JP2010076272A - Genuineness-determinable printed matter using special luminescence - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide printed matter which enables determination of its genuineness through the fluorescent emission of two fluorescent materials in an almost isochromatic state or in a heterochromatic state, depending on different observation conditions, with the use of an ink composition containing a resin composition which gives a fluorescent emission under specified conditions. <P>SOLUTION: A first printing region on the surface of a base is printed in a first ink containing a resin composition which gives an emission in a first luminescent color by a two photon excitation which brings about the excitation of an exciting substance by forming an exciting substance through irradiating a first excitation wavelength range λ1, and through irradiating a second excitation wavelength range λ2 after irradiating the first excitation wavelength range λ1. Next, a second printing region is printed in a second ink containing a fluorescent pigment which gives an emission in a second luminescent color not containing the resin composition giving an emission by the two photon excitation. In this case, the first ink and the second ink are almost isochromatic or heterochromatic, and observed in an almost isochromatic state or a heterochromatic state under a visible light. After irradiating the first excitation wavelength range λ1, the second excitation wavelength range λ2 is also, irradiated. As a result, the first printing region and the second printing region give fluorescent emission in an almost isochromatic state or a heterochromatic state. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention is required to prevent counterfeiting of valuables such as banknotes, passports, securities, stamps, product tags, toll roads, various tickets, etc., and has a fluorescent emission under predetermined conditions. It is about.

  Anti-counterfeiting technology is applied to valuable goods such as banknotes, passports, securities, stamps, product tags, toll road tickets, and various valuable tickets. Therefore, for such valuables, printed matter is formed using ink containing an inorganic or organic fluorescent material, and it does not normally emit fluorescence under visible light, but emits fluorescence when irradiated with ultraviolet light. False discrimination is performed.

  For example, fluorescent dye A having an absorption peak wavelength for fluorescence emission at 300 to 400 nm and emitting fluorescence in the visible region, and p-quaterphenyl and p-terphenyl emitting fluorescence in the ultraviolet region of 300 to 400 , 2,5-diphenyloxazole, 2- (1-naphthyl) -5-phenyloxazole, 2-phenyl-5- (4-biphenyl)-, 1,3,4-oxadiazole A fluorescent ink composition for ink-jet using at least one of these as an essential constituent material is disclosed (for example, see Patent Document 1).

  Further, a fluorescent light-emitting ink containing a phosphor that emits fluorescence when irradiated with ultraviolet light and an ink vehicle, and a printed product of the ink, and having a wavelength in the first visible light region when irradiated with ultraviolet light of the first wavelength. A first phosphor that emits fluorescence and is substantially transparent to visible light, and has a wavelength in a second visible light region different from the wavelength in the first visible light region by irradiation with ultraviolet light of the second wavelength. A fluorescent light-emitting ink and a fluorescent image formed product containing a second fluorescent material that emits fluorescence and is substantially transparent to visible light are disclosed (for example, see Patent Document 2).

  In addition, by forming a pattern group consisting of patterns of metallic colorants that appear to be the same color under visible light but have different hue, brightness, and saturation under a light source having a predetermined spectral energy distribution, So-called pair printing, in which a pattern made of a metallic colorant can appear or be erased when irradiated with light from a light source having a spectral energy distribution of or through a filter having a predetermined spectral transmittance. Has been disclosed (for example, see Patent Document 3).

  In addition, at least two of the two or more printed areas are printed with different fluorescent inks, the two different fluorescent inks are visible in the same color under visible light, and one of the two different fluorescent inks The ink contains two fluorescent pigments exhibiting different fluorescence emission colors, and the emission color resulting from the additive color mixture of each fluorescence emission color and the emission color of the other fluorescence emission ink are visually recognized as the same color, and the specific filter , An anti-counterfeit printed matter is disclosed in which only a print area printed with one fluorescent light-emitting ink can be visually recognized (see, for example, Patent Document 4).

Japanese Examined Patent Publication No. 04-062871 (page 1-5) Japanese Patent Laid-Open No. 10-251570 (page 1-11, FIGS. 4, 5) Japanese Examined Patent Publication No. 61-037636 (first page) Japanese Patent Laying-Open No. 2005-262681 (page 1-7)

However, the fluorescent light-emitting inks of Patent Documents 1 and 2 form printed matter using ink containing an inorganic or organic fluorescent material. Inorganic or organic fluorescent materials are generally expensive special fluorescent inks, and as a result, printed matter printed with such inks is also expensive. In recent years, fluorescent light-emitting inks have become easily available, and their effectiveness in fields such as counterfeiting, alteration, and falsification has declined. Furthermore, with the recent popularization and development of printers, counterfeiting by printers tends to increase. there were. In addition, a printed matter using an ink containing an inorganic or organic fluorescent material emits light by an ultraviolet irradiation device having an ultraviolet intensity of about 1.5 mW / cm ² used in a general handy type or the like. There is a risk that the area where the fluorescent light-emitting ink is used is easily judged and forged.

  The metameric pair printing of Patent Document 3 tries to counterfeit and tamper with one of the colors confirmed under visible light unless you know that the pattern is formed by two types of colorants having different spectral energy distributions. Therefore, authenticity determination can be easily performed by irradiating light having a predetermined spectral energy distribution. However, at present, this metameric pair printing technology has become a general anti-counterfeiting technology, and analysis technology has also been advanced, so it turns out that metameric pair printing is performed relatively easily. As a result, the forgery resistance has been lowered.

  Moreover, although the fluorescence emission pair printed matter of patent document 4 looks the same color under visible light and an ultraviolet-ray, when it observed through a specific filter, it was a forgery prevention printed matter which can visually recognize only one printing area | region. However, in order to fluoresce in the same color, one ink must contain two or more fluorescent luminescent pigments that have the same color as the fluorescent color of the other ink. In addition, it is necessary to adjust the content of the fluorescent light-emitting pigment, and as a result, three different fluorescent light-emitting pigments are required, resulting in a relatively high cost. Furthermore, since it is clear that a specific wavelength spectrum exists for fluorescent light-emitting ink, it is clear that some kind of phenomenon appears when observing with several types of filters, and it is not very advanced. It did not have an anti-counterfeiting effect.

The present invention aims to solve such a conventional problem, and uses an ink composition containing a resin composition that fluoresces under a predetermined condition even if an inorganic or organic fluorescent material is not contained. The printed material can be confirmed to be substantially the same color or different color under a predetermined observation condition, but can be confirmed as a different color or substantially the same color under other observation conditions, and is used particularly in a general 365 nm handy type or the like. Even after irradiating ultraviolet rays with an ultraviolet irradiation device having an ultraviolet intensity of about 1.5 mW / cm ² , it does not emit fluorescence, and after irradiation with about 50 mJ / cm ² of medium wave ultraviolet rays with a metal halide lamp, a mercury lamp, etc. in the case where ultraviolet intensity which is used in handheld or the like is irradiated with ultraviolet irradiation apparatus of about 1.5 mW / cm ^2, benefit the feature that it is possible to obtain a fluorescence And aims to propose its specific fluorescence emission color, the printed matter was realized pair printed with common fluorescence emission color.

The ultraviolet intensity irradiated by the ultraviolet irradiation apparatus used in the general 365 nm handy type described above is about 1.5 mW / cm ² as an example in the present specification, and a metal halide lamp, a mercury lamp, etc. the irradiation amount of medium wave ultraviolet rays to be irradiated with ultraviolet irradiation apparatus is will be described as about 50 mJ / cm ^2, it is not limited thereto, in particular a metal halide lamp, the ultraviolet irradiation apparatus of a mercury lamp or the like, the device itself However, the present invention is not limited to this, and any device capable of irradiating medium-wave ultraviolet light may be used. Furthermore, the irradiation amount of medium-wave ultraviolet light may be irradiated for a long time if the ultraviolet light intensity is low. This produces the same effect, and it is important to irradiate medium wave ultraviolet rays.

  The present invention relates to a true / false discrimination printed matter using a special light emission having a first print area and a second print area in at least a part of a printed pattern formed on a substrate, the first print area Forms an excited substance by irradiating ultraviolet rays in the first wavelength range λ1, and after irradiating ultraviolet rays in the first wavelength range λ1, irradiates ultraviolet rays in the second wavelength range λ2, thereby exciting the excited substance. Printed with a first ink containing a resin composition that emits light in a first emission color by two-photon excitation, the second printing region contains a fluorescent pigment that emits light in a second emission color, and two Printed with a second ink that does not contain a resin composition that emits light by photon excitation, the first ink and the second ink are substantially the same color, and the first print area and the second print area are under visible light. Is observed as substantially the same color, and is irradiated with ultraviolet rays in the second wavelength region λ2. Then, only the second print region is observed by emitting fluorescence in the second emission color, and after irradiating ultraviolet rays in the first wavelength region λ1, further irradiating ultraviolet rays in the second wavelength region λ2, The authenticity determination printed matter using special light emission, wherein the first print area emits fluorescence in the first emission color and the second print area emits fluorescence in the second emission color.

  The first ink and the second ink of substantially the same color in the printed matter for authenticity determination using the special light emission of the present invention are such that the first ink includes a predetermined color material, and the second ink has a predetermined color. The same color material as the material, or the mixed color of the plurality of color materials contained in the first ink and the mixed color of the plurality of color materials contained in the second ink are the same It is characterized by that.

  The first ink and the second ink having substantially the same color in the printed matter for authenticity determination using the special light emission of the present invention are characterized in that the first ink and the second ink are colorless and transparent.

  The first ink and the second ink of substantially the same color in the printed matter for authenticity determination using the special light emission of the present invention are such that the first ink and the second ink contain functional materials of the same color. Characterize.

  The functional material contained in the first ink and the second ink in the true / false discrimination printed matter using the special light emission of the present invention is a glittering material, a magnetic material, a conductive material and / or a chromic material. And

  In the true / false discrimination printed matter using the special light emission of the present invention, the fluorescent pigment that emits the second emission color contained in the second ink is substantially the same color as the first emission color of the first ink. It is a fluorescent pigment that emits light, and the first print area and the second print area are observed as substantially the same color under visible light, and when irradiated with ultraviolet rays in the second wavelength range λ2, only the second print area is the first print area. The first print region and the second print region are observed by fluorescing as the luminescent color of 2 and irradiated with ultraviolet rays in the second wavelength region λ2 after being irradiated with ultraviolet rays in the first wavelength region λ1. Is observed with fluorescence emission substantially in the same color.

  The fluorescent pigment that emits the second emission color contained in the second ink of the authenticity discrimination printed matter using the special emission of the present invention emits light in a color different from the first emission color of the first ink. It is a fluorescent pigment, and the first print area and the second print area are observed as the same color under visible light. When irradiated with ultraviolet rays in the second wavelength band λ2, only the second print area emits fluorescence. Observed, after irradiating ultraviolet rays in the first wavelength range λ1, and further irradiating ultraviolet rays in the second wavelength range λ2, the first printed region and the second printed region are fluorescently emitted in different colors and observed. It is characterized by being.

  The present invention relates to a true / false discrimination printed matter using a special light emission having a first print area and a second print area in at least a part of a printed pattern formed on a substrate, the first print area Forms an excited substance by irradiating with ultraviolet rays in the first wavelength band λ1, and after irradiating with ultraviolet rays in the first wavelength band λ1, irradiates ultraviolet rays in the second wavelength band λ2, thereby exciting the excited substance. Printed with a first ink containing a resin composition that emits light in a first emission color by two-photon excitation, the second printing region contains a fluorescent pigment that emits light in a second emission color, and Printed with a second ink that does not contain a resin composition that emits light by two-photon excitation, the first ink and the second ink are different colors, and the first print area and the second print area are under visible light. Is observed as a different color, and ultraviolet rays in the second wavelength region λ2 By irradiating, only the second printing region is observed to emit fluorescence in the second emission color, and after irradiating with ultraviolet rays in the first wavelength region λ1, further irradiating with ultraviolet rays in the second wavelength region λ2. Thus, the authenticity determination printed matter using special light emission in which the first print area emits fluorescence in the first emission color and the second print area emits fluorescence in the second emission color.

  The first ink and the second ink of different colors of the true / false discrimination printed matter using the special light emission of the present invention are such that the first ink contains a predetermined color material, and the second ink is a predetermined color material. Or a mixed color of a plurality of color materials contained in the first ink and a mixed color of a plurality of color materials contained in the second ink are different. It is characterized by.

  The first ink and the second ink of different colors of the authenticity determination printed matter using the special light emission of the present invention, the ink of either the first ink or the second ink comprises a color material, The other ink is colorless and transparent.

  The first ink and the second ink of different colors of the authenticity printed matter using the special light emission of the present invention include a functional material in which the first ink has a predetermined interference color, and the second ink Comprises a pearl pigment having an interference color different from the predetermined interference color.

  The functional material contained in the first ink and the second ink in the true / false discrimination printed matter using the special light emission of the present invention is a glittering material, a magnetic material, a conductive material and / or a chromic material. And

  In the true / false discrimination printed matter using the special light emission of the present invention, the fluorescent pigment that emits the second emission color contained in the second ink is substantially the same color as the first emission color of the first ink. It is a fluorescent pigment that emits light. When the first print region and the second print region are observed as different colors under visible light, and irradiation with ultraviolet rays in the second wavelength region λ2, only the second print region is the second print region. The first print region and the second print region are observed by emitting fluorescent light as the emission color of the first and second ultraviolet rays in the second wavelength region λ2 after irradiation with the ultraviolet rays in the first wavelength region λ1. It is characterized by being observed with fluorescence emission substantially in the same color.

  The authenticity discrimination printed matter using the special light emission of the present invention includes a resin composition that emits light in the first emission color by two-photon excitation contained in the first ink, a resin containing a polyfunctional acrylate, and a light absorption And a radical photopolymerization initiator that generates radicals by intramolecular cleavage by the method, wherein the resin comprising a polyfunctional acrylate has a functional group density of acryloyl group of 0.5 mmol / g or more. It is characterized by having.

  The authenticity discrimination printed matter using the special light emission of the present invention includes a resin composition that emits light in the first emission color by two-photon excitation contained in the first ink, a resin containing a polyfunctional acrylate, and a light absorption A resin assembly comprising a radical photopolymerization initiator that generates radicals by intramolecular cleavage by means of a resin, the resin comprising a polyfunctional acrylate has an ethylenically unsaturated group and a bisphenol skeleton in the molecule. It is characterized by that.

  The true / false discrimination printed matter using the special light emission of the present invention is characterized in that the first wavelength region λ1 is 260 nm or more and less than 330 nm, and the second wavelength region λ2 is 330 nm or more and 410 nm or less.

The printed matter using the special light emission of the present invention can be recognized as a pattern printed with one color ink at first glance, but the ultraviolet intensity used in a general handy type is 1.5 mW. Upon irradiation with ultraviolet rays / cm ² about ultraviolet irradiation device, confirmed that only a part of the pattern fluoresce, further, a metal halide lamp, a medium wave ultraviolet mercury lamp or the like at 50 mJ / cm ² about ultraviolet radiation device After irradiating with ultraviolet rays, when the ultraviolet rays are irradiated with an ultraviolet irradiation device having an ultraviolet intensity of about 1.5 mW / cm ² that is used in a general handy type, it is confirmed as a pattern printed with one color ink with the naked eye. It is possible to achieve a high level of anti-counterfeiting and anti-copying effects, such that the formed area can be confirmed by fluorescent emission with substantially the same color or different color.

Further, when the printed matter using the special light emission of the present invention is confirmed with the naked eye, it is visually recognized that a pattern is formed with two colors of ink, and the ultraviolet intensity used in a general handy type is 1. When ultraviolet rays are irradiated with an ultraviolet irradiation device of about 5 mW / cm ^2, it can be confirmed that only a part of the pattern emits fluorescence, and further, an ultraviolet irradiation device of about 50 mJ / cm ² of medium wave ultraviolet rays with a metal halide lamp, a mercury lamp or the like. After irradiating with UV light, when the UV light is irradiated with an UV irradiation device with a UV intensity of about 1.5 mW / cm ² that is used in general handy type, the areas printed with two different colors of ink are approximately equal. It is possible to achieve a high level of anti-counterfeiting and anti-copying effects that can be confirmed by fluorescent emission of color.

  Further, the printed matter using the special light emission of the present invention is formed with an excitation intermediate (excited state) by irradiating medium wave ultraviolet rays with an ultraviolet irradiation device such as a metal halide lamp or a mercury lamp. Fluorescence emission can be obtained by irradiating ultraviolet rays with an ultraviolet irradiation device used in the type or the like, but the excited intermediate (excited state) returns to the ground state due to thermal radiation metabolism over time, or heated ( Fluorescence emission intensity is attenuated, and finally fluorescent light is emitted even when irradiated with ultraviolet rays by an ultraviolet irradiation device used in a general handy type or the like. Disappear. In this case, an excitation intermediate (excited state) is formed by irradiating medium-wave ultraviolet light again with an ultraviolet irradiation device such as a metal halide lamp or a mercury lamp, and ultraviolet irradiation used in general handy types again. Fluorescence emission can be obtained by irradiating the apparatus with ultraviolet rays. Therefore, since a resin composition characterized by these states being reversible can be obtained, it is effective for a certificate using the light emission time.

Since the printed matter using the special light emission of the present invention contains only one kind of expensive inorganic or organic fluorescent material, a printed matter having two fluorescent light emission can be obtained. You can create printed materials.

  The best mode for carrying out the present invention will be described with reference to the drawings. However, the present invention is not limited to the best mode for carrying out the invention described below, and various other embodiments are included within the scope of the technology described in the claims.

As shown in FIG. 2, the printed matter using the special light emission of the present invention has a predetermined pattern 2 formed on at least a part of the substrate 1, and the first printed area 2 a is formed on at least a part of the pattern 2. And a second printed area 2b. At least one of the first printing area and the second printing area is printed with an ink having the functionality described later. Medium wave ultraviolet rays are applied to the printed matter with an ultraviolet irradiation device such as a metal halide lamp or a mercury lamp. For example, after irradiating about 50 mJ / cm ^{2 and then} irradiating with ultraviolet light having a UV intensity of about 1.5 mW / cm ² with an ultraviolet irradiation device used in a general handy type, etc. Only a part of the printed pattern emits fluorescence, and is visually recognized in a state different from the state in which the printed matter is visually recognized under visible light.

  In the printed matter using the special light emission of the present invention, the ink having the above-described functionality will be described below.

(Ink 1)
Ink 1 for printing either the first printing region or the second printing region of the printed material in the present invention is a resin composition comprising a resin containing a polyfunctional acrylate and a radical photopolymerization initiator. 1 is an ink containing at least 1, and this radical photopolymerization initiator generates radicals by intramolecular cleavage by light absorption. Moreover, the resin containing a polyfunctional acrylate needs to have a functional group density of acryloyl group of 0.5 mmol / g or more.

  Resins composed of a polyfunctional acrylate monomer and / or a polyfunctional acrylate oligomer and having a functional group density of acryloyl group of 0.5 mmol / g or more include, for example, 1,4-butanediol diacrylate, 1,4-butanediol oligo Acrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol oligoacrylate, hydroxypivalate neopentyl glycol diacrylate, tricyclodecane dimethanol acrylate, trimethylolpropane triacrylate, trimethylolpropane oligoacrylate, pentaerythritol Triacrylate, tris (acryloxyethyl) isocyanurate, pentaerythritol tetraacrylate, pentaerythritol oligoacrylate, pentae Sri tall tetraacrylate, ditrimethylolpropane tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, epoxy acrylate, urethane acrylate.

  Furthermore, the functional group density of the acryloyl group of the resin comprising a polyfunctional acrylate monomer and / or a polyfunctional acrylate oligomer is preferably 3.0 mmol / g or more. In addition, when the functional group density of the functional group density of the acryloyl group is less than 0.5 mmol / g, light emission is difficult.

  Further, the radical photopolymerization initiator comprises α-hydroxy ketones, a compound represented by the formula (1) and / or α-amino ketones, a compound represented by the formula (2).

（ただし、Ｒ_１、Ｒ_２、Ｒ_３、Ｒ_４、Ｒ_５、Ｒ_６、Ｒ_７、Ｒ_８、Ｒ_９、Ｒ_１０、Ｒ_１１及びＲ_１２は、それぞれ独立に水素原子又はアルキル基を表す。）

(However, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ , R ₁₀ , R ₁₁ and R ₁₂ each independently represent a hydrogen atom or an alkyl group. .)

（ただし、Ｒ_１３、Ｒ_１４、Ｒ_１５、Ｒ_１６、Ｒ_１７、Ｒ_１８及びＲ_１９は、それぞれ独立に水素原子又はアルキル基を表す。）

(However, R < ₁₃ >, R <_14> , R <_15> , R <_16> , R <_17> , R <_18> and R < ₁₉ > each independently represents a hydrogen atom or an alkyl group.)

In the above formula (1), R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ , R ₁₀ , R ₁₁ and R ₁₂ are each independently a hydrogen atom. Or it is preferable that it is an alkyl group. Especially, it is more preferable that it is a compound represented by following formula (3). The compound represented by the formula (3) is 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] -phenyl} -2-methyl-propan-1-one. As a commercial product, there is Irgacure127 (manufactured by Ciba Specialty Chemicals).

In the above formula (2), it is preferable that R ₁₃ , R ₁₄ , R ₁₅ , R ₁₆ , R ₁₇ , R ₁₈ and R ₁₉ are each independently a hydrogen atom or an alkyl group. Especially, it is more preferable that it is a compound represented by following formula (4). The compound represented by the formula (4) is 2-methyl-1 [4-methylthio] phenyl] -2-morpholinopropan-1-one, and Irgacure907 (manufactured by Ciba Specialty Chemicals) is available.

  The radical photopolymerization initiator is preferably a resin containing 0.1 to 10% by weight with respect to 100% by weight of the resin containing a polyfunctional acrylate monomer and / or a polyfunctional acrylate oligomer.

(Ink 2)
Further, another ink 2 for printing either the first printing region or the second printing region of the printed material in the present invention is a resin composition comprising a polyfunctional acrylate and a radical photopolymerization initiator. This multifunctional acrylate has an ethylenically unsaturated group and a bisphenol skeleton in the molecule, and the radical photopolymerization initiator cleaves radicals by intramolecular cleavage by light absorption. It is what happens.

  The polyfunctional acrylate is a resin composition comprising at least one compound represented by formula (5), formula (6) or formula (7):

（ただし、Ｒ_１、Ｒ_２、Ｒ_３及びＲ_４は、それぞれ独立に水素原子又はアルキル基を示し、ｍ及びｎは、０〜３０の繰り返しの数を示す。）

(However, R ₁ , R ₂ , R ₃ and R ₄ each independently represent a hydrogen atom or an alkyl group, and m and n represent the number of 0 to 30 repeats.)

（ただし、Ｒ_５及びＲ_８は、それぞれ独立に水素原子又はアルキル基を示し、Ｒ_６及びＲ_７は、それぞれ独立に水素原子又はアシル基、（メタ）アクリロイル基を示し、ｘは、０〜３０の繰り返しの数を示す。）

(However, R ₅ and R ₈ each independently represent a hydrogen atom or an alkyl group, R ₆ and R ₇ each independently represent a hydrogen atom, an acyl group, or a (meth) acryloyl group, and x represents 0 to 0 Indicates the number of repetitions of 30.)

（ただし、Ｒ_９、Ｒ_１０、Ｒ_１１、Ｒ_１２、Ｒ_１３及びＲ_１４は、それぞれ独立に水素原子又はアルキル基を示し、Ｒ_１５、Ｒ_１６及びＲ_１７は、それぞれ独立に水素原子又はアシル基、（メタ）アクリロイル基を示し、ｙは、０〜３０の繰り返しの数を示す。）

(However, R ₉ , R ₁₀ , R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ each independently represent a hydrogen atom or an alkyl group, and R ₁₅ , R ₁₆ and R ₁₇ are each independently a hydrogen atom or acyl. Group represents a (meth) acryloyl group, and y represents the number of repetitions of 0 to 30.)

  Examples of the polyfunctional acrylate having an ethylenically unsaturated group and a bisphenol skeleton in the molecule include bisphenol F di (meth) acrylate, EO-modified bisphenol F-type di (meth) acrylate, and PO-modified bisphenol F-type di ( (Meth) acrylate, bisphenol F type epoxy (meth) acrylate, phenol novolac type epoxy (meth) acrylate, cresol novolac type epoxy (meth) acrylate, acid modified bisphenol F type epoxy (meth) acrylate, acid modified phenol novolac type epoxy (meta) ) Acrylate, acid-modified cresol novolac type epoxy (meth) acrylate, and the like.

  The radical photopolymerization initiator is preferably a resin composition containing 0.1 to 10% by weight with respect to 100% by weight of the resin containing a polyfunctional acrylate.

  The resin compositions 1 and 2 blended in the two inks described above form an excitation substance by irradiation with ultraviolet rays in the first wavelength region λ1, and after irradiation with ultraviolet rays in the first wavelength region λ1, It emits light by two-photon excitation in which the excitation substance is excited by irradiating ultraviolet rays in the wavelength range λ2. The relationship between the first wavelength region λ1 and the second wavelength region λ2 is characterized by λ1 <λ2, wherein the first wavelength region λ1 is 260 nm or more and less than 330 nm, and the second wavelength region λ2 is 330 nm or more. It is 410 nm or less, and if it is outside this range, it becomes difficult to emit light.

  FIG. 1 is a schematic diagram of the two-photon excited fluorescence emission of the resin compositions 1 and 2 described above. The resin composition in the ground state (S0) absorbs light in the first wavelength region λ1, enters the first excited singlet state (S1), and enters the first excited triplet state (T1) at the intersystem crossing. Become. Next, the light in the second wavelength band λ2 is absorbed, and the second level excited second singlet state (S2) is obtained. At the intersystem crossing, the second excited triplet state (T2) is obtained. The second excited triplet state (T2) emits light and returns to the first excited triplet state (T1). The first excited triplet state (T1) returns to the ground state (S0) due to non-radiative deactivation. The first excited triplet state (T1) is a hydrogen atom of a methylene group of a bisphenol skeleton of a polyfunctional acrylate having an ethylenically unsaturated group and a bisphenol skeleton in the molecule, or 2-hydroxy-1- {4- [ 4- (2-hydroxy-2-methyl-propionyl) -benzyl] -phenyl} -2-methyl-propan-1-one methylene group hydrogen atom and / or 2-methyl-1 [4-methylthio The hydrogen atom at the α-position of the alkylthio group of phenyl] -2-morpholinopropan-1-one was pulled out by Norrish type 2 reaction and stabilized to some extent by π-electron conjugation with the benzene ring It is considered to be an excited state (intermediate) having a lifetime.

  The emission peak wavelength of the resin composition 1 that emits light by two-photon excitation is in the range of 580 to 680 nm, and the emission peak wavelength of the resin composition 2 is in the range of 540 to 610 nm.

The resin composition 1 or 2 is applied on a glass plate, and the ultraviolet ray intensity of about 1.5 mW / cm ² is used for each resin composition in a general handy type. Does not emit fluorescence. However, when a medium-wave ultraviolet ray is irradiated with an ultraviolet irradiation device of about 50 mJ / cm ² with a metal halide lamp, a mercury lamp or the like, an excitation intermediate (excitation state) having an excitation peak wavelength of 330 to 410 nm is formed. When ultraviolet light is irradiated with an ultraviolet irradiation device having an ultraviolet intensity of about 1.5 mW / cm ² used in a handy type or the like, the resin composition 1 fluoresces in orange or red with an emission peak wavelength of around 580 to 680 nm. The resin composition 2 fluoresces in a lemon color or yellow color with an emission peak wavelength in the vicinity of 540 to 610 nm.

  The ink composition comprising the two resin compositions 1 or 2 described above can be used as OP varnish, transparent ink, or the like. Further, it can be used as an ink composition comprising the resin composition 1 or 2 containing a coloring material. The coloring material in the present invention can contain at least one compound selected from the group consisting of a coloring dye, a coloring pigment, a fluorescent dye, a fluorescent pigment, and a pearl pigment. Further, depending on the type of extender compounded for viscosity adjustment, some pigments exhibit a slight coloring effect (for example, white), and this coloring effect can also be used as the color adjustment of the present invention. Furthermore, a polymerization accelerator, a polymerization inhibitor, an antifoaming agent, and the like can be appropriately mixed.

In the present invention, the first print area and the second print area are substantially equal in color, in the L ^* a ^* b ^* color system, means that the color difference is in the range of ΔE ^* ab = 0-2. When the print areas are not adjacent to each other, the color difference is difficult to understand.

(First embodiment)
A first embodiment of a printed matter using special light emission according to the present invention will be described below.
FIG. 2 shows that a sun pattern 2 is formed on a part of the paper base 1, a first print area 2a at the center of the sun pattern 2, and a second print area on the outside so as to surround the center. 2b. At least one of the first print area and the second print area is printed with the ink 1 or 2 having the above-described functionality. In the first embodiment, it is assumed that the second printing region 2b arranged outside so as to surround the central portion of the sun pattern 2 is printed with an ink having a functionality in which the resin composition 1 is blended. explain.

The ink for forming the second printing region 2b is blended with at least the resin composition 1 described above. The ink for forming the first printing region 2a is irradiated with ultraviolet rays having an ultraviolet intensity of about 1.5 mW / cm ² , for example, with an ultraviolet irradiation device used in a general handy type or the like. A fluorescent pigment that emits fluorescence is blended, and the resin composition 1 or 2 is not blended. Since the first print area 2a and the second print area 2b are printed so as to be visually recognized in substantially the same color under visible light, the two inks for printing both print areas are substantially the same. A color pigment of the same color is blended, or it is made colorless and transparent without blending a color pigment. Prepare the first printing area 2a which is the central part of the sun pattern 2 and the two printing plates for the second printing area 2b which are arranged outside so as to surround the central part. Printing is performed on a paper substrate with ink by a predetermined printing method.

When the printed matter of the first embodiment is observed under visible light, the first print region 2a and the second print region 2b are confirmed to exhibit the same color pigment color, and the sun as shown in FIG. As shown in FIG. 4 (b), it cannot be visually recognized by the naked eye due to its colorlessness. In FIG. 4B, for the sake of explanation, the outline of the sun pattern 2 is expressed by a dotted line, but it is actually colorless and cannot be visually recognized in this way. When this printed matter is irradiated with ultraviolet rays having an ultraviolet intensity of about 1.5 mW / cm ² with an ultraviolet irradiation apparatus used in a general handy type as shown in FIG. Only the first printing region 2a formed with the ink containing the pigment appears to emit fluorescence as shown in FIG. 4 (c) or (d).

However, with a metal halide lamp, mercury lamp, or the like as shown in FIG. 3B, medium wave ultraviolet rays are irradiated with an ultraviolet irradiation device of, for example, about 50 mJ / cm ² , and ultraviolet rays that are used again in general handy type etc. When the irradiation device irradiates, for example, ultraviolet rays having an ultraviolet intensity of about 1.5 mW / cm ² , as shown in FIG. 4E, the circular pattern of the first printing area 2a and the first printing area Both of the second print regions 2b arranged so as to surround the circle pattern 2a fluoresce with substantially the same color, and can be confirmed as the sun pattern 2 that fluoresced. Therefore, in the observation situation when ultraviolet rays are irradiated with a general ultraviolet ray irradiation device after irradiation with visible light and medium wave ultraviolet rays, the first printing region 2a and the second printing region 2b exhibit the same color, Although it cannot be distinguished as a printing region, each printing region is visually recognized separately only when ultraviolet rays are irradiated only by a general ultraviolet irradiation device.

  In the first embodiment described above, the case where the emission colors of the fluorescence emission of the first printing area 2a and the second printing area 2b are substantially the same color has been described. However, the fluorescence emission of the first printing area 2a is described. The emission color may be different from the emission color of the fluorescence emission of the second print region 2b. In that case, a fluorescent pigment that emits fluorescence with an ultraviolet irradiation device used in a general handy type or the like, which has a light emission color different from that of the resin composition 1 or 2 used in the present invention described above, is blended. It ’s fine.

  In this case, as shown in FIG. 5 (a), it is observed that two regions are formed with one ink under visible light. However, in a general handy type ultraviolet lamp, FIG. As shown in FIG. 5 (c), only one pattern emits light, and once irradiated with a medium wave ultraviolet ray by an ultraviolet irradiation device such as a metal halide lamp or a mercury lamp, and then irradiated with a general handy type ultraviolet lamp. ), The two regions fluoresce in different colors.

  Further, it is needless to say that the same applies to the case where the emission color of the fluorescent light is changed by printing the first printing area 2a and the second printing area 2b with a colorless and transparent ink which does not contain a coloring pigment. .

(Second Embodiment)
A second embodiment of the printed matter using the special light emission of the present invention will be described below. Note that a part of the description overlapping the first embodiment is partially omitted.

  FIG. 6 is an enlarged view of only the sun pattern 2 printed on the printed matter using the special light emission of the present invention shown in FIG. In the second embodiment, at least the resin composition 1 or 2 described above is blended in the ink for forming the second print region 2b. In the second embodiment, the first print area 2a and the second print area 2b are formed so as to be visually recognized as different colors in observation under visible light. For example, the first print area A different color pigment may be blended in each of the inks for printing 2a and the second print area 2b, and either one of the first print area 2a and the second print area 2b may be mixed. A color pigment may be blended in the ink, and the other ink may be colorless and transparent without blending a color pigment. In addition, the resin composition 1 or 2 mentioned above is not mix | blended with the ink which prints the 1st printing area | region 2a. Prepare the first printing area 2a which is the central part of the sun pattern 2 and the two printing plates for the second printing area 2b which are arranged outside so as to surround the central part. Printing is performed on a paper substrate with ink by a predetermined printing method.

More specifically, with reference to the drawings, if the ink for printing the first printing region 2a is irradiated with a green color pigment and a general handy type ultraviolet lamp, the fluorescent light is emitted in yellowish green. When the yellow coloring pigment and the resin composition 2 are blended in the ink that prints the second printing region 2b, the printed matter of the second embodiment is observed under visible light. The print area 2a is green, and the second print area 2b is yellow, with different colors, and looks as a sun pattern 2 as shown in FIG. When this printed matter is irradiated with ultraviolet rays using an ultraviolet irradiation device 3a having an ultraviolet intensity of about 1.5 mW / cm ² used in a general handy type as shown in FIG. Only the first print region 2a formed with the ink containing the pigment appears to emit fluorescent light in a yellow color as shown in FIG. 6 (b).

However, an ultraviolet ray irradiation device 3b such as a metal halide lamp or a mercury lamp as shown in FIG. 3B irradiates an ultraviolet ray of about 50 mJ / cm ² , and the ultraviolet intensity used in a general handy type is 1 again. When ultraviolet rays are irradiated using the ultraviolet ray irradiation device 3a of about 5 mW / cm ² , as shown in FIG. 6C, the circular pattern of the first printing region 2a and the first printing region 2a Both of the second printing regions 2b arranged so as to surround the circle pattern of the light fluoresce in a substantially same color yellow system, and it can be confirmed as the sun pattern 2 that fluoresced.

In addition, the ink for forming one of the first printing area 2a and the second printing area 2b is colorless and transparent without containing a coloring pigment, and the other ink is blended with a coloring pigment so that visible light is visible. Below, only the printing area formed with the ink containing the color pigment is visually recognized, and the ultraviolet intensity used in the general handy type as shown in FIG. 3A is about 1.5 mW / cm ² . When ultraviolet rays are irradiated using the ultraviolet irradiation device 3a, only the printing area formed with the ink containing the fluorescent pigment is made to emit fluorescent light, and the ultraviolet irradiation device 3b such as a metal halide lamp or a mercury lamp as shown in FIG. 50 mJ / cm ² about ultraviolet rays are irradiated again irradiated with ultraviolet light using general UV intensity which is used in handheld or the like of 1.5 mW / cm ² about ultraviolet irradiation apparatus 3a If, it is also possible to first print area 2a and a second print area 2b causes the fluorescence emission both at a substantially uniform color.

  In this case, for example, when the circular pattern of the first printing region 2a, which is the central part of the sun pattern 2, is irradiated with a red color pigment and a general handy type ultraviolet lamp, the fluorescence that emits red fluorescence In the ink which mixes a pigment and prints the 2nd printing area | region 2b, the resin composition 2 is mix | blended, and a coloring pigment is not mix | blended. When this printed pattern is observed under visible light, as shown in FIG. 7 (a), the circular pattern of the first printed region 2a, which is the central part of the sun pattern 2, can be visually recognized in red, The second print area 2b is not visible because it is colorless and transparent. For the sake of explanation, in FIG. 7, it is indicated by a dotted line.

  When the sun pattern 2 is irradiated with ultraviolet rays by a general hand-held type ultraviolet lamp, as shown in FIG. 7B, the first print region 2a, which is the central portion of the sun pattern 2, is formed. Only the circular pattern is confirmed by fluorescent emission in red.

  Further, when the sun pattern 2 is irradiated with medium wave ultraviolet rays by an ultraviolet irradiation device 3b such as a metal halide lamp or a mercury lamp, and again irradiated with ultraviolet rays by a general handy type ultraviolet lamp, FIG. ), The first print area 2a and the second print area 2b both emit red light.

  In the above-described example, a color pigment is blended in the first printing area 2a, and the second printing area 2b is colorless and transparent. Conversely, the first printing area 2a is colorless and transparent, You may mix | blend a color pigment with the area | region 2b. In the second embodiment, two print areas are visually recognized as different colors under visible light, and are irradiated with medium-wave ultraviolet light by an ultraviolet irradiation device 3b such as a metal halide lamp or a mercury lamp. When the ultraviolet ray is irradiated with ultraviolet rays, the fluorescent light is emitted in substantially the same color system.

  In the first embodiment and the second embodiment described above, the type of the substrate is not particularly limited, and paper, plastic, cloth, or the like can be used. Moreover, about the printed matter of this invention, in order to confirm light emission with the naked eye, it is preferable to have an ink film thickness of about 2-150 micrometers.

  Furthermore, although the printing method used for the printed matter of the present invention is not particularly limited, a method of printing by intaglio printing capable of forming an ink film thickness, gravure printing, flexographic printing, screen printing or the like is preferable.

  EXAMPLES Hereinafter, although this invention is demonstrated further in detail using an Example, the content of this invention is not limited to the range of these Examples.

  Dipentaerythritol penta (hexa) acrylate (Toa Gosei Co., Ltd., Aronix M-400) 70 wt%, neopentyl glycol modified trimethylolpropane diacrylate (Nippon Kayaku Co., Ltd. KAYARAD R-604) 10 wt%, urethane acrylate (Arakawa) Industrial Co., Ltd. Beam Set 505A-6) A resin composition prepared at a rate of 20 wt% was added to a photopolymerization initiator 2-hydroxy-1- {4- [2- (2-hydroxy-2-methyl-propionyl) -benzyl]. -Phenyl} -2-methyl-propan-1-one (Ciba Specialty Chemicals Irgacure127), 4% by weight, defoaming agent (BYK-1790, manufactured by Big Chemie), 0.5% by weight. An ink composition 2a that emits light by photon excitation was obtained. In addition, the functional group density of this ink composition is 7.77 mmol / g.

  Dipentaerythritol penta (hexa) acrylate (Toa Gosei Co., Ltd., Aronix M-400) 70 wt%, neopentyl glycol modified trimethylolpropane diacrylate (Nippon Kayaku Co., Ltd. KAYARAD R-604) 10 wt%, urethane acrylate (Arakawa) Industrial Co., Ltd. Beam Set 505A-6) For a resin composition of 95.5 wt% adjusted at a ratio of 20 wt%, red fluorescent pigment (Riedel dehaen Rot CD740) 0.5 wt%, photopolymerization initiator 1-hydroxy-cyclohexyl- Phenyl-ketone (Ciba Specialty Chemicals Irgacure 184) outer split 2 wt%, defoaming agent (BYK-1790 manufactured by Big Chemie Co., Ltd.) outer split 0.5 wt%, adjusted to a ratio of 0.5 wt. The product 2b was obtained.

  Example 1 Printing on a high-quality paper by flexographic printing using an anilox roll of 140 lines / inch so as to have a first region with the ink composition 2a and a second region with the ink composition 2b 1 forgery prevention printed matter was obtained.

  The first region and the second region of the anti-counterfeit printed matter of Example 1 were colorless and transparent under visible light.

For the anti-counterfeit printed matter of Example 1, UVP Inc. When UV irradiation of 365 nm was observed using a UV hand lamp manufactured by 3UV series, only the second region of the ink composition 2b emitted red light. When the anti-counterfeit printed matter of Example 1 was irradiated with ultraviolet rays of about 50 mJ / cm ² with an ultraviolet irradiation device such as a metal halide lamp or a mercury lamp, and again irradiated with ultraviolet rays of 365 nm with a UV hand lamp, the first region and the first region were observed. Both areas fluoresced red.

  Dipentaerythritol penta (hexa) acrylate (Toa Gosei Co., Ltd., Aronix M-400) 70 wt%, neopentyl glycol modified trimethylolpropane diacrylate (Nippon Kayaku Co., Ltd. KAYARAD R-604) 10 wt%, urethane acrylate (Arakawa) Industrial Co., Ltd. Beam Set 505A-6) 2 wt% of red pigment Novo Palm Carmine HF4C, photopolymerization initiator 2-hydroxy-1- {4- [4- (2) with respect to 98 wt% of resin composition adjusted at a ratio of 20 wt% -Hydroxy 2-methyl-propionyl) -benzyl] -phenyl} -2-methyl-propan-1-one (Ciba Specialty Chemicals Irgacure127) 2% by weight, antifoaming agent (BYK-1790 manufactured by Big Chemie) 0. An ink composition 2a that was adjusted at a rate of 5 wt% and emitted light by two-photon excitation was obtained. In addition, the functional group density of this resin composition is 7.77 mmol / g.

  Dipentaerythritol penta (hexa) acrylate (Toa Gosei Co., Ltd. Aronix M-400) 70 wt%, Neopentylglycol-modified trimethylolpropane diacrylate (Nippon Kayaku Co., Ltd. KAYARAD R-604) 10 wt%, Urethane acrylate (Arakawa) Industrial Co., Ltd. Beam Set 505A-6) 2 wt% of red pigment Novo Palm Carmine HF4C, 5 wt% of green fluorescent pigment (D1164 manufactured by Nemoto Special Chemical Co., Ltd.), photopolymerization, with respect to 93 wt% of resin composition adjusted at 20 wt% Initiator 1-Hydroxy-cyclohexyl-phenyl-ketone (Ciba Specialty Chemicals Irgacure184) 2% by weight, defoaming agent (BYK-1790 manufactured by Big Chemie Co., Ltd.) 0.5% by weight To obtain a fluorescent light-emitting ink composition 2b which does not emit light.

  Example 1 Printing on a high-quality paper by flexographic printing using an anilox roll of 200 lines / inch so that the first area is formed by the ink composition 2a and the second area is formed by the ink composition 2b. 2 was obtained.

  The first region and the second region of the anti-counterfeit printed matter of Example 2 can be recognized as red, which is the color of the mixed color pigment, under visible light, and the first region and the second region are substantially the same color. Observed.

For the anti-counterfeit printed matter of Example 2, UVP Inc. When UV irradiation of 365 nm was observed using a UV hand lamp manufactured by 3UV series, only the second region of the ink composition 2b emitted green light. When the anti-counterfeit printed matter of Example 2 was irradiated with ultraviolet rays of about 50 mJ / cm ² with an ultraviolet irradiation device such as a metal halide lamp or a mercury lamp, and again irradiated with 365 nm ultraviolet rays with a UV hand lamp, the first region was red. In addition, the second region fluoresced in green and in a different color.

  Tripropylene glycol diacrylate (Toagosei Co., Ltd., Aronix M-220) 15 wt%, Dipentaerythritol penta (hexa) acrylate (Toagosei Co., Ltd. M-400 30 wt%, EO-modified bisphenol F diacrylate (Nippon Kayaku Co., Ltd.) Kayrad R-712) 40 wt%, Epoxy acrylate (Nippon Kayaku Co., Ltd. ZFA-265H) 80 wt% of resin composition adjusted to a proportion of green pearl pigment Iriodin231 (Merck Co., Ltd.) 20 wt%, photopolymerization started Agent 2-Hydroxy-2-methyl-1-phenyl-propan-1-one (Ciba Specialty Chemicals Darocure 1173) 4% by weight, defoaming agent (BYK-1790 manufactured by Big Chemie) 0.5% by weight And an ink composition 2b that emits light by two-photon excitation was obtained.

  Isobornyl acrylate (Osaka Organic Chemical Co., Ltd. IBXA) 10wt%, Tripropylene glycol diacrylate (Toagosei Co., Ltd., Aronix M-220) 30wt%, Dipentaerythritol hexaacrylate (Nippon Kayaku Co., Ltd. Kayrad DPHA) 30wt% , Urethane acrylate (Nippon Kayaku UX-8101) 15 wt%, EO-modified bisphenol A type diacrylate (Toagosei Co., Ltd., Aronix M-210) resin composition adjusted at a ratio of 15 wt%, red pearl pigment Iriodin211 ( Merck Co., Ltd.) 20 wt%, 1 wt. Of fluorescent pigment in which red fluorescent pigment (Riedel dehaen Rot CD740) and green fluorescent pigment (D1164 manufactured by Nemoto Special Chemical Co., Ltd.) were mixed at a ratio of 1: 5, photopolymerization initiator 2-hydroxy -2-methyl-1-phenyl-propan-1-one (Ciba Pesharuti Chemicals Darocure 1173) outer percentage 4 wt%, adjusted at a ratio of defoamer (BYK Co. BYK-1790) 0.5wt%, to give the fluorescent luminous ink composition 2a does not emit light by two-photon excitation.

  Example 1 Printing on a high-quality paper by flexographic printing using an anilox roll of 300 lines / inch so that the first area is formed by the ink composition 2a and the second area is formed by the ink composition 2b. 3 was obtained.

  In the anti-counterfeit printed matter of Example 3, under visible light, the first region was able to recognize the interference color of the red pearl, and the second region was able to recognize the interference color of the green pearl.

For the anti-counterfeit printed matter of Example 3, UVP Inc. When UV irradiation of 365 nm was observed using a UV hand lamp manufactured by 3UV series, only the first region of the ink composition 2a emitted yellow light. When the anti-counterfeit printed matter of Example 3 was irradiated with ultraviolet rays of about 100 mJ / cm ² with an ultraviolet irradiation device such as a metal halide lamp or a mercury lamp, and again irradiated with 365 nm ultraviolet rays with a UV hand lamp, the first region and the first region were observed. The two areas both fluoresced substantially in the same color of yellow.

  Tripropylene glycol diacrylate (Toagosei Co., Ltd., Aronix M-220) 15 wt%, Dipentaerythritol penta (hexa) acrylate (Toagosei Co., Ltd. M-400 30 wt%, EO-modified bisphenol F diacrylate (Nippon Kayaku Co., Ltd.) Kayalad R-712) 40 wt%, epoxy acrylate (Nippon Kayaku Co., Ltd. ZFA-265H) 15 wt%, photopolymerization initiator 2-hydroxy-2-methyl-1-phenyl-propan-1-one (Ciba Specialty Chemicals) Darocure 1173) was adjusted at a ratio of 4 wt% of outer crack and 0.5 wt% of an antifoam (BYK-1790 manufactured by Big Chemie) to obtain an ink composition 2b that emits light by two-photon excitation.

  Isobornyl acrylate (Osaka Organic Chemical Co., Ltd. IBXA) 10wt%, Tripropylene glycol diacrylate (Toagosei Aronix M-220) 30wt%, Dipentaerythritol hexaacrylate (Nippon Kayaku Kayrad DPHA) 30wt% , Urethane acrylate (Nippon Kayaku UX-8101) 15wt%, EO-modified bisphenol A type diacrylate (Toagosei Co., Ltd., Aronix M-210) FGL 1.8wt%, Fast Red 8153 0.2wt%, Green Fluorescent Pigment (Nemoto Special Chemical Co., Ltd. D1164) 0.67wt, Red Fluorescent Pigment (Riedel dehaen Rot CD740) 0.33wt, Photopolymerization Initiator 2-Hydroxy-2 -Methyl-1-phenyl-propane-1- (Ciba Specialty Chemicals Darocure 1173) 4% by weight, defoamer (BYK-1790 manufactured by Big Chemie) 0.5wt%, adjusted to a ratio of 0.5 wt% to obtain a fluorescent ink 2a that does not emit light by two-photon excitation It was.

  Example 1 Printing on a high-quality paper by flexographic printing using an anilox roll of 200 lines / inch so that the first area is formed by the ink composition 2a and the second area is formed by the ink composition 2b. 4 was obtained.

  In the anti-counterfeit printed matter of Example 4, the second area was colorless under visible light, so that it could not be recognized as a design, and only the first area could be recognized as orange, which is the color of the mixed pigment.

For the anti-counterfeit printed matter of Example 4, UVP Inc. When UV irradiation of 365 nm was observed using a UV hand lamp manufactured by 3UV series, only the first region of the ink composition 2a emitted yellow light. When the anti-counterfeit printed matter of Example 4 was irradiated with ultraviolet rays of about 80 mJ / cm ² with an ultraviolet irradiation device such as a metal halide lamp and a mercury lamp, and again irradiated with ultraviolet rays of 365 nm with a UV hand lamp, the first region and the first region were observed. The two areas both fluoresced substantially in the same color of yellow.

It is a schematic diagram which shows the excitation state at the time of irradiating the ultraviolet-ray of 2nd wavelength range (lambda) 2 after irradiating the ultraviolet-ray of 1st wavelength range (lambda) 1. It is a figure which shows an example of the printed matter which has the confidential information of this invention. It is a figure explaining the method to observe the printed matter which has the confidential information of this invention. It is a figure explaining 1st Embodiment of the printed matter which has the confidential information of this invention. It is a figure explaining another form of 1st Embodiment of the printed matter which has the confidential information of this invention. It is a figure explaining 2nd Embodiment of the printed matter which has the confidential information of this invention. It is a figure explaining another form of 2nd Embodiment of the printed matter which has the confidential information of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Base material 2 Print pattern 2a 1st printing area 2b 2nd printing area 3a Handy type ultraviolet irradiation device 3b Ultraviolet irradiation apparatuses, such as a metal halide lamp and a mercury lamp

Claims (16)

At least a part of the printed pattern formed on the base material is a true / false discrimination printed matter using special light emission having a first print area and a second print area,
The first printing region forms an excitation substance by irradiation with ultraviolet rays in the first wavelength region λ1, and after irradiating with ultraviolet rays in the first wavelength region λ1, irradiates ultraviolet rays in the second wavelength region λ2. And printed with a first ink containing a resin composition that emits light in a first emission color by two-photon excitation excited by the excitation substance,
The second printing region is printed with a second ink that contains a fluorescent pigment that emits light in a second emission color and does not contain a resin composition that emits light by the two-photon excitation,
The first ink and the second ink are substantially the same color,
The first print area and the second print area are observed as substantially the same color under visible light, and only the second print area is exposed to the second wavelength area λ2 by irradiating ultraviolet rays in the second wavelength band λ2. The first print region is observed by being emitted with fluorescent light of two emission colors, and further irradiated with ultraviolet rays in the second wavelength region λ2 after being irradiated with ultraviolet rays in the first wavelength region λ1. The authenticity-determined printed matter using special light emission, wherein the second print region emits fluorescence in the second light emission color in the light emission color.   The first ink and the second ink having substantially the same color are configured such that the first ink includes a predetermined color material, and the second ink includes the same color material as the predetermined color material. Or a mixed color of a plurality of color materials contained in the first ink and a mixed color of a plurality of color materials contained in the second ink are the same An authenticity printed matter using the special light emission according to claim 1.   2. The authenticity using special light emission according to claim 1, wherein the first ink and the second ink having substantially the same color are colorless and transparent in the first ink and the second ink. Discrimination printed matter.   2. The first ink and the second ink of the substantially equal color, wherein the first ink and the second ink contain a functional material of substantially the same color. True / false discrimination printed matter using special light emission.   5. The authenticity discrimination printed matter using special light emission according to claim 4, wherein the functional material is a glitter material, a magnetic material, a conductive material and / or a chromic material. The fluorescent pigment that emits the second emission color contained in the second ink is a fluorescent pigment that emits light in substantially the same color as the first emission color of the first ink,
The first print area and the second print area are observed as substantially the same color under visible light, and when the ultraviolet ray in the second wavelength band λ2 is irradiated, only the second print area is the second print area. Fluorescent emission is observed as a luminescent color, and after irradiating ultraviolet rays in the first wavelength range λ1, further irradiating ultraviolet rays in the second wavelength range λ2, the first printing region and the second printing are performed. The authenticity determination printed matter using special light emission according to any one of claims 1 to 5, wherein the region is observed by fluorescence emission substantially in the same color. The fluorescent pigment that emits the second emission color contained in the second ink is a fluorescent pigment that emits light in a color different from the first emission color of the first ink,
The first print area and the second print area are observed as substantially the same color under visible light, and when the ultraviolet ray in the second wavelength band λ2 is irradiated, only the second print area emits fluorescence. Observed, after irradiating ultraviolet rays in the first wavelength range λ1, and further irradiating ultraviolet rays in the second wavelength range λ2, the first printing region and the second printing region emit fluorescence in different colors. The true / false discrimination printed matter using the special light emission according to any one of claims 1 to 6, wherein the printed matter is observed. At least a part of the printed pattern formed on the base material is a true / false discrimination printed matter using special light emission having a first print area and a second print area,
The first printing region forms an excitation substance by irradiation with ultraviolet rays in the first wavelength region λ1, and after irradiating with ultraviolet rays in the first wavelength region λ1, irradiates ultraviolet rays in the second wavelength region λ2. And printed with a first ink containing a resin composition that emits light in a first emission color by two-photon excitation excited by the excitation substance,
The second printing region is printed with a second ink that contains a fluorescent pigment that emits light in a second emission color and does not contain a resin composition that emits light by the two-photon excitation,
The first ink and the second ink are different colors,
The first print area and the second print area are observed as different colors under visible light, and only the second print area is exposed to the second wavelength by irradiating ultraviolet rays in the second wavelength band λ2. The first printing region is observed by emitting fluorescence in the first emission region, and after irradiating ultraviolet rays in the first wavelength region λ1, and further irradiating ultraviolet rays in the second wavelength region λ2. Authenticity discrimination printed matter using special light emission, wherein the second print region emits fluorescence in the second emission color as the emission color.   The first ink and the second ink of the different colors are such that the first ink includes a predetermined color material, and the second ink includes a color material of a color different from the predetermined color material. The mixed color of the plurality of color materials contained in the first ink is different from the mixed color of the plurality of color materials contained in the second ink. Item 9. A printed matter for authenticity determination using the special light emission according to Item 8.   The first ink and the second ink of the different colors include either the first ink or the second ink containing the predetermined color material, and the other ink is colorless. The authenticity printed matter using special light emission according to claim 8, which is transparent.   The first ink and the second ink of the different colors include a functional material in which the first ink has a predetermined interference color, and the second ink is different from the predetermined interference color. The authenticity discrimination printed matter using special light emission according to claim 8, comprising a pearl pigment which becomes an interference color.   12. The authenticity discrimination printed matter using special light emission according to claim 11, wherein the functional material is a glitter material, a magnetic material, a conductive material and / or a chromic material. The fluorescent pigment that emits the second emission color contained in the second ink is a fluorescent pigment that emits light in substantially the same color as the first emission color of the first ink,
When the first print area and the second print area are observed as different colors under visible light and are irradiated with ultraviolet rays in the second wavelength band λ2, only the second print area emits the second light emission. Fluorescent emission as a color is observed, and after irradiating ultraviolet rays of the first wavelength region λ1, and further irradiating ultraviolet rays of the second wavelength region λ2, the first printing region and the second printing region The printed matter for authenticity determination using special light emission according to any one of claims 8 to 12, wherein the printed matter is observed by fluorescence emission substantially in the same color. The resin composition that emits light in the first emission color by two-photon excitation contained in the first ink includes a resin containing a polyfunctional acrylate and radical light that undergoes intramolecular cleavage by light absorption to generate radicals. A resin assembly comprising a polymerization initiator,
The true / false discrimination using special luminescence according to any one of claims 1 to 13, wherein the resin comprising the polyfunctional acrylate has a functional group density of acryloyl group of 0.5 mmol / g or more. Printed matter. The resin composition that emits light in the first emission color by two-photon excitation contained in the first ink includes a resin containing a polyfunctional acrylate and radical light that undergoes intramolecular cleavage by light absorption to generate radicals. A resin assembly comprising a polymerization initiator,
14. The authenticity using special luminescence according to claim 1, wherein the resin containing the polyfunctional acrylate has an ethylenically unsaturated group and a bisphenol skeleton in the molecule. Discrimination printed matter.   16. The special light emission according to claim 1, wherein the first wavelength region λ1 is 260 nm or more and less than 330 nm, and the second wavelength region λ2 is 330 nm or more and 410 nm or less. Used authenticity printed matter.

Images