JP2022140258A - Gravure print ink set, printed material, and packaging material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a recyclable gravure print ink set, a printed material, and a packaging material.

SOLUTION: A gravure print ink set contains a cyan ink containing a phthalocyanine pigment represented by formula (1) and a binder resin, a yellow ink containing an isoindoline pigment represented by general formula (2) and a binder resin, and a magenta ink containing at least one pigment selected from the group consisting of general formulae (3)-(5) and a binder resin.

SELECTED DRAWING: None

COPYRIGHT: (C)2022,JPO&INPIT

Description

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

In recent years, plastic products such as packages using plastic films and plastic bottles have been discarded or dumped into the ocean as garbage, which has become a problem of environmental pollution. These plastic products are decomposed in seawater to become submicron-sized fragments (microplastics) and float in seawater. Such microplastics have fine irregularities on their surfaces and have the property of easily adsorbing harmful chemical substances. Also, the microplastics themselves may contain harmful chemicals.
There is also concern that harmful chemical substances derived from microplastics accumulate in the bodies of marine organisms and affect ecosystems when marine organisms misidentify microplastics as food and ingest them. Furthermore, there is concern that harmful chemical substances may accumulate in the human body as a result of humans ingesting the marine organisms.

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

As the above (1), for example, there is a method of sorting plastic products by resin, removing impurities, pulverizing, washing, and melting to make pellets, and using the pellets to make new products. . However, when resins are melted, heat of 200°C or higher is normally applied, so if ink containing a large amount of halogen atoms or primary aromatic amines adheres to plastic products, they may be exposed to halogen gas or acid gas. A certain amount of hydrogen chloride, etc., may be generated and damage the equipment. Also, primary aromatic amines can 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 detached from the plastic product, the detached ink must be finally discarded after being subjected to a treatment such as incineration. Therefore, if the ink contains a large amount of halogen atoms or primary aromatic amines, halogen gas may be generated during incineration, which may damage the incinerator and may generate harmful gases such as dioxin. Aromatic amines may affect the human body. Also, if the ink contains heavy metals that affect the soil, it is difficult to dispose of it in a landfill because the metal remains unburned when incinerated.

Similarly for (2) and (3) above, if the ink adhering to plastic products contains halogen atoms, halogen gas or hydrogen chloride may be generated, which may damage the furnace, and may generate harmful gases such as dioxin. There is In the case of (3), if the ink adhering to the plastic products contains heavy metals that affect the soil, the metals remain without burning even if they are incinerated, making landfill disposal difficult.

In this way, it is difficult to recycle plastic products that are safe and have a reduced environmental impact. , and there has been no report of a gravure printed material capable of forming a plastic product excellent in safety and health and in reducing environmental load.

Japanese Patent No. 6631964

SUMMARY OF THE INVENTION It is an object of the present invention to provide recyclable gravure printing 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 provides 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: A gravure printing ink set comprising:

[In general formula (2), X ₁ to X ₄ each 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. _X5 and _X6 each independently represent a hydrogen atom or an alkyl group. A represents a group represented by general formula (2-1) or (2-2).
In general formula (2-1), Y ₁ represents —O— or —NH—, X ₇ is a hydrogen atom, an alkyl group,
or represents an aryl group.
In general formula (2-2), X ₈ and X ₉ each independently represent a hydrogen atom or an alkyl group. ]

[In general formula (3), X ₁₀ to X ₁₇ each independently represent a hydrogen atom or an alkyl group.
In general formula (4), X ₁₈ to X ₂₇ each independently represent a hydrogen atom, an alkyl group, a cyano group, an alkoxy group, a thioalkyl group, or an aryl group which may have a substituent.
In general formula (5), Y ₂ represents —O— or —NR—, and R represents a hydrogen atom, an alkyl group, or an aryl group which may have 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 general formulas (3) to (5) contains a pigment represented by general formula (3).

The present invention further relates to the above gravure printing ink set, which contains a releasable clear ink.

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

The present invention relates to the above-mentioned printed matter including a layer having releasability.

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

The present invention can provide recyclable gravure printing ink sets, printed matter, and packaging materials.

The gravure printing ink set of the present invention comprises a cyan ink containing a phthalocyanine pigment represented by formula (1) and a binder resin, a yellow ink containing an isoindoline pigment represented by general formula (2) and a binder resin, and It is characterized by containing a magenta ink containing at least one pigment selected from the group consisting of general formulas (3) to (5) and a binder resin.
Cyan, which forms the three primary colors, by specifying that the pigments contained in cyan ink, yellow ink, and magenta ink do not contain halogen atoms or heavy metals that affect the environment, and do not contain or generate primary aromatic amines. , yellow, and magenta, the content of halogen atoms, heavy metals that affect the environment, and primary aromatic amines can be greatly reduced.
By reducing the amount of halogen atoms, it is possible to reduce the generation of toxic gases such as dioxins during combustion and improve safety during combustion. In addition, since generation of hydrogen chloride gas can be reduced, corrosion of 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 eventually ecosystems when landfilling waste.
Reducing the amount of primary aromatic amines can reduce the production of toxic fumes during combustion and the release of potentially health-threatening chemicals into the environment during landfills.
As a result, printed matter and packaging materials obtained using the ink set have significantly reduced contents of the above components, and are excellent in terms of health and safety and environmental conservation.
The present invention will be described in detail below.

In this specification, "(meth)acryloyl", "(meth)acryl", "(meth)acrylic acid", "(meth)acrylate", and "(meth)acrylamide" are not particularly explained. Unless specified otherwise, each represents "acryloyl and/or methacryloyl", "acrylic and/or methacrylic", "acrylic acid and/or methacrylic acid", "acrylate and/or methacrylate", and "acrylamide and/or methacrylamide" .

<Gravure printing ink set>
The gravure printing ink set used in the present invention contains pigments, binder resins, organic solvents, and, if necessary, pigment dispersants, leveling agents, antifoaming agents, waxes, plasticizers, infrared absorbers, ultraviolet absorbers, and other auxiliary agents. This set includes three color inks, cyan ink, magenta ink, and yellow ink.
The gravure printing ink set of the present invention may contain other inks such as black ink, white ink, and special color ink within a range that does not impair the effects of the present invention.

<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, or heavy metals that affect the environment, and has excellent trapping properties. A gravure ink set can be provided that has the required hue.

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

Any known method may be used for the production of metal phthalocyanine. For example, phthalates, urea, metals or metal salts, catalysts, etc. may be heated in the presence or absence of an organic solvent. can be manufactured.

After synthesis, the pigment (1) is preferably washed with water or an organic solvent after separation from the reaction solvent such as solvent filtration or solvent distillation. Acid or alkali may be used for washing. If further purification is required, impurities may be removed by known purification techniques such as sublimation, acid paste, acid slurry, reprecipitation, recrystallization and extraction.

In addition, the phthalocyanine pigment represented by formula (1) may be used as it is synthesized, but depending on the purpose such as transition to a desired crystal form, control of particle size, imparting easy dispersibility, etc. , it is preferable to carry out a pigmentation operation. Pigmentization is the process of processing crude pigments, called crude pigments, which have large crystals and a wide particle size distribution, to a state that can be used as pigments through processes such as purification, control of crystal shape and particle size, and surface treatment. Examples of treatments include solvent method, solvent milling method, and solvent salt milling method. As a pretreatment for the pigmentation treatment, an operation such as acid paste or dry milling may be performed, or a plurality of pigmentation methods may be used in combination.

Moreover, the cyan ink in the present invention may contain any combination of known colorants as required without departing from the effects of the present invention.
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 general formula (2), X ₁ to X ₄ each 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. _X5 and _X6 each independently represent a hydrogen atom or an alkyl group. A represents a group represented by general formula (2-1) or (2-2).
In 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 general formula (2-2), X ₈ and X ₉ each independently represent a hydrogen atom or an alkyl group.

By including the isoindoline pigment (2) in the yellow ink, the ink set of the present invention does not contain halogen atoms, primary aromatic amines, or heavy metals that affect the environment, and has excellent trapping properties. A gravure printing ink set can be provided that has the necessary hues for the inks.

In the general formula (2), the alkyl group (-R) in X ₁ to X ₆ 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 condensed structure. Any polycyclic structure may be used.
Examples of alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, octadecyl, isopropyl, isobutyl, and 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 and 4-decylcyclohexyl group.

The alkyl group may have a structure in which two or more alkyl groups (one of which 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, an 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 groups include -C ₂ H ₄ -O-C ₂ H ₅ .

In general formula (2), the number of carbon atoms in the alkyl group in X ₁ to X ₆ is preferably 1 to 10, more preferably 1 to 6, still more preferably 1 to 4, and particularly preferably 1 or two.

In general formula (2), the alkoxy groups in X ₁ to X ₄ are groups (-OR) in which an oxygen atom is bonded to the above alkyl group (-R).

In general formula (2), the aryl group (--Ar) in X ₁ to X ₄ means an atomic group obtained by removing one hydrogen atom from an aromatic hydrocarbon.
Aryl groups include, for example, phenyl, tolyl, xylyl, biphenylyl, terphenylyl, quarterphenylyl, pentalenyl, indenyl, naphthyl, binaphthalenyl, ternaphthalenyl, quarternaphthalenyl, and azulenyl groups. , heptalenyl group, biphenylenyl group, indacenyl group, fluoranthenyl group, acephenanthrilenyl group, aceanthrilenyl group, phenalenyl group, fluorenyl group, anthryl group, bianthracenyl group, teranthracenyl group, quarteranthracenyl group , anthraquinolyl group, phenanthryl group, triphenylenyl group, pyrenyl group, chrysenyl group, naphthacenyl group, preiadenyl group, picenyl group, perylenyl group, pentaphenyl group, pentacenyl group, tetraphenylenyl group, hexaphenyl group, hexacenyl group, rubisenyl group, coronenyl group, trinaphthylenyl group, heptaphenyl group, heptacenyl group, pyrantrenyl group, or ovalenyl group, methoxyphenyl group and ethoxyphenyl group.
The number of carbon atoms in the aryl group is preferably 6-30, more preferably 6-20. Most preferably the aryl group is a phenyl group.

In general formula (2), the aryloxy group in X ₁ to X ₄ is a group (-OAr) in which an oxygen atom is bonded to the above aryl group (-Ar). In one embodiment, the aryloxy group is preferably a phenoxy group.

In the general formula (2), the thioalkyl group in X ₁ to X ₄ is a group (-SR) in which a sulfur atom is bonded to the above alkyl group. In one embodiment, the thioalkyl group is preferably a group in which a sulfur atom is attached to an alkyl group having a linear structure.
A thioaryl group is a group (-SAr) in which a sulfur atom is bonded to the above aryl group. In one embodiment, the thioaryl group is preferably a thiophenyl group.

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

In general formula (2-1), Y ₁ represents -O- or -NH-, preferably -NH-.
In _X7 , the description in the previous general formula (2) can be used for the alkyl group and the aryl group. From the viewpoint of heat resistance, weather resistance, and dispersion stability, the number of carbon atoms in the alkyl group is preferably 1 to 10, more preferably 1 to 6, still more preferably 1 to 4, and particularly preferably 1 or 2.

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

Pigments (6) to (24) represented by the following formulas (6) to (24) are preferable as the isoindoline pigment (2) represented by the general formula (2).

Among them, from the viewpoint of heat resistance, weather resistance, and dispersion stability, more preferably at least one selected from the group consisting of pigments (6) to (8) represented by the above formulas (6) to (8) pigments.

The isoindoline pigment (2) is preferably used after being processed into fine particles by performing a refining treatment. The refinement treatment includes, for example, a dissolution precipitation method represented by acid pasting, solvent salt milling, dry milling, and the like. The average primary particle size of the pigment particles after refining is preferably 20 to 300 nm, more preferably 50 to 150 nm. The particle diameter of the pigment particles may grow depending on the solvent salt milling conditions.

The isoindoline pigment (2) represented by the general formula (2) may be used alone, or two
More than one type may be used in combination.
When the yellow ink in the present invention contains two or more isoindoline pigments (2), the production method thereof includes the following.
(I) a method of synthesizing two or more at once (co-synthesis method), (II) a method of mixing two or more isoindoline pigments when preparing a dispersion, (III) two or more isoindoline pigments together. and (IV) a method of combining the above methods.
Among them, (I) a cosynthesis method, (III) a method of pigmenting together using an acid pasting method and a solvent salt milling method, and (IV) a method of combining (I) and (III). Either.

The yellow ink in the invention may contain any combination of known colorants, if necessary, without departing from the effects of the invention.
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 invention contains at least one pigment selected from the group consisting of the following general formulas (3) to (5) and a binder resin.

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

The ink set of the present invention contains, in the magenta ink, at least one pigment selected from the group consisting of the general formulas (3) to (5), so that halogen atoms, primary aromatic amines, environmentally friendly It is possible to provide a gravure printing ink set that does not contain influential heavy metals, has excellent trapping properties, and has the hue necessary for printing inks.

[Pigment Represented by Formula (3)]
Pigment (3) represented by 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 condensed structure. Any polycyclic structure may be used.

Examples of the alkyl group include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, dodecyl group, octadecyl group, trifluoromethyl group, and isopropyl 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 (one of which 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, an 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 groups include -C ₂ H ₄ -O-C ₂ H ₅ .

The number of carbon atoms in the alkyl group of X ₁₀ to X ₁₇ is preferably 1-10, more preferably 1-6, still more preferably 1-4, 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, etc. are known, and from the viewpoint that the content of anilines, which are primary aromatic amines, is very small, (1) thermal process is preferable. It's a process.

Pigments (25) to (29) represented by the following formulas (25) to (29) are preferable as the pigment (3) represented by the general formula (3).

[Pigment Represented by Formula (4)]
Pigment (4) represented by general formula (4) is a diketopyrrolopyrrole (DPP) pigment.
As for the alkyl groups for X ₁₈ to X ₂₇ in general formula (4), the descriptions for X ₁₀ to X ₁₇ in general formula (3) above can be used. The number of carbon atoms in the alkyl groups in X ₁₈ to X ₂₇ is preferably 1-10, more preferably 1-6, even more preferably 1-4, 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 alkyl group (-R).

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

In general formula (4), the optionally substituted aryl group (—Ar) 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 pentalenyl group, an indenyl group, a naphthyl group, a binaphthalenyl group, a ternaphthalenyl group, a quarternaphthalenyl group, and an azulenyl group. group, heptalenyl group, biphenylenyl group, indacenyl group, fluoranthenyl group, acephenanthrilenyl group, aceanthrilenyl group, phenalenyl group, fluorenyl group, anthryl group, bianthracenyl group, teranthracenyl group, quarteranthracenyl anthraquinolyl group, phenanthryl group, triphenylenyl group, pyrenyl group, chrysenyl group, naphthacenyl group, preiadenyl group, picenyl group, perylenyl group, pentaphenyl group, pentacenyl group, tetraphenylenyl group, hexaphenyl group, hexacenyl group, Rubicenyl group, coronenyl group, trinaphthylenyl group, heptaphenyl group, heptacenyl group, pyrantrenyl group, or obalenyl group, methoxyphenyl group and ethoxyphenyl group.
The aryl group in X ₁₈ to X ₂₇ preferably has 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms. A phenyl group is most preferred as the aryl group.

The method for producing the diketopyrrolopyrrole pigment (4) used in the present invention is not particularly limited. It can be produced by reacting with

Pigments (30) to (41) represented by the following formulas (30) to (41) are preferable as the pigment (4) represented by the general formula (4).

[Pigment Represented by Formula (5)]
Pigment (5) represented by general formula (5) is a perylene pigment.
In general formula (5), for the alkyl group in -NR- of Y ₂ , the description of X ₁₀ to X ₁₇ in general formula (3) above can be used. The number of carbon atoms in the alkyl group in -NR- of Y ₂ is preferably 1 to 10, more preferably 1 to 6, even more preferably 1 to 4, and particularly preferably 1 or 2.

In general formula (5), for the aryl group that may have a substituent in -NR- of Y ₂ , the description of X ₁₈ to X ₂₇ in general formula (4) above can be used. The aryl group in -NR- of Y ₂ preferably has 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms. A phenyl group is most preferred 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.; Hunger, Industrial Organic Pigments: Production, Properties, Applications, 1993, p467-480. The method for producing the perylene pigment is not limited to this method.

Pigments (42) to (53) represented by the following formulas (42) to (53) are preferable as the pigment (5) represented by the general formula (5).

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

The magenta ink in the present invention may contain any combination of known colorants as required without departing from the effects of the present invention.
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>
Binder resins used in the ink set for gravure printing of the present invention include, for example, polyurethane resins, ethylene-vinyl acetate copolymer resins, vinyl acetate resins, nitrocellulose resins, polyamide resins, acrylic resins, polyester resins, alkyd resins, Rosin-based resins, rosin-modified maleic acid resins, ketone resins, cyclized rubbers, butyral, and petroleum resins.
From the viewpoint of containing no halogen atoms, the binder resin preferably does not contain vinyl chloride-vinyl acetate copolymer resin, chlorinated polypropylene resin, polyvinyl chloride resin, chlorinated rubber, or the like. However, it does not exclude inclusion within the range that does not deviate from the effects of the present invention.
These binder resins are independently selected for each color of cyan, yellow, and magenta, and one type may be used alone, or two or more types may be used in combination.

[Polyurethane resin]
A polyurethane resin is preferably used as the binder resin in the present invention.
Polyurethane resins in the present specification include polyurethane urea resins, and can be obtained by conventionally known methods.
As a known method, for example, a urethane prepolymer having an isocyanate group at the end obtained by reacting a polyol and a diisocyanate compound at a rate in which the isocyanate group is excessive is subjected to chain extension having an amino group in an appropriate solvent. A two-step method of reacting with an agent and/or a terminal blocking agent; Alternatively, a single step of reacting polypropylene glycol, a combined polyol, a diisocyanate compound, a chain extender having an amino group and/or a terminal blocking agent in an appropriate solvent at once. law;
Examples of the above solvents 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; Hydrocarbon solvents such as methylcyclohexane and ethylcyclohexane; or mixed solvents thereof.
Among these methods, the two-step method is preferred 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 groups of the urethane prepolymer to the amino groups of the chain extender and terminal blocker (moles of isocyanate groups/moles of amino groups) is 1/1. It is preferably in the range of 3 to 1/0.9. When the equivalent ratio between the isocyanate group and the amino group is 1/1.3 or more, the chain extender and/or terminal blocking agent remaining unreacted is reduced, and yellowing of the polyurethane resin and odor after printing are prevented. can be suppressed. When the equivalent ratio between the isocyanate group and the amino group is 1/0.9 or less, the obtained polyurethane resin has an appropriate molecular weight, and a resin that provides 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 printed film, and the oil resistance are excellent. , excellent gloss of the printed film.

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

<Ink production>
The cyan, yellow, and magenta inks of the present invention can be produced by, for example, dissolving and/or dispersing a coloring agent containing a predetermined pigment and a binder resin in an organic solvent. Specifically, a pigment, a binder resin solution, and, if necessary, a pigment dispersant or the like are added and mixed and dispersed to produce a pigment dispersion. It can be produced by blending agents and the like.

The particle size distribution of the pigment in the pigment dispersion can be adjusted by adjusting the size of the grinding media of the disperser, the filling rate of the grinding media, the dispersion processing time, the ejection speed of the pigment dispersion, the viscosity of the pigment dispersion, and the like. can. As the dispersing machine, a commonly used roller mill, ball mill, pebble mill, attritor, sand mill, or the like can be used. If air bubbles or unexpected coarse particles are contained in the ink, it is preferable to remove them by filtration or the like, as they reduce the quality of printed matter. A conventionally known filter can be used.

[Organic solvent]
Organic solvents that may be used in the gravure printing ink set of the present invention include known organic solvents such as aromatic organic solvents such as toluene and xylene; 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, and propylene glycol monomethyl ether acetate; Alcohol-based organic solvents such as n-propanol, isopropanol, ethanol methanol, ethanol, n-propanol, isopropanol, and n-butanol; glycol ether solvents such as ethylene glycol monopropyl ether and propylene glycol monomethyl ether; These organic solvents are preferably used in combination of two or more.
Among them, 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 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 sedimentation of the pigment and appropriately dispersing the pigment, and preferably 1,000 mPa·s or less from the viewpoint of work efficiency during ink production and printing. The above viscosity is a value measured at 25° C. with a Brookfield viscometer manufactured by Tokimec.

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

The above halogen content can be determined by a measuring method based on JIS K0127 (2013). In this measurement method, a sample that has been pretreated by the combustion method is quantified by the ion chromatography method. It can be determined by quantifying the halogen content of the sample obtained by performing pretreatment by the combustion method by ion chromatography.

[Primary aromatic amine]
In the gravure printing ink set of the present invention, all three colors do not contain primary aromatic amines, or if they do contain them in very small amounts, the amount of primary aromatic amines in the ink set is greatly reduced. can do.
The term "primary aromatic amine" as used herein 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 in the cyan ink is preferably 10 ppm or less, more preferably 1 ppm or less, and still more preferably 500 ppb (detection limit) or less based on the weight of the non-volatile matter of the ink.
The amount of the primary aromatic amine in the yellow ink is preferably 10 ppm or less, more preferably 1 ppm or less, and still more preferably 500 ppb (detection limit) or less based on the weight of the non-volatile matter of the ink.
The amount of the primary aromatic amine in the magenta ink is preferably 10 ppm or less, more preferably 1 ppm or less, and even more preferably 500 ppb (detection limit) or less, based on the weight of the non-volatile matter of the ink.
Among them, it is particularly preferable that the amount of the primary aromatic amine contained in each of the cyan ink, the yellow ink, and the magenta ink is 500 ppb or less. 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 the ink set becomes 500 ppb or less, which is more excellent in safety and reduces the environmental load. can.

[Heavy metals that affect the environment]
In the gravure printing ink set of the present invention, all three colors do not contain heavy metals that affect the environment, or even if they contain a very small amount, the amount of heavy metals that affect the environment as an ink set can be greatly reduced. can be reduced.
Heavy metals are metals with a specific gravity of 4 or more, and many heavy metals are toxic to plants or affect humans and the environment, so the allowable amount in soil is regulated.
For example, copper and zinc are known to inhibit the growth of plants when taken in excess, while mercury, cadmium, lead, hexavalent chromium, arsenic, and the like are known to affect human health.
In addition, excessive intake of other heavy metals by plants causes growth inhibition and chlorosis, and the impact on microorganisms in the soil reduces the ability to decompose organic matter. It burns printing ink and becomes a detriment when trying to landfill.

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. Although iron is also a heavy metal, it is essential for the growth of plants, and it is known that there is no problem even if it is present in the soil in trace amounts.

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

The amount of heavy metals that affect the environment in cyan ink is preferably 100 ppm or less, more preferably 50 ppm or less, and still more preferably 10 ppm or less, based on the weight of non-volatile matter in the ink.
The amount of heavy metals that affect the environment in yellow ink is preferably 100 ppm or less, more preferably 50 ppm or less, and even more preferably 10 ppm or less, based on the mass of the non-volatile matter of the ink.
The amount of heavy metals that affect the environment in magenta ink is preferably 100 ppm or less, more preferably 50 ppm or less, and even more preferably 10 ppm or less, based on the mass of non-volatile matter in the ink.
Among them, it is particularly preferable that the amount of heavy metals affecting the environment contained in the cyan ink, the yellow ink, and the magenta ink is 10 ppm or less. 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 becomes 10 ppm or less, and it is possible to improve safety and reduce the environmental load. can.

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

<Clear ink with releasability>
The gravure printing ink set of the present invention may further contain a releasable clear ink. The term “releasable clear ink” refers to a print layer formed from the clear ink that has the property of being neutralized with an alkaline aqueous solution and dissolved or swollen, thereby detaching from the substrate layer.
The basic compound used in the alkaline aqueous solution is not particularly limited, and examples thereof include sodium hydroxide (NaOH), potassium hydroxide (KOH), calcium hydroxide (Ca(OH) ₂ ), ammonia, barium hydroxide (Ba (OH) ₂ ), sodium carbonate (Na ₂ CO ₃ ). More preferably, it is at least one selected from the group consisting of sodium hydroxide and potassium hydroxide.
In this specification, the process of neutralizing with an alkaline aqueous solution and dissolving or swelling may be referred to as "alkali treatment". In addition, a layer that can be detached by alkali treatment is sometimes referred to as a "detachment layer". In other words, the printed layer formed of the releasable clear ink corresponds to the releasable layer (release layer).

[Resin containing hydroxyl group]
The releasable clear ink preferably contains a carboxy group-containing resin, and is suitably used as a primer composition to be printed on the substrate layer before the color ink.
The carboxy group-containing resin is not particularly limited, and can be selected from conventionally known resins, and may be used singly or in combination of two or more. Examples of the resin skeleton of the carboxy group-containing resin include acrylic resins, urethane resins, polyester resins, amino resins, phenol resins, epoxy resins, and cellulose, and urethane resins are preferable because of their good lamination 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, the releasability with an alkaline aqueous solution becomes good, and when it is 35 mgKOH/g or less, the substrate adhesion becomes good, so it is preferable.
The acid value of the carboxy group-containing urethane resin is preferably 15 mgKOH/g or more,
More preferably 15 to 70 mgKOH/g, still more preferably 20 to 50 mgKOH/g. When it is 15 mgKOH/g or more, it is preferable because the removability with an alkaline aqueous solution is improved, and when it is 70 mgKOH/g, it is preferable because adhesion to the substrate and retort resistance when used as a packaging material are improved.
Both hydroxyl value and acid value are values measured according to JISK0070.

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, it is possible to avoid the effects of excessive high-molecular-weight components, unreacted components, side-reacted components and other low-molecular-weight components. Retort resistance aptitude is improved.
In addition, the smaller the molecular weight distribution, that is, the sharper the molecular weight distribution, the more uniform the dissolution and peeling action by the alkaline aqueous solution occurs, and the detachability is improved, which is preferable. The molecular weight distribution is more preferably 5 or less, still more preferably 4 or less. Also, 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 urethane resin containing a carboxyl group is not particularly limited, and for example, it is preferably a resin obtained by reacting polyol, hydroxy acid and polyisocyanate. By using a hydroxy acid, an acid value can be imparted to the urethane resin, and the releasability can be improved. More preferably, it is a resin obtained by reacting a polyol, a hydroxy acid and a polyisocyanate, and a polyamine.

The releasable clear ink may further contain polyisocyanate as a curing component. The polyisocyanate is not particularly limited and can be selected from conventionally known polyisocyanates, such as aliphatic polyisocyanates and araliphatic polyisocyanates.
In addition, the clear ink having releasability may contain other components other than the hydroxyl group-containing resin and polyisocyanate. Similar to the cyan, yellow, and magenta inks described above, organic solvents, blocking agents, etc. may be added. agents can be added.

<Printed Matter>
The printed material of the present invention has a printed layer formed from the above gravure printing ink set and a substrate layer, and the cyan ink, yellow ink and magenta ink in the ink set of the present invention are printed on the substrate. can be obtained.
The method of gravure printing is not particularly limited, and can be appropriately selected from known methods. The method of gravure printing is roughly divided into surface printing and reverse printing. A printed matter can be obtained by printing in order of black ink.
Further, for example, when the base material is a transparent film in reverse printing, a printed material can be obtained by printing black ink, cyan ink, magenta ink, yellow ink, and white ink in this order on the base material. can.
When the ink set of the present invention contains clear ink, the clear ink is preferably printed on the substrate before the color inks.
The thickness of the printed layer can be appropriately selected according to the application, the type and number of inks to be used, and the number of times of overprinting, but it is usually in the range of 0.5 to 10 μm.

[Base material layer]
Examples of base materials 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; vinyl base material; polyvinylidene chloride base material; cellophane base material; paper base material; aluminum foil base material; The substrate may be either film-like or sheet-like. Among them, a polyester base material and a polyamide base material having a high glass transition point are preferably used.

The surface of the substrate may be vapor-deposited with metal oxide or the like, or may be coated with polyvinyl alcohol or the like. Examples of such surface-treated substrates include GL-AE manufactured by Toppan Printing Co., Ltd. and IB-PET-PXB manufactured by Dai Nippon Printing Co., Ltd., the surface of which is vapor-deposited with aluminum oxide. The substrate may optionally be treated with additives such as antistatic agents and UV inhibitors, and may be corona treated or low temperature plasma treated.

[Layer having releasability (releasing layer)]
The printed matter of the present invention can contain a layer having releasability. Here, the term "having releasability" refers to those having the property of being neutralized with an alkaline aqueous solution, dissolved or swollen, and thereby detached from the substrate layer. The layer having releasability may be a printed layer formed from the clear ink described above, or may be a layer other than the printed layer.
The thickness of the releasable layer is not particularly limited and is usually in the range of 0.5 to 5 μm.

<Packaging material>
The shape of the packaging material of the present invention is not limited as long as the above-mentioned printed material is used for at least a part thereof. The packaging material includes, for example, a configuration in which a printed material and a sealant base material are laminated together via an adhesive layer made of a known adhesive, such as a four-side seal package, a three-side seal package, a pillow package, and a stick. Bags, gusset bags, square-bottom bags, standing pouches, deep draw containers, vacuum packages, skin packs, zipper bags, spout pouches, twist packaging, wrap packaging, shrink packaging, labels, paper packs for liquids, paper trays, etc. It can be suitably used for a package having a shape.

[Adhesive layer]
Examples of adhesive components 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; polyurethanes; Epoxy adhesive; Phenolic resin; Nylon 6, Nylon 66, Nylon 12, polyamide resin such as copolyamide; Polyolefin, carboxylic acid-modified polyolefin, metal-modified polyolefin, etc. Vinyl acetate adhesive; cellulose adhesive; (meth)acrylic adhesive; polyimide resin; amino resin such as urea resin and melamine resin; rubber such as chloroprene rubber, nitrile rubber and styrene-butadiene rubber; silicone resin is mentioned.
These adhesive components may be used singly or in combination of two or more. Among these adhesive components, polyurethane adhesives are preferably used.

The polyurethane-based adhesive is a reactive adhesive containing polyol and polyisocyanate, and may have releasability. Releasable polyurethane adhesives include, for example, lamination adhesives described in JP-A-2020-084130.
Such a polyurethane adhesive having releasability preferably has an acid value of 5 to 45 mgKOH/g. Moreover, it is preferable that the polyol constituting the polyurethane-based adhesive includes a polyester polyol, and the polyisocyanate includes one selected from the group consisting of an aliphatic polyisocyanate and an araliphatic polyisocyanate.
The thickness of the adhesive layer is usually in the range of 1-6 μm.

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

<Measurement of amine value>
The amine value is the number of mg of potassium hydroxide equivalent to the acid required to neutralize 1 g of the solid content sample. After that, it is a value calculated from the titration amount.

<Molecular weight and molecular weight distribution>
Weight-average molecular weight (Mw), number-average molecular weight (Mn) and molecular weight distribution (Mw/Mn) are measured by GPC (gel permeation chromatography) under the following conditions, and polystyrene is used as a standard substance, and the converted molecular weight is asked.
GPC device: Showa Denko Shodex GPC-104
Column: The following columns were connected in series and used.
Showa Denko Shodex LF-404 2 Showa Denko 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>
Acid value and hydroxyl value were measured according to the method described in JIS K 0070 (1992).

<Production of pigment>
(Synthesis Example A-1) Synthesis of phthalocyanine compound [1] To 400 parts of 1-pentanol, 100 parts of o-phthalodinitrile and 119 parts of 1,8-diazabicyclo[5.4.0]undec-7-ene The mixture was heated with stirring and refluxed for 6 hours. After completion of the reaction, the resulting blue precipitate was filtered off and washed with methanol to obtain a blue cake.
Next, the resulting 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 the stirring was over, the blue precipitate was filtered off, washed with water, dried at 80° C. and pulverized to obtain a blue powder.
Next, the blue powder was added to 1000 parts of tetrahydrofuran, and the mixture was heated and stirred at 80° C. for 2 hours. After stirring, the blue precipitate was filtered off, 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] In 400 parts of 1-pentanol, 100 parts of o-phthalodinitrile, copper (I) chloride 19.3
and 119 parts of 1,8-diazabicyclo[5.4.0]undec-7-ene were mixed, heated and stirred, and refluxed for 6 hours. After completion of the reaction, the resulting blue precipitate was filtered off and washed with methanol to obtain a blue cake.
Next, the resulting 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 the stirring was over, the blue precipitate was filtered off, washed with water, dried at 80° C. and pulverized to obtain a blue powder.
Next, the 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 stirring, the sulfuric acid solution was added dropwise to 4000 parts of water while stirring to obtain a blue precipitate. The resulting blue precipitate was filtered off, washed with water, dried at 80° C. and pulverized to obtain a blue powder.
Next, the blue powder was added to 1000 parts of tetrahydrofuran, stirred, and refluxed for 2 hours. After 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] Into a four-necked flask equipped with a reflux condenser, a dropping funnel, and a stirrer, 800 parts of water, 60 parts of 1,3-diiminoisoindoline, and 28% 120 parts of ammonia water was sequentially added and stirred. A solution prepared by dissolving 42.58 parts of 2-cyano-N-methylacetamide in 160 parts of water was added dropwise thereto over 30 minutes using a dropping funnel. The mixture was heated and stirred at 30° C. until 1,3-diiminoisoindoline as a starting material disappeared. The reaction slurry was filtered using a Buchner funnel. Furthermore, the filtrate was added to 1600 parts of water and stirred at 40°C for 30 minutes. The slurry was filtered to obtain non-volatile matter. The disappearance of raw materials was confirmed by UPLC (ultra-high-speed high-separation liquid chromatography, manufactured by Waters).
Next, 60 parts of the non-volatile matter, 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 stirred. On the other hand, 461 parts of water and 194 parts of 80% acetic acid were added to a 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 stirring liquid of the non-volatile matter, and the mixture was heated to 85° C. and stirred to complete the reaction. The heating and stirring was continued until the non-volatile matter used as the raw material disappeared. Disappearance of raw materials 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 matter. The non-volatile matter 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 four-necked flask equipped with a reflux condenser, a dropping funnel and a stirrer and stirred. 128 parts of barbituric acid was added thereto and 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 a glass flask and stirred at 30°C. This stirred liquid was put into the heated solution, and the temperature was raised to 85° C. and stirred to complete the reaction. The heating and stirring was continued until the non-volatile matter used as the raw material disappeared. Disappearance of raw materials was confirmed by UPLC.
Then, after cooling to room temperature, it was washed three times with 2000 parts of water to obtain a non-volatile matter. The non-volatile matter 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] Instead of 40.74 parts of barbituric acid, 35.77 parts of barbituric acid and 6.31 parts of 1,3-dimethylbarbituric acid were used. 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 was tetrazotized by a conventional method using 3 times the molar amount of hydrochloric acid and 2 times the molar amount of sodium nitrite. A 0.125 mol/l tetrazo aqueous solution was prepared. On the other hand, 54.3 parts of acetoaceto-2,5-dimethoxy-4-chloroanilide was dissolved in an aqueous solution containing 14.4 parts of sodium hydroxide to prepare an aqueous coupler solution of 0.259 mol/l at 25°C. Also, as an acidic aqueous solution, 30 parts of 80% acetic acid, nonionic surfactant Cadenax DMC-W (trade name, manufactured by Lion Specialty Chemicals Co., Ltd.) 2.4 parts converted to active ingredients and 500 parts of acetic acid solution consisting of water. Prepared and charged to a reactor with stirrer. An aqueous coupler solution was injected into this acetic acid solution at a flow rate of 19.3 ml/min for 40 minutes to precipitate the coupler. 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. The injection took about 40 minutes until tetrazo was slightly detected on the surface of the reaction liquid. The coupling reaction rate was 91.8%. Thereafter, after heating to 70°C, filtration, purification and drying at 85°C gave 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 thoroughly dispersed in an aqueous hydrochloric acid solution. After adding ice to the dispersion in an ice bath and confirming that the temperature was below 0° C., 423 parts of a 38% sodium nitrite solution was added dropwise for diazotization. After completion of the dropwise addition, the mixture was stirred for 1 hour while confirming that nitrite ions were excessive with a potassium iodide starch paper, and then filtered to obtain a tetrazo solution. The tetrazo solution was used after adding sulfamic acid just before the coupling reaction until excess nitrite ions were no longer observed on potassium iodide starch paper. On the other hand, 750 parts of 5-acetoacetamide-benzimidazolone was added to 6,000 parts of water, stirred for 10 minutes and then brought to a temperature of 20-25°C. After adding 880 parts of a 29% aqueous sodium hydroxide solution and confirming that the solution was sufficiently dissolved, the mixture was filtered. The filtrate was adjusted to a total volume of 12,000 parts at 5° C. using water and ice, and 676 parts of 80% acetic acid was added over 20 minutes to obtain a coupler slurry. 10 parts of a condensation product of stearyl chloride and taurine was added as a coupling aid.
The tetrazo solution was injected under the surface of the coupler slurry at 18-22° C. for 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 mixture 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 presscake was stirred with water to form a paste, and water and isobutanol were added to form a 4% suspension of pigment solids in a 35% isobutanol water mixture.
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., the isobutanol was distilled off azeotropically by introducing steam. The aqueous pigment suspension was suction filtered, washed with a small amount of water, dried in a vacuum dryer at 70° C. and 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 (0.5 mol), 500 parts of methanol, and 4.65 parts (0.045 mol) of 35% hydrochloric acid were weighed into a 1-liter pressure-resistant glass autoclave, and after sealing, the oxygen in the reaction vessel was sufficiently removed with nitrogen gas. After the replacement, the gauge pressure was set to 0 kg/cm ² , and the temperature was raised from room temperature to 100° C. over 15 minutes while stirring vigorously, followed by reaction for 3 hours. The maximum pressure in the reaction vessel during the reaction was 3.8 kg/cm ² . After the reaction, the reaction system was cooled to 30° C. or lower and then opened to the atmospheric pressure. 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. Moreover, the purity was 99.5%.
Then, 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 200 ml flask having an outlet valve at the bottom under a nitrogen gas atmosphere. The mixture was heated to 120-170° C. with stirring at . On the other hand, 150 parts of the dimethylnaphthalene isomer mixture was heated to 280° C. or higher in a 500 ml flask under a nitrogen gas atmosphere with stirring. After introducing the above hot mixture over 20-40 minutes, the mixture was held at 280-283° C. (reflux) for 30 minutes. From the moment 2,5-dianilino-3,6-dihydroterephthalic acid dimethyl ester and the dimethylnaphthalene isomer mixture at 120-170° C. were introduced into the boiling dimethylnaphthalene isomer mixture, accompanied by the evolution of methanol6,13. -The formation reaction of 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 atmosphere was removed and the contents were filtered, washed with 500 parts of hot methanol and dried to give 24.47 parts (98.2% of theory) of 6,13-dihydroquinacridone. Obtained. The purity was greater than 99% by IR and absorbance.
10 parts of the 6,13-dihydroquinacridone obtained above and 80 parts of methanol were placed in a 200 ml flask equipped with a reflux device and stirred. Add 12 parts of a 50% aqueous sodium hydroxide solution and stir at 40° C. for 30 minutes. Then add 26 parts of 10% sulfuric acid dropwise for hydrolysis. 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 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 .5 parts (0.5 mol), 500 parts of methanol, and 4.65 parts (0.045 mol) of 35% hydrochloric acid were weighed into a 1-liter pressure-resistant glass autoclave, and after sealing, the reaction vessel was sufficiently filled with nitrogen gas. After oxygen was replaced, the gauge pressure was set to 0 kg/cm ² , and the temperature was raised from room temperature to 100° C. over 15 minutes while vigorously stirring, followed by reaction for 3 hours. The maximum pressure in the reaction vessel during the reaction was 3.8 kg/cm ² . After the reaction, the reaction system was cooled to 30° C. or lower and then opened to the atmospheric pressure. 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. Moreover, 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 added to a 200 ml flask having an outlet valve at the bottom, The mixture was heated to 120-170° C. while stirring under 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 under a nitrogen gas atmosphere with stirring. After introducing the above hot mixture over 20-40 minutes, the mixture was held at 280-283° C. (reflux) for 30 minutes. From the moment 2,5-dianilino-3,6-dihydroterephthalic acid dimethyl ester and the dimethylnaphthalene isomer mixture at 120 to 170° C. were introduced into the boiling dimethylnaphthalene isomer mixture, 2,9 with the evolution of methanol. -Dimethyl-6,13-dihydroquinacridone formation reaction started, and the generation of methanol almost stopped immediately after the start of reflux at 283°C. After cooling to 100.degree. 96.71%) was obtained.
10 parts of the 2,9-dimethyl-6,13-dihydroquinacridone obtained above and 80 parts of methanol were placed in a 200 ml flask equipped with a reflux device and stirred. Add 12 parts of a 50% aqueous sodium hydroxide solution and stir at 40° C. for 30 minutes. Then add 26 parts of 10% sulfuric acid dropwise for hydrolysis. 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 less in an ice bath, add 9 parts of the crude 2,9-dimethyl-quinacridone obtained above to 90 parts of 98% sulfuric acid stirred in a flask, taking care that the temperature does not rise above 30°C. was added while After the total amount was added, the mixture was stirred at 30°C or lower for 1 hour. The above sulfuric acid solution was added dropwise to 1000 parts of stirred water at 10°C while paying attention to bumping. After completion of dropping, the mixture was filtered and washed with water until it became neutral to obtain a press cake. Water was added to the resulting presscake, and the pH was adjusted to 9.0 with sodium hydroxide. Water and isobutanol were added to form a 4% suspension of pigment solids. This suspension was refluxed for 2 hours, after which isobutanol was distilled off until the liquid temperature reached 99°C. After cooling to 70°C, 8.9 parts of quinacridone compound [2] shown in Table 4 was obtained through filtration, washing with hot water at 60°C, drying and pulverization.

(Synthesis Example A-11) Synthesis of quinacridone compound [3] Cooled to 10°C or less in an ice bath, added to 90 parts of 98% sulfuric acid stirred in a flask, was added the crude 2,9- obtained in Synthesis Example A-10. 6.3 parts of dimethyl-quinacridone and 2.7 parts of the quinacridone compound [1] obtained in Synthesis Example A-9 were added while taking care that the temperature did not exceed 30°C. After the total amount was added, the mixture was stirred at 30°C or lower for 1 hour. The above sulfuric acid solution was added dropwise to 1000 parts of stirred water at 10°C while paying attention to bumping. After completion of dropping, the mixture was filtered and washed with water until it became neutral to obtain a press cake. Water was added to the resulting presscake, and the pH was adjusted to 9.0 with sodium hydroxide. Then, 0.09 part of a condensation product of stearic chloride and taurine was added to the pigment in a 35% aqueous isobutanol solution. Water and isobutanol were added to form a 4% solids suspension. This suspension was refluxed for 2 hours, after which isobutanol was distilled off until the liquid temperature reached 99°C. After cooling to 70°C, 8.9 parts of the quinacridone compound [3] shown in Table 4 was obtained through filtration, washing with hot water at 60°C, drying and pulverization.

(Synthesis Example A-12) Synthesis of DPP compound [1] In a stainless steel reaction vessel equipped with a reflux tube, 180 parts of tert-amyl alcohol dehydrated with molecular sieves and 147 parts of sodium-tert-amyl alkoxide were added under a nitrogen atmosphere. The mixture was added and 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 the mixture. The heated solution of this mixture was slowly added dropwise at a constant rate over 2 hours into the above alcoholate solution heated to 100° C. with vigorous stirring. After completion of the dropwise addition, 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 a glass jacketed reaction vessel and cooled to -10°C. The cooled mixture is rotated at 4000 rpm using a high-speed stirring disperser, and the previously obtained alkali metal salt solution of the 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 kept at -5 ° C. or less. was added in portions over approximately 120 minutes, adjusting the . After addition of the alkali metal salt, red crystals precipitated to form a red suspension. Subsequently, the resulting red suspension was replaced with a methanol slurry using an ultrafiltration device, held at 40°C for 2 hours, washed with water and filtered, and the cake was dried at 80°C for 24 hours and pulverized. By doing so, 114.2 parts of DPP compound [1] shown in Table 4 was obtained.

(Synthesis Example A-13) Synthesis of DPP compound [2] In a stainless steel reaction vessel equipped with a reflux tube, 180 parts of tert-amyl alcohol dehydrated with molecular sieves and 147 parts of sodium-tert-amyl alkoxide were added under a nitrogen atmosphere. The mixture was added and 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 dissolved by heating to 90° C. with stirring to prepare a solution of these mixtures. The heated solution of this mixture was slowly added dropwise at a constant rate over 2 hours into the above alcoholate solution heated to 100° C. with vigorous stirring. After completion of the dropwise addition, 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 a glass jacketed reaction vessel and cooled to -10°C. The cooled mixture is rotated at 4000 rpm using a high-speed stirring disperser, and the previously obtained alkali metal salt solution of the 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 kept at -5 ° C. or less. was added in portions over approximately 120 minutes, adjusting the . After addition of the alkali metal salt, red crystals precipitated to form a red suspension. Subsequently, the resulting red suspension was replaced with a methanol slurry using an ultrafiltration device, held at 40°C for 2 hours, washed with water and filtered, and the cake was dried at 80°C for 24 hours and pulverized. By doing so, 174.5 parts of DPP compound [2] shown in Table 4 was obtained.

(Synthesis Example A-14) Synthesis of quinacridone/DPP compound For 100 parts of N-methyl-2-pyrrolidone being stirred in a light-shielded container, the quinacridone compound [1] obtained in Synthesis Example A-9 ( 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 taking care not to cause dusting. After confirming sufficient dispersion, 3.8 parts of potassium tert-butoxy were gradually added. After confirming the dissolution, the mixture was stirred at 20°C or lower for 1 hour. After slowly pouring the above solution into a stirred solution of 5 parts of 80% acetic acid added to 1000 parts of water at 20° C., the solution is stirred for 1 hour, filtered, washed with water, dried, and pulverized, as 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, under a nitrogen atmosphere, 500 parts of diethylene glycol dimethyl ether, 170.7 parts of potassium-tert-butoxide, 1,5-diazabicyclo [1] 4.3.0]Non-5-ene (DBN) (251.9 parts) 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 heated and stirred at 130° C. for 3 hours. After cooling the reaction solution 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 resulting solid was reslurried with 200 parts of water and 200 parts of methanol, filtered, washed with water, acetone and dichloromethane, dried at 120° C. under reduced pressure for 8 hours, and pulverized to give a 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, and 1,5-diazabicyclo [2] were added under a nitrogen atmosphere. 4.3.0]Non-5-ene (DBN) (235.2 parts) was added, and the mixture was heated and stirred at 130° C. for 1 hour. Next, 100 parts of N-methyl-1,8-naphthalimide was added, and the mixture was heated and stirred at 130° C. for 3 hours. After cooling the reaction solution 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 resulting solid was reslurried with 200 parts of water and 200 parts of methanol, filtered, washed with water, acetone and dichloromethane, dried at 120° C. under reduced pressure for 8 hours, and pulverized to give a 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 an additional 1 hour. was added and cooled to below 5°C. Then, a solution prepared by dissolving 50.3 parts of sodium nitrite in 150 parts of water was added, and the mixture was stirred for 2 hours while maintaining the temperature at 5°C or less. Then, a buffer solution prepared by mixing and stirring 794 parts of 25% aqueous sodium hydroxide solution, 696 parts of 80% acetic acid and 587 parts of ice was added to prepare a diazo solution. Separately, 117.3 parts of 3-hydroxy-2-naphthoic acid was dissolved in 980 parts of water and 696 parts of a 25% aqueous sodium hydroxide solution to prepare a coupler solution. The diazo solution was charged into a single batch reactor equipped with a stirrer and the coupler solution was injected over 40 minutes while stirring. The resulting red slurry was stirred at 60°C for 1 hour, separated by filtration, 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, distillation was carried out at 80° C. under reduced pressure for 4 hours to obtain the 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 dissolved by stirring at 90°C for 2 hours. The obtained solution was cooled to 75° C., the acid chloride of the azo compound [R1′] obtained above was added, and the mixture was stirred at 90° C. for 1 hour, 100° C. for 1 hour, and 120° C. for 2 hours. After confirming that no more gas was released, the reactor was cooled to 100°C. The slurry was separated by filtration, washed with 1800 parts of 2-nitrotoluene, 1800 parts of methanol and 3600 parts of water, dried under reduced pressure at 120° C. for 8 hours, and pulverized to obtain the azo compound [R1]232. 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 further stirred for 1 hour. , and 500 parts of ice were added to cool to 5°C or less. Then, a solution prepared by dissolving 33.6 parts of sodium nitrite in 100 parts of water was added, and the mixture was stirred for 2 hours while maintaining the temperature at 5°C or lower. Then, a buffer solution prepared by mixing and stirring 531 parts of 25% aqueous sodium hydroxide solution, 465 parts of 80% acetic acid and 587 parts of ice was added to prepare a diazo solution. On the other hand, 149.2 parts of N-(4-chloro-2,5-dimethoxyphenyl)-3-hydroxy-2-naphthalenecarboxamide (naphthol AS-LC) was added to 980 parts of methanol and 466 parts of a 25% aqueous sodium hydroxide solution. to prepare a coupler solution. The diazo solution was charged into a single batch reactor equipped with a stirrer and the coupler solution was injected over 40 minutes while stirring. The resulting 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.

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

(Production of polyurethane resin solution [2])
PPA (poly(propylene glycol) adipate diol with a number average molecular weight of 2,000) was added to 161 ml while introducing nitrogen gas in a reactor equipped with a reflux condenser, dropping funnel, gas inlet tube, stirrer, and thermometer. 9 parts, 27.7 parts of 2,2-dimethylolbutanoic acid (DMBA), 96.4 parts of isophorone diisocyanate (IPDI), and 200 parts of methyl ethyl ketone (MEK) were charged and reacted at 90 ° C. for 5 hours to form terminal isocyanate groups. A resin solution of a urethane prepolymer having 13.6 parts of 2-(2-aminoethylamino)ethanol (AEA), 0.5 parts of ethanolamine (MEA), and 350 parts of isopropyl alcohol (IPA) are added to the resulting isocyanate-terminated urethane prepolymer resin solution. The mixture was added dropwise at room temperature over 60 minutes, and further reacted at 70° C. for 3 hours. Furthermore, the solid content is adjusted using 150 parts of MEK, and the 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.

<Production of gravure printing ink>
(Production Example B-1)
6.5 parts of phthalocyanine compound [1], 34.5 parts of polyurethane resin solution [1], 20 parts of N-propyl acetate, and 5 parts of isopropyl alcohol are stirred and mixed, kneaded in a sand mill, and then 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)
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 amount shown in Table 6.

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

[Method for measuring halogen content]
Each ink was applied onto a transparent substrate so as to have a thickness of 2.0 μm after drying. After drying at 80° C., 0.5 g was scraped off. The amount of halogen (ppm) in each ink solid content was determined by quantifying by ion chromatography after pretreatment of the scraped film by the combustion method.

[Method for measuring the amount of primary aromatic amine]
Each ink weighed so that the solid content was 2 g was adjusted to 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. 1 ml of the DMF solution was then mixed with 9 ml of 4% ammonia/methanol solution and filtered again through a 0.2 μm filter. Using this solution, HPLC measurement was performed according to the method described in AP (89) 1 test method (ETAD212). A calibration curve for primary aromatic amines that could be mixed was prepared to determine the amount of primary aromatic amines in the solid content of the ink. The detection limit was 500 ppb (0.5 ppm), and those that could not be detected were expressed as less than 0.5 ppm (<0.5).

[Amount of heavy metals that affect the environment]
Each ink was dried at 80°C to dryness. The dry matter was subjected to acid decomposition using a microwave sample pretreatment device (ETHOS1, manufactured by Milestone General Co.) to extract metals contained in the dry matter. The amount of heavy metals contained in the extract was measured using a multi-type ICP emission spectrometer (manufactured by Agilent, 720-ES), and the amount (ppm) of heavy metals affecting the environment in the solid content of the ink was calculated. Those in which heavy metals were not detected were N.C. D. was described.

<Evaluation of ink set>
[Examples A-1 to A-32, Comparative Examples A-1 to A-17]
The resulting 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 methods. Table 7 shows the results.

[Trapping property]
(cyan ink/magenta ink)
Cyan ink and magenta ink were each diluted with mixed solvent 1 (methyl ethyl ketone: N-propyl acetate: isopropanol = 40: 40: 20) so that the viscosity was 16 seconds (25°C, Zahn cup No. 3). .
Cyan and magenta were overprinted in this order on the corona discharge-treated surface of a 12 μm-thick corona discharge-treated polyester (PET) film (E-5100 manufactured by Toyobo Co., Ltd.) to obtain a printed matter.
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. The cyan ink uses a Helio 175-line gradation plate (plate compression, 75% solid pattern and 100% to 3% gradation pattern), and the magenta ink uses a Helio 175-line gradation plate (plate type elongate, 75% solid pattern and 100% to 100%). 3% gradation pattern) was used.

(cyan ink/yellow ink)
Cyan ink and yellow ink were each diluted with mixed solvent 1 so that the viscosity was 16 seconds (25° C., Zahn cup No. 3).
On the corona discharge-treated surface of a 12 μm-thick corona discharge-treated polyester film (E-5100 manufactured by Toyobo Co., Ltd.), cyan and yellow were overprinted in this order to obtain a printed matter.
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. The cyan ink uses a Helio 175-line gradation plate (plate compression, 75% solid pattern and 100% to 3% gradation pattern), and the yellow ink uses a Helio 175-line gradation plate (plate type elongate, 75% solid pattern and 100% to 100%). 3% gradation pattern) was used.

(Yellow ink/Magenta ink)
Each of the yellow ink and the magenta ink was diluted with the mixed solvent 1 so as to have a viscosity of 16 seconds (25° C., Zahn cup No. 3).
On the corona discharge-treated surface of a 12 μm-thick corona discharge-treated polyester film (E-5100 manufactured by Toyobo Co., Ltd.), yellow and magenta were overprinted in this order to obtain a printed matter.
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 a Helio 175-line gradation plate (plate elongate, 75% solid pattern and 100% to 3% gradation pattern), and magenta ink uses a Helio 175-line gradation plate (plate elongate, 75% solid pattern and 100% to 3%). % gradation pattern) was used.

The trapping properties of the gradation overprinted portion of the resulting printed material were 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)
△: Printing unevenness occurs at plate depth of 70% or more and less than 80% (usable)
×: Printing unevenness occurs at a plate depth of 80% or more, or all the overlapping inks are halftone dots and do not spread (cannot be used)

[Gamut evaluation]
Cyan ink, magenta ink, and yellow ink were diluted with the mixed solvent 1 so that the viscosity was 16 seconds (25° C., Zahn cup No. 3). Using each diluted ink, print in the order of cyan, magenta, and yellow, and print the single-color solid area (cyan, magenta, yellow), and the single-color solid overprint area (cyan x magenta, cyan x yellow, yellow x magenta). A printed matter was obtained. The printing conditions are shown below.

(Printing conditions)
Printing press: Fuji Kikai 5-color machine Cyan plate: Helio 175 L/inch, Stylus angle 120°, Elongate Magenta plate: Helio 175 L/inch, Stylus angle 120°, Compress Yellow plate: Helio 175 L/inch, Stylus angle 120°, Compress Printing speed: 150 m/min Substrate: Corona-treated biaxially oriented polypropylene (OPP) film (Pyrene P-2161, 20 μm, manufactured by Toyobo Co., Ltd.)
Drying temperature: 50°C

The density values of the single-color solid portions (yellow, magenta, and cyan) of the printed matter were measured using Gretag Macbeth D196. In addition, using SpectroEye manufactured by gretagmacbeth as a measuring instrument, the single-color solid area and the overprinted area were measured under the conditions of D50 light source, 2-degree observation field, 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, there are a total of 6 single-color solid areas (yellow, magenta, cyan) and single-color solid overlapping areas (cyan x magenta, cyan x yellow, yellow x magenta). A hexagon was created that plotted the a* versus b* values of the color. The area ratio was obtained when the area of Comparative Example A-5 was assumed to be 100%, and the area ratio was evaluated according to the following criteria. - indicates unevaluated.
○: area ratio is 90% or more (good)
△: Area ratio is 85% or more and less than 90% (usable)
×: area ratio is less than 85% (cannot be used)

According to Table 7, 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 terms of safety and health and environmental protection. In addition, the gravure printing ink set of the present invention had good trapping properties for each color. This is presumed to be the effect of the combination of pigments specific to the present application.
Among them, cyan ink containing a phthalocyanine pigment represented by formula (1), yellow ink containing isoindoline pigment represented by formulas (6) to (8), and quinacridone represented by formulas (16) and (17). magenta ink containing pigment (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, and A-30) had a very wide gamut and excellent color reproducibility.

On the other hand, Comparative Examples A-1 to A-17 cannot solve the problem of the present application because they contain inks containing a large amount of any one of halogen atoms, primary aromatic amines, and heavy metals that affect the environment.

<Manufacturing clear ink having releasability>
(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 size of 3.8 μm) Three parts were stirred and mixed using a disper to obtain clear ink [1].

<Production of releasable adhesive>
(Preparation of laminate adhesive solution [1])
A four-necked separable flask was charged with 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. An esterification reaction was carried out. After a predetermined amount of water was distilled off, the pressure was gradually reduced to 1 mmHg or less, and deglycolization was carried out at 240 to 260° C. for 5 hours. After that, 2 parts of isophorone diisocyanate was gradually added, and reaction was carried out at 150° C. for about 2 hours to obtain a polyester polyurethane polyol. 2.83 parts of trimellitic anhydride was added to 100 parts of this polyester polyurethane polyol and reacted at 180° C. for about 2 hours. Then, the mixture 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 an ethyl acetate solution of HDI biuret with a non-volatile content of 95% were mixed, and ethyl acetate was added to obtain a laminate adhesive solution [1] having a non-volatile content of 30%.

<Manufacture of packaging materials>
[Example B-1] Packaging material 1
The clear ink [1] described above 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 mixed solvent 1 so that the viscosity was 16 seconds (25° C., Zahn cup No. 3).
Gravure proofing 5-color machine with 20 μm plate depth gravure plates, clear ink [1], cyan ink [1], yellow ink [1], and magenta ink [1], using diluted inks Using an ink set, clear ink [1], cyan ink [1], yellow ink [1], and magenta ink [1] were overprinted in this order on a corona-treated oriented polypropylene film having a thickness of 20 μm. Each of the units was dried at 50°C to obtain a printed matter having a configuration of "OPP substrate/releasing layer (clear ink)/cyan, yellow or magenta printed layer" and including a layer having releasability. .
Next, on the printed layer of the obtained printed matter, the laminating adhesive solution [1] is applied using a dry laminating machine, and at a line speed of 40 m / min, a 25 μm thick aluminized unoriented polypropylene (VMCPP) film A packaging material 1 having a configuration of "OPP base material/releasable print layer/three-color overprint layer/releasable adhesive layer/VMCPP base material" and having a detachable layer. Obtained.

[Examples B-2 to B-32, Comparative Examples B-1 to B-17] Packaging materials 2 to 49
Packaging materials 2 to 49 having a release 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 resulting 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 deposited on the bottom was collected, washed with deionized water, and then dried. Using the dried printed layer, the amount of halogen, the amount of primary aromatic amine, and the amount of heavy metals that affect the environment were measured in the same manner as the gravure printing ink evaluation described above. Table 8 shows the results.

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

On the other hand, in the packaging materials of Comparative Examples B-1 to B-17, the amount of halogen, the amount of primary aromatic amine, or the amount of heavy metals that affect the environment contained in the printed layer after desorption treatment However, it is not possible to solve the problems of safety and health and environmental load reduction.

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: , a set of gravure printing inks.

[In general formula (2), X ₁ to X ₄ each 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. _X5 and _X6 each independently represent a hydrogen atom or an alkyl group. A represents a group represented by general formula (2-1) or (2-2).
In general formula (2-1), Y ₁ represents —O— or —NH—, X ₇ is a hydrogen atom, an alkyl group,
or represents an aryl group.
In general formula (2-2), X ₈ and X ₉ each independently represent a hydrogen atom or an alkyl group. ]

[In general formula (3), X ₁₀ to X ₁₇ each independently represent a hydrogen atom or an alkyl group.
In general formula (4), X ₁₈ to X ₂₇ each independently represent a hydrogen atom, an alkyl group, a cyano group, an alkoxy group, a thioalkyl group, or an aryl group which may have a substituent.
In general formula (5), Y ₂ represents —O— or —NR—, and R represents a hydrogen atom, an alkyl group, or an aryl group which may have 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 general formulas (3) to (5) comprises a pigment represented by general formula (3). The gravure printing ink set according to any one of claims 1 to 3, further comprising a releasable clear ink. A printed matter comprising a printing layer formed from the gravure printing ink set according to any one of claims 1 to 4, and a substrate layer. 6. The printed matter according to claim 5, comprising a layer having releasability. A packaging material using the printed matter according to claim 5 or 6.