JP6981562B1 - Gravure printing ink sets, printed matter, and packaging materials - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a gravure printing ink set excellent in safety and health and environmental protection, which does not contain halogen atoms, heavy metals affecting the environment, and primary aromatic amines, or even if they contain them, the amount thereof is extremely small. Providing printed matter and packaging materials. SOLUTION: The above-mentioned problems are a cyan ink containing a phthalocyanine pigment represented by the formula (1) and a binder resin, a yellow ink containing an isoindoline pigment represented by the general formula (2) and a binder resin, and a general one. It is solved by a gravure printing ink set containing magenta ink containing at least one pigment selected from the group consisting of the formulas (3) to (5) and a binder resin. [Selection diagram] None

Description

The present invention relates to a gravure printing ink set containing cyan ink, yellow ink, and magenta ink, and a printed matter and a packaging material using the ink set.

In recent years, plastic products such as packages and plastic bottles using plastic films have been disposed of and dumped as garbage in the ocean, which has become a problem of environmental pollution. These plastic products are decomposed in seawater into submicron-sized fragments (microplastics) that float in seawater. Such microplastics have fine irregularities on the surface and have a property of easily adsorbing harmful chemical substances. In addition, the microplastic itself may contain harmful chemical substances.
Then, when marine organisms mistakenly ingest microplastics as food, there is a concern that harmful chemical substances derived from microplastics may accumulate in the bodies of marine organisms and affect the ecosystem. Furthermore, when humans ingest the marine organisms, there is concern that harmful chemical substances will accumulate in the human body.

As an attempt to reduce microplastics, plastic products are recycled, and the main recycling methods include (1) material recycling, (2) chemical recycling, and (3) thermal recycling.

Examples of the above (1) include a method in which plastic products are sorted by resin, impurities are removed, and then crushed, washed, and melted to form pellets, and the pellets are used to make new products. .. However, when the resin is melted, heat of 200 ° C. or higher is usually applied. Therefore, if the plastic product contains an ink containing a large amount of halogen atoms or primary aromatic amines, use a halogen gas or an acid gas. Some hydrogen chloride etc. may be generated and damage the equipment. In addition, primary aromatic amines may affect the human body.
Further, Patent Document 1 discloses a technique for desorbing ink or the like from a plastic film with an alkaline aqueous solution. However, even if the ink can be desorbed from the plastic product, the desorbed ink must be finally disposed of after being incinerated or the like. Therefore, if the ink contains a large amount of halogen atoms or primary aromatic amines, halogen gas may be generated during incineration to damage the incinerator, and harmful gases such as dioxins may be generated. Aromatic amines can affect the human body. In addition, since the metal remains unburned even when incinerated, it is difficult to dispose of it in landfill if the ink contains heavy metals that affect the soil.

Similarly, in the above (2) and (3), if the ink adhering to the plastic product contains halogen atoms, halogen gas or hydrogen chloride may be generated and damage the furnace, and harmful gas such as dioxin may be generated. There is. Further, in the case of (3), when the ink adhering to the plastic product contains heavy metals that affect the soil, the metals remain unburned even when incinerated, and it is difficult to dispose of them in landfill.

In this way, it is difficult to recycle plastic products that are safe and have a reduced environmental impact, and they do not contain halogen atoms, primary aromatic amines, and heavy metals that affect the environment, or even if they do, the amount is extremely small. Therefore, no gravure printed matter capable of forming a plastic product excellent in safety and health and reduction of environmental load has been reported.

Japanese Patent No. 6631964

The subject of the present invention is gravure printing excellent in safety and health and environmental protection, which does not contain halogen atoms, heavy metals that affect the environment, and primary aromatic amines, or even if they contain them, the amount thereof is extremely small. The purpose is to provide ink sets, printed matter, and packaging materials.

［一般式（２）中、Ｘ_１〜Ｘ_４は、それぞれ独立して、水素原子、ニトロ基、アルキル基、アルコキシ基、アリール基、アリールオキシ基、チオアルキル基、又はチオアリール基を表す。Ｘ_５及びＸ_６は、それぞれ独立して、水素原子、又はアルキル基を表す。Ａは、一般式（２−１）、又は（２−２）で表される基を表す。
一般式（２−１）中、Ｙ₁は−Ｏ−又は−ＮＨ−を表し、Ｘ_７は水素原子、アルキル基、又はアリール基を表す。
一般式（２−２）中、Ｘ_８及びＸ_９は、それぞれ独立して、水素原子又はアルキル基を表す。］

［一般式（３）中、Ｘ_１０〜Ｘ_１７は、それぞれ独立して、水素原子、又はアルキル基を表す。
一般式（４）中、Ｘ_１８〜Ｘ_２７は、それぞれ独立して、水素原子、アルキル基、シアノ基、アルコキシ基、チオアルキル基、又は置換基を有してよいアリール基を表す。
一般式（５）中、Ｙ_２は−Ｏ−又は−ＮＲ−を表し、Ｒは、水素原子、アルキル基、又は置換基を有してよいアリール基を表す。］ The present invention is a cyan ink containing a pigment represented by the following formula (1) and a binder resin.
A yellow ink containing a pigment represented by the following general formula (2) and a binder resin, and a magenta ink containing at least one pigment selected from the group consisting of the following general formulas (3) to (5) and a binder resin. With respect to gravure printing ink sets, including.

[In the general formula (2), X _{1 to} X ₄ independently represent a hydrogen atom, a nitro group, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a thioalkyl group, or a thioaryl group. X ₅ and X ₆ each independently represent a hydrogen atom or an alkyl group. A represents a group represented by the general formula (2-1) or (2-2).
In the general formula (2-1), Y ₁ represents -O- or -NH-, and X ₇ represents a hydrogen atom, an alkyl group, or an aryl group.
In the general formula (2-2), _{X 8} and _{X 9} each independently represent a hydrogen atom or an alkyl group. ]

[In the general formula (3), X _{10 to} X ₁₇ each independently represent a hydrogen atom or an alkyl group.
In the general formula (4), X _{18 to} X ₂₇ each independently represent an aryl group which may have a hydrogen atom, an alkyl group, a cyano group, an alkoxy group, a thioalkyl group, or a substituent.
In the general formula (5), Y ₂ represents -O- or -NR-, and R represents an aryl group which may have a hydrogen atom, an alkyl group, or a substituent. ]

The present invention relates to the above gravure printing ink set, wherein the pigment represented by the general formula (2) contains at least one pigment selected from the group consisting of the following formulas (6) to (8).

The present invention relates to the above gravure printing ink set, wherein at least one pigment selected from the group consisting of the general formulas (3) to (5) contains a pigment represented by the general formula (3).

In the present invention, the amount of halogen contained in the cyan ink, the yellow ink, and the magenta ink is 100 ppm or less, and the amount of the primary aromatic amine is 500 ppb or less, respectively. The present invention relates to the above-mentioned gravure printing ink set having an amount of 10 ppm or less.

The present invention further relates to the above gravure printing ink set, which comprises a clear ink having desorption property.

The present invention relates to a printed matter including a printed layer formed from the gravure printing ink set and a base material layer.

The present invention relates to the above printed matter, which comprises a removable layer.

The present invention relates to a packaging material using the above printed matter.

INDUSTRIAL APPLICABILITY According to the present invention, a gravure printing ink set excellent in safety and health and environmental protection, which does not contain halogen atoms, heavy metals affecting the environment, and primary aromatic amines, or even if the amount thereof is extremely small, is contained. , Printed matter, and packaging materials can be provided.

The gravure printing ink set of the present invention includes a cyan ink containing a phthalocyanine pigment represented by the formula (1) and a binder resin, a yellow ink containing an isoindoline pigment represented by the general formula (2) and a binder resin, and a yellow ink. It is characterized by containing a magenta ink containing at least one pigment selected from the group consisting of the general formulas (3) to (5) and a binder resin.
Cyan that forms the three primary colors by specifying the pigments contained in cyan ink, yellow ink, and magenta ink as those that do not contain halogen atoms and heavy metals that affect the environment, and do not contain or generate primary aromatic amines. The contents of halogen atoms, environmentally damaging heavy metals, and primary aromatic amines can be significantly reduced in all three colors, yellow, magenta, and magenta.
By reducing the amount of halogen atoms, the generation of toxic gas such as dioxin during combustion can be reduced, and the safety during combustion can be improved. In addition, since the generation of hydrogen chloride gas and the like can be reduced, corrosion to an incinerator or the like can be prevented.
By reducing the amount of heavy metals that affect the environment, it is possible to reduce the impact on soil, plants, and even ecosystems when landfilling waste.
By reducing the amount of primary aromatic amines, it is possible to reduce the generation of toxic gases during combustion and the outflow of chemical substances into the environment that may endanger health during landfill.
As a result, the printed matter and the packaging material obtained by using the ink set have a significantly reduced content of the above-mentioned components, and are excellent in safety and hygiene and environmental protection.
Hereinafter, the present invention will be described in detail.

In addition, in this specification, the notation of "(meth) acryloyl", "(meth) acrylic", "(meth) acrylic acid", "(meth) acrylate", and "(meth) acrylamide" is particularly described. Unless otherwise indicated, they represent "acrylloyl and / or methacrylic acid", "acrylic and / or methacrylic acid", "acrylic acid and / or methacrylic acid", "acrylate and / or methacrylate", and "acrylamide and / or methacrylic acid", respectively. ..

<Gravure printing ink set>
The gravure printing ink set used in the present invention assists pigments, binder resins, organic solvents, and other pigment dispersants, leveling agents, defoaming agents, waxes, plasticizers, infrared absorbers, and ultraviolet absorbers as necessary. It is a set containing three color inks of cyan ink, magenta ink, and yellow ink containing agents.
The gravure printing ink set of the present invention may contain other inks such as black ink, white ink, and spot color ink as long as the effects of the present invention are not impaired.

<Cyan ink>
The cyan ink in the present invention contains a phthalocyanine pigment (1) represented by the following formula (1) and a binder resin.

The ink set of the present invention contains the phthalocyanine pigment (1) in the cyan ink, so that it does not contain halogen atoms, primary aromatic amines, and heavy metals that affect the environment, and has excellent trapping properties as a printing ink. It is possible to provide a gravure printing ink set having a required hue.

The method for producing the pigment (1) represented by the formula (1) is not particularly limited, and for example, a specific metallic phthalocyanine can be synthesized by a demetallizing reaction by contacting with an acid.
Examples of the metallic phthalocyanine include lithium phthalocyanine, sodium phthalocyanine, calcium phthalocyanine, and magnesium phthalocyanine.
Examples of the acid include sulfuric acid and hydrochloric acid.
Further, a method of directly obtaining from phthalonitrile, 1,3-diiminoisoindoline or the like can also be mentioned.

Any known method may be used for producing metallic phthalocyanine, and for example, phthalic acids, urea, metals or metal salts, catalysts and the like may be heated in the presence or absence of an organic solvent. Can be manufactured.

After synthesis, the pigment (1) is preferably separated from the reaction solvent such as filtration of the solvent and distilling off the solvent, and then washed with water or an organic solvent. Acids and alkalis may be used for cleaning. If further purification is required, impurities may be removed by operations such as sublimation, acid paste, acid slurry, reprecipitation, recrystallization, and extraction, which are known purification techniques.

Further, the phthalocyanine pigment represented by the formula (1) may be used as it is synthesized, but it may be used for purposes such as transfer to a desired crystal type, control of particle size, and impartation of easy dispersibility. , It is preferable to carry out the operation of pigmentation. Pigmentization is the process of processing a crude pigment called crudo, which is a coarse crystal and has a wide particle size distribution, into a state where it can be used as a pigment through processes for the purposes of purification, control of crystal shape and particle size, surface treatment, etc. Examples of the treatment include a solvent method, a solvent milling method, and a solvent salt milling method. As a pretreatment for the pigmentation treatment, operations such as acid paste and dry milling may be further performed, or a plurality of pigmentation methods may be used in combination.

Further, the cyan ink in the present invention may contain any combination of known colorants, if necessary, as long as the effects of the present invention are not deviated.
The content of the colorant containing the phthalocyanine pigment (1) in the cyan ink is preferably 4 to 15% by mass, more preferably 5 to 12% by mass, based on the mass of the cyan ink.

<Yellow ink>
The yellow ink in the present invention contains an isoindoline pigment (2) represented by the following general formula (2) and a binder resin.

In the general formula (2), X _{1 to} X ₄ independently represent a hydrogen atom, a nitro group, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a thioalkyl group, or a thioaryl group. X ₅ and X ₆ each independently represent a hydrogen atom or an alkyl group. A represents a group represented by the general formula (2-1) or (2-2).
In the general formula (2-1), Y ₁ represents -O- or -NH-, and X ₇ represents a hydrogen atom, an alkyl group, or an aryl group.
In the general formula (2-2), _{X 8} and _{X 9} each independently represent a hydrogen atom or an alkyl group.

The ink set of the present invention contains the above-mentioned isoindoline pigment (2) in the yellow ink, so that it does not contain halogen atoms, primary aromatic amines, and heavy metals that affect the environment, and has excellent trapping properties for printing. It is possible to provide a gravure printing ink set having a hue required as an ink.

In the general formula (2), an alkyl group (-R) in X ₁ to X ₆ refers to removing one atomic hydrogen atoms from a hydrocarbon, a linear structure, branched structure, single ring structures, or condensation Any of the polycyclic structures may be used.
Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a dodecyl group, an octadecyl group, an isopropyl group, an isobutyl group and an isopentyl group. Group, 2-ethylhexyl group, 2-hexyldodecyl group, sec-butyl group, tert-butyl group, sec-pentyl group, tert-pentyl group, tert-octyl group, neopentyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group , Cyclohexyl group, adamantyl group, norbornyl group, boronyl group, 4-decylcyclohexyl group and the like.

The alkyl group may have a structure in which two or more alkyl groups (where one is an alkylene group) are bonded to each other via a linking group. Specific examples of the linking group include an ester bond (-COO-), an ether bond (-O-), and a sulfide bond (-S-). That is, in the present specification, the alkyl group includes, for example, a group represented by "-R'-OR"(R'represents an atomic group obtained by removing one hydrogen atom from the above alkyl group). Specific examples of such a group include -C ₂ H _4- OC ₂ H ₅ .

In the general formula _(2), the carbon number of the alkyl group in X 1 to X ₆ is preferably 1 to 10, more preferably 1 to 6, more preferably from 1 to 4, particularly preferably 1 Or 2.

In the general formula _(2), the alkoxy group in X 1 to X ₄ is a group corresponding to the alkyl groups mentioned above (-R) bound (-OR).

Formula (2) _in, X 1 to X ₄ definitive aryl group (-Ar) means removing one atomic hydrogen atom from an aromatic hydrocarbon.
Examples of the aryl group include a phenyl group, a trill group, a xylyl group, a biphenylyl group, a terphenylyl group, a quarterphenylyl group, a pentarenyl group, an indenyl group, a naphthyl group, a binaphthalenyl group, a turnaphthalenyl group, a quarternaphthalenyl group and an azulenyl group. , Heptalenyl group, biphenylenyl group, indacenyl group, fluoranthenyl group, acephenantrilenyl group, aceanthryleneyl group, phenalenyl group, fluorenyl group, anthryl group, bianthrasenyl group, taranthrasenyl group, quarter anthrasenyl group , Anthraquinolyl group, phenanthryl group, triphenylenyl group, pyrenyl group, chrysenyl group, naphthalsenyl group, pryadenyl group, pisenyl group, peryleneyl group, pentaphenyl group, pentasenyl group, tetraphenylenyl group, hexaphenyl group, hexasenyl group, rubisenyl Examples thereof include a group, a coronenyl group, a trinaphthylenyl group, a heptaphenyl group, a heptasenyl group, a pyrantrenyl group, or an ovalenyl group, a methoxyphenyl group and an ethoxyphenyl group.
The aryl group preferably has 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms. Most preferably, the aryl group is a phenyl group.

In the general formula _(2), an aryloxy group in X 1 to X _4, is a group in which an oxygen atom of the above aryl group (-Ar) bound (-OAr). In one embodiment, the aryloxy group is preferably a phenoxy group.

In the general formula _(2), X 1 ~X ₄ definitive thioalkyl group is a group (-SR) where the sulfur atom to an alkyl group as described above bonded. In one embodiment, the thioalkyl group is preferably a group in which a sulfur atom is bonded to an alkyl group having a linear structure.
The thioaryl group is a group (-SAr) in which a sulfur atom is bonded to the above-mentioned aryl group. In one embodiment, the thioaryl group is preferably a thiophenyl group.

_{In one embodiment, X 1 to} X ₄ in the general formula (2) are independently a hydrogen atom, a nitro group, an alkyl group having 1 to 6 carbon atoms, and an alkoxy group (the alkyl group has 1 to 6 carbon atoms). ), A phenyl group, a phenoxy group, a thioalkyl group (the alkyl group has 1 to 6 carbon atoms), and a thiophenyl group is preferably selected.

In the general formula (2-1), Y ₁ represents −O− or −NH−, preferably −NH−.
In X _7, alkyl and aryl groups may incorporated description in the preceding formula (2). From the viewpoint of heat resistance, weather resistance, and dispersion stability, the alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, still more preferably 1 to 4 carbon atoms, and particularly preferably 1 to 4 carbon atoms. 1 or 2.

In _{X 8} and _{X 9} in formula (2-2), the alkyl group has the same meaning as previously described. From the viewpoint of heat resistance, weather resistance, and dispersion stability, the alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, still more preferably 1 to 4 carbon atoms, and particularly preferably 1 to 4 carbon atoms. 1 or 2.

The isoindoline pigment (2) represented by the general formula (2) is preferably the pigments (6) to (24) represented by the following formulas (6) to (24).

Above all, from the viewpoint of heat resistance, weather resistance, and dispersion stability, at least one selected from the group consisting of pigments (6) to (8) represented by the above formulas (6) to (8) is more preferable. It contains the pigment of.

The isoindoline pigment (2) is preferably used after being finely divided and processed into fine particles. Examples of the miniaturization treatment include a dissolution precipitation method typified by acid pacing, solvent salt milling, and dry milling. The average primary particle size of the finely divided pigment particles is preferably 20 to 300 nm, more preferably 50 to 150 nm. Depending on the solvent salt milling conditions, the particle size of the pigment particles may grow.

The isoindoline pigment (2) represented by the general formula (2) may be used alone or in combination of two or more.
When the yellow ink in the present invention contains two or more kinds of isoindoline pigments (2), the following can be mentioned as a method for producing the same.
(I) A method of synthesizing two or more kinds at once (co-synthesis method), (II) a method of mixing two or more kinds of isoindoline pigments at the time of preparing a dispersion, (III) a method of mixing two or more kinds of isoindoline pigments together. A method of pigmenting using an acid pacing method, an acid slurry method, a dry milling method, a salt milling method, a solvent salt milling method, a solvent method, etc., and (IV) a method combining the above methods.
Of these, preferred are (I) co-synthesis method, (III) acid pacing method together, method of pigmentation using solvent salt milling method, and (IV) method of combining (I) and (III). Either.

The yellow ink in the present invention may contain, if necessary, any combination of known colorants as long as the effects of the present invention are not deviated.
The content of the colorant containing the isoindoline pigment (2) in the yellow ink is preferably 4 to 15% by mass, more preferably 5 to 12% by mass, based on the mass of the yellow ink. ..

<Magenta ink>
The magenta ink in the present invention contains at least one pigment selected from the group consisting of the following general formulas (3) to (5) and a binder resin.

In the general formula (3), X _{10 to} X ₁₇ each independently represent a hydrogen atom or an alkyl group.
In the general formula (4), X _{18 to} X ₂₇ each independently represent an aryl group which may have a hydrogen atom, an alkyl group, a cyano group, an alkoxy group, a thioalkyl group, or a substituent.
In the general formula (5), Y ₂ represents -O- or -NR-, and R represents an aryl group which may have a hydrogen atom, an alkyl group, or a substituent.

The ink set of the present invention contains at least one pigment selected from the group consisting of the above general formulas (3) to (5) in magenta ink, so that it can be used for halogen atoms, primary aromatic amines, and the environment. It is possible to provide a gravure printing ink set that is excellent in trapping property and has a hue required as a printing ink without containing heavy metals that affect the printing ink.

[Pigment represented by the general formula (3)]
The pigment (3) represented by the general formula (3) is a quinacridone pigment.
In the general formula (3), the _{alkyl group (-R) in X 10 to} X ₁₇ means an atomic group obtained by removing one hydrogen atom from a hydrocarbon, and has a linear structure, a branched structure, a monocyclic structure, or a condensation. Any of the polycyclic structures may be used.

Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a dodecyl group, an octadecyl group, a trifluoromethyl group and an isopropyl group. Group, isobutyl group, isopentyl group, 2-ethylhexyl group, 2-hexyldodecyl group, sec-butyl group, tert-butyl group, sec-pentyl group, tert-pentyl group, tert-octyl group, neopentyl group, cyclopropyl group , Cyclobutyl group, cyclopentyl group, cyclohexyl group, adamantyl group, norbornyl group, boronyl group, 4-decylcyclohexyl group and the like.

The alkyl group may have a structure in which two or more alkyl groups (where one is an alkylene group) are bonded to each other via a linking group. Specific examples of the linking group include an ester bond (-COO-), an ether bond (-O-), and a sulfide bond (-S-). That is, in the present specification, the alkyl group includes, for example, a group represented by "-R'-OR"(R'represents an atomic group obtained by removing one hydrogen atom from the above alkyl group). .. Specific examples of such a group include -C ₂ H _4- OC ₂ H ₅ .

The _{number of carbon atoms of the alkyl group in X 10 to} X ₁₇ is preferably 1 to 10, more preferably 1 to 6, still more preferably 1 to 4, and particularly preferably 1 or 2.

The quinacridone pigment (3) used in the present invention can be synthesized by a known method. Industrially, (1) thermal process, (2) PPA process and the like are known, and (1) thermal is preferable from the viewpoint that the content of aniline, which is a primary aromatic amine, is very small. It is a process.

The pigment (3) represented by the general formula (3) is preferably the pigments (25) to (29) represented by the following formulas (25) to (29).

[Pigment represented by the general formula (4)]
The pigment (4) represented by the general formula (4) is a diketopyrrolopyrrole (hereinafter DPP) pigment.
_{As the alkyl group in X 18 to} X ₂₇ of the general formula (4), _{the description in X 10 to} X ₁₇ of the above general formula (3) can be incorporated. The _{number of carbon atoms of the alkyl group in X 18 to} X ₂₇ is preferably 1 to 10, more preferably 1 to 6, still more preferably 1 to 4, and particularly preferably 1 or 2.

In the general formula (4), the _{alkoxy group in X 18 to} X ₂₇ is a group (-OR) in which an oxygen atom is bonded to the above-mentioned alkyl group (-R).

In the general formula _(4), thioalkyl group in X 18 _{to X 27} is a group (-SR) where the sulfur atom to an alkyl group as described above bonded. In one embodiment, the thioalkyl group is preferably a group in which a sulfur atom is bonded to an alkyl group having a linear structure.

In the general formula (4), the _{aryl group (-Ar) which may have a substituent in X 18 to} X ₂₇ is an atomic group obtained by removing one hydrogen atom from an aromatic hydrocarbon.
Examples of the aryl group include a phenyl group, a tolyl group, a xylyl group, a biphenylyl group, a terphenylyl group, a quarterphenylyl group, a pentarenyl group, an indenyl group, a naphthyl group, a binaphthalenyl group, a turnaphthalenyl group, a quarternaphthalenyl group and an azulenyl group. Group, heptalenyl group, biphenylenyl group, indacenyl group, fluoranthenyl group, acephenantrilenyl group, aceanthryleneyl group, phenalenyl group, fluorenyl group, anthryl group, bianthrasenyl group, taranthrasenyl group, quarter anthrasenyl group Group, anthraquinolyl group, phenanthryl group, triphenylenyl group, pyrenyl group, chrysenyl group, naphthalsenyl group, pryadenyl group, pisenyl group, perylenelyl group, pentaphenyl group, pentasenyl group, tetraphenylenyl group, hexaphenyl group, hexasenyl group, Examples thereof include a rubisenyl group, a coronenyl group, a trinaphthylenyl group, a heptaphenyl group, a heptasenyl group, a pyrandrenyl group, or an ovalenyl group, a methoxyphenyl group and an ethoxyphenyl group.
The aryl group in X _{18 to} X ₂₇ has preferably 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms. The phenyl group is most preferable as the aryl group.

The method for producing the diketopyrrolopyrrole pigment (4) used in the present invention is not particularly limited, and for example, as disclosed in JP-A-58-210084, the corresponding aromatic nitrile and succinic acid diester are contained in an organic solvent. It can be manufactured by reacting with.

The pigment (4) represented by the general formula (4) is preferably the pigments (30) to (41) represented by the following formulas (30) to (41).

[Pigment represented by the general formula (5)]
The pigment (5) represented by the general formula (5) is a perylene pigment.
In the general formula (5), the alkyl group in −NR— of _{Y 2} can incorporate the description in _{X 10 to} X _{17 of the above general formula (3).} Y number of carbon atoms in the alkyl group in -NR- ₂ is preferably 1 to 10, more preferably 1 to 6, more preferably 1 to 4, particularly preferably 1 or 2.

In the general formula (5), the aryl group which may have a substituent in −NR— of _{Y 2} can be incorporated from the description in _{X 18 to} X _{27 of the above general formula (4).} Y number of carbon atoms of the aryl group in -NR- ₂ is preferably 6 to 30, more preferably 6 to 20. The phenyl group is most preferable as the aryl group.

The perylene pigment (5) used in the present invention can be produced by a known method. For example, W. Herbst, K. et al. Examples include Hunger, Industrial Organic Pigments: Production, Properties, Applications, 1993, p467-p480 and the like. The method for producing the perylene pigment is not limited to this method.

The pigment (5) represented by the general formula (5) is preferably the pigments (42) to (53) represented by the following formulas (42) to (53).

In the magenta ink in the present invention, the pigments represented by the general formulas (3) to (5) may be used alone or in combination of two or more. When two or more kinds of pigments represented by the general formulas (3) to (5) are used in combination, they may be used as a solid solution.

The magenta ink in the present invention may contain any combination of known colorants, if necessary, as long as the effects of the present invention are not deviated.
The content of the colorant containing the pigments (3) to (5) in the magenta ink is preferably 4 to 15% by mass, more preferably 5 to 12% by mass, based on the mass of the magenta ink. Is.

<Binder resin>
The binder resin used in the gravure printing ink set of the present invention is, for example, a polyurethane resin, an ethylene-vinyl acetate copolymer resin, a vinyl acetate resin, a nitrocellulose resin, a polyamide resin, an acrylic resin, a polyester resin, an alkyd resin, and the like. Examples thereof include rosin-based resin, rosin-modified maleic acid resin, ketone resin, cyclized rubber, butyral, and petroleum resin.
From the viewpoint of containing no halogen atom, the binder resin preferably does not contain vinyl chloride-vinyl acetate copolymer resin, chlorinated polypropylene resin, polyvinyl chloride resin, rubber chloride and the like. However, it does not exclude inclusion within a range that does not deviate from the effect of the present invention.
These binder resins are independently selected for each of the colors cyan, yellow, and magenta, and one type may be used alone or two or more types may be used in combination.

[Polyurethane resin]
As the binder resin in the present invention, a polyurethane resin is preferably used.
The polyurethane resin in the present specification includes a polyurethane urea resin, and can be obtained by a conventionally known method.
As a known method, for example, a urethane prepolymer having an isocyanate group at the terminal obtained by reacting a polyol and a diisocyanate compound at a ratio of an excess of isocyanate groups is used to extend a chain having an amino group in an appropriate solvent. A two-step method of reacting with an agent and / or a terminal-blocking agent; or a one-step method of reacting polypropylene glycol, a combined polyol, a diisocyanate compound, a chain extender having an amino group and / or a terminal-blocking agent at once in a suitable solvent. Law;
Examples of the solvent include ester solvents such as ethyl acetate, propyl acetate and butyl acetate; ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone; alcohol solvents such as methanol, ethanol, isopropyl alcohol and n-butanol; A hydrocarbon solvent such as methylcyclohexane or ethylcyclohexane; or a mixed solvent thereof; may be mentioned.
Among these methods, the two-step method is preferable from the viewpoint of obtaining a more uniform polyurethane resin. When the polyurethane resin is produced by the two-step method, the equivalent ratio of the isocyanate group of the urethane prepolymer to the amino group of the chain extender and the terminal blocker (moll of isocyanate group / mol of amino group) is 1/1. It is preferably in the range of 3 to 1 / 0.9. When the equivalent ratio of the isocyanate group to the amino group is 1 / 1.3 or more, the chain extender and / or the terminal sequestering agent remaining unreacted is reduced, and the polyurethane resin is yellowed and has an odor after printing. It can be suppressed. When the equivalent ratio of the isocyanate group to the amino group is 1 / 0.9 or less, the molecular weight of the obtained polyurethane resin becomes appropriate, and a resin having suitable film strength after printing can be obtained.

The weight average molecular weight of the polyurethane resin is preferably in the range of 15,000 to 100,000. When the weight average molecular weight of the polyurethane resin is 15,000 or more, the blocking resistance of the ink, the strength of the printing film, and the oil resistance are excellent, and when it is 100,000 or less, the viscosity of the obtained ink is in an appropriate range. , Excellent gloss of printing film.

Further, the polyurethane resin preferably has an amine value from the viewpoint of printability and laminate strength. The amine value is preferably 0.5 to 20 mgKOH / g, more preferably 1 to 15 mgKOH / g.

The content of the binder resin in each color ink is preferably 4 to 25% by mass, more preferably 6 to 20% by mass, based on the mass of the ink.

<Manufacturing of ink>
The cyan, yellow, and magenta color inks in the present invention can be produced, for example, by dissolving and / or dispersing a colorant containing a predetermined pigment and a binder resin in an organic solvent. Specifically, a pigment, a binder resin solution, a pigment dispersant and the like are added as necessary, and the mixture is mixed and dispersed to produce a pigment dispersion, and then other additions are added to the obtained pigment dispersion as necessary. It can be manufactured by blending an agent or the like.

The particle size distribution of the pigment in the pigment dispersion can be adjusted by adjusting the size of the crushed media of the disperser, the filling rate of the crushed media, the dispersion treatment time, the discharge rate of the pigment dispersion, the viscosity of the pigment dispersion, and the like. can. As the disperser, generally used roller mills, ball mills, pebble mills, attritors, sand mills and the like can be used. If the ink contains air bubbles or unexpectedly coarse particles, it is preferable to remove them by filtration or the like in order to deteriorate the quality of the printed matter. As the filter, a conventionally known one can be used.

[Organic solvent]
As the organic solvent that may be used in the gravure printing ink set of the present invention, known organic solvents can be used, for example, aromatic organic solvents such as toluene and xylene; and ketone organic solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone. Ester-based organic solvents such as ethyl acetate, n-propyl acetate, butyl acetate, propylene glycol monomethyl ether acetate; alcohol-based organic solvents such as n-propanol, isopropanol, ethanolmethanol, ethanol, n-propanol, isopropanol, n-butanol; Glycol ether-based solvents such as ethylene glycol monopropyl ether and propylene glycol monomethyl ether; can be mentioned. It is preferable to use a mixture of two or more of these organic solvents.
Above all, it is preferable to use a mixed solvent of an ester-based organic solvent and an alcohol-based organic solvent. The mass ratio of the ester-based organic solvent to the alcohol-based organic solvent (mass of the ester-based organic solvent: mass of the alcohol-based organic solvent) is preferably 95: 5 to 40:60, more preferably 90: 10 to 50. : 50.
The content of the organic solvent in each color ink is preferably in the range of 60 to 90% by mass, more preferably 70 to 85% by mass, based on the mass of the ink.

The viscosity of each color ink is preferably 10 mPa · s or more from the viewpoint of preventing the pigment from settling and appropriately dispersing, and preferably 1,000 mPa · s or less from the viewpoint of workability efficiency during ink production or printing. The viscosity is a value measured at 25 ° C. with a B-type viscometer manufactured by Tokimec.

[Halogen amount]
In the gravure printing ink set of the present invention, all three colors do not contain halogen atoms, or even if they do contain halogen atoms, the amount of halogen is extremely small, so that the amount of halogen as an ink set can be significantly reduced.
The amount of halogen in the cyan ink is preferably 200 ppm or less, more preferably 100 ppm or less, based on the mass of the non-volatile content of the ink.
The amount of halogen in the yellow ink is preferably 200 ppm or less, more preferably 100 ppm or less, based on the mass of the non-volatile ink.
The amount of halogen in the magenta ink is preferably 200 ppm or less, more preferably 100 ppm or less, based on the mass of the non-volatile ink content.
Above all, it is particularly preferable that the amount of halogen contained in the cyan ink, the yellow ink, and the magenta ink is 100 ppm or less, respectively. By setting the amount of halogen in each ink to 100 ppm or less, the amount of halogen as an ink set becomes 100 ppm or less, which is more excellent in safety and can reduce the environmental load.

The halogen amount can be determined by a measuring method based on JIS K0127 (2013). In this measuring method, a sample pretreated by a combustion method is quantified by an ion chromatograph method. In the present specification, the ink is dried, the film thereof is scraped off, and the scraped dry matter is used. It can be determined by performing pretreatment by a combustion method and quantifying the halogen content of the obtained sample by ion chromatography.

[Primary aromatic amine]
Since all three colors of the gravure printing ink set of the present invention do not contain or have a very small amount of primary aromatic amine, the amount of primary aromatic amine as an ink set is significantly reduced. can do.
The primary aromatic amine in the present specification is a general term for compounds in which one hydrogen atom of ammonia is replaced with an aromatic atomic group.

The amount of the primary aromatic amine of the cyan ink is preferably 10 ppm or less, more preferably 1 ppm or less, and further preferably 500 ppb (detection limit) or less, based on the mass of the non-volatile content of the ink.
The amount of the primary aromatic amine of the yellow ink is preferably 10 ppm or less, more preferably 1 ppm or less, and further preferably 500 ppb (detection limit) or less, based on the mass of the non-volatile content of the ink.
The amount of the primary aromatic amine of magenta ink is preferably 10 ppm or less, more preferably 1 ppm or less, and further preferably 500 ppb (detection limit) or less, based on the mass of the non-volatile ink.
Above all, it is particularly preferable that the amount of the primary aromatic amine contained in the cyan ink, the yellow ink and the magenta ink is 500 ppb or less, respectively. By setting the amount of the primary aromatic amine in each ink to 500 ppb or less, the amount of the primary aromatic amine as an ink set becomes 500 ppb or less, which is more safe and reduces the environmental load. can.

[Heavy metals that affect the environment]
Since the gravure printing ink set of the present invention does not contain heavy metals that affect the environment in all three colors, or even if they contain a very small amount, the amount of heavy metals that affect the environment as an ink set is significantly reduced. Can be reduced.
Heavy metals are metals with a specific density of 4 or more, and most of the heavy metals are toxic to plants or affect people and the environment, so the permissible amount in soil is regulated.
For example, copper and zinc are known to cause growth inhibition when plants overdose, and mercury, cadmium, lead, hexavalent chromium, arsenic and the like have been found to have an effect on human health.
In addition, other heavy metals also have a large effect on soil, such as growth inhibition and chlorosis when plants are overdose, and organic matter resolution is reduced due to the effect on microorganisms in the soil, and they adhere to plastic packaging materials. It will be a harmful effect when printing ink is burned and an attempt is made to bury it.

On the other hand, among heavy metals, gold, platinum, titanium, vanadium, niobium, zirconium, and tungsten are known to exist stably in soil or have no toxicity to plants and the like. Iron is also a heavy metal, but it is indispensable for the growth of plants, and it is known that there is no problem even if it is present in soil if it is in a trace amount.

Therefore, the heavy metals that affect the environment in the present specification include chromium (Cr), manganese (Mn), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), arsenic (As), and the like. Selenium (Se), Ittrium (Y), Molybdenum (Mo), Palladium (Pd), Silver (Ag), Cadmium (Cd), Tin (Sn), Mercury (Hg), Antimony (Sb), Lead (Pb) means.

The amount of heavy metal affecting the environment of the cyan ink is preferably 100 ppm or less, more preferably 50 ppm or less, still more preferably 10 ppm or less, based on the mass of the non-volatile content of the ink.
The amount of heavy metal affecting the environment of the yellow ink is preferably 100 ppm or less, more preferably 50 ppm or less, still more preferably 10 ppm or less, based on the mass of the non-volatile ink content.
The amount of heavy metal affecting the environment of magenta ink is preferably 100 ppm or less, more preferably 50 ppm or less, still more preferably 10 ppm or less, based on the mass of the non-volatile ink content.
Above all, it is particularly preferable that the amount of heavy metals that affect the environment contained in the cyan ink, the yellow ink, and the magenta ink is 10 ppm or less, respectively. By setting the amount of heavy metals that affect the environment in each ink to 10 ppm or less, the amount of heavy metals that affect the environment as an ink set is 10 ppm or less, which is more safe and reduces the environmental load. can.

In the present specification, the amount of heavy metals that affect the environment is determined by acid-decomposing the dried ink using a microwave sample pretreatment device (ETHOS1 manufactured by Milestone General Co., Ltd.) to remove the metal contained in the ink. After extraction, the content of heavy metals in the non-volatile content of the ink can be determined by measuring the amount of heavy metals contained in the extract using a multi-type ICP emission spectrophotometer (720-ES, manufactured by Agilent).

<Clear ink with desorption>
The gravure printing ink set of the present invention may further contain a clear ink having desorption property. The "clear ink having desorption property" refers to an ink having a property that the printed layer formed by the clear ink is neutralized with an alkaline aqueous solution and is dissolved or swollen to be peeled off from the base material layer.
The basic compound used in the alkaline aqueous solution is not particularly limited, and is, for example, sodium hydroxide (NaOH), potassium hydroxide (KOH), calcium hydroxide (Ca (OH) ₂ ), ammonia, barium hydroxide (Ba). (OH) ₂ ) and sodium carbonate (Na ₂ CO ₃ ) can be mentioned. More preferably, it is at least one selected from the group consisting of sodium hydroxide and potassium hydroxide.
In the present specification, the step of neutralizing with an alkaline aqueous solution to dissolve or swell may be referred to as "alkaline treatment". Further, a layer having desorption property by alkaline treatment may be referred to as a "desorption layer". That is, the print layer formed by the clear ink having desorption property corresponds to the layer having desorption property (detachable layer).

[Hydroxy group-containing resin]
The clear ink having desorption property preferably contains a carboxy group-containing resin, and is suitably used as a primer composition to be printed on a substrate layer before a color ink.
The carboxy group-containing resin is not particularly limited and can be selected from conventionally known resins, and may be used alone or in combination of two or more. Examples of the resin skeleton of the carboxy group-containing resin include acrylic resin, urethane resin, polyester resin, amino resin, phenol resin, epoxy resin, and cellulose, and urethane resin is preferable because it has good laminating suitability. ..

The hydroxyl value of the carboxy group-containing urethane resin is preferably 1 to 35 mgKOH / g, more preferably 10 to 30 mgKOH / g. When it is 1 mgKOH / g or more, it is preferable because the desorption property by an alkaline aqueous solution is good, and when it is 35 mgKOH / g or less, it is preferable because the substrate adhesion is good.
The acid value of the carboxy group-containing urethane resin is preferably 15 mgKOH / g or more, more preferably 15 to 70 mgKOH / g, and even more preferably 20 to 50 mgKOH / g. When it is 15 mgKOH / g or more, it is preferable because the desorption property by an alkaline aqueous solution is good, and when it is 70 mgKOH / g, it is preferable because the substrate adhesion and the retort resistance when used as a packaging material are good.
Both the hydroxyl value and the acid value are values measured according to JIS K0070.

The weight average molecular weight of the carboxy group-containing urethane resin is preferably 10,000 to 100,000, more preferably 15,000 to 70,000, still more preferably 15,000 to 50,000.

The molecular weight distribution (Mw / Mn) of the carboxy group-containing urethane resin is preferably 6 or less. When the molecular weight distribution is 6 or less, the influence caused by the excessive high molecular weight component, the unreacted component, the side reaction component and other low molecular weight components can be avoided, and the desorption property and the drying property of the primer composition can be avoided. Good retort resistance.
Further, the smaller the molecular weight distribution, that is, the sharper the molecular weight distribution, the more uniformly the dissolution / exfoliation action by the alkaline aqueous solution occurs and the desorption property is improved, which is preferable. The molecular weight distribution is more preferably 5 or less, still more preferably 4 or less. The molecular weight distribution is preferably 1.5 or more, more preferably 1.2 or more.

The carboxy group-containing urethane resin may have an amine value. When the carboxy group-containing urethane resin has an amine value, the amine value is preferably 0.1 to 20 mgKOH / g, more preferably 1 to 10 mgKOH / g.

The carboxy group-containing urethane resin is not particularly limited, and is preferably a resin obtained by reacting a polyol, a hydroxy acid and a polyisocyanate, for example. By using a hydroxy acid, an acid value can be imparted to the urethane resin, and the desorption property can be improved. More preferably, it is a resin obtained by reacting a resin obtained by reacting a polyol, a hydroxy acid and a polyisocyanate with a polyamine.

The clear ink having desorption property may further contain polyisocyanate as a curing component. The polyisocyanate is not particularly limited and can be selected from conventionally known polyisocyanates, and examples thereof include aliphatic polyisocyanates and aromatic aliphatic polyisocyanates.
In addition, the desorbable clear ink may contain other components other than the hydroxyl group-containing resin and polyisocyanate, and like the above-mentioned cyan, yellow, and magenta color inks, an organic solvent, a blocking agent, and the like are added. The agent can be blended.

<Printed matter>
The printed matter of the present invention has a print layer formed from the gravure printing ink set and a base material layer, and the cyan ink, yellow ink, and magenta ink in the ink set of the present invention are printed on the base material. Can be obtained.
The gravure printing method is not particularly limited and can be appropriately selected from known methods. The gravure printing method is roughly divided into front printing and back printing. For example, when the base material is white paper or white film in front printing, yellow ink, magenta ink, cyan ink, etc. are applied on the base material. A printed matter can be obtained by printing in the order of black ink.
Further, for example, when the base material is a transparent film in back printing, a printed matter can be obtained by printing on the base material in the order of black ink, cyan ink, magenta ink, yellow ink, and white ink. can.
When the ink set of the present invention contains a clear ink, it is preferable that the clear ink is printed on a substrate before the color ink.
The thickness of the print layer can be appropriately selected depending on the intended use, the type and number of inks used, and the number of times of overprinting, but is usually in the range of 0.5 to 10 μm.

[Base layer]
Examples of the base material include polyolefin base materials such as polyethylene and polypropylene; polycarbonate base materials; polyester base materials such as polyethylene terephthalate and polylactic acid; polystyrene base materials; polystyrene resins such as AS and ABS; polyamide base materials; polyvinyl chloride. Examples include vinyl base material; polyvinylidene chloride base material; cellophane base material; paper base material; aluminum foil base material; composite base material composed of these composite materials; The base material may be in the form of a film or a sheet. Of these, polyester base materials and polyamide base materials having a high glass transition point are preferably used.

The surface of the base material may be vapor-filmed with a metal oxide or the like, or may be coated with polyvinyl alcohol or the like. Examples of such a surface-treated base material include GL-AE manufactured by Toppan Printing Co., Ltd. and IB-PET-PXB manufactured by Dai Nippon Printing Co., Ltd., in which aluminum oxide is vapor-deposited on the surface. The base material may be treated with additives such as an antistatic agent and an ultraviolet inhibitor, if necessary, and may be corona-treated or low-temperature plasma-treated.

[Layer with desorption (demovable layer)]
The printed matter of the present invention can include a layer having desorption property. Here, "having desorption" refers to a person having the property of being neutralized with an alkaline aqueous solution and having the property of exfoliating from the base material layer by dissolving or swelling. The layer having desorption property may be a print layer formed from the above-mentioned clear ink, or may be a layer other than the print layer.
The thickness of the layer having desorption property is not particularly limited, and is usually in the range of 0.5 to 5 μm.

<Packaging material>
The packaging material of the present invention is not limited in shape as long as it is made of at least a part of the above-mentioned printed matter. Examples of the packaging material include a structure in which a printed matter and a sealant base material are bonded to each other via an adhesive layer made of a known adhesive, and a four-way seal package, a three-way seal package, a pillow package, and a stick are used. Various types of bags, gusset bags, square bottom bags, standing pouches, deep squeezed containers, vacuum packages, skin packs, chuck bags, spout pouches, twist wrapping, wrapping wrapping, shrink wrapping, labels, liquid paper packs, paper trays, etc. It can be suitably used for a package having a shape.

[Adhesive layer]
Examples of the adhesive component that can be used to form the adhesive layer include polyester resins such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polyethylene isophthalate, and polycarbonate; polyether adhesives; polyurethane. Adhesives; Epoxy adhesives; Phenolic resin-based resins; Polyethylene-based resins such as nylon 6, nylon 66, nylon 12, and copolymerized polyamides; Polyethylene-based adhesives such as polyolefins, carboxylic acid-modified polyolefins, and metal-modified polyolefins, poly Vinyl acetate adhesive; Cellulous adhesive; (Meta) acrylic adhesive; Polyethylene resin; Amino resin such as urea resin and melamine resin; Rubber such as chloroprene rubber, nitrile rubber, styrene-butadiene rubber; Silicon resin Can be mentioned.
One of these adhesive components may be used alone, or two or more thereof may be used in combination. Among these adhesive components, a polyurethane adhesive is preferably used.

The polyurethane-based adhesive is a reactive adhesive containing a polyol and a polyisocyanate, and may be desorbable. Examples of the removable polyurethane adhesive include the laminated adhesive described in Japanese Patent Application Laid-Open No. 2020-084130.
The polyurethane adhesive having such desorption property preferably has an acid value of 5 to 45 mgKOH / g. Further, it is preferable that the polyol constituting the polyurethane adhesive contains a polyester polyol, and the polyisocyanate contains one selected from the group consisting of an aliphatic polyisocyanate and an aromatic aliphatic polyisocyanate.
The thickness of the adhesive layer is usually in the range of 1 to 6 μm.

The present invention will be described in detail with reference to the following examples, but the present invention is not limited to these examples. In the following description, "parts" and "%" represent "parts by mass" and "% by mass" unless otherwise specified.

<Measurement of amine value>
The amine value is the number of mg of acid and equivalent potassium hydroxide required to neutralize 1 g of the solid content sample, and the titration amount up to the equivalence point was determined by the potential difference titration method using a 0.1 N hydrochloric acid aqueous solution. Later, it is a value calculated from the titration amount.

<Molecular weight and molecular weight distribution>
The weight average molecular weight (Mw), number average molecular weight (Mn) and molecular weight distribution (Mw / Mn) were measured by GPC (gel permeation chromatography) under the following conditions, and polystyrene was used as the standard substance as the converted molecular weight. I asked.
GPC device: Showa Denko's Shodex GPC-104
Column: The following columns were connected in series and used.
Showa Denko's Shodex LF-404 2 pieces Showa Denko's Shodex LF-G
Detector: RI (Differential Refractometer)
Measurement conditions: Column temperature 40 ° C
Eluent: Tetrahydrofuran Flow rate: 0.3 mL / min

<Acid value and hydroxyl value>
The acid value and the hydroxyl value were measured according to the method described in JIS K 0070 (1992).

<Manufacturing of pigments>
(Synthesis Example A-1) Synthesis of phthalocyanine compound [1] 100 parts of o-phthalodinitrile and 119 parts of 1,8-diazabicyclo [5.4.0] undec-7-ene are added to 400 parts of 1-pentanol. The mixture was mixed, heated and stirred, and refluxed for 6 hours. After completion of the reaction, the obtained blue precipitate was filtered off and washed with methanol to obtain a blue cake.
Then, the obtained cake was put into 1000 parts of water and stirred, 31.58 parts of 98% sulfuric acid was added, and the cake was heated and stirred at 80 ° C. for 3 hours. After completion of stirring, the blue precipitate was filtered off, washed with water, dried at 80 ° C., and pulverized to obtain a blue powder.
Then, the blue powder was added to 1000 parts of tetrahydrofuran, and the mixture was heated and stirred at 80 ° C. for 2 hours. After completion of stirring, the blue precipitate was separated by filtration, washed with methanol, and dried under reduced pressure to obtain 95 parts of the phthalocyanine compound [1] shown in Table 1.

(Synthesis Example A-2) Synthesis of phthalocyanine compound [2] 400 parts of 1-pentanol, 100 parts of o-phthalodinitrile, 19.3 parts of copper (I) chloride, 1,8-diazabicyclo [5.4. 0] 119 parts of Undeca-7-en were mixed, heated and stirred, and refluxed for 6 hours. After completion of the reaction, the obtained blue precipitate was filtered off and washed with methanol to obtain a blue cake.
Then, the obtained cake was put into 1000 parts of water and stirred, 31.58 parts of 98% sulfuric acid was added, and the mixture was heated and stirred at 80 ° C. for 3 hours. After completion of stirring, the blue precipitate was filtered off, washed with water, dried at 80 ° C., and pulverized to obtain a blue powder.
Next, blue powder was added to 800 parts of 98% sulfuric acid, and the mixture was heated and stirred at 60 ° C. for 3 hours. After the stirring was completed, the sulfuric acid solution was added dropwise to 4000 parts of water with stirring to obtain a blue precipitate. The obtained blue precipitate was filtered off, washed with water, dried at 80 ° C., and pulverized to obtain a blue powder.
Then, 1000 parts of tetrahydrofuran was added with blue powder, and the mixture was stirred and refluxed for 2 hours. After completion of stirring, the blue precipitate was filtered off, washed with methanol and dried under reduced pressure to obtain 110 parts of the phthalocyanine compound [2] shown in Table 1.

(Synthesis Example A-3) Synthesis of Isoindoline Compound [1] 800 parts of water, 60 parts of 1,3-diiminoisoindoline, 28% in a 4-necked flask equipped with a reflux condenser, a dropping funnel, and a stirrer. 120 parts of aqueous ammonia was added in this order, and the mixture was stirred. A solution prepared by dissolving 42.58 parts of 2-cyano-N-methylacetamide in 160 parts of water was added dropwise thereto using a dropping funnel in 30 minutes. The mixture was heated and stirred at 30 ° C. until the raw material 1,3-diiminoisoindoline disappeared. The reaction slurry was filtered off using a Büchner funnel. Further, the filter was added to 1600 parts of water, and the mixture was stirred at 40 ° C. for 30 minutes. The slurry was filtered off to obtain a non-volatile component. The disappearance of the raw material was confirmed by UPLC (ultra-high-speed high-separation liquid chromatography Waters).
Next, 60 parts of the non-volatile content, 480 parts of water, and 162 parts of 80% acetic acid were added to a four-necked flask equipped with a reflux condenser, a dropping funnel, and a stirrer, and the mixture was stirred. On the other hand, 461 parts of water and 194 parts of 80% acetic acid were added to the glass flask, 40.74 parts of barbituric acid was added thereto, and the mixture was stirred at 65 ° C. The heated solution of this mixture was put into the above-mentioned non-volatile stirring solution, and the temperature was raised to 85 ° C. for further completion of the reaction, and the mixture was stirred. The heating and stirring was carried out until the above-mentioned non-volatile component used as a raw material disappeared. The disappearance of the raw material was confirmed by UPLC.
Then, after cooling to room temperature, it was washed with 2400 parts of water three times to obtain a non-volatile component. This non-volatile component was dried in a hot air dryer at 80 ° C. to obtain 84.91 parts of the isoindoline compound [1] shown in Table 2.

(Synthesis Example A-4) Synthesis of Isoindoline Compound [2] 800 parts of water and 800 parts of 80% acetic acid were added to a 4-necked flask equipped with a reflux condenser, a dropping funnel and a stirrer, and the mixture was stirred. 128 parts of barbituric acid was added thereto, and the mixture was stirred at 65 ° C. to dissolve the barbituric acid. On the other hand, 800 parts of water and 60.00 parts of 1,3-diiminoisoindoline were added to the glass flask, and the mixture was stirred at 30 ° C. This stirring solution was put into the above-mentioned heating and dissolving solution, and the temperature was raised to 85 ° C. to complete the reaction, and the mixture was stirred. The heating and stirring was carried out until the above-mentioned non-volatile component used as a raw material disappeared. The disappearance of the raw material was confirmed by UPLC.
Then, after cooling to room temperature, it was washed with 2000 parts of water three times to obtain a non-volatile component. This non-volatile component was dried in a hot air dryer at 80 ° C. to obtain 144.17 parts of the isoindoline compound [2] shown in Table 2.

(Synthesis Example A-5) Synthesis of Isoindoline Compound [3] Same as Synthesis Example A-3 except that 49.65 parts of 1,3-dimethylbarbituric acid was used instead of 40.74 parts of barbituric acid. To obtain 91.96 parts of the isoindoline compound [3] shown in Table 2.

(Synthesis Example A-6) Synthesis of Isoindoline Compound [4] Other than using 35.77 parts of barbituric acid and 6.31 parts of 1,3-dimethylbarbituric acid instead of 40.74 parts of barbituric acid. Was synthesized in the same manner as in Synthesis Example A-3 to obtain 85.97 parts of the isoindoline compound [4] shown in Table 2.

(Synthesis Example A-7) Synthesis of azo compound [Y1] 3,3'-dichlorobenzidine hydrochloride is tetrazozated by a conventional method using 3 times mol of hydrochloric acid and 2 times mol of sodium nitrite, at 10 ° C. A 0.125 mol / l tetrazo aqueous solution was prepared. On the other hand, 54.3 parts of acetacet-2,5-dimethoxy-4-chloroanilide was dissolved in an aqueous solution containing 14.4 parts of sodium hydroxide to prepare a 0.259 mol / l coupler aqueous solution at 25 ° C. In addition, as an acidic aqueous solution, 30 parts of 80% acetic acid, 2.4 parts of the active ingredient equivalent of the nonionic surfactant Cadenax DMC-W (trade name, manufactured by Lion Specialty Chemicals Co., Ltd.) and 500 parts of an acetic acid solution consisting of water were used. It was prepared and charged into a reactor having a stirrer. The coupler was precipitated by injecting the coupler aqueous solution into this acetic acid solution at a flow rate of 19.3 ml / min for 40 minutes. An injection tube having an outlet was set in this coupler slurry, and injection of the tetrazo aqueous solution was started at a flow rate of 18.4 ml / min. It took about 40 minutes for injection until a slight amount of tetrazo was detected on the reaction surface. The coupling reaction rate was 91.8%. After that, it was heated to 70 ° C., filtered and purified, and dried at 85 ° C. to obtain 73.1 parts of the azo compound [Y1] shown in Table 3.

(Synthesis Example A-8) Synthesis of azo compound [Y2] 345 parts of 1,2-bis- (2-aminophenoxy) ethane was added to 4,500 parts of water, 654 parts of 35% hydrochloric acid was added, and the mixture was stirred for 3 hours. , Was sufficiently dispersed in an aqueous hydrochloric acid solution. After adding ice to the dispersion in an ice bath and confirming that the temperature was 0 ° C. or lower, 423 parts of a 38% sodium nitrite solution was added dropwise to diazotize. After completion of the dropping, the mixture was stirred with potassium iodide starch paper for 1 hour while confirming that the nitrite ion was excessive, and then filtered to obtain a tetrazo solution. Immediately before the coupling reaction, the tetrazo solution was used after adding sulfamic acid until no excess nitrite ion was observed on the potassium iodide starch paper. On the other hand, 750 parts of 5-acetacetamide-benzimidazolone was added to 6,000 parts of water, and after stirring for 10 minutes, the temperature was adjusted to 20 to 25 ° C. 880 parts of a 29% aqueous sodium hydroxide solution was added, and after sufficient dissolution was confirmed, filtration was performed. The filtrate was prepared at 5 ° C. using water and ice to a total volume of 12,000 parts, and 676 parts of 80% acetic acid was added over 20 minutes to obtain a coupler slurry. As a coupling aid, 10 parts of a condensation product of stearate chloride and taurine was added thereto.
The tetrazo solution was injected under the surface of the coupler slurry under the condition of 18 to 22 ° C. over 5 hours. At that time, the injection rate was adjusted so that excess tetrazo salt was not detected. During the coupling, the pH value was always kept at 6.0 by adding a small amount of 2N aqueous sodium hydroxide solution.
After completion of the coupling, the cake was heated to 90 ° C., held for 30 minutes or more, cooled to 70 ° C., filtered and washed with water to obtain a press cake. The press cake was stirred with water to make a paste, and water and isobutanol were added so that the pigment solid content in the 35% isobutanol water mixture was a 4% suspension.
The suspension was heated to 150 ° C. within 1 hour in a stirred autoclave and kept at this temperature for 3 hours. After cooling to about 80 ° C., isobutanol was azeotropically distilled by introducing steam. The aqueous pigment suspension was suction-filtered, washed with a little water, dried at 70 ° C. in a vacuum dryer, and then pulverized to obtain 998 parts of the azo compound [Y2] shown in Table 3.

(Synthesis Example A-9) Synthesis of quinacridone compound [1] Well-dried 1,4-cyclohexanedione-2,5-di (carboxylic acid methyl ester) 45.6 parts (0.2 mol), aniline 46.57 Weigh parts (0.5 mol), 500 parts of methanol, and 4.65 parts of 35% hydrochloric acid (0.045 mol) into a 1 liter pressure-resistant glass autoclave, seal the mixture, and then use nitrogen gas to sufficiently remove the oxygen in the reaction vessel. After the substitution, the gauge pressure ^{was set to 0 kg / cm 2} , and the temperature was raised from room temperature to 100 ° C. in 15 minutes with vigorous stirring, and then the reaction was carried out for 3 hours. The maximum pressure of the reaction vessel during the reaction was 3.8 kg / cm ² . After the reaction, the mixture was cooled to 30 ° C. or lower, opened to atmospheric pressure, 18 parts of a 10% sodium hydroxide aqueous solution was added, and the mixture was stirred for 10 minutes and then filtered. The filtered cake was thoroughly washed with methanol heated to 60 ° C. The yield of 2,5-dianilino-3,6-dihydroterephthalic acid dimethyl ester produced was 75.07 parts, which was 99.3% of the theoretical yield. The purity was 99.5%.
Next, 30 parts of the 2,5-dianilino-3,6-dihydroterephthalic acid dimethyl ester obtained above and 150 parts of the dimethylnaphthalene isomer mixture were placed in a flask having an outlet valve at the bottom of 200 ml under a nitrogen gas atmosphere. The mixture was heated to 120 to 170 ° C. with stirring. On the other hand, 150 parts of the dimethylnaphthalene isomer mixture was heated to 280 ° C. or higher in a 500 ml flask while stirring in a nitrogen gas atmosphere. After introducing the above-mentioned thermal mixture over 20 to 40 minutes, the mixture was held at 280 to 283 ° C. (reflux) for 30 minutes. From the moment when the 2,5-dianilino-3,6-dihydroterephthalic acid dimethyl ester and dimethylnaphthalene isomer mixture at 120 to 170 ° C. were introduced into the boiling dimethylnaphthalene isomer mixture, 6,13 with the generation of methanol. -The reaction to form dihydroquinacridone started, and the generation of methanol almost disappeared immediately after the start of reflux at 283 ° C. After cooling to 100 ° C., the nitrogen gas atmosphere is released, the contents are filtered, washed with 500 parts of hot methanol, and dried to add 24.47 parts of 6,13-dihydroquinacridone (98.2% of the theoretical amount). Obtained. The purity was 99% or more according to IR and absorbance.
10 parts of 6,13-dihydroquinacridone and 80 parts of methanol obtained above were placed in a 200 ml flask equipped with a reflux device and stirred. Add 12 parts of 50% sodium hydroxide aqueous solution and stir at 40 ° C. for 30 minutes, then add 26 parts of 10% sulfuric acid and hydrolyze, immediately add 10 parts of m-nitrobenzene sulfonic acid sodium, and immediately add 50% water. After adding 3 parts of an aqueous sodium oxide solution, the mixture was refluxed for 4 hours. The mixture was filtered, washed with water, dried and pulverized to obtain 9.82 parts of the quinacridone compound [1] (unsubstituted quinacridone) shown in Table 4.

(Synthesis Example A-10) Synthesis of quinacridone compound [2] 45.60 parts (0.2 mol) of well-dried 1,4-cyclohexanedione-2,5-di (carboxylic acid methyl ester) and p-toluidine 53. Weigh 5.5 parts (0.5 mol), 500 parts of methanol, and 4.65 parts of 35% hydrochloric acid (0.045 mol) into a 1 liter pressure-resistant glass autoclave, seal the mixture, and then sufficiently use nitrogen gas in the reaction vessel. After replacing the oxygen, the gauge pressure ^{was set to 0 kg / cm 2} , and the temperature was raised from room temperature to 100 ° C. in 15 minutes with vigorous stirring, and then the reaction was carried out for 3 hours. The maximum pressure of the reaction vessel during the reaction was 3.8 kg / cm ² . After the reaction, the mixture was cooled to 30 ° C. or lower, opened to atmospheric pressure, 18 parts of a 10% sodium hydroxide aqueous solution was added, and the mixture was stirred for 10 minutes and then filtered. The filtered cake was thoroughly washed with methanol heated to 60 ° C. The yield of 2,5-di-p-toluidino-3,6-dihydroterephthalic acid dimethyl ester produced was 75.07 parts, which was 99.3% of the theoretical yield. The purity was 99.5%.
Then, 30 parts of the 2,5-di-p-toluidino-3,6-dihydroterephthalic acid dimethyl ester obtained above and 150 parts of the dimethylnaphthalene isomer mixture were placed in a flask having an outlet valve at the bottom of 200 ml. The mixture was heated to 120 to 170 ° C. with stirring under a nitrogen gas atmosphere. On the other hand, 150 parts of the dimethylnaphthalene isomer mixture was heated to 280 ° C. or higher in a 500 ml flask while stirring in a nitrogen gas atmosphere. After introducing the above-mentioned thermal mixture over 20 to 40 minutes, the mixture was held at 280 to 283 ° C. (reflux) for 30 minutes. From the moment when the 2,5-dianilino-3,6-dihydroterephthalic acid dimethyl ester and dimethylnaphthalene isomer mixture at 120 to 170 ° C. were introduced into the boiling dimethylnaphthalene isomer mixture, 2,9 with the generation of methanol. The reaction to form -dimethyl-6,13-dihydroquinacridone started, and the generation of methanol almost disappeared immediately after the start of reflux at 283 ° C. After cooling to 100 ° C., the nitrogen gas atmosphere is released, the contents are filtered, washed with 500 parts of hot methanol, dried and dried to 24.44 parts of 2,9-dimethyl-6,13-dihydroquinacridone (theoretical amount). 96.71%) was obtained.
10 parts of 2,9-dimethyl-6,13-dihydroquinacridone and 80 parts of methanol obtained above were placed in a 200 ml flask equipped with a reflux device and stirred. Add 12 parts of 50% sodium hydroxide aqueous solution and stir at 40 ° C. for 30 minutes, then add 26 parts of 10% sulfuric acid and hydrolyze, immediately add 10 parts of m-nitrobenzene sulfonic acid sodium, and immediately add 50% water. After adding 3 parts of an aqueous sodium oxide solution, the mixture was refluxed for 4 hours. The mixture was filtered, washed with water, dried and pulverized to obtain 9.60 parts of crude 2.9-dimethyl-quinacridone.
Next, cool to 10 ° C or lower in an ice bath, and add 9 parts of the crude 2.9-dimethyl-quinacridone obtained above to 90 parts of 98% sulfuric acid stirred in the flask, taking care that the temperature does not rise above 30 ° C. While added. After adding the whole amount, the mixture was stirred at 30 ° C. or lower for 1 hour. The above sulfuric acid solution was added dropwise to 1000 parts of agitated water at 10 ° C., paying attention to bumping. After the dropping was completed, the cake was filtered and washed with water until it became neutral to obtain a pressed cake. Water was added to the obtained press cake, the pH was adjusted to 9.0 with sodium hydroxide, and then 0.09 part of the condensation product of chloride stearate and taurine was added to a 35% isobutanol water mixed solution. Water and isobutanol were added so that the pigment solid content became a 4% suspension. The suspension was refluxed for 2 hours and then isobutanol was distilled off until the liquid temperature reached 99 ° C. After cooling to 70 ° C., filtration, washing with warm water at 60 ° C., drying, and pulverization were performed to obtain 8.9 parts of the quinacridone compound [2] shown in Table 4.

(Synthesis Example A-11) Synthesis of quinacridone compound [3] In 90 parts of 98% sulfuric acid cooled in an ice bath to 10 ° C. or lower and stirred in a flask, the crude 2,9- obtained in Synthesis Example A-10 was added. 6.3 parts of dimethyl-quinacridone and 2.7 parts of the quinacridone compound [1] obtained in Synthesis Example A-9 were added carefully so that the temperature did not exceed 30 ° C. After adding the whole amount, the mixture was stirred at 30 ° C. or lower for 1 hour. The above sulfuric acid solution was added dropwise to 1000 parts of agitated water at 10 ° C., paying attention to bumping. After the dropping was completed, the cake was filtered and washed with water until it became neutral to obtain a pressed cake. Water was added to the obtained press cake and the pH was adjusted to 9.0 with sodium hydroxide, and then 0.09 part of the condensation product of chloride stearate and taurine was added to the pigment in a 35% isobutanol water mixed solution. Water and isobutanol were added so that the solid content was a 4% suspension. The suspension was refluxed for 2 hours and then isobutanol was distilled off until the liquid temperature reached 99 ° C. After cooling to 70 ° C., filtration, washing with warm water at 60 ° C., drying, and pulverization were performed to obtain 8.9 parts of the quinacridone compound [3] shown in Table 4.

(Synthesis Example A-12) Synthesis of DPP compound [1] 180 parts of tert-amyl alcohol and 147 parts of sodium-tert-amyl alkoxide dehydrated with molecular sieves under a nitrogen atmosphere in a stainless steel reaction vessel equipped with a reflux tube. In addition, the mixture was heated to 100 ° C. with stirring to prepare an alcoholate solution. On the other hand, 90 parts of diisopropyl succinate and 91.8 parts of benzonitrile were added to a glass flask and heated to 90 ° C. with stirring to dissolve them to prepare a solution of a mixture thereof. The heated solution of this mixture was slowly added dropwise to the alcoholate solution heated to 100 ° C. at a constant rate over 2 hours with vigorous stirring. After completion of the dropping, heating and stirring were continued at 90 ° C. for 2 hours to obtain an alkali metal salt of a diketopyrrolopyrrole compound. Further, 600 parts of methanol, 600 parts of water, and 358 parts of acetic acid were added to the reaction vessel with a glass jacket, and the mixture was cooled to −10 ° C. While rotating this cooled mixture at 4000 rpm using a high-speed stirring disperser, an alkali metal salt solution of the previously obtained diketopyrrolopyrrole compound cooled to 75 ° C. is added little by little. did. At this time, the rate of adding the alkali metal salt of the diketopyrrolopyrrole compound at 75 ° C. while cooling so that the temperature of the mixture consisting of methanol, acetic acid, and water is always maintained at −5 ° C. or lower. Was added in small portions over approximately 120 minutes. After the addition of the alkali metal salt, red crystals were precipitated and a red suspension was formed. Subsequently, the obtained red suspension was replaced with a methanol slurry by an ultrafiltration device, held at 40 ° C. for 2 hours, washed with water, filtered off, and the cake was dried at 80 ° C. for 24 hours and pulverized. By doing so, 114.2 parts of the DPP compound [1] shown in Table 4 was obtained.

(Synthesis Example A-13) Synthesis of DPP compound [2] 180 parts of tert-amyl alcohol and 147 parts of sodium-tert-amyl alkoxide dehydrated with molecular sieves under a nitrogen atmosphere in a stainless steel reaction vessel equipped with a reflux tube. In addition, the mixture was heated to 100 ° C. with stirring to prepare an alcoholate solution. On the other hand, 90 parts of diisopropyl succinate and 159.5 parts of 4-cyanobiphenyl were added to a glass flask and heated to 90 ° C. with stirring to dissolve them to prepare a solution of a mixture thereof. The heated solution of this mixture was slowly added dropwise to the alcoholate solution heated to 100 ° C. at a constant rate over 2 hours with vigorous stirring. After completion of the dropping, heating and stirring were continued at 90 ° C. for 2 hours to obtain an alkali metal salt of a diketopyrrolopyrrole compound. Further, 600 parts of methanol, 600 parts of water, and 358 parts of acetic acid were added to the reaction vessel with a glass jacket, and the mixture was cooled to −10 ° C. While rotating this cooled mixture at 4000 rpm using a high-speed stirring disperser, an alkali metal salt solution of the previously obtained diketopyrrolopyrrole compound cooled to 75 ° C. is added little by little. did. At this time, the rate of adding the alkali metal salt of the diketopyrrolopyrrole compound at 75 ° C. while cooling so that the temperature of the mixture consisting of methanol, acetic acid, and water is always maintained at −5 ° C. or lower. Was added in small portions over approximately 120 minutes. After the addition of the alkali metal salt, red crystals were precipitated and a red suspension was formed. Subsequently, the obtained red suspension was replaced with a methanol slurry by an ultrafiltration device, held at 40 ° C. for 2 hours, washed with water, filtered off, and the cake was dried at 80 ° C. for 24 hours and pulverized. By doing so, 174.5 parts of the DPP compound [2] shown in Table 4 was obtained.

(Synthesis Example A-14) Synthesis of quinacridone / DPP compound The quinacridone compound [1] obtained in Synthesis Example A-9 was compared with 100 parts of N-methyl-2-pyrrolidone stirred in a light-shielded container. 7 parts of unsubstituted quinacridone) and 3 parts of the DPP compound [1] (unsubstituted diketopyrrolopyrrole pigment) obtained in Synthesis Example A-12 were added while being careful not to fly the powder. After confirming that it was sufficiently dispersed, 3.8 parts of tert-butoxypotassium was gradually added. After confirming the dissolution, the mixture was stirred at 20 ° C. or lower for 1 hour. The solution is slowly poured into a solution prepared by adding 5 parts of 80% acetic acid to 1000 parts of stirred water at 20 ° C., stirred for 1 hour, filtered, washed with water, dried and pulverized, and is shown in Table 5. 9.6 parts of a solid solution pigment (quinacridone / DPP compound) of unsubstituted quinacridone and unsubstituted diketopyrrolopyrrole was obtained.

(Synthesis Example A-15) Synthesis of Perylene Compound [1] In a stainless steel reaction vessel equipped with a reflux tube, 500 parts of diethylene glycol dimethyl ether, 170.7 parts of potassium-tert-butoxide, 1,5-diazabicyclo [ 4.3.0] 251.9 parts of non-5-ene (DBN) was added, and the mixture was heated and stirred at 130 ° C. for 1 hour. Then, 100 parts of 1,8-naphthalimide was added, and the mixture was further heated and stirred at 130 ° C. for 3 hours. The reaction mixture was cooled to room temperature, the precipitate was filtered off, washed with 300 parts of diethylene glycol dimethyl ether, and dried under reduced pressure for 12 hours. The obtained solid was resurrected with 200 parts of water and 200 parts of methanol, washed with water, acetone and dichloromethane, dried under reduced pressure at 120 ° C. for 8 hours, and pulverized to obtain the perylene compound shown in Table 5. [1] 188.1 parts were obtained.

(Synthesis Example A-16) Synthesis of Perylene Compound [2] In a stainless steel reaction vessel equipped with a reflux tube, 500 parts of diethylene glycol dimethyl ether, 159.4 parts of potassium-tert-butoxide, 1,5-diazabicyclo [ 4.3.0] 235.2 parts of non-5-ene (DBN) was added, and the mixture was heated and stirred at 130 ° C. for 1 hour. Then, 100 parts of N-methyl-1,8-naphthalimide was added, and the mixture was further heated and stirred at 130 ° C. for 3 hours. The reaction mixture was cooled to room temperature, the precipitate was filtered off, washed with 300 parts of diethylene glycol dimethyl ether, and dried under reduced pressure for 12 hours. The obtained solid was resurrected with 200 parts of water and 200 parts of methanol, washed with water, acetone and dichloromethane, dried under reduced pressure at 120 ° C. for 8 hours, and pulverized to obtain the perylene compound shown in Table 5. [2] 188.2 parts were obtained.

(Synthesis Example A-17) Synthesis of azo compound [R1] 100 parts of 2,5-dichloroaniline was added to 1375 parts of water and stirred for 2 hours, then 35% hydrochloric acid was added and stirred for another 1 hour, and ice 500 was added. The mixture was added and cooled to 5 ° C. or lower. Then, a solution prepared by dissolving 50.3 parts of sodium nitrite in 150 parts of water was added, and the mixture was kept at 5 ° C. or lower and stirred for 2 hours. Then, a buffer solution in which 794 parts of a 25% sodium hydroxide aqueous solution, 696 parts of 80% acetic acid, and 587 parts of ice were mixed and stirred was added to prepare a diazo solution. On the other hand, 117.3 parts of 3-hydroxy-2-naphthoic acid was dissolved with 980 parts of water and 696 parts of a 25% sodium hydroxide aqueous solution to prepare a coupler solution. The diazo solution was charged into a batch type single reaction vessel equipped with a stirrer, and the coupler solution was injected over 40 minutes while stirring. The obtained red slurry was stirred at 60 ° C. for 1 hour, filtered, washed with water, dried at 80 ° C. for 16 hours, and pulverized to obtain 210.0 parts of the azo compound [R1'].
Next, 210.0 parts of the azo compound [R1'] and 2 parts of N, N-dimethylformamide were added to 1050 parts of 2-nitrotoluene, and the mixture was stirred at room temperature. Then, 96.8 parts of thionyl chloride was added, and the suspension was heated and stirred at 120 ° C. for 4 hours. In order to remove excess thionyl chloride, the mixture was distilled off at 80 ° C. under reduced pressure for 4 hours to obtain an acid chloride of the azo compound [R1']. On the other hand, 41.6 parts of 2-chloro-1,4-phenylenediamine was added to 991 parts of 2-nitrotoluene, and the mixture was stirred at 90 ° C. for 2 hours to dissolve. The obtained solution is cooled to 75 ° C., the acid chloride of the azo compound [R1'] obtained above is added, and the mixture is stirred at 90 ° C. for 1 hour, 100 ° C. for 1 hour and 120 ° C. for 2 hours, and hydrochloric acid. After confirming that the gas was no longer released, the mixture was cooled to 100 ° C. The azo compound [R1] 232. I got 3 copies.

(Synthesis Example A-18) Synthesis of azo compound [R2] 100 parts of 3-amino-4-methoxybenzanilide was added to 1375 parts of water and stirred for 2 hours, then 35% hydrochloric acid was added and stirred for another 1 hour. , 500 parts of ice was added and cooled to 5 ° C. or lower. Then, a solution prepared by dissolving 33.6 parts of sodium nitrite in 100 parts of water was added, and the mixture was kept at 5 ° C. or lower and stirred for 2 hours. Then, a buffer solution in which 531 parts of a 25% sodium hydroxide aqueous solution, 465 parts of 80% acetic acid, and 587 parts of ice were mixed and stirred was added to prepare a diazo solution. On the other hand, 149.2 parts of N- (4-chloro-2,5-dimethoxyphenyl) -3-hydroxy-2-naphthalenecarboxyamide (naphthol AS-LC), 980 parts of methanol and 466 parts of 25% sodium hydroxide aqueous solution. To prepare a coupler solution. The diazo solution was charged into a batch type single reaction vessel equipped with a stirrer, and the coupler solution was injected over 40 minutes while stirring. The obtained red slurry was stirred at 60 ° C. for 1 hour, filtered, washed with water, dried at 80 ° C. for 16 hours, and pulverized to obtain 231.7 parts of the azo compound [R2] shown in Table 5.

<Manufacturing of polyurethane resin>
(Manufacturing of polyurethane resin solution [1])
54.719 parts of polyester diol with a number average molecular weight of 2,000, 3.989 parts of isophorone diisocyanate, and 10.0 parts of n-propyl acetate obtained from adipic acid and 3-methyl-1,5-pentanediol are placed under a nitrogen stream. The reaction was carried out at 85 ° C. for 3 hours, 10.0 parts of n-propyl acetate was added and cooled to obtain 78.718 parts of a solvent solution of the terminal isocyanate prepolymer. Next, a solvent solution 78 of the obtained terminal isocyanate prepolymer was mixed with 1.031 parts of isophoronediamine, 0.261 parts of di-n-butylamine, 30.4 parts of n-propyl acetate and 19.6 parts of isopropyl alcohol. .718 parts were gradually added at room temperature and then reacted at 50 ° C. for 1 hour to obtain a polyurethane resin solution [1] having a solid content of 30%, a weight average molecular weight of 60,000 and an amine value of 3.0 mgKOH / g. ..

(Manufacturing of polyurethane resin solution [2])
161 PPA (poly (propylene glycol) adipatediol with a number average molecular weight of 2,000) is introduced while introducing nitrogen gas in a reactor equipped with a reflux condenser, a dropping funnel, a gas introduction tube, a stirrer, and a thermometer. .9 parts, 2,2-dimethylolbutanoic acid (DMBA) 27.7 parts, isophorone diisocyanate (IPDI) 96.4 parts, methyl ethyl ketone (MEK) 200 parts were charged and reacted at 90 ° C. for 5 hours to form a terminal isocyanate group. A resin solution of a urethane prepolymer having the above was obtained. To the obtained terminal isocyanate group urethane prepolymer resin solution, 13.6 parts of 2- (2-aminoethylamino) ethanol (AEA), 0.5 part of ethanolamine (MEA), and 350 parts of isopropyl alcohol (IPA) were added. The mixture was added dropwise at room temperature over 60 minutes, and further reacted at 70 ° C. for 3 hours. Further, the solid content was adjusted using 150 parts of MEK, and a polyurethane resin having a solid content of 30%, a weight average molecular weight of 35,000, Mw / Mn = 3.0, an acid value of 35.0 mgKOH / g, and a hydroxyl value of 25.7 mgKOH / g. A solution [2] was obtained.

<Manufacturing of gravure printing ink>
(Manufacturing Example B-1)
6.5 parts of the phthalocyanine compound [1], 34.5 parts of the polyurethane resin solution [1], 20 parts of N-propyl acetate, and 5 parts of isopropyl alcohol are stirred and mixed, kneaded with a sand mill, and then the polyurethane resin solution [1]. 20 parts, 11 parts of N-propyl acetate and 3 parts of isopropyl alcohol were added to obtain cyan ink [1].

(Manufacturing Examples B-2 to B-18)
The inks shown in Table 6 were obtained in the same manner as in Production Example B-1 except that 6.5 parts of the phthalocyanine compound [1] was changed to the compounds shown in Table 6 and the amounts shown in Table 6.

<Evaluation of gravure printing ink>
For the obtained ink, the amount of halogen, the amount of primary aromatic amine, and the amount of heavy metals affecting the environment in the solid content were measured as follows. The results are shown in Table 6.

[Measurement method of halogen amount]
Each ink was applied onto a transparent substrate so that the thickness after drying was 2.0 μm. After drying at 80 ° C., 0.5 g was scraped off. The amount of halogen (ppm) in each ink solid was determined by pretreating the scraped film by a combustion method and then quantifying it by ion chromatography.

[Measuring method for the amount of primary aromatic amine]
Each ink weighed so that the solid content was 2 g was fixed in 50 ml with DMF and dispersed in an ultrasonic bath for 2 hours. The prepared dispersion was filtered through a 0.2 μm filter to obtain a DMF solution. Then, 1 ml of the DMF solution was mixed with 9 ml of a 4% ammonia / methanol solution and filtered again with a 0.2 μm filter. Using this solution, HPLC measurement was performed by the method described in AP (89) 1 test method (ETAD212). A calibration curve of primary aromatic amines that could be mixed was prepared, and the amount of primary aromatic amines in the ink solids was determined. The detection limit was 500 ppb (0.5 ppm), and those that could not be detected were described as less than 0.5 ppm (<0.5).

[Amount of heavy metals that affect the environment]
Each ink was dried at 80 ° C. and allowed to dry. The dry matter was acid-decomposed using a microwave sample pretreatment device (ETHOS1 manufactured by Milestone General Co., Ltd.) to extract the metal contained in the dry matter. The amount of heavy metals contained in the extract was measured using a multi-type ICP emission spectrophotometer (720-ES, manufactured by Agilent), and the amount (ppm) of heavy metals affecting the environment in the ink solids was calculated. If no heavy metal was detected, N. D. It was written as.

<Evaluation of ink set>
[Examples A-1 to A-32, Comparative Examples A-1 to A-17]
The obtained inks were combined as shown in Table 7 to form ink sets 1-49.
The obtained ink set was evaluated for trapping property and gamut by the following method. The results are shown in Table 7.

[Trapping property]
(Cyan ink / Magenta ink)
Cyan ink and magenta ink were each diluted with a mixed solvent 1 (methyl ethyl ketone: N-propyl acetate: isopropanol = 40: 40: 20) so as to have a viscosity of 16 seconds (25 ° C., Zahn cup No. 3). ..
A printed matter was obtained by overlay printing on the corona discharge-treated surface of a corona discharge-treated polyester (PET) film (E-5100 manufactured by Toyobo Co., Ltd.) having a thickness of 12 μm in the order of cyan and magenta.
The printing conditions were a temperature of 25 ° C., a humidity of 60%, a printing speed of 100 m / min, and a printing distance of 4000 m. Cyan ink uses Helio 175-line gradation version (plate type compressed, 75% solid pattern and 100% to 3% gradation pattern), and magenta ink uses Helio 175-line gradation version (plate type Elongate, 75% solid pattern and 100% ~. 3% gradation pattern) was used.

(Cyan ink / Yellow ink)
The cyan ink and the yellow ink were each diluted with the above-mentioned mixing solvent 1 so as to have a viscosity of 16 seconds (25 ° C., Zahn cup No. 3).
A printed matter was obtained by overlay printing in the order of cyan and yellow on the corona discharge treated surface of a corona discharge treated polyester film (E-5100 manufactured by Toyobo Co., Ltd.) having a thickness of 12 μm.
The printing conditions were a temperature of 25 ° C., a humidity of 60%, a printing speed of 100 m / min, and a printing distance of 4000 m. Cyan ink uses Helio 175-line gradation version (plate type compressed, 75% solid pattern and 100% to 3% gradation pattern), and yellow ink uses Helio 175-line gradation version (plate type Elongate, 75% solid pattern and 100% ~. 3% gradation pattern) was used.

(Yellow ink / Magenta ink)
The yellow ink and the magenta ink were each diluted with the above-mentioned mixing solvent 1 so as to have a viscosity of 16 seconds (25 ° C., Zahn cup No. 3).
A printed matter was obtained by overlay printing in the order of yellow and magenta on the corona discharge treated surface of a corona discharge treated polyester film (E-5100 manufactured by Toyobo Co., Ltd.) having a thickness of 12 μm.
The printing conditions were a temperature of 25 ° C., a humidity of 60%, a printing speed of 100 m / min, and a printing distance of 4000 m. Yellow ink uses Helio 175-line gradation version (plate type Erongate, 75% solid pattern and 100% to 3% gradation pattern), and magenta ink uses Helio 175-line gradation version (plate type Erongate, 75% solid pattern and 100% to 3). % Gradation pattern) was used.

The trapping property of the obtained gradation overprinted portion of the printed matter was observed using a microscope (VHX-5000) manufactured by KEYENCE CORPORATION, and evaluated according to the following criteria.
◯: Printing unevenness occurs at a plate depth of less than 70% (good)
Δ: Printing unevenness occurs when the plate depth is 70% or more and less than 80% (usable).
X: Printing unevenness occurs at a plate depth of 80% or more, or all the overlapping inks become halftone dots and do not spread wet (cannot be used).

[Gamut evaluation]
Cyan ink, magenta ink, and yellow ink were diluted with the above-mentioned mixing solvent 1 so as to have a viscosity of 16 seconds (25 ° C., Zahn cup No. 3). Using each diluted ink, print in the order of cyan, magenta, and yellow printing, and print the single-color solid part (cyan, magenta, yellow) and the single-color solid printing layer (cyan x magenta, cyan x yellow, yellow x magenta). A printed matter having was obtained. The printing conditions are shown below.

(Printing conditions)
Printing machine: Fuji Machinery 5-color machine Cyan version: Helio 175L / inch, stylus angle 120 °, Elongate magenta version: Helio 175L / inch, stylus angle 120 °, compressed yellow version: Helio 175L / inch, stylus angle 120 °, Compressed printing speed: 150 m / min Substrate: Corona-treated biaxially stretched polypropylene (OPP) film (Pyrene P-2161, 20 μm manufactured by Toyo Spinning Co., Ltd.)
Drying temperature: 50 ° C

With respect to the obtained printed matter, the density value of the monochromatic solid portion (yellow, magenta, cyan) of the printed matter was measured using Gretag Macbeth D196. In addition, using a SpectroEye manufactured by gretagmacbeth as a measuring device, the monochromatic solid part and the overprinting part were measured under the conditions of a D50 light source, a two-degree observation field of view, a white background (using a standard white plate), and no filters.
In a two-dimensional space with a * as the horizontal axis and b * as the vertical axis, a single-color solid part (yellow, magenta, cyan) and a single-color solid overprint part (cyan x magenta, cyan x yellow, yellow x magenta) total 6 A hexagon was created by plotting the a * vs. b * values of the colors. The area ratio when the area of Comparative Example A-5 was 100% was obtained, and the area ratio was evaluated according to the following criteria. -Indicates that it has not been evaluated.
◯: Area ratio is 90% or more (good)
Δ: Area ratio is 85% or more and less than 90% (usable)
X: Area ratio is less than 85% (cannot be used)

According to Table 7, in the gravure printing ink set of the present invention, which is a combination of three-color inks containing specific pigments, each ink contains halogen atoms, primary aromatic amines, and heavy metals that affect the environment. It was not contained, or even if it was contained, the amount was extremely small, and it was excellent in safety and health and environmental protection. Further, the gravure printing ink set of the present invention had good trapping property of each color. It is presumed that this is the effect of the combination of pigments specific to the present application.
Among them, cyan ink containing a phthalocyanine pigment represented by the formula (1), yellow ink containing an isoindolin pigment represented by the formulas (6) to (8), and quinacridone represented by the formulas (16) and (17). Gravure printing ink sets containing magenta inks containing pigments (Examples A-1 to A-3, A-6, A-9 to A-11, A-14, A-17 to A-19, A-22). , A-25 to A-27, A-30) had a very wide gamat and excellent color reproducibility.

On the other hand, Comparative Examples A-1 to A-17 contain an ink having a high content of any one of a halogen atom, a primary aromatic amine, and a heavy metal that affects the environment, and thus cannot solve the problem of the present application.

<Manufacturing of clear ink with desorption>
(Preparation of clear ink [1])
Polyurethane resin solution [2] (solid content 30%) 87 parts, ethyl acetate (EA) 5 parts, IPA 5 parts, silica ("P-73" manufactured by Mizusawa Chemical Co., Ltd., hydrophilic silica particles with an average particle diameter of 3.8 μm) Three parts were stirred and mixed using a disper to obtain clear ink [1].

<Manufacturing of adhesive with desorption>
(Preparation of Laminate Adhesive Solution [1])
82 parts of terephthalic acid, 682 parts of isophthalic acid, 236 parts of adipic acid, 236 parts of ethylene glycol, 525 parts of neopentyl glycol and 405 parts of 1,6-hexanediol were placed in a four-neck separable flask at 220 to 260 ° C. An esterification reaction was carried out. After distilling a predetermined amount of water, the pressure was gradually reduced to 1 mmHg or less, and a deglycolation reaction was carried out at 240 to 260 ° C. for 5 hours. Then, 2 parts of isophorone diisocyanate was gradually added, and the reaction was carried out at 150 ° C. for about 2 hours to obtain a polyester polyurethane polyol. To 100 parts of this polyester polyurethane polyol, 2.83 parts of trimellitic anhydride was added, and the mixture was reacted at 180 ° C. for about 2 hours. Then, it was diluted with ethyl acetate to a non-volatile content of 50% to obtain a partially acid-modified polyester polyol solution having a number average molecular weight of 6,000 and an acid value of 16.5 mgKOH / g.
100 parts of the obtained polyol solution and 7.94 parts of HDI Biuret's non-volatile content 95% ethyl acetate solution were mixed, and ethyl acetate was added to obtain a laminated adhesive solution [1] having a non-volatile content of 30%.

<Manufacturing of packaging materials>
[Example B-1] Packaging material 1
The above-mentioned clear ink [1] was diluted with an EA / IPA mixed solvent (mass ratio 70/30) so as to have a viscosity of 15 seconds (25 ° C., Zahn cup No. 3).
Cyan ink [1], yellow ink [1], and magenta ink [1] were diluted with the above-mentioned mixing solvent 1 so as to have a viscosity of 16 seconds (25 ° C., Zahn cup No. 3).
Each diluted ink contains a gravure calibration five-color machine equipped with a gravure plate with a plate depth of 20 μm, clear ink [1], cyan ink [1], yellow ink [1], and magenta ink [1]. Using an ink set, clear ink [1], cyan ink [1], yellow ink [1], and magenta ink [1] are overprinted on a corona-treated stretched polypropylene film having a thickness of 20 μm in this order. Each unit was dried at 50 ° C. to obtain a printed matter having a composition of "OPP base material / desorption layer (clear ink) / cyan, yellow or magenta printing layer" and including a desorption-removing layer. ..
Next, a laminate adhesive solution [1] was applied onto the printed layer of the obtained printed matter using a dry laminating machine, and an aluminum-deposited unstretched polypropylene (VMCPP) film having a thickness of 25 μm at a line speed of 40 m / min. The packaging material 1 has a structure of "OPP base material / print layer having desorption property / three-color layered printing layer / adhesive layer having desorption property / VMCPP base material" and has a desorption layer. Obtained.

[Examples B-2 to B-32, Comparative Examples B-1 to B-17] Packaging materials 2-49
Packaging materials 2 to 49 having a desorbing layer were obtained in the same manner as in Example B-1 except that the ink set was changed to the ink shown in Table 8.

<Evaluation of packaging materials>
A test piece having a size of 4 cm × 4 cm was cut out from the obtained packaging material, immersed in 50 g of a 2% sodium hydroxide aqueous solution, and then stirred at 40 ° C. for 30 minutes. After stopping the stirring, the printed layer precipitated on the bottom was collected, washed with ion-exchanged water, and then dried. Using a dry printing layer, the amount of halogen, the amount of primary aromatic amine, and the amount of heavy metals affecting the environment were measured in the same manner as in the evaluation of the gravure printing ink described above. The results are shown in Table 8.

According to Table 8, as in Examples B-1 to B-32, the packaging material using the gravure printing ink set of the present invention has a primary halogen content in the printing layer after the desorption treatment. The amount of aromatic amines and the amount of heavy metals that affect the environment are extremely small. That is, even when the packaging material is recycled or discarded, it is excellent in terms of safety and health and reduction of environmental load.

On the other hand, the packaging material of Comparative Examples B-1 to B-17 is either the amount of halogen contained in the printed layer after the desorption treatment, the amount of primary aromatic amine, or the amount of heavy metal affecting the environment. It is not possible to solve the problems of safety and health and reduction of environmental load.

Claims (7)

Cyan ink containing a pigment represented by the following formula (1) and a binder resin,
A yellow ink containing a pigment represented by the following general formula (2) and a binder resin, and a magenta ink containing at least one pigment selected from the group consisting of the following general formulas (3) to (5) and a binder resin. Including
The amount of halogen contained in the cyan ink, the yellow ink, and the magenta ink is 100 ppm or less, the amount of primary aromatic amine is 500 ppb or less, and the amount of heavy metal affecting the environment is 10 ppm, respectively. The following gravure printing ink set.

[In the general formula (2), X _{1 to} X ₄ independently represent a hydrogen atom, a nitro group, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a thioalkyl group, or a thioaryl group. X ₅ and X ₆ each independently represent a hydrogen atom or an alkyl group. A represents a group represented by the general formula (2-1) or (2-2).
In the general formula (2-1), Y ₁ represents -O- or -NH-, and X ₇ represents a hydrogen atom, an alkyl group, or an aryl group.
In the general formula (2-2), _{X 8} and _{X 9} each independently represent a hydrogen atom or an alkyl group. ]

[In the general formula (3), X _{10 to} X ₁₇ each independently represent a hydrogen atom or an alkyl group.
In the general formula (4), X _{18 to} X ₂₇ each independently represent an aryl group which may have a hydrogen atom, an alkyl group, a cyano group, an alkoxy group, a thioalkyl group, or a substituent.
In the general formula (5), Y ₂ represents -O- or -NR-, and R represents an aryl group which may have a hydrogen atom, an alkyl group, or a substituent. ] The gravure printing ink set according to claim 1, wherein the pigment represented by the general formula (2) contains at least one pigment selected from the group consisting of the following formulas (6) to (8).

The gravure printing ink set according to claim 1 or 2, wherein at least one pigment selected from the group consisting of the general formulas (3) to (5) contains a pigment represented by the general formula (3). The gravure printing ink set according to any one of claims 1 to 3 , further comprising a clear ink having desorption property. A printed matter including a printing layer formed from the gravure printing ink set according to any one of claims 1 to 4 and a base material layer. The printed matter according to claim 5 , which comprises a layer having a removable property. A packaging material using the printed matter according to claim 5 or 6.