WO2010089943A1 - Printing ink or toner containing dihydroperimidine squarylium compound, printed matter, method for detection of information, and method for ascertaining the genuineness of articles or substrates - Google Patents

Abstract

A printing ink or toner containing a compound represented by general formula (1) [wherein R¹, R², R³, R⁴, R⁵, R⁶, R⁷ and R⁸ are each independently a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group; or, alternatively, R¹ and R², R² and R³, R³ and R⁴, R⁵ and R⁶, R⁶ and R⁷, or R⁷ and R⁸ may be bonded to each other to form a five- or six-membered ring].  Provided are an infrared ink or toner which can be read by means of infrared light; printed matter using the same; a method for detection of information; and a method for ascertaining the genuineness of articles or substrates.

Description

Printing ink or toner containing dihydroperimidine squarylium compound, printed matter, information detection method, and product or support authenticity verification method

The present invention relates to the use of a dihydroperimidine squarylium compound, and relates to a printing ink or toner containing a dihydroperimidine squarylium compound, a printed matter, an information detection method, and a method of authenticating a product or a support. More specifically, an infrared printing ink or toner used for secret information printed matter that can be read by infrared rays, using a specific dihydroperimidine squarylium compound that absorbs the near infrared region of the electromagnetic spectrum of 750 nm to 1500 nm, particularly 800 nm to 1200 nm, And an information detection method. The present invention also relates to a method for authenticating a product by detecting or measuring infrared absorption of the dihydroperimidine squarylium compound.

Traditionally, prepaid cards, credit cards, bank cards, identification cards, licenses, tickets, admission tickets, membership cards, cards such as securities, securities, banknotes, tickets, and certificates are generally paper or plastic substrate surfaces Processing means such as printing, engraving, embossing, laser, electric discharge, laminating or vapor deposition, and functional materials such as magnetic materials, conductive materials, photosensitive materials, heat-sensitive materials, foamed materials, light-emitting materials and detection means corresponding to the function Various attempts have been made, for example, to make a collation means for preventing falsification, forgery prevention, identification, etc., alone or in combination, or improving the environmental resistance of built-in information.

Among these functional materials, methods for reading information using a substance that absorbs infrared rays are already known. For example, Japanese Patent Publication No. 46-25288, Japanese Patent Laid-Open No. 58-45999, and Table 2005-537319. The Gazette discloses a method of forming a pattern such as letters and barcodes using materials having a difference in infrared reflectance, and discriminating through a filter that blocks visible light and transmits near-infrared light. ing.
Near infrared absorbers include black pigments such as carbon black, iron oxide and titanium oxide, blue pigments such as bitumen, phthalocyanine series, naphthalocyanine series, metal complex salts, anthraquinone series, cyanine dye series, and polymethine dye series. Infrared absorbers are known. However, when dark pigments are used, the infrared absorbing materials used in these pigments also absorb visible light, so the resulting hue is limited to black, brown and blue dark colors. Not only is the range narrowed, but it is difficult to make copying impossible with a color copying machine or the like.

Japanese Unexamined Patent Publication No. 3-79683 discloses a near-infrared absorbing ink containing a metal naphthophthalocyanine compound. However, it cannot be said that the visible light absorption is sufficiently small, and visual recognition and copying cannot be completely prevented.
Japanese Patent Application Laid-Open No. 2000-309736 discloses an ink composition and printed matter using tin-doped indium oxide (ITO) powder as an infrared absorber. However, ITO powder has a large absorption on the longer wavelength side than the wavelength of 1300 nm, but there is a problem that the reading accuracy is low because the absorption intensity in the near-infrared region shorter than 1200 nm suitable for laser reading is small. .

An object of the present invention is to provide a printing ink or toner that cannot be visually recognized and detected by visible light. In addition, an information detection method for detecting information with an infrared detector on a printed matter on which information is printed using these printing inks or toners, or a product marked with these compounds is detected or measured with an infrared detector. It is an object of the present invention to provide a method for determining authenticity or proving it.

Conventional metal complex salts, anthraquinone, cyanine dye-based and polymethine-based infrared absorbers have side absorption in the visible range, are not visible, lack confidentiality, and have poor light resistance. It is not suitable for uses such as securities / certificate documents, or over-the-counter display, transportation, etc. under conditions such as exposure to sunlight.

As a near-infrared absorber that can be used as a verification means for falsification, forgery prevention, identification, etc., it is required to satisfy the following three performances at a high level.
(1) It must be colorless and transparent without absorption in the visible range.
(2) High absorption in the near infrared region and high optical reading accuracy.
(3) Light resistance equal to or higher than that of conventional printing ink (ink).

The present invention aims to solve the above problems by using a dihydroperimidine squarylium compound having a specific chemical structure as a near-infrared absorber.

Conventionally, in Japanese Patent No. 3590694, dihydroperimidine squarylium compounds are described as antihalation and irradiation prevention dyes for silver halide photographic light-sensitive materials such as heat-developable light-sensitive materials. The antihalation and irradiation dyes are dyes for preventing bleeding of an image due to reflection of a near infrared laser used for image exposure, and are required to absorb reflected light and scattered light. The functions and effects of the present invention are completely different from those of near-infrared absorbing dyes used for collation means such as falsification prevention, forgery prevention and identification of documents and cards in the present invention.

As a result of intensive studies, the present inventors have found that the above object of the present invention can be achieved by the following means.
<1> Printing ink or toner containing a compound represented by the following general formula (1):

(Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group. R ¹ and R ² , R ² and R ³ , R ³ and R ⁴ , R ⁵ and R ⁶ , R ⁶ and R ⁷ , or R ⁷ and R ⁸ are bonded to each other to form a 5-membered or 6-membered ring. May be.)
<2> R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ in the general formula (1) are each independently a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. The printing ink or toner according to <1>, which is a cyclopentyl or cyclohexyl group, or a phenyl or naphthyl group.
<3> The printing ink or toner according to <1> or <2>, wherein R ¹ , R ⁴ , R ⁵ and R ⁸ in the general formula (1) are hydrogen atoms.
<4> The printing ink or toner according to any one of <1> to <3>, further comprising a colorant and a binder.
<5> The printing ink or toner according to <4>, wherein the colorant is a dye or pigment having absorption in the visible region.
<6> The compound according to any one of <1> to <5>, wherein the compound represented by the general formula (1) is contained in an amount of 0.01% by mass to 5.0% by mass with respect to the total amount of ink or toner. Printing ink or toner.
<7> A printed matter on which information is printed using the printing ink or toner according to any one of <1> to <6>.
<8> An information detection method for detecting information printed on the printed matter by scanning the printed matter according to <7> with an infrared detector.
<9> A mark containing a compound represented by the following general formula (1) is applied to a product or a support, and then the mark is irradiated with infrared rays to detect light absorption by the compound represented by the general formula (1) Or a method of proving authenticity of a product or support that includes a measuring step:

(Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group. R ¹ and R ² , R ² and R ³ , R ³ and R ⁴ , R ⁵ and R ⁶ , R ⁶ and R ⁷ , or R ⁷ and R ⁸ are bonded to each other to form a 5-membered or 6-membered ring. May be.)
<10> R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ in the general formula (1) are each independently a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. , A cyclopentyl or cyclohexyl group, or a phenyl or naphthyl group. The method for proving authenticity of the product or support according to <9>.
<11> A method for proving authenticity of the product or support according to <9> or <10>, wherein R ¹ , R ⁴ , R ⁵ and R ⁸ in the general formula (1) are hydrogen atoms.

According to the present invention, a printing ink or toner having high transparency, no secondary absorption in the visible region, and near-infrared absorption is provided. Further, a printed matter using the printing ink or toner of the present invention has no visibility and is detected by scanning with an infrared detector, and thus has high confidentiality. Therefore, it is particularly preferably used for collation means such as falsification prevention, forgery prevention and identification of documents and cards.
Further, if a mark containing the compound of the general formula (1) of the present invention is added to a general product, the mark cannot be visually recognized and can be detected only by infrared rays. And can be used for certification.
Furthermore, since the printing ink or toner of the present invention is excellent in light fastness and heat and wet heat fastness, the printed matter and mark produced can be used stably in various usage and storage environments. it can.

This is a spectral absorption spectrum of the ink in the near infrared to visible range.

Hereinafter, the present invention will be described in more detail. In the present specification, “˜” is used to mean a lower limit value and an upper limit value of numerical values described before and after.

(Compound represented by the general formula (1))
The compound represented by the general formula (1) of the present invention will be described.

In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group. R ¹ and R ² , R ² and R ³ , R ³ and R ⁴ , R ⁵ and R ⁶ , R ⁶ and R ⁷ , or R ⁷ and R ⁸ are bonded to each other to form a 5-membered or 6-membered ring May be.

The alkyl group may have a branch or may form a ring. The number of carbon atoms of the alkyl group is preferably 1-20, and more preferably 1-18.

Each of the alkyl group, the cycloalkyl group, and the aryl group may have a substituent.
The following can be mentioned as an example of a substituent of a substituted alkyl group and a substituted cycloalkyl group.
・ Halogen atom (for example, chlorine atom, bromine atom, iodine atom),
-Alkyl group [Represents a linear, branched, or cyclic substituted or unsubstituted alkyl group. They are alkyl groups (preferably alkyl groups having 1 to 30 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, t-butyl, n-octyl, eicosyl, 2-chloroethyl, 2-cyanoethyl, 2-ethylhexyl) A cycloalkyl group (preferably a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, such as cyclohexyl, cyclopentyl, 4-n-dodecylcyclohexyl), a bicycloalkyl group (preferably having 5 to 30 carbon atoms). A substituted or unsubstituted bicycloalkyl group, that is, a monovalent group obtained by removing one hydrogen atom from a bicycloalkane having 5 to 30 carbon atoms, for example, bicyclo [1,2,2] heptan-2-yl, bicyclo [2,2,2] octane-3-yl), a tricyclo structure with more ring structures Domo is intended to cover. An alkyl group (for example, an alkyl group of an alkylthio group) in the substituents described below also represents such an alkyl group. ],

・ Alkenyl group [represents a linear, branched, cyclic substituted or unsubstituted alkenyl group. They are alkenyl groups (preferably substituted or unsubstituted alkenyl groups having 2 to 30 carbon atoms, such as vinyl, allyl, prenyl, geranyl, oleyl), cycloalkenyl groups (preferably substituted or substituted groups having 3 to 30 carbon atoms). An unsubstituted cycloalkenyl group, that is, a monovalent group obtained by removing one hydrogen atom of a cycloalkene having 3 to 30 carbon atoms (for example, 2-cyclopenten-1-yl, 2-cyclohexen-1-yl), Bicycloalkenyl group (a substituted or unsubstituted bicycloalkenyl group, preferably a substituted or unsubstituted bicycloalkenyl group having 5 to 30 carbon atoms, that is, a monovalent group obtained by removing one hydrogen atom of a bicycloalkene having one double bond. For example, bicyclo [2,2,1] hept-2-en-1-yl, bicyclo 2,2,2] oct-2-en-4-yl). ],

An alkynyl group (preferably a substituted or unsubstituted alkynyl group having 2 to 30 carbon atoms, such as ethynyl, propargyl, trimethylsilylethynyl group, aryl group (preferably a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, For example, phenyl, p-tolyl, naphthyl, m-chlorophenyl, o-hexadecanoylaminophenyl),
A heterocyclic group (preferably a monovalent group obtained by removing one hydrogen atom from a 5- or 6-membered substituted or unsubstituted aromatic or non-aromatic heterocyclic compound, more preferably a carbon number of 3 To 30- or 5-membered aromatic heterocyclic group such as 2-furyl, 2-thienyl, 2-pyrimidinyl, 2-benzothiazolyl),

・ Cyano group, ・ Hydroxyl group, ・ Nitro group, ・ Carboxyl group,
An alkoxy group (preferably a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, such as methoxy, ethoxy, isopropoxy, t-butoxy, n-octyloxy, 2-methoxyethoxy),
An aryloxy group (preferably a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, such as phenoxy, 2-methylphenoxy, 4-t-butylphenoxy, 3-nitrophenoxy, 2-tetradecanoylamino Phenoxy),
A silyloxy group (preferably a silyloxy group having 3 to 20 carbon atoms, such as trimethylsilyloxy, t-butyldimethylsilyloxy),
A heterocyclic oxy group (preferably a substituted or unsubstituted heterocyclic oxy group having 1 to 30 carbon atoms, 1-phenyl-tetrazol-5-oxy, 2-tetrahydropyranyloxy),

An acyloxy group (preferably a formyloxy group, a substituted or unsubstituted alkylcarbonyloxy group having 2 to 30 carbon atoms, a substituted or unsubstituted arylcarbonyloxy group having 6 to 30 carbon atoms, such as formyloxy, acetyloxy, Pivaloyloxy, stearoyloxy, benzoyloxy, p-methoxyphenylcarbonyloxy),
A carbamoyloxy group (preferably a substituted or unsubstituted carbamoyloxy group having 1 to 30 carbon atoms, such as N, N-dimethylcarbamoyloxy, N, N-diethylcarbamoyloxy, morpholinocarbonyloxy, N, N-di -N-octylaminocarbonyloxy, Nn-octylcarbamoyloxy),

An alkoxycarbonyloxy group (preferably a substituted or unsubstituted alkoxycarbonyloxy group having 2 to 30 carbon atoms, such as methoxycarbonyloxy, ethoxycarbonyloxy, t-butoxycarbonyloxy, n-octylcarbonyloxy),
An aryloxycarbonyloxy group (preferably a substituted or unsubstituted aryloxycarbonyloxy group having 7 to 30 carbon atoms, such as phenoxycarbonyloxy, p-methoxyphenoxycarbonyloxy, pn-hexadecyloxyphenoxycarbonyloxy ),
Amino groups (preferably amino groups, substituted or unsubstituted alkylamino groups having 1 to 30 carbon atoms, substituted or unsubstituted anilino groups having 6 to 30 carbon atoms, such as amino, methylamino, dimethylamino, anilino N-methyl-anilino, diphenylamino),

Acylamino group (preferably formylamino group, substituted or unsubstituted alkylcarbonylamino group having 1 to 30 carbon atoms, substituted or unsubstituted arylcarbonylamino group having 6 to 30 carbon atoms, such as formylamino, acetylamino Pivaloylamino, lauroylamino, benzoylamino, 3,4,5-tri-n-octyloxyphenylcarbonylamino),
Aminocarbonylamino group (preferably substituted or unsubstituted aminocarbonylamino having 1 to 30 carbon atoms, such as carbamoylamino, N, N-dimethylaminocarbonylamino, N, N-diethylaminocarbonylamino, morpholinocarbonylamino) ,
An alkoxycarbonylamino group (preferably a substituted or unsubstituted alkoxycarbonylamino group having 2 to 30 carbon atoms, such as methoxycarbonylamino, ethoxycarbonylamino, t-butoxycarbonylamino, n-octadecyloxycarbonylamino, N-methyl- Methoxycarbonylamino),
Aryloxycarbonylamino group (preferably a substituted or unsubstituted aryloxycarbonylamino group having 7 to 30 carbon atoms, such as phenoxycarbonylamino, p-chlorophenoxycarbonylamino, mn-octyloxyphenoxycarbonylamino) ,

A sulfamoylamino group (preferably a substituted or unsubstituted sulfamoylamino group having 0 to 30 carbon atoms, such as sulfamoylamino, N, N-dimethylaminosulfonylamino, Nn-octylaminosulfonyl amino),
Alkyl and arylsulfonylamino groups (preferably substituted or unsubstituted alkylsulfonylamino having 1 to 30 carbon atoms, substituted or unsubstituted arylsulfonylamino having 6 to 30 carbon atoms, such as methylsulfonylamino, butylsulfonylamino, Phenylsulfonylamino, 2,3,5-trichlorophenylsulfonylamino, p-methylphenylsulfonylamino),
・ Mercapto group,
An alkylthio group (preferably a substituted or unsubstituted alkylthio group having 1 to 30 carbon atoms, such as methylthio, ethylthio, n-hexadecylthio),
An arylthio group (preferably a substituted or unsubstituted arylthio having 6 to 30 carbon atoms, such as phenylthio, p-chlorophenylthio, m-methoxyphenylthio),

A heterocyclic thio group (preferably a substituted or unsubstituted heterocyclic thio group having 2 to 30 carbon atoms, such as 2-benzothiazolylthio, 1-phenyltetrazol-5-ylthio),
A sulfamoyl group (preferably a substituted or unsubstituted sulfamoyl group having 0 to 30 carbon atoms, such as N-ethylsulfamoyl, N- (3-dodecyloxypropyl) sulfamoyl, N, N-dimethylsulfamoyl, N -Acetylsulfamoyl, N-benzoylsulfamoyl, N- (N′-phenylcarbamoyl) sulfamoyl),
・ Sulfo group,

Alkyl and arylsulfinyl groups (preferably substituted or unsubstituted alkylsulfinyl groups having 1 to 30 carbon atoms, substituted or unsubstituted arylsulfinyl groups having 6 to 30 carbon atoms, such as methylsulfinyl, ethylsulfinyl, phenylsulfinyl, p -Methylphenylsulfinyl),
Alkyl and arylsulfonyl groups (preferably substituted or unsubstituted alkylsulfonyl groups having 1 to 30 carbon atoms, substituted or unsubstituted arylsulfonyl groups having 6 to 30 carbon atoms, such as methylsulfonyl, ethylsulfonyl, phenylsulfonyl, p- Methylphenylsulfonyl),
Acyl group (preferably formyl group, substituted or unsubstituted alkylcarbonyl group having 2 to 30 carbon atoms, substituted or unsubstituted arylcarbonyl group having 7 to 30 carbon atoms, substituted or unsubstituted carbon group having 4 to 30 carbon atoms A heterocyclic carbonyl group bonded to a carbonyl group at a carbon atom (eg, acetyl, pivaloyl, 2-chloroacetyl, stearoyl, benzoyl, pn-octyloxyphenylcarbonyl, 2-pyridylcarbonyl, 2-furylcarbonyl),
Aryloxycarbonyl group (preferably a substituted or unsubstituted aryloxycarbonyl group having 7 to 30 carbon atoms, such as phenoxycarbonyl, o-chlorophenoxycarbonyl, m-nitrophenoxycarbonyl, pt-butylphenoxycarbonyl) ,

An alkoxycarbonyl group (preferably a substituted or unsubstituted alkoxycarbonyl group having 2 to 30 carbon atoms, such as methoxycarbonyl, ethoxycarbonyl, t-butoxycarbonyl, n-octadecyloxycarbonyl),
A carbamoyl group (preferably a substituted or unsubstituted carbamoyl having 1 to 30 carbon atoms such as carbamoyl, N-methylcarbamoyl, N, N-dimethylcarbamoyl, N, N-di-n-octylcarbamoyl, N- ( Methylsulfonyl) carbamoyl),
Aryl and heterocyclic azo groups (preferably substituted or unsubstituted arylazo groups having 6 to 30 carbon atoms, substituted or unsubstituted heterocyclic azo groups having 3 to 30 carbon atoms, such as phenylazo, p-chlorophenylazo, 5 -Ethylthio-1,3,4-thiadiazol-2-ylazo),
An imide group (preferably N-succinimide, N-phthalimide),
A phosphino group (preferably a substituted or unsubstituted phosphino group having 2 to 30 carbon atoms, such as dimethylphosphino, diphenylphosphino, methylphenoxyphosphino),

A phosphinyl group (preferably a substituted or unsubstituted phosphinyl group having 2 to 30 carbon atoms, such as phosphinyl, dioctyloxyphosphinyl, diethoxyphosphinyl),
A phosphinyloxy group (preferably a substituted or unsubstituted phosphinyloxy group having 2 to 30 carbon atoms, such as diphenoxyphosphinyloxy, dioctyloxyphosphinyloxy),
A phosphinylamino group (preferably a substituted or unsubstituted phosphinylamino group having 2 to 30 carbon atoms, such as dimethoxyphosphinylamino, dimethylaminophosphinylamino),
A silyl group (preferably a substituted or unsubstituted silyl group having 3 to 30 carbon atoms, such as trimethylsilyl, t-butyldimethylsilyl, phenyldimethylsilyl).

Among the above functional groups, those having a hydrogen atom may be substituted with the above groups by removing this. Examples of such functional groups include an alkylcarbonylaminosulfonyl group, an arylcarbonylaminosulfonyl group, an alkylsulfonylaminocarbonyl group, and an arylsulfonylaminocarbonyl group. Examples thereof include methylsulfonylaminocarbonyl, p-methylphenylsulfonylaminocarbonyl, acetylaminosulfonyl, and benzoylaminosulfonyl groups.

In the present invention, an aryl group means an unsubstituted or substituted aryl group. The aryl group in the present invention may be condensed with an aliphatic ring, another aromatic ring or a heterocyclic ring. In the present invention, the number of carbon atoms of the aryl group is preferably 6 to 40, more preferably 6 to 30, and still more preferably 6 to 20. Among them, the aryl group is preferably phenyl or naphthyl, particularly preferably phenyl.

The aryl part of the substituted aryl group is the same as the above aryl group. Examples of the substituent of the substituted aryl group are the same as those described above as examples of the substituent of the alkyl portion of the substituted alkyl group.

Next, the compound and ion represented by the general formula (1) will be described. The compound represented by the general formula (1) can take a tautomer depending on the structure and the environment in which the compound is placed. Although described in this specification in one of the representative forms, tautomers different from those described in this specification are also included in the compounds used in the present invention.

In general formula (1), the alkyl groups represented by R ¹ to R ⁸ are preferably each independently an alkyl group having 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms (for example, methyl, ethyl, propyl). Butyl, hexyl, undecyl). In addition, halogen atoms (F, Cl, Br), alkoxycarbonyl (eg, methoxycarbonyl, ethoxycarbonyl), hydroxy, alkoxy (eg, methoxy, ethoxy, phenoxy, isobutoxy) or acyloxy (eg, acetyloxy, butyryloxy, hexyl) Oxy, benzoyloxy) and the like may be substituted.

In the general formula (1), the cycloalkyl groups represented by R ¹ to R ⁸ are preferably each independently cyclopentyl or cyclohexyl.
In the general formula (1), the aryl groups represented by R ¹ to R ⁸ preferably each independently have a carbon number of 6 to 12, more preferably a phenyl group or a naphthyl group.

The aryl groups represented by R ¹ to R ⁸ may each independently have a substitution. Examples of the substituent include alkyl groups having 1 to 8 carbon atoms (eg, methyl, ethyl, butyl), alkoxy groups having 1 to 6 carbon atoms (eg, methoxy, ethoxy), aryloxy groups (eg, phenoxy, p- Chlorophenoxy), halogen atoms (F, Cl, Br), alkoxycarbonyl (eg methoxycarbonyl, ethoxycarbonyl), cyano group, nitro group and carboxyl group.

Preferably, in the general formula (1), R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. , A cyclopentyl or cyclohexyl group, or a phenyl or naphthyl group.
Preferably, in the general formula (1), R ¹ , R ⁴ , R ⁵ and R ⁸ are hydrogen atoms.

Preferably, in the general formula (1), R ¹ , R ⁴ , R ⁵ and R ⁸ are hydrogen atoms, and R ² , R ³ , R ⁶ and R ⁷ are each independently selected from 1 to 20 carbon atoms. An alkyl group, a cyclopentyl or cyclohexyl group, or a phenyl or naphthyl group.

Specific examples of the compound represented by the general formula (1) of the present invention are shown below, but the present invention is not limited thereto.

 

The compounds represented by the general formula (1) of the present invention are disclosed in, for example, Japanese Patent No. 3590694, Japanese Patent Application Laid-Open No. 2002-167521, and J. Org. CHEM. SOC. , CHEM. COMMUN. , P. 452-454 (1993) can be synthesized with reference to the method described therein.

(Printing ink and toner)
The printing ink or toner of the present invention is characterized by containing at least one compound represented by the general formula (1).
The printing ink of the present invention can be applied to both printing and printer. For example, printing inks such as gravure ink, flexo ink, offset ink, screen ink and letterpress ink, or inks of various printers such as thermal transfer printers, ink jet printers, impact printers, laser printers and the like are included. Preferred inks include printing inks such as gravure ink, gravure ink, flexo ink, offset ink, screen ink, letterpress ink, ink jet printer, impact printer, and laser printer offset ink.

In the present invention, any toner containing at least one compound represented by the general formula (1) can be applied. These are micro-sized particles used in laser printers and copying machines, in which dye particles or pigment particles are adhered to plastic particles having charging properties. The printed matter is formed by transferring the toner onto paper using the static electricity of the toner and fixing it with heat. In the toner of the present invention, at least one infrared absorber represented by the general formula (1) is melted or adhered to the plastic particles.

The ink or toner of the present invention may contain a pigment or dye having absorption in the visible region together with the infrared absorbing material represented by the general formula (1). These pigments include chrome yellow, cadmium yellow, yellow iron oxide, titanium yellow, naphthol yellow, Hansa yellow, pigment yellow, benzidine yellow, permanent yellow, Quinoline Yellow, Anthrapyrimidine Yellow, Permanent Orange, Molybdenum Orange, Vulcan Fast Orange, Benzidine Orange, Indanthrine Brilliant Orange, Iron Oxide, Persimmon, Permanent Brown, Rose Iron oxide red, antimony powder, permanent red, fire red ( ire red, Brilliant Carmine, Light Fast Red Toner, Permanent Carmine, Pyrazolone Red, Bordeaux, Helio-Bordeaux, Rhodamine Lake, DuPont Oil・ Red, Thioindigo Red, Thioindigo Maron, Watching Red Strontium, cobalt purple, Fast Violet, Dioxane Violet, Methyl Violet Lake, Methylene Blue, Aniline Blue, Cobalt blue, cerulean blue, calco oil blue, non Genus phthalocyanine blue, phthalocyanine blue, ultramarine blue, indanthrene blue, indigo, chrome green, cobalt green, pigment green B, green gold, phthalocyanine green, malachite green oxalate and polychromo-bromo Examples include copper phthalocyanine.

(Printed matter using printing ink and toner)
The printed matter printed using the printing ink and toner of the present invention refers to a printed matter printed on a support such as paper using the printing ink and toner of the present invention. Examples of the support include paper, plastic, wood, metal and the like.

(Information detection method)
As the light source of the information detection method of the present invention, any light source may be used as long as it has radiation energy in the infrared region of 650 nm to 1500 nm, but a laser, a light emitting diode, or the like can be preferably used. It is also possible to reduce noise in the light source or detection unit using a band pass filter or the like.
Information detection is performed by scanning the printed matter with an infrared detector.

As a system that can be used in the method for proving authenticity of a product or a support in the present invention, infrared rays reflected by irradiating the printed matter containing the infrared absorbing material represented by the general formula (1) with infrared rays from the light source are reflected. Or by measuring the reflectance of infrared light and analyzing the pattern, altitude information can be read. Furthermore, in order to make forgery more difficult, it can be combined with other methods to increase the accuracy of judgment of authenticity. As another method, it may be used in combination with optical variable devices such as moire and hologram, embossing, and the like.

The details will be described below.

(1) Gravure / Intaglio Pattern Printing Ink An appropriate gravure ink for intaglio pattern printing contains an infrared absorbing material represented by the general formula (1), a binder, and a volatile solvent. Preferably, it further contains a colorant. More preferably, an antioxidant, a surfactant, an inorganic filler and the like may be contained.

The choice of resin for the rotogravure ink depends on the solvent and the substrate to be printed and the end use of the print. Detailed examples of resins suitable for ink production, including those of the gravure type, can be found in “Synthetic Resins”, by Werner Husen, The American Ink Maker, June 1952, 63 and “Synthetic Resins for Inks”, John P. . It is described by Petrone, The American Ink Maker, Volume 49, March-October 1971. Useful resins include rosins and modified rosins such as calcium and zinc resinates and variants thereof. Other suitable resins include
(A) Various modified versions of petroleum resins or cyclopentadiene resins, examples of which are described in US Pat. No. 3,084,147 and British Patent No. 1,369,370, the disclosures of which are incorporated herein by reference. And (b) a modified resin having a softening point of 145 ° C. (this modified resin has a capability of inducing stable viscosity and excellent printability as described in Japanese Patent No. 47994/72). , A fraction having a boiling point of 140 ° C. to 220 ° C. is collected from cracked oil obtained from pyrolysis of petroleum, and the fraction is polymerized using a Friedel-Crafts catalyst to obtain a resin having a softening point of 160 ° C. The resin is reacted with an unsaturated carboxylic acid or anhydride thereof in an amount of 0.01 mole to 0.4 mole per 100 grams of resin, and then 0.2 mole to 2. 0 mole In obtained by esterifying a resin obtained using a monohydric alcohol) and the like.

Volatile solvent components are aliphatic or cycloaliphatic hydrocarbons such as hexane, heptane and cyclohexane or aromatic hydrocarbons such as xylene, toluene (eg tolusol 25), high flash naphtha, benzene and chlorobenzene. Also good. Other solvents include C _1-4 -alkanols, acetates of C _1-5 -alkanols, glycol ethers having a BP of 115 ° C. to 180 ° C., C _1-5 -aliphatic ketones and cyclohexanone. It is done. The resin must be soluble in the solvent and easily separated from them. Since the drying of the gravure ink is due to the evaporation of the solvent, the ink vehicle is essentially a resin and a solvent. Depending on the particular combination of resin and solvent, various types of vehicles can be used.

A preferred antioxidant is a phenolic or amine antioxidant, and a preferred antioxidant composition is a mixture of a phenolic antioxidant and an amine antioxidant. Preferred antioxidant compositions comprise 10% to 90% by weight of phenolic antioxidants, more preferably 25% to 75% by weight, and 90% to 10% by weight of amine antioxidants, more preferably. Contains 75% to 25% by weight.

Suitable amine antioxidants include octylated diphenylamine, isopropoxydiphenylamine, aldol-α-naphthylamine condensation product of diphenylamine and acetone, N, N′-diphenyl-p-phenylenediamine, phenyl-β-naphthylamine, polymerization 1,2-dihydro-2,2,4-trimethylquinoline, N, N′-di (2-octyl) -p-phenylenediamine, other aromatic amines, diphenylamines and mixtures thereof. Suitable phenolic antioxidants include 4,4′-isopropylidene-diphenol, styrenated phenol, hindered phenol, 4,4′-thiobis (6-tert-butyl-o-cresol), p-butylphenol. P- (i-propyl) phenol, 2,4-dimethyl-6-octylphenol, 2,6-di-t-butyl-4-methylphenol, 2,6-di-t-butyl-4-ethylphenol, 2,6-di-t-butyl-4-n-butylphenol, 2,2'-methylenebis- (4-methyl-6-t-butylphenol), 2,2'-methylenebis (4-ethyl-6-t- Butyl-phenol), 2,4-dimethyl-6-t-butylphenol, 4-hydroxymethyl-2,6-di-t-butylphenol, n-octadecyl- Chromatography data (3,5-di -t- butyl-4-hydroxyphenyl) propionate, mixtures thereof and the like. Preferred phenolic antioxidants are sterically crowded phenols.

An intaglio pattern printing ink containing an antioxidant or an antioxidant composition can be produced by a conventional method. For example, an ink vehicle is manufactured by dissolving 100 parts by mass of a resin and 1 part by mass of an antioxidant or an antioxidant composition in 200 parts by mass or less of a high boiling petroleum solvent. A preferred solvent, for example a mixture of 70% by weight of toluene, 4% by weight of xylene and 26% by weight of lactol spirit (in contrast to an aliphatic solvent with a Kauributanol value of 35-45: Kauributanol value) It has a Kauributanol value of 105.

The infrared absorber incorporated in the ink composition in an amount of 0.01% by mass to 5.0% by mass, preferably 0.1% by mass to 3.0% by mass, based on the total mass of the ink, is supported by After application to the body, a detectable transparent infrared-absorbing ink is provided which is visible only when the support is properly illuminated by an infrared sensitive detector.

If the ink also contains a pigmented colorant, the printed pattern is visually detectable, but the printed support (substrate) is printed with an ink that does not contain an infrared absorber in a similar manner. It can also be distinguished from the support.

An infrared absorber or pigmented colorant (eg, phthalocyanine blue, benzidine yellow, channel black, carmine 6B or titanium white) is added to the ink vehicle, preferably as a dispersion, and the mixture is placed on a ball mill and placed in the ink vehicle. Grind until a uniform dispersion of the pigment is obtained. The resulting ink concentrate can be subsequently diluted with additional solvent to a concentration suitable for use in the printing operation.

A typical gravure ink composition for intaglio pattern printing comprises an antioxidant composition of 0.005% to 0.5% by weight, a resin of 10% to 50% by weight and an infrared absorber based on the total weight of the ink. 0.01% by weight to 5.0% by weight, preferably 0.1% by weight to 3.0% by weight and / or 50 parts to 100 parts of pigmented colorant per 100 parts of resin, with the balance being toluene, It consists essentially of a mixture of hydrocarbon solvents such as xylene and lactol distillate. The viscosity of the ink at the time of use is preferably 5 poise or less, and more preferably 0.5 poise to 1.0 poise. The amount of the antioxidant composition used is preferably 0.005% to 0.5% by mass, more preferably 0.025% to 0.5% by mass, based on the total mass of the ink.

In order to improve the printability, flow behavior and pigment wetting, other additives are also blended in an amount of 1% to 15% by weight (more preferably 1% to 10% by weight) with respect to the resin. be able to. Waxes such as ester waxes, amide waxes and hydrocarbon waxes can be added in an amount of 0.1% to 5% by weight. Other compatible additives such as ethyl cellulose or ethyl hydroxycellulose can be used to improve ink film adhesion, scuff resistance, gloss, and the like. The printing ink is preferably used without a plasticizer, but the plasticizer can be added to achieve a special effect.

Suitable supports include those conventionally used in intaglio printing, such as paper, cellophane and metal films, such as aluminum films.

(2) Toner The toner in the present invention contains an infrared absorber represented by the general formula (1) and a binder. Preferably it contains a colorant. Furthermore, you may contain antioxidant, surfactant, an inorganic filler, etc.
As the toner, a conventional toner in which the infrared absorber represented by the general formula (1) is melted or dispersed in a binder that forms a matrix of toner particles may be used. A toner containing an infrared absorber represented may be used.
<Conventional toner>
The flash fixing toner contains a binder, a colorant, and an infrared absorber represented by the general formula (1).
The infrared absorber represented by the general formula (1) is preferably contained in an amount of 0.01% by mass to 5.0% by mass, more preferably 0.1% by mass to 3.% by mass based on the total mass of the toner. 0% by mass). The infrared absorber represented by the general formula (1) is preferably contained by being melted or dispersed in a binder that forms a matrix of toner particles.

Preferred binders used for flash fixing toners include, for example, polystyrenes; copolymers of styrene and (meth) acrylic acid esters, acrylonitrile or maleic acid esters; poly (meth) acrylic acid esters; polyesters; polyamides; Phenolic resins; hydrocarbon resins; and petroleum resins, which can be used alone or in combination with other binders or additives.
Preferred binders are bisphenol A and epichlorohydrin polyester resins and epoxy resins.

Preferred colorants used in the flash fixing toner include, for example, one or more pigments or colorants such as chrome yellow, cadmium yellow, yellow iron oxide, titanium yellow, naphthol yellow, hansa yellow, pigment yellow, and benzidine.・ Yellow, Permanent Yellow, Quinoline Yellow, Anthrapyrimidine Yellow, Permanent Orange, Molybdenum Orange, Vulcan Fast Orange, Benzidine Orange, Indanthrene Brilliant Orange, Iron Oxide, Persimmon, Permanent Brown, Rose iron oxide red, antimony powder, permanent red, fire red, brilliant carmine, light Fast Red Toner, Permanent Carmine, Pyrazolone Red, Bordeaux, Helio-Bordeaux, Rhodamine Lake, DuPont Oil Red, Thioindigo Red, Thioindigo Maron, Watching Red Strontium, Cobalt Purple, Fast Violet, Dioxane Violet, Methyl Violet Lake, Methylene Blue, Aniline Blue, Cobalt Blue, Serulean Blue, Calco Oil Blue, Non-Metallic Phthalocyanine Blue, Phthalocyanine Blue, Ultramarine blue, indanthrene blue, indigo, chrome green, cobalt green, pigment green B, green gold, phthalocyan Down-green, malachite green oxalate and Porikuromo - is bromo copper phthalocyanine. The amount of the colorant can vary over a wide range, but it is preferable to add 3 to 5 parts by mass based on 100 parts by mass of the binder.

The flash fixing toner may contain additional components such as waxes, charge control agents, and / or flow-enhancers.
Preferred waxes are polyolefin type or natural waxes such as carnauba wax, montan wax and natural paraffin, polyethylene, polypropylene, polybutylene, ethylene-propylene copolymer, ethylene-butene copolymer, ethylene-pentene copolymer, ethylene-3-methyl-1- Butene copolymers and copolymers of olefins with other monomers such as vinyl esters, halo-olefins, (meth) acrylic acid esters, and (meth) acrylic acid or derivatives. The waxy component preferably has a mass average molecular weight of 1,000 to 45,000 daltons.

Examples of preferred charge control agents include nigrosine, monoazo dyes, zinc, hexadecyl succinate, alkyl esters or alkyl amides of naphthoic acid, nitrohumic acid, N, N-tetramethyldiamine benzophenone, N, N— There are metal complexes of tetramethylbenzidine, triazines and salicylic acid. In the case of a colorant other than black, the charge control agent is preferably substantially colorless.

Examples of preferred free-flowing agents include inorganic materials such as colloidal silica, hydrophobic silica, hydrophobic titania, hydrophobic zirconia and talc particulates, and organic materials such as polystyrene beads and (meth) acrylic beads. is there.

When the infrared absorber is melted or dispersed in the binder, it is preferable that the coupling agent and the infrared absorber (and any other components described above) are mixed and kneaded together. After the resulting mixture is cooled and ground, the particles are classified.

<Chemically manufactured toner>
The infrared absorber represented by the general formula (1) can be blended with a chemically produced toner. One or more polymers of various molecular weights can be mixed to control the molecular weight distribution and toner melt rheological properties. Examples of suitable polymers are styrene-acrylate copolymers, styrene-butadiene copolymers, polyesters and hydrocarbon resins.

When a colorant is added to the toner to form a colored image on the printed support, a charge control agent and a wax may be added so that the toner can be easily peeled off from the fusing roller. Suitable colorants include pigments (including magnetic pigments under the condition that they do not interfere with the absorption of infrared radiation by the infrared absorber) and dyes. The charge control agent preferably includes metal complexes such as complexes of Zn, Al, Fe or Cr and polymer materials such as phenolic polymers. As waxes, preferably hydrocarbon waxes such as paraffin, polyethylene or polypropylene wax, waxes derived from carbon monoxide and hydrogen, such as Fischer-Tropsch wax, natural product waxes such as carnauba wax and synthetic There may be mentioned waxes such as ester or amide waxes.

The toner can also include a surfactant and an inorganic or organic filler such as silica, titania, alumina or polymer particles to control fluidity, charging performance or transfer characteristics.

(3) UV curable ink In order to give a mark containing a compound (infrared absorber) represented by general formula (1) to a product or a support, UV containing an infrared absorber represented by general formula (1) A curable ink can be used.

A preferred UV curable ink composition comprises an alkoxylated or polyalkoxylated acrylate monomer, a photoinitiator, an infrared absorber and a colorant as described in US Pat. No. 6,114,406. .
Preferred UV curable ink jet compositions comprise from 80% to 95% by weight of a multifunctional alkoxylated and / or polyalkoxylated acrylate monomer, an infrared absorber and optionally a colorant based on the total composition.

The amount of acrylate monomer, photopolymerization initiator, infrared absorber and colorant can vary according to the specific equipment and application. However, the amount of the photopolymerization initiator is preferably 1% by mass to 15% by mass of the total composition.

The polyfunctional alkoxylated or polyalkoxylated acrylate monomer material can contain one or more di- or tri-acrylates, or higher functionality alkoxylated or polyalkoxylated acrylic monomers, alone or in combination with one or more. It can be used with bi- and / or trifunctional materials. The number of alkyleneoxy groups is preferably 1 to 20 per monomer molecule, and each such group is preferably C _2-4 -alkyleneoxy, in particular ethyleneoxy (EO) or propyleneoxy (PO). .

Suitable multifunctional alkoxylated or polyalkoxylated acrylates are alkoxylation, preferably ethoxylated or propoxylated adducts of neopentyl glycol diacrylate, butanediol diacrylate, trimethylpropane tri-acrylate and glyceryl triacrylate .

The ink is a monofunctional alkoxylated or polyalkoxylated acrylate monomer such as tetrahydrofurfuryl acrylate, cyclohexyl acrylate, alkyl acrylate, nonyl-phenol acrylate and polyethylene- or polypropylene-glycol acrylate, one or more alkoxylated, especially ethoxylated or The propoxylated adduct can be contained in an amount of 10% by mass or less.

The ink is a non-alkoxylated monofunctional or polyfunctional radiation curable monomer such as octyl acrylate, decyl acrylate, N-vinyl pyrrolidone, ethyl diglycol acrylate, isobornyl acrylate, ethyl-hexyl acrylate, lauryl acrylate , Butanediol monoacrylate, β-carboxyethyl acrylate, i-butyl acrylate, polypropylene glycol monomethacrylate, 2-hydroxyethyl methacrylate, hexanediol di (meth) acrylate, tetraethylene glycol diacrylate, tripropylene glycol diacrylate, butanediol 5 masses of diacrylate, polyethylene glycol diacrylate and triethylene glycol dimethacrylate It is also possible to include the following.

Examples of commercially available photopolymerization initiators preferably include xanthones, thioxanthones, benzophenones, quinones, and phosphine oxides. Examples of co-initiators that can be formulated with primary photoinitiators include amines and aminobenzoates. When the ink contains a primary photopolymerization initiator and a co-polymerization initiator, the total amount is preferably within the above preferred range. The aminobenzoate and acrylated amine co-polymerization initiator are preferably used with xanthone and / or thioxanthone primary photopolymerization initiators.

The term “radiation curable” means that the composition is curable by application of UV radiation. Such compositions are substantially colorless and curable varnishes or bases, or the composition includes a colorant (ie, a material that provides visible or related optical properties such as fluorescence). In the case, it may be ink. When a colorant is blended, the ink preferably contains 1% by mass to 10% by mass of the colorant with respect to the ink.

Preferred colorants are dispersed in the ink composition in the form of fine particles using two types: (a) a dye that is substantially soluble in the ink composition, and (b) a suitable dispersant. Divided into pigments. Typical pigments include Pigment Red 57: 1, Pigment Red 52: 2, Pigment Red 48: 2, Pigment Blue 15: 3, Pigment Green 7, Pigment Yellow 83, and Pigment Yellow 13 and Pigment 6. When the colorant is carbon black or contains carbon black, it is usually unnecessary to add an infrared absorber because carbon black has strong absorption in the IR region of the spectrum.

The ink can also contain other minor components such as surfactants, leveling additives, photopolymerization initiators, stabilizers, wetting agents and pigment stabilizers. The latter may be in particular in the form of a high molecular weight block copolymer, for example polyester, polyurethane or polyacrylate type, and is usually incorporated at a level of 2.5% to 100% by weight of the pigment. Specific examples include Dispersbyk 161 or 162 (manufactured by BYK Chemie) and Solsperse hyperdispersant (manufactured by Avecia). Preferable photopolymerization initiators and stabilizers include those disclosed in European Patent Application No. EP0465039A. A preferred surfactant is non-ionic, such as Fluorad FC430 (manufactured by 3M Corp.). When blended, such surfactants are preferably blended in an amount of 0.1% to 10% by weight of the total composition.

The ink or varnish preferably contains substantially or no organic solvent. The organic solvent is preferably contained in an amount of less than 10% of the total composition, more preferably less than 5%, still more preferably less than 1%, and most preferably less than 0.1%.

The compound represented by the general formula (1) is not limited to use in the above UV curable ink, and can be used in any other UV curable ink that is soluble or dispersible.

(4) Lithographic printing ink The lithographic printing ink composition of the present invention contains an infrared-absorbing material represented by the general formula (1), a binder, and a volatile solvent. Preferably, it further contains a colorant. More preferably, an antioxidant, a surfactant, an inorganic filler and the like may be contained.

The binder is preferably derived from a cross-linked resin made, for example, by grafting a polyepoxide to an available carboxyl group on a phenolic or maleic acid-modified rosin ester resin and then has at least 12 carbon atoms. Solubilize with fatty alcohol.

The phenolic or maleic acid-derived rosin ester resin preferably has a number average molecular weight of 1,500 to 3,000. The polyepoxide is preferably a diepoxide, more preferably an aromatic or alicyclic diepoxide, and particularly preferably a bisphenol A diepoxide. The molecular weight of the polyepoxide is preferably 560 daltons or less, more preferably 100 to 500 daltons, particularly 300 to 500 daltons.

The phenolic or maleic acid-derived rosin ester resin preferably has four components: (a) a polyol, (b) a monobasic aliphatic carboxylic acid, (c) a rosin or modified rosin, and (d) a polycarboxylic acid. And / or its anhydride reaction product. The polyol is preferably a thiol, examples being trimethylolethane, trimethylolpropane, glycerol and hexanetriol. Preferred monobasic aliphatic carboxylic acids have 8 to 20 carbon atoms and include, for example, stearic acid, lauric acid, palmitic acid, oleic acid and purified tall oil fatty acids. Preferred rosins and modified rosins are selected from tall oil rosins, wood rosins, hydrogenated rosins and dehydrogenated rosins. The polycarboxylic acid or anhydride may be aliphatic or aromatic, such as phthalic anhydride, trimellitic anhydride, tetrahydrophthalic anhydride, maleic anhydride, isophthalic acid, fumaric acid and mixtures thereof. Is mentioned.

The phenolic or maleic acid-modified rosin resin can be made by a two-step process, in which the polyol, monobasic aliphatic carboxylic acid, and rosin or modified rosin are preferably 250 ° C. to 290 ° C. The reaction is carried out at a temperature of 260 ° C. to 280 ° C., preferably an acidity index of 1 to 10. In the second stage, polycarboxylic acid or anhydride is added and the reaction is preferably continued at a temperature of 150 ° C to 220 ° C, more preferably 170 ° C to 200 ° C, preferably 20 to 90, more preferably 20 ° C. An acidity index of ˜50. As a result, all of the monobasic aliphatic carboxylic acid groups and most of the rosin carboxylic acid groups react at 250 ° C. to 290 ° C., and aromatic carboxylic acids are added as pendant groups at 150 ° C. to 220 ° C.

The polymer obtained by grafting the polyepoxide onto the ink resin becomes oil-insoluble, whereby the squalene (skin oil) resistance is enhanced, the solvent is easily released, and heat set drying is improved. Since the crosslinked resin has little solubility, an aliphatic alcohol having at least 12 carbon atoms, preferably 12 to 24 carbon atoms, more preferably 12 to 13 carbon atoms, such as Neodol 23 ( It is retained in the solution by blending Shell Oil Co.).

High-boiling point solvents such as Magie 470 and Magie 500 (Magie Brosers Oil Company, 9101 Fullerton Ave., Franklin Park, Ill) to achieve ink roller stability required for high speed lithographic web printing It preferably contains a petroleum distillate varnish solvent. This aliphatic alcohol is used to dissolve the resin in a solvent. Some evaporation of alcohol in the paper adsorption and heat drying process affects the balance of solubility, causing the resin to settle out of the solution and become dry even when the ink film is touched. As more alcohol evaporates, the ink dries faster. The proper amount of alcohol is such that the ink can be sent to the printing roller of the press and printed on paper without drying during the printing process.

The infrared absorber represented by the general formula (1) is preferably 0.01% to 5.0% by mass, more preferably 0.1% to 3.0% by mass, based on the total mass of the ink composition. Blended. The infrared absorber blended in this amount is printed on the support and is detected only when the support is illuminated by an infrared detector.

If the ink also contains a colorant, the printed pattern can be detected visually, but the printed support can be distinguished in a similar manner from a support printed with an ink that does not contain an infrared absorber. . The colorant may be any of a variety of conventionally known organic or inorganic pigments, such as molybdate orange, titanium white, phthalocyanine blue, and carbon black. The content of the colorant is preferably 5% by mass to 30% by mass based on the total mass of the ink.

Modifiers such as plasticizers; wetting agents for colorants; leveling agents such as lanolin, paraffin wax, and natural waxes; slip agents such as low molecular weight polyethylenes and microcrystalline petroleum waxes can also be incorporated into the ink. Such a modifier is preferably used in an amount of 3% by mass or less, more preferably 1% by mass or less, based on the total mass of the ink. Other ingredients are also conventionally used in inks and coatings to modify adhesion, toughness, and other basic properties can be used.

The ink for lithographic printing can be produced by an arbitrary method such as a three-roll mill according to a known dispersion method, for example, a mixing and filtering step. The ink can be applied to the support, preferably paper, in any known and conventional manner.

(5) Inkjet printing (IJP) ink The organic solvent-based inkjet printing ink composition preferably contains at least one aromatic sulfonamide or hydroxybenzoic acid ester dissolved in an organic solvent.

Aromatic sulfonamides are preferably optionally substituted toluenesulfonamides such as p-toluenesulfonamide, N-ethyl-p-toluenesulfonamide, N-butyl-p-toluene-sulfonamide and N-cyclohexyl-p. -Toluenesulfonamide. This aromatic sulfonamide is preferably incorporated into the organic solvent-based IJP ink in an amount of 0.1% to 40% by weight.

Hydroxybenzoic acid esters are preferably alkyl esters, especially those containing 6 to 12 carbon atoms, such as 2-ethylhexyl-p-hydroxybenzoate and n-nonyl-p-hydroxy-benzoate. The hydroxybenzoic acid ester is preferably blended into the organic solvent-based IJP ink in an amount of 0.1% to 40% by weight.

Aromatic sulfonamides and hydroxybenzoic acid esters have high polarity and effectively inhibit dye crystallization.
The infrared absorbent represented by the general formula (1) of the present invention is preferably 0.01% by mass to 5.0% by mass, more preferably 0.1% by mass to 3.% by mass based on the total mass of the ink. When blended with ink in an amount of 0% by weight and coated on a support, it is detected only by an infrared detector, thus providing an invisible infrared absorbing ink.

If the ink also contains a colorant, the printed pattern is visually detectable, but the printed support can be distinguished from a support printed with ink that does not contain an infrared absorber in a similar manner. . The colorant may be any dye that is soluble in the organic solvent blended in the ink composition or soluble in the aromatic sulfonamide or hydroxybenzoic acid ester. Usually useful dyes include azo dyes, metal complex salt dyes, naphthol dyes, anthraquinone dyes, indigo dyes, carbonium dyes, quinoimine dyes, cyanine dyes, quinoline dyes, nitro dyes, nitroso dyes, benzoquinone dyes, naphthoquinone dyes, Examples include phthalimide dyes, perinone dyes, and phthalocyanine dyes. These dyes can be used independently or in combination. The dye used as the colorant is preferably 0.1% to 10% by weight, more preferably 0.5% to 5% by weight in the ink composition, based on the total weight of the ink. Blended.

The organic solvent used in the IJP ink of the present invention depends on the dye or the dye mixture, but since most dyes are polar, a highly polar solvent functions as a good solvent, and a nonpolar solvent functions as a poor solvent. To do. Therefore, highly polar solvents with a high ability to dissolve dyes are preferred for the production of IJP inks. However, less polar solvents can also be used if they are mixed with aromatic sulfonamides or hydroxybenzoates or combined with higher polarity solvents. Specific examples of organic solvents that can be used in IJP inks include aliphatic hydrocarbons; naphthenic hydrocarbons; aromatic hydrocarbons such as mono- or disubstituted alkylnaphthalenes, biphenyls, xylylethane, and alkyl of phenethylcumene. Derivatives; glycols; mono- or di-alkyl ethers of glycols and esters of glycols; fatty acids and esters thereof; nitrogen-containing compounds such as amides and pyrrolidone compounds. However, the organic solvent that can be used for the production of the IJP ink is not limited thereto.

The higher the boiling point of the solvent, the less the evaporation and the slower the drying. However, a solvent having a high boiling point tends to produce a highly viscous ink, making it difficult to eject the ink smoothly. On the other hand, ink obtained with a solvent having a low boiling point is dried too quickly and is dried at the nozzle orifice. Accordingly, an appropriate solvent having a desired viscosity and boiling point is selected in consideration of the ink drying prevention means employed in the print head.

This application refers to Japanese Patent Application No. 2009-24196 filed in Japan on February 4, 2009 as a reference document, and includes all disclosed in the document.

The present invention will be described in detail by the following examples, but the present invention is not limited to these examples.
In the examples, all parts and ratios are by “mass” unless otherwise stated.

[Example 1]
1. Preparation of ink Ink compositions for lithographic printing were prepared at the mixing ratios shown in Table 1. Ink compositions (1a) to (1f) were obtained using the compound represented by the general formula (1) of the present invention and the comparative compound as the infrared absorber. Infrared absorbers used with the ink composition No. are shown in Table 2.

2. Performance Evaluation The following evaluations were performed on the obtained ink formulations (1a) to (1f).
(1) Measurement of spectral absorption spectrum The spectral absorption spectra of Compound 9 and Comparative Compound 3 used in the ink formulations (1b) and (1f) were measured with a Hitachi spectrophotometer U-4100.
Measurement conditions: A sample prepared by dissolving 3.2 mg of the compound 9 of the present invention in 1.0 L of THF was placed in a 1 cm cell and measured with a Hitachi spectrophotometer U-4100. On the other hand, as a comparative example, a sample in which 4.9 mg of comparative compound 3 was dissolved in 1.0 L of THF was measured in the same manner.

The obtained spectral absorption spectrum is shown in FIG.
As is apparent from FIG. 1, the comparative compound 3 shows side absorption in the visible range, whereas when the compound 9 represented by the general formula (1) of the present invention is used, a high near-infrared wavelength is around 800 nm. In contrast to absorption, there is very little side absorption in the visible range.
Therefore, the ink composition (1b) using the compound 9 represented by the general formula (1) of the present invention is not visually recognized when used in a security printing ink, and has a higher accuracy by an infrared detector. Can be detected.

(2) Evaluation of light resistance and heat fastness of printed matter Using each of the obtained ink compositions (1a) to (1f), a printed matter was produced using plain paper as a support.

<Evaluation of light resistance>
Each obtained printed matter was irradiated with a xenon lamp at 95,000 lux for the time shown in Table 2. The concentration at each near-infrared spectral absorption maximum wavelength before and after the xenon lamp irradiation was measured, and the residual ratio was obtained.
<Evaluation of heat fastness and wet heat fastness>
Each obtained printed matter was stored at 80 ° C. for the time indicated in each table, the concentration at each near infrared spectral absorption maximum wavelength before and after that was measured, the residual ratio was determined, and each heat fastness was evaluated. . Moreover, it preserve | saved at the time of 60 degreeC and relative humidity (RH) 90% for the time as described in each table | surface, the density | concentration in each near infrared region spectral absorption maximum wavelength before and behind that was measured, and the residual rate was calculated | required, Each wet heat fastness was evaluated.

The results obtained are shown in Table 2. The printed matter formed from the ink compositions (1a) to (1c) of the present invention has unexpectedly high light fastness, heat fastness, and wet heat fastness compared to the comparative ink compositions (1d) to (1f). Showed sex.

[Example 2]
1. Ink preparation Ink compositions for intaglio printing were prepared at the blending ratios shown in Table 3. Ink compositions (2a) to (2f) were obtained using the compound represented by the general formula (1) of the present invention and a comparative compound as the infrared absorber. Infrared absorbers used with the ink composition No. are shown in Table 4.

2. Performance Evaluation 1) Preparation of Printed matter Using each of the obtained ink compositions (2a) to (2f), a printed matter printed on plain paper as a support was prepared.

2) Evaluation of light resistance and heat fastness of printed matter The obtained printed matter was evaluated in the same manner as in Example 1. The results obtained are shown in Table 4.
As in Example 1, the printed matter formed from the ink compositions (2a) to (2c) of the present invention had unexpectedly high light fastness compared to the comparative ink compositions (2d) to (2f). It showed heat fastness and wet heat fastness.

[Example 3]
1. Preparation of Ink UV curable ink compositions were prepared at the compounding ratios shown in Table 5. Ink compositions (3a) to (3g) were obtained using the compound represented by the general formula (1) of the present invention and a comparative compound as the infrared absorber. Infrared absorbers used with the ink composition No. are shown in Table 6.

2. Performance Evaluation 1) Preparation of Printed Product Using the obtained UV curable ink compositions (3a) to (3g), each containing a compound represented by the general formula (1) (infrared absorber) using plain paper as a support Mark was given.

2) Evaluation of light resistance and heat fastness of printed matter The obtained printed matter was evaluated in the same manner as in Example 1. The obtained results are shown in Table 6.
As in Example 1, the prints formed with the UV curable ink compositions (3a) to (3d) of the present invention were unexpectedly higher than the comparative UV curable ink compositions (3e) to (3g). It exhibited light fastness, heat fastness, and wet heat fastness.

[Example 4]
1. Preparation of ink-jet ink A solvent-based ink-jet ink composition was prepared at the compounding ratio shown in Table 7. Ink compositions (4a) to (4f) were obtained using the compound represented by the general formula (1) of the present invention and a comparative compound as the infrared absorber. Infrared absorbers used with the ink composition No. are shown in Table 8.

2. Performance Evaluation 1) Production of Printed Material Using the obtained ink-jet ink compositions (4a) to (4f), printed materials were produced, each printed on plain paper as a support.

2) Evaluation of light resistance and heat fastness of printed matter The obtained printed matter was evaluated in the same manner as in Example 1. The obtained results are shown in Table 8.
As in Example 1, the printed materials formed from the ink compositions (4a) to (4c) of the present invention have unexpectedly high light fastness compared to the comparative ink compositions (4d) to (4f). It showed heat fastness and wet heat fastness.

Ink, toner and information detection method using them provided by the present invention include prepaid cards, credit cards, bank cards, identification cards, licenses, tickets, admission tickets, membership cards, securities cards, and securities. , Bills, tickets, certificates, etc. can be used as collating means for falsification, forgery prevention, identification and the like.

Claims (11)

1. Printing ink or toner containing a compound represented by the following general formula (1):
   

   

   
   (Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group. R ¹ and R ² , R ² and R ³ , R ³ and R ⁴ , R ⁵ and R ⁶ , R ⁶ and R ⁷ , or R ⁷ and R ⁸ are bonded to each other to form a 5-membered or 6-membered ring. May be.)
2. R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ in the general formula (1) are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, cyclopentyl or The printing ink or toner according to claim 1, which is a cyclohexyl group, or a phenyl or naphthyl group.
3. The printing ink or toner according to claim 1 or 2, wherein R ¹ , R ⁴ , R ⁵ and R ⁸ in the general formula (1) are hydrogen atoms.
4. The printing ink or toner according to any one of claims 1 to 3, further comprising a colorant and a binder.
5. The printing ink or toner according to claim 4, wherein the colorant is a dye or pigment having absorption in the visible region.
6. The printing ink according to any one of claims 1 to 5, wherein the compound represented by the general formula (1) is contained in an amount of 0.01% by mass to 5.0% by mass with respect to the total amount of the ink or toner. Or toner.
7. A printed matter on which information is printed using the printing ink or toner according to any one of claims 1 to 6.
8. An information detection method for detecting information printed on the printed matter by scanning the printed matter according to claim 7 with an infrared detector.
9. A mark containing a compound represented by the following general formula (1) is imparted to a product or a support, and then the mark is irradiated with infrared rays to detect or measure light absorption by the compound represented by the general formula (1). A method of proving authenticity of a product or support that includes a process:
   

   

   
   (In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ each represent a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group. R ¹ and R ² , R ² and R ³ , R ³ and R ⁴ , R ⁵ and R ⁶ , R ⁶ and R ⁷ , or R ⁷ and R ⁸ may be bonded to each other to form a 5-membered or 6-membered ring. .)
10. R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ in the general formula (1) are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, cyclopentyl or The method for proving authenticity of a product or a support according to claim 9, which is a cyclohexyl group or a phenyl or naphthyl group.
11. The method for proving authenticity of a product or a support according to claim 9 or 10, wherein R ¹ , R ⁴ , R ⁵ and R ⁸ in the general formula (1) are hydrogen atoms.

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