Marking paper products

FIELD: textiles, paper.

SUBSTANCE: invention relates to marked paper products. Described is a method of production of a marked paper product , using irradiation of the area of the paper product with an electron beam with a dose of 0.10 Mrad to about 5 Mrad, where the electrons have the energy of about 0.25 MeV to 10 MeV. The irradiation is carried out under the conditions selected to change the functionalisation of the specified area of the paper product. The said area may be made in the form of a "watermark" or a symbol.

EFFECT: invention provides the marking on the paper products, which is invisible for the naked eye, which is difficult to copy without enough sophisticated equipment, which makes it difficult to counterfeit.

7 cl, 5 dwg

 

Area of technology

This invention relates to methods and systems for marking paper products, such as money, and products made using such methods and systems.

The level of technology

Paper, in the sense in which this term is used here, refers to a variety of sheet materials made of cellulose, used for writing, printing, packaging and other applications. The paper can be used, as an example, but without limitation, in the following applications: paper money, Bank notes, certificates of stocks and bonds, cheques, postage stamps etc., in books, magazines, Newspapers and artwork for packaging, e.g. cardboard, corrugated cardboard, paper bags, envelopes, thin wrappers, boxes, household products, e.g. toilet paper, paper tissue, paper towels and paper napkins, paper honeycomb structure, used as the core material in composite materials, building materials, building cardboard, disposable clothing and in various industrial applications, including abrasive paper, sandpaper, blotting paper, litmus paper, universal indicator paper, paper chromatography, battery separators and capacitor insulators.

In a number of�areas of application, for example, when paper is used as money and other financial applications, it is often necessary to "mark" or "mark" the paper with special markings that cannot be seen with the naked eye and/or which is difficult to forge. Marking can be used, for example, to prevent or detect counterfeit money, works of art and other valuable documents. The marking can also be used on money for the purpose of tracking and/or identification, for example, in the case of theft or criminal transactions.

Summary of the invention

The basis of the invention lies partly in the fact that irradiation of paper at appropriate levels functionalization of the exposed paper may change, making paper distinguishable, for example by infrared spectrometry (IR) or other methods, from paper, not exposed to radiation. In some cases, the paper can also be distinguished from the paper, which had been irradiated, but in other operating environments. As a result, paper products, money for example, you can "mark" described here means. In some implementations, the marking cannot be seen with the naked eye, for example, it is detected with instruments. In other implementations, the markings can be seen with the naked eye. In the General case Mar�iruku difficult to replicate, without complicated equipment what makes it a forgery.

"Functionalization" we mean a functional group that is present on or in the paper.

In one aspect, the invention provides methods of making labeled paper products. Some methods include irradiation of paper products in conditions that are selected to modify functionalization at least the field of paper products.

Some implementations include one or more of the following features. The paper can be irradiated with ionizing radiation. Dose of ionizing radiation may be at least such as 0.10 Mrad, e.g., at least 0.25 Mrad. The dose of ionizing radiation can be adjusted in the range of from about 0.25 to about 5 Mrad. The radiation may include radiation gamma rays and/or electron beam radiation or other particles. The electrons in the electron beam can have an energy factor of at least 0.25 MeV, e.g., from about 0.25 MeV to about 7.5 MeV.

The methods can further include the neutralization of irradiated paper products. For example, the neutralization can be carried out in the presence of a gas selected to react with radicals present in the irradiated piece of paper.

In some cases, only a portion irradiated paper products. In some cases, neutralizes�I only part of the irradiated area or only a portion of paper products as a whole. For example, the area that should remain unmarked and/or may not be neutralized, it is possible to mask.

Exposure can occur during the formation of paper products. The formation may include the amalgamation of the material of the pulp in a wet paper web. The irradiation can be carried out on damp cloth or paper before the formation of the wet paper web. The forming may further include drying the wet paper web, and the irradiation may occur after drying. In some implementations, powders, granules, chemical solvents, dyes, inks or gases can be used, separately or jointly, before, during or after the formation of paper.

In another aspect, the invention provides branded paper products, including cellulose or drevesnosmolyanoy fibrous material containing functional groups not present in natural occurrence of cellulose or drevesnostruzhechnogo fibrous material from which is obtained a marked piece of paper.

Cellulose or drevesnosmolyanoy material in the piece of paper you can choose, for example, from the group consisting of fibers extracted from wood and paper raw materials, materials based on vegetable fibers,for example, cotton, hemp, flax, rice, sugar cane, bagasse, straw, bamboo, kenaf, jute and the Gorgons, and their mixtures. In some embodiments, the metal or inorganic fibers can also be incorporated in the cellulose or drevesnosmolyanoy material or is included in the irradiated portion of the paper products.

In another aspect the invention provides a method of identification, if your product is marked out of paper. The method involves the comparison of functionalization of the sample articles of paper with the functionalization of a labeled paper products.

In some cases, the method includes the determination of the functionalization of a sample of paper products using infrared spectrometry (IR). The method may include comparing the number of carboxylic groups present in the sample articles of paper with the number of carboxyl groups present in the labeled product from the paper.

In some cases, the functionalization is determined using atomic force microscopy (AFM) and chemical force microscopy (CFM) or electron spin resonance (ESR).

A piece of paper may represent, for example, the money or the work of art.

In any of the ways described here functionalization may include increasing the number of carboxyl groups present�treated in the paper. The number of carboxyl groups is determined by titration.

Irradiated material also may include a functional group selected from the group consisting of aldehyde groups, nitroso groups, nitrile groups, nitro groups, ketone groups, amino groups, alkyl amino groups, alkyl groups, chloralkali groups, chlortetracycline groups, and enol groups.

In some implementations, the irradiated material may include many sharidny units in the molecular chain, and from about 1 out of every 5 to about 1 out of every 1500 sharidny units contains a nitroso, nitro, or nitrile group, for example, from about 1 out of every 10 to about 1 out of every 1000 sharidny units of each chain contains a nitroso, nitro, or nitrile group, or from about 1 out of every 35 to about 1 out of every 750 sharidny units of each chain contains a nitroso, nitro, or nitrile group. In some cases, the irradiated material contains a mixture of nitrile groups and carboxyl groups.

In some embodiments, sacharine unit can include essentially only group of the same type, for example, a carboxyl group, a nitrile group, nitrosopropane or a nitro group.

Used herein, the term "paper" includes cellulosic sheet material and composite sheet materials, soderzhaschayasya. For example, paper may include pulp in a plastic matrix, or pulp combined with additives or binders.

In any of the ways described here, the radiation can be supplied from the device being in the shelter.

Unless otherwise noted, all used here is the technical and scientific terms should be understood in the same sense in which they understand the experts in the field of technology to which the invention relates. Although in practice or testing of the present invention can be used in the methods and materials similar or equivalent described herein; suitable methods and materials are described below. All of the above publications, patent applications, patents, and other references are included here in order of reference in full. In case of conflict, the present description of the invention, including definitions, will control. In addition, the materials, methods and examples are illustrative only and do not purport to limit.

Other characteristics and advantages of the invention clear from the following detailed description and from the claims.

Description of the drawings

Fig.1 - diagram of the papermaking system.

Fig.2 - diagram showing the change of molecular and/or supramolecular structure of fibrous mater�Ala.

Fig.3 is a perspective view with local incision gamma irradiator, a prisoner in a concrete shelter.

Fig.4 is an enlarged view in perspective of the area R shown in Fig.3.

Fig.5 - scheme of the accelerator DC.

Detailed description

As discussed above, the basis of the invention lies partly in the fact that by irradiating a fibrous material, i.e., cellulose and drevesnoplitnye materials, at appropriate levels, you can modify the molecular structure of at least a cellulose fibrous parts of the material, changing the functionalization of fibrous material. In addition to the markings paper change functionalization may also positively influence the surface properties of paper products, for example, the absorption capacity of the surface in relation to coatings, inks and dyes.

In addition, changes in the molecular structure can include changing any one or more of the average molecular weight, average crystallinity, surface area, polymerization, porosity, branching, grafted copolymerization and the size of the domain of cellulose. These changes in molecular structure can, in turn, lead to favorable changes in the physical characteristics exhibited fibrous materials. Such changes are considered in detail in us Pat�/ application US No. 12/417707, filed April 3, 2009, the complete disclosure of which is incorporated here by reference.

Radiation can be applied at one or more selected stages of the paper production process. In some cases, the radiation will be to increase the strength and tear resistance of paper by increasing the strength of cellulosic fibers, which are made of paper. In addition, the processing of cellulosic material radiation can sterilize the material that inhibits the growth of mold, mildew and things on paper. Radiation in General is carried out in a controlled and timed mode to provide optimum properties for the particular application by selecting the type or types of applied radiation and/or dose or doses of the applied radiation.

Low dose of ionizing radiation can be applied, for example, after cooking and prior to the amalgamation of boiled fibers in the fabric to a wet fibrous web to a paper cloth during or after drying or to the dried paper to a cloth, for example, before, during or after subsequent processing steps, for example, sorting by size, coating and calendering. In the General case, it is preferable to apply the radiation to the blade, when it has a relatively low moisture content. In the example shown in Fig.1, the irradiation can be realized during the drying and Windows�atelnoe processing, for example, between operations of sorting by size, drying, pressing and calendering, or during subsequent processing, for example, to complete the paper in the roll, cut the roll or in the form of sheets.

As noted above, in some embodiments, radiation is applied to more than one point in the production process. For example, ionizing radiation can be used in a relatively high dose to form or aid in forming the slurry, and then, later, in a relatively lower dose to change functionalization of paper. If desired, a high dose of radiation can be applied to the finished paper in selected areas of the paper web to create a locally weakened areas, for example, to provide zones of the gap.

Practically with the use of modern technology in the most General case, it is desirable to integrate the stage of irradiation in the paper production process, or after cooking and before putting the pulp in a papermaking machine, after the release of the fabric from the paper machine, usually after drying, and sorting by size, either during or after processing of the fabric in the final product. In some cases, the finished or existing piece of paper, such as money, art work or documents, it is possible to irradiate the marking of the product. However, as noted above, the irradiation can be carried out at any desired stage of the process.

Exposure to influence functional groups of the material

After processing one or more ionizing radiations, for example, by photon radiation (e.g. x-rays or gamma rays), electron beam radiation or by irradiation with particles heavier than electrons that are positively or negatively charged (e.g., protons or carbon ions), the paper is ionized, that is, the paper includes radicals at levels that are logged, for example, using a spectrometer on the basis of electron spin resonance. After ionization of the paper can be neutralized to reduce the level of radicals in the ionized material to radicals, for example, could no longer be detected by a spectrometer on the basis of electron spin resonance. For example, the radicals can be neutralized by applying sufficient pressure to ionized material and/or by providing a contact of the ionized material with a fluid medium such as gas or liquid which reacts with radicals (neutralizes it). Various gases, such as nitrogen or oxygen, or liquid can be used to at least contribute to the neutralization of radicals and functionalization of ionized material of the desired functional�groups. Thus, irradiation, followed by neutralization, can be used to supply the pulp or paper of the desired functional groups, including, for example, one or more of the following: aldehyde groups, enol groups, nitroso groups, nitrile group, nitro group, ketone groups, amino groups, alkyl amino groups, alkyl groups, chloraniline group, chlortetracycline groups and/or carboxyl groups. These groups increase the hydrophilicity plot of the piece, where they are present. In some implementations, the paper web is exposed and neutralized before or after the processing steps, e.g., coating and calendering, to influence the functionality and/or on the surface of the paper and, thus, to influence the absorption capacity in relation to ink and other properties of paper.

Fig.2 illustrates changing a molecular and/or supramolecular structure of fibrous material such as paper raw materials, paper-based semi-finished product (for example, a wet paper web, or paper by pre-treatment of fibrous material with ionizing radiation, such as electrons or ions having sufficient energy to ionize the material, to provide a first level of radicals. As shown in Fig.2, if the ionized material remains in the atmosphere�e, he will be oxidized, for example, to the extent that the carboxyl group will be generated in the reaction with atmospheric oxygen. Since the radicals can "live" for some time after irradiation, for example, more than 1 days, 5 days, 30 days, 3 months, 6 months or even more than 1 year, the material properties can continue to change over time, which in some cases may be undesirable.

Detection of radicals in irradiated samples by spectroscopy based on electron spin resonance and the lifetimes of the radicals in these samples are discussed in the article Bartolotta, etc., Physics in Medicine and Biology, 46 (2001), 461-471 and article Bartolotta, etc., Radiation Protection Dosimetry, vol. 84, No. 1-4, pp. 293-296 (1999). As shown in Fig.2, the ionized material can be neutralized for functionalization and/or stabilization of the ionized material.

In some embodiments, the neutralization involves the application of pressure to ionized material, for example, by mechanical deformation of the material, for example, direct mechanical compression of the material in one, two or three dimensions, or the application of pressure to a fluid medium, which is immersed in a material, for example, isostatic pressing. The pressure can be made, for example by passing the paper through the clamp. In such cases, the deformation of the material itself leads to �the approximation radicals, often trapped in the crystalline domains, is sufficient to radicals recombinable or reacted with another group. In some cases the pressure applied in conjunction with heating, for example, by indicating the amount of heat sufficient to raise the temperature of the material above the melting point or softening point of component of the ionized material, such as lignin, cellulose or hemicellulose. Heating can increase the mobility of the molecules in the material that can contribute to neutralize the radicals.

When the pressure is used for neutralization, the pressure may exceed about 1000 psi,for example, to exceed about 1250 psi, 1450 psi 3625 psi 5075 psi 7250 psi, 10000 psi, or even exceed 15000 psi.

In some embodiments, the neutralization includes contacting the ionized material with a fluid medium such as liquid or gas, for example, a gas that can react with radicals, for example, acetylene or a mixture of acetylene in nitrogen, ethylene, chlorinated afilename or chlortetracycline, propylene or mixtures of these gases. In other specific embodiments, the neutralization includes contacting the ionized material with a liquid, such as liquid, soluble in or at least is able to penetrate the ionized material and Rea�yuusei with radicals, for example, a diene, such as 1,5-cyclooctadiene. In some specific embodiments, the neutralization includes contacting the ionized material with an antioxidant such as vitamin E. If desired, the material may include multiple antioxidant in it, and neutralization may be caused by contacting the antioxidant dispersed in the material, with the radicals.

Possible other ways of neutralization. For example, any method of neutralizing radicals in polymeric materials described in patent publication No. 2008/0067724 Muratoglu, etc. and in US patent No. 7166650, Muratoglu, etc., the disclosure of which is included here in order of reference in full, can be used to neutralize any described herein ionized material. In addition, a suitable neutralizing agent (described as a "sensitizer" in the above disclosures Muratoglu) and/or any antioxidant described in any one of the links Muratoglu, can be used to neutralize any ionized material.

The functionalization can be extended by using multiple charged ions. For example, if it is desirable to enhance oxidation, irradiation can be used ions of oxygen. If you require a nitrogen functional group, it is possible to use ions of nitrogen or any ion that includes nitrogen. Similarly, if Tr�needed sulfuric or phosphoric group, the irradiation can be used ions of sulfur or phosphorus.

In some embodiments, after neutralization neutralized material can be treated with one or more additional doses of radiation (e.g., ionizing or non-ionizing radiation, and/or can be oxidized for additional changes to molecular and/or supramolecular structure.

In some embodiments, the fibrous material is irradiated in the atmosphere of an inert gas such as helium or argon, prior to neutralization.

Location of functional groups can be controlled, for example, choosing the specific type and dose of ionizing particles. For example, gamma radiation tend to affect the functionality of the molecules in the paper, whereas electron-beam radiation tend to affect the functionality of the molecules, mainly on the surface.

In some cases, the functionalization material may occur simultaneously with the irradiation, and not as a result of a single stage of neutralization. In this case you can have different effect on the type of functional groups and degree of oxidation, for example, by controlling the gas shell of the irradiated material, through which the irradiating beam. Suitable gases include nitrogen, oxygen, air, ozone, nitrogen dioxide, sulfur dioxide and chlorine.

In some embodiments, f�nctionality leads to the formation of enol groups in the fibrous material. When fibrous material is paper, it can enhance the absorption capacity of the paper against the ink, adhesives, coatings, etc. and can provide the place the grafted copolymerization. Enol group can contribute to the reduction of molecular weight, especially in the presence of added(oops) bases or acids. Thus, the presence of such groups can contribute to cooking. In the finished product of the paper in the General case, the pH fairly close to neutral, so that these groups do not lead to a dangerous decrease in molecular weight.

Masking

In some cases it may be desirable to irradiate and/or to neutralize only a small area of paper products, for example, to create a "watermark" or to irradiate a specific symbol printed on paper, for example, the "E" on the money. In such cases, the remaining part of the paper products that should remain unmarked, it is possible to mask.

If the irradiation subject is only a small part, the remaining portion is masked with a material that is opaque to radiation, such as lead or other heavy metal. The mask must be thick enough so that the rays could not pass through it, or to weaken the radiation passing through it, sufficiently to prevent marking. If you want to label to�particular symbol for example on E-money, the product of the paper should be positioned relative to the mask so that the symbol to be labeled, was aligned with the hole in the mask. Methods such masking is well known, for example, in the semiconductor industry.

If neutralization is subject to only a small part, the remainder of the paper products can be masked during the neutralization, for example, a material that prevents contact paper products with a liquid or gas, used in the neutralization.

Irradiation with a beam of particles in fluids

In some cases, paper or cellulose or drevesnoplitnye starting materials can be irradiated by the particle beam in the presence of one or more additional fluids (e.g., gases and/or liquids). Irradiation of the material by the beam of particles in the presence of one or more additional fluids can improve the processing efficiency.

In some embodiments, the material is irradiated with a particle beam in the presence of a fluid medium, for example air. For example, particles, accelerated in the accelerator, can come out of the accelerator through the exit window (for example, a thin membrane such as a metal foil), to pass through the volume of space occupied by the fluid, and then to fall on the material. In addition to direct treatment� some material particles generate additional chemical species due to the interaction with the particles of the fluid (for example, ions and/or radicals generated by the various components of air, such as ozone and oxides of nitrogen). These generated chemical species can also interact with the material. For example, any of the produced oxidizing agent can oxidize the material.

In certain embodiments, additional fluids can selectively enter into the channel of the particle beam before the beam will fall on the material. As discussed above, the reaction between the particles of the beam particles and introduced fluids can generate additional chemical species which react with the material and can facilitate functionalization of the material, and/or otherwise selectively modify certain properties of the material. One or more additional fluids can be directed into the channel of the beam, for example, from the feed tube. The direction and flow rate input(s) fluid(s) can be selected according to the desired dose rate and/or desired direction to control the processing efficiency as a whole, including the effects caused by the processing of particles, and the effects resulting from interaction between dynamically generated particles from injected fluid with the material. In addition to air illustrative fluids that you can enter in the ion beam, includes oxygen, nitrogen, one or more noble and elegant�competitions gases one or more Halogens and hydrogen.

Cooling of irradiated materials

During the processing of the above materials with ionizing radiation, especially at high dose rate, for example, when the dose rate in excess of 0.15 Mrad per second, e.g., of 0.25 Mrad/s to 0.35 Mrad/s, 0.5 Mrad/s, and 0.75 Mrad/s or even more than 1 Mrad/sec, the material can absorb a lot of heat causing the temperature rise of the material. Although higher temperatures in some embodiments, the implementation can be useful, for example, when it is desirable to accelerate the reaction, it is desirable to control the heat to keep control of chemical reactions initiated by ionizing radiation, for example, cross-linking and/or conducting the graft copolymerization.

For example, according to one method, the material is irradiated at the first temperature with ionizing radiation, such as photons, electrons or ions (for example, single or multiple charged cations or anions), for a sufficient time and/or in a sufficient dose to bring the material to a second temperature higher than the first temperature. Then, the irradiated material is cooled to a third temperature, lower than the second temperature. If desired, the cooled material can be treated one or more times OBS�rising, for example, ionizing radiation. If desired, cooling can be applied to the material after and/or during each radiation treatment.

Cooling in some cases may include contacting the material with a fluid medium, for example gas, at a temperature below the first or second temperature, for example, with gaseous nitrogen at or about 77 K. In some implementations you can use even water, for example, water at a temperature lower than nominal room temperature (e.g. 25 degrees Celsius).

Types of radiation

Radiation can be provided, for example, in the form of: 1) heavy charged particles such as alpha particles, 2) electrons, produced, for example, in beta decay or electron beam accelerators, or 3) electromagnetic radiation, for example gamma rays, x-rays or ultraviolet rays. Different forms of radiation ionize cellulose or drevesnosmolyanoy material by means of certain interactions, depending on the energy of the radiation.

Heavy charged particles include alpha particles, which are nuclei of helium atoms and produced by the alpha decay of various radioactive nuclei, such as isotopes of bismuth, polonium, astatine, radon, France, radium, some actinides, for example, actinium, thorium, uranium, neptunium, curium,California, americium and plutonium.

The electrons interact via Coulomb scattering and bremsstrahlung generated by changing the speed of electrons. Electrons can also generate radioactive nuclei that undergo beta decay, for example, isotopes of iodine, cesium, technetium, and iridium. Alternative as a source of electrons can be used electron gun based on thermionic emission.

Electromagnetic radiation interacts in three processes: photoelectric absorption, Compton scattering and the birth of steam. The predominant interaction is determined by the energy of the incident radiation and the atomic number of the material. The summation of the interactions that contribute to the radiation absorbed in the cellulosic material, it is possible to Express the mass absorption coefficient.

Electromagnetic radiation is divided into gamma rays, x-rays, ultraviolet rays, infrared rays, microwaves or radio waves, depending on their wavelength.

According to Fig.3 and 4 (an enlarged view of a portion R), gamma radiation can be achieved by using a gamma irradiator 10 includes a source 408 of gamma radiation, for example, tablets60Co, a work table 14 for placing the irradiated materials, and storage 16, e.g., made of a plurality iron plates. �all these components are enclosed in a concrete protective bag (shelter) 20, which includes a maze 22, which is leaded door 26. Storage 16 forms many channels 30, for example, sixteen or more channels, allowing for sources of gamma radiation through the store to the desktop.

During the work of the irradiated sample is placed on the desktop. The irradiator is designed to deliver the desired dose, and a device for monitoring is connected to the experimental block 31. The operator then leaves a protective cell, passing through the maze and through the leaded door. The operator takes place at the controls 32, giving the command to the computer 33 to raise the radiation sources 12 in the operating position using the cylinder 36 attached to the hydraulic pump 40.

Gamma radiation has the advantage of considerable depth of penetration. Sources of gamma rays include radioactive nuclei, for example, isotopes of cobalt, calcium, technetium, chromium, gallium, indium, iodine, iron, krypton, samarium, selenium, sodium, thallium, and xenon.

Sources of x-rays include the collision of the electron beam with a metal target, for example, of tungsten or molybdenum or alloys or compact light sources, for example, commercially manufactured by the company Lyncean Technologies, Inc., Palo Alto, California.

Sources of ultraviolet �of zlecenia include deuterium or cadmium lamps.

Sources of infrared radiation include ceramic lamp with window made of sapphire, or zinc selenide.

Sources of microwaves include klystrons, RF sources slavinskogo type or atomic beam sources, which use gases such as hydrogen, oxygen or nitrogen.

In some embodiments, as the radiation source used in the electron beam. The electron beam has the advantages of high dose rate (e.g., 1, 5, or even 10 Mrad per second), high performance, less protective and restrictive equipment. Electrons more effectively to cause a split chain. In addition, electrons with energies of 4-10 MeV can have a depth of penetration of from 5 to 30 mm or more, for example 40 mm.

Electron beams can be generated, for example, electrostatic generators, cascade generators, transformer generators, low energy accelerators with a scanning system, low energy accelerators with a linear cathode, linear accelerators and pulsed accelerators. Electrons as an ionizing radiation source can be useful, for example, for relatively thin materials, for example, less than 0.5 inch, e.g., less than 0.4 inch, 0.3 inch, 0.2 inch, or less than 0.1 inch. In some embodiments, the OSU�of estline energy of each electron of the electron beam is from about 0.25 MeV to about 7.5 MeV (million electron volts), for example, from about 0.5 MeV to about 5.0 MeV, or from about 0.7 MeV to about 2.0 MeV. The device for electron beam irradiation can be obtained commercially from Ion Beam Applications, Louvan-La-Neuve, Belgium or the Titan Corporation, San Diego, California. The typical energy of an electron can be 1, 2, and 4.5, 7.5, or 10 MeV. Typical power device for electron beam irradiation can be 1, 5, 10, 20, 50, 100, 250 or 500 kW. A typical dose can be set 1, 5, 10, 20, 50, 100 or 200 kGy.

Compromises in consideration of specifications for the power device of the electron beam irradiation include operating costs, capital costs, depreciation, and the area occupied by the device. Tradeoffs in considering the levels of irradiation dose of electron beam irradiation are the issues of energy and environment, safety and health (ESH). Generators usually are enclosed in the shelter, for example, of lead or concrete.

A device for electron beam irradiation can produce either a fixed beam or a scanning beam. The scanning beam can be concentrated on large scale scanning and high speed scanning that can effectively replace large fixed beam width. Also, the range scan can be 0.5 m, 1 m, 2 m or more.

According to vari�ntam implementation in which the irradiation is electromagnetic radiation, the electromagnetic radiation may have a photon energy (in electron-volts), for example, more than 102eV, for example, more than 103, 104, 105, 106or even more than 107eV. In some embodiments, the electromagnetic radiation has a photon energy of 104up to 107for example , from 105up to 106eV. Electromagnetic radiation may have a frequency of, for example, more than 1016Hz, more than 1017Hz, 1018, 1019, 1020or even more than 1021Hz. In some embodiments, the electromagnetic radiation has a frequency between 1018up to 1022Hz, for example, from 1019up to 1021Hz.

One type of accelerator that can be used to accelerate ions produced by using the sources discussed above, is a Dynamitron® (available, for example, from Radiation Dynamics Inc., now a division of the IBA, Louvan-La-Neuve, Belgium). Diagram 1500 accelerator Dynamitron® shown in Fig.5. Accelerator 1500 includes an injector 1510 (which includes the ion source and accelerating column 1520, which includes a plurality of ring electrodes 1530. Injector column 1510 and 1520 are enclosed in the casing 1540, the air which is pumped out by a vacuum pump 1600.

Injector 1510 generates an ion beam 1580 and introduces �ucok 1580 in accelerator column 1520. Ring electrodes 1530 are maintained at different electrical potentials, whereby ions are accelerated when passing through the gaps between the electrodes (for example, ions are accelerated in the gaps, but not in the electrodes where the electric potentials are homogeneous). With the passage of the ions from the top of the column 1520 its lower part, as shown in Fig.5, the average speed of the ions increases. The interval between successive annular electrodes 1530 are usually increased in accordance with increasing the average velocity of the ions.

After accelerated ions pass along the length of the column 1520, an accelerated ion beam 1590 is removed from the casing 1540 through the guide tube 1555. The length of the guide tube 1555 is selected so that the proper screen (for example, the concrete screen) could be placed next to the column 1520, isolating the column. After passing through the tube 1555, ion beam 1590 passes through the scanning magnet 1550. The scanning magnet 1550, acting under the control of external logic devices (not shown) may controllably swing the accelerated ion beam 1590 in two-dimensional plane perpendicular to the Central axis of the column 1520. According to Fig.5, ion beam 1590 passes through the window 1560 (e.g., a window or screen of metal foil) and then sent to the scanning magnet 1550 to fall on selected�s sample plots 1570.

In some embodiments, the electric potentials applied to electrodes 1530 are static potentials generated by, for example, a source of DC potential. In certain embodiments, some or all of the electric potentials applied to electrodes 1530 are changing potentials generated by a source of alternating potential. Suitable variables sources of large electric potentials include sources of enhanced fields, such as klystrons. Accordingly, depending on the nature of the potentials applied to electrodes 1530, 1500 accelerator can operate in pulsed or continuous mode.

To achieve a selected energy of accelerated ions at the outlet end of the column length of column 1520 1520 and the potentials applied to electrodes 1530 are selected based on considerations known in the art. However, it is noteworthy that to reduce the length of the column 1520 instead of a single charged ions can be used multiple charged ions. Thus, accelerating the selected action of an electrical potential difference between two electrodes is greater for an ion bearing a charge of magnitude 2 or more than for an ion bearing a charge of magnitude 1. Thus, an arbitrary ion X2+may be accelerated to a final energy E on FR�had a shorter length, than the corresponding arbitrary ion X+. Thrice and four times charged ions (for example, X3+and X4+) may be accelerated to a final energy E on shorter distances. Thus, the length of the column 1520 can be significantly reduced when the ion beam 1580 includes, basically, a multiple charged ions.

To accelerate positively charged ions, the potential difference between the electrodes column 1530 1520 are selected so that the field strength in Fig.5 increased in a downward direction (e.g., to the lower part of the column 1520). On the contrary, when the 1500 accelerator is used to accelerate negatively charged ions, a potential difference between the electrodes 1530 in the column 1520 have the opposite sign, and the field strength in Fig.5 increases upward (e.g., toward the top of the column 1520). Reconfiguration of electric potentials applied to electrodes 1530, is a routine procedure, so the accelerator in 1500 to rebuild relatively quickly with the acceleration of positive ions to accelerate negative ions and Vice versa. Similarly, the accelerator 1500, you can quickly rebuild with the acceleration of single charged ions to accelerate multiple charged ions and Vice versa.

To generate ions suitable for ion beams that can be used when treatment� paper or original pulp or drevesnoplitochnykh materials you can use different ways. After generating the ions are usually accelerated in accelerators of one or more different types and then sent to bombardment of the material being processed. Different types of accelerators and equipment for generating an ion beam as described in the application US No. 12/417707 included here in the order of reference.

Dose

In some embodiments, the irradiating (with any radiation source or combination of sources) is performed until such time as the material will not take the dose at least of 0.05 Mrad, e.g., at least 0.1, and 0.25, and 1.0, 2.5 or 5.0 Mrad. In some embodiments, the irradiation is carried out until, until the material will not take the dose from 0.1 to 2.5 Mrad. Other suitable ranges can be from 0.25 to 4.0 mrad Mrad, 0.5 Mrad to 3.0 mrad 1.0 Mrad 2.5 Mrad.

Achieved the degree of functionalization in the General case, the higher, the higher dose.

In some embodiments, the irradiation is carried out with the dose rate from 5.0 to 1500,0 krad/h, for example, from 10.0 to 750,0 krad/h, and 50.0 to 350.0 krad/h. When you need high performance, for example, during high-speed paper production process, radiation can be applied at dose rates, for example, from 0.5 to 3.0 mrad/s or even greater with the use of cooling to avoid overheating of the irradiated mate�Yala.

In some embodiments, providing the irradiation of the coated paper, coating paper includes a polymer that is capable of cross-linking, for example, diacrylate or polyethylene. In some cases, the polymer forms cross-links upon irradiation of paper that can further contribute to the optimization of resistance to abrasion and other surface properties of the paper. In these embodiments, the radiation dose is selected high enough to achieve the desired functionalization of the paper, i.e. at least from about 0.25 to about 2.5 Mrad, depending on the material, and at the same time low enough to avoid negative influence on the coating of paper. The upper limit of the dose will vary depending on the composition of the coating, but in some embodiments, the preferred dose is less than about 5 Mrad.

In some embodiments, the implementation uses two or more radiation source, for example, two or more ionizing radiation. For example, samples can be processed in any order beam of electrons, followed by gamma radiation and/or UV light having a wavelength from about 100 nm to about 280 nm. In some embodiments, the samples are processed by three sources of ionizing radiation, e.g., electron beam electric�new, gamma rays and energetic UV light.

Identification of marked paper products

Paper products, labeled using the methods described herein, can be distinguished from similar-looking unmarked paper products by determining the functionality of paper. For example, to prepare IFS image of the desired paper using the infrared spectrometer and compare the picture with "control" if a snapshot of the marked paper. For example, if you marked the paper was functionalized to increase the number of carboxyl groups in the paper, if a picture of the paper under test to determine whether she was similarly marked, shall have carboxyl peak at substantially the same height as carboxyl peak in control of if picture.

Alternative ways of testing the paper for marking include AFM, CFM and ESR.

Supplement to the paper

Any of numerous additives and coatings used in paper production, can be added to or applied to fibrous materials, paper or any other described herein materials and products. Additives include fillers, such as calcium carbonate, pigments for plastic, graphite, wollastonite, mica, glass, fiberglass, quartz and talc, inorganic flame retardants, such�EP, the trihydrate of aluminum oxide or magnesium hydroxide; organic flame retardants, such as chlorinated or brominated organic compounds, carbon fibers and metal fibers or powders (e.g., aluminum, stainless steel). These supplements can enhance, extend or alter the electrical or mechanical properties, properties, compatibility, or other properties. Other additives include starch, lignin, flavors, binders, antioxidants, cloud emulsions, thermal stabilizers, colorants, e.g., dyes and pigments, polymers, e.g., degradable polymers, photostabilizers and biocides. Illustrative biodegradable polymers include polyhydroxybutyrate, for example, polylactic acid called PLA, polyglycolide and copolymers of lactic acid and glycolic acid, poly(hydroxybutyric acid), poly(hydroxyvalerenic acid), poly[lactide-co-e-caprolactone)], poly[glycolide-co-(e-caprolactone)], polycarbonates, poly(amino acids), poly(hydroxyalkanoate)s, polyanhydrides, polyarteritis and mixtures of these polymers.

At desire it is possible to add various additives for cross-linking. Such additives include materials that are capable to the formation of cross-links, and materials that will contribute to the formation of cross-linkages� in cellulose or drevesnosmolyanoy the material in the paper. Additives for cross-linking include, but are not limited to, lignin, starch, diacrylate, compounds of butadiene and polyethylene. In some implementations, such additions are made in concentrations from about 0.25% to about 2.5%, e.g. from about 0.5% to about 1.0%.

When incorporated, such additives they may be present in amounts, calculated on the basis of dry weight, from less than about 1 percent up to about 80 percent based on the total weight of fibrous material. More typically in the range of from about 0.5 percent to about 50 percent by weight, e.g. from about 0.5 percent to about 5 percent, 10 percent, 20 percent, 30 percent or more, e.g., 40 percent.

Any additives described herein can be encapsulated, for example spray drying, or microencapsulate, for example, additives to protect from heat or moisture during manipulation.

Suitable coatings include any of a number of coatings used in paper production to ensure specific surface characteristics, including characteristics of the performance required for specific applications printing.

As mentioned above, in the composition of the paper may be incorporated various fillers. For example, it is possible to use inorganic fillers, e.g., calcium carbonate (e.g., precipitated Carbo�at calcium carbonate or natural calcium), aragonite clay, orthorhombic clays, calcitrol clay, rhombohedral clay, kaolin clay, bentonite clay, dicalcium phosphate, tricalcium phosphate, calcium pyrophosphate, insoluble sodium metaphosphate, precipitated calcium carbonate, magnesium orthophosphate, trimagnesium, hydroxyapatite, synthetic apatites, alumina, quartz xerogel, metal aluminosilicate complexes, sodium silicates of aluminum, zirconium silicate, silicon dioxide, or a combination of inorganic additives. Fillers can be, for example, a particle size greater than 1 micron, for example, more than 5, 10, or 25 microns or even more than 35 microns.

Fillers of nanometer scale can also be used separately or in conjunction with a fibrous material of any size and/or shape. Fillers may be in the form of, for example, particles, plates or fibers. For example, you can use nanometer size clay, silicon and carbon nanotubes and silicon nanowires and carbon. The filler can have a transverse dimension less than 1000 nm, e.g., less 900, 800, 750, 600, 500, 350, 300, 250, 200 or 100 nm or even less than 50 nm.

In some embodiments, nanoglide is a montmorillonite. Such clays are available from Nanocor, Inc. and Southern Clay Products and are described in patents US №№ 6849680 and 6737464. Clay can be subjected to a surface treatment to �of remesiana, for example, polymeric or fibrous material. For example, the clay can be subjected to a surface treatment so that its surface had ionic nature, for example, cationic or anionic.

You can also use aggregated or agglomerated fillers of nanometer scale or fillers of nanometer scale assembled in supramolecular structures, for example, self-assembling supramolecular structures. Aggregated or supramolecular fillers may have an open or closed structure and may have various shapes, for example, cells, tubes, or spheres.

The lignin content

Reviewed here paper products may contain lignin, for example, to 1, 2, 3, 4, 5, 7,5, 10, 15, 20 or even 25% by weight lignin. This is the lignin content can be explained by the presence of lignin in drevesnosmolyanoy(s) material(s) used(s) for the production of paper. Alternative or additionally, the lignin may be added to the paper as an additive, as mentioned above. In this case, the lignin can be added in solid form, for example in the form of powder or other material in the form of particles, or can be dissolved or diluted and added in a liquid form. In the latter case, the lignin can be dissolved in a solvent or solvent system. The solvent or solvent system may interconnect with�SQL in one phase or of two or more phases. Solvent system for cellulose and drevesnoplitochnykh materials include system DMSO-salt. Such systems include, for example, DMSO, together with a salt of lithium, magnesium, potassium, sodium or zinc. Lithium salts include LiCl, LiBr, LiI, lithium perchlorate and lithium nitrate. Magnesium salts include magnesium nitrate and magnesium chloride. Potassium salts include iodide and potassium nitrate. Examples of salts include sodium iodide and sodium nitrate. Examples of zinc salts include the chloride and nitrate of zinc. Any salt may be anhydrous or hydrogenated. Typical loading salt in DMSO is from about 1 to about 50 percent, e.g. from about 2 to about 25, from about 3 to about 15 or from about 4 to about 12.5 percent by weight.

In some cases, the lignin will form cross-links in the paper during exposure, further improving the physical properties of paper.

Paper types

Paper is often classified by weight. The weight assigned to a paper is the weight of a stack of 500 sheets of variables "basic sizes", before the paper is cut to size for sale to final consumers. For example, a ream of 20 lb. paper size of 8½ × 11" weighs 5 pounds, because it's cut from a larger sheet into four pieces. In the United States, paper for printing in General has a weight of 20 pounds, 24 pounds, or a maximum of 32 Fung�and. Binding material in General has a weight of 68 pounds and 110 pounds or more.

In Europe the weight is expressed in grams per square meter (g/m2or just g). Printing paper in General has a weight of from 60 g to 120 g. All items heavier than 160 g is considered to be the cardboard. Therefore, the weight of the stack depends on the size of paper, for example, a stack of A4 size (210 mm × 297 mm) (approx 8,27" x 11,7") weighs 2.5 kilograms (about 5.5 pounds).

The density of paper ranges from 250 kg/m3(16 lb/ft3for swipe up to 1500 kg/m3(94 lb/ft3for some special kinds of paper. In some cases the density of printing paper is about 800 kg/m3(50 lb/ft3).

The described processes are suitable for use with all these papers, and also other types of paper, for example, corrugated cardboard, cardboard and other paper products. Described here the process can be used for processing paper, which is used, for example, in any of the following applications: as postage stamps, paper money, notes, securities, cheques, etc., in books, magazines, Newspapers, and works of art, and for packaging, e.g. cardboard, corrugated cardboard, paper bags, envelopes and boxes. The paper may be single-layer or multilayer paper or maybe about�Asociate part of the laminate. Marking can be used in trade to indicate the purchase, use, or other events. For example, the markings can be used to "extinguish" postal payment or to indicate where and/or when you purchased the product.

Paper can be made from any desired type of fiber, including fiber extracted from wood pulp and recycled paper, and fibers obtained from other sources. Materials based on plant fibers, such as cotton, hemp, flax and rice, can be used separately or in conjunction with each other or with wood fibers. Other, non-timber sources of fibre include, but are not limited to, sugar cane, bagasse, straw, bamboo, kenaf, jute, flax fibers and cotton. A variety of synthetic fibers such as polypropylene and polyethylene, as well as other ingredients, for example, inorganic fillers, can be included in the composition of the paper as a means of imparting desirable physical properties. It may be desirable to implement these non-wood fiber in the paper used for special applications, e.g. for paper money, fine stationery, art paper and other applications requiring high strength or aesthetic characteristics.

The paper can be irradiated before or after printing.

Technical water

In the disclosed here p�acesso every time when water is used in any process, it can be waste water, such as municipal wastewater or household waste water. In some embodiments, the implementation of domestic or commercial wastewater sterilised prior to use. Sterilization can be carried out by any desired method, for example, by irradiation, steam or chemical sterilization.

Other implementation options

It is apparent that although the invention is described in connection with its detailed description, the foregoing description is intended to illustrate the invention but not to limit its scope, which is defined by the scope of the following claims.

Other aspects, advantages and modifications are in the scope of the following claims.

1. A method of manufacturing a labeled paper products, wherein the method comprises irradiation of the area of paper products electron beam with a dose, of from 0.10 Mrad to about 5 Mrad, where the electrons have an energy of from about 0.25 MeV to 10 MeV, in conditions that are selected to modify functionalization of the specified area of paper products, so to label a piece of paper marking which cannot be seen with the naked eye.

2. A method according to claim 1, wherein the irradiation is carried out under conditions selected to increase the number of�and carboxyl groups, present in the irradiated area paper products.

3. A method according to claim 1, wherein using irradiation to generate radicals in the irradiated area paper products.

4. A method according to claim 3, which additionally includes the neutralization of the radicals to obtain a neutralized paper products.

5. A method according to claim 4, wherein the neutralization is carried out in the presence of a gas selected to react with radicals present in the irradiated piece of paper, and reacts with radicals.

6. A method according to claim 1, which additionally includes masking the rest of the paper products that differ from the specified area, a material that is opaque to radiation.

7. A method according to claim 1, wherein the specified region is formed in the form of a watermark or symbol.



 

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