JP2011149107A - Falsification-preventing paper - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a falsification-preventing paper enabling signs of falsification to be easily visually checked when printing ink is intended to be removed by using various kinds of organic solvents to falsify the content printed on the surface of a printed matter, causing little change with time in color and having high stability. <P>SOLUTION: The falsification-preventing paper is constituted of two or more paper layers comprising a paper layer (1) containing a water-insoluble and organic solvent-soluble dye and/or pigment, and a paper layer (2) free from the water-insoluble and organic solvent-soluble dye and/or pigment, regulated so that the paper layer (2) free from the water-insoluble and organic solvent-soluble dye and/or pigment may form the outmost paper layer of at least one surface of the falsification-preventing paper. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a falsification preventing sheet. More specifically, the present invention relates to a tamper-proof sheet that allows a person with malicious intent to tamper with an organic solvent so that the trace can be easily visually confirmed.

  Securities such as banknotes, stock certificates, checks, gift certificates, ID cards such as passports, various admission tickets, sealed labels for expensive products, protective labels for branded products, labels for protecting personal information, etc. are not used illegally. Various tampering prevention measures are taken.

For example, Patent Document 1 proposes an anti-counterfeit paper in which fluorescent dye particles that are water-insoluble and organic solvent-soluble are contained in the paper. It is possible to confirm falsification by presenting. However, in this case, it is necessary to use a special light source such as a black light that can be irradiated with ultraviolet rays in order to visually recognize the tampering trace.

  Therefore, it has been proposed to provide tamper-proof means that can be easily viewed without using special equipment under natural light or normal illumination. Patent Document 2 discloses a forgery-preventing sheet material provided with a coating layer containing a water-insoluble and organic solvent-soluble dye and / or pigment, which is visible to visible traces of tampering caused by dripping of an organic solvent. Visible below. However, due to the compatibility between organic solvent-soluble dyes and / or pigments and organic compounds such as synthetic resins used as binders for base materials and coating layers, some of the dyes and pigments are transferred to the coating layers over time. There is a problem that the color of the sheet changes due to the phenomenon of melting out, so-called bleed out. In addition, even when the dye or pigment is present only in the base material and not contained in the coating layer, the dye or pigment contained in the base material is colored by heating or light at the point of direct contact with the coating layer. Sometimes occurred. Furthermore, when the base material is a film or synthetic paper, the bleed-out extends to the base material. In addition, for use in securities, labels, etc., it is necessary to print on the anti-counterfeit sheet or to be applied with an adhesive or pressure sensitive adhesive. There was also a problem that bleedout of dyes and pigments occurred due to the adhesive component. As described above, since the color of the sheet is changed by bleed-out or coloring by heating regardless of whether or not tampering has occurred, there is a problem that it is not possible to clearly determine whether or not tampering has occurred.

JP 2000-129596 A JP 2008-31594 A

  When various organic solvents are used for the purpose of falsifying the printed content of printed matter, it is a falsification-preventing paper in which the traces of the tampering can be easily seen. It is an object of the present invention to provide a falsification-preventing paper in which the color change of the paper due to pigment bleed-out is small. Also consider falsification-preventing paper that is not affected by discoloration caused by bleed-out. Furthermore, the present invention provides a highly stable falsification preventing paper that does not generate color due to heat or light even when a coating layer is provided.

  That is, the invention according to claim 1 of the present invention is a tamper-proof paper composed of two or more paper layers, a paper layer (1) containing a water-insoluble and organic solvent-soluble dye and / or pigment, A paper layer (2) that does not contain insoluble and organic solvent-soluble dyes and / or pigments, and the outermost paper layer on at least one side of the falsification preventing paper is water-insoluble and organic solvent-soluble. A tamper-proof paper characterized in that it is a paper layer (2) containing no dye and / or pigment.

  The invention according to claim 2 of the present invention is a falsification preventing paper comprising three or more paper layers, wherein the outermost paper layers on both sides of the falsification preventing paper are the water-insoluble and organic solvent-soluble dye and 2. The falsification preventing paper according to claim 1, wherein the paper layer (2) does not contain a pigment.

  The invention according to claim 3 of the present invention is characterized in that a coating layer is provided on the surface of the outermost paper layer (2) which does not contain a water-insoluble and organic solvent-soluble dye and / or pigment. The falsification preventing paper according to claim 1 or 2.

  The invention according to claim 4 of the present invention is the falsification preventing paper according to any one of claims 1 to 3, wherein the ISO whiteness (JIS P-8148: 2001) is 80% or more.

  Hereinafter, a paper layer (1) containing a water-insoluble and organic solvent-soluble dye and / or pigment is referred to as “paper layer (1)”, and a water-insoluble and organic solvent-soluble dye and / or pigment-free paper layer (2). ) Is called “paper layer (2)”.

  According to the falsification-preventing paper according to the present invention, for example, a malicious person removes printing ink components at a printing location using various organic solvents for the purpose of falsifying the display contents of securities etc. using the present invention. In this case, since the organic solvent penetrates into the paper and the dyes and pigments contained in the paper layer (1) are eluted and color develops, a third party can easily see the trace of tampering. Furthermore, since the outermost paper layer of the falsification preventing paper is the paper layer (2), the printing ink component does not reach the paper layer (1) when printing is performed on the surface of the outermost paper layer. And pigment elution does not occur. In addition, since the present invention has a configuration in which a coating layer is provided on the surface of the paper layer (2), the dyes and pigments contained in the paper layer (1) are not directly in contact with the coating layer and are eluted in the coating layer. It is possible to prevent color development.

FIG. 1 is a schematic diagram showing a cross-sectional view of an example of the falsification preventing paper according to claim 1 of the present invention. FIG. 2 is a schematic diagram showing a cross-sectional view of an example of the falsification preventing paper according to claim 2 of the present invention. FIG. 3 is a schematic diagram illustrating a circular paper machine, which is an example of an apparatus for making the falsification preventing paper of the present invention. FIG. 4 is a schematic view showing a cross-sectional view of an example of the falsification preventing paper according to claim 3 of the present invention. FIG. 5 is a schematic view showing an example of use when the present invention is applied to a check. FIG. 6 is a schematic view showing an example of use when the present invention is applied to a sealed label.

  In the present invention, water-insoluble and organic solvent-soluble dyes and / or pigments are used. In general, falsification prevention papers are printed with oil-soluble ink, and variable information such as address, name, and amount is written with oil-based pens such as ball-point pens that use oil-soluble ink. In many cases, an organic solvent is used to falsify these printing information and variable information. Therefore, by using water-insoluble and organic solvent-soluble dyes and / or pigments in the paper, when falsified using an organic solvent, the color of the falsified portion can be colored, so that the traces of falsification can be easily visually confirmed. it can. On the other hand, if a water-soluble dye or pigment is used, it is not only difficult to visually recognize the trace of the alteration, but it is not suitable because the dye or pigment dissolves in water during the paper manufacturing process.

  Any dye that is insoluble in water and soluble in organic solvents can be used as the water-insoluble and organic solvent-soluble dye used in the present invention. For example, various dyes such as azo series, aminoketone series, coumarin series, oxazole series, pyrarizone series, anthraquinone series are included, but not limited thereto. This type of dye is sold by a dye maker, but examples include “Oil Red 5B” (manufactured by Orient Chemical Industries), “Yellowfluor 10GN” (manufactured by LANXESS), “ “Kayaset Flavin FN” (manufactured by Nippon Kayaku Co., Ltd.), “Leucopher EF 2N” (manufactured by Clariant Japan), “TBO” (manufactured by Sumitomo Seika Co., Ltd.), “Kayaset Red SF-R” (Japan) Kayaku Co., Ltd.), “VALIFAST BLUE 1605” (manufactured by Orient Chemical Industries, Ltd.), “Oil Green BG” (manufactured by Orient Chemical Industries, Ltd.), “VALIFAST RED 2303” (Orient Chemical Industries, Ltd.) Manufacturing), “Oil Blue BOS” (Orient Chemical) Manufacturing Co., Ltd.), "SPILON RED GEH Special" (Hodogaya Chemical Industry Co., Ltd.), "Macrolex Violet 3R" (Manufactured by Lanxess Co., Ltd.), "MACROLEX Red 5B FG" (Manufactured by Lanxess Co., Ltd.) , “MACROLEX Green 5B” (manufactured by LANXESS Corporation), “MACROLEX Blue RR” (manufactured by LANXESS Corporation), “Kayalon Polyester Navy Blue TKN-SF 200” (manufactured by Nippon Kayaku Co., Ltd.), “Kayfect Blue” "T" (manufactured by Nippon Kayaku Co., Ltd.), "Kayaset Blue 814" (manufactured by Nippon Kayaku Co., Ltd.), "SPILON BLUE 2BNH" (manufactured by Hodogaya Chemical Co., Ltd.), "SPIRON GREEN 3GNH Spe" Cial "(manufactured by Hodogaya Chemical Co., Ltd.) and the like, but is not limited thereto. Among these, azo dyes, aminoketone dyes, coumarin dyes, and anthraquinone dyes are particularly preferable because the color development under visible light is colored and bright.

  Water-insoluble and organic solvent-soluble pigments used in the present invention are azo, phthalocyanine, anthraquinone, perlin, pyranthrone, quinacridone, dioxazine, isoindolinone, thioindigo, quinophthalone, and metal. Organic pigments such as pigments, carbons, sulfur oxides, cuprous oxides, sulfates, carbonates, silicates, chromates, aluminates, ferrocyanates, etc. Although it is mentioned, it is not limited to these. Examples of product names include “TB-200 Red GY”, “TB-500 Orange R”, “TB-520 BLUE 2B”, “TB-510 Green B”, “Seika First Carmine 1476T-7”, “A120 "Red", "430 Brilliant Bordeaux 10B", "Mono Azo Lake 10G", "Seika First Red 116", "Seika First Yellow 1983-10G" (all manufactured by Dainichi Seika Kogyo Co., Ltd.), etc. Is not to be done. In particular, it is preferable to use an azo pigment or a phthalocyanine pigment because the color development under visible light is colored and vivid.

  The water-insoluble and organic solvent-soluble dyes and / or pigments used in the present invention may be used alone or in combination of two or more. In particular, by selecting and mixing different dyes and / or pigments that can be dissolved in two or more types of organic solvents having different solubility parameters, it becomes possible to respond widely to tampering using various organic solvents. Therefore, it is preferable.

  Various organic solvents used for falsification include methanol, ethanol, normal propyl alcohol, isopropyl alcohol, aniline, acetone, methyl ethyl ketone, chloroform, cresol, acetonitrile, benzene, normal hexane, cyclohexane, ethyl acetate, toluene, xylene, octane, etc. Various organic solvents and mixtures thereof, naphtha which is a petroleum middle distillate, fats and oils, and the like can be considered. These organic solvents differ in the types of dyes and pigments that can be eluted due to differences in solubility parameters. Therefore, as described above, two or more kinds of water-insoluble and organic solvent-soluble dyes and / or pigments are mixed and included in the present invention, thereby exhibiting color developability with respect to a plurality of organic solvents having different solubility. As compared with the case where the dye or the pigment is used alone, the tamper-preventing effect can be easily obtained.

  The solubility parameter is a value called an sp value, and is one factor that determines the solubility of the polymer, dye, pigment, and the like with the solvent. In general, polar polymers, dyes, pigments, and the like tend to be soluble in polar solvents and are less soluble in nonpolar solvents. On the other hand, non-polar polymers, dyes, pigments and the like tend to reverse. A factor for judging the strength of this affinity is a solubility parameter, which is indicated by δ. When the molar heat of vaporization of the solvent is ΔH and the molar volume is V, it is defined as δ = (ΔH / V) 1/2.

  The falsification preventing paper of the present invention is composed of two or more paper layers. The production method is not particularly limited, and a known paper machine such as a long paper machine, a circular paper machine, or a short paper machine can be used in appropriate combination. FIG. 3 is a schematic diagram illustrating a three-layer structure of a circular net paper machine as an example of a manufacturing method. The circular net paper machine is characterized by a structure in which a cylindrical wire 31 is inserted into a bat 30. The diluted paper raw pulp is fed into the vat 30, and as the cylindrical wire 31 rotates, the paper material sticks to the surface of the net and becomes wet paper. The wet paper attached to the wire 31 is transferred to the blanket 32. As shown in FIG. 3, paper having a layer structure of two or more layers can be made by arranging a plurality of cylinders in series.

The falsification preventing paper of the present invention comprises a paper layer (1) and a paper layer (2). For example, in the case of two paper layers, one paper layer is the paper layer (1) and the remaining one paper layer is the paper layer (2). An example of this configuration is shown in FIG. The reason why the paper layer (1) is provided is to make it possible to visually recognize traces of tampering with the organic solvent as described above, and the organic solvent penetrates into the paper and the dye or pigment contained in the paper layer (1). When this value is reached, the effect of coloring the dye or pigment is obtained.

As described above, printing using oil-soluble ink is often performed as an application of the falsification preventing paper of the present invention. Alternatively, an adhesive layer or a pressure-sensitive adhesive layer may be applied when used as a label. When such an oil-soluble ink or adhesive component is directly applied to the surface of the paper layer (1), it directly touches the dye or pigment contained in the paper layer (1), causing bleeding out. For example, offset printing often uses inks mainly composed of oxidative polymerization type dry oil, etc., and its vehicle is synthetic resin such as rosin-modified phenol, petroleum resin, alkyd resin, linseed oil, drill oil, large Dry oils such as bean oil and synthetic dry oil, other solvents and auxiliaries are used, and these ink components cause bleeding out. Therefore, the present invention requires that the paper layer (2) is at least the outermost paper layer on one side of the paper. By applying printing or an adhesive layer on the surface of the paper layer (2) that is the outermost paper layer, an ink component such as a vehicle or an adhesive component is directly applied to the dye or pigment contained in the paper layer (1). Touching can be prevented. In particular, in the case of a vehicle having quick drying properties, the solvent evaporates before reaching the paper layer (1) even if it penetrates the paper layer (2). When the present invention is composed of three or more paper layers, the outermost paper layers on both sides thereof are preferably the paper layer (2). In this case, it is possible to provide printing and an adhesive layer on both sides of the present invention. FIG. 2 illustrates a configuration of a three-layer paper layer according to the present invention, in which the outermost paper layers on both sides of the paper are the paper layer (2). The “outermost paper layer” refers to, for example, a paper layer that is the uppermost layer and a paper layer that is the lowermost layer when viewed in cross-sectional views such as FIG. 1 and FIG.

As a method of providing the paper layer (1) and the paper layer (2), for example, in FIG. 3, a pulp raw material containing a water-insoluble and organic solvent-soluble dye and / or pigment and a water-insoluble and organic solvent-soluble dye and / or A pulp raw material not containing a pigment is prepared. Then, the former pulp raw material is applied only to the central bat 33 and the latter pulp raw material is applied to the bats 34 other than the bat 33, whereby the paper layer (1) is provided on the intermediate paper layer and the outermost paper on both sides. Paper for falsification as shown in FIG. 2 containing the paper layer (2) in the layer can be produced.

As the raw fiber for the paper layer (1) and the paper layer (2), wood pulp generally used for papermaking, for example, softwood bleached kraft pulp (NBKP), hardwood bleached kraft pulp (LBKP), softwood bleached monkey A single or mixture of phytopulp (NBSP), thermomechanical pulp (TMP), or the like can be used. In addition, hemp, bamboo, cocoon, kenaf, cocoon, cocoon, cotton and other non-wood pulp, cationized pulp, mercerized pulp and other modified pulp, microfibrillated pulp, rayon, vinylon, nylon, acrylic, Recycled fibers such as polyester, semi-synthetic fibers, and synthetic fibers can be appropriately mixed with the raw material fibers. The wood pulp content is preferably 30% by mass or more for each paper layer.

Various internal chemicals for papermaking can be used for the raw fiber as necessary. Examples of the internal additive include a sizing agent, a wet paper strength enhancer, a dry paper strength enhancer, a filler, a drainage yield improver, a water resistance agent, a fixing agent, an antifoaming agent, and a slime control agent. However, it is desirable that an organic compound that is compatible with water-insoluble and organic solvent-soluble dyes and / or pigments is not contained in the paper layer as much as possible. For example, the organic compound may be less than 3% of the entire paper layer. . Examples of the organic compound include natural resins, synthetic resins, natural rubbers, synthetic rubbers, proteins, sugars, fats and oils, urethanes, alkaloids, tannins, other natural polymer compounds, and other synthetic polymer compounds. When these organic compounds are contained in the paper layer, there is a possibility that the dye or pigment contained in the paper layer (1) will elute when in contact to cause bleeding out.

The basis weight of the present invention, but are not particularly limited, for example, be a ^{30~250g / m 2, 60~100g / m} 2 is preferred.

  Further, as long as the performance of the present invention is not impaired, processing such as calendering, super calendering, and soft nip calendering may be performed during the paper making process or after the paper making process.

  In the present invention, a coating layer can be provided on the surface of the paper layer (2) which is the outermost paper layer on one or both sides of the paper. An example of this is shown in FIG. When the outermost paper layer on both sides of the paper is the paper layer (2), a coating layer may be provided on both sides, or a coating layer may be provided only on one side. By providing the coating layer, various functions can be imparted to the paper. For example, by providing a coating layer in which a pigment such as kaolin or calcium carbonate and a binder are mixed, offset printing suitability, opacity, whiteness and the like can be improved. Or the coating layer corresponding to various printing and media, such as an inkjet receptive layer, a heat sensitive layer, and a sublimation heat transfer layer, can also be provided. In the present invention, since the coating layer is provided on the surface of the paper layer (2), the binder in the coating layer and the dye or pigment of the paper layer (1) are not in direct contact. Therefore, for example, even if the coating layer is eluted by heat or the like, coloring of the dye or the pigment can be prevented.

The pigment used for the coating layer may be blended with a filler generally used for papermaking. Fillers include clay, light calcium carbonate, heavy calcium carbonate, kaolin, titanium dioxide, talc, colloidal silica, alumina, aluminum hydroxide, calcium sulfate, barium sulfate, zinc oxide, satin white, synthetic amorphous silica, silica Fillers such as aluminum silicate, magnesium silicate, calcium silicate, magnesium carbonate, and zeolite can be used alone or in combination of two or more as required.

As the binder contained in the coating layer, water-soluble vinyl resins such as polyvinyl alcohol, modified polyvinyl alcohol, and polyvinylpyrrolidone, starch or starch derivatives such as starch, oxidized starch, and modified starch, carboxymethylcellulose, carboxyethylcellulose, casein, soybean Protein, gelatin, polymethyl methacrylate, methyl methacrylate / butadiene copolymer, SBR, MBR, urea resin, melamine resin, acrylic resin, styrene acrylic resin, maleic anhydride resin, acrylic ester, ethylene / vinyl acetate copolymer, Cross-linked polymethyl methacrylate and the like can be used alone or in combination.

Moreover, a general paper processing chemical can be used for the coating material for forming the coating layer as long as the performance of the present invention is not impaired. For example, auxiliary agents such as antifoaming agents, antifoaming agents, antistatic agents, antioxidants, ultraviolet absorbers, thickeners, dispersants, water resistance agents, preservatives, dyes, pigments can be used as necessary. .

As a coating method for the coating layer, general coating methods such as a blade coater, a bar coater, an air knife coater, a die coater, a curtain coater, a size press coater, a gate roll coater, and various printing methods can be used. The coating layer is preferably provided in an amount of 0.05 to 40 g / m ² in terms of dry weight per unit area of paper.

  In the present invention, the ISO whiteness specified in JIS P-8148 (2001) is preferably 80% or more. For example, as shown in FIG. 1, when an anti-falsification paper in which the outermost paper layer on one side is the paper layer (2) and the other side is the paper layer (1) is used as a label, the paper layer (2) Printing is performed on the surface, and an adhesive is applied to the surface of the opposite paper layer (1). In this case, the dye or pigment of the paper layer (1) may elute into the pressure-sensitive adhesive layer and develop a color. When the ISO whiteness is less than 80%, the color development may also occur from the paper layer (2) side. Although it may be visually recognized, if it is 80% or more, the possibility that the color development is visually recognized is drastically reduced. In this way, even if a color of a dye or pigment occurs on one side for some reason, if the ISO whiteness is 80% or more, it will not be affected by the color when viewed from the opposite side. Can be easily confirmed. The ISO whiteness is measured from the surface on the side where the outermost paper layer is the paper layer (2). When the outermost paper layers on both sides of the present invention are both paper layers (2), at least one value may be included in the above range of ISO whiteness. The means for setting the ISO whiteness in the above range is not particularly limited. For example, bleached pulp having a high ISO whiteness may be used as the raw fiber for the paper layer, or the blending ratio thereof may be adjusted as appropriate. Furthermore, it is preferable to increase the number and basis weight of paper layers containing a large amount of raw material fibers having high whiteness. Moreover, ISO whiteness can also be improved by using fluorescent dyes, fillers, or the like for the internal additive chemicals or the coating layer.

  In the falsification preventing paper of the present invention, it is preferable to use the surface on the side where the outermost paper layer is the paper layer (2) as the surface that is generally visually recognized like the front surface of a label or the like. Thereby, since the color change is not recognized in the surface by which it is visually recognized, it can be used conveniently as a falsification prevention paper.

  FIG. 5 is a schematic view showing an example in which the present invention is used for a check. When an organic solvent is dropped to try to falsify the number written in the amount entry column 52, water-insoluble and organic solvent-soluble dyes and / or pigments contained in the paper are dissolved and a color 51 is formed in a circular shape. Show. In this way, tampering can be easily recognized.

  FIG. 6 is a schematic view showing an example in which the present invention is used for a sealed label. After the envelope 60 is closed, a seal label 61 created using the falsification preventing paper of the present invention is attached. When the adhesive used for the sealing label 61 is peeled off with an organic solvent, and the document in the envelope is tampered with and the sealing label is re-applied, the water-insoluble and organic solvent contained in the paper Soluble dyes and / or pigments dissolve and color 62 is produced. As a result, traces of opening the seal remain, and it becomes impossible to forge or alter the label by removing the label, falsifying the internal material, and re-applying the label as it was.

  When the present invention is used as a means for preventing forgery of securities such as gift certificates and checks, a means for enhancing the effect of preventing forgery can be used in combination as long as the color developability by the solvent is not inhibited. For example, various watermarks, chemical reaction (anti-counterfeiting technology using chemical reaction such as color reaction in response to acid or alkali chemicals), security thread pasting or paper making, strips and other particles mixed, The anti-counterfeiting effect can be enhanced by using anti-counterfeiting means such as colored fiber, fluorescent fiber, and magnetic fiber.

[Preparation of paper stock]
50 parts by weight of softwood bleached kraft pulp and 50 parts by weight of hardwood bleached kraft pulp were mixed with 350 ml freeness. S. F. This was beaten into 10 parts by weight of kaolin, 0.3 parts by weight of a polyacrylamide type paper strength enhancer (trade name “Paper Strength Agent DA4112”, manufactured by Seiko PMC Co., Ltd.), and a rosin type sizing agent (trade name “Size”). Pine N771 ”(manufactured by Arakawa Chemical Industries, Ltd.) 1.0 part by mass and an appropriate amount of a sulfuric acid band were added to prepare a paper stock. This is paper stock 2. 0.005 parts by weight, average particle diameter of water-insoluble and organic solvent-soluble anthraquinone dye (trade name “MACROLEX Red Violet R” manufactured by Lanxess Co., Ltd.) having an average particle diameter of 4 μm, based on pulp solids. Was added to the pulp solid content by 0.005 parts by mass of 3 μm of water-insoluble and organic solvent-soluble pyralizone dye (trade name “Kayaset Flavine FN” manufactured by Nippon Kayaku Co., Ltd.). This is paper 1.

[Example 1]
The falsification prevention paper which consists of two layers of a surface layer and a back layer is illustrated. Using a circular net paper machine, paper 2 is applied to the front layer and paper 1 is applied to the back layer, and each sheet is made up to 45 g / m ² and a tamper-proof paper sample having a basis weight of 90 g / m ^2. Got.

[Example 2]
The falsification prevention paper which consists of three layers of a surface layer, an intermediate | middle layer, and a back layer is illustrated. Using a circular net paper machine, paper 2 is applied to the front and back layers, and paper 1 is applied to the intermediate layer, and they are combined to 30 g / m ^2, and the basis weight is 90 g / m ² . A prevention paper sample was obtained.

[Example 3]
70 parts by weight of kaolin, 30 parts by weight of calcium carbonate, and a styrene / butadiene copolymer latex (trade name “Smartex SN-322” manufactured by Nippon A & L Co., Ltd.) as a binder. % By mass) was prepared according to a conventional method. This was the surface layer of 10 g / m ² applied to the surface of the tamperproof paper obtained in Example 1 using an air knife coater, basis weight was obtained tamperproof paper samples 100 g / m ^2.

[Example 4]
For a tamper-proof paper consisting of two layers, a surface layer and a back layer, using a circular paper machine, paper 2 is applied to the front layer, paper 1 is applied to the back layer, the surface layer is 60 g / m ² , and the back layer is 30 g. / M ² to make a paper sample to prevent tampering with a basis weight of 90 g / m ² .

[Comparative Example 1]
The falsification prevention paper which consists of only one layer is illustrated. A stock 1 was applied using a circular paper machine to obtain a tamper-proof paper sample having a basis weight of 90 g / m ² .

[Comparative Example 2]
The falsification prevention paper which consists of two layers of a surface layer and a back layer is illustrated. Using the cylinder paper machine, by applying the respective stock 1 on the surface layer and the backing layer, respectively combined paper making such that 45 g / m ^2, to obtain a tamperproof paper samples having a basis weight of 90 g / m ² .

[Comparative Example 3]
The falsification prevention paper which consists of three layers of a surface layer, an intermediate | middle layer, and a back layer is illustrated. Using a circular net paper machine, the base material 1 is applied to the front and back layers, and the base material 2 is applied to the intermediate layer, and they are combined so that each becomes 30 g / m ^2, and the basis weight is 90 g / m ² . A prevention paper sample was obtained.

[Comparative Example 4]
The same aqueous coating as in Example 3 to 10 g / m ² coated on the surface of the tamperproof paper obtained in Comparative Example 2 using an air knife coater, basis weight was obtained tamperproof paper samples 100 g / m ^2.

[Comparative Example 5]
The falsification prevention paper which consists of two layers of a surface layer and a back layer is illustrated. Using the cylinder paper machine, by applying the respective stock 2 in the surface layer and the backing layer, respectively combined paper making such that 45 g / m ^2, to obtain a tamperproof paper samples having a basis weight of 90 g / m ² .

[Solvent color development evaluation test]
Toluene and isopropyl alcohol were dropped on both sides of the falsification-preventing paper samples (30 cm × 30 cm) obtained in Examples and Comparative Examples, respectively, at 5 locations, and the locations where these organic solvents were evaporated were visible under visible light. Was visually observed. The evaluation criteria were as follows, and ○ was accepted. In addition, it confirmed that the same result was obtained for visible light used for evaluation both under natural light and under illumination with an incandescent bulb.
○: Color development is recognized in any organic solvent ×: Color development is not recognized at all

[Bleed-out evaluation test]
Rosin modified phenolic resin (trade name “F-7305” manufactured by Dainippon Ink & Chemicals, Inc.) 34.5 parts, soybean oil 15 parts, linseed oil 10 parts, alkyd resin 30 parts, tall oil fatty acid ester 10 parts and aluminum A total of 100 parts of 0.5 part of chelate was heated at 190 ° C. for 1 hour to prepare a varnish. The varnish is used as an offset ink component on the surface of the falsification-preventing paper samples of Examples and Comparative Examples or on the surface of the coating layer (Comparative Example 1 is an arbitrary surface) (print name tester "PM-902PT") Offset printing (printing speed 2.0 m / sec) was performed using SMT. This was allowed to stand for 7 days in an environment of 23 ° C. and 50% relative humidity, and then the occurrence of bleeding out was visually evaluated. Evaluation criteria were as follows, and ○ was accepted.
○: No bleed-out has occurred.
X: Bleed-out has occurred, and color change of the sample due to it is recognized.

[Heat color development evaluation test]
In order to evaluate the presence or absence of coloration due to heating, the anti-tamper paper samples of Examples and Comparative Examples were placed in an oven heated to 120 ° C., heated for 10 minutes, then naturally cooled to 25 ° C., and both sides of the sample visually observed did. Evaluation criteria were as follows, and ○ was accepted.
○: No color development occurred.
X: Color development clearly occurred.

[Label suitability evaluation test]
Acrylic adhesive (trade name “Olivein BPW6111” manufactured by Toyo Ink Co., Ltd.) was converted into dry weight by the doctor blade method on the surface of the back layer of the anti-tamper paper sample (Comparative Example 1 is an arbitrary surface). The pressure-sensitive adhesive layer was formed by coating to 15 g / m ² and drying by heating. After drying, the sample was observed from the surface layer (Comparative Example 1 was the surface opposite to the coated surface), and the discoloration of the paper surface due to bleeding out was visually evaluated. Evaluation criteria were evaluated in three stages as follows, and Δ or more was regarded as acceptable.
○: Discoloration is not confirmed.
Δ: Slight discoloration is observed.
X: Discoloration is clearly recognized.

[ISO whiteness]
The ISO whiteness was measured according to JIS P-8148: 2001 with the surface of the paper layer (2) as the outermost paper layer or the surface of the coating layer facing upward. In addition, about Example 2 and Comparative Examples 1-3, it measured so that arbitrary surfaces might face up.

The evaluation results are shown in Table 1.

  As is clear from the results of Examples 1 to 4 and Comparative Examples 1 to 5, when various organic solvents are dropped on the surface of the tamper-proof paper sample obtained in Examples and Comparative Examples, the sample having the paper layer (1). All of these were confirmed to develop well. On the other hand, in Comparative Example 5 having no paper layer (1), no color development was observed. As in the case of the organic solvent, water was dropped on the samples of Examples and Comparative Examples, but no color was observed in all of the Examples and Comparative Examples. Further, when the same aqueous paint as in Example 3 was applied to the surface layer of Comparative Example 5 and a solvent color development evaluation test was performed, no color development was confirmed for the dropped organic solvent.

As a result of the bleed-out evaluation test, it was confirmed that no bleed-out occurred in the samples in which the varnish as the printing ink component was printed on the surface of the paper layer (2) as in Examples 1, 2, and 4. On the other hand, as in Comparative Examples 1 to 3, all the samples in which the varnish was printed on the surface of the paper layer (1) were bleed out, and discoloration of the samples due to the bleeding was observed. In addition, when varnish was similarly printed on both surfaces of the surface layer and the back layer of the samples of Example 2 and Comparative Example 3, Example 2 did not cause bleed out on both sides, but the sample of Comparative Example 3 showed both sides. In both cases, discoloration due to bleed out was observed.

  As a result of the heating color development evaluation test, the sample of Example 3 showed no color development, but the sample of Comparative Example 4 showed red spots on the coated surface. In the sample of Comparative Example 4, since the paper layer (1) is in contact with the coating layer, it is presumed that the dye existing near the surface of the paper layer (1) was colored by the binder of the coating layer that was dissolved by heating. The

  In the label suitability evaluation test, when Example 1 and Example 4 were compared, coloring of the dye contained in the paper layer (1) was observed when the back layer was observed. However, when the color development was observed from the surface layer side, the color development was slightly observed in Example 1, but was not confirmed in Example 4 with high ISO whiteness.

The falsification preventing paper of the present invention has the following effects.
(1) Passports, traveler's checks, checks, bills, identification cards, etc. often use oil-based inks with variable information such as name, amount, etc. Often affixed. According to the present invention, the variable information using the oil-soluble ink using a solvent is altered, or the protective sheet is peeled off using the solvent, and the trace when attempting to replace the photograph is a special instrument. Since it is visible under visible light without being used, the tamper-proof paper of the present invention can be suitably used for such anti-counterfeiting applications.
(2) In addition, taking advantage of the fact that traces of fraud using solvents and commercially available label peelers can be easily seen, proof of brand products, electronic device seals (credit card readers and other illegal internal specifications) For the purpose of preventing brand rewriting), it can also be suitably used for brand protection label applications.
(3) The dye and / or pigment used in the present invention can be appropriately selected according to the organic solvent expected to be used for falsification. In addition, by simultaneously using two or more kinds of dyes and / or pigments having different solubility parameters, a wide variety of solvents can be used. Furthermore, because of the difference in solubility, the shape of the tampering trace is not constant, such as circular or speckled, and thus a higher tampering prevention effect can be obtained.
(4) Further, when processing such as formation of a coating layer or an adhesive layer is performed on the anti-tamper paper of the present invention, a layer containing a water-insoluble and organic solvent-soluble dye and / or pigment is a synthetic resin or the like. To provide anti-tamper paper with high storage stability that does not cause bleed-out of dyes and / or pigments over time and color development due to heating because it is separated from coating layers and adhesive layers containing organic compounds Can do.

DESCRIPTION OF SYMBOLS 1 Paper layer containing water-insoluble and organic solvent-soluble dye and / or pigment 2 Paper layer not containing water-insoluble and organic solvent-soluble dye and / or pigment 10 Example of the present invention in which the paper layer is composed of two layers 20 Examples of the present invention in which the paper layer is composed of three layers 30 Batting machine of a circular net paper machine 31 Cylindrical wire 32 Blanket 33 Bat in the center of the paper netting machine 34 Batting of the web netting machine 40 A coating layer is provided. Examples of the present invention 41 Coating layer 50 Check 51 Color development of dye and / or pigment when tampered 52 Amount entry column 60 Envelope 61 Sealing label 62 Color development of dye and / or pigment when tampered

Claims (4)

In a tamper-proof paper composed of two or more paper layers, a paper layer (1) containing a water-insoluble and organic solvent-soluble dye and / or pigment, and a water-insoluble and organic solvent-soluble dye and / or pigment, And a paper layer (2) in which the outermost paper layer on at least one side of the falsification-preventing paper does not contain the water-insoluble and organic solvent-soluble dye and / or pigment. ) Anti-tamper paper characterized by A tamper-proof paper composed of three or more paper layers, wherein the outermost paper layers on both sides of the tamper-proof paper do not contain the water-insoluble and organic solvent-soluble dye and / or pigment (2) The falsification preventing paper according to claim 1, wherein   The falsification according to claim 1 or 2, wherein a coating layer is provided on the surface of the outermost paper layer which is a paper layer (2) containing no water-insoluble and organic solvent-soluble dye and / or pigment. Prevention paper. The tamper-proof sheet according to claim 1, wherein the ISO whiteness (JIS P-8148: 2001) is 80% or more.

Images