CN101614995B - Anti-copying film and preparation method thereof - Google Patents
Anti-copying film and preparation method thereof Download PDFInfo
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- CN101614995B CN101614995B CN2009100900517A CN200910090051A CN101614995B CN 101614995 B CN101614995 B CN 101614995B CN 2009100900517 A CN2009100900517 A CN 2009100900517A CN 200910090051 A CN200910090051 A CN 200910090051A CN 101614995 B CN101614995 B CN 101614995B
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- cellulose nitrate
- photosensitizer
- aminoacetophenone
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- indoline
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Abstract
The invention provides a copying-proof film and a preparation method thereof. The copying-proof film is mainly prepared from mixture comprising photochromic agent, photosensitizer and zapon, and the copying-proof film does not react with cellulosic paper if covered on a cellulosic paper, has favourable character reading effect and can obtain favourable copying-proof effect. The copying-proof film preparation method of the invention can prepare the copying-proof film with less steps, simple technology and no need of special devices.
Description
Technical field
The present invention relates to a kind of anti-copy film and preparation method thereof.Particularly, the present invention relates to the anti-copy film made by the potpourri that comprises photochromic agent, photosensitizer and zapon and the preparation method of this anti-copy film.
Background technology
As everyone knows, (wavelength is under 200～800nm) the effect to photochromic material usually, gives self or other medium with reversible variable color in visible light or UV-irradiation.Photochromic anti-reprography utilizes this specific character of photochromic material and grows up.When the photochromic material absorption causes the rayed of photochromic action, therefore this material becomes to coloured and absorb ultraviolet light or visible light, thereby under normal illumination, make information and the background put down in writing on the source document that enough contrasts visually be arranged, but under suitable rayed, background wherein just obtains fairly obvious colour developing effect, thereby reaches the anti-purpose of duplicating.
Usually, common photochromic material almost can not absorb ultraviolet light or the visible light that general duplicating machine sends, need to add photosensitizer and form " chromic systems ", for example, Chinese patent CN1032827A disclosed by photochromic material 1 ', 1 ', 1 '-trimethyl-2 '-indoline-2-spiral shell-7-nitro naphtho-(2,1-b) pyrans and photosensitizer 1, the anti-photocopying materials that the 2-dihydroxy anthraquinone forms.But, may react with the macromolecule medium of source document for some responsive photochromic materials or photosensitizer, so this patent of invention is made microcapsules by a kind of assist medium with " chromic systems " or is dissolved in and prevents in the polymkeric substance of plasticising that " chromic systems " and macromolecule medium from reacting.The technology of making microcapsules is loaded down with trivial details, process conditions require height, and this causes the process complexity of its preparation anti-copy film; And select solubilized described " chromic systems " and the plasticized polymer that do not influence the effect of reading file simultaneously also is suitable difficulty.
In addition, U.S. Pat 3,887,742 disclose with photochromic material and have made anti-photocopying materials and anti-copy film, should anti-photocopying materials or anti-copy film to wavelength less than the light reflectivity of 600nm less than 13%, and reach anti-requirement of duplicating by overlapping multilayer film.But formed multilayer anti-copy film has increased the difficulty of reading, and the technology of formation multilayer anti-copy film is also comparatively complicated.
Summary of the invention
The purpose of this invention is to provide a kind of file that can guarantee effectively and and have preferable reading effect and photochromic agent wherein and photosensitizer behind the film and do not react, can purchase simultaneously and prevent the anti-copy film that is copied effectively with cellulose paper.
Another object of the present invention provides a kind of method for preparing described anti-copy film, and the processing step that this preparation method relates to is few, technology is simple, need not special equipment and promptly can be made into described anti-copy film.
The present invention is by realizing above-mentioned purpose by the following technical solutions:
1. anti-copy film, it is characterized in that: described anti-copy film is made by the potpourri that comprises photochromic agent, photosensitizer and zapon, and wherein the weight ratio of photochromic agent, photosensitizer and zapon is 2～5: 2～20: 30～90.
2. according to above-mentioned the 1st described anti-copy film, it is characterized in that: described photochromic agent is selected from spiro-pyrans, Luo oxazine, metal dithizonate and derivant, triphenyl methane and derivant thereof, fulgide and their combination; And/or described photosensitizer is selected from 4-aminoacetophenone, diphenylthanedione, camphorquinone, 4-phenyl acetophenone, 1,2-dihydroxy anthraquinone and their combination; And/or described zapon is a cellulose nitrate.
3. according to above-mentioned the 1st described anti-copy film, it is characterized in that: described photochromic agent is a spiro-pyrans Huo Luo oxazine, and described photosensitizer is 4-aminoacetophenone or diphenylthanedione.
4. according to above-mentioned the 1st described anti-copy film, it is characterized in that: described anti-copy film is made by the potpourri that comprises spiro-pyrans, 4-aminoacetophenone and cellulose nitrate, and wherein the weight ratio of spiro-pyrans, 4-aminoacetophenone and cellulose nitrate is 2～3: 2～10: 30～60.
5. according to above-mentioned the 1st described anti-copy film, it is characterized in that: described anti-copy film is made by the potpourri that comprises Luo oxazine, diphenylthanedione and cellulose nitrate, and wherein the weight ratio of Luo oxazine, diphenylthanedione and cellulose nitrate is 2～3: 2～10: 30～60.
6. according to above-mentioned the 1st described anti-copy film, it is characterized in that: described anti-copy film is by comprising 6,8-two bromo-1 ', 3 ', 3 '-trimethyl spiral shell (indoline-2,2 ' [2H] benzo [b] pyrans), the potpourri of 4-aminoacetophenone and cellulose nitrate is made, wherein 6,8-two bromo-1 ', 3 ', 3 '-part by weight of trimethyl spiral shell (indoline-2,2 ' [2H] benzo [b] pyrans), 4-aminoacetophenone and cellulose nitrate is 2: 2: 35.
7. according to above-mentioned the 1st described anti-copy film, it is characterized in that: described anti-copy film is by comprising 1,3,3-trimethyl spiral shell { indoline-2,3 '-potpourri of [3H] naphtho--[2,1-b] [1,4] } oxazine, benzil and cellulose nitrate makes, wherein 1,3,3-trimethyl spiral shell indoline-2,3 '-[3H] naphtho--[2,1-b] part by weight of [1,4] } oxazine, benzil and cellulose nitrate is 3: 2: 40.
8. method for preparing anti-copy film is characterized in that: the potpourri that will comprise photochromic agent, photosensitizer and zapon stirs fast and fully mixes; Wet lapping 4-8 minute; After NaOH solution with 10% transfers to 8～10 with the pH value of this potpourri, on the paper medium, apply into the film that thickness is 50～200 μ m, wherein the part by weight of photochromic agent, photosensitizer and zapon is 2～5: 2～20: 30～90, and described photochromic agent is selected from spiro-pyrans, Luo oxazine, metal dithizonate and derivant, triphenyl methane and derivant thereof, fulgide and their combination; And/or described photosensitizer is selected from 4-aminoacetophenone, diphenylthanedione, camphorquinone, 4-phenyl acetophenone, 1,2-dihydroxy anthraquinone and their combination; And/or described zapon is a cellulose nitrate.
9. according to above-mentioned the 8th described method, it is characterized in that: described photochromic agent is 6,8-two bromo-1 ', 3 ', 3 '-trimethyl spiral shell (indoline-2,2 ' [2H] benzo [b] pyrans), described photosensitizer is the 4-aminoacetophenone, described zapon is a cellulose nitrate, wherein 6, and 8-two bromo-1 ', 3 ', 3 '-part by weight of trimethyl spiral shell (indoline-2,2 ' [2H] benzo [b] pyrans), 4-aminoacetophenone and cellulose nitrate is 2: 2: 35, and described potpourri also contains an amount of spreading agent, defoamer and thinning agent.
10. according to above-mentioned the 8th described method, it is characterized in that: described photochromic agent is 1,3,3-trimethyl spiral shell { indoline-2,3 '-[3H] naphtho--[2,1-b] [1,4] } oxazine, described photosensitizer is a benzil, described zapon is a cellulose nitrate, wherein 1,3,3-trimethyl spiral shell { indoline-2,3 '-[3H] naphtho--[2,1-b] weight ratio of [1,4] } oxazine, benzil and cellulose nitrate is 3: 2: 40, and described potpourri also contains an amount of spreading agent, defoamer and thinning agent.
Compared with prior art, the present invention has following technological merit:
1. anti-copy film of the present invention can effectively prevent to be copied, and guarantees simultaneously to have better reading effect after file film.In existing anti-copy film, make the anti-copy film of multilayer in order to guarantee anti-fully photocopying effect, thereby be difficult to guarantee good reading effect.The present invention adopts zapon and photochromic agent and photosensitizer to organically combine and makes the good individual layer anti-copy film of light transmission, has avoided multilayer film to read the bad shortcoming of performance, and the zapon with extinction has guaranteed good reading effect.
2. anti-copy film good stability of the present invention.This anti-copy film not with cellulose paper media in organic polymer react.
3. anti-copy film preparation method of the present invention is simple.The processing step that anti-copy film preparation method of the present invention relates to is few, and to process conditions, equipment require low.
In a word, the present invention is the anti-copy film of being made by the potpourri that comprises photochromic agent, photosensitizer and zapon, utilize a kind of " chromic systems " to combine with the zapon material with anti-photocopying effect, prevent the effect that is copied guaranteeing under the situation of abundant reading effect that material to need to be keep secret plays, simultaneously " chromic systems " not with cellulose paper in macromolecular material react.This anti-copy film effect is good, and preparation technology is simple.
Description of drawings
Fig. 1 is that expression (A) applies the source document of anti-copy film of the present invention and the comparison diagram that (B) applies the hard-copy file of anti-copy film of the present invention.
Fig. 2 is the collection of illustrative plates of the reflectivity of the embodiment of the invention 1 and 4 prepared anti-copy films.
Embodiment
The anti-copy film that the present invention is made, its color is orange or brown, and its structure is the hyaline membrane of individual layer, mainly relies on the acting in conjunction of photochromic material and photochromics in the film and absorbing light, cause duplicating machine light major part in specific wavelength to be absorbed, thereby make duplicating to carry out.The anti-copy film that the present invention makes is a single layer structure, be covered in literal table and film have only one deck, rely on file that absorption of incident light is reached anti-purpose of duplicating, do not need multilayer film compound, and adopt and to have the zapon of extinction, thereby guaranteed good reading effect.Anti-copy film of the present invention relies on the light absorptive of photochromic material and photochromics to reach anti-purpose of duplicating, thereby has good anti-photocopying effect too for the writing beyond image or the black.Therefore, this anti-copy film has purposes more widely than other anti-photocopying materials that occur before.
The present inventor is by a large amount of experiments and theoretical research, employing is made anti-copy film of the present invention by the potpourri that comprises photochromic agent, photosensitizer and zapon, and wherein the weight ratio of photochromic agent, photosensitizer and zapon is 2～5: 2～20: 30～90.Described photochromic agent is selected from spiro-pyrans, Luo oxazine, metal dithizonate and derivant, triphenyl methane and derivant thereof, fulgide and their combination.Described photosensitizer is selected from 4-aminoacetophenone, diphenylthanedione, camphorquinone, 4-phenyl acetophenone, 1,2-dihydroxy anthraquinone and their combination.Zapon of the present invention is the nitrate paint that does not contain pigment, has the zapon of extinction, and zapon of the present invention adopts the cellulose nitrate with extinction.
In a preferred embodiment of the present invention, described photochromic agent is a spiro-pyrans Huo Luo oxazine, and described photosensitizer is 4-aminoacetophenone or diphenylthanedione.More preferably, described photochromic agent is a spiro-pyrans, and described photosensitizer is the 4-aminoacetophenone, and the weight ratio of spiro-pyrans, 4-aminoacetophenone and cellulose nitrate is 2～3: 2～10: 30～60.Further preferably, described photochromic agent Shi Luo oxazine, described photosensitizer is a diphenylthanedione, wherein the weight ratio of Luo oxazine, diphenylthanedione and cellulose nitrate is 2～3: 2～10: 30～60.
In order to make the excellent effect of described anti-copy film, the potpourri of further preferably making described anti-copy film also comprises spreading agent, defoamer and/or thinning agent.Spreading agent can adopt organic dispersing agent commonly used, for example 1,3 butylene glycol; Defoamer can use the normal defoamer that uses, for example methyl-silicone oil in the film forming matter.Wherein the part by weight of photochromic agent and spreading agent and defoamer can be 2～5: 0.5～1: 0.2～0.5, and the amount of thinning agent then decides according to specific circumstances, gets final product in right amount.
In further preferred embodiment, photochromic agent of the present invention is preferably 6,8-two bromo-1 ', 3 ', 3 '-trimethyl spiral shell (indoline-2,2 ' [2H] benzo [b] pyrans)
Perhaps be preferably 6-nitro-1 ', 3 ', 3 '-trimethyl spiral shell (indoline-2,2 ' [2H] benzo [b] pyrans)
Perhaps be preferably 1,3,3-tri-methyl indole quinoline spiral shell aphthopyrans
In further preferred embodiment, photochromic agent of the present invention is preferably 1,3,3-trimethyl spiral shell { indoline-2,3 '-[3H] naphtho--[2,1-b] [1,4] } oxazine
Anti-copy film preparation method's of the present invention step comprises: the potpourri that will comprise photochromic agent, photosensitizer and zapon stirs fast and fully mixes; Wet lapping 3-10 minute, more preferably about 4-8 minute, most preferably 5 minutes; With the NaOH solution of 5-10%, preferred 10% NaOH solution applies into the film that thickness is 50～200 μ m after the pH value of this potpourri is transferred to 8～10 on cellulose paper media.Preferably applying into thickness is 80～180 μ m, and for example applying into thickness is 80 μ m, 90 μ m, 100 μ m, 120 μ m, 140 μ m and 150 μ m.In this preparation method, the part by weight of photochromic agent, photosensitizer and zapon is generally 2～5: 2～20: 30～90, and the preferred weight ratio is 2～3: 2～10: 30～60.More preferably, described photochromic agent is a spiro-pyrans Huo Luo oxazine, and described photosensitizer is 4-aminoacetophenone or diphenylthanedione, and described zapon is a cellulose nitrate.The method of coating film forming of the present invention can be used method in the art commonly used, and for example blade coating, spin coating, brushing, rod such as are coated with at method.
In order to obtain to have the anti-copy film of excellent effect more, in the preparation method of described anti-copy film, the potpourri of further preferably making described anti-copy film also comprises spreading agent, defoamer and/or thinning agent.Spreading agent can adopt organic dispersing agent commonly used, for example 1,3 butylene glycol; Defoamer can use the normal defoamer that uses, for example methyl-silicone oil in the film forming matter.Wherein the part by weight of photochromic agent and spreading agent and defoamer can be 2～5: 0.5～1: 0.2～0.5, and the amount of thinning agent then decides according to specific circumstances, gets final product in right amount.
Embodiment
Below further explain and explanation the present invention, but following specific embodiment can not be used to limit protection scope of the present invention by specific embodiment.The various changes and modifications of following specific embodiment all are included in the appended claim book institute restricted portion.
Embodiment 1
With 6,8-two bromo-1 ', 3 ', 3 '-trimethyl spiral shell (indoline-2,2 ' [2H] benzo [b] pyrans) 2.0g, 4-aminoacetophenone 2.0g, cellulose nitrate (zapon that red lion coating international corporation makes) 35g, 1,3-butylene glycol 0.5g, methyl-silicone oil 0.5g and proper amount of diluting stir fast with abundant mixing, and wet lapping is about 6 minutes then, and the NaOH solution with 10% is regulated pH value to 8～9.Be coated on the paper document with SZQ wet film preparing device then.This is filmed to orange after the curing, and film thickness is 150 μ m.The file that makes is at room temperature placed after 200 days after the black and white copying machine duplicates, and the copy of acquisition can not be read, and has uniform black background.Wherein there is the printer paper photocopying effect of printing type face to see Fig. 1.
With 6-nitro-1 ', 3 ', 3 '-trimethyl spiral shell (indoline-2,2 ' [2H] benzo [b] pyrans) 1.5g, 4-aminoacetophenone 2.0g, cellulose nitrate (zapon that red lion coating international corporation makes) 35g, 1,3-butylene glycol 0.5g, methyl-silicone oil 0.5g and proper amount of diluting stir fast with abundant mixing, wet lapping was regulated pH value to 8～9 with 10%NaOH solution about 5 minutes then.Be coated on the paper document with the wet film preparing device then.This is filmed to orange after the curing, and film thickness is 180 μ m.The file that makes is at room temperature placed after 200 days after the black and white copying machine duplicates, and the copy of acquisition can not be read, and has uniform black background.
Embodiment 3
With 1,3,3-tri-methyl indole quinoline spiral shell aphthopyrans 2.5g, 4-aminoacetophenone 2.0g, cellulose nitrate (zapon that red lion coating international corporation makes) 35g, 1,3-butylene glycol 0.5g 0.5g, methyl-silicone oil 0.5g and proper amount of diluting stir fast with abundant mixing, wet lapping is 5 minutes then, and the NaOH solution with 10% is regulated pH value to 8～9.Be coated on the paper document with the wet film preparing device then.This is filmed to brown after the curing, and film thickness is 160 μ m.After the black and white copying machine duplicated, the copy of acquisition can not be read, and has uniform black background with the file that makes.
Embodiment 4
With 1,3,3-trimethyl spiral shell { indoline-2,3 '-[3H] naphtho--[2,1-b] [1,4] } oxazine 3.0g, diphenylthanedione 2.0g, cellulose nitrate (zapon that red lion coating international corporation makes) 40.0g, 1,3 butylene glycol 0.5g, methyl-silicone oil 0.5g and proper amount of diluting stir fast with abundant mixing, wet lapping is 5 minutes then, and the NaOH solution with 10% is regulated pH value to 8～9.Be coated on the paper document with the wet film preparing device then.This is filmed to brown after the curing, and film thickness is 170 μ m.After the black and white copying machine duplicated, the copy of acquisition can not be read, and has uniform black background with the file that makes.
Fig. 2 has shown that embodiment 1 and the surface reflectivity of 4 prepared anti-copy films in the 300-700nm scope are extremely low, show that the word read effect of anti-copy film of the present invention is splendid.
Claims (13)
Priority Applications (1)
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| CN2009100900517A CN101614995B (en) | 2009-07-30 | 2009-07-30 | Anti-copying film and preparation method thereof |
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| CN2009100900517A CN101614995B (en) | 2009-07-30 | 2009-07-30 | Anti-copying film and preparation method thereof |
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| CN101614995B true CN101614995B (en) | 2011-11-23 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103526646A (en) * | 2013-09-26 | 2014-01-22 | 昆山市长宏印刷厂 | Anti-copying computer printing paper |
| CN111519469B (en) * | 2020-05-18 | 2021-12-24 | 湖南翰坤实业有限公司 | Anti-patting paper material and preparation method thereof |
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Assignee: BEIJING JINCHEN CICCONE SECURITY PRINTING CO., LTD. Assignor: Beijing Technology and Business University Contract record no.: 2012110000109 Denomination of invention: Copying-proof film and preparation method thereof Granted publication date: 20111123 License type: Exclusive License Open date: 20091230 Record date: 20120626 |
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Granted publication date: 20111123 Termination date: 20190730 |