplicator of routine this compound molecule being worked, to obtain significant effect be impossible, even can not accomplish this point when using the compound of high concentration.The factor of restriction is: the energy that duplicator provided should be in the sensitive wave length scope of above-claimed cpd molecule absorption, promptly less than 350nm.
But, support be copied file glass itself with regard to filtering less than whole radiation of 320nm, and available energy between 320～350nm is very low, this type with the duplicator that uses has nothing to do.
The objective of the invention is to propose a kind of new method, this method is by using a chromic systems, and any copy can not be read or different with original document, and the radiation that this individual system is emitted the lamp in the conventional duplicator is responsive.
According to the present invention, get in touch by in chromic systems, making at least a photosensitizer and at least a photochromic material, realize above-mentioned purpose.The energy that absorbs when file is copied mainly is visible light and black light.The effect of photosensitizer is the radiation that absorbs visible light and black light, and removes the laser photochromic material by the transmission of energy, thereby it is coloured that it is become.
" chromic systems " speech of Shi Yonging is meant herein: one or more photochromic materials, or the combination of one or more photochromic materials and one or more photosensitizers, they can be at random mix with pigment as colouring agent.
From context of the present invention as can be seen: some photochromic materials may with the medium of file (film, paper ...) interact.For example, (inhaling the boundless and indistinct of the boundless and indistinct pocket of million cooked foods high post cooked food fears and carries ouch rank cadmium arsine Song a small handdrum with beads striking when rotated marine crab and fall milk and press and smooth the pupa white silk and imitate the surplus of M ü gown mystery shelf tomb Buddhist nunnery halogen fluid gold-plating and prolong and closely question the proud smile of rose and let out ひ and mourn to incite and gnaw edge nurse green pepper ㄊ emigrant aster table and hack badger and imitate from κ structure Buddhist nunnery halogen fluid spouse's the tired of the lie Dao boundless and indistinct of the cooked food ┗ rice weevil croak hasty and careless rifle Buddhist nunnery halogen fluid that owes that walks lamely that falls from the sky or outer space that prolongs in effect by chemical bond or solvation or physicochemical interaction
According to the present invention, chromic systems is incorporated in the medium by a kind of individual method." introduce " being meant,, photochromic material is attached in the medium with a kind of like this method in order to prevent above-mentioned interaction by a kind of individual method.
Medium may be that stationery maybe may be to be made of a kind of polymer film.Particularly, the present invention expands to and covers on medium to a paper (or other material) base that one deck is made of transparent or semitransparent film, and the information of putting down in writing on the paper substrate is that significantly for this medium is applied on the paper substrate, the one side of this medium is glued.
As mentioned above, prevent with duplicating of carrying out of toner cartridge type duplicator normally feasible by the paper that uses special color.For a long time, this method is development to some extent, and its basic principle is summarized as follows.
Use the duplicator of common paper to have:
At first, has illuminating system (bulb, a flash tube,), the meaningful clear and definite spectral power distribution of this system, secondly, have a light sensor system of accepting original image, this system has the sensitiveness that the function with said system lamp radiation spectrum wavelength changes.
The optical sensor of toner cartridge type duplicator changes with different types of machine: selenium, zinc oxide, cadmium sulfide, or organic matter (PVK).
The quality of copy depends on the contrast between the information of the background of file and file record.The contrast that eyes are seen is different with the contrast that the duplicator optical system is found out.For the combination of any given background (coloured or other) and prospect, the quality of copy depends on the special sensitiveness of photo-conduction cell of the radiation spectrum and the duplicator (monochrome) of duplicator illuminating lamp.
Light radiation shines on the opaque medium and may be absorbed or return, and term " radiation of returning " comprises two kinds of scattering and radiation reflected.Any ray that turns back to the duplicator photo-conduction cell disturbs the charge density on this element partly, therefore forms white on copy.When medium be coloured and also above writing when being black, the quality of duplicating will depend on that the color of medium and photo-conduction cell are to the sensitiveness from the actual wavelength that returns of original document.
The effect that the duplicator of some type duplicates blue look background is better, and has any problem for the duplicating of red and yellow background, and some duplicator is then better to the yellow background photocopying effect in addition, and has any problem for the duplicating of blue look background.
When carrying out single-color copying with black, can find out immediately: according to the duplicator that uses, yellow and blue look does not leave vestige on copy, have only redness passable.Yet, in the color photocopying of carrying out according to three looks (or four looks) principle, had been noted that these phenomenons, and carried out technical compensation.
Below demonstration is based on that single-color copying (for example using black) carries out, and will describe some extra details in detail for color photocopying in case of necessity.
It mainly is that red Colored Paper can not duplicate file that CA1187914 and US3887742 patent have been used.Photo-conduction cell is insensitive to the wavelength that returns from coloured media, concerning duplicator, medium and above writing between do not have contrast, copy is a black as a result.
If a chromic systems is added on the paper, and change its color under by the illuminating effect that illuminating lamp provided of duplicator, when duplicating, just can change the contrast of original document so.In this case, chromic systems has changed the radiation of returning from medium in the duplicating process.As mentioned above, the radiation of returning comprises two kinds of scattering and reflected radiations.When duplicating, in fact the discoloration of medium will not have contrast to duplicator.
By coloured background is combined with chromic systems, can obtain a stronger effect.Yet,, so, photochromic material is added to the basic medium that can use a kind of light color on the paper, or even uses blank sheet of paper to become possibility if the color developing effect of chromic systems is enough to eliminate during the duplicating medium and the contrast between the writing above it.
Therefore propose to use a kind of medium for original document, this medium can be arbitrarily painted with the mixture of blue look, yellow and redness (even a small amount of black), but adopt this method, the visual contrast between coloured background and printing writing is fairly good, so that this document can normal reading.
Obtain strong or weak colour developing effect and depend on the relative scale of various basic colouring agents, this ratio depends on the character of the coloring material of use again.As mentioned above, it also is possible not using any colouring agent.
In theory, the present invention can use any photochromic material, and no matter its whether be the solid larva of a tapeworm or the cercaria of a schistosome send the by force inferior ü of brown little J fall an ancient spear the onion bones of the body of rotten Zan onion scalds character used in proper names and in rendering some foreign names onion Chinese ostrich standing grain character used in proper names and in rendering some foreign names onion milli street frame R Ge plays proud Feng of the outstanding Yun of to hold in the mouth vinegar black mole emigrant onion bones of the body that feed when a unit of weight used in ancient China, equal to six liang spouse supports tool Na Wei Laos gold-plating
It is as follows to enumerate some possible photochromic materials by halves:
Silver salt, metal oxide, inorganic complex, unorganic glass, nitron class, poly-methane cationic colorant, tetrachloro ketone dihydronaphthalene, sydnones, indigo blue derivative colouring agent, spiral shell dihydro indolizine, indenone oxide, fulgide, dianthracene ketone, azobenzene, triphenyl methane derivative, metal dithizone derivative, spiro-pyrans, Luo oxazine ...
When being subjected to the radiation that duplicator sends, these photochromic materials can show good photochromic ability (Photocolorability).In general, this radiation wavelength is greater than 360nm.
Skilful many photochromic materials seldom meet this wavelength, so photochromic function is very poor.By using photosensitizer to make them have the good photochromic ability is possible, and these photosensitizers are responsive De ， And in greater than the 360nm wave-length coverage and are used for the energy that they absorb is passed to photochromic material, make their activation (painted) thus.How the law of photochemistry makes photosensitizer adapt to the photochromic material that will be activated if having been illustrated.
Can use any known photosensitizer, yet for organic matter, can use the derivative of following material: benzene, acetone, xanthene ketone, acetophenone, benzophenone, 1,2,3,4-dibenzo naphthalene, anthraquinone, Mischler Cetone, naphthalene,
, diacetyl, benzil, pyrene, En, perylene, metal complex ...They must combine with photochromic material fully under suitable defined terms, and Here it is, and finger should use a kind of special process as detailed below, especially by grafting with photosensitizer and photochromic material combination.
Can use photochromic material like this.If they are solids, can be dispersed in them in the macromolecule medium of original document, regrettably,, usually need to use a kind of assist medium particularly for some responsive photochromic materials.Have a problem to be, photochromic material or photosensitizer may react with the macromolecule medium of original document.
Therefore, usually be necessary to join in the medium or avoid on the medium interacting by additive with photochromic material and it, this medium has nothing in common with each other for the residue of the macromolecule medium of file, and this individual phenomenon can be carried out in the following way:
By the mode of polymer or painting layer, by the plasticity particulate, by microcapsules or insoluble small medium.Therefore the present invention proposes a kind of medium that prevents hard-copy file, and this medium can be by optionally painted, and has the chromic systems of an energy-sensitive that the lamp of duplicator is sent.This system has nothing in common with each other with respect to the medium of file, in order that: obtain the optimum efficiency between photosensitizer and photochromic material, and avoid producing any interaction or reaction with file medium.
The present invention also provides a kind of individual's file medium (check, opera ticket ...), under the effect of light radiation, can check this medium according to change in color.
Present each those method that have nothing in common with each other of detailed consideration:
1) coating of polymer, paint, coating or printing ink or film.
Photochromic material and photosensitizer are dissolved in the polymer of plasticising with the additive that plays stabilization, and the product that obtains can be coated:
A) on macromolecular medium, perhaps with the form of film or use the solution that in common volatile or polymerisable solvent, forms.This coating can be coated on the whole surface, also can only be coated on the part surface, for example with the form of pattern.
B) be blended in the medium.
Can use any polymer, especially film forming polymer: polystyrene, polyester, polyurethane, Merlon, polyvinyl polymer, acrylate copolymer ...
2) photochromic particulate.
The plasticity particulate that comprises photochromic material, photosensitizer, additive, polymer and plasticizer is formed.Use the conventional method of making polymer particles, can obtain this product:
A) above-mentioned substance mixes before monomer polymerization.
B) use a kind of volatile media solvent, above-mentioned composition is diffused in the particulate of the system of giving, this solvent is a kind of good solvent for photochromic material and other additive, and it is a kind of sweller for polymer.When preparation finished, this solvent was fallen by natural evaporation.Then, these particulates can be joined in the macromolecular material that constitutes the basic medium of original document.
Can be by engraving ⒘ with road green pepper ㄖ ticket abdomen Buddhist nunnery halogen fluid Feng rank!= ⒘＜outstanding Yun craftsman suck Lu capsule wine Cannibals purchase a flat iron plate for making cakes fragrance love tomb Buddhist nunnery halogen fluid onion brown school dream ⒘ J and be willing to merchant Kuo pound standing grain ∥ mace man ask the slow earwig of suburb outstanding Yun mould is willing to not have the bright of ancient type of banner hoisted on a featherdecked mast rank technetium humorous pool alkynes male move back farce ripples treasure=ripples ancient piece of jade, round, flat and with a hole in its centre pool group take off run quickly [catfish imperial mandate Feng hold in the mouth Qiang move back the even glycosides of Jia agnail J gown dizzy ⒕ cutter in the Meng steal certain pool slowly bits suck cherry ⒘ H glycosides and steal to make a noise and originally fear badly this pocket of the proud of bamboo quiet raised paths between fields instep .5～2 times.In case think that swelling has reached gratifying degree, just at this mixture of stirring at room, with its filtration and remove the solvent of swelling, another method is with hot-air this mixture to be sprayed to enter in the vertical pipe, reclaims photochromic particulate with a cyclone separator then.Also can use any other drying means.After removing sweller, photochromic particulate can contain plasticizer.The photochromic particulate that will prepare in this way subsequently joins for example a kind of liquid and covers with paint, lacquer, colour wash, etc. in the solution.
3) photochromic micro-encapsulation.
The preparation of microcapsules is known, therefore can adopt the preparation method of any maturation.Usually, photochromic material, photosensitizer, additive, polymer and plasticizer are dissolved in a kind of high boiling usual vehicle.Under the situation that at random is added with wetting agent, to be dispersed in the solution that said method makes in second kind of solvent (as water) that can not mix with it by strong agitation, form a kind of emulsion or microemulsion thus, add chemical reagent subsequently, around constituting the emulsion droplet, form undissolved macromolecule top layer by interfacial reaction.Microcapsules and second kind of separated from solvent that will in this way obtain by physical method, and at random carry out drying.Can join these microcapsules in the stock of original document medium or above it then.The advantage of these microcapsules at first is: in this case, individual composite photochromic system comprises a kind of solvent, and it plays activation in photochromic mechanism; Next is: can control the parameter that influences photochromic effect preferably, for example use the concentration of material.
The preparation of microcapsules needs a kind of solvent, it has higher boiling, low-steam pressure, near the density of a unit, to ultraviolet ray and visible light (the low absorbability of maximum λ＜320nm), it is a kind of good solvent for photochromic material, photosensitizer, additive and polymers thing, and it not with polar solvent for example water, alcohol ... mix.Some examples of indefiniteness comprise: the aromatic derivative that can at random be hydrogenated (as hydrogenated terphenyl,
Flower hydrocarbon, 1,2,3,4-tetrahydronaphthalene, decahydronaphthalenes ...), the ester that uses as plastic plasticizer sometimes (for example dioctyl phthalate, butyl laurate, butyl stearate ...) and ether (for example diethylene glycol dimethyl ether, diethylidene glycol butyl oxide ...).
Then photochromic material, photosensitizer, additive, polymer and arbitrarily wetting agent put into solution, if necessary, can heat.As can be seen, term " additive " comprises can guarantee any material that photochromic material really works described in technical literature, also must guarantee other material (antioxidant that it is using simultaneously ...) in stability.Because polymer has increased the viscosity of photochromic material solution and may promote its photochemical properties, it is favourable therefore using polymer.The polymer (or copolymer) that is fit to comprising: polystyrene, polyvinyl chloride, polymethyl methacrylate, PMA, polyurethane, polyimides, polyoxyethylene allyl diglycol, Pioloform, polyvinyl acetal, gelatin, rubber.The concentration of various materials changes according to their character and the effect of requirement, and it is difficult setting up a boundary.
Use following two kinds of methods of operating can prepare microcapsules, for example: 1/ with 55 ℃, the photochromic solution of 40ml joins is 55 ℃ equally, carry out strong agitation in gelatin (11%) aqueous solution of 180 grams, the gum Arabics (11%) of still 55 ℃ of addings, PH9,180 grams and 630 gram water are in emulsion again.Add 10ml glutaraldehyde (25%) then, when stirring, mixture promptly is cooled to 10 ℃.After 1 hour, adding the poly-ethylene methacrylic copolymer of 15ml maleic anhydride etherificate also stirs this mixture 1 hour, add 5ml sodium carbonate liquor (20%) then and an amount of sodium hydrate aqueous solution (10%) transfers to 10 with pH value, give over to the dispersion liquid that obtains standby at last.
2/ 1 kinds of mixture A are made up of following composition:
The urea aldehyde that 95 grams have 45% reactive resin and 35% solid content gives condensation product, and 60 restrain acrylamide copolymer and 40% acrylic acid aqueous solution and the 850 gram distilled water that the carbamide with about 76% reactive resin and about 71% solid content gives condensation product, 240 grams 20%.
200 gram water are joined among the above-mentioned mixture A of 800 grams, under stirring fast, add 800 gram photochromic solutions then again, add remaining mixture A and 1400 grams distilled water subsequently, continue to stir 30 minutes and pH value was transferred to 4.7 with acetic acid as attenuant.Continuous stirring is 30 minutes again, in water-bath whole mixture is warming up to 55 ℃, and continues to stir 2 hours in this temperature, cools off lentamente then after 5～6 hours pH value is transferred to 10, and this has just obtained a kind of operable at any time microcapsule solution.
4) insoluble photochromic material.
Micro medium exists with the powder type that solia particle constitutes, and these solia particles may derive from inorganic matter (silica, zeolite, molecular sieve ... particulate) or organic matter, the polished ň upturned soil of for example crosslinked polymerization ant divinyl benzene copolymer).These micro mediums are not that to have the cavity (hole) that can hold chemical substance be exactly to have absorbent properties, and this performance can interact these micro mediums by physical chemistry to keep chemical substance.Therefore the mixture of being made up of photochromic material, photosensitizer, additive and polymer can be attached on this micro medium or in this micro medium.Then just can this photochromic mixture be incorporated in the base material of original document medium or above it.
By photochromic solids preparation of granules micro medium.Solia particle (3～5 μ m) mixed with above-mentioned photochromic solution obtain these particles.Consequent mixture is that each particulate all is individual liquid in appearance.These particulates can apply by the following method then.Be added with under the situation of wetting agent, with photochromic microparticulate in polyvinyl alcohol aqueous suspension (having the water-soluble performance of film forming ability), with the blade mixer with mixture stir about 1 hour.Utilize the quality of microexamination coating then.This suspension directly can be used or it is under agitation filtered and drying.This preparation can be adopted following ratio.
10～30 parts of photochromic particulates, polyvinyl alcohol 1-5 part, 0～0.1 part of wetting agent, 60～90 parts in water.Also can use other coating method.
Now, can be described the anti-side of duplicating of the present invention.Its main points are original documents of the information preparation that makes a kind of special macromolecule medium be used for printing will to put down in writing, and printing wherein is to use following conventional method to carry out: typewriting, hectographic printing, font printing, laser printing, mimeograph, duplicating, hand-drawing ...Those methods that use describes in detail are above made this medium, and if the photochromic material that uses cover whole spectral regions and can not read to cause original copy, so given original document needs not to be coloured.
As can be seen, many photochromic materials that the combination of different qualities system and use have different chemical structures are possible, and if necessary, it also is possible adding colouring agent in different systems.
The method that proposes when carrying out colour (three looks or four looks) duplicating, makes copy with original document different thereby this method makes color produce very big variation for preventing that monochrome (black) duplicating is effective especially.
This special medium can have different forms, but in most of the cases, it is plane, is convenient to its use like this.As a rule, it perhaps is made of the scraps of paper transparent, translucent or the plastic opaque film constitutes.
Special media of the present invention is made up of optional colorant, photochromic material, photosensitizer and above-mentioned all background medias.This background media is:
A kind of plastic film of producing with the common process method, and the polymer that is fit to comprises copolymer, polyester, polyvinyl acetate, Merlon, the hydrochloride rubber of cellulose and derivative, polyvinyl chloride, polyolefin, polyolefin and polyvinyl acetate Or has the paper of fibre structure: based on the paper of natural fabric (for example cellulose), based on the paper of synthetic fiber (for example regenerated cellulose or polypropylene).After making, these paper also contain additive and filler usually.
Special media by the conventional method preparation is suitable for every kind of material.Chromic systems and the colouring agent that has nothing in common with each other all can be joined in the medium, perhaps be adsorbed on its surface, for example method by covering with paint, lacquer, colour wash, etc.
The colouring agent that uses must be compatible with the polymeric material of background media.For opaque medium, can use pigment.General fibre cellulose fiber for paper substrate can use following primary colours: blue, yellow, red, brown, black.The pigment of these colors is by BAYER, BASF, any the company's preparation in SANDOZ and the CLBA company.
Certainly, by using pure pigment and pigment composition can obtain coloured paper equally.Dyestuff or pigment can be wrapped with capsule, and be adhered to by covering with paint.Coloured pigment can add in the preparation process of photochromic material, has so just produced a kind of photochromic coating.In this case, can coating be coated on small size or the whole surface with a brush.
In the duplicating process, the original document that is made of anti-replicating medium presents a kind of temporary transient auxiliary colour developing effect.This colour developing effect is owing to photochromic action causes, and continues for some time, and length during this period of time depends on the material of use.Therefore after duplicating, original document can recover their original appearance.
Enumerate the example of the special media of the following original document that is used to make not reproducible of the present invention.
Usually, duplicator comprises three types the xerox that uses monochromatic (black), and they use flash lamp, tungsten sodium lamp or fluorescent tube shot file.
Can find the copy that obtains with one-color copier (for example black and white) by background (medium) and the contrast between writing of measuring original document.This measurement can be carried out with two kinds of methods: 1/. pair of original document that comprises boldface type carries out visual measurement.In this case as can be seen copy be can not mu love mould /. the original document that has only a blackstreak is carried out technical measurement.In this case, use reflectometer or microdensitometer to measure formed two interregional reflections or absorption difference.
When relating to color photocopying, this check is then estimated purely.
Embodiment 1
Make a kind of anti-paper that duplicates by the following method, it has brown color (Pantone 173c, wherein Pantone is a registration mark) and contains photochromic micro-encapsulation.This paper that uses is based on the cellulose that has common fillers.
Use above-mentioned No. 1 method of operating, concentration of ordinary dissolution is 4 * 10 in hydrogenated terphenyl
-21 of mol ', 1 ', 3 '-trimethyl-2 '-(2,1-b) pyrans and concentration are 2 * 10 to indoline-2-spiral shell-7-nitro naphtho-
-11 of mol, the 2-dihydroxy anthraquinone is made photochromic micro-encapsulation.
In a kind of coating that uses adhesive (starch, polyvinyl alcohol), apply these microcapsules to thickness and be about 10 microns, be i.e. 10 gram/rice
2, paper.On this anti-copy paper, stamp boldface type, and after on three kinds of monochromes (black) duplicator it being duplicated, the copy that is obtained can not be read, and uniform black background is arranged.The contrast measurement of copy being carried out with reflectometer demonstrates between the background of copy and the writing does not have difference.And brown original document can be read fully.After being copied the machine irradiation, original document recovers its initial color after about 10 seconds.
When using the electrostatic color copy machine to duplicate, to compare with original document, copy has the tone of a blue look.
Embodiment 2
A kind ofly have darkorange (Pantone 166c) and the anti-copy paper of photochromic micro-encapsulation is prepared as follows:
This paper that uses is based on the cellulose that has common fillers.Use above-mentioned No. 2 methods of operating, concentration of ordinary dissolution is 5 * 10 in hydrogenated terphenyl
-21 of mol ', 3 ', 3 '-trimethyl-2 '-indoline-2-spiral shell-6,8-dibromo benzo (b) pyrans, concentration are 2 * 10
-1The polystyrene of the 4-aminoacenaphthene of mol and 3% even molecular weight prepares microcapsules.
Apply microcapsules to thickness by the coating that has adhesive and be about 10 microns, be i.e. 10 gram/rice
2. paper.Stamp boldface type and duplicate back (using black) on this anti-copy paper, the copy of acquisition can not be read, and has uniform black background.The contrast measurement of copy being carried out with reflectometer demonstrates between the background of copy and the printing writing does not have difference.The darkorange original document is fully readable.Illuminated back original document returns to its normal color after 2 seconds.
Embodiment 3
A kind of anti-copy paper preparation method who has brown (Pantone173c) and a photochromic micro-encapsulation is as follows:
What use is common paper.Use above-mentioned No. 1 method, concentration of ordinary dissolution is 4 * 10 in decahydronaphthalenes
-2The 6-methyl mercapto-3 of mol '-methyl-2 '-benzothiazole quinoline-2-spiral shell-3-methyl-8-methoxyl group-6-nitro benzo (b) pyrans, concentration is 10
-1The 4-phenyl acetophenone of mol and 5% polystyrene prepare photochromic micro-encapsulation.Applying these microcapsules to thickness by the coating that uses adhesive is 10 microns, i.e. 10 gram/rice
2. paper.
After stamping information, brown original document is fully readable.And with after monochromatic (black) Xerox duplicating, the copy that obtains can not be read, and has uniform (black) background.
After the duplicator irradiation, original document returns to its priming color with 5 times in second.
Embodiment 4
Having the brown color (Pantone 173c) and the anti-copy paper of microcapsules prepares by the following method:
Use the paper (cellulose) of general type.
Use No. 2 method, with tetrahydronaphthalene as solvent, wherein be dissolved with 1 ', 1 ', 3 '-trimethyl-2 '-indoline-2-spiral shell-7-nitro benzo (2,1-b) pyrans, its concentration is 3 * 10
-2Mol, 4-phenyl acetophenone, concentration are 10
-1Mol and 8% polystyrene (low molecular weight) prepare photochromic micro-encapsulation.
After stamping information in the above, brown original document is fully readable.And can not read with the copy that monochromatic (black) duplicator obtains.The contrast of measuring copy with reflectometer shows there is not contrast.
Embodiment 5
Preparation has the anti-copy paper of brown color (Pantone173c) and photochromic micro-encapsulation as follows:
The paper that uses is cellulose paper.Using No. 1 method, is 4 * 10 with concentration
-21 of mol ', 1 ', 3 '-trimethyl-2 '-(2,1-b) pyrans, concentration are respectively 10 to indoline-2-spiral shell-7-nitro naphtho-
-2The 4-phenyl acetophenone and 1 of mol, the 2-dihydroxy anthraquinone, and 3% polymethyl methacrylate prepares photochromic micro-encapsulation.
With starch it is coated on the paper, microcapsules is coated to thickness is about 10 microns, be i.e. 10 gram/rice
2. paper.
After stamping boldface type, file is fully readable.The copy that obtains by Xerox is also can't reading of deceiving entirely.
Embodiment 6
The anti-copy paper that has light orange (Pantone164c) and photochromic micro-encapsulation, preparation by the following method:
This paper is cellulose-based.Use two kinds of microcapsules, as first kind of capsule of embodiment 1 described method preparation, second kind of capsule of method preparation of embodiment 3, these two kinds of capsules with same umber mix then, again this mixture is coated on the medium by the coating that has used adhesive (polyvinyl alcohol), to thickness be 10 microns, i.e. 10 gram/rice
2
The medium that obtains is a light orange, and it is readable stamping the original document that obtains behind the information in the above, then can not read from monochrome (black) copy that original document obtains.
Embodiment 7
It is as follows to make the paper that only comprises photochromic micro-encapsulation:
The paper that uses is cellulose-based.Utilizing and wherein being dissolved with concentration is 4 * 10
-2Two sulphur pumps and the concentration of mol are 10
-1The hydrogenation three collection preparation photochromic micro-encapsulations of the 4-hydroxyl two collection ketone of mol.
By with adhesive (polyvinyl alcohol) it being coated in method on the paper, it is 10 microns that microcapsules are coated to thickness, i.e. 10 gram/rice
2The paper that obtains thus is orange.After stamping the black font on this paper, the copy that duplicates with monochromatic Xerox be can not read and have a uniform black surface.
After the irradiation, mistake original document in 15 second recovers its just normal color approximately.
Embodiment 8
The anti-copy paper that only comprises a kind of photochromic micro medium, it is prepared by following method:
The paper that uses is to give earlier the fiber handled with polyvinyl alcohol.Prepare photochromic micro medium: preparation 10～3000 * 10 earlier
-10The microporosity micro medium CPG(Control Pore Glass of m), its granular size is 10 microns, and concentration of ordinary dissolution is 3 * 10 in 1% polyoxyethylene allyl diglycol 700 aqueous solution then
-3Three (N, N-dimethylamino-4-phenyl-1) ethyl nitrile of mol, concentration are 10
-2The potassium cyanide of mol and concentration are 10
-2The carbon tetrabromide of mol prepares a kind of solution, and this solution is joined in the micro medium, and consumption is the 0.5ml/g micro medium.
For fear of any exudate, with said method this system is coated layer of polyethylene alcohol, then this mixture is coated on the paper of original document medium, just obtained almost colourless anti-copy paper in this way.Behind printing information on this medium, the copy that obtains with monochromatic (black) Xerox has the even appearance of black that can not read.
After two minutes, original document recovers its priming color.
Embodiment 9
Prepare anti-copy paper according to embodiment 4 except that replacing the cellulose paper with synthetic paper.This synthetic paper is by the bonding polyethylene fiber preparation of polyvinyl alcohol
Its result can compare with embodiment 4 fully.
Embodiment 10
Except that replacing with transparent vulpak sheet (thickness is 0.1mm) the cellulose paper, prepare a kind of transparent anti-duplicating plastic film according to the method for embodiment 4.
Its result can compare with embodiment fully.
Embodiment 11
Prepare a kind of anti-copy paper that has brown (Pantone173c) and photochromic big molecular coatings by the following method:
What use is cellulose paper, in order to prevent with cellulose fibre any reaction to take place, applies this paper with polyvinyl alcohol and carries out auxiliary processing.
Ethyl acetate with 50/50 and toluene mixture are as solvent, and wherein adding concentration is 4 * 10
-31,1 of mol, 3-trimethyl-2 '-(2,1-b) pyrans, concentration are 2 * 10 to indoline-2-spiral shell-7-nitro naphtho-
-2The 4-phenyl acetophenone of mol, 20% polyvinyl butyral resin and 1% butyl laurate are made a kind of solution as plasticizer, apply with it.
With Meyer rod or brush photochromic polymer coating or paint are coated on the whole surface of paper or only are coated on the part surface.After the solvent evaporation, obtain a kind of brown medium.After stamping information in the above, with black replicating original file, the copy that obtains is complete black, therefore can't read.
Embodiment 12
The anti-copy paper method that preparation has brown (Pantone173c) and photochromic micro medium is as follows:
What use is cellulose paper.Use 10-3000 * 10
-10The microporosity micro medium CPG(Controlled Pore Glass of m), its mean particle size is 10 microns, makes photochromic micro medium.With 1 ', 1 ', 3 '-trimethyl-2 '-(2,1-b) pyrans is with 4 * 10 for indoline-2-spiral shell-7-nitro naphtho-
-2The concentration of mol and 4-phenyl acetophenone are with 2 * 10
-1The concentration of mol is dissolved in the decahydronaphthalenes, obtains a kind of photochromic solution, and it is joined in the micro medium, and concentration is the 0.5ml/g micro medium.
For fear of produce any possible exudate from this individual system, it is coated layer of polyethylene alcohol with said method.Can directly use this medium and drying-free in this case.This mixture of preparation is coated on the Colored Paper, and coating thickness is 10 microns, i.e. 10 gram/rice
2The anti-copy paper that obtains with the method is brown.
After stamping the black font on this medium, the outward appearance that the copy that uses monochromatic (black) Xerox to obtain has even black and can not read.
Embodiment 13
Colored pigment is joined the method for carrying out embodiment 12 in the photochromic solution.This mixture has the performance of photochromic coating, is suitable for covering with paint, lacquer, colour wash, etc. with paint brush or other method.
Embodiment 14
A kind of anti-copy paper that has color and photochromic particulate is prepared by following method:
This paper is cellulose type paper.This particulate is based on the divinylbenzene of crosslinked polystyrene and 2%.They obtain by emulsion polymerisation, and its diameter is about 5 microns.Make these particulates photochromic by the swelling in photochromic solution.
With the cyclohexane give is solvent, and wherein concentration of ordinary dissolution is 10
-21 of mol ', 1 ', 3 '-trimethyl-2 '-indoline-2-spiral shell-7-nitro naphtho-(2,1-b) pyrans, concentration is 5 * 10
-2The 4-phenyl acetophenone of mol and a kind of plasticizer, promptly 8% heavy butyl laurate is made photochromic solution.
At 20 ℃, under the stirring at low speed, make this particulate swelling in above-mentioned solution.With the growth of microscope supervision particulate, it is 8 microns up to diameter.After the cooling, with swelling micro particle filtering and dry.
With adhesive (polyvinyl alcohol) these particulates are coated on the paper, are about 15 microns to thickness, i.e. 10 gram/rice
2The medium that obtains thus is brown, stamp the black font in the above after, original document is fully readable, and the copy that uses monochromatic (black) Xerox to obtain is deceived entirely, and can't read.
Embodiment 15
The anti-copy paper that a kind of orange (Pantone165c) contains photochromic micro-encapsulation prepares by the following method:
What use is cellulose paper.As solvent, wherein concentration of ordinary dissolution is 5 * 10 with Santosol
-21 of mol ', 3 ', 3 '-trimethyl-2 '-indoline-2-spiral shell-1, (2,1-b) oxazine and concentration are that the benzil of 0.25mol prepares microcapsules to 4-naphtho-(3H).Applying microcapsules to thickness with adhesive is 10 microns, promptly about 10 gram/rice
2. paper.
Stamp black information look on this paper, the copy that uses monochromatic (black) duplicator to duplicate can not be read fully, spends about 3 seconds, and this paper returns to its priming color.
Embodiment 16
Except using by grafting benzyl De Luo oxazine on its alkyl chain, promptly 3 ', 3 '-dimethyl-1 '-(4-(phenyl second 26 phenylenes)-1-fourth two bases)-2 '-indoline-2-spiral shell-1,4-benzo (3H) (2,1-b) beyond the oxazine, prepare anti-copy paper by embodiment 15 described methods.
Embodiment 17
Concentration of ordinary dissolution is 5 * 10 in the mixture of 50/50 toluene and ethyl acetate
-21 of mol ', 3 ', 3 '-trimethyl-2 '-indoline-2-spiral shell-1,4-(3H) (3,2-f) (2,1-b) oxazine and concentration are that the camphorquinone of 2.5mol and 10% polyethyl methacrylate prepare a kind of polymer coating or paint to benzo to pyrido.Available Meycr rod is coated onto it on orange (Pantone164c) cellulose paper, to thickness be 40 microns.
The copy that is printed on this medium of black literal can not be read fully.This document returns to its priming color after 5 seconds.
Embodiment 18
Orange (Pantone157c) anti-copy paper has photochromic particulate.This particulate is that granular size is that 200 orders are to 400 orders based on the divinylbenzene of crosslinked polystyrene and 2%.
Is 5 * 10 with these particles being dissolved with concentration
-26 of mol '-chloro-1 ', 3 ', 3 '-trimethyl-2 '-indoline-2-spiral shell-1, (2,1-b) oxazine and concentration are swelling in the toluene solution of the benzil of 0.25mol and 1% butyl laurate to 4-naphtho-(3H), make it to become photochromic.
Use a kind of adhesive (polyvinyl alcohol) that particulate is coated on the paper.After its chromic systems is intensified, cross approximately 5 second its priming color of medium recovery.The copy that is printed on this medium of black literal can not be read.
Use can be protected authentic document not carry out duplicity to it by duplicator based on the medium of above-mentioned paper and duplicate.Some original document kinds that are suitable for comprise book, magazine, report and mail ...
However, use this white or colour still must take the various anti-property measures of giving can not copy paper the time.At first be noted that the printing ink of use.Black, redness, avy blue or darkviolet printing ink form mark on paper be no problem.But should avoid using light color, white or Yellow ink are because they can hinder anti-photocopying effect.For example, use toner cartridge type duplicator that the anti-copy paper that is printed on white ink is duplicated, resulting copy background is a black, but top white writing is visible.Be necessary equally to avoid the writing of medium is corrected because it can destroy can not the copy paper medium performance.Especially to avoid using rubber, typing error correction fluid (white), printing ink stain remover, any chemicals or paint.
In order to solve the problem of correction, use a kind of viscosity, the paper that can not duplicate is feasible.The user can be bonded at the paper that can not duplicate wrong place, under the situation of not destroying medium character basically with its correction.On the other hand, also can use coating described in embodiment 11 and 13 and paint.Available conventional method prepares viscosity, the paper that can not duplicate.
Embodiment 19
In order to obtain a kind of glued membrane (3 gram dried glue/rice
2), with conventional method apply 10% give the gelatinized starch aqueous solution.After the drying, the viscosity anti-copy paper that obtains can use in the moistening back of glue, for example, is used on the surface of the scraps of paper.The preparation of the anti-paper that duplicates is carried out with above-mentioned same method.
The paper that can not duplicate that can prepare viscosity by conventional method.
Embodiment 20
In order to prevent to adhere to, siloxane paint is sprayed on (60 gram/rice on the common paper
2), the acrylic emulsion (PMA and acrylic acid) that sprays one deck 50% dried extract more equably is on siloxane paint, above then photochromic anti-copy paper being attached to, so just viscosity being transferred on the anti-copy paper, and obtained the viscosity anti-copy paper.Above-mentioned anti-copy paper can be used for this purpose.This viscosity anti-copy paper that uses the same method can be used as any sticky paper system and uses.
This viscosity can not also can be used for making the original document part to duplicate by copy paper, for example, a part of if desired printed image is that some speech, name, numeral, signature, detail drawing or the like are not replicated, as long as the paper that can not duplicate is attached to suitable position, and it is just passable to continue to put on suitable writing.When using Xerox to duplicate this document, the part of reproducible will not be black, and the remainder of original document will be readable.
The problem that the copy invention takes place in can not the duplicating medium process will be described in detail.These media are effective especially for static and toner cartridge type duplicator, prevailing type in these duplicators yes duplicator.
Fully narrated the effect of using monochromatic (normally black) Xerox.
In monochromatic system, image receiving system form back umbrella despot carve green loess hills ┭ zhang R Ge of dysentery cough closely question De from " school leads and stares at happiness and go back the bery despot and carve the choke ⒑ that remonstrates with of dysentery pen and warm up ⒗ and avoid ⒒ dregs of rice gown cap convulsion ⒚ saddle cloth nurse hurdle and fall rose from ≈ and fall female from " difficult zhang of and extensive commonplace mould ⑶ move the loess hills that washes and send waste jasmine mu and love and imitate
For " colour " duplicator, they adopt electrostatic methods and three looks or four looks " toner " work, and do not use other colour reproduction systems, for example money base photography or additive method.Use the color photocopying part that anti-copy paper of the present invention obtains because the color of duplicating is different with original document, its quality obviously descends.
There are many colourless or coloured photochromic films to use.At first there are some to be printed on the film of the original document of image.This film has above-mentioned character that can not copy paper, and the narration of any relevant paper is equally applicable to film.
The photochromic film of reproducible not can be used for protection with the plain paper medium of general fibre or synthetic paper medium or film, and is printed on writing and the file that obtains.In these cases, with reproducible not, the topped above-mentioned file of photochromic film.These methods are the lamination or the method for plasticating.Can use any lamination and the method for plasticating, as bonding, hot pressing, adhesive film etc.Lamination and the method for plasticating can topped be wanted all or part of of protected file, and can topped its one side or two-sided.
Making not like this, the original document of reproducible is feasible.
Embodiment 21
According to a kind of transparent anti-duplicate film of embodiment 10 preparations, and must discern uncoated one side.Topped the file of wanting lamination with transparent film, must make uncoated one side paste file, then with the hot pressing under 60～80 ℃ temperature of this sub-assembly.The given effect of the original document that obtains thus can be compared with embodiment 11 fully.The copy that uses monochromatic (black) duplicator to obtain is black entirely, and not readable.
Embodiment 22
Prepare a kind of viscosity anti-copy film according to the narration among the embodiment 10.Can replace the acrylic emulsion adhesive with the butadiene-styrene rubber that is dissolved in ethyl acetate-acetone-toluene mixed solvent.The film of making can be used for lamination file, especially paper base file.The lamination file of the not reproducible that in this way obtains has the identical performance of anti-replicating original file with the foregoing description.
As can be seen, use all original documents of photochromic material preparation, when being exposed to the light radiation of sunlight, high energy bulb (especially halogen lamp) or a plurality of fluorescent tube light source, demonstrate slight hyperchromicity.Therefore, light or white original document just presents light colour if be exposed under the daylight.But this does not influence the reading of file.If original document itself is coloured, this change in color almost be can't see.
Therefore under medium illumination condition, for example 50 rein in, help this original document is duplicated, read and handle.
Claims (10)
1, a kind of photosensitive medium that is used to write with printing type face, it comprises a kind of photochromic material at least, and wherein this medium further comprises at least a and photochromic photosensitizer that combines of looking for.
2, according to the medium of claim 1, wherein photochromic material and photosensitizer are to join in the medium with the method that has nothing in common with each other.
3, according to the medium of claim 1, also comprise at least a colouring agent.
4, according to the medium of claim 1, wherein photochromic material and photosensitizer are with at least a adding in the following form: polymer or ink lay, microcapsules, particulate and insoluble micro medium.
5, according to the medium of claim 1, wherein by disturbing background document and contrast between top writing to make that copy is different with original document maybe can't be read.
6, according to the medium of claim 1, wherein this medium constitutes a kind of paper mold medium.
7, according to the medium of claim 1, wherein this medium is to be made of polymer film.
8, according to the medium of claim 7, wherein this medium comprises an adhesive faces.
9, according to the medium of claim 7, wherein polymer film combines with paper substrate.
10, a kind of method of anti-duplicating is characterized in that printing on the medium of claim 1 or writing.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR8710845 | 1987-07-30 | ||
| FR8710845A FR2618812B1 (en) | 1987-07-30 | 1987-07-30 | ANTICOPY PRINT-WRITE MEDIUM AND ASSOCIATED METHOD |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1032827A true CN1032827A (en) | 1989-05-10 |
Family
ID=9353739
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN88109081A Pending CN1032827A (en) | 1987-07-30 | 1988-07-29 | Write or anti-medium and the correlation technique that duplicates of printing type face |
Country Status (10)
| Country | Link |
|---|---|
| EP (1) | EP0302774A3 (en) |
| JP (1) | JPS6490480A (en) |
| CN (1) | CN1032827A (en) |
| AU (1) | AU610614B2 (en) |
| DK (1) | DK425988A (en) |
| FI (1) | FI883572A (en) |
| FR (1) | FR2618812B1 (en) |
| NO (1) | NO883384L (en) |
| NZ (1) | NZ225591A (en) |
| PT (1) | PT88130A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111519469A (en) * | 2020-05-18 | 2020-08-11 | 湖南翰坤实业有限公司 | Anti-patting paper material and preparation method thereof |
| CN115045137A (en) * | 2022-05-16 | 2022-09-13 | 江苏卫星新材料股份有限公司 | Light-variable special paper and preparation method thereof |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB9007387D0 (en) * | 1990-04-02 | 1990-05-30 | Nocopi Int Inc | A switchon-switchoff,multistate,interactive,antiphotocopying,antifraud and antifaxing system |
| ES2066685B1 (en) * | 1992-10-28 | 1995-11-16 | Teledata S A | PROCEDURE FOR TREATING PAPER, PROTECTING IT AGAINST UNAUTHORIZED PHOTOCOPIES. |
| US5720897A (en) * | 1995-01-25 | 1998-02-24 | University Of Florida | Transition metal bleach activators for bleaching agents and detergent-bleach compositions |
| ZA9710835B (en) * | 1996-12-23 | 1998-06-12 | Standard Register Co | Photochromic security system. |
| CN103526646A (en) * | 2013-09-26 | 2014-01-22 | 昆山市长宏印刷厂 | Anti-copying computer printing paper |
| CN109837031A (en) * | 2017-11-29 | 2019-06-04 | 北京康得新功能材料有限公司 | A kind of anti-copy pre-coating film and preparation method thereof |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3597082A (en) * | 1967-02-20 | 1971-08-03 | Litton Business Systems Inc | Uncopyable photochromic paper |
| DE2048853C3 (en) * | 1969-10-07 | 1978-05-11 | Xerox Corp., Rochester, N.Y. (V.St.A.) | Process for the production of non-copyable documents |
| US3713861A (en) * | 1969-12-04 | 1973-01-30 | Xerox Corp | Inhibitor device |
| IL42090A (en) * | 1973-04-22 | 1977-01-31 | Yeda Res & Dev | Photocopying prevention |
-
1987
- 1987-07-30 FR FR8710845A patent/FR2618812B1/en not_active Expired - Fee Related
-
1988
- 1988-07-25 EP EP88401929A patent/EP0302774A3/en not_active Withdrawn
- 1988-07-27 AU AU20096/88A patent/AU610614B2/en not_active Ceased
- 1988-07-27 NZ NZ225591A patent/NZ225591A/en unknown
- 1988-07-28 PT PT88130A patent/PT88130A/en not_active Application Discontinuation
- 1988-07-29 FI FI883572A patent/FI883572A/en not_active Application Discontinuation
- 1988-07-29 JP JP63190483A patent/JPS6490480A/en active Pending
- 1988-07-29 CN CN88109081A patent/CN1032827A/en active Pending
- 1988-07-29 DK DK425988A patent/DK425988A/en not_active Application Discontinuation
- 1988-07-29 NO NO88883384A patent/NO883384L/en unknown
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111519469A (en) * | 2020-05-18 | 2020-08-11 | 湖南翰坤实业有限公司 | Anti-patting paper material and preparation method thereof |
| CN115045137A (en) * | 2022-05-16 | 2022-09-13 | 江苏卫星新材料股份有限公司 | Light-variable special paper and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| FI883572A0 (en) | 1988-07-29 |
| NO883384D0 (en) | 1988-07-29 |
| JPS6490480A (en) | 1989-04-06 |
| NZ225591A (en) | 1989-09-27 |
| DK425988A (en) | 1989-01-31 |
| NO883384L (en) | 1989-01-31 |
| FI883572A (en) | 1989-01-31 |
| AU2009688A (en) | 1989-06-29 |
| AU610614B2 (en) | 1991-05-23 |
| PT88130A (en) | 1989-06-30 |
| EP0302774A3 (en) | 1989-03-01 |
| FR2618812A1 (en) | 1989-02-03 |
| EP0302774A2 (en) | 1989-02-08 |
| FR2618812B1 (en) | 1990-04-27 |
| DK425988D0 (en) | 1988-07-29 |
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