CN1094435C - Pressure sensitive fluorescent anti-fake manifold paper - Google Patents
Pressure sensitive fluorescent anti-fake manifold paper Download PDFInfo
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- CN1094435C CN1094435C CN99106889A CN99106889A CN1094435C CN 1094435 C CN1094435 C CN 1094435C CN 99106889 A CN99106889 A CN 99106889A CN 99106889 A CN99106889 A CN 99106889A CN 1094435 C CN1094435 C CN 1094435C
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Abstract
The present invention belongs to pressure-sensitive carbon paper. The back surfaces of the upper part and the middle part of the pressure-sensitive carbon paper is coated with coating comprising an organic ultraviolet fluorescent complex, and the visualization duplication writing generated by hand writing or typewriting with the pressure-sensitive carbon paper shows an implicit fluorescent color under the irradiation of ultraviolet light. The pressure-sensitive carbon paper has good anti-counterfeiting performance, and is used for new notes in the fields of commerce, banking, finance, etc.
Description
The present patent application is that denomination of invention is the dividing an application of patent application of " anti-fake fluorescent pressure-sensitive carbon paper and preparation method thereof ", and the applying date of original application is 96100339.1 for the 96.1.23 application number.
Affiliated technical field
The claimed technical scheme of the present invention relates to the carbon paper that utilizes the feasible color of covering of pressure to show, and promptly is commonly called as pressure-sensitive carbon paper.
Background technology
At present in the carbon paper of the employed multi-joint manifolding receipts in field such as commerce, finance, finance, roughly there is folder page to be coated with carbon (pigment) carbon paper, to carry on the back and be coated with carbon (pigment) carbon paper and NCR three classes.The first two class is coated with carbon carbon paper in use many defectives, few as manifolding connection number, uses trouble, can not be applicable to office automation, and paper is not attractive in appearance, and therefore the connection of the upper and lower end of easy set-off bill etc. when writing is eliminated just gradually.The substitute is NCR, it is easy to use, paper is attractive in appearance, writes Shi Buhui and produces the set-off phenomenon, and the multi-joint manifolding of energy is applicable to office automation, adopts in the bill of many industries at present.Yet the carbon paper of above-mentioned existing type does not nearly all have false proof function, anti-counterfeiting performance is very weak in other words, is forged by the offender easily.For this reason, the someone develops fluorescent pressure-sensitive carbon paper, to strengthen the anti-counterfeiting performance of manifolding bill.JP05-214278 has introduced a kind of pressure-sensitive carbon paper that scribbles common coloured organic fluorescent dye, because these organic fluorescent dyes have color, does not possess disguise, and raw material obtains easily in addition, so the bill of making of this paper still easily is forged.JP59-98892 and JP04-363289 have introduced the pressure-sensitive carbon paper that scribbles inorganic fluorescent substance respectively.The writing of this class carbon paper can show certain fluorescence color under the UV-irradiation of particular range of wavelengths.Because fluorescence color is hidden under visible light, has improved the anti-counterfeiting performance of pressure-sensitive carbon paper.Yet, the particle size of inorganic fluorescent pigment is generally bigger, if grind too carefully, can destroy its microstructure again and brightness is reduced, therefore, all poor by coating dispersiveness and stability that inorganic fluorescent pigment makes, perhaps fluorescent brightness is low, and bad adaptability is again because its kind is single, raw material also obtains easily, so its anti-counterfeiting performance is still not ideal enough.
Content of the present invention
Technical problem to be solved by this invention is: provide a kind of Bulk coat system uniform and stable, also be implied with fluorescent pressure-sensitive carbon paper high brightness fluorescence, high anti-counterfeiting performance in the duplication handwriting of showing one's color.
The present invention solves this technical problem the technical scheme that is adopted: anti-fake fluorescent pressure-sensitive carbon paper of the present invention is with paper, middle with paper with constitute with paper down by last.Of the present invention going up with paper is to contain organic ultraviolet fluorescence complex, colourless toner solutions, buffer, adhesive and auxiliary agent, it forms weight ratio, and to be followed successively by 5: 5: 2～3: 0.6～1.5: 0.2～1 solid content be 25 ± 5% coating A, be uniformly applied to the commercially available common pressure sensitivity body paper back side and make with Kohler coater, or will contain organic Ultraluminescence complex, buffer, adhesive and auxiliary agent, it forms weight ratio, and to be followed successively by 10: 2～3: 0.6～1.5: 0.2～1 solid content be 25 ± 5% coating B, is uniformly applied on the commercially available common NCR with Kohler coater and makes with the paper back side.Owing on commercially available common NCR, contained colourless toner solutions composition, thereby of the present invention the going up with paper that above-mentioned two kinds of method for makings obtain is to form the same a kind of paper identical with function with the back side of paper is former.Be that same being applied under the commercially available common NCR with quadrat method of above-mentioned coating A made with the paper back side with paper in of the present invention, or above-mentioned coating B used to be applied in the commercially available common NCR with quadrat method make with the paper back side.Owing to contained colourless toner solutions composition with the paper back side is former in the commercially available common NCR, thus above-mentioned two kinds of method for makings obtain of the present invention in be the composition same a kind of paper identical with paper with function.The following paper of using that adopts commercially available common NCR down with paper of the present invention.
Be 5 ± 2g/m with paper and middle weight on the invention described above with the coating that forms behind the coating composition of the paper back side
2
Used organic ultraviolet fluorescence complex is by Eu
3+And/or Sm
3+With the complex of TTA (TTA) and/or trifluoroacetylacetone (TFA) and/or Hexafluoro acetone and/or diphenylguanidine and/or triphenyl phosphorous oxide and/or trioctylphosphine oxide and/or HEDTA (hydroxyethylethylene diamine tri-acetic acid) and/or EDTA (ethylenediamine tetra-acetic acid) and/or diphenyl-methane and/or two ethane and/or 2-naphthoyltrifluoroacetone composition or by Ga
3+And/or Sc
3+With the complex of HNT (2-hydroxyl-1-naphthalene (first) aldehyde-thiosemicarbazone) and/or the amino composition of salicylidene or by Ga
3+And/or Al
3+And/or In
3+With the complex of azo dyes composition or by Al
3+And/or Ga
3+And/or In
3+And/or La
3+And/or Y
3+And/or the complex of dysprosium ion and/or terbium ion and morin and/or quinoline and/or Luo Daming dyestuff and/or 4-sulfo group phenyl-2-methyl-pyrazolone-5 composition.
Used buffer is one or more the mixture in wheaten starch, farina, cellulose fine-powder, the wax pocket dispersion liquid; Adhesive therefor is one or more the mixture in styrene-butadiene latex, vinyl acetate latex, acrylic latex, soluble starch, polyvinyl alcohol, sodium carboxymethylcellulose, the methylcellulose; Adjuvant used is TiO
2, CaO, MgO, ZnO, CaCO
3, MgCO
3, Al (OH)
3, in one or more mixture; Used colourless colour former is the crystal violet lactones, to toluenesulfinic acid bis(dimethylamino)benzhydrol ester, benzoyl leucomethylene blue, 4,4 '-two (diethylamine) benzohydrol, spiro-pyrans, rhodamine lactone, indoles are red, one or more the mixture in the peacock green lactone; The solvent of colourless colour former is high boiling organic solvents such as diisopropyl naphthalene.
In the above-mentioned coating used organic ultraviolet fluorescence complex and colourless toner solutions with can wrap up with micro-capsule respectively earlier before other components are mixed, perhaps organic ultraviolet fluorescence complex is wrapped in microcapsules jointly with colourless toner solutions mixing.
The preparation method of the used organic ultraviolet fluorescence of the present invention complex knownly (sees D.E.Williams, Analytical Chemistry, 43 (1); B.Budesinsky, Anal.Chim.Acta, 42,455-465; T.Shigematsu, Anal.Chim.Acta, 46,101-106; R.P.Fisher, Analytical Chemistry, 43 (3), 454-), Gede Anti-fake Tech. Co., Nankai Univ. is existing to produce.Other component raw materials all can be from commercially available acquisition.
The preparation of microcapsules can be adopted melamine to add formaldehyde or urea to add the in-situ polymerization method of formaldehyde or adopt polyisocyanates to add known method such as the interfacial polymerization of amine or gelatin-gum arabic complex coacervation among the present invention.
The operating position of fluorescent pressure-sensitive carbon paper of the present invention is such: when last with paper on pen write or when typewriting with typewriter, the coating that contains the Ultraluminescence complex can come out, imbibition is middle with paper with down with on the paper to following one page, and reacts with developer and develop the color.The writing of these colour developings can demonstrate distinct fluorescence color under the irradiation of uviol lamp (common detect counterfeit money machine).
The invention has the beneficial effects as follows, fluorescent pressure-sensitive carbon paper of the present invention is in that to have kept common NCR fully easy to use, and the paper cleaning is attractive in appearance, can multi-jointly make carbon copies, when being applicable to plurality of advantages such as office automation, increased effective fluorescence falsification preventing function.Compare with the existing pressure-sensitive carbon paper that contains inorganic fluorescent pigment, because organic ultraviolet fluorescence complex of the present invention is easier to be littler by porphyrize, particle than inorganic fluorescent pigment, and dispersed, compatibility is all good, therefore, the coating fineness that is made by it is good, and uniform and stable.The slickness and the wear-resisting wiping of the pressure-sensitive copy paper and coating that makes with this coating are good, thus make implicit fluorescent duplicated writing link up, smooth.On the other hand, because inorganic fluorescent pigment kind is more single, the inorganic fluorescent pigment that higher fluorescent brightness is arranged all is jaundice, green, blue-fluorescence mostly, and organic ultraviolet fluorescence complex of the present invention is numerous in variety, jaundice look, green, blue-fluorescence not only arranged, the very strong red fluorescence of the brightness of sending is more arranged.Therefore, if in paper or be body paper with the coated paper that adds fluorescent whitening agent down with paper, adopts the coating that contains organic Ultraluminescence complex of the present invention to compare and uses the coating that contains inorganic fluorescent pigment that more obvious fluorescent effect is arranged.It is big to add the synthetic difficulty of organic ultraviolet fluorescence complex, raw material is difficult for obtaining, therefore, its anti-counterfeiting performance is far superior to the fluorescent pressure-sensitive carbon paper with existing other fluorescent material making, and its Application in Anti-counterfeiting in commercial, finance, financial field is become a reality.
The specific embodiment
Embodiment 1
Elder generation is with the mixture and the Eu of crystal violet lactone 5g and benzoyl leucomethylene blue 1.7g and 93.3g diisopropyl naphthalene
3+Make the microcapsules suspension with the in-situ polymerization method that melamine adds formaldehyde respectively with the complex 100g of trifluoroacetylacetone (TFA) and diphenylguanidine.Respectively half mixes to get above-mentioned two kinds of microcapsules suspensions, and adding 24.8g solid content is 50% styrene-butadiene latex, TiO
22g and 31g wheaten starch and suitable quantity of water, making total solid content is 25%, stirs at normal temperatures, makes stable coating.On Kohler coater, this coating is uniformly coated on 40g/m
2The back side of commercially available common pressure sensitivity body paper, promptly make going up of fluorescent pressure-sensitive carbon paper after the drying and use paper, its coating dry weight is 5 ± 1g/m
2Above-mentioned coating is uniformly coated on the back side of using paper under the commercially available common NCR, promptly makes the middle paper of using of fluorescent pressure-sensitive carbon paper after the drying, its coating dry weight is 5 ± 1g/m
2With going up of making thus with paper and in be of the present inventionly to use paper, file to constitute fluorescent pressure-sensitive carbon paper of the present invention down with paper and with the following of commercially available common NCR with paper.When writing or with after the typewriter typewriting with pen on paper last, in paper on and down with paper on show blue writing.With the UV-irradiation of 255～430nm, produce distinct red fluorescence in the blue writing.
Embodiment 2
The wheaten starch that replaces among the embodiment 1 with wax pocket dispersion liquid 166.8g is a buffer, and other prescriptions and technology are all with embodiment 1.The use result of prepared fluorescent pressure-sensitive carbon paper is with embodiment 1, but its resistance to water and the manifolding rate of transform improve.
Embodiment 3
2.25g crystal violet lactone and 0.75g benzoyl methylenum careuleum joined dissolving is uniformly dispersed in the 45g diisopropyl naphthalene, and then add 48gSm
3+With the complex of Hexafluoro acetone, stir, make to be uniformly dispersed, again this dispersion liquid is joined in the aqueous solution of styrene-maleic anhydride copolymer (PH=4) of 100g5%, high-speed stirred gets finely dispersed O/w emulsion.This emulsion is made the microcapsules suspension with the method for embodiment 1.In this microcapsules suspension, add solid content and be 50% 12.4g styrene-butadiene latex and weight percent concentration and be 10% 62g polyvinyl alcohol water solution and 31g cellulose fine-powder and TiO
23g and suitable quantity of water, making total solid content is 25%, stirs at normal temperatures, makes stable coating, and this coating is uniformly coated on 40g/m with Kohler coater
2The common pressure sensitivity body paper back side, promptly make going up of fluorescent pressure-sensitive carbon paper after the drying and use paper, its coating dry weight is 5 ± 1g/m
2With above-mentioned coating, use with quadrat method and evenly be coated onto the back side of using paper under the commercially available common NCR, make the middle paper of using of fluorescent pressure-sensitive carbon paper after the drying, its coating dry weight is 5 ± 1g/m
2With going up of making thus with paper and in be of the present inventionly to use paper down with paper and with the following of commercially available common NCR with paper, constitute fluorescent pressure-sensitive carbon paper of the present invention.Use and show that the result is with embodiment 1.
Embodiment 4
With 50gEu
3+With the complex of thiophene acetyl trifluoroacetone and triphenylphosphinc oxide, make the microcapsules suspension with the gelatin-gum arabic complex coacervation.Adding 12.5g solid content is 50% styrene-butadiene latex, 14g wheaten starch and the ultra-fine CaCO of 2g
3And suitable quantity of water, making total solid content is 25%, stirs at normal temperatures, makes stable coating.On Kohler coater, this coating is uniformly coated on going up of common NCR uses the paper back side, promptly make going up of fluorescent pressure-sensitive carbon paper after the drying and use paper, its coating dry weight is 5 ± 1g/m
2Above-mentioned coating used to be applied in the commercially available common NCR with quadrat method use the paper back side, make after the drying and use paper in of the present invention, its coating dry weight is 5 ± 1g/m
2Following being with paper of commercially available common NCR of the present inventionly down used paper, constitutes fluorescent pressure-sensitive carbon paper of the present invention thus.Use and show that the result is with embodiment 1.
Claims (3)
1. anti-fake fluorescent pressure-sensitive carbon paper, by the last paper of using, in with paper with time constitute with paper, it is characterized in that: of the present invention going up with paper is to contain organic ultraviolet fluorescence complex, colourless toner solutions, buffer, adhesive and auxiliary agent, it forms weight ratio 5: 5: 2 successively～3: 0.6～1.5: 0.2～1, solid content is 25 ± 5% coating A, be uniformly applied to the commercially available common pressure sensitivity body paper back side and make with Kohler coater, or will contain organic Ultraluminescence complex, buffer, adhesive and auxiliary agent, it is formed weight ratio and is followed successively by 10: 2～3: 0.6～1.5: 0.2～1, solid content is 25 ± 5% coating B, is uniformly applied on the commercially available common NCR with Kohler coater and makes with the back side of paper; Be above-mentioned coating A to be used to be applied under the commercially available common NCR with quadrat method make with paper in of the present invention, or above-mentioned coating B used to be applied to quadrat method make with the paper back side in the commercially available common NCR with the paper back side; The following paper of using that adopts commercially available common NCR down with paper of the present invention; Used organic ultraviolet fluorescence complex is by Eu
3+And/or Sm
3+With the complex of TTA and/or trifluoroacetylacetone (TFA) and/or Hexafluoro acetone and/or diphenylguanidine and/or triphenyl phosphorous oxide and/or trioctylphosphine oxide and/or hydroxyethylethylene diamine tri-acetic acid and/or ethylenediamine tetra-acetic acid and/or diphenyl-methane and/or two ethane and/or 2-naphthoyltrifluoroacetone composition or by Ga
3+And/or Sc
3+With the complex of 2-hydroxyl-1-naphthalene (first) aldehyde-thiosemicarbazone and/or the amino composition of salicylidene or by Ga
3+And/or Al
3+And/or In
3+With the complex of azo dyes composition or by Al
3+And/or Ga
3+And/or In
3+And/or La
3+And/or Y
3+And/or the complex of dysprosium ion and/or terbium ion and morin and/or quinoline and/or Luo Daming dyestuff and/or 4-sulfo group phenyl-2-methyl-pyrazolone-5 composition; Used buffer is one or more the mixture in wheaten starch, farina, cellulose fine-powder, the wax pocket dispersion liquid in the coating; Adhesive therefor is one or more the mixture in styrene-butadiene latex, vinyl acetate latex, acrylic latex, soluble starch, polyvinyl alcohol, sodium carboxymethylcellulose, the methylcellulose; Adjuvant used is TiO
2, CaO, MgO, ZnO, CaCO
3, MgCO
3, Al (OH)
3In one or more mixture; Used colourless colour former is the crystal violet lactones, to toluenesulfinic acid bis(dimethylamino)benzhydrol ester, benzoyl leucomethylene blue, 4,4 '-two (diethylamine) benzohydrol, spiro-pyrans, rhodamine lactone, indoles are red, one or more the mixture in the peacock green lactone; The solvent of used colourless colour former is a diisopropyl naphthalene.
2. according to the described anti-fake fluorescent pressure-sensitive carbon paper of claim 1, it is characterized in that in the present invention being 5 ± 2g/m with paper and middle weight with the coating that forms behind the coating composition of the paper back side
2
3. according to the described anti-fake fluorescent pressure-sensitive carbon paper of claim 1, it is characterized in that used organic ultraviolet fluorescence complex and colourless toner solutions with wrap up with micro-capsule respectively earlier before other components are mixed, perhaps organic ultraviolet fluorescence complex is wrapped in microcapsules jointly with colourless toner solutions mixing.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99106889A CN1094435C (en) | 1999-05-21 | 1999-05-21 | Pressure sensitive fluorescent anti-fake manifold paper |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99106889A CN1094435C (en) | 1999-05-21 | 1999-05-21 | Pressure sensitive fluorescent anti-fake manifold paper |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 96100339 Division CN1046905C (en) | 1996-01-23 | 1996-01-23 | Anti-fake fluorescent pressure-sensitive carbon paper and making method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1244465A CN1244465A (en) | 2000-02-16 |
| CN1094435C true CN1094435C (en) | 2002-11-20 |
Family
ID=5272571
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN99106889A Expired - Fee Related CN1094435C (en) | 1999-05-21 | 1999-05-21 | Pressure sensitive fluorescent anti-fake manifold paper |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1094435C (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103437248B (en) * | 2013-08-10 | 2016-02-24 | 广东冠豪高新技术股份有限公司 | A kind of anti-counterfeiting carbonless copy paper and production method with safety line |
| CN105133419A (en) * | 2015-09-06 | 2015-12-09 | 安徽金亿禾特种纸有限公司 | Waterproof carbon paper |
| CN105239452A (en) * | 2015-09-06 | 2016-01-13 | 安徽金亿禾特种纸有限公司 | Production process of carbon paper |
| CN105133425A (en) * | 2015-09-06 | 2015-12-09 | 安徽金亿禾特种纸有限公司 | Low-toxicity carbonless copy paper coating line |
| DE112019007066T5 (en) * | 2019-03-22 | 2021-12-23 | Robert Bosch Gesellschaft mit beschränkter Haftung | Forgery-proof paper product based on microstructure recognition, manufacturing processes and authentication processes therefor |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4570170A (en) * | 1983-10-06 | 1986-02-11 | Mitsubishi Paper Mills, Ltd. | Thermosensitive recording material |
| JPH04219266A (en) * | 1990-11-30 | 1992-08-10 | Oji Paper Co Ltd | Ink jet recording paper |
| WO1993025393A1 (en) * | 1992-06-10 | 1993-12-23 | Alfred Doi | Ultraviolet protective coatings for heat sensitive record materials |
-
1999
- 1999-05-21 CN CN99106889A patent/CN1094435C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4570170A (en) * | 1983-10-06 | 1986-02-11 | Mitsubishi Paper Mills, Ltd. | Thermosensitive recording material |
| JPH04219266A (en) * | 1990-11-30 | 1992-08-10 | Oji Paper Co Ltd | Ink jet recording paper |
| WO1993025393A1 (en) * | 1992-06-10 | 1993-12-23 | Alfred Doi | Ultraviolet protective coatings for heat sensitive record materials |
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| Publication number | Publication date |
|---|---|
| CN1244465A (en) | 2000-02-16 |
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