CN101666060B - Altering prevention paper and preparing method thereof - Google Patents
Altering prevention paper and preparing method thereof Download PDFInfo
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- CN101666060B CN101666060B CN200910176476XA CN200910176476A CN101666060B CN 101666060 B CN101666060 B CN 101666060B CN 200910176476X A CN200910176476X A CN 200910176476XA CN 200910176476 A CN200910176476 A CN 200910176476A CN 101666060 B CN101666060 B CN 101666060B
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Abstract
The invention relates to altering prevention paper and a preparation method thereof, which can be widely applied to altering prevention and anti-counterfeiting of negotiable securities, certificates, bills and secret documents and the like. The altering prevention paper contains altering-prevention agents and/or anti-counterfeiting substances, the using amount of the altering-prevention agents is0.003-0.2 percent according to the total weight of the altering-prevention agents, and the altering-prevention agent is phthalocyanine dye, azoic compound and anthraquinone compound; the altering prevention paper contains 0.03-3g anti-counterfeiting substances in every square meter, the anti-counterfeiting substances are cobalt compound and inducting agents containing manganese ions, the mole ratio of the cobalt compound and inducting agents is 1:1-10:1. The altering prevention paper can be manufactured on a common fourdrinier wire paper machine and a mould paper machine and is compatible with anti-counterfeiting characteristics such as watermark, fine line, special fiber and the like. The altering prevention paper has good inductivity and durability to correction fluid such as organic solvent, acid, alkali, oxidants, reducing agents and erasing fluid, can effectively prevent altering and counterfeiting, and has the characteristics of public identification and being difficult to counterfeit.
Description
Technical field
The present invention relates to a kind of altering prevention paper and preparation method thereof, this altering prevention paper can be widely used in the anti-correction of security, certificate, bill, classified document etc. and false proof.
Background technology
Along with the progress and the expanding economy of science and technology, many marketable securities, certificate, classified document have been subjected to being altered the threat of forging, and many lawless persons utilize and alter the forgery means, carry out fraud, have upset normal financial order and civil order.A series of anti-correction technology is arisen at the historic moment, and compound film technology is a purpose stop to alter to forge, and the safety ink protection is printed on the information on the paper, but these still can not tackle the problem at its root, and has only the use altering prevention paper, just can reach the purpose for the treatment of both principal and secondary aspect of disease.So altering prevention paper arises at the historic moment.
The approach that information is endowed on the paper mainly contains: press printing; Printer prints; Scan and copy; Give by means of stationery etc. by people's hand.The reproduction of information realizes on paper by printing ink and ink.Printing ink and ink all form by colouring agent (dyestuff, pigment etc.) is dissolved or is dispersed in the solvent that is dissolved with binder, stabilizing agent and other auxiliary agents.Classify with regard to used solvent, have water-based, oily ink (printing ink) to distinguish.Used dyestuff has ACID DYES, basic-dyeable fibre, direct dyes etc.Correction fluid be exactly by with printing ink, ink generation physical-chemical reaction, its color is thin out, even a class material that disappears.At present, the commodity of existing correction fluid are many on the market, how with eradicator, opaquing fluid etc. as trade name.Though trade name is not quite similar, but on its chemical composition, mainly comprise following a few class material: organic solvent, mainly comprise ethanol, acetone, ethyl acetate, benzene, turpentine wet goods organic solvent, be mainly used in correction to oily ink (printing ink) information of giving; Acid, alkali mainly are hydrochloric acid, oxalic acid, NaOH etc., and the auxiliary constituent of correction fluid is with organic solvent, oxidant, reductant acting in conjunction; Oxidant, reductant mainly are hydrogen peroxide, hypochlorite (sodium), potassium permanganate, sodium hydrogensulfite etc., are used for the correction of information that water-base ink (printing ink) etc. is given.
Altering prevention paper is started to walk early abroad, and development is fast, and the altering prevention paper that appears at France the earliest is by dosing aldehydes matter in paper, still, because aldehydes matter has oxidisability, making that this paper life-span is very short.Afterwards, states such as Japan, Britain, Germany had taked to add aromatic series organic matters such as the complex compound, acid-base indicator, tannic acid, phenols of some metal etc., existed false proof narrow range, and were only effective to a certain class correction fluid; The paper life-span is short; In atmospheric environment, shortcoming such as easy to change.The progress and the expanding economy of science and technology, an urgent demand improves the quality of altering prevention paper.
Therefore, develop a kind of false proof wide ranges, the paper life-span is long, and is not easy to change, and the altering prevention paper of good stability just becomes the technical barrier that those skilled in the art's urgent need will solve.
Summary of the invention
One of purpose of the present invention is to provide a kind of altering prevention paper.
For achieving the above object, the present invention takes following technical scheme:
Scheme one
A kind of altering prevention paper is characterized in that: contain the anti-agent of altering in altering prevention paper, by the gross weight of altering prevention paper, the consumption of described anti-correction agent is 0.003%-0.2%, is preferably 0.003-0.1%; Described anti-correction agent be light resistance greater than 2 grades, heat resistance is greater than 110 ℃ solvent dye.
A kind of optimal technical scheme is characterized in that: described anti-correction agent is phthalein mountain valley with clumps of trees and bamboo dyestuff, azo-compound, anthraquinone compounds or other dyestuff, and described phthalein mountain valley with clumps of trees and bamboo dyestuff is blue 67 dyestuffs or blue 70 dyestuffs; Described azo-compound is yellow 146 dyestuffs, yellow 88 dyestuffs, yellow 25 dyestuffs, yellow 89 dyestuffs, orange 11 dyestuffs, brown 44 dyestuffs, red 130 dyestuffs, red 233 dyestuffs, red 125 dyestuffs, red 122 dyestuffs, pink 127 dyestuffs, black 29 dyestuffs, solvent yellow 19 (pure molten everbright fast yellow) or transparent yellow 101; Described anthraquinone compounds is blue 136 dyestuffs, transparent violet B, transparent violet RR, transparent plastic indigo plant 501, transparent blue RP, solvent green 601, transparent green 5B or Oil Violet 401; Described other dyestuff is transparent red EG, transparent orange 3G or transparent yellow 3G.
A kind of optimal technical scheme is characterized in that: also contain retention agent in the described altering prevention paper, by the gross weight of altering prevention paper, the consumption of described retention agent is 0.6%-10%, is preferably 0.6-5%; Described retention agent is melamine resin (MF), expoxy propane or cationic starch etc.
Scheme two
A kind of altering prevention paper is characterized in that: contain anti-counterfeiting substances in altering prevention paper, contain 0.03-3 gram anti-counterfeiting substances in every square metre of altering prevention paper; Described anti-counterfeiting substances is cobalt compound and the induction agent that contains manganese ion, and the mol ratio of the two is 1: 1-10: 1.
A kind of optimal technical scheme is characterized in that: described cobalt compound is cobaltous sulfate, cobalt nitrate or cobalt chloride; The described induction agent that contains manganese ion is manganese sulfate, manganese nitrate, manganese carbonate or manganese chloride.
Described anti-counterfeiting substances can boil with Cypres such as PVA, starch, gelatin, also can dissolve the back and add in the surface size; The consumption of false proof reagent is relevant with main sizing material character, page characteristic etc., according to the difference of main sizing material character, can should guarantee that still every square metre one-tenth paper contains the 0.03 false proof reagent that restrains at least between the 2%-12% of surface size (weight).Suggestion uses PVA, gelatin to be main sizing material applying glue, if use the starch applying glue, preferably uses plasm-glue-blending earlier.
Three of scheme
A kind of altering prevention paper, it is characterized in that: in altering prevention paper, contain anti-agent and the anti-counterfeiting substances of altering, gross weight by altering prevention paper, the anti-consumption of altering agent is 0.003%-0.2%, be preferably 0.003-0.1%, described anti-correction agent be light resistance greater than 2 grades, heat resistance is greater than 110 ℃ solvent dye; Contain 0.03-3 gram anti-counterfeiting substances in every square metre of altering prevention paper, described anti-counterfeiting substances is cobalt compound and the induction agent that contains manganese ion, and the mol ratio of the two is 1: 1-10: 1.
A kind of optimal technical scheme is characterized in that: described anti-correction agent is phthalein mountain valley with clumps of trees and bamboo dyestuff, azo-compound, anthraquinone compounds or other dyestuff, and described phthalein mountain valley with clumps of trees and bamboo dyestuff is blue 67 dyestuffs or blue 70 dyestuffs; Described azo-compound is yellow 146 dyestuffs, yellow 88 dyestuffs, yellow 25 dyestuffs, yellow 89 dyestuffs, orange 11 dyestuffs, brown 44 dyestuffs, red 130 dyestuffs, red 233 dyestuffs, red 125 dyestuffs, red 122 dyestuffs, pink 127 dyestuffs, black 29 dyestuffs, solvent yellow 19 (pure molten everbright fast yellow) or transparent yellow 101; Described anthraquinone compounds is blue 136 dyestuffs, transparent violet B, transparent violet RR, transparent plastic indigo plant 501, transparent blue RP, solvent green 601, transparent green 5B or Oil Violet 401; Described other dyestuff is transparent red EG, transparent orange 3G or transparent yellow 3G.
A kind of optimal technical scheme is characterized in that: described cobalt compound is cobaltous sulfate, cobalt nitrate or cobalt chloride; The described induction agent that contains manganese ion is manganese sulfate, manganese nitrate, manganese carbonate or manganese chloride.
A kind of optimal technical scheme is characterized in that: also contain retention agent in the described altering prevention paper, by the gross weight of altering prevention paper, the consumption of described retention agent is 0.6%-10%, is preferably 0.6-5%; Described retention agent is melamine resin (MF), expoxy propane or cationic starch etc.
Another object of the present invention is to provide a kind of preparation method of altering prevention paper.
Scheme one
A kind of manufacture method of altering prevention paper is characterized in that: will prevent altering agent and join in the paper pulp, and after mixing, produce according to common offset paper technology; Described anti-correction agent be light resistance greater than 2 grades, heat resistance is greater than 110 ℃ solvent dye, by the gross weight of altering prevention paper, the anti-consumption of altering agent is 0.003%-0.2%, is preferably 0.003-0.1%.
A kind of optimal technical scheme is characterized in that: also retention agent is proportionally joined in the paper pulp, by the gross weight of altering prevention paper, the consumption of retention agent is 0.6%-10%, is preferably 0.6-5%; Described retention agent is melamine resin (MF), expoxy propane or cationic starch etc.Retention agent can improve anti-the keeping of agent of altering.
A kind of optimal technical scheme is characterized in that: described anti-correction agent is located to add in the paper pulp in troughing, machine chest, mediation pond or the pond of manufacturing paper with pulp etc., and after mixing, online is manufactured paper with pulp.
Scheme two
A kind of preparation method of altering prevention paper is characterized in that: will prevent altering agent and join in the coating fluid, and after mixing, produce according to art paper technology; Described anti-correction agent be light resistance greater than 2 grades, heat resistance is greater than 110 ℃ solvent dye, by the gross weight of altering prevention paper, the anti-consumption of altering agent is 0.003%-0.2%, is preferably 0.003-0.1%.
Among the preparation method of scheme one and scheme two, described anti-correction agent is phthalein mountain valley with clumps of trees and bamboo dyestuff, azo-compound, anthraquinone compounds or other dyestuff, and described phthalein mountain valley with clumps of trees and bamboo dyestuff is blue 67 dyestuffs or blue 70 dyestuffs; Described azo-compound is yellow 146 dyestuffs, yellow 88 dyestuffs, yellow 25 dyestuffs, yellow 89 dyestuffs, orange 11 dyestuffs, brown 44 dyestuffs, red 130 dyestuffs, red 233 dyestuffs, red 125 dyestuffs, red 122 dyestuffs, pink 127 dyestuffs, black 29 dyestuffs, solvent yellow 19 (pure molten everbright fast yellow) or transparent yellow 101; Described anthraquinone compounds is blue 136 dyestuffs, transparent violet B, transparent violet RR, transparent plastic indigo plant 501, transparent blue RP, solvent green 601, transparent green 5B or Oil Violet 401; Described other dyestuff is transparent red EG, transparent orange 3G or transparent yellow 3G.
Scheme three
A kind of preparation method of altering prevention paper is characterized in that: anti-counterfeiting substances is joined in the surface size, after mixing, produce according to common offset paper technology; Contain 0.03-3 gram anti-counterfeiting substances in every square metre of altering prevention paper, described anti-counterfeiting substances is cobalt compound and the induction agent that contains manganese ion, and the mol ratio of the two is 1: 1-10: 1.
Described anti-counterfeiting substances can boil with Cypres such as PVA, starch, gelatin, also can dissolve the back and add in the surface size; The consumption of false proof reagent is relevant with main sizing material character, page characteristic etc., according to the difference of main sizing material character, can should guarantee that still every square metre one-tenth paper contains the 0.03 false proof reagent that restrains at least between the 2%-12% of surface size (weight).Suggestion uses PVA, gelatin to be main sizing material applying glue, if use the starch applying glue, preferably uses plasm-glue-blending earlier.
Scheme four
A kind of manufacture method of altering prevention paper is characterized in that: anti-counterfeiting substances is joined in the coating fluid, after mixing, produce according to art paper technology; Contain 0.03-3 gram anti-counterfeiting substances in every square metre of altering prevention paper, described anti-counterfeiting substances is cobalt compound and the induction agent that contains manganese ion, and the mol ratio of the two is 1: 1-10: 1.
In the manufacture method of scheme three and scheme four, described cobalt compound is cobaltous sulfate, cobalt nitrate or cobalt chloride; The described induction agent that contains manganese ion is manganese sulfate, manganese nitrate, manganese carbonate or manganese chloride.
Scheme five
A kind of manufacture method of altering prevention paper is characterized in that: will prevent altering agent and join in the paper pulp, and mix; Anti-counterfeiting substances is joined in the surface size, produce according to common offset paper technology; Described anti-correction agent be light resistance greater than 2 grades, heat resistance is greater than 110 ℃ solvent dye, by the gross weight of altering prevention paper, the anti-consumption of altering agent is 0.003%-0.2%, is preferably 0.003-0.1%; Contain 0.03-3 gram anti-counterfeiting substances in every square metre of altering prevention paper; Described anti-counterfeiting substances is cobalt compound and the induction agent that contains manganese ion, and the mol ratio of the two is 1: 1-10: 1.
A kind of optimal technical scheme is characterized in that: also retention agent is proportionally joined in the paper pulp, by the gross weight of altering prevention paper, the consumption of retention agent is 0.6%-10%, is preferably 0.6-5%; Described retention agent is melamine resin (MF), expoxy propane or cationic starch etc.Retention agent can improve anti-the keeping of agent of altering.
A kind of optimal technical scheme is characterized in that: described anti-correction agent is located to add in the paper pulp in troughing, machine chest, mediation pond or the pond of manufacturing paper with pulp etc., and after mixing, online is manufactured paper with pulp.
Scheme six
A kind of manufacture method of altering prevention paper is characterized in that: will prevent altering agent and anti-counterfeiting substances joins in the coating fluid, and after mixing, produce according to art paper technology; Described anti-correction agent be light resistance greater than 2 grades, heat resistance is greater than 110 ℃ solvent dye, by the gross weight of altering prevention paper, the anti-consumption of altering agent is 0.003%-0.2%, is preferably 0.003-0.1%; Contain 0.03-3 gram anti-counterfeiting substances in every square metre of altering prevention paper, described anti-counterfeiting substances is cobalt compound and the induction agent that contains manganese ion, and the mol ratio of the two is 1: 1-10: 1.
In the manufacture method of scheme five and scheme six, described anti-correction agent is phthalein mountain valley with clumps of trees and bamboo dyestuff, azo-compound, anthraquinone compounds or other dyestuff, and described phthalein mountain valley with clumps of trees and bamboo dyestuff is blue 67 dyestuffs or blue 70 dyestuffs; Described azo-compound is yellow 146 dyestuffs, yellow 88 dyestuffs, yellow 25 dyestuffs, yellow 89 dyestuffs, orange 11 dyestuffs, brown 44 dyestuffs, red 130 dyestuffs, red 233 dyestuffs, red 125 dyestuffs, red 122 dyestuffs, pink 127 dyestuffs, black 29 dyestuffs, solvent yellow 19 (pure molten everbright fast yellow) or transparent yellow 101; Described anthraquinone compounds is blue 136 dyestuffs, transparent violet B, transparent violet RR, transparent plastic indigo plant 501, transparent blue RP, solvent green 601, transparent green 5B or Oil Violet 401; Described other dyestuff is transparent red EG, transparent orange 3G or transparent yellow 3G.
Described cobalt compound is cobaltous sulfate, cobalt nitrate or cobalt chloride; The described induction agent that contains manganese ion is manganese sulfate, manganese nitrate, manganese carbonate or manganese chloride.
The basic principle of technique scheme is in the manufacture process of paper, add specific anti-correction and/or anti-counterfeiting substances, being somebody's turn to do anti-correction and/or anti-counterfeiting substances can react with correction fluid, like this, when the people attempts to alter information on the paper, will stay obvious, lasting, visible vestige, thereby be easy to be identified.
According to different printing instructions for use and false proof requirement (means and the material of giving information determine), select different materials for use or be used in combination mutually.For coated paper, anti-correction agent and anti-counterfeiting substances can join in the coating fluid, are coated in the page surface equably by coating.After becoming paper, can detect observation paper change color with organic solvent, acid, alkali, oxidant, reductant.Compare with the aromatic series organic matter that other altering prevention papers adopt, have environmental protection, do not influence paper durability, use advantages such as storage condition is loose.Can not influence the result of use of papermaking auxiliary materials such as general sizing agent, filler.Be suitable for the large-scale production of pulping and paper-making fully.
The invention has the advantages that:
Altering prevention paper of the present invention can be realized manufacturing paper with pulp on common fourdrinier wire, cylinder mould machine, can with anti-counterfeiting characteristic compatibilities such as watermark, safety line, special fibre.Can combine with functional paper production technologies such as pressure-sensitive, temperature-sensitives.Correction fluids such as organic solvent, acid, alkali, oxidant, reductant, eradicator had good irritability, good endurance, can can not satisfy the requirement of circulation uses such as marketable securities, certificate, classified document, long preservation because of the paper metachromatism appears in climate change.Can effectively prevent from alter to forge, have and be easy to popular identification, be difficult to the characteristics of forging again.Can be widely used in the false proof of security, certificate, bill, classified document.The security that improves marketable securities, certificate, classified document etc. had positive effect.Market prospects are wide, have a high potential.
The present invention will be further described below by the specific embodiment, but and do not mean that limiting the scope of the invention.
The specific embodiment
Embodiment 1
Produce according to common offset paper technology, in the pond of manufacturing paper with pulp, add transparent violet B dyestuff, after mixing, add melamine resin (retention agent), the consumption of transparent violet B dyestuff is 0.05% of an altering prevention paper gross weight, the consumption of retention agent is 3% of an altering prevention paper gross weight, and online is manufactured paper with pulp, and batches through moulding, squeezing, top sizing, drying, press polish.
Alter with organic solvents such as ethanol, acetone, benzene, have the purple vestige to occur on the paper.Paper strength, whiteness, colourity, printing performance etc. are not affected.Press the GB464.1-89 regulation, wear out, after wearing out, alter check with organic solvents such as ethanol, acetone, benzene again, still occur the purple vestige on the paper.After one week of insolation, the paper outward appearance does not have marked change to paper in the sun, alters with organic solvents such as ethanol, acetone, benzene, still occurs the purple vestige on the paper.Like this, if when having the human organic solvent to alter information on the paper, on the paper purple vestige can appear.
Embodiment 2
Produce according to common offset paper technology, in troughing, add blue 67 dyestuffs, after mixing, add expoxy propane, the consumption of blue 67 dyestuffs is 0.003% of an altering prevention paper gross weight, the consumption of expoxy propane is 0.6% of an altering prevention paper gross weight, and online is manufactured paper with pulp, and batches through moulding, squeezing, top sizing, drying, press polish.Alter with organic solvents such as ethanol, acetone, benzene, have blue trace to occur on the paper.
Embodiment 3
Produce according to common offset paper technology, in machine chest, add yellow 88 dyestuffs, after mixing, add cationic starch, the consumption of yellow 88 dyestuffs is 0.2% of an altering prevention paper gross weight, the consumption of cationic starch is 10% of an altering prevention paper gross weight, and online is manufactured paper with pulp, and batches through moulding, squeezing, top sizing, drying, press polish.Alter with organic solvents such as ethanol, acetone, benzene, have yellow vestige to occur on the paper.
Embodiment 4
Produce according to common offset paper technology, in the mediation pond, add transparent orange 3G dyestuff, after mixing, add melamine resin, the consumption of transparent orange 3G dyestuff is 0.15% of an altering prevention paper gross weight, the consumption of melamine resin is 5% of an altering prevention paper gross weight, and online is manufactured paper with pulp, and batches through moulding, squeezing, top sizing, drying, press polish.Alter with organic solvents such as ethanol, acetone, benzene, have orange vestige to occur on the paper.
Embodiment 5
Produce according to common offset paper technology, add red 122 dyestuffs of 0.01% (by the gross weight of altering prevention paper) in the pond of manufacturing paper with pulp, after mixing, online is manufactured paper with pulp, and batches through moulding, squeezing, top sizing, drying, press polish.Alter with organic solvents such as ethanol, acetone, benzene, have red vestige to occur on the paper.
Embodiment 6
Produce according to common offset paper technology, add the transparent green 5B dyestuff of 0.003% (by the gross weight of altering prevention paper) in troughing, after mixing, online is manufactured paper with pulp, and batches through moulding, squeezing, top sizing, drying, press polish.Alter with organic solvents such as ethanol, acetone, benzene, have green vestige to occur on the paper.
Embodiment 7
Produce according to common offset paper technology, add black 29 dyestuffs of 0.1% (by the gross weight of altering prevention paper) in the mediation pond, after mixing, online is manufactured paper with pulp, and batches through moulding, squeezing, top sizing, drying, press polish.Alter with organic solvents such as ethanol, acetone, benzene, have the black vestige to occur on the paper.
Embodiment 8
Produce according to common offset paper technology, add solvent green 601 dyestuffs of 0.2% (by the gross weight of altering prevention paper) in machine chest, after mixing, online is manufactured paper with pulp, and batches through moulding, squeezing, top sizing, drying, press polish.Alter with organic solvents such as ethanol, acetone, benzene, have green vestige to occur on the paper.
Embodiment 9
Blue 136 dyestuffs are joined in the coating fluid, after mixing, produce according to art paper technology, the consumption of blue 136 dyestuffs is 0.003% of an altering prevention paper gross weight.Alter with organic solvents such as ethanol, acetone, benzene, have blue trace to occur on the paper.
Embodiment 10
Brown 44 dyestuffs are joined in the coating fluid, after mixing, produce according to art paper technology, the consumption of brown 44 dyestuffs is 0.1% of an altering prevention paper gross weight.Alter with organic solvents such as ethanol, acetone, benzene, have brown vestige to occur on the paper.
Embodiment 11
Transparent red EG dyestuff is joined in the coating fluid, after mixing, produce according to art paper technology, the consumption of transparent red EG dyestuff is 0.2% of an altering prevention paper gross weight.Alter with organic solvents such as ethanol, acetone, benzene, have red vestige to occur on the paper.
With the altering prevention paper of embodiment 2-11 gained, carry out the detection of paper strength, whiteness, colourity, printing performance etc., to compare with not adding the anti-sample of altering agent and retention agent, performance is not affected.Press the GB464.1-89 regulation, wear out, after wearing out, alter check with organic solvents such as ethanol, acetone, benzene again, still occur the vestige of respective color on the paper.After one week of insolation, the paper outward appearance does not have marked change to paper in the sun, alters with organic solvents such as ethanol, acetone, benzene, still occurs the vestige of respective color on the paper.
Embodiment 12
Cobaltous sulfate and manganese sulfate are joined in the PVA applying glue liquid according to mol ratio at 1: 1, carry out in the machine or off-machine sizing with this kind glue to paper, contain 0.6 gram cobaltous sulfate and manganese sulfate in every square metre of altering prevention paper, can make the paper that acid, alkali, oxidant, reductant is had induction.
Embodiment 13
Cobalt nitrate and manganese chloride are joined in the starch applying glue liquid according to mol ratio at 5: 1, carry out in the machine or off-machine sizing with this kind glue to paper, contain 3 gram cobalt nitrate and manganese chlorides in every square metre of altering prevention paper, can make the paper that acid, alkali, oxidant, reductant is had induction.
Embodiment 14
Cobalt chloride and manganese nitrate are joined in the gelatin applying glue liquid according to mol ratio at 10: 1, carry out in the machine or off-machine sizing with this kind glue to paper, contain 1 gram cobalt nitrate and manganese chloride in every square metre of altering prevention paper, can make the paper that acid, alkali, oxidant, reductant is had induction.
Embodiment 15
Cobalt chloride and manganese carbonate are joined in the gelatin applying glue liquid according to mol ratio at 10: 1, carry out in the machine or off-machine sizing with this kind glue to paper, contain 1 gram cobalt chloride and manganese carbonate in every square metre of altering prevention paper, can make the paper that acid, alkali, oxidant, reductant is had induction.
Embodiment 16
Cobalt nitrate and manganese sulfate (both mol ratios are 2: 1) are joined in the coating fluid, after mixing, produce, contain 0.6 gram cobalt nitrate and manganese sulfate in every square metre of altering prevention paper according to art paper technology.Can make the paper that acid, alkali, oxidant, reductant is had induction.
Embodiment 17
Cobaltous sulfate and manganese nitrate (both mol ratios are 1: 1) are joined in the coating fluid, after mixing, produce, contain 0.03 gram cobalt nitrate and manganese sulfate in every square metre of altering prevention paper according to art paper technology.Can make the paper that acid, alkali, oxidant, reductant is had induction.
The altering prevention paper that embodiment 12-17 makes, when being applied on the paper with sulfuric acid, oxalic acid, hydrochloric acid, nitric acid, acetate, formic acid etc., pink appears on the paper, when being applied on the paper with NaOH, potassium hydroxide, ammoniacal liquor etc., occur brownly on the paper, when altering, occur brown on the paper with oxidants such as clorox, hydrogen peroxide, when altering with sodium hydrogensulfite, crocus appears on the paper.Paper strength, whiteness, colourity, printing performance etc. are not affected.Press GB464.1-89 regulation, wear out, or paper is in the sun after one week of insolation, the paper outward appearance does not have marked change, alters with mentioned reagent, still occurs corresponding color vestige on the paper.
Embodiment 18
In the mediation pond, add transparent orange 3G dyestuff, after mixing, add cationic starch, the consumption of transparent orange 3G dyestuff is 0.003% of an altering prevention paper gross weight, the consumption of cationic starch is 0.6% of an altering prevention paper gross weight, online is manufactured paper with pulp, and batches through moulding, squeezing, middle part applying glue (any glue and consumption among the use embodiment 12-15), drying, press polish.Alter with organic solvents such as ethanol, acetone, benzene, have orange vestige to occur on the paper.When being applied on the paper with sulfuric acid, oxalic acid, hydrochloric acid, nitric acid, acetate, formic acid etc., pink appears on the paper, when being applied on the paper with NaOH, potassium hydroxide, ammoniacal liquor etc., occur brown on the paper, when altering with oxidants such as clorox, hydrogen peroxide, occur brownly on the paper, when altering, occur crocus on the paper with sodium hydrogensulfite.Paper strength, whiteness, colourity, printing performance etc. are not affected.Press GB464.1-89 regulation, wear out, or paper is in the sun after one week of insolation, the paper outward appearance does not have marked change, alters with mentioned reagent, still occurs corresponding color vestige on the paper.
Embodiment 19
In the mediation pond, add yellow 146 dyestuffs, after mixing, add melamine resin, the consumption of yellow 146 dyestuffs is 0.2% of an altering prevention paper gross weight, the consumption of melamine resin is 10% of an altering prevention paper gross weight, online is manufactured paper with pulp, and batches through moulding, squeezing, middle part applying glue (any glue and consumption among the use embodiment 12-15), drying, press polish.Alter with organic solvents such as ethanol, acetone, benzene, have yellow vestige to occur on the paper.When being applied on the paper with sulfuric acid, oxalic acid, hydrochloric acid, nitric acid, acetate, formic acid etc., pink appears on the paper, when being applied on the paper with NaOH, potassium hydroxide, ammoniacal liquor etc., occur brown on the paper, when altering with oxidants such as clorox, hydrogen peroxide, occur brownly on the paper, when altering, occur crocus on the paper with sodium hydrogensulfite.Paper strength, whiteness, colourity, printing performance etc. are not affected.Press GB464.1-89 regulation, wear out, or paper is in the sun after one week of insolation, the paper outward appearance does not have marked change, alters with mentioned reagent, still occurs corresponding color vestige on the paper.
Embodiment 20
In the mediation pond, add blue 501 dyestuffs of transparent plastic, after mixing, add expoxy propane, the consumption of blue 501 dyestuffs of transparent plastic is 0.1% of an altering prevention paper gross weight, the consumption of expoxy propane is 8% of an altering prevention paper gross weight, online is manufactured paper with pulp, and batches through moulding, squeezing, middle part applying glue (any glue and consumption among the use embodiment 12-15), drying, press polish.Alter with organic solvents such as ethanol, acetone, benzene, have blue trace to occur on the paper.When being applied on the paper with sulfuric acid, oxalic acid, hydrochloric acid, nitric acid, acetate, formic acid etc., pink appears on the paper, when being applied on the paper with NaOH, potassium hydroxide, ammoniacal liquor etc., occur brown on the paper, when altering with oxidants such as clorox, hydrogen peroxide, occur brownly on the paper, when altering, occur crocus on the paper with sodium hydrogensulfite.Paper strength, whiteness, colourity, printing performance etc. are not affected.Press GB464.1-89 regulation, wear out, or paper is in the sun after one week of insolation, the paper outward appearance does not have marked change, alters with mentioned reagent, still occurs corresponding color vestige on the paper.
Embodiment 21
Blue 70 dyestuffs, cobaltous sulfate, manganese chloride (mol ratio of cobaltous sulfate and manganese chloride=3: 1) are joined in the coating fluid, after mixing, produce according to art paper technology, the consumption of blue 70 dyestuffs is 0.1% of an altering prevention paper gross weight, contains 0.8 gram cobaltous sulfate and manganese chloride in every square metre of altering prevention paper.Alter with organic solvents such as ethanol, acetone, benzene, have blue look vestige to occur on the paper.When being applied on the paper with sulfuric acid, oxalic acid, hydrochloric acid, nitric acid, acetate, formic acid etc., pink appears on the paper, when being applied on the paper with NaOH, potassium hydroxide, ammoniacal liquor etc., occur brown on the paper, when altering with oxidants such as clorox, hydrogen peroxide, occur brownly on the paper, when altering, occur crocus on the paper with sodium hydrogensulfite.42 pairs of body paper foldings time, whiteness 93.4%, colourity (L94.3 a-0.1 b 3.45), surface strength are good, after adding blue 70 dyestuffs, cobaltous sulfate, manganese chloride, 43 pairs of paper foldings time, whiteness 92.8%, colourity (L 92.4 a 1.2 b 2.8), surface strength are good, and front and back are compared paper performance and are not affected.Anti-forge paper wears out in 105 ± 2 ℃ of baking ovens, or in the sun after one week of insolation, the paper outward appearance does not have marked change, alters with mentioned reagent, still occurs corresponding color vestige on the paper.
Embodiment 22
Oil Violet 401, cobalt nitrate, manganese carbonate (mol ratio of cobaltous sulfate and manganese chloride=10: 1) are joined in the coating fluid, after mixing, produce according to art paper technology, the consumption of Oil Violet 401 is 0.2% of an altering prevention paper gross weight, contains 0.03 gram cobaltous sulfate and manganese chloride in every square metre of altering prevention paper.Alter with organic solvents such as ethanol, acetone, benzene, have the purple vestige to occur on the paper.When being applied on the paper with sulfuric acid, oxalic acid, hydrochloric acid, nitric acid, acetate, formic acid etc., pink appears on the paper, when being applied on the paper with NaOH, potassium hydroxide, ammoniacal liquor etc., occur brown on the paper, when altering with oxidants such as clorox, hydrogen peroxide, occur brownly on the paper, when altering, occur crocus on the paper with sodium hydrogensulfite.42 pairs of body paper foldings time, whiteness 93.4%, colourity (L94.3 a-0.1 b 3.45), surface strength are good, after adding Oil Violet 401, cobalt nitrate, manganese carbonate, 43 pairs of paper foldings time, whiteness 92.8%, colourity (L 92.4 a 1.2 b 2.8), surface strength are good, and front and back are compared paper performance and are not affected.Anti-forge paper wears out in 105 ± 2 ℃ of baking ovens, or in the sun after one week of insolation, the paper outward appearance does not have marked change, alters with mentioned reagent, still occurs corresponding color vestige on the paper.
Embodiment 23
Red 233 dyestuffs, cobalt chloride, manganese sulfate (mol ratio of cobaltous sulfate and manganese chloride=1: 1) are joined in the coating fluid, after mixing, produce according to art paper technology, the consumption of red 233 dyestuffs is 0.003% of an altering prevention paper gross weight, contains 3 gram cobaltous sulfate and manganese chlorides in every square metre of altering prevention paper.Alter with organic solvents such as ethanol, acetone, benzene, have red vestige to occur on the paper.When being applied on the paper with sulfuric acid, oxalic acid, hydrochloric acid, nitric acid, acetate, formic acid etc., pink appears on the paper, when being applied on the paper with NaOH, potassium hydroxide, ammoniacal liquor etc., occur brown on the paper, when altering with oxidants such as clorox, hydrogen peroxide, occur brownly on the paper, when altering, occur crocus on the paper with sodium hydrogensulfite.42 pairs of body paper foldings time, whiteness 93.4%, colourity (L94.3 a-0.1 b 3.45), surface strength are good, after adding red 233 dyestuffs, cobalt chloride, manganese sulfate, 43 pairs of paper foldings time, whiteness 92.8%, colourity (L 92.4 a 1.2 b 2.8), surface strength are good, and front and back are compared paper performance and are not affected.Anti-forge paper wears out in 105 ± 2 ℃ of baking ovens, or in the sun after one week of insolation, the paper outward appearance does not have marked change, alters with mentioned reagent, still occurs corresponding color vestige on the paper.
Claims (8)
1. an altering prevention paper contains the anti-agent of altering in altering prevention paper, and by the gross weight of altering prevention paper, the consumption of described anti-correction agent is 0.003%-0.2%; Described anti-correction agent is that light resistance is greater than 2 grades, heat resistance is greater than 110 ℃ solvent dye, it is characterized in that: also contain 0.03-3 gram anti-counterfeiting substances in every square metre of altering prevention paper, described anti-counterfeiting substances is cobalt compound and the induction agent that contains manganese ion, and the mol ratio of the two is 1: 1-10: 1.
2. altering prevention paper according to claim 1 is characterized in that: described anti-correction agent is phthalein mountain valley with clumps of trees and bamboo dyestuff, azo-compound, anthraquinone compounds or other dyestuff, and described phthalein mountain valley with clumps of trees and bamboo dyestuff is blue 67 dyestuffs or blue 70 dyestuffs; Described azo-compound is yellow 146 dyestuffs, yellow 88 dyestuffs, yellow 25 dyestuffs, yellow 89 dyestuffs, orange 11 dyestuffs, brown 44 dyestuffs, red 130 dyestuffs, red 233 dyestuffs, red 125 dyestuffs, red 122 dyestuffs, pink 127 dyestuffs, black 29 dyestuffs, solvent yellow 19 or transparent yellow 101; Described anthraquinone compounds is blue 136 dyestuffs, transparent violet B, transparent violet RR, transparent plastic indigo plant 501, transparent blue RP, solvent green 601, transparent green 5B or Oil Violet 401; Described other dyestuff is transparent red EG, transparent orange 3G or transparent yellow 3G.
3. altering prevention paper according to claim 1 is characterized in that: also contain retention agent in the described altering prevention paper, by the gross weight of altering prevention paper, the consumption of described retention agent is 0.6%-10%; Described retention agent is melamine resin, expoxy propane or cationic starch.
4. altering prevention paper according to claim 1 is characterized in that: described cobalt compound is cobaltous sulfate, cobalt nitrate or cobalt chloride; The described induction agent that contains manganese ion is manganese sulfate, manganese nitrate, manganese carbonate or manganese chloride.
5. the manufacture method of an altering prevention paper is characterized in that: will prevent altering agent and join in the paper pulp, and mix; Anti-counterfeiting substances is joined in the surface size, produce according to common offset paper technology; Described anti-correction agent be light resistance greater than 2 grades, heat resistance is greater than 110 ℃ solvent dye, by the gross weight of altering prevention paper, the anti-consumption of altering agent is 0.003%-0.2%; Contain 0.03-3 gram anti-counterfeiting substances in every square metre of altering prevention paper; Described anti-counterfeiting substances is cobalt compound and the induction agent that contains manganese ion, and the mol ratio of the two is 1: 1-10: 1.
6. the manufacture method of altering prevention paper according to claim 5, it is characterized in that: also retention agent is proportionally joined in the paper pulp, by the gross weight of altering prevention paper, the consumption of retention agent is 0.6%-10%; Described retention agent is melamine resin, expoxy propane or cationic starch.
7. the manufacture method of altering prevention paper according to claim 6 is characterized in that: described anti-correction agent adds in the paper pulp at troughing, machine chest, mediation pond or the Chi Chu that manufactures paper with pulp, and after mixing, online is manufactured paper with pulp.
8. the manufacture method of an altering prevention paper is characterized in that: will prevent altering agent and anti-counterfeiting substances joins in the coating fluid, and after mixing, produce according to art paper technology; Described anti-correction agent be light resistance greater than 2 grades, heat resistance is greater than 110 ℃ solvent dye, by the gross weight of altering prevention paper, the anti-consumption of altering agent is 0.003%-0.2%; Contain 0.03-3 gram anti-counterfeiting substances in every square metre of altering prevention paper, described anti-counterfeiting substances is cobalt compound and the induction agent that contains manganese ion, and the mol ratio of the two is 1: 1-10: 1.
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| CN200910176476XA CN101666060B (en) | 2009-09-16 | 2009-09-16 | Altering prevention paper and preparing method thereof |
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| CN201010623311.5A Division CN102174785B (en) | 2009-09-16 | 2009-09-16 | Alteration resistant paper and preparation method thereof |
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| CN101666060B true CN101666060B (en) | 2011-10-12 |
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| CN102304878B (en) * | 2011-09-16 | 2013-02-27 | 江南大学 | Color developing anti-counterfeit paper made from environment-friendly insoluble azo dye and preparation method thereof |
| CN102517999B (en) * | 2011-12-30 | 2014-08-13 | 珠海经济特区红塔仁恒纸业有限公司 | Double-sizing preparation process for liquid packaging white cardboard |
| CN107591083A (en) * | 2017-10-14 | 2018-01-16 | 洪亚锋 | A kind of antifalsification label preparation method |
| CN110219209A (en) * | 2019-06-24 | 2019-09-10 | 安徽顺彤包装材料有限公司 | A kind of anti-fake wrapping paper and preparation method thereof |
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