JPH07164729A - Security ink printed matter - Google Patents

Abstract

PURPOSE:To improve a shelf stability and a light resistance by a method wherein a security ink printed matter is formed by providing a protective layer containing UV absorber having absorption in a specific wave range on a printing layer containing a near IR rays absorbing dyestuff. CONSTITUTION:A security ink printed matter is formed by laminating a protective layer containing a UV absorber having absorption in a wave range of 250-400nm on a printing layer containing a near IR absorbing dyestuff. This security ink printed matter is sensitized by a near infrared light of 700-1800nm but hardly colored by a light of 400-700nm and hardly colored after printing, thus having an excellent shelf stability after printing and light resistance. The near IR absorbing dyestuff in use preferably has a high molar absorptivity in a laser range, and an anthraquinone, a phthalocyanine, or the like can be used. As the UV absorber having absorption in a wave range of 250-400nm, a benzotriazole UV absorber, a benzophenone UV absorber, or the like can be preferably used.

Description

Detailed Description of the Invention

[0001]

The present invention relates to near infrared rays (700-1).
(800 nm) detection for prepaid cards, gift certificates, securities, etc., or OCR reading by near-infrared detection, position confirmation, equipment malfunction prevention, etc. More specifically, a dithiol complex compound which is a near infrared absorber, a printing layer containing a phthalocyanine or naphthalocyanine compound,
The present invention relates to a security ink printed matter having a protective layer containing an ultraviolet absorber, excellent in light resistance stability, and excellent in near infrared sensitivity.

[0002]

2. Description of the Related Art There are several methods for preventing forgery of prepaid cards, but the most common method is
There is a method of providing a print / printed portion that cannot be read by visible light (human eyes). In this case, there is usually a method using a near infrared (700 to 1800 nm) oscillation / detector. However, as a corresponding ink system,
High visible transparency, excellent storage stability as printed matter,
Also, no security ink printed matter has been found that is excellent in light resistance stability of the printed portion.

[0003]

An object of the present invention is to provide a security ink printed matter which is sensitive to near infrared rays (700 to 1800 nm), has excellent storage stability, and can obtain a printed matter having excellent light resistance. Is to provide.

[0004]

Means for Solving the Problems The inventors of the present invention have made extensive studies in order to solve the above problems, and as a result, the conventional printed matter is decomposed by ultraviolet rays and its light resistance is lowered, It was found that the deterioration of the printed matter due to the light can be prevented by providing the protective layer containing the agent, and the present invention has been completed. That is, the present invention has a wavelength of 250 to 4 on a printing layer containing a near infrared absorbing dye.
The present invention relates to a security ink printed matter, which comprises forming a protective layer containing an ultraviolet absorber having absorption at 00 nm. The present invention is a near infrared ray (700 ~
Sensitive to 1800 nm, visible region (400-700n
(EN) A security ink printed matter in which a colored matter (m) is less colored, excellent storage stability after printing, and a printed matter excellent in light resistance can be obtained.

The near-infrared absorbing dye used in the present invention has absorption in the near-infrared region (700 to 1800 nm) and is not particularly limited as long as it is a dye corresponding to the wavelength of the laser used, but the visible region ( (400 to 700 nm) with less coloring and a large molar absorption coefficient in the laser region is desirable. Examples thereof include anthraquinone, naphthoquinone, phthalocyanine, naphthalocyanine, dithiol complex and aminium salt. Particularly desirable dyes are dithiol complex compounds represented by the general formula (1) (formula 5) or the general formulas (2) and (formula 6), and the general formula (3)
Examples thereof include the phthalocyanine compound represented by (Chemical formula 7) or the naphthalocyanine compound represented by the general formula (4) (Chemical formula 8).

[0006]

[Chemical 5] [Wherein, A ^{1 to} A ⁸ are each independently a hydrogen atom, a halogen atom, a nitro group, a cyano group, a thiocyanate group, a cyanate group, an acyl group, a carbamoyl group, an alkylaminocarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group. Group, substituted or unsubstituted alkyl group, substituted or unsubstituted aryl group, substituted or unsubstituted alkoxy group,
A substituted or unsubstituted aryloxy group, a substituted or unsubstituted alkylthio group, a substituted or unsubstituted arylthio group, a substituted or unsubstituted alkylamino group, or a substituted or unsubstituted arylamino group, and Two matching substituents may be connected via a linking group.
R ^{1 to} R ⁴ are each independently a substituted or unsubstituted alkyl group,
It represents a substituted or unsubstituted aryl group. M represents a divalent metal atom, a trivalent or tetravalent substituted metal atom, or an oxymetal. ]

[0007]

[Chemical 6] [Wherein B ^{1 to} B ⁴ are each independently a hydrogen atom, a cyano group, an acyl group, a carbamoyl group, an alkylaminocarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a substituted or unsubstituted alkyl group, a substituted or It represents an unsubstituted aryl group, and two adjacent substituents may be connected via a linking group. M represents a divalent metal atom, a trivalent or tetravalent substituted metal atom, or an oxymetal. ]

[0008]

[Chemical 7] [In the formula, C ^{1 to} C ¹⁶ are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryl An oxy group, a substituted or unsubstituted alkylthio group or a substituted or unsubstituted arylthio group, and C ¹ , C ² , C ³ , C ⁴ , C ⁵ and C ⁶ , C ⁷
And in each combination of C ^8, C ⁹ and C ¹⁰ and C ¹¹ and C ^12, C ¹³ and C ¹⁴ and C ¹⁵ and C ^16, does not become a combination of hydrogen atom at the same time. M represents a divalent metal atom, a trivalent or tetravalent substituted metal atom, or an oxymetal. ]

[0009]

[Chemical 8] [Wherein, D ^{1 to} D ²⁴ are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryl group] An oxy group, a substituted or unsubstituted alkylthio group, or a substituted or unsubstituted arylthio group, and D ¹ , D ² , D ³ , D ⁴ , D ⁵ , D ⁶ , D ⁷
And D ⁸ and D ⁹ and D ¹⁰ and D ¹¹ and D ¹² , D ¹³ and D ¹⁴ , D ¹⁵ and D ¹⁶ , D ¹⁷ and D ¹⁸ , D ¹⁹ and D ²⁰ , D ²¹ and D ²² , D ²³ and D.
^In each of the ²⁴ combinations, no combination is simultaneously a hydrogen atom. M represents a divalent metal atom, a trivalent or tetravalent substituted metal atom, or an oxymetal. ] In the dithiol compound represented by the above formula (1) or (2), the phthalocyanine represented by the formula (3) or the naphthalocyanine represented by the formula (4), A ^{1 to} A
^{8, B 1 ~B 4, R} 1 ~R 4, C 1 ~C 16, D 1 ~D 24
Specific examples of the substituent represented by are described below. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

Examples of the substituted or unsubstituted alkyl group are methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, sec-butyl group, t-butyl group. , N-pentyl group, iso-pentyl group, neo-pentyl group, 1,2-dimethyl-propyl group, n-hexyl group, cyclo-
Hexyl group, 1,3-dimethyl-butyl group, 1-iso-propylpropyl group, 1,2-dimethylbutyl group, n-heptyl group,
1,4-dimethylpentyl group, 2-methyl 1-iso-propylpropyl group, 1-ethyl-3-methylbutyl group, n-octyl group,
Carbon number 1 to 2-ethylhexyl group, 3-methyl-1-iso-propylbutyl group, 2-methyl-1-iso-propyl group, 1-t-butyl-2-methylpropyl group, n-nonyl group, etc. 20 linear or branched alkyl group, methoxymethyl group, methoxyethyl group, ethoxyethyl group, propoxyethyl group, butoxyethyl group, γ-methoxypropyl group, γ-ethoxypropyl group, methoxyethoxyethyl group, ethoxyethoxyethyl Group, dimethoxymethyl group, diethoxymethyl group, dimethoxyethyl group, alkoxyalkyl group such as diethoxyethyl group, alkoxyalkoxyalkyl group,
Alkoxyalkoxyalkoxyalkyl group, chloromethyl group, 2,2,2-trichloroethyl group, trifluoromethyl group, 2,2,2-trichloroethyl group, 1,1,1,3,3,3, -hexafluoro -2-Halogenated alkyl group such as propyl group,
Examples thereof include an alkylaminoalkyl group, a dialkylaminoalkyl group, an alkoxycarbonylalkyl group, an alkylaminocarbonylalkyl group and an alkoxysulfonylalkyl group.

Further, examples of the substituted or unsubstituted alkoxy group include methoxy group, ethoxy group, n-propyloxy group, iso-propyloxy group, n-butyloxy group, iso-
Butyloxy group, sec-butyloxy group, t-butyloxy group, n-pentyloxy group, iso-pentyloxy group, neo-
Pentyloxy group, 1,2-dimethyl-propyloxy group,
n-hexyloxy group, cyclo-hexyloxy group, 1,3-dimethyl-butyloxy group, 1-iso-propylpropyloxy group, 1,2-dimethylbutyloxy group, n-heptyloxy group, 1,4-dimethyl Pentyloxy group, 2-methyl-1-iso-
Propylpropyloxy group, 1-ethyl-3-methylbutyloxy group, n-octyloxy group, 2-ethylhexyloxy group, 3-methyl-1-iso-propylbutyloxy group, 2-methyl-1-iso-propyl 1 to 2 carbon atoms such as oxy group, 1-t-butyl-2-methylpropyloxy group, n-nonyloxy group
0 linear or branched alkoxy group, methoxymethoxy group, methoxyethoxy group, ethoxyethoxy group, propoxyethoxy group, butoxyethoxy group, γ-methoxypropyloxy group, γ-ethoxypropyloxy group, methoxyethoxyethoxy group, ethoxy Alkoxyalkoxy groups such as ethoxyethoxy group, dimethoxymethoxy group, diethoxymethoxy group, dimethoxyethoxy group, diethoxyethoxy group, alkoxyalkoxyalkoxy groups such as methoxyethoxyethoxy group, ethoxyethoxyethoxy group, butyloxyethoxyethoxy group, alkoxy Alkoxyalkoxyalkoxy group, chloromethoxy group, 2,2,2-trichloroethoxy group, trifluoromethoxy group, 2,2,2-trichloroethoxy group, 1,1,1,3,3,3, -hexafluoro- 2-propyloxy group And other halogenated alkoxy groups, dimethylaminoethoxy groups, diethylaminoethoxy groups and other alkylaminoalkoxy groups, dialkylaminoalkoxy groups, and the like.

Examples of the substituted or unsubstituted aryl group are halogenated phenyl groups such as phenyl group, chlorophenyl group, dichlorophenyl group, bromophenyl group, fluorinated phenyl group and iodinated phenyl group, tolyl group, xylyl group, Examples thereof include a mesityl group, an ethylphenyl group, a methoxyphenyl group, an ethoxyphenyl group and a pyridyl group. Examples of the substituted or unsubstituted aryloxy group include phenoxy group, naphthoxy group, alkylphenoxy group and the like.

The substituted or unsubstituted alkylthio group includes methylthio group, ethylthio group, n-propylthio group,
iso-propylthio group, n-butylthio group, iso-butylthio group, sec-butylthio group, t-butylthio group, n-pentylthio group, iso-pentylthio group, neo-pentylthio group, 1,2-
Dimethyl-propylthio group, n-hexylthio group, cyclo-
Hexylthio group, 1,3-Dimethyl-butylthio group, 1-iso-
Propylpropylthio group, 1,2-dimethylbutylthio group,
n-heptylthio group, 1,4-dimethylpentylthio group, 2-methyl 1-iso-propylpropylthio group, 1-ethyl-3-methylbutylthio group, n-octylthio group, 2-ethylhexylthio group, 3- A straight chain having 1 to 20 carbon atoms such as methyl-1-iso-propylbutylthio group, 2-methyl-1-iso-propylthio group, 1-t-butyl-2-methylpropylthio group, n-nonylthio group or the like. Branched alkylthio group, methoxymethylthio group,
Methoxyethylthio group, ethoxyethylthio group, propoxyethylthio group, butoxyethylthio group, γ-methoxypropylthio group, γ-ethoxypropylthio group, methoxyethoxyethylthio group, ethoxyethoxyethylthio group, dimethoxymethylthio group, Alkoxyalkylthio groups such as diethoxymethylthio group, dimethoxyethylthio group, diethoxyethylthio group, alkoxyalkoxyalkylthio groups, alkoxyalkoxyalkoxyalkylthio groups, chloromethylthio group, 2,2,2-trichloroethylthio group, trifluoromethylthio group Group, 2,2,2-trichloroethylthio group, 1,1,1,3,3,3, -hexafluoro-2-
Examples thereof include halogenated alkylthio groups such as propylthio group, dimethylaminoethylcythio groups, alkylaminoalkylthio groups such as diethylaminoethylthio group, and dialkylaminoalkylthio groups.

Examples of the substituted or unsubstituted alkylthio group include methylthio group, ethylthio group, n-propylthio group,
iso-propylthio group, n-butylthio group, iso-butylthio group, sec-butylthio group, t-butylthio group, n-pentylthio group, iso-pentylthio group, neo-pentylthio group, 1,2-
Dimethyl-propylthio group, n-hexylthio group, cyclo-
Hexylthio group, 1,3-Dimethyl-butylthio group, 1-iso-
Propylpropylthio group, 1,2-dimethylbutylthio group,
n-heptylthio group, 1,4-dimethylpentylthio group, 2-methyl 1-iso-propylpropylthio group, 1-ethyl-3-methylbutylthio group, n-octylthio group, 2-ethylhexylthio group, 3- A straight chain having 1 to 20 carbon atoms such as methyl-1-iso-propylbutylthio group, 2-methyl-1-iso-propylthio group, 1-t-butyl-2-methylpropylthio group, n-nonylthio group or the like. Branched alkylthio group, methoxymethylthio group,
Methoxyethylthio group, ethoxyethylthio group, propoxyethylthio group, butoxyethylthio group, γ-methoxypropylthio group, γ-ethoxypropylthio group, methoxyethoxyethylthio group, ethoxyethoxyethylthio group, dimethoxymethylthio group, Alkoxyalkylthio groups such as diethoxymethylthio group, dimethoxyethylthio group, diethoxyethylthio group, alkoxyalkoxyalkylthio groups, alkoxyalkoxyalkoxyalkylthio groups, chloromethylthio group, 2,2,2-trichloroethylthio group, trifluoromethylthio group Group, 2,2,2-trichloroethylthio group, 1,1,1,3,3,3, -hexafluoro-2-
Examples thereof include halogenated alkylthio groups such as propylthio group, dimethylaminoethylcythio groups, alkylaminoalkylthio groups such as diethylaminoethylthio group, and dialkylaminoalkylthio groups. Examples of the substituted or unsubstituted arylthio group include phenylthio group, naphthylthio group, alkylphenylthio group and the like.

Examples of the divalent metal represented by M include Cu (II), Zn (II), Co (II) and Ni (I).
I), Ru (II), Rh (II), Pd (II), Pt (I
I), Mn (II), Mg (II), Ti (II), Be (I
I), Ca (II), Ba (II), 1d (II), Hg (I
I), Pb (II), Sn (II) and the like. Examples of mono-substituted trivalent metals include Al-Cl, Al-Br,
Al-F, Al-I, Ga-Cl, Ga-F, Ga-
I, Ga-Br, In-Cl, In-Br, In-I,
In-F, Tl-Cl, Tl-Br, Tl-I, Tl-
_{F, Al-C 6 H 5} , Al-C 6 H 4 (CH 3), In
_{-C 6 H 5, In-C} 6 H 4 (CH 3), In-C 6 H
_{5, Mn (OH), Mn} (OC 6 H 5), Mn [OSi
(CH _{3) 3],} Fe-Cl, include Ru-Cl, etc.. Examples of the di-substituted tetravalent metal include CrCl ₂ and Si.
Cl ₂ , SiBr ₂ , SiF ₂ , SiI ₂ , ZrC
l ₂ , GeCl ₂ , GeBr ₂ , GeI ₂ , GeF ₂ ,
SnCl ₂ , SnBr ₂ , SnF ₂ , TiCl ₂ , Ti
Br ₂ , TiF ₂ , Si (OH) ₂ , Ge (OH) ₂ ,
Zr (OH) ₂ , Mn (OH) ₂ , Sn (OH) ₂ , T
iR ₂ , CrR ₂ , SiR ₂ , SnR ₂ , GeR ₂ [R
Represents an alkyl group, a phenyl group, a naphthyl group, and a derivative thereof], Si (OR ') ₂ , Sn (OR') ₂ ,
Ge (OR ') ₂ , Ti (OR') ₂ , Cr (OR ')
₂ [R ′ represents an alkyl group, a phenyl group, a naphthyl group, a trialkylsilyl group, a dialkylalkoxysilyl group and derivatives thereof], Sn (SR ″) ₂ , Ge (S
R ″) ₂ (R ″ represents an alkyl group, a phenyl group, a naphthyl group, or a derivative thereof), etc. Examples of the oxy metal include VO, MnO, and TiO.

Of these, 700 is particularly preferable.
It is a compound having a large absorption in the range of up to 1000 nm, has good solubility in the resin binder to be used, and is a compound which is easy to manufacture ink. In particular, the compound of formula (1) or formula (2) and, in formula (3) or formula (4), C ¹ and C ⁴ , C ⁵ and C ⁸ , C ⁹ and C ¹² , C ¹³ and C ¹⁶ , D ³ and D
⁴ , a combination of D ⁹ and D ¹⁰ , D ¹⁵ and D ¹⁶ , and D ²¹ and D ²² , at least one of which is a substituted or unsubstituted alkoxy group having 2 to 20 carbon atoms, or a substituted or unsubstituted alkoxy group having 6 to 20 carbon atoms. Which is an aryloxy group having 2 to 20 carbon atoms, a substituted or unsubstituted alkylthio group having 2 to 20 carbon atoms, or a substituted or unsubstituted aryloxy group having 6 to 20 carbon atoms, and M
Is preferably Cu, Ni, Co, Fe, Pd, VO, or TiO.

The printing layer containing the near-infrared absorbing dye used in the present invention is not particularly limited as long as it is a printing layer having a required amount of absorption in a specific near-infrared region, but it is usually a fat. A group ester resin, an acrylic resin, a melamine resin, a urethane resin, an aromatic ester resin, a polycarbonate resin or the like is used as a binder and mixed with a near infrared absorbing dye to form a printing layer. That is, an ink is prepared by dissolving the resin and the near infrared absorbing dye in a halogen-based, alcohol-based, ketone-based, ester-based, aliphatic hydrocarbon-based, aromatic hydrocarbon-based, or ether-based solvent,
Print the required characters, numbers, barcodes, patterns, etc.,
A print layer can be formed by distilling off the solvent. The amount of the near-infrared absorbing dye used is not a uniform determination because it varies depending on the molar absorption coefficient of the near-infrared absorbing dye used, the required absorption amount, the thickness of the printed matter, etc. To 0.01 to 20% by weight
Is. More preferably, it is 0.1 to 10% by weight. The thickness of the printing layer is usually 0.5 to 1 so that it cannot be sensed by touch as a security ink printed matter.
About 0 μm is preferable.

If necessary, additives such as plasticizers, antioxidants, thickeners and waxes which are added to ordinary gravure inks, screen inks and the like may be added to the inks. Further, an ultraviolet absorber, a singlet oxygen quencher, a triplet radical trapping agent, etc. may be added. Further, a thermosetting resin or a photocurable resin can be used as the binder. In particular, an ink using an acrylate-based photocurable resin that does not contain a volatile organic solvent is a pollution-free type and is often used because it is suitable for mass printing such as offset printing. When preparing an ink using a photocurable resin, usually, an acrylate-based monomer and / or oligomer, or a methacrylate-based monomer and / or
Alternatively, the above-mentioned near-infrared absorbing dye is contained in an oligomer or a mixture of several kinds selected from them, which further contains a photopolymerization initiator. In addition, thermal polymerization inhibitors, plasticizers, etc. that are added to ordinary photocurable inks,
Antioxidants, thickeners, waxes, etc. may be added. Or UV absorber, singlet oxygen quencher,
A triplet radical trapping agent may be added in some cases. After printing the photocurable ink, the ink is cured by UV irradiation from a mercury lamp or a metal halide lamp.

The protective layer containing an ultraviolet absorber used in the present invention is not particularly limited as long as it does not hinder reading with a laser after being formed on the printing layer. As the manufacturing method, the following two methods are usually available. The first method is a highly transparent film containing an ultraviolet absorber, for example, an aliphatic ester resin film, an acrylic resin film, a melamine resin film, a urethane resin film, an aromatic ester resin film, a polycarbonate resin film, Vinyl chloride resin film, aliphatic hydrocarbon resin film,
Polysulfone resin film, polyamide resin film,
This is a method in which a resin film such as a polyimide resin film, a polyethylene film, a polypropylene film, or a polystyrene film is attached onto a printed matter. When pasting, use general-purpose epoxy, acrylic, polyolefin, modified polyolefin adhesive,
It can also be thermocompression bonded. Further, it is possible to mix an ultraviolet absorber into the adhesive by using the adhesive as a protective layer. The thickness of the protective film is usually 10 to 1000 μm.

The second method is a method in which a transparent ink containing an ultraviolet absorber is prepared and coated on the printed matter or partially overcoated on the printed surface. In this method, as the transparent ink, general-purpose aliphatic ester resin, acrylic resin, melamine resin, urethane resin, aromatic ester resin, polycarbonate resin, etc. are halogen-based, alcohol-based, ketone-based, ester-based, The protective layer can be formed by dissolving the solvent in an aliphatic hydrocarbon-based, aromatic hydrocarbon-based, or ether-based solvent to prepare an ink, applying the ink, and then distilling the solvent off. If necessary, additives such as plasticizers, antioxidants, thickeners and waxes which are added to ordinary gravure inks, screen inks and the like can be added to the inks. Alternatively, a singlet oxygen quencher and a triplet radical trapping agent can be added. Moreover, a thermosetting ink or a photocurable ink can also be used. When a photocurable ink is used, it is usually an acrylate-based monomer and / or oligomer, or a methacrylate-based monomer and / or oligomer,
Alternatively, the photopolymerization initiator is contained in a mixture of several kinds selected from them. In addition, thermal polymerization inhibitors, plasticizers, antioxidants, thickeners, waxes, etc., which are added to ordinary photocurable inks, may be added. Alternatively, a singlet oxygen quencher and a triplet radical trapping agent can be added. After printing the photocurable ink, the ink is cured by UV irradiation from a mercury lamp or a metal halide lamp. In this case, the thickness of the protective layer is usually the same as that of the printing layer, or can be increased if necessary, and is preferably about 0.5 to 100 μm.

In either of the first and second methods, the film or ink used for the protective layer is usually transparent, but dyes and pigments may be used as long as they do not hinder the reading of the printed surface by a laser. It is also a preferable method to add a pigment or the like for coloring or to incorporate a pattern or a picture.
That is, by coloring the protective layer with a dye having absorption in the wavelength range of 400 to 700 nm or incorporating a pattern or a picture, it is possible to make the lower printing surface less noticeable.

Wavelength contained in the protective layer is 250 to 400 nm
UV absorbers with absorption of 400-700n
There is no particular limitation as long as the compound has a small absorption in the visible region of m and a large absorption in the range of 250 to 400 nm. For example, light stabilizers described in "Photopolymer deterioration and stabilization" (Zenjiro Osawa, CMC), for example, benzotriazole ultraviolet absorbers, benzophenone ultraviolet absorbers, salicylate ultraviolet absorbers, acrylates. Examples of the ultraviolet absorber include oxalic acid anilide ultraviolet absorbers. Particularly preferred compounds include a benzotriazole-based UV absorber represented by the following general formula (5) (Chemical formula 9), a benzophenone-based external ray absorber represented by the following general formula (6) (Chemical formula 9), and a general formula below. (7) Salicylic acid ester-based ultraviolet absorber represented by (Chemical formula 9), acrylate-based ultraviolet absorber represented by the following general formula (8) (Chemical formula 9), represented by the following general formula (9) (Chemical formula 9) Ogizaric acid anilide type ultraviolet absorbers are used.

[0023]

[Chemical 9] [In the formula, R ⁵ to R ¹² each independently represent a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, R ¹² ~
R ^49's each independently represent a hydrogen atom, a halogen atom, a hydroxy group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, X represents a hydrogen atom, a substituted or unsubstituted alkyl group, and n is 3 Represents an integer of 20. ]

The amount of the ultraviolet absorber contained in the protective layer is not limited to any particular value because it is determined depending on the type of the ultraviolet absorber used or the thickness of the protective layer. It is preferably used in the range of 0.01 to 50% by weight with respect to the protective layer. A particularly preferable amount of the ultraviolet absorber is 1 to 20% by weight. Based on the above embodiment, a security ink printed matter produced by forming a protective layer containing an ultraviolet absorber having absorption at a wavelength of 250 to 400 nm on a printed layer containing a near infrared absorbing dye, It is possible to provide an excellent prepaid card which has excellent light resistance and is not sensed by touch, which is extremely valuable in practical use.

[0025]

EXAMPLES The present invention will now be described in more detail by way of examples. The present invention is not limited thereby. The phthalocyanine compound and the naphthalocyanine compound represented by the formulas (10) to (14) shown in the examples are obtained by simplifying the structure represented by the formula (3) or the formula (4). .

Example 1 Polymethylmethacrylate (PMMA) pellets, 5
g, and 0.1 g of copper phthalocyanine represented by the following formula (10) (Formula 10) were dissolved in 30 ml of ethyl acetate to prepare an ink. Apply this ink to the coil bar (No. 12)
Was used to coat PET synthetic paper [Lumira white type manufactured by Toray Industries, Inc.], and the solvent was removed by drying at room temperature for 1 hour to prepare a base printing layer. A transparent PET film containing 3% by weight of a benzophenone-based ultraviolet absorber [Chemisolve 1001 manufactured by Chemipro Kasei Co., Ltd.] was attached thereto by using an epoxy adhesive. Coating surface is Shimadzu Corporation spectrophotometer UV2200
At, the total reflection at an incident angle of 45 ° was measured (magnesium oxide standard). When the reflectance of visible light was calculated according to JIS-R-3106, it was 75%. The minimum reflectance in the near infrared region was 13% (770 nm). The coating surface of the synthetic paper was heated at 63 ° C.
A light resistance test was conducted by irradiating with a carbon arc lamp for 24 hours. After the test, when the reflectance was measured in the same manner, the visible light reflectance was 77% and the minimum reflectance was 15% (770 nm).
The change in reflectance before and after the test was small, and the light resistance was good.

[0027]

[Chemical 10]

Example 2 The base printing layer prepared in Example 1 was used as a UV absorber for a benzotriazole type UV absorber [Kyodo Yakuhin Co., Ltd.].
Made from Biosorb 583] added with 3% by weight of ethylene-
The PET films were attached using a vinyl acetate (EVA) adhesive. When the reflectance was measured in the same manner as in Example 1, the visible light reflectance was 76% and the minimum reflectance was 16% (770n.
m). When the reflectance was measured by performing a light resistance test for 24 hours in the same manner as in Example 1, the visible light reflectance was 78%,
The minimum reflectance was 18% (770 nm), the reflectance change before and after the test was small, and the light resistance was good.

Example 3 Saturated polyester resin [Vylon 20 manufactured by Toyobo Co., Ltd.
0] 5 g and 0.1 g of copper phthalocyanine represented by the following formula (11) (formula 11) were dissolved in 30 ml of toluene to prepare an ink. After coating this ink on PET synthetic paper using a coil bar (No. 12),
The solvent was removed by drying for a period of time to prepare a printed layer serving as a base. A transparent PET film containing 3% by weight of a salicylic acid ester-based ultraviolet absorber [Biosorb 130 manufactured by Kyodo Chemical Co., Ltd.] was attached thereto by using an epoxy adhesive. When the reflectance was measured in the same manner as in Example 1,
Visible light reflectance 78%, minimum reflectance 15% (792 nm)
Met. The same 24-hour light resistance test as in Example 1 was performed to measure the reflectance. The visible light reflectance was 79% and the minimum reflectance was 17% (792 nm). The sex was good.

[0030]

[Chemical 11]

Example 4 Except for using the VO phthalocyanine represented by the following formula (12) (Chemical formula 12) in place of the copper phthalocyanine represented by the formula (11), a printing layer and a printing layer were prepared in the same manner as in Example 3. A protective layer was prepared. When the reflectance was measured in the same manner as in Example 1, the visible light reflectance was 80% and the minimum reflectance was 18% (76
0 nm). A light resistance test was conducted for 24 hours in the same manner as in Example 1, and the reflectance was measured.
%, The minimum reflectance was 20% (760 nm), the reflectance change before and after the test was small, and the light resistance was good.

[0032]

[Chemical 12]

Example 5 5 g of an acrylate monomer (light acrylate BP-4EA manufactured by Kyoeisha Yushi Kagaku Kogyo Co., Ltd.), 0.1 g of copper phthalocyanine used in Example 3 and a benzotriazole-based ultraviolet absorber (Kyodo Chemical Co., Ltd. ) Biosorb 583)
0.1 g, photopolymerization catalyst (Kayakyu D manufactured by Nippon Kayaku Co., Ltd.)
0.2 g of ETX) was dissolved to prepare an ultraviolet curable ink. This ink was coated on PET synthetic paper using a spin coater, and then 400 mJ / with a high-pressure mercury lamp (using Ushio's rapid cure irradiation device).
The ink was cured by irradiating with cm ² of light to prepare a printed layer as a base. Furthermore, instead of adding no copper phthalocyanine, which is a near-infrared absorbing dye, a benzotriazole-based ultraviolet absorber (Biosorb 58 manufactured by Kyodo Yakuhin Co., Ltd.).
Except that the addition amount of 3) was increased to 0.5 g, an ultraviolet curable ink was prepared by the same procedure as above, and a protective layer was coated and cured by a spin coater on the above base printed matter by the same procedure. I went. When the reflectance was measured in the same manner as in Example 1, the visible light reflectance was 75% and the minimum reflectance was 12% (798 nm). A light resistance test was conducted for 24 hours in the same manner as in Example 1, and the reflectance was measured. The visible light reflectance was 78% and the minimum reflectance was 16% (798n).
m), the change in reflectance before and after the test was small, and the light resistance was good.

Example 6 Polymethylmethacrylate (PMMA) pellets, 5
g and a benzotriazole-based ultraviolet absorber (Ciba-
An ink for a protective layer was prepared by dissolving 0.3 g of Geinuy's Tinuvin-P) and 30 ml of ethyl acetate.
The coil bar (No.
After coating with 12), it was dried at room temperature for 1 hour to remove the solvent. When the reflectance was measured in the same manner as in Example 1, the visible light reflectance was 78% and the minimum reflectance was 13%.
(798 nm). When the reflectance was measured by performing a light resistance test for 24 hours in the same manner as in Example 1, the visible light reflectance was 79% and the minimum reflectance was 18% (798 nm). The sex was good.

Example 7 Acrylate Monomer [Aronix M315 (2.5 g manufactured by Toagosei Kagaku Kogyo Co., Ltd. and Osaka Organic Chemical Co., Ltd.)
Mixture of bis coat 295 (2.5 g)] and copper phthalocyanine 0.1 represented by the following formula (13)
g, 0.1 g of a benzophenone-based ultraviolet absorber (Kemipro Kasei Co., Ltd. Chemisolve 1001), and 0.1 g of a photopolymerization catalyst (Merck KK-made Darocur 1173) were dissolved to prepare a UV-curable ink. This ink was coated on PET synthetic paper using a spin coater, and then the ink was cured by irradiating it with 400 mJ / cm ² of light from a high-pressure mercury lamp (using a rapid cure irradiator manufactured by Ushio Co., Ltd.) to form a base printing layer. Was produced. Furthermore, except that copper phthalocyanine which is a near-infrared absorbing dye is not added, an ultraviolet curable ink is prepared by the same operation as above, and a protective layer is coated on the above base printing layer by a spin coater by the same operation. went. When the reflectance was measured in the same manner as in Example 1, the visible light reflectance was 77%,
The minimum reflectance was 20% (789 nm). A light resistance test was conducted for 24 hours in the same manner as in Example 1, and the reflectance was measured. The visible light reflectance was 79% and the minimum reflectance was 24% (789
nm), the change in reflectance before and after the test was small, and the light resistance was good.

[0036]

[Chemical 13]

Example 8 Printing was carried out in the same manner as in Example 3 except that copper naphthalocyanine represented by the following formula (14) (Chemical formula 14) was used in place of the copper phthalocyanine represented by the formula (11). A layer and a protective layer were prepared. When the reflectance was measured in the same manner as in Example 1, the visible light reflectance was 80% and the minimum reflectance was 20% (7
85 nm). A light resistance test was conducted for 24 hours in the same manner as in Example 1, and the reflectance was measured. The visible light reflectance was 8
The reflectance was 2% and the minimum reflectance was 24% (785 nm), and the change in reflectance before and after the test was small and the light resistance was good.

[0038]

[Chemical 14]

Example 9 Example 3 was repeated except that 0.5 g of the dithiol complex represented by the following formula (15) (Chemical formula 15) was used in place of 0.1 g of the copper phthalocyanine represented by the formula (11). A printing layer and a protective layer were prepared in exactly the same manner. When the reflectance was measured in the same manner as in Example 1, the visible light reflectance was 82% and the minimum reflectance was 13% (868 nm). As in Example 1, 2
When the reflectance was measured by performing a light resistance test for 4 hours, the visible light reflectance was 83% and the minimum reflectance was 16% (868 nm), and the change in reflectance before and after the test was small and the light resistance was good.

[0040]

[Chemical 15]

Comparative Example 1 The reflectance of the printed layer, which was prepared in Example 3 and was not used as the protective layer containing the ultraviolet absorber, was measured in the same manner as in Example 1. The visible light reflectance was 80. %, And the minimum reflectance was 14% (792 nm). As in Example 1, 2
When a reflectance was measured by performing a light resistance test for 4 hours, the visible light reflectance was 82% and the minimum reflectance was 58% (792 nm). The reflectance change before and after the test was large and the light resistance was insufficient. It was

Comparative Example 2 The reflectance of the printed layer, which was prepared in Example 7 and was not used as the protective layer containing the ultraviolet absorber, was measured in the same manner as in Example 1, and the visible light reflectance was 79. %, And the minimum reflectance was 14% (789 nm). As in Example 1, 2
When the reflectance was measured by performing a light resistance test for 4 hours, the visible light reflectance was 85% and the minimum reflectance was 54% (789 nm). The reflectance change before and after the test was large and the light resistance was insufficient. It was

Comparative Example 3 The reflectance of the printed layer, which was prepared in Example 9 and did not have the protective layer containing the ultraviolet absorber, was measured in the same manner as in Example 1, and the visible light reflectance was 83. %, And the minimum reflectance was 12% (868 nm). As in Example 1, 2
When a light resistance test was performed for 4 hours and the reflectance was measured, the visible light reflectance was 84% and the minimum reflectance was 38% (868 nm). The reflectance change before and after the test was large and the light resistance was insufficient. It was

Examples 10 to 13 and Comparative Examples 4 to 7 Using the dithiol compounds (Compound Nos. 16 to 19) shown in Table 1 (Table 1), UV absorption was performed in the same manner as in Example 9 or Comparative Example 3. When a protective layer containing an agent is provided,
A comparison was carried out after the light resistance test in the case of not providing it. The results are shown in Table 2 (Table 2). A protective layer was provided in the examples, and no protective layer was provided in the comparative examples.

[0045]

[Table 1] Table-1

[0046]

[Table 2] Since the printed matter of the present invention has little coloring of the near-infrared absorber used, the printed layer has high transparency, and when printed on white paper, even if the minimum reflectance in the near-infrared region is reduced to about 10 to 20%. The visible light reflectance was 75% or more.

[0047]

INDUSTRIAL APPLICABILITY In the present invention, by providing a protective layer containing an ultraviolet absorber having absorption at a wavelength of 250 to 400 nm on a printing layer containing a near infrared absorbing dye,
This makes it possible to obtain a printed matter having high light resistance. INDUSTRIAL APPLICABILITY The security ink printed matter of the present invention can provide an excellent prepaid card with no reading error and is not visually noticeable, and is extremely valuable in practical use.

Claims (5)

[Claims] 1. A security ink printed matter, which comprises forming a protective layer containing an ultraviolet absorber having absorption at a wavelength of 250 to 400 nm on a printed layer containing a near infrared absorbing dye. 2. A near-infrared absorbing dye is a dithiol compound represented by general formula (1) (chemical formula 1), a dithiol compound represented by general formula (2) (chemical formula 2), or a general formula (3) (chemical formula 1). The security ink printed matter according to claim 1, which is at least one kind of near-infrared absorbing dye composed of a phthalocyanine compound represented by 3) or a naphthalocyanine compound represented by the general formula (4) (formula 4). [Chemical 1] [Wherein, A ^{1 to} A ⁸ are each independently a hydrogen atom, a halogen atom, a nitro group, a cyano group, a thiocyanate group, a cyanate group, an acyl group, a carbamoyl group, an alkylaminocarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group. Group, substituted or unsubstituted alkyl group, substituted or unsubstituted aryl group, substituted or unsubstituted alkoxy group,
A substituted or unsubstituted aryloxy group, a substituted or unsubstituted alkylthio group, a substituted or unsubstituted arylthio group, a substituted or unsubstituted alkylamino group, or a substituted or unsubstituted arylamino group, and Two matching substituents may be connected via a linking group.
R ^{1 to} R ⁴ are each independently a substituted or unsubstituted alkyl group,
It represents a substituted or unsubstituted aryl group. M represents a divalent metal atom, a trivalent or tetravalent substituted metal atom, or an oxymetal. ] [Chemical 2] [Wherein B ^{1 to} B ⁴ are each independently a hydrogen atom, a cyano group, an acyl group, a carbamoyl group, an alkylaminocarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a substituted or unsubstituted alkyl group, a substituted or It represents an unsubstituted aryl group, and two adjacent substituents may be connected via a linking group. M represents a divalent metal atom, a trivalent or tetravalent substituted metal atom, or an oxymetal. ] [Chemical 3] [In the formula, C ^{1 to} C ¹⁶ are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryl An oxy group, a substituted or unsubstituted alkylthio group, or a substituted or unsubstituted arylthio group, and C ¹ , C ² , C ³ , C ⁴ , C ⁵ and C ⁶ , C ⁷
And in each combination of C ^8, C ⁹ and C ¹⁰ and C ¹¹ and C ^12, C ¹³ and C ¹⁴ and C ¹⁵ and C ^16, does not become a combination of hydrogen atom at the same time. M represents a divalent metal atom, a trivalent or tetravalent substituted metal atom, or an oxymetal. ] [Chemical 4] [In formula (4), D ^{1 to} D ²⁴ are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted A substituted aryloxy group, a substituted or unsubstituted alkylthio group, or a substituted or unsubstituted arylthio group, and D ¹ , D ² , D ³ , D ⁴ , D ^5, and D ⁶ , D ⁷ and D ⁸ And D ⁹ and D ¹⁰ and D ¹¹ and D ¹² , D ¹³ and D
¹⁴ and D ¹⁵ and D ¹⁶ and D ¹⁷ and D ¹⁸ , D ¹⁹ and D ²⁰ , D ²¹ and D ²²
Each of the combinations D ²³ and D ²⁴ does not become a combination of hydrogen atoms at the same time. M represents a divalent metal atom, a trivalent or tetravalent substituted metal atom, or an oxymetal. ] 3. The security ink printed matter according to claim 1, wherein the ultraviolet absorber is an absorber having a maximum absorption wavelength in the range of 250 to 400 nm. 4. The security ink printed matter according to claim 1, wherein the protective layer containing an ultraviolet absorber comprises an acrylate-based ultraviolet curable resin. 5. The security ink printed matter according to claim 1, wherein the protective layer is colored with a dye having an absorption in the wavelength range of 400 to 700 nm, or a pattern or a picture is drawn.