JP6985831B2 - Ink composition, printed matter printed using the ink composition - Google Patents

Description

The present invention relates to an ink composition and a printed matter printed using the ink composition.

So-called ultraviolet-excited illuminants typified by phosphors, phosphors, phosphors, etc. have the property of being excited and emitting light by irradiating with ultraviolet rays. This phenomenon of light emission can be easily visually confirmed, and it is difficult to reproduce it with a copy made by a copier or an output piece made by a home printer. Therefore, it is a genuine product for security printed matter such as banknotes and securities. It has been widely used as one of the authenticity discrimination elements for distinguishing between a counterfeit product and a counterfeit product.

Examples of the above-mentioned authenticity discrimination technique include an anti-counterfeiting system using white ink containing titanium as an ultraviolet blocking material (Patent Document 1), an anti-counterfeiting system using metallic ink (Patent Document 2), and the like. Examples thereof include an anti-counterfeiting system (Patent Document 3) using a receiving layer coating solution containing an active yttrium oxide phosphor with europium and an active zinc silicate phosphor with manganese.

Japanese Unexamined Patent Publication No. 2013-91296 Japanese Unexamined Patent Publication No. 2012-25092 Japanese Unexamined Patent Publication No. 2013-6356

On the other hand, in order to apply the above-mentioned authenticity determination technique to a plastic film printed matter, an ink composition for security printing having flexographic printing or gravure printing suitability is required. Generally, in the printing configuration used for such printing, when the packaging material is made into a bag, what is printed on the front surface is called front printing, or is printed on the back surface, and the printed surface is printed as required. Printing is called back printing, in which an adhesive or anchor coating agent is applied and lamination is applied.

However, the ink compositions used in Patent Document 1 and Patent Document 2 are offset printing ink compositions, and when these are used as flexographic or gravure printing compositions, the inks have different viscosity and solubility. Problems such as impaired storage stability and reduced doctor breakability due to changes in the dispersed state of the pigment are likely to occur. Further, although Patent Document 3 is a gravure printing method, it is inferior in doctor cutting property and weather resistance.

As described above, the printability such as the dispersion stability of the pigment (dye), the weather resistance of the printed matter, the light emission suitability of the printed matter, and the blocking resistance of the printed matter, which are the performances required for flexo printing or gravure printing ink composition, is sufficiently provided. At present, no ink composition for security printing has been found yet.

The present invention has been made in view of the above circumstances, and an ink composition having sufficient printability such as pigment dispersion stability, weather resistance of printed matter, light emission suitability of printed matter, and blocking resistance of printed matter. The purpose is to provide.

（一般式（１）中、Ｒ^１〜Ｒ^５は、独立して、水素原子、ハロゲン原子、メチル基、エチル基、メトキシ基、またはエトキシ基を表し、Ｒ^６〜Ｒ^９は、独立して、水素原子、ハロゲン原子、メチル基、エチル基、メトキシ基、またはエトキシ基を表し、Ｒ^６〜Ｒ^９のうち、少なくとも１つは、ハロゲン原子、メチル基、エチル基、メトキシ基、またはエトキシ基を表す。）で表される化合物、一般式（２）：

（一般式（２）中、Ｒ^１〜Ｒ^５は、独立して、水素原子、ハロゲン原子、メチル基、エチル基、メトキシ基、またはエトキシ基を表し、Ｒ^６〜Ｒ^９は、独立して、水素原子、ハロゲン原子、メチル基、エチル基、メトキシ基、またはエトキシ基を表し、Ｒ^６〜Ｒ^９のうち、少なくとも１つは、ハロゲン原子、メチル基、エチル基、メトキシ基、またはエトキシ基を表す。）で表される化合物、および一般式（３）：

（一般式（３）中、Ｒ^１〜Ｒ^５は、独立して、水素原子、ハロゲン原子、メチル基、エチル基、メトキシ基、またはエトキシ基を表し、Ｒ^６〜Ｒ^９は、独立して、水素原子、ハロゲン原子、メチル基、エチル基、メトキシ基、またはエトキシ基を表し、Ｒ^６〜Ｒ^９のうち、少なくとも１つは、ハロゲン原子、メチル基、エチル基、メトキシ基、またはエトキシ基を表す。）で表される化合物からなる群より選ばれる１種以上の蛍光性有機顔料であり、前記バインダー樹脂が、ポリウレタン樹脂、およびポリアミド樹脂からなる群より選ばれる１種以上であるベースポリマーと、セルロース誘導体であり、前記ベースポリマーと前記セルロース誘導体の質量比（ベースポリマー／セルロース誘導体）が６５／３５〜９０／１０であるインキ組成物に関する。 That is, the present invention is an ink composition containing a pigment, a binder resin, and a solvent, and the pigment is the general formula (1) :.

(In the general formula (1), R ^{1 to} R ⁵ independently represent a hydrogen atom, a halogen atom, a methyl group, an ethyl group, a methoxy group, or an ethoxy group, and R ^{6 to} R ⁹ independently represent. , A hydrogen atom, a halogen atom, a methyl group, an ethyl group, a methoxy group, or an ethoxy group ^{, and at least one of R 6 to} R ⁹ is a halogen atom, a methyl group, an ethyl group, a methoxy group, or an ethoxy group. The compound represented by), the general formula (2) :.

(In the general formula (2), R ^{1 to} R ⁵ independently represent a hydrogen atom, a halogen atom, a methyl group, an ethyl group, a methoxy group, or an ethoxy group, and R ^{6 to} R ⁹ independently represent. , A hydrogen atom, a halogen atom, a methyl group, an ethyl group, a methoxy group, or an ethoxy group ^{, and at least one of R 6 to} R ⁹ is a halogen atom, a methyl group, an ethyl group, a methoxy group, or an ethoxy group. The compound represented by), and the general formula (3) :.

(In the general formula (3), R ^{1 to} R ⁵ independently represent a hydrogen atom, a halogen atom, a methyl group, an ethyl group, a methoxy group, or an ethoxy group, and R ^{6 to} R ⁹ independently represent. , A hydrogen atom, a halogen atom, a methyl group, an ethyl group, a methoxy group, or an ethoxy group ^{, and at least one of R 6 to} R ⁹ is a halogen atom, a methyl group, an ethyl group, a methoxy group, or an ethoxy group. It is one or more fluorescent organic pigments selected from the group consisting of the compounds represented by), and the binder resin is one or more selected from the group consisting of a polyurethane resin and a polyamide resin. The present invention relates to an ink composition which is a cellulose derivative and has a mass ratio (base polymer / cellulose derivative) of the base polymer to the cellulose derivative of 65/35 to 90/10.

The present invention also relates to a printed matter printed using the ink composition.

The ink composition of the present invention contains a pigment, a binder resin, and a solvent, the pigment is a fluorescent organic pigment having a specific structure, and the binder resin is composed of a polyurethane resin and a polyamide resin. One or more base polymers and cellulose derivatives of choice. In the present invention, by blending the pigment into a binder resin containing a base polymer composed of a specific ratio and a cellulose derivative, the dispersion stability of the pigment, the weather resistance of the printed matter, the light emission suitability of the printed matter, and the blocking resistance of the printed matter are present. Since it is possible to provide an ink composition having sufficient printability such as, it is suitable as an ink composition for security printing. Further, the above-mentioned pigment (fluorescent organic pigment) does not emit fluorescence to visible light, but emits fluorescence when exposed to ultraviolet light such as black light, whereas it is generally known fluorescence. Since the pigment also fluoresces against visible light, the ink composition of the present invention is an ink composition useful for determining authenticity under black light irradiation.

The ink composition of the present invention contains a pigment, a binder resin, and a solvent.

（一般式（１）中、Ｒ^１〜Ｒ^５は、独立して、水素原子、ハロゲン原子、メチル基、エチル基、メトキシ基、またはエトキシ基を表し、Ｒ^６〜Ｒ^９は、独立して、水素原子、ハロゲン原子、メチル基、エチル基、メトキシ基、またはエトキシ基を表し、Ｒ^６〜Ｒ^９のうち、少なくとも１つは、ハロゲン原子、メチル基、エチル基、メトキシ基、またはエトキシ基を表す。）で表される化合物、一般式（２）：

（一般式（２）中、Ｒ^１〜Ｒ^５は、独立して、水素原子、ハロゲン原子、メチル基、エチル基、メトキシ基、またはエトキシ基を表し、Ｒ^６〜Ｒ^９は、独立して、水素原子、ハロゲン原子、メチル基、エチル基、メトキシ基、またはエトキシ基を表し、Ｒ^６〜Ｒ^９のうち、少なくとも１つは、ハロゲン原子、メチル基、エチル基、メトキシ基、またはエトキシ基を表す。）で表される化合物、および一般式（３）：

（一般式（３）中、Ｒ^１〜Ｒ^５は、独立して、水素原子、ハロゲン原子、メチル基、エチル基、メトキシ基、またはエトキシ基を表し、Ｒ^６〜Ｒ^９は、独立して、水素原子、ハロゲン原子、メチル基、エチル基、メトキシ基、またはエトキシ基を表し、Ｒ^６〜Ｒ^９のうち、少なくとも１つは、ハロゲン原子、メチル基、エチル基、メトキシ基、またはエトキシ基を表す。）からなる群より選ばれる１種以上の蛍光性有機顔料である。前記顔料は、少なくとも１種を用いればよく、２種以上を組み合わせて用いることができる。 <Pigment>
The pigment of the present invention has the general formula (1):

(In the general formula (1), R ^{1 to} R ⁵ independently represent a hydrogen atom, a halogen atom, a methyl group, an ethyl group, a methoxy group, or an ethoxy group, and R ^{6 to} R ⁹ independently represent. , A hydrogen atom, a halogen atom, a methyl group, an ethyl group, a methoxy group, or an ethoxy group ^{, and at least one of R 6 to} R ⁹ is a halogen atom, a methyl group, an ethyl group, a methoxy group, or an ethoxy group. The compound represented by), the general formula (2) :.

(In the general formula (2), R ^{1 to} R ⁵ independently represent a hydrogen atom, a halogen atom, a methyl group, an ethyl group, a methoxy group, or an ethoxy group, and R ^{6 to} R ⁹ independently represent. , A hydrogen atom, a halogen atom, a methyl group, an ethyl group, a methoxy group, or an ethoxy group ^{, and at least one of R 6 to} R ⁹ is a halogen atom, a methyl group, an ethyl group, a methoxy group, or an ethoxy group. The compound represented by), and the general formula (3) :.

(In the general formula (3), R ^{1 to} R ⁵ independently represent a hydrogen atom, a halogen atom, a methyl group, an ethyl group, a methoxy group, or an ethoxy group, and R ^{6 to} R ⁹ independently represent. , Hydrogen atom, halogen atom, methyl group, ethyl group, methoxy group, or ethoxy group ^{, and at least one of R 6 to} R ⁹ is a halogen atom, methyl group, ethyl group, methoxy group, or ethoxy group. It is one or more kinds of fluorescent organic pigments selected from the group consisting of.). At least one of the pigments may be used, and two or more of them may be used in combination.

In the general formula (1), R ^{1 to} R ⁵ independently represent a hydrogen atom, a halogen atom, a methyl group, an ethyl group, a methoxy group, or an ethoxy group, and R ^{6 to} R ⁹ independently represent. , Hydrogen atom, halogen atom, methyl group, ethyl group, methoxy group, or ethoxy group ^{, and at least one of R 6 to} R ⁹ (two in total among biphenyl groups) is a halogen atom, a methyl group, Represents an ethyl group, a methoxy group, or an ethoxy group. ^{From the viewpoint of availability of the compound, one or two of R 1 to} R ⁵ of the compound represented by the general formula (1) are a halogen atom, a methyl group, an ethyl group, a methoxy group, or an ethoxy. It is preferably a group, and it is preferable that ^{one or two of R 6 to} R ⁹ are a halogen atom, a methyl group, an ethyl group, a methoxy group, or an ethoxy group. Among the halogen atoms, a chlorine atom is preferable.

In the general formula (2), R ^{1 to} R ⁵ independently represent a hydrogen atom, a halogen atom, a methyl group, an ethyl group, a methoxy group, or an ethoxy group, and R ^{6 to} R ⁹ independently represent. , Hydrogen atom, halogen atom, methyl group, ethyl group, methoxy group, or ethoxy group ^{, and at least one of R 6 to} R ⁹ (two in total among biphenyl groups) is a halogen atom, a methyl group, Represents an ethyl group, a methoxy group, or an ethoxy group. ^{From the viewpoint of availability of the compound, one or two of R 1 to} R ⁵ of the compound represented by the general formula (2) are a halogen atom, a methyl group, an ethyl group, a methoxy group, or an ethoxy. It is preferably a group, and it is preferable that ^{one or two of R 6 to} R ⁹ are a halogen atom, a methyl group, an ethyl group, a methoxy group, or an ethoxy group. Among the halogen atoms, a chlorine atom is preferable.

In the general formula (3), R ^{1 to} R ⁵ independently represent a hydrogen atom, a halogen atom, a methyl group, an ethyl group, a methoxy group, or an ethoxy group, and R ^{6 to} R ⁹ independently represent. , Hydrogen atom, halogen atom, methyl group, ethyl group, methoxy group, or ethoxy group ^{, and at least one of R 6 to} R ⁹ (two in total among biphenyl groups) is a halogen atom, a methyl group, Represents an ethyl group, a methoxy group, or an ethoxy group. ^{From the viewpoint of availability of the compound, one or two of R 1 to} R ⁵ of the compound represented by the general formula (3) are a halogen atom, a methyl group, an ethyl group, a methoxy group, or an ethoxy. It is preferably a group, and it is preferable that ^{one or two of R 6 to} R ⁹ are a halogen atom, a methyl group, an ethyl group, a methoxy group, or an ethoxy group. Among the halogen atoms, a chlorine atom is preferable.

Examples of the pigment include C.I. I. Pigment Yellow 12, C.I. I. Pigment Yellow 13, C.I. I. Pigment Yellow 14, C.I. I. Pigment Yellow 15, C.I. I. Pigment Yellow 16, C.I. I. Pigment Yellow 17, C.I. I. Pigment Yellow 55, C.I. I. Pigment Yellow 63, C.I. I. Pigment Yellow 77, C.I. I. Pigment Yellow 81, C.I. I. Pigment Yellow 83, C.I. I. Pigment Yellow 87, C.I. I. Pigment Yellow 106, C.I. I. Pigment Yellow 113, C.I. I. Pigment Yellow 114, C.I. I. Pigment Yellow 124, C.I. I. Pigment Yellow 126, C.I. I. Pigment Yellow 127, C.I. I. Pigment Yellow 152, C.I. I. Pigment Yellow 170, C.I. I. Pigment Yellow 172, C.I. I. Pigment Yellow 176, C.I. I. Pigment Orange 15, C.I. I. Pigment Orange 16 and the like. Among these, C.I. I. Pigment Yellow 14, C.I. I. Pigment orange 16 is preferred.

<Binder resin>
The binder resin of the present invention contains one or more base polymers selected from the group consisting of polyurethane resins and polyamide resins, and cellulose derivatives. The polyamide resin is suitable for using the ink composition of the present invention for front printing such that it is printed on the surface of a packaging material when it is made into a bag, while the polyurethane resin is suitable. It is suitable for backprint printing in which the ink composition of the present invention is printed on the back surface of a packaging material, an adhesive or an anchor coating agent is applied to the printed surface as necessary, and lamination processing is performed. ..

<Polyurethane resin>
The polyurethane resin of the present invention is a resin having two or more urethane bonds in the molecule and can be used without particular limitation. For example, a urethane prepolymer obtained by reacting a diisocyanate compound with a diol compound can be further added. Examples thereof include those obtained by reacting a chain extender and a reaction terminator. At least one type of polyurethane resin may be used, and two or more types may be used in combination.

Examples of the diisocyanate compound include aliphatic diisocyanate compounds such as hexamethylene diisocyanate and 2,2,4-trimethylhexamethylene diisocyanate; alicyclic diisocyanate compounds such as isophorone diisocyanate and hydrogenated xylylene diisocyanate; xylylene diisocyanate and α. , Α, α', α'-Aromatic aliphatic diisocyanate compounds such as tetramethylxylylene diisocyanate; Examples include aromatic diisocyanate compounds such as toluylene diisocyanate and diphenylmethane diisocyanate. Among these, alicyclic or aromatic aliphatic diisocyanate compounds are preferable, and isophorone diisocyanate, α, α, α', are particularly preferable from the viewpoint that the reaction is easily controlled and the obtained polyurethane resin has a good balance of performance. α'-Tetramethylxylylene diisocyanate is preferred. At least one type of the diisocyanate compound may be used, and two or more types may be used in combination.

Examples of the diol compound include polymer diols such as polyester diol compounds, polyether diol compounds, polycarbonate compounds, and polybutadiene glycol compounds. At least one diol compound may be used, and two or more diol compounds may be used in combination.

The number average molecular weight of the diol compound is preferably 400 or more, more preferably 1,000 or more, from the viewpoint of pigment dispersibility. The number average molecular weight of the diol compound is preferably 10,000 or less, more preferably 6,000 or less, from the viewpoint of enhancing the reactivity with the diisocyanate compound.

Examples of the polyester diol compound include low molecular weight diol components (linear glycols such as ethylene glycol, 1,3-propanediol and 1,4-butanediol; 1,2-propanediol, neopentyl glycol and 3). -Branched glycols such as methyl-1,5-pentanediol and 2,4-diethyl-1,5-pentanediol; ether-based diols such as diethylene glycol and triethylene glycol) and dicarboxylic acid components (succinic acid and adipine). Examples thereof include those obtained by reacting saturated and unsaturated aliphatic dicarboxylic acids such as acid and maleic acid; aromatic dicarboxylic acids such as phthalic acid).

Examples of the polyether diol compound include a polyester diol compound obtained by ring-opening a cyclic ester compound (lactone, etc.), or a diol compound ((poly) alkylene glycol compound, bisphenol, etc.) and oxyalkylene (ethylene oxide, etc.). Examples thereof include a polyether diol compound obtained by double-adding (such as propylene oxide) and tetrahydrofuran.

The diol compound is preferably a polyester diol or a polyether diol from the viewpoint of various physical characteristics of the ink.

As the chain extender, a compound having two or more functional groups (amino group, hydroxyl group, etc.) capable of reacting with an isocyanate group in the molecule can be used. Examples of the compound containing two or more amino groups in the molecule include diamines having two primary amino groups (ethylenediamine, 1,3-propylenediamine, 1,4-butylenediamine, hexamethylenediamine, isophoronediamine, etc.). ) Diamines having one primary amino group and one secondary amino group (2-ethylaminoethylamine, etc.)) Polyamines having two primary amino groups and one or more secondary amino groups (diethylenetriamine, triethylene) (Tetramine, etc.) and the like. Examples of the hydroxyl group-containing compound containing two or more hydroxyl groups in the molecule include low-molecular-weight diols (ethylene glycol, propylene glycol, butylene glycol, diethylene glycol, triethylene glycol, etc.). Further, as a compound having two amino groups and one hydroxyl group in the molecule, for example, 1 mol of ethylene oxide is added to the above-mentioned diamines having two primary amino groups such as aminoethylethanolamine and aminopropylethanolamine. Things and the like can be mentioned. At least one type of chain extender may be used, and two or more types may be used in combination.

As the chain extender, a compound having three or more functional groups such as an amino group and a hydroxyl group can be used from the viewpoint of introducing a functional group such as a hydroxyl group or an amino group into the molecule of the polyurethane resin. Examples of the compound having three or more functional groups such as an amino group and a hydroxyl group include glycerin and aminoethylethanolamine.

As the reaction terminator, a compound having at least one functional group (amino group, hydroxyl group, etc.) capable of reacting with an isocyanate group in the molecule can be used, and specifically, monoalcohols (methanol, ethanol, etc.), Examples thereof include monoamines (n-butylamine, di-n-butylamine, etc.) and alkanolamines (monoethanolamine, ethylethanolamine, diethanolamine) having one amino group and one hydroxyl group in the molecule. Further, as the reaction terminator, the compound mentioned as the chain extender can also be used. The reaction terminator has been exemplified as an alkanolamine having one amino group and one hydroxyl group in the molecule and the chain extender from the viewpoint of introducing a functional group such as a hydroxyl group or an amino group into the molecule of the polyurethane resin. Diamines having two primary amino groups and low molecular weight diols can be used. At least one type of reaction terminator may be used, and two or more types may be used in combination.

In the production of the urethane prepolymer obtained by reacting the diisocyanate compound with the diol compound, the equivalent ratio of NCO of the diisocyanate compound to OH of the diol compound (the equivalent of NCO of the diisocyanate compound / the equivalent of OH of the diol compound) is 1. The reaction is preferably 3 to 3, and more preferably 1.5 to 2.

The chain extender is preferably reacted with the remaining isocyanate group of the prepolymer in the range of about 0.5 to 0.95 equivalent. Further, it is preferable that the reaction terminator is reacted at a ratio of about 2 mol with 1 mol of the polyurethane resin after chain extension.

The weight average molecular weight of the polyurethane resin is preferably 5,000 to 50,000, more preferably 10,000 to 30,000. The weight average molecular weight of the present invention can be measured by a gel permeation chromatography (GPC) method. As an example, using Water2690 (manufactured by Waters) as a GPC device, PLgel 5μ as a column, and MIXED-D (manufactured by Polymer Laboratories) as a developing solvent, tetrahydrofuran, column temperature 25 ° C., flow velocity 1 ml / min, RI. Chromatography can be performed under the conditions of a detector, a sample injection concentration of 10 mg / ml, and an injection amount of 100 microliters, and the weight average molecular weight in terms of polystyrene can be obtained.

The polyurethane resin is preferably a polyurethane resin having a functional group such as a hydroxyl group or an amino group. As a method for obtaining a polyurethane resin having such a functional group, a method using the above-mentioned compound having three or more functional groups such as an amino group and a hydroxyl group as a chain extender, and the above-mentioned chain extender and the reaction terminator are used. A known method such as a method of reacting the diisocyanate compound at a molar ratio of less than 1.0 times that of the diol compound can be adopted without using the compound.

<Polyamide resin>
The polyamide resin of the present invention is a resin having two or more amide bonds in the molecule and can be used without particular limitation. For example, it can be obtained by reacting an acid component containing a polymerized fatty acid with an amine component containing a polyamine. Things can be mentioned.

The polymerized fatty acid is generally obtained by polymerizing an unsaturated fatty acid having 10 to 22 carbon atoms or an esterified product thereof. Examples of the polymerized fatty acid include monobasic fatty acid, dimerized polymerized fatty acid, and trimerized polymerized fatty acid.

The acid component includes aliphatic dicarboxylic acids such as succinic acid, adipic acid, azelaic acid and maleic acid; alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid; dicarboxylic acids such as aromatic dicarboxylic acids such as isophthalic acid and terephthalic acid. , Acetic acid, stearic acid, oleic acid, monocarboxylic acid such as linoleic acid and the like can be included.

The polyamines are aliphatic polyamines such as ethylenediamine, propylenediamine, hexamethylenediamine, methylaminopropylamine, diethylenetriamine and triethylenetetramine; alicyclic polyamines such as cyclohexylene diamine and isophorone diamine; xylylene diamine, phenylenediamine and diamino. Examples include aromatic polyamines such as diphenylmethane.

Further, the amine component may include primary and secondary monoamines such as butylamine, octylamine, diethylamine, monoethanolamine, monopropanolamine, diethanolamine and dipropanolamine.

As a method for synthesizing the polyamide resin, the ratio of carboxyl group / amino group of the reaction component is 0.9 / 1-1 / 0.9, preferably 1/1, and the reaction temperature is 160 to 280 ° C., preferably 180. It is desirable to react at ~ 230 ° C. under a reduced pressure of about 100 torr in the final stage.

<Cellulose derivative>
The cellulose derivative of the present invention is, for example, a lower acyl group substituent such as nitrocellulose (nitro group substituent), cellulose acetate, cellulose acetate propionate, cellulose acetate butyrate, a lower alkyl group substituent such as methyl cellulose or ethyl cellulose, and the like. Examples thereof include those having a hydroxyl group such as benzyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose and hydroxymethylpropyl cellulose. As the cellulose derivative, nitrocellulose is preferable from the viewpoint of pigment dispersibility, and lower acyl group substituents and lower alkyl group substituents are preferable from the viewpoint of ink film physical characteristics. The degree of substitution of the hydroxyl group of the cellulose derivative is preferably about 30 to 85%. At least one type of cellulose derivative may be used, and two or more types may be used in combination.

The weight average molecular weight of the cellulose derivative is preferably 10,000 to 500,000, more preferably 10,000 to 300,000. The weight average molecular weight can be obtained by the same method as the weight average molecular weight of the polyurethane resin.

As the binder resin of the present invention, other resins other than the polyurethane resin, the polyamide resin, and the cellulose derivative can be used. Examples of the other resin include vinyl chloride / vinyl acetate copolymer, (meth) acrylic copolymer, butyral resin and the like.

<Solvent>
The solvent of the present invention can be used without particular limitation, but from the viewpoint of consideration for the environment, it is preferable that the solvent does not contain an aromatic hydrocarbon-based organic solvent. Examples of such a solvent include alcohol-based organic solvents such as methanol, ethanol, n-propanol, isopropanol and butanol; ketone-based organic solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone; methyl acetate, ethyl acetate, propyl acetate and butyl acetate. Esther-based organic solvents such as; aliphatic hydrocarbon-based organic solvents such as n-hexane, n-heptane, n-octane; alicyclic hydrocarbon-based organic solvents such as cyclohexane, methylcyclohexane, ethylcyclohexane, cycloheptane, cyclooctane, etc. Examples include solvents. At least one type of the solvent may be used, and two or more types may be used in combination in consideration of the solubility and drying property of the binder resin. However, from the viewpoint of considering the environment, it is preferable to suppress the use of a ketone-based organic solvent among the above-mentioned solvents.

When the ink composition of the present invention is applied to a flexographic printing ink composition, the total ratio of the alcohol-based organic solvent and the ester-based organic solvent in the solvent is 90% by mass or more. Is preferable, and 95% by mass or more is more preferable.

When the ink composition of the present invention is applied to a front printing gravure printing ink composition, the solvent is an alcohol-based organic solvent, an ester-based organic solvent, and an alicyclic hydrocarbon-based organic solvent in the solvent. The total ratio of the above is preferably 90% by mass or more, and more preferably 95% by mass or more. Further, when the ink composition of the present invention is applied to the back printing gravure printing ink composition, the total ratio of the alcohol-based organic solvent and the ester-based organic solvent in the solvent is 90% by mass. The above is preferable, and 95% by mass or more is more preferable.

Hereinafter, the ratio of each component contained in the ink composition of the present invention will be described.

The pigment is preferably 50 to 200 parts by mass with respect to 100 parts by mass of the binder resin. From the viewpoint of fluorescence characteristics, the pigment is preferably 50 parts by mass or more, more preferably 75 parts by mass or more, and has pigment dispersibility and printability with respect to 100 parts by mass of the binder resin. From the viewpoint, it is preferably 200 parts by mass or less, and more preferably 150 parts by mass or less.

In the binder resin, the mass ratio of the base polymer to the cellulose derivative (base polymer / cellulose derivative) is 65/35 to 90/10. When the polyamide resin is used as the base polymer, the mass ratio of the base polymer to the cellulose derivative is preferably 85/15 or less from the viewpoint of improving the dispersibility of the pigment. Further, the mass ratio of the base polymer to the cellulose derivative is preferably 70/30 or more, preferably 70/30 or more, when the polyurethane resin is used as the base polymer, from the viewpoint of improving the adhesion to the substrate. It is more preferably / 25 or more.

When the ink composition of the present invention is applied to a flexographic printing ink composition, the ratio of the solvent is preferably 55 to 80% by mass, more preferably 60 to 75% by mass in the ink composition. preferable. When the ink composition of the present invention is applied to a gravure printing ink composition, the ratio of the solvent is preferably 65 to 90% by mass, more preferably 70 to 85% by mass in the ink composition. preferable.

The total ratio of the pigment, the binder resin, and the solvent is preferably 80% by mass or more, more preferably 90% by mass or more, and more preferably 95% by mass, from the viewpoint of considering printability in the ink composition. It is more preferably mass% or more, and even more preferably 98% by mass or more.

The ink composition of the present invention includes metal chelate cross-linking agents such as titanium chelate and zirconium chelate; waxes such as polyolefin wax and paraffin wax; saturated fatty acid amides and unsaturated fatty acid amides, as long as the performance of the ink composition is not deteriorated. Fatty acid amides such as modified fatty acid amides; hard resins such as dimer acid-based resins, rosin-based resins, maleic acid-based resins, petroleum resins, terpene resins, ketone resins, dammer resins, copal resins, chlorinated polypropylene, and polypropylene oxides; leveling agents. , A surfactant, a plasticizer and the like can be arbitrarily added.

<Preparation method of ink composition>
The method for preparing the ink composition of the present invention is not particularly limited, and for example, the above components are added in order or at the same time to a bead mill, a ball mill, a sand mill, an attritor, a roll mill, a pearl mill, a high-speed stirrer, and the like. It can be prepared by mixing with a paint conditioner or the like.

<How to make printed matter>
The printed matter of the present invention is obtained by applying (printing) the ink composition to a support (base material) and drying it, and an ink layer (printing film) is formed on the support. .. As the printing method, it is preferable to use a flexographic printing machine or a gravure printing machine. The drying may be provided with a step of evaporating the solvent with hot air or the like. As the printing conditions by the printing machine, conventionally known conditions can be appropriately adopted.

The support (base material) may be any of metal, wood, paper and plastic, but among these, a plastic film is preferable. Examples of the plastic film include polyesters such as polyethylene terephthalate and polyethylene naphthalate, polycycloolefins, polyacetates, polyethersulfones, polycarbonates, polyamides, polyimides, (meth) acrylic polymers, polyvinyl chlorides, and polyvinylidene chlorides. Examples thereof include films such as polystyrene, polyvinyl alcohol, polyarylate, polyphenylene sulfide, and cellulose-based polymers such as diacetyl cellulose and triacetyl cellulose.

The pigment of the present invention has, as the binder resin, a polyester resin, a polyurethane resin, a polyamide resin, a cellulose derivative, a vinyl chloride / vinyl acetate copolymer, an ethylene / vinyl acetate copolymer, and a (meth) acrylic copolymer. , Butyral resin, rosin resin, styrene-maleic acid resin, epoxy resin, phenol resin, chlorinated polyolefin resin, alkyd resin, etc. are used to disperse pigments in various media such as water and organic solvents to make printing ink. By doing so, it is possible to print by various known printing methods. Examples of such a printing method include the above-mentioned gravure printing and flexographic printing, as well as offset printing, sheet-fed printing, and digital printing (inkprint method, toner method). Similar to the ink composition of the present invention, the printing ink can be applied to determine the authenticity of a printed matter under irradiation with ultraviolet rays such as black light.

Hereinafter, the present invention will be described with reference to Examples and the like, but the present invention is not limited thereto.

<Manufacturing example 1>
<Manufacturing of polyurethane resin varnish for flexographic back printing>
In a four-necked flask equipped with a stirrer, a cooling tube and a nitrogen gas introduction tube, 100 parts by mass of a poly (3-methyl-1,5-pentylene adipate) diol having a number average molecular weight of 1,000 and 44.4 parts of isophorone diisocyanate. A mass portion was charged and reacted at 100 to 105 ° C. for 6 hours while introducing nitrogen gas. After allowing to cool to near room temperature, 94.9 parts by mass of propyl acetate and 379.4 parts by mass of isopropyl alcohol were added, and then 7.1 parts by mass of isophorondiamine and 4.2 parts by mass of aminoethylethanolamine were added to carry out a chain extension reaction. Then, 2.4 parts by mass of ethylenediamine was further added to terminate the reaction to obtain a polyurethane resin varnish for flexo back printing (solid content: 25% by mass, mass average molecular weight of polyurethane resin about 12,000).

<Manufacturing of polyurethane resin varnish for gravure back printing>
In a four-necked flask equipped with a stirrer, a cooling tube and a nitrogen gas introduction tube, 100 parts by mass of a poly (3-methyl-1,5-pentylene adipate) diol having a number average molecular weight of 1,000 and 44.4 parts of isophorone diisocyanate. A mass portion was charged and reacted at 100 to 105 ° C. for 6 hours while introducing nitrogen gas. After allowing to cool to near room temperature, 379.4 parts by mass of propyl acetate and 94.9 parts by mass of isopropyl alcohol were added, and then 7.1 parts by mass of isophorondiamine and 4.2 parts by mass of aminoethylethanolamine were added to carry out a chain extension reaction. Then, 2.4 parts by mass of ethylenediamine was further added to terminate the reaction to obtain a polyurethane resin varnish for gravure back printing (solid content: 25% by mass, mass average molecular weight of polyurethane resin about 12,000).

<Manufacturing example 2>
<Manufacturing of polyamide resin varnish for flexographic printing>
A polyamide resin varnish for flexographic printing having a solid content of 50% is obtained by dissolving 50 parts by mass of a polyamide resin (Pneumide 850, manufactured by Harima Kasei Co., Ltd.) in a mixed solvent consisting of 25 parts by mass of normal propyl alcohol and 25 parts by mass of isopropyl alcohol. Obtained.

<Manufacturing of polyamide resin varnish for gravure printing>
Polyamide resin (Neumide 850, manufactured by Harima Kasei Co., Ltd.) 25 parts by mass is dissolved in a mixed solvent consisting of 37.5 parts by mass of methylcyclohexane and 37.5 parts by mass of isopropyl alcohol to dissolve a 25% solid content polyamide for flexographic printing. Obtained a resin varnish.

<Manufacturing example 3>
<Manufacturing of cellulose derivative varnish for flexographic front printing and back printing>
28.6 parts by mass of nitrocellulose (SS1 / 8S, manufactured by KOREA CNC, solid content 70% by mass) is dissolved in a mixed solvent consisting of 16 parts by mass of propyl acetate and 55.4 parts by mass of normal propyl alcohol, and the solid content is 20. A mass% of nitrocellulose derivative varnish for front printing and back printing was obtained.

<Manufacturing of cellulose derivative varnish for gravure front printing and back printing>
28.6 parts by mass of nitrocellulose (SS1 / 4S, manufactured by KOREA CNC, solid content 70% by mass) is dissolved in a mixed solvent consisting of 64 parts by mass of propyl acetate and 7.4 parts by mass of normal propyl alcohol, and the solid content is 20. A nitrocellulose derivative varnish for gravure front printing and back printing of mass% was obtained.

<Examples 1-1 to 4-4, Comparative Examples 1-1 to 4-7>
<Preparation of ink composition>
The materials shown in Tables 1 to 4 were kneaded with a paint conditioner to prepare ink compositions of Examples 1-1 to 4-4 and Comparative Examples 1-1 to 4-7. The numerical values shown in Table 1 are mass%.

<Making printed matter>
<Preparation of flexographic printed matter for front printing>
The ink compositions of Examples 1-1 to 1-4 and Comparative Examples 1-1 to 1-7 obtained above were applied to a PET film (trade name "E5102 # 12", manufactured by Toyobo Co., Ltd.) on a flexo. After printing and drying with a printing machine (coating speed: 100 m / min, 60 ° C.) for 1 day, the following evaluation was performed.

<Making flexographic printed matter for back printing>
The ink compositions of Examples 2-1 to 2-4 and Comparative Examples 2-1 to 2-7 obtained above were applied to a PET film (trade name "E5102 # 12", manufactured by Toyobo Co., Ltd.) on a flexo. After printing and drying with a printing machine (coating speed: 100 m / min, 60 ° C.) for 1 day, the following evaluation was performed.

<Making gravure printed matter for front printing>
The ink compositions of Examples 3-1 to 3-4 and Comparative Examples 3-1 to 3-7 obtained above were applied to a PET film (trade name "E5102 # 12", manufactured by Toyobo Co., Ltd.) in a gravure manner. After printing and drying with a printing machine (coating speed: 100 m / min, printing plate: direct 175-line solid plate, drying temperature: 50 ° C. (air volume 80%)), the following evaluation was performed. ..

<Making gravure printed matter for back printing>
The ink compositions of Examples 4-1 to 4-4 and Comparative Examples 4-1 to 4-7 obtained above were applied to a PET film (trade name "E5102 # 12", manufactured by Toyobo Co., Ltd.) in a gravure manner. After printing and drying with a printing machine (coating speed: 100 m / min, printing plate: direct 175-line solid plate, drying temperature: 50 ° C. (air volume 80%)), the following evaluation was performed. ..

The ink compositions or printed matter obtained in the above Examples and Comparative Examples were evaluated as follows. The evaluation results are shown in Tables 1 to 4.

<Evaluation of dispersion stability>
For the evaluation of dispersion stability, the viscosity (initial viscosity) of each ink composition obtained above was measured at 30 rpm of a B-type viscometer. Further, each ink composition was sealed in a glass bottle and left at 40 ° C. for 7 days, and then the viscosity (viscosity with time) at 30 rpm of a B-type viscometer was measured and evaluated in the following three stages.
A: Initial viscosity is 2.0 ± 1.0 ps and viscosity over time is less than ± 0.2 ps of initial viscosity B: Initial viscosity is 2.0 ± 1.0 ps and viscosity over time is ± 0. 2ps or more C: Initial viscosity does not reach 2.0 ± 1.0ps

<Evaluation of weather resistance>
The weather resistance was evaluated by irradiating each printed matter obtained above with light with a fade meter and visually evaluating the degree of discoloration in the following three stages.
A: No discoloration after 40 hours of irradiation B: No discoloration after 20 hours of irradiation, but there is discoloration after 40 hours of irradiation C: Slight discoloration after 20 hours of irradiation

<Evaluation of luminescence suitability>
The light emission suitability was evaluated by holding a black light over each of the printed matter obtained above, and visually evaluating the light emission from the printed matter in the following two stages.
A: emits light C: does not emit light

<Evaluation of blocking resistance>
The blocking resistance was evaluated by combining the printed and non-printed surfaces of each printed matter obtained above, squeezing them with a vise, leaving them at 40 ° C for 12 hours, and then peeling them off by hand. The strength of the resistance was evaluated in the following three stages.
A: There is no peeling of the printed film and no peeling resistance is felt. B: There is no peeling of the printed film, but peeling resistance is felt. C: There is peeling of the printed film and peeling resistance is strongly felt.

<Evaluation of adhesiveness>
In the evaluation of the adhesiveness, the cellophane tape was attached to the printed matter in each of the printed matter obtained above, and the degree of peeling of the printed film from the film when the cellophane tape was rapidly peeled off was evaluated in the following three stages.
A: There is no peeling of the print film from the film B: There is peeling of the print film from the film, but the peeling area is less than 30% C: There is peeling of the printing film from the film, and the peeling area is 30% or more. Is

<Evaluation of abrasion resistance>
Using a Gakushin type friction fastness tester (trade name "RT200", manufactured by Daiei Kagaku Seiki Co., Ltd.), bleach the printed matter of each printed matter with a bleached cloth (trade name "Attached white cloth Kanakin No. 3 for dyeing fastness test"). Friction was performed 100 times under a load of 200 g, and the degree of peeling of the printed film from the film was evaluated in the following three stages.
A: There is no peeling of the print film from the film B: There is peeling of the print film from the film, but the peeling area is less than 30% C: There is peeling of the printing film from the film, and the peeling area is 30% or more. Is

<Evaluation of laminate strength>
The evaluation of the laminate strength was performed by mixing an adhesive (trade name "Takelac A-515" and trade name "Takenate A-50" in a 10/1 mass ratio with the printed film in each printed matter obtained above, and acetic acid. A solid content adjusted to 30% by mass with ethyl, both manufactured by Mitsui Chemicals, was applied, and a polyethylene film (trade name "Unilux LS-711C # 50", manufactured by Idemitsu Unitech) was attached. After aging at 40 ° C. for 72 hours, the peel strength at a peeling speed of 300 mm / min was evaluated in the following three stages.
A: Strength is 500 g / 15 mm or more B: Strength is 200 g or more and less than 500 g / 15 mm C: Strength is less than 200 g / 15 mm

<Evaluation of doctor cutability>
The evaluation of the doctor breakability was performed by printing the ink compositions according to Examples 3-1 to 4-4 and Comparative Examples 3-1 to 4-7 obtained above with a gravure printing machine at a printing speed of 100 m /. The state of the printed surface at the time of minutes was evaluated in the following three stages.
A: Plate fog, betasji, two-two stains (linear stains) do not occur B: Plate fog, betasji, two-two stains (linear stains) occur slightly C: Plate fog, betasji, two-two stains (linear stains) ) Etc. occur a lot

In Tables 1 to 4,
Pigment Yellow 14 is described by C.I. I. Pigment Yellow 14 (In the general formula (1), R ^{1 to} R ⁴ are hydrogen atoms, R ⁵ is a methyl group, R ⁶ is a hydrogen atom, R ⁷ is a chlorine atom, and R ^{8 to} R ⁹ are hydrogen atoms). ;
Pigment Orange 16 is described by C.I. I. Pigment orange 16 (in the general formula (1), R ^{1 to} R ⁵ are hydrogen atoms, R ⁶ is a hydrogen atom, R ⁷ is a methoxy group, and R ^{8 to} R ⁹ are hydrogen atoms);
Pigment Yellow 74 is described by C.I. I. Pigment Yellow 74;
Pigment Orange 13 is described in C.I. I. Pigment Orange 13;
The yellow fluorescent pigment is FZ-3045S Lemon Yellow (manufactured by Shinroihi);
The orange fluorescent pigment indicates FZ-3044 Orange (manufactured by Shinroihi);

Claims (4)

A flexographic printing ink composition containing a pigment, a binder resin, and a solvent.
The ink composition is used for determining the authenticity of printed matter under ultraviolet irradiation.
The pigment is the general formula (1) :.

(In the general formula (1), R ^{1 to} R ⁵ independently represent a hydrogen atom, a halogen atom, a methyl group, an ethyl group, a methoxy group, or an ethoxy group, and R ^{6 to} R ⁹ independently represent. , Hydrogen atom, halogen atom, methyl group, ethyl group, methoxy group, or ethoxy group ^{, and at least one of R 6 to} R ⁹ is a halogen atom, methyl group, ethyl group, methoxy group, or ethoxy group. Represents a compound, represented by)
General formula (2):

(In the general formula (2), R ^{1 to} R ⁵ independently represent a hydrogen atom, a halogen atom, a methyl group, an ethyl group, a methoxy group, or an ethoxy group, and R ^{6 to} R ⁹ independently represent. , A hydrogen atom, a halogen atom, a methyl group, an ethyl group, a methoxy group, or an ethoxy group ^{, and at least one of R 6 to} R ⁹ is a halogen atom, a methyl group, an ethyl group, a methoxy group, or an ethoxy group. The compound represented by), and the general formula (3) :.

(In the general formula (3), R ^{1 to} R ⁵ independently represent a hydrogen atom, a halogen atom, a methyl group, an ethyl group, a methoxy group, or an ethoxy group, and R ^{6 to} R ⁹ independently represent. , A hydrogen atom, a halogen atom, a methyl group, an ethyl group, a methoxy group, or an ethoxy group ^{, and at least one of R 6 to} R ⁹ is a halogen atom, a methyl group, an ethyl group, a methoxy group, or an ethoxy group. It is one or more kinds of fluorescent organic pigments selected from the group consisting of the compounds represented by).
The binder resin is a base polymer selected from the group consisting of polyurethane resin and polyamide resin, and a cellulose derivative.
An ink composition characterized in that the mass ratio of the base polymer to the cellulose derivative (base polymer / cellulose derivative) is 65/35 to 90/10. The ink composition according to claim 1, wherein the pigment is 50 to 200 parts by mass with respect to 100 parts by mass of the binder resin. The pigment is C.I. I. Pigment Yellow 12, C.I. I. Pigment Yellow 13, C.I. I. Pigment Yellow 14, C.I. I. Pigment Yellow 15, C.I. I. Pigment Yellow 16, C.I. I. Pigment Yellow 17, C.I. I. Pigment Yellow 55, C.I. I. Pigment Yellow 63, C.I. I. Pigment Yellow 77, C.I. I. Pigment Yellow 81, C.I. I. Pigment Yellow 83, C.I. I. Pigment Yellow 87, C.I. I. Pigment Yellow 106, C.I. I. Pigment Yellow 113, C.I. I. Pigment Yellow 114, C.I. I. Pigment Yellow 124, C.I. I. Pigment Yellow 126, C.I. I. Pigment Yellow 127, C.I. I. Pigment Yellow 152, C.I. I. Pigment Yellow 170, C.I. I. Pigment Yellow 172, C.I. I. Pigment Yellow 176, C.I. I. Pigment Orange 15, and C.I. I. The ink composition according to claim 1 or 2, wherein the ink composition is one or more selected from the group consisting of pigment orange 16. A printed matter characterized by being printed using the ink composition according to any one of claims 1 to 3.