CN1046906C - Anti-fake fluorescent pressure-sensitive carbon paper generating invisible duplication handwriting and making method thereof - Google Patents
Anti-fake fluorescent pressure-sensitive carbon paper generating invisible duplication handwriting and making method thereof Download PDFInfo
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- CN1046906C CN1046906C CN96100340A CN96100340A CN1046906C CN 1046906 C CN1046906 C CN 1046906C CN 96100340 A CN96100340 A CN 96100340A CN 96100340 A CN96100340 A CN 96100340A CN 1046906 C CN1046906 C CN 1046906C
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- paper
- oil
- carbon paper
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- pressure
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Abstract
The present invention belongs to pressure-sensitive carbon paper. Colorless coating or printing ink containing organic ultraviolet fluorescent complexes are coated or printed on the back surfaces of the upper part and the middle part of the pressure-sensitive carbon paper, so that the duplication writing generated by hand writing or typewriting with the pressure-sensitive carbon paper is cryptomorphic and shows a fluorescent color only under the irradiation of ultraviolet light within a specific wavelength range. Consequently, the pressure-sensitive carbon paper can effectively prevent the fake signature and the alteration of written evidence. The pressure-sensitive carbon paper has advantages of simple and convenient use, beautiful paper surface and multiple duplications, and is novel carbon paper used for faking prevention for various fields of commerce, banking and finance.
Description
The invention belongs to the carbon paper that utilizes the feasible color of covering of pressure to show, promptly be commonly called as pressure-sensitive carbon paper, and preparation method thereof.
JP05-214278 has introduced a kind of pressure-sensitive carbon paper that scribbles common coloured organic fluorescent dye, and the duplication handwriting that this class carbon paper produces is all shown one's color, and the writing ratio of showing one's color is easier to by counterfeit or altered.JP59-98892 and JP04-363289 have introduced the pressure-sensitive carbon paper that scribbles inorganic fluorescent substance, though the duplication handwriting of its generation is stealthy, but the inorganic fluorescent substance dispersiveness is bad, the poor stability of formed coating system, the inorganic fluorescent substance kind is more single in addition, therefore raw material obtains easily, and the false proof usefulness of the fluorescent pressure-sensitive carbon paper of making of their is not high.
It is stealthy, numerous in variety the purpose of this invention is to provide a kind of duplication handwriting, and novel fluorescence pressure-sensitive carbon paper of efficient anti-counterfeiting performance and preparation method thereof is arranged.
The object of the present invention is achieved like this: the anti-fake fluorescent pressure-sensitive carbon paper that the present invention produces invisible duplication handwriting is by scribbling overleaf the colourless coating that contains organic Ultraluminescence complex or being printed on CB paper of the present invention (upper paper using) that the body paper of the colorless fluorescent printing ink that contains organic Ultraluminescence complex forms and scribbling or be not coated with adsorbent coating and the back side in the front and scribble the colourless coating that contains organic Ultraluminescence complex or be printed on the CF paper of the present invention (lower paper using) that body paper the CBF paper of the present invention (middle paper using) that forms and the body paper that scribbles or be not coated with the adsorbent coating in the front of the colorless fluorescent printing ink that contains organic Ultraluminescence complex form and consist of. The composition (weight ratio) that contains organic Ultraluminescence complex colorless coating is the organic ultraviolet fluorescence complex:buffer:adhesive:auxiliary agent=10:2～3:0.6～1.5:0.2～1, coating weight are 5 ± 2g/m2The composition of colorless fluorescent printing ink (weight ratio) is the organic ultraviolet fluorescence complex: wax: plasticizer: mineral oil or vegetable oil: the organic gel pledge: inorganic filler=15～40: 5～30: 1～10: 0～40: 10～40: 1～10; The composition of adsorbent coating (weight ratio) is an adsorbent: adhesive: inorganic filler=100: 10～20: 5～25.
Used organic ultraviolet fluorescence complex is by Eu
3+And/or Sm
3+With the complex of TTA (being TTA) and/or trifluoroacetylacetone (TFA) and/or Hexafluoro acetone and/or diphenylguanidine and/or triphenyl phosphorous oxide and/or trioctylphosphine oxide and/or HEDTA (being hydroxyethylethylene diamine tri-acetic acid) and/or EDTA (being 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 (being 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 (as fluorescence gallium or dodecyl fluorescence gallium) 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 formed of dysprosium ion and/or terbium ion and morin and/or quinoline (as oxine or 8-quinolinol or 5,7-dichloro-8-hydroxyquinoline) and/or 4-sulfo group phenyl-2-methyl-pyrazolone-5.
Used buffer is one or more the mixture in wheaten starch, farina, cellulose fine-powder, the wax pocket; Adhesive therefor is one or more the mixture in styrene-butadiene latex, vinyl acetate latex, acrylic latex, soluble starch, polyvinyl alcohol, sodium carboxymethylcellulose, ethyl cellulose, the methylcellulose; Adjuvant used is Al (OH)
3, TiO
2, CaO, MgO, CaCO
3, MgCO
3, one or more the mixture among the ZnO; Used wax is at least a in refining Brazil wax, decolouring montan wax, paraffin, rice wax, microwax, Tissuemat E, beeswax, candelila wax, the vaseline; Used plasticizer is xylenylphosphate, tricresyl phosphate (TGP) triphenyl phosphate (TPP), tributyl phosphate, dibutylphosphoric acid ester, the hard ester alcohol ester of di(2-ethylhexyl)phosphate, dioctyl phthalate, diisooctyl phthalate, dibutyl phthalate.At least a in repefral, dioctyl adipate (DOA), the di-n-octyl sebacate (DOS); Used mineral oil and/or vegetable oil are at least a in kerosene, light diesel, machine oil, soybean oil, linseed oil, coconut oil, peanut oil, castor oil, the rapeseed oil; Used organic gel pledge is at least a in rosin, Abietyl modified phenolic resin, zinc abietate, rosin acid calcium, ester gum, pentalyn, the ethylene-vinyl acetate copolymer; Used inorganic filler is Al (OH)
3, CaCO
3, BaSO
4, gloss white, ZnO, TiO
2, at least a in the lithopone; Sorbent used is one or more mixture in activated clay, bentonite, kaolin, the active land plaster.
The preparation method of the used organic ultraviolet fluorescence complex of the present invention had report in many documents, as D.E.Williams, and Analytical Chemistry, 43 (1); B.Budesinsky, Anal.Chim.Acta, 42,455-465; T.Shigematsu, Ahal.Chim.Acta, 46,101-106; R.P.Fisher, AnalyticalChemistry, 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.
Making fluorescent pressure-sensitive carbon paper of the present invention has following two kinds of methods, can select wherein any one for use.
First method, earlier the organic ultraviolet fluorescence complex is wrapped up with microcapsules, be equipped with buffer, adhesive and the auxiliary agent of regulation ratio consumption again, be made into the colourless coating (solid content is 25 ± 5%) of coating usefulness, with Kohler coater above-mentioned coating be uniformly applied to the commercially available common body paper back side respectively at last and promptly make CB paper of the present invention and CBF paper respectively with the positive body paper back side that has scribbled the adsorbent coating identical with CF paper.With adsorbent and adhesive and inorganic filler to scale, and add certain water gaging and mix that to make solid content be 45 ± 5% coating, again this coating evenly is coated onto commercially available common body paper front with knife type coater and promptly makes CF paper of the present invention, or be CF paper of the present invention directly with commercially available common body paper.
Second method, with bag or be not enclosed with the organic ultraviolet fluorescence complex of microcapsules and wax, plasticizer, mineral oil and/or vegetable oil, organic gel pledge and the inorganic filler of regulation ratio consumption mixes, grinds and make colorless fluorescent printing ink, with printing equipment this printing ink is imprinted on the commercially available common body paper back side respectively again and promptly makes CB paper of the present invention and CBF paper respectively with the body paper back side that the front has scribbled identical adsorbent coating with CF paper.The same first method of the making of CF paper.
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 methods such as the interfacial polymerization of amine or gelatin-gum arabic complex coacervation among the present invention.
When on CB paper of the present invention, writing or right with typewriter typewriting with pen, the colourless coating that contains the organic ultraviolet fluorescence complex can be transferred to down on one page paper, and by the CBF paper and the imbibition of CF paper institute of one page down, but under visible light, do not show any writing, when writing place or typewriting place, but demonstrate the fluorescent writing of distinct color immediately with uviol lamp (common detect counterfeit money machine) irradiation.
Compared with prior art, the advantage that the present invention has is: because the duplication handwriting that the present invention in use produces is stealthy, forge the personator and be difficult to find, almost stopped the generation of illegal activities such as personation signature, correction bill, improved false proof usefulness greatly.In addition 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 or the printing ink fineness that are made by it are good, and uniform and stable.Thereby the pressure-sensitive copy paper and coating that makes with this coating or printing ink or the slickness and the wear-resisting wiping of ink film are all good, thus make invisible fluorescent duplicated writing link up, smooth.On the other hand, because inorganic fluorescent pigment kind is more single, the emission spectrum scope is narrower, all be jaundice, green, blue-fluorescence mostly, and organic ultraviolet fluorescence complex of the present invention is numerous in variety, jaundice look, green, blue-fluorescence are not only arranged, and more has to send out hunting pink fluorescence.Therefore, if CBF or CF are body paper with the coated paper that adds fluorescent whitening agent, adopt the coating of organic Ultraluminescence complex that contains of the present invention than more obvious fluorescent effect being arranged with the coating that contains inorganic fluorescent pigment.It is big to add the synthetic difficulty of organic ultraviolet fluorescence complex, and raw material is difficult for obtaining, and therefore, its anti-counterfeiting performance is far superior to the fluorescent pressure-sensitive carbon paper with existing other fluorescent material making.
Embodiment 1
Get 45g Eu
3+Make the microcapsules suspension with the complex of trifluoroacetylacetone (TFA) and diphenylguanidine with the in-situ polymerization method that melamine adds formaldehyde, add 10.8g styrene-butadiene latex (50% solid content), 13.5g wheaten starch and suitable quantity of water (making total solid content is 25%) again, stir at normal temperatures and make uniform and stable coating.On Kohler coater, this coating is evenly coated 50g/m
2Commercially available common body paper on, make CB paper of the present invention after the drying, the coating dry weight is 5 ± 1g/m
2With activated clay, styrene-butadiene latex, CaCO
3, TiO
2With 100: 12.5: 5: 2 proportioning fed intake, and added the even suspension that suitable quantity of water is mixed with 50% solid content.On knife type coater this coating is evenly coated same body paper front, make CF paper of the present invention after the drying, coating quantitatively is 5 ± 1g/m
2Use method identical and coating to be coated with at the above-mentioned CF paper back side, promptly make CBF paper of the present invention with making CB paper.With above-mentioned CB paper, CBF paper, CF paper file constitutes fluorescent pressure-sensitive carbon paper of the present invention together.When writing with pen on the CB paper or, on CBF paper and CF paper, producing invisible duplication handwriting with after the typewriter typewriting, only ultraviolet ray (excitation wavelength be 255～430nm) irradiations down, just can write or the red fluorescence writing of distinctness is seen in manifolding place of typewriting.
Embodiment 2
Get In
3+Complex 25g with dodecyl fluorescence gallium is formed makes the microcapsules suspension with the gelatin-gum arabic complex coacervation, adds cellulose fine-powder 7.5g again, 10% polyvinyl alcohol water solution 30g, TiO
21g stirs at normal temperatures, makes stable coating.Below operation is all with example 1.The invisible duplication handwriting that is produced is shown as the yellow fluorescence writing under the UV-irradiation of 255～430nm excitation wavelength.
Embodiment 3
The microcapsules suspension that contains organic Ultraluminescence complex that preparation earlier and example 1 are identical, and it is spray dried to the solid microscapsule powder.Get this solid microscapsule powder of 12.5g, join by 10g rosin phenolic resin, 5g soybean oil, 8g kerosene, 5.5g Brazil wax, 3g atoleine, the hard ester alcohol ester of 4g di(2-ethylhexyl)phosphate and 2gTiO
2In the link stuff of being formed, mix, grind and make printing ink, print to 50g/m with printing machine at last
2The pressure sensitivity body paper back side promptly make CB paper of the present invention.The method for making of CF paper is with embodiment 1.This printing ink is printed to the CF paper back side promptly make CBF paper of the present invention.Using method is with embodiment 1, and the invisible duplication handwriting that is produced is to demonstrate red fluorescence under the ultraviolet ray irradiation of 255～430nm in excitation wavelength.
Embodiment 4
Get Ga
3+With the complex 12.5g of 8-quinoline mercaptan, join by 8g rosin triglyceride, enduring of 3g linseed oil, 7g machine oil, 4g paraffin, 3.5g decolouring montan wax, 3g coconut oil, 2g atoleine, 3g vaseline, 2g diisooctyl phthalate, 2gCaCO
3In the link stuff of being formed, stir, grind and make printing ink, this printing ink printed to 45g/m with printing machine
2The pressure sensitivity body paper on promptly make CB paper of the present invention.Below operation is with embodiment 3.Using method is with embodiment 1.The invisible duplication handwriting that is produced demonstrates green fluorescence under the UV-irradiation of 255～430nm excitation wavelength.
Embodiment 5
With the wheaten starch 13.5g among the wax pocket dispersion liquid 35.5g replacement embodiment 1, other are all with embodiment 1.But the resistance to water of the fluorescent pressure-sensitive carbon paper that makes thus and the manifolding rate of transform are more excellent.
Claims (1)
1, a kind of anti-fake fluorescent pressure-sensitive carbon paper that produces invisible duplication handwriting,, it is characterized in that with paper, middle with paper with constitute down by last with paper: of the present invention go up with paper be with by bag or the organic ultraviolet fluorescence complex that is not enclosed with microcapsules and wax, plasticizer, mineral oil and/or vegetable oil, organic gel pledge and inorganic filler by 15～40: 5～30: 1～10: 10～40: 10～40: 1～10 weight ratio form mix after the colorless fluorescent printing ink made of grinding be imprinted on the commercially available common body paper back side with printing equipment and make; Of the present invention down with paper be with by adsorbent, adhesive and inorganic filler by 100: 10～20: 5～25 weight ratio, adding suitable quantity of water, to mix the solid content of making be that 45 ± 5% adsorbent coating material is coated onto evenly with knife type coater that commercially available common body paper is positive to be made, and is to descend to use paper with commercially available common body paper directly perhaps; In of the present invention with paper by time making with the above-mentioned colorless fluorescent printing ink of the back up of paper of the present invention; Wherein used organic ultraviolet fluorescence complex is by Eu
3+And/or Sm
3+With the complex of TTA and/or trifluoroacetylacetone (TFA) 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 4-sulfo group phenyl-2-methyl-pyrazolone-5 composition; Used wax is at least a in refining Brazil wax, decolouring montan wax, paraffin, rice wax, microwax, Tissuemat E, beeswax, candelila wax, the vaseline; Used plasticizer is at least a in xylenylphosphate, tricresyl phosphate, triphenyl phosphate, tributyl phosphate, dibutylphosphoric acid ester, the hard ester alcohol ester of di(2-ethylhexyl)phosphate, dibutyl phthalate, diisooctyl phthalate, DOP dioctyl phthalate, repefral, dioctyl adipate, the di-n-octyl sebacate; Used mineral oil and/or vegetable oil are at least a in kerosene, light diesel, machine oil, soybean oil, linseed oil, coconut oil, peanut oil, castor oil, the rapeseed oil; Used organic gel pledge is at least a in rosin, rosin modified phenolic resin, zinc abietate, rosin acid calcium, ester gum, pentalyn, the ethylene-vinyl acetate copolymer; Used inorganic filler is Al (OH)
3, CaCO
3, BaSO
4, gloss white, ZnO, TiO
2, at least a in the lithopone; Sorbent usedly be in activated clay, the swelling, one or more the mixture among the high mountain range scholar, active land plaster.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96100340A CN1046906C (en) | 1996-01-23 | 1996-01-23 | Anti-fake fluorescent pressure-sensitive carbon paper generating invisible duplication handwriting and making method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96100340A CN1046906C (en) | 1996-01-23 | 1996-01-23 | Anti-fake fluorescent pressure-sensitive carbon paper generating invisible duplication handwriting and making method thereof |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN99106888A Division CN1094434C (en) | 1999-05-21 | 1999-05-21 | Pressure sensitive manifold paper capable of producing invisible fluorescent duplicated anti-fake writing |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1135421A CN1135421A (en) | 1996-11-13 |
| CN1046906C true CN1046906C (en) | 1999-12-01 |
Family
ID=5116543
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN96100340A Expired - Fee Related CN1046906C (en) | 1996-01-23 | 1996-01-23 | Anti-fake fluorescent pressure-sensitive carbon paper generating invisible duplication handwriting and making method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1046906C (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102310023A (en) * | 2010-06-30 | 2012-01-11 | 乐凯集团第二胶片厂 | Manufacture method of microcapsule display panel |
| CN103113782B (en) * | 2013-02-05 | 2014-10-01 | 陕西科技大学 | Preparation process of titanium dioxide containing double-wavelength light absorption water-based anti-forgery ink additive |
| 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 |
| CN106398305B (en) * | 2016-08-30 | 2017-11-07 | 苏州丰倍生物科技有限公司 | A kind of environment-friendly type leuco dye vegetable oil solvent |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4388362A (en) * | 1980-10-17 | 1983-06-14 | Ricoh Co., Ltd. | Released heat-sensitive recording paper |
| CN86100977A (en) * | 1985-02-05 | 1986-08-06 | 希巴-盖吉股份公司 | Laser marking of pigmented systems |
| CN1038972A (en) * | 1988-06-25 | 1990-01-24 | 朱华 | A kind of pressure-sensing carbon paper and production method thereof |
| JPH04219266A (en) * | 1990-11-30 | 1992-08-10 | Oji Paper Co Ltd | Ink jet recording paper |
| JPH05214278A (en) * | 1992-01-31 | 1993-08-24 | Kanzaki Paper Mfg Co Ltd | Capsuled ink composition and sheet |
-
1996
- 1996-01-23 CN CN96100340A patent/CN1046906C/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4388362A (en) * | 1980-10-17 | 1983-06-14 | Ricoh Co., Ltd. | Released heat-sensitive recording paper |
| CN86100977A (en) * | 1985-02-05 | 1986-08-06 | 希巴-盖吉股份公司 | Laser marking of pigmented systems |
| CN1038972A (en) * | 1988-06-25 | 1990-01-24 | 朱华 | A kind of pressure-sensing carbon paper and production method thereof |
| JPH04219266A (en) * | 1990-11-30 | 1992-08-10 | Oji Paper Co Ltd | Ink jet recording paper |
| JPH05214278A (en) * | 1992-01-31 | 1993-08-24 | Kanzaki Paper Mfg Co Ltd | Capsuled ink composition and sheet |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1135421A (en) | 1996-11-13 |
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