CN104988793A - Reversible photochromic anti-counterfeit paper and preparation method thereof - Google Patents
Reversible photochromic anti-counterfeit paper and preparation method thereof Download PDFInfo
- Publication number
- CN104988793A CN104988793A CN201510330867.8A CN201510330867A CN104988793A CN 104988793 A CN104988793 A CN 104988793A CN 201510330867 A CN201510330867 A CN 201510330867A CN 104988793 A CN104988793 A CN 104988793A
- Authority
- CN
- China
- Prior art keywords
- photo
- induced reversible
- account
- paper
- gross mass
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 230000002441 reversible effect Effects 0.000 title claims abstract description 91
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000000126 substance Substances 0.000 claims abstract description 42
- 238000000576 coating method Methods 0.000 claims abstract description 31
- 239000011248 coating agent Substances 0.000 claims abstract description 30
- 239000012876 carrier material Substances 0.000 claims abstract description 8
- 239000003973 paint Substances 0.000 claims abstract description 7
- 239000011122 softwood Substances 0.000 claims abstract description 5
- 238000001035 drying Methods 0.000 claims abstract description 3
- 239000002023 wood Substances 0.000 claims abstract description 3
- 239000000049 pigment Substances 0.000 claims description 47
- VTYYLEPIZMXCLO-UHFFFAOYSA-L calcium carbonate Substances [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 32
- 238000003756 stirring Methods 0.000 claims description 26
- 239000002270 dispersing agent Substances 0.000 claims description 18
- 239000005995 Aluminium silicate Substances 0.000 claims description 16
- 239000002174 Styrene-butadiene Substances 0.000 claims description 16
- 235000012211 aluminium silicate Nutrition 0.000 claims description 16
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 claims description 16
- 235000010216 calcium carbonate Nutrition 0.000 claims description 16
- 239000013530 defoamer Substances 0.000 claims description 16
- 238000000227 grinding Methods 0.000 claims description 16
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 16
- 239000004816 latex Substances 0.000 claims description 16
- 229920000126 latex Polymers 0.000 claims description 16
- 239000011115 styrene butadiene Substances 0.000 claims description 16
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 16
- 229920000578 graft copolymer Polymers 0.000 claims description 15
- 239000001254 oxidized starch Substances 0.000 claims description 14
- 235000013808 oxidized starch Nutrition 0.000 claims description 14
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 14
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 14
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 8
- 239000000758 substrate Substances 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 238000002845 discoloration Methods 0.000 claims description 7
- 238000004061 bleaching Methods 0.000 claims description 6
- 239000006185 dispersion Substances 0.000 claims description 6
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 claims description 6
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 claims description 6
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 claims description 6
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 claims description 4
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 claims description 4
- 229940048086 sodium pyrophosphate Drugs 0.000 claims description 4
- 235000019818 tetrasodium diphosphate Nutrition 0.000 claims description 4
- 229920002522 Wood fibre Polymers 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000002025 wood fiber Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims 2
- 230000014759 maintenance of location Effects 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 230000008859 change Effects 0.000 abstract description 2
- 238000001514 detection method Methods 0.000 abstract 1
- 239000002657 fibrous material Substances 0.000 abstract 1
- 238000005286 illumination Methods 0.000 description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000000463 material Substances 0.000 description 8
- 238000000034 method Methods 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 5
- 229920001661 Chitosan Polymers 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005242 forging Methods 0.000 description 2
- 239000011121 hardwood Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 235000019982 sodium hexametaphosphate Nutrition 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- BCHZICNRHXRCHY-UHFFFAOYSA-N 2h-oxazine Chemical compound N1OC=CC=C1 BCHZICNRHXRCHY-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000008236 heating water Substances 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- -1 isopropyl alcohols Chemical class 0.000 description 1
- 239000003094 microcapsule Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Landscapes
- Paper (AREA)
Abstract
The invention belongs to the technical field of anti-counterfeit paper manufacturing, and particularly discloses reversible photochromic anti-counterfeit paper and a preparation method thereof. The reversible photochromic anti-counterfeit paper is composed of a reversible color-shifting coating and paper-base carrier materials, the reversible color-shifting coating is composed of paint including reversible photochromic substances, and the paper-base carrier materials are formed by one or two fibrous materials of bleached softwood or bleached broadleaf wood through perpermaking. The preparation method comprises the steps that the reversible photochromic substances are added into the paint to be made into the reversible photochromic paint; the surfaces of the paper-base carrier materials are coated with a reversible photochromic paint, a reversible photochromic coating is formed after drying is conducted, and the reversible photochromic anti-counterfeit paper is obtained. According to the reversible photochromic anti-counterfeit paper and the preparation method thereof, the reversible photochromic substances are added into the paint to be applied to anti-counterfeit paper, and the reversible photochromic anti-counterfeit paper and the preparation method thereof have the advantages of being fast in detection, good in thermal stability, long in retention cycle, good in reversibility of color change and strong in anti-counterfeit capacity.
Description
Technical field
The invention belongs to cheque paper manufacturing technology field, be specifically related to a kind of photo-induced reversible color-changing anti-counterfeit paper and preparation method thereof.
Background technology
Along with development that is economic and society, kind and the demand of speciality paper product constantly increase, competition between commodity is also more and more fierce, and in order to prevent illegal competitor from copying independent research product, anti-counterfeiting technology is applied in the middle of the exploitation of new product more and more.With regard to existing anti-counterfeiting technology, be divided into physical security, chemistry is false proof and biology is false proof.Optical means wherein in physical method is widely used because of simple to operate, and wherein photochromism is comparatively common, and ultraviolet light induced variable color detects easy, and can repeatedly operate, and is current most widely used general and the most ripe photochromism anti-forging technology.But at photochromism anti-forging technical elements, the research in past makes coating or ink mainly with the form of microcapsules, the shortcomings such as realize multilayer reversible color, there is poor durability, aberration is few, and retention cycle is short.
Spiro-pyrans is as photochromic organic monomer, by illumination isomerization, form the reversible transition of colourless closed loop body spiro-pyrans and coloured open loop body, owing to having special photosensitive effect and fluorescent effect, become one of attractive host molecule in anti-fake material field.Spiropyran compounds closed loop configuration is relatively stable, and be not subject to extraneous factor (temperature, concentration, pH etc.) impact, and open loop structure is comparatively subject to extraneous factor impact, especially temperature influence is larger.Due to spiropyran compounds open loop structure poor heat stability, limit its large-scale application in field of photovoltaic materials.Therefore the current research to spiropyran compounds mainly concentrates on and solves heat irreversible.
Summary of the invention
For solving the shortcoming and defect part of prior art, primary and foremost purpose of the present invention is to provide a kind of photo-induced reversible color-changing anti-counterfeit paper.This photo-induced reversible color-changing anti-counterfeit paper, by adding photo-induced reversible electrochromic substance in coating, is coated in paper substrate surfaces of carrier materials and forms photo-induced reversible discoloration coating, gives paper photo-induced reversible color shifting properties, thus reaches false proof object.
Another object of the present invention is to the preparation method that above-mentioned photo-induced reversible color-changing anti-counterfeit paper is provided.
For achieving the above object, the present invention adopts following technical scheme:
A kind of photo-induced reversible color-changing anti-counterfeit paper, this photo-induced reversible color-changing anti-counterfeit paper is made up of photo-induced reversible discoloration coating and paper substrate carrier material, described photo-induced reversible discoloration coating is made up of the coating containing photo-induced reversible electrochromic substance, and paper substrate carrier material is manufactured paper with pulp by the one in bleached softwood wood or bleaching broad-leaved wood fiber raw material or two kinds and formed.
The described coating containing photo-induced reversible electrochromic substance is: comprise the pigment that 60 ~ 80 parts by mass kaolin and 20 ~ 40 parts by mass grinding calcium carbonates (GCC) form, and account for pigment gross mass 1% ~ 2% photo-induced reversible electrochromic substance, account for pigment gross mass 10% ~ 20% styrene-butadiene latex, account for pigment gross mass 0.2% ~ 1% dispersant, account for the oxidized starch of pigment gross mass 0 ~ 5% and account for the defoamer of pigment gross mass 0.2% ~ 0.5%.
Described photo-induced reversible electrochromic substance is shitosan spiro-pyrans graft copolymer.
Described shitosan spiro-pyrans graft copolymer can obtain in accordance with the following methods:
(1) according to document (Lin Youwen, Xu Chen, Lu Canhui. cm-chitosan synthesis condition research [J]. chemistry world, 2000,41 (8): 415-417.DOI:10.3969/j.issn.0367-6358.2000.08.006.) method described in prepares cm-chitosan: in there-necked flask, add shitosan 1 part of (parts by mass, down together), isopropyl alcohol 15 parts, mass concentration are 30%NaOH aqueous slkali 25 parts, heating water bath, stir and drip the acetic acid 6 parts (adding in 30min) be dissolved in 20 parts of isopropyl alcohols down, at 65 DEG C, react 8h; Reaction is finished, cooling, and point water-yielding stratum sticky matter, adds 50 parts of distilled water, fully stirs and uses mass fraction 10%HCl to regulate pH=7, elimination insoluble matter; The methyl alcohol adding 4 times amount in filtrate fully precipitates, and filters, and absolute ethanol washing precipitates, and solid, in the oven dry of 100 DEG C, baking oven, is ground to 200 orders, obtains cm-chitosan after oven dry;
(2) according to document (Liu Maodong. the research [D] of chitosan graft/doping spiro-pyrans, spiral shell oxazine and photochromic properties. Northwest Normal University, method 2005.DOI:10.7666/d.y721789.) prepares shitosan spiro-pyrans graft copolymer: take a certain amount of cm-chitosan, adds excessive SOCl
2, backflow 48h, NaOH solution is except tail gas; Distillation removing SOCl
2, obtain yellowish-brown powder chloride shitosan; Finally, get the spiro-pyrans of chloride shitosan and triplication, join in the excessive propanone solution containing a small amount of NaOH respectively, backflow 15h, after having reacted, in apparatus,Soxhlet's, use acetone, water washing respectively to cleaning solution no longer variable color, obtain shitosan spiro-pyrans graft copolymer.
Described dispersant is one or several the mixing in calgon, sodium pyrophosphate or Sodium Polyacrylate.
Described defoamer is polyoxyethylene ether.
The preparation method of above-mentioned photo-induced reversible color-changing anti-counterfeit paper, comprises the following steps:
(1) take raw material according to following ratio: comprise the pigment that 60 ~ 80 parts by mass kaolin and 20 ~ 40 parts by mass grinding calcium carbonates (GCC) form, and account for pigment gross mass 1% ~ 2% photo-induced reversible electrochromic substance, account for pigment gross mass 10% ~ 20% styrene-butadiene latex, account for pigment gross mass 0.2% ~ 1% dispersant, account for the oxidized starch of pigment gross mass 0 ~ 5% and account for the defoamer of pigment gross mass 0.2% ~ 0.5%;
(2) the photo-induced reversible electrochromic substance that step (1) weighs up is added in kaolin, grinding calcium carbonate (GCC), styrene-butadiene latex, dispersant, oxidized starch and defoamer the coating made containing photo-induced reversible electrochromic substance;
(3) paint containing photo-induced reversible electrochromic substance step (2) obtained, at paper substrate carrier surface, forms photo-induced reversible discoloration coating after drying, obtains described photo-induced reversible color-changing anti-counterfeit paper.
The concrete steps of described step (2) are: join in the water of 100 parts by mass by kaolin and grinding calcium carbonate (GCC), then add dispersant high speed dispersion 10 ~ 15min under 8000 ~ 15000r/min rotating speed; Add a part of defoamer again, stir 2 ~ 5min in 800 ~ 1500r/min; Add styrene-butadiene latex and oxidized starch again, stir 5 ~ 10min in 8000 ~ 15000r/min; Add another part defoamer again, stir 2 ~ 5min in 800 ~ 1500r/min; Finally add photo-induced reversible electrochromic substance, stir 5 ~ 10min in 8000 ~ 15000r/min, obtain the described coating containing photo-induced reversible electrochromic substance.
Compared with prior art, the present invention has the following advantages and beneficial effect:
(1) the invention provides a kind of photo-induced reversible color-changing anti-counterfeit paper and manufacture method thereof, the method adopts shitosan and spiro-pyrans graft copolymer to be used as photo-induced reversible electrochromic substance, conventional means is adopted to add in the middle of coating by this material, to the coatings of this material be contained on paper substrate again by conventional papermaking coating technique, produce the cheque paper with photo-induced reversible color shifting properties, simple to operate, be convenient to industrial applications.
(2) the present invention adopts shitosan spiro-pyrans graft copolymer as photo-induced reversible electrochromic substance, overcome spiropyran compounds open loop structure to heat-labile shortcoming, obtained photo-induced reversible color-changing anti-counterfeit paper has thermal reversibility, not by the impact of environment temperature, develop the color sensitive, easy to use, retention cycle is long.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described in further detail, but embodiments of the present invention are not limited thereto.
Embodiment 1
A preparation method for photo-induced reversible color-changing anti-counterfeit paper, comprises the following steps:
(1) take each raw material according to following ratio: the pigment be made up of 70 parts by mass kaolin and 30 parts by mass grinding calcium carbonates (GCC), and account for pigment gross mass 1% photo-induced reversible electrochromic substance shitosan spiro-pyrans graft copolymer, account for pigment gross mass 15% styrene-butadiene latex, account for pigment gross mass 0.5% sodium hexametaphosphate dispersant, account for the oxidized starch of pigment gross mass 3% and account for the defoamer polyoxyethylene ether of pigment gross mass 0.2%;
(2) kaolin step (1) weighed up and grinding calcium carbonate (GCC) join in the water of 100 parts by mass, then add sodium hexametaphosphate dispersant high speed dispersion 13min under 10000r/min rotating speed; Add half polyoxyethylene ether again, stir 3min in 1000r/min; Add styrene-butadiene latex and oxidized starch again, stir 8min in 10000r/min; Add second half polyoxyethylene ether again, stir 3min in 1000r/min; Finally add photo-induced reversible electrochromic substance shitosan spiro-pyrans graft copolymer, stir 8min in 10000r/min, obtain the coating containing photo-induced reversible electrochromic substance;
(3), on the paper base material of being manufactured paper with pulp to full bleaching softwood pulp by coater by the coating containing photo-induced reversible electrochromic substance obtained for step (2), photo-induced reversible color-changing anti-counterfeit paper after oven dry, is obtained.Under ultra violet lamp, this cheque paper is aobvious red, and under visible light illumination, this cheque paper reverts to rapidly again colourless.Be placed in by this cheque paper at 45 DEG C of temperature and take out after 24h, under ultra violet lamp, this cheque paper is aobvious red, and under visible light illumination, this cheque paper reverts to rapidly again colourless.After this cheque paper normal temperature is preserved 100 days, under ultra violet lamp, this cheque paper is aobvious red, and under visible light illumination, this cheque paper reverts to rapidly again colourless.
Embodiment 2
A preparation method for photo-induced reversible color-changing anti-counterfeit paper, comprises the following steps:
(1) take each raw material according to following ratio: the pigment be made up of 70 parts by mass kaolin and 30 parts by mass grinding calcium carbonates (GCC), and account for pigment gross mass 2% photo-induced reversible electrochromic substance shitosan spiro-pyrans graft copolymer, account for pigment gross mass 20% styrene-butadiene latex, account for the dispersant sodium pyrophosphate of pigment gross mass 0.5% and account for the defoamer polyoxyethylene ether of pigment gross mass 0.5%;
(2) kaolin step (1) weighed up and grinding calcium carbonate (GCC) join in the water of 100 parts by mass, then add dispersant sodium pyrophosphate high speed dispersion 10min under 15000r/min rotating speed; Add half polyoxyethylene ether again, stir 2min in 1500r/min; Add styrene-butadiene latex again, stir 10min in 8000r/min; Add second half polyoxyethylene ether again, stir 2min in 1500r/min; Finally add photo-induced reversible electrochromic substance shitosan spiro-pyrans graft copolymer, stir 5min in 15000r/min, obtain the coating containing photo-induced reversible electrochromic substance;
(3), on the paper base material of being manufactured paper with pulp to full bleaching softwood pulp by coater by the coating containing photo-induced reversible electrochromic substance obtained for step (2), photo-induced reversible color-changing anti-counterfeit paper after oven dry, is obtained.Under ultra violet lamp, this cheque paper is aobvious red, and under visible light illumination, this cheque paper reverts to rapidly again colourless.Be placed in by this cheque paper at 45 DEG C of temperature and take out after 24h, under ultra violet lamp, this cheque paper is aobvious red, and under visible light illumination, this cheque paper reverts to rapidly again colourless.After this cheque paper normal temperature is preserved 100 days, under ultra violet lamp, this cheque paper is aobvious red, and under visible light illumination, this cheque paper reverts to rapidly again colourless.
Embodiment 3
A preparation method for photo-induced reversible color-changing anti-counterfeit paper, comprises the following steps:
(1) take each raw material according to following ratio: the pigment be made up of 60 parts by mass kaolin and 40 parts by mass grinding calcium carbonates (GCC), and account for pigment gross mass 2% photo-induced reversible electrochromic substance shitosan spiro-pyrans graft copolymer, account for pigment gross mass 10% styrene-butadiene latex, account for pigment gross mass 0.2% dispersant Sodium Polyacrylate, account for the oxidized starch of pigment gross mass 5% and account for the defoamer polyoxyethylene ether of pigment gross mass 0.3%;
(2) kaolin step (1) weighed up and grinding calcium carbonate (GCC) join in the water of 100 parts by mass, then add dispersant Sodium Polyacrylate high speed dispersion 15min under 8000r/min rotating speed; Add half polyoxyethylene ether again, stir 5min in 800r/min; Add styrene-butadiene latex and oxidized starch again, stir 5min in 8000r/min; Add second half polyoxyethylene ether again, stir 2min in 1000r/min; Finally add photo-induced reversible electrochromic substance shitosan spiro-pyrans graft copolymer, stir 8min in 10000r/min, obtain the coating containing photo-induced reversible electrochromic substance;
(3), on the paper base material of being manufactured paper with pulp to full bleaching hardwood pulp by coater by the coating containing photo-induced reversible electrochromic substance obtained for step (2), photo-induced reversible color-changing anti-counterfeit paper after oven dry, is obtained.Under ultra violet lamp, this cheque paper is aobvious red, and under visible light illumination, this cheque paper reverts to rapidly again colourless.Be placed in by this cheque paper at 45 DEG C of temperature and take out after 24h, under ultra violet lamp, this cheque paper is aobvious red, and under visible light illumination, this cheque paper reverts to rapidly again colourless.After this cheque paper normal temperature is preserved 100 days, under ultra violet lamp, this cheque paper is aobvious red, and under visible light illumination, this cheque paper reverts to rapidly again colourless.
Embodiment 4
A preparation method for photo-induced reversible color-changing anti-counterfeit paper, comprises the following steps:
(1) take each raw material according to following ratio: the pigment be made up of 80 parts by mass kaolin and 20 parts by mass grinding calcium carbonates (GCC), and account for pigment gross mass 1.5% photo-induced reversible electrochromic substance shitosan spiro-pyrans graft copolymer, account for pigment gross mass 15% styrene-butadiene latex, account for pigment gross mass 1% dispersant Sodium Polyacrylate, account for the oxidized starch of pigment gross mass 2% and account for the defoamer polyoxyethylene ether of pigment gross mass 0.3%;
(2) kaolin step (1) weighed up and grinding calcium carbonate (GCC) join in the water of 100 parts by mass, then add dispersant Sodium Polyacrylate high speed dispersion 10min under 15000r/min rotating speed; Add half polyoxyethylene ether again, stir 3min in 1000r/min; Add styrene-butadiene latex and oxidized starch again, stir 5min in 15000r/min; Add second half polyoxyethylene ether again, stir 3min in 1000r/min; Finally add photo-induced reversible electrochromic substance shitosan spiro-pyrans graft copolymer, stir 5min in 15000r/min, obtain the coating containing photo-induced reversible electrochromic substance;
(3), on the paper base material of being manufactured paper with pulp to 50% bleaching needle-point leaf pulp and 50% bleached hardwood pulp by coater by the coating containing photo-induced reversible electrochromic substance obtained for step (2), photo-induced reversible color-changing anti-counterfeit paper after oven dry, is obtained.Under ultra violet lamp, this cheque paper is aobvious red, and under visible light illumination, this cheque paper reverts to rapidly again colourless.Be placed in by this cheque paper at 45 DEG C of temperature and take out after 24h, under ultra violet lamp, this cheque paper is aobvious red, and under visible light illumination, this cheque paper reverts to rapidly again colourless.After this cheque paper normal temperature is preserved 100 days, under ultra violet lamp, this cheque paper is aobvious red, and under visible light illumination, this cheque paper reverts to rapidly again colourless.
Above-described embodiment is the present invention's preferably embodiment; but embodiments of the present invention are not restricted to the described embodiments; change, the modification done under other any does not deviate from Spirit Essence of the present invention and principle, substitute, combine, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (7)
1. a photo-induced reversible color-changing anti-counterfeit paper, is characterized in that, this photo-induced reversible color-changing anti-counterfeit paper is made up of photo-induced reversible discoloration coating and paper substrate carrier material; Described photo-induced reversible discoloration coating is made up of the coating containing photo-induced reversible electrochromic substance, and paper substrate carrier material is manufactured paper with pulp by the one in bleached softwood wood or bleaching broad-leaved wood fiber raw material or two kinds and formed.
2. a kind of photo-induced reversible color-changing anti-counterfeit paper according to claim 1, it is characterized in that, the described coating containing photo-induced reversible electrochromic substance is: the pigment comprising 60 ~ 80 parts by mass kaolin and 20 ~ 40 parts by mass grinding calcium carbonates composition, and account for pigment gross mass 1% ~ 2% photo-induced reversible electrochromic substance, account for pigment gross mass 10% ~ 20% styrene-butadiene latex, account for pigment gross mass 0.2% ~ 1% dispersant, account for the oxidized starch of pigment gross mass 0 ~ 5% and account for the defoamer of pigment gross mass 0.2% ~ 0.5%.
3. a kind of photo-induced reversible color-changing anti-counterfeit paper according to claim 2, is characterized in that, described photo-induced reversible electrochromic substance is shitosan spiro-pyrans graft copolymer.
4. a kind of photo-induced reversible color-changing anti-counterfeit paper according to claim 2, is characterized in that, described dispersant is one or several the mixing in calgon, sodium pyrophosphate or Sodium Polyacrylate.
5. a kind of photo-induced reversible color-changing anti-counterfeit paper according to claim 2, it is characterized in that, described defoamer is polyoxyethylene ether.
6. the preparation method of a kind of photo-induced reversible color-changing anti-counterfeit paper according to claim 2, is characterized in that, comprise the following steps:
(1) take raw material according to following ratio: comprise 60 ~ 80 parts by mass kaolin and 20 ~ 40 parts by mass grinding calcium carbonates composition pigment, and account for pigment gross mass 1% ~ 2% photo-induced reversible electrochromic substance, account for pigment gross mass 10% ~ 20% styrene-butadiene latex, account for pigment gross mass 0.2% ~ 1% dispersant, account for the oxidized starch of pigment gross mass 0 ~ 5% and account for the defoamer of pigment gross mass 0.2% ~ 0.5%;
(2) the photo-induced reversible electrochromic substance that step (1) weighs up is added in kaolin, grinding calcium carbonate, styrene-butadiene latex, dispersant, oxidized starch and defoamer the coating made containing photo-induced reversible electrochromic substance;
(3) paint containing photo-induced reversible electrochromic substance step (2) obtained, at paper substrate carrier surface, forms photo-induced reversible discoloration coating after drying, obtains described photo-induced reversible color-changing anti-counterfeit paper.
7. preparation method according to claim 6, it is characterized in that, the concrete steps of described step (2) are: kaolin and grinding calcium carbonate are joined in the water of 100 parts by mass, then add dispersant high speed dispersion 10 ~ 15min under 8000 ~ 15000r/min rotating speed; Add a part of defoamer again, stir 2 ~ 5min in 800 ~ 1500r/min; Add styrene-butadiene latex and oxidized starch again, stir 5 ~ 10min in 8000 ~ 15000r/min; Add other a part of defoamer again, stir 2 ~ 5min in 800 ~ 1500r/min; Finally add photo-induced reversible electrochromic substance, stir 5 ~ 10min in 8000 ~ 15000r/min, obtain the described coating containing photo-induced reversible electrochromic substance.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510330867.8A CN104988793B (en) | 2015-06-15 | 2015-06-15 | A kind of photo-induced reversible color-changing anti-counterfeit paper and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510330867.8A CN104988793B (en) | 2015-06-15 | 2015-06-15 | A kind of photo-induced reversible color-changing anti-counterfeit paper and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104988793A true CN104988793A (en) | 2015-10-21 |
| CN104988793B CN104988793B (en) | 2017-03-08 |
Family
ID=54300676
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510330867.8A Expired - Fee Related CN104988793B (en) | 2015-06-15 | 2015-06-15 | A kind of photo-induced reversible color-changing anti-counterfeit paper and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104988793B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105837707A (en) * | 2016-04-13 | 2016-08-10 | 贵州省生物研究所 | High-molecular polymer containing spiropyran group and preparation method thereof and application thereof |
| CN107558302A (en) * | 2017-09-29 | 2018-01-09 | 成都新柯力化工科技有限公司 | A kind of fluorescent fiber cheque paper 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 |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003029003A1 (en) * | 2001-09-28 | 2003-04-10 | Giesecke & Devrient Gmbh | Security paper |
| CN101294359A (en) * | 2007-04-25 | 2008-10-29 | 广东冠豪高新技术股份有限公司 | Temperature-range false-proof non-carbon CF paper and producing method thereof |
| CN101649585A (en) * | 2009-07-24 | 2010-02-17 | 东莞市天盛特种纸制品有限公司 | Manufacture method of anti-counterfeiting variable color lines of paper |
| CN104004426A (en) * | 2014-06-17 | 2014-08-27 | 上海交通大学 | Polymer waterborne paint with corresponding features to ultraviolet light |
-
2015
- 2015-06-15 CN CN201510330867.8A patent/CN104988793B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003029003A1 (en) * | 2001-09-28 | 2003-04-10 | Giesecke & Devrient Gmbh | Security paper |
| CN101294359A (en) * | 2007-04-25 | 2008-10-29 | 广东冠豪高新技术股份有限公司 | Temperature-range false-proof non-carbon CF paper and producing method thereof |
| CN101649585A (en) * | 2009-07-24 | 2010-02-17 | 东莞市天盛特种纸制品有限公司 | Manufacture method of anti-counterfeiting variable color lines of paper |
| CN104004426A (en) * | 2014-06-17 | 2014-08-27 | 上海交通大学 | Polymer waterborne paint with corresponding features to ultraviolet light |
Non-Patent Citations (1)
| Title |
|---|
| 冯光华: "含螺吡喃、螺噁嗪类基团高分子聚合物的制备和光致变色性质研究", 《工程科技I辑》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105837707A (en) * | 2016-04-13 | 2016-08-10 | 贵州省生物研究所 | High-molecular polymer containing spiropyran group and preparation method thereof and application thereof |
| CN107558302A (en) * | 2017-09-29 | 2018-01-09 | 成都新柯力化工科技有限公司 | A kind of fluorescent fiber cheque paper and preparation method thereof |
| CN107558302B (en) * | 2017-09-29 | 2020-03-17 | 成都新柯力化工科技有限公司 | Fluorescent fiber anti-counterfeiting paper 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 |
|---|---|
| CN104988793B (en) | 2017-03-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104672733B (en) | A kind of wet sensitive colour changing antiforge function material and its preparation method and application | |
| Fu et al. | Temperature sensitive colour-changed composites | |
| Wang et al. | Stable and tunable plasmon resonance of molybdenum oxide nanosheets from the ultraviolet to the near-infrared region for ultrasensitive surface-enhanced Raman analysis | |
| CN103215029B (en) | Nanometer complex phase photochromic material and preparation method | |
| CN104988793A (en) | Reversible photochromic anti-counterfeit paper and preparation method thereof | |
| Ma et al. | Stimuli‐responsive photofunctional materials for green and security printing | |
| Abdollahi et al. | Photoluminescent nanoinks with multilevel security for quick authentication of encoded optical tags by sunlight: effective physicochemical parameters on responsivity, printability, and brightness | |
| Li et al. | A multifunctional coordination polymer for photochromic films, smart windows, inkless and erasable prints and anti-counterfeiting | |
| CN104312195A (en) | Disulfonic acid liquid florescent whitening agent composition, synthesis method and applications thereof | |
| Fan et al. | Customizable High-Contrast Optical Responses: Dual Photosensitive Colors for Smart Textiles | |
| CN104299511B (en) | Application of reversible photochromic wood anti-counterfeit label | |
| CN102965095A (en) | Inorganic/organic hybrid photochromic material, preparation method and application | |
| CN105303961B (en) | A kind of anti-counterfeit structure based on chemical reaction discoloration | |
| Wang et al. | Methyl red modified crystal violet lactone microcapsules for natural and composite fabrics producing a violet to orange-red effect at low temperature | |
| Zhang et al. | A metastable-state photoacid-based metal organic framework with multi-stimuli-responsive chromism | |
| Al-Qaysi et al. | A luminescent europium complex for wide-range pH sensors and sensor microtiterplates | |
| Li et al. | A novel photochromic complex based on a viologen ligand with rapid inkless and erasable printing, anti-counterfeiting and amine-selective responses | |
| Zhang et al. | Photoswitchable chemical sensing based on the colorimetric pH response of ring-opened naphthopyrans | |
| Gao et al. | Construction of durable and original color constancy photochromic cotton fabrics by a facile esterification strategy | |
| CN108300002A (en) | A kind of hypovanadic oxide-based thermochromism solid-liquid compound material and its preparation method and application | |
| Zhang et al. | Positive and negative photochromic and fluorescent color-changing cotton fabrics for information switching and encryption | |
| Pardo et al. | Reaching bistability in a photochromic spirooxazine embedded sol–gel hybrid coatings | |
| CN104341442A (en) | Reversible photochromic violagen terbium complex monocrystal and preparation method thereof | |
| Zhang et al. | Synthesis and application of a multifunctional fluorescent polymer based on coumarin | |
| CN102851771A (en) | Color-changing fabric and weaving method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20170308 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |