RU2243307C1 - Securities protected against forgery, method for manufacture and materials used in manufacture (modifications) - Google Patents

Abstract

FIELD: protection of printed papers or manuscripts against forgery, discharge, applicable, for example, for manufacture of documents and bank notes.

SUBSTANCE: the method consists in introduction in the paper suspension at least of one guard material-compound containing substances capable of formation of a visually detected coloured compound at interaction with an organic solvent used for decoloration of the image and/or text. Then, sheet formation, compaction, drying and processing with a binding solution containing functional agents are performed. An indicator imparting a sensitivity to the paper at an interaction with an inorganic substance used for the discharge is used as the binding solution.

EFFECT: simplified process and enhanced degree of protection against forgery.

9 cl, 6 ex

Description

The invention relates to the field of manufacturing securities that are protected from counterfeiting, for example, from etching of printed or handwritten text, and can be used for the manufacture of documents, banknotes, etc.

Counterfeiting of documents by etching involves applying certain chemicals to a document that interact with components of printing inks, ink, ink, etc., and this interaction can be like a chemical (for example, the interaction of strong oxidizing agents with organic pigments of printing inks with the formation of colorless compounds ), as well as physical (an example is the extraction of ink dyes, stamp ink, etc. from organic paper with organic solvents), after which, on a bleached place in the document, New labels can be applied by typographic or other means.

The essence of protecting documents from counterfeiting by etching is to introduce certain chemicals into the paper on which the document is printed, or into printing ink.

It is known, for example, the production of printing inks with photochromism - a reversible color change when exposed to light.

The presence of photochromism of printing inks judges the authenticity of printing products, such as business and securities.

A colorless graphic image printed on paper using ink according to the formulations described in RU patent No. 2139900, 1999, when exposed to filtered UV light (365 nm) for 5-10 seconds becomes visible, acquiring a blue color. The color disappears after the termination of irradiation after 1-1.5 minutes. The cyclic nature of the optical effect depends on the chemical structure of the photochromic compound.

A similar principle is based on a study of the authenticity of documents made with ballpoint pen inks containing resins and triarylmethane dyes.

A sample containing a handwritten image is treated at least twice with a stream of air containing pairs of the processing agent in an amount of at least 5-10 ^-7 g / d, and the analysis consists in determining at least two dependencies in the form of S-shaped curves characterizing the color change of the image, determined through the intensity of the reflected light from the processing time of the sample, determined by the saturation of the handwritten image with piperidine vapors, the measurement of the characteristics of the curves and the prescription of the handwritten image days in accuracy with an accuracy of 25% in empirical form (RU No. 2091767, 1997).

However, the authentication methods described above are rather complicated.

Other anti-counterfeiting methods are based on the manufacture of papers with one or more security features, including chemical protection.

One of the requirements for counterfeit securities and documents is that the print on the substrate adheres well to the latter, especially under harsh operating conditions, including mechanical abrasion or accidental washing, as well as deliberate destruction of the text.

The closest in technical essence and the achieved result is a method of manufacturing a security paper with security features, including feeding fibers for making paper into a paper machine, introducing at least one security feature into the paper during its manufacture, forming paper, applying to paper with a security feature introduced into the paper before drying the binder and sizing the paper, choosing the composition of a substantially transparent coating, applying the coating composition to one silt and both sides of a glued paper that contains a pigment-free polyurethane, preferably containing functional additives, and fluorescent iridescent additives are recommended as functional additives (RU No. 2138593, 1999).

The known method is complex, multi-stage and time-consuming.

It is an object of the present invention to provide a simple method for manufacturing paper that is protected against counterfeiting by etching using both organic solvents and inorganic substances.

The problem is solved by the described method of manufacturing a security paper that is protected from etching of the image and / or text, including preparing a suspension of paper pulp, introducing at least one security material into it, casting the paper, pressing, drying, processing with a binder solution containing functional additives, which, as a protective material introduced into the suspension of paper pulp, use a composition containing substances capable of interacting with an organic solvent used to I bleaching images and / or text form visually detectable colored compound, as well as a functional additive binder solution comprising an indicator, giving the paper sensitivity by reacting with an inorganic substance used for etching.

Preferably, security material is added to the pulp suspension in an amount of 0.3-0.6% by weight of the fiber in the paper suspension.

Preferably, an aqueous solution based on polyvinyl alcohol containing glycerol or Na-carboxymethyl cellulose and a functional additive in an amount of 0.25-0.35 wt.% Are used as a binder.

The method is also characterized in that acetate and diphenyl guanidine chloride are introduced into the binder solution as a functional indicator additive.

The problem is also solved by the described protective material used in the manufacture of securities by the method described above, which has the following composition, wt. hours:

1,4-dimesidinantraquinone 1-1.5

Glycerin or an aqueous solution of Na-carboxymethyl cellulose

with a concentration of 1-5% 2-6

Surfactant 0.05-2.5

Additionally, the composition may contain alcohol-soluble nigrosine in an amount of 1 wt. hours

The problem is also solved by the functional additive used as an indicator in the manufacture of paper price, according to the method described above, having the following composition, wt. hours:

Indicator m-cresol purple 2

Indicator Bromocresol Purple 1

Methyl orange indicator 1

Diphenylguanidine acetate or chloride 45-65

Another variant of the functional additive used as an indicator has the following composition, wt. hours:

Dinaftylfluorescin 1

Diphenylguanidine Acetate or Chloride 10-20

The problem is solved by the declared security, protected from the etching of the image and / or text obtained in accordance with the claimed method.

The following are specific examples of implementation and the results obtained.

Example 1

The paper is prepared from a suspension containing bleached sulfate cellulose fibers, milled to 40-50 ° SR. Chalk in the amount of 10-12% to the fiber, alkyl ketene dimer in the amount of 0.4-0.8% to the fiber, modified cationic starch in the amount of 0.4-1.0% to the fiber are successively introduced into the suspension of milled cellulose. In the resulting paper pulp is introduced protective material, which is the following composition, parts by weight:

1,4-dimesidinoantraquinone 1

Glycerin 4

Surfactant 2.5

Said composition is introduced at the rate of 0.3% by weight of sulphate pulp. Then all the components are mixed with paper pulp. From the pulp thus prepared, paper is cast on a paper machine. The molded paper is pressed and dried, and then impregnated in the size bath with an aqueous binder solution containing wt.%:

Polyvinyl alcohol 1

Glycerin 1

Functional supplement 0.3

while the functional additive is made in the form of a mixture of 1 wt.h. bromocresol purple, 2 parts by weight meta-cresol purple, 1 parts by weight methyl orange and 45 parts by weight diphenyl guanidine acetate.

The impregnated paper is dried, processed on a machine calender and cut into sheets. The resulting paper is sensitive to the effects of etching agents, namely

- when exposed to alkaline solutions on paper (aqueous solutions of caustic soda, soda, soap, detergents), a bright purple spot forms on the paper;

- when exposed to household bleaches (sodium hypochlorite, hydrogen peroxide), a spot of light brown or violet-brown color forms on the paper;

- when exposed to acid solutions on paper (aqueous solutions of sulfuric, hydrochloric, citric acids), a pink spot forms on the paper;

- when organic solvents (acetone, white spirit, benzene, etc.) are exposed to the paper, a blue spot forms on the paper, and therefore the paper is protected from etching of a wide range of etching agents.

Example 2

The paper is prepared from a suspension containing fibers of bleached sulfate pulp and cotton pulp, milled to 40-50 ° SR. Chalk in the amount of 10-12% to the fiber, alkyl ketene dimer in the amount of 0.4-0.8% to the fiber, modified cationic starch in the amount of 0.4-1.0% to the fiber are successively introduced into the suspension of milled cellulose. In the resulting paper pulp is introduced protective material, which is the following composition, parts by weight:

1,4-dimesidinoantraquinone 1

Alcohol-soluble nigrosine 1

An aqueous solution of Na-carboxymethyl cellulose

with a concentration of 5% 3

Surfactant 0.05

The composition is introduced at the rate of 0.2% by weight of sulphate pulp. Then all the components are mixed with paper pulp. From the pulp thus prepared, paper is cast on a paper machine. The cast paper is pressed and dried, and then impregnated in a size bath with an aqueous solution of a binder containing, wt.%:

Polyvinyl alcohol 1

Glycerin 1

Functional additive 0.3,

while the functional additive is made in the form of a mixture of 1 wt. including dinaphthylfluorescein and 15 wt. including diphenylguanidine acetate.

The impregnated paper is dried, processed on a machine calender and cut into sheets. The resulting paper is sensitive to the effects of etching agents, namely

- when exposed to alkaline solutions on paper (aqueous solutions of caustic soda, soda, soap, detergents), a lilac stain forms on the paper;

- when exposed to household bleaches (sodium hypochlorite, hydrogen peroxide), a spot of light brown or violet-brown color forms on the paper;

- when exposed to acid solutions on paper (aqueous solutions of sulfuric, hydrochloric, citric acids), a pink spot forms on the paper;

- when organic solvents (acetone, white spirit, benzene, ethyl alcohol, etc.) are exposed to the paper, blue or dark gray spots form on the paper, and, therefore, the paper is protected from etching of a wide range of etching agents.

Example 3

The paper is prepared from a suspension containing fibers of bleached sulfate pulp and cotton pulp, milled to 40-50 ° SR. Chalk in the amount of 10-12% to the fiber, alkyl ketene dimer in the amount of 0.4-0.8% to the fiber, modified cationic starch in the amount of 0.4-1.0% to the fiber are successively introduced into the suspension of milled cellulose. In the resulting paper pulp is introduced protective material, which is the following composition, parts by weight:

1,4-dimesidinoantraquinone 1

Alcohol-soluble nigrosine 1

Glycerin 2 wt. h

Surfactant - 0.1

The composition is introduced at the rate of 0.6% by weight of sulphate pulp. Then all the components are mixed with paper pulp. From the pulp thus prepared, paper is cast on a paper machine. The cast paper is pressed and dried, after which it is impregnated in an adhesive bath with an aqueous binder solution containing diphenylguanidine chloride as a functional additive and indicator, containing, wt.%:

Polyvinyl alcohol 1

Glycerin 1

Diphenylguanidine chloride 0.25

The impregnated paper is dried, processed on a machine calender and cut into sheets. The resulting paper is sensitive to the effects of etching agents, namely

- when exposed to household bleaches (sodium hypochlorite, hydrogen peroxide), a spot of light brown or violet-brown color forms on the paper;

- when exposed to organic solvents on paper (acetone, white spirit, benzene, ethyl alcohol, etc.), blue or dark gray spots form on the paper,

and therefore, the paper is protected from etching a wide range of etching agents.

Example 4

The paper is prepared from a suspension containing bleached sulfate cellulose fibers, milled to 40-50 ° SR. Chalk in the amount of 10-12% to the fiber, alkyl ketene dimer in the amount of 0.4-0.8% to the fiber, modified cationic starch in the amount of 0.4-1.0% to the fiber are successively introduced into the suspension of milled cellulose. In the resulting paper pulp is introduced protective material, which is the following composition, parts by weight:

1,4-dimesidinoantraquinone 1.5

Alcohol-soluble nigrosine 1

An aqueous solution of Na-carboxymethyl cellulose

with a concentration of 1% 6

Surfactant 0.1

Said composition is introduced at the rate of 0.3% by weight of sulphate pulp. Then all the components are mixed with paper pulp. From the pulp thus prepared, paper is cast on a paper machine. The cast paper is pressed and dried, and then impregnated in the size bath with an aqueous solution of a binder of the following composition, wt.%:

Polyvinyl alcohol 1

Glycerin 1

Functional Additive 0.25

while the functional additive is made in the form of a mixture of 1 wt.h. bromocresol purple, 2 parts by weight meta-cresol purple, 1 parts by weight methyl orange and 65 parts by weight diphenylguanidine chloride.

The impregnated paper is dried, processed on a machine calender and cut into sheets. The resulting paper is sensitive to the effects of etching agents, namely

- when exposed to alkaline solutions on paper (aqueous solutions of caustic soda, soda, soap, detergents), a bright purple spot forms on the paper;

- when exposed to household bleaches (sodium hypochlorite, hydrogen peroxide), a spot of light brown or violet-brown color forms on the paper;

- when exposed to acid solutions on paper (aqueous solutions of sulfuric, hydrochloric, citric acids), a pink spot forms on the paper;

- when exposed to organic solvents on paper (acetone, white spirit, benzene, ethyl alcohol, etc.), blue or dark gray spots form on the paper,

and therefore, the paper is protected from etching a wide range of etching agents.

Example 5

The paper is prepared as in Example 4, however, a functional additive in the amount of 0.35 wt.%, Which contains an indicator consisting of 1 wt.h., is introduced into the binder solution. dinaphthylfluorescin and 10 parts by weight diphenylguanidine acetate.

Example 6

The paper is prepared in the same way as in example 4, but a functional additive in the amount of 0.25 wt.%, Which has the following composition, wt. hours:

Dinaftylfluorescin 1

Diphenylguanidine chloride 20

In examples 5, 6, the obtained paper during its testing showed the following results:

- when exposed to alkaline solutions on paper (aqueous solutions of caustic soda, soda, soap, detergents), a bright purple spot forms on the paper;

- when exposed to household bleaches (sodium hypochlorite, hydrogen peroxide), a spot of light brown or violet-brown color forms on the paper;

- when exposed to acid solutions on paper (aqueous solutions of sulfuric, hydrochloric, citric acids), a pink spot forms on the paper;

- when exposed to organic solvents on paper (acetone, white spirit, benzene, ethyl alcohol, etc.), blue or dark gray spots form on the paper,

and therefore, paper is protected from etching a wide range of etching agents.

It should be noted that outside the claimed set of features in the compositions introduced at each stage of the proposed method, that is, as part of the protective material introduced into the paper pulp, and as part of a functional additive containing an indicator, the sensitivity of the paper decreases to one or another reagent, then there is a degree of protection against counterfeiting by etching drops.

Claims (9)

1. A method of manufacturing a security paper, which is protected from etching the image and / or text, comprising preparing a suspension of paper pulp, introducing at least one security material into it, casting the paper, pressing, drying, processing with a binder solution containing functional additives, characterized in that as a protective material introduced into the suspension of paper pulp, use a composition containing substances capable of interacting with an organic solvent used to bleach the image and / and text, form a visually detectable colored compound, and as a functional additive, the binder solution contains an indicator that gives the paper sensitivity when interacting with the inorganic substance used for etching. 2. The method according to claim 1, characterized in that the protective material is introduced into the suspension of paper pulp in an amount of 0.3-0.6% by weight of the fiber in the paper suspension. 3. The method according to claim 1, characterized in that as the binder use an aqueous solution based on polyvinyl alcohol containing glycerin or Na-carboxymethyl cellulose and a functional additive in an amount of 0.25-0.35 wt.%. 4. The method according to claim 1, characterized in that as a functional additive indicator in the binder solution is introduced acetate or diphenylguanidine chloride. 5. Security material used in the manufacture of a security according to the method described in claims 1 to 4, characterized in that it has the following composition, parts by weight: 1,4-Dimesidinantraquinone 1-1.5 Glycerin or Na- aqueous solution carboxymethyl cellulose concentration 1-5% 2-6 Surfactant 0.05-2.5 6. The security material according to claim 5, characterized in that it additionally contains alcohol-soluble nigrosine in an amount of 1 wt.h. 7. A functional additive used as an indicator in the manufacture of a security according to the method described in claims 1 to 4, characterized in that it has the following composition, parts by weight: Indicator m-cresol purple 2 Indicator Bromocresol Purple 1 Methyl orange indicator 1 Diphenylguanidine acetate or chloride 45-65 8. A functional additive used as an indicator in the manufacture of a security according to the method described in claims 1-4, characterized in that it has the following composition, parts by weight: Dinaftylfluorescin 1 Diphenylguanidine Acetate or Chloride 10-20 9. Security paper, protected from etching of the image and / or text, characterized in that it is made by the method described in claims 1 to 4.