JP5402455B2 - Gravure ink - Google Patents

Description

  An object of the present invention is to provide a gravure ink which is composed of a pigment, a dispersant, a binder resin, and a solvent and has excellent storage stability with respect to pigment dispersibility and fluidity, stability on a printing press, and excellent laminating properties. .

Gravure printing is widely used for the purpose of imparting cosmetics and functionality to a substrate. When used in packaging materials, cosmetics may affect the sales of products. In recent years, a design that is gorgeous and has a high degree of printing difficulty has been adopted, and various high functionality has been added. High-quality printed materials are required. Therefore, attempts have been made to improve performance from various directions in printing manufacturers and printing ink manufacturers.
In general, in gravure inks, it is known that it is difficult to stably disperse pigments at a high concentration, which causes various problems with respect to storage stability and stability on a printing press. For example, a dispersion containing a pigment composed of fine particles tends to re-aggregate with time, resulting in defects such as a decrease in printing density, density unevenness, and plate fog due to deterioration of a gravure doctor. In this case, improvement is attempted by selecting pigments, pigment derivatives, dispersants, binder resins, solvents, and additives. However, the required quality has not been achieved in terms of long-term storage stability and long-term stability on the printing press, shortening the remaining use period, complicated printing management and inspection work, etc. Have problems that cause

  Therefore, in general, a dispersant is used in order to keep the dispersion state good. The dispersant has a structure of a part that adsorbs to the pigment and a part that has a high affinity for the resin and the solvent, and the balance of the two determines the performance of the dispersant. The dispersant is properly used according to the pigment surface state, but a basic dispersant is generally used for the acidic pigment or acidic derivative. Dispersants having an amino group as a basic functional group are described in, for example, Patent Literature 1, Patent Literature 2, Patent Literature 3, Patent Literature 4, Patent Literature 5, Patent Literature 6, and the like.

  However, the dispersants described in Patent Document 1, Patent Document 2, and Patent Document 3 have a dispersion ability, but have limited side chains and limited types of solvents and binder resins that can be used. In addition, the dispersants described in Patent Document 4, Patent Document 5, and Patent Document 6 have a certain degree of dispersion ability, but it was necessary to increase the amount of use in order to produce a stable dispersion with low viscosity. However, increasing the amount used is not preferable in view of development in inks, paints, etc., because the resistance of the coating film may be reduced.

  Patent Document 7 and Patent Document 8 describe a polyurethane resin characterized by using a polyol obtained by polymerizing a compound having a polymerizable unsaturated bond using a mercaptan compound having two hydroxyl groups as an initiator. However, when this was used as a dispersant, no amine remained as a basic site, so that sufficient dispersibility could not be obtained with respect to pigments having a surface biased to an acid.

Patent Document 9 describes a polyurethane / urea resin characterized by using a polyol obtained by polymerizing a compound having a polymerizable unsaturated bond using a mercaptan compound having two hydroxyl groups as an initiator. Due to the particulate polyurethane, when this was used as a dispersant, sufficient dispersibility could not be obtained with respect to pigments having an acid-biased surface.
Japanese Patent Laid-Open No. 9-169821 JP-A-9-194585 JP 2004-089787 A JP-A-1-236930 Japanese Patent Laid-Open No. 3-103478 Japanese Patent Laid-Open No. 16-344795 Japanese Patent Publication No.57-500246 JP-A-63-066211 Japanese Patent Laid-Open No. 5-194702

The present invention is a gravure ink that is excellent in storage stability of residual matter relating to dispersibility and fluidity, stability on a printing machine for a long time (plate fog), and laminating suitability during retort processing, and is not limited to acidic pigments, binder resins or solvents. The purpose is to provide.

The present invention relates to a urethane prepolymer having two isocyanate groups in one terminal region obtained by reacting a hydroxyl group of a vinyl polymer (A) having two hydroxyl groups in one terminal region and an isocyanate group of diisocyanate (B). A dispersant, pigment, and polyurethane / urea obtained by reacting an isocyanate group of (E) with a primary and / or secondary amino group of an amine compound containing polyamine (C) and having an amine value of 1 to 100 mg KOH / g A gravure ink comprising a resin, a vinyl chloride-vinyl acetate copolymer, a nitrocellulose resin, a polyamide resin, one or more binder resins selected from a chlorinated polypropylene resin, and a solvent.
Further, the gravure ink is characterized in that the dispersant is used in an amount of 3 to 12 parts by weight with respect to 100 parts by weight of the pigment.
The gravure ink is at least one dye selected from the group of dye derivatives having an acidic substituent represented by the following general formula (1), the following general formula (2), and the following general formula (3). A gravure ink comprising a derivative, wherein the pigment derivative is used in an amount of 3 to 10 parts by weight per 100 parts by weight of the pigment.

General formula (1):
PZ ¹
(In general formula (1), P represents azo, benzimidazolone, phthalocyanine, quinacridone, anthraquinone, dioxazine, diketopyrrolopyrrole, quinophthalone, isoindolinone, isoindoline, perylene. Z ¹ is a sulfonic acid group or a carboxyl group, which is a kind of organic dye residue selected from the group, perinone, flavanthrone, pyranthrone, and anthrapyrimidine.
General formula (2):
(PZ ² ) [N ⁺ (R ¹ , R ² , R ³ , R ⁴ )]
(In general formula (2), P represents azo, benzimidazolone, phthalocyanine, quinacridone, anthraquinone, dioxazine, diketopyrrolopyrrole, quinophthalone, isoindolinone, isoindoline, perylene. R ¹ is an alkyl group having 5 to 20 carbon atoms, R ² , R ³ , and R ¹ is an organic dye residue selected from the group consisting of a perine, perinone, flavanthrone, pyranthrone, and anthrapyrimidine R ⁴ are each independently a hydrogen atom or an alkyl group having a carbon number of 1 to 20, Z ² is SO ₃ ^- or COO ^- and is).
General formula (3):
(P−Z ² ) M ⁺ / l
(In the general formula (3), P represents azo, benzimidazolone, phthalocyanine, quinacridone, anthraquinone, dioxazine, diketopyrrolopyrrole, quinophthalone, isoindolinone, isoindoline, perylene. Is an organic pigment residue selected from the group consisting of perylene, flavanthrone, pyranthrone, and anthrapyrimidine, and M is a sodium atom, potassium atom, calcium atom, barium atom, strontium atom or aluminum atom, l Is the valence of M, and Z ² is SO ₃ ⁻ or COO ⁻ .)
Further, the present invention relates to a gravure ink wherein the polyurethane / urea resin is obtained by reacting a polyester polyol, a polyether polyol, a low molecular polyol, a polyisocyanate, a chain extender, and a terminal terminator.

With the gravure ink of the present invention, dispersibility and fluidity that were not obtained in the past were obtained, and re-aggregation of the pigment over time was also suppressed. (Cover) is also obtained. Furthermore, since the heat resistance of the coating film is also maintained, it is possible to provide a gravure ink that is excellent in lamination suitability during retort processing and is optimal for general-purpose binder resins and solvents.

Hereinafter, “(meth) acryloyl”, “(meth) acryl”, “(meth) acrylic acid”, “(meth) acrylate”, “(meth) acryloyloxy”, or “(meth) acrylamide” Unless otherwise specified, “acryloyl and / or methacryloyl”, “acrylic and / or methacrylic”, “acrylic acid and / or methacrylic acid”, “acrylate and / or methacrylate”, “acryloyloxy and / or Or “methacryloyloxy” or “acrylamide and / or methacrylamide”.
The dispersant used in the present invention is
A hydroxyl group of the vinyl polymer (A) having two hydroxyl groups in one end region;
An isocyanate group of a urethane prepolymer (E) having two isocyanate groups in one terminal region formed by reacting an isocyanate group of diisocyanate (B);
Primary and / or secondary amino groups of amine compounds comprising polyamine (C) [and optionally monoamine (D)];
It is synthesized by reacting.

  Each component of the dispersant used in the present invention will be described.

<Vinyl polymer (A) having two hydroxyl groups in one end region>
The vinyl polymer (A) having two hydroxyl groups in one end region (hereinafter sometimes abbreviated as vinyl polymer (A)) has two hydroxyl groups and one thiol group in the molecule. It can be obtained by radical polymerization of the ethylenically unsaturated monomer (a2) in the presence of the compound (a1). The vinyl polymer portion of the vinyl polymer (A) is a portion having a high affinity for a pigment carrier such as a binder resin and a solvent that is a dispersion medium, and is represented by the following general formula (4).

  General formula (4):

[In general formula (4),
R ⁶ is a residue obtained by removing a hydroxyl group and a thiol group from the compound (a1),
R ⁷ is a residue excluding the double bond site and R ⁸ from the ethylenically unsaturated monomer (a2),
R ⁸ is a hydrogen atom or a methyl group,
n is an integer of 2 or more, preferably an integer of 3 to 200.

Here, R ⁶ is a terminal region in the vinyl polymer (A). ]
<Compound (a1) having two hydroxyl groups and one thiol group in the molecule>
The compound (a1) having two hydroxyl groups and one thiol group in the molecule (hereinafter sometimes referred to as compound (a1)) includes two hydroxyl groups and one thiol group in the molecule. Is not particularly limited, for example, 1-mercapto-1,1-methanediol, 1-mercapto-1,1-ethanediol, 3-mercapto-1,2-propanediol (thioglycerin, or Also called thioglycerol), 2-mercapto-1,2-propanediol, 2-mercapto-2-methyl-1,3-propanediol, 2-mercapto-2-ethyl-1,3-propanediol, 1- Mercapto-2,2-propanediol, 2-mercaptoethyl-2-methyl-1,3-propanediol, or 2-mercapto Chill-2-ethyl-1,3-propanediol.

The residue R ⁶ excluding the hydroxyl group and the thiol group from the compound (a1) in the general formula (4) is not particularly limited, but from the viewpoint of compatibility with the solvent, varnish, or binder resin, the number of carbon atoms is 1 to 1. 20 linear or branched alkyl groups are preferable, and linear or branched alkyl groups having 1 to 7 carbon atoms such as the compound (a1) listed above are more preferable. Two hydroxyl groups and one thiol group may be bonded to different carbons, partially bonded to the same carbon, or all bonded to the same carbon.

  A compound (a1), an ethylenically unsaturated monomer (a2), and optionally a polymerization initiator are mixed in accordance with the molecular weight of the vinyl polymer (A) having two hydroxyl groups in one end region of interest. Then, the vinyl polymer (A) can be obtained by heating. The compound (a1) is preferably obtained by bulk polymerization or solution polymerization using 0.5 to 30 parts by weight with respect to 100 parts by weight of the ethylenically unsaturated monomer (a2), more preferably 1 to 20 parts. Part by weight, more preferably 2 to 15 parts by weight, particularly preferably 2 to 10 parts by weight. The reaction temperature is 40 to 150 ° C, preferably 50 to 110 ° C. If the amount is less than 0.5 parts by weight, the molecular weight of the vinyl polymer portion is too high, and the absolute amount increases as an affinity portion for the pigment carrier and the solvent, and the dispersibility effect itself may decrease. When the content exceeds 30% by weight, the molecular weight of the vinyl polymer part (A) is too low, and as an affinity site for the pigment carrier and the solvent, the effect of steric repulsion is lost, and it is difficult to suppress pigment aggregation. There is a case.

<Polymerization initiator>
In the polymerization, 0.001 to 5 parts by weight of a polymerization initiator can be arbitrarily used with respect to 100 parts by weight of the ethylenically unsaturated monomer (a2). As the polymerization initiator, an azo compound and an organic peroxide can be used. Preferably, an azo compound is used.

  Examples of the azo compounds include 2,2′-azobis (isobutyronitrile), 2,2′-azobis (2-methylbutyronitrile), 1,1′-azobis (cyclohexane 1-carbonitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (2,4-dimethyl-4-methoxyvaleronitrile), dimethyl 2,2′-azobis (2-methylpropionate) ), 4,4′-azobis (4-cyanovaleric acid), 2,2′-azobis (2-hydroxymethylpropionitrile), or 2,2′-azobis [2- (2-imidazoline-2- Yl) propane] and the like.

  Examples of organic peroxides include benzoyl peroxide, t-butyl perbenzoate, cumene hydroperoxide, diisopropyl peroxydicarbonate, di-n-propyl peroxydicarbonate, di (2-ethoxyethyl) peroxy Examples include dicarbonate, t-butyl peroxyneodecanoate, t-butyl peroxybivalate, (3,5,5-trimethylhexanoyl) peroxide, dipropionyl peroxide, or diacetyl peroxide.

  These polymerization initiators can be used alone or in combination of two or more.

<Polymerization solvent>
In the case of solution polymerization, as a polymerization solvent, ethyl acetate, n-propyl acetate, n-butyl acetate, isobutyl acetate, toluene, xylene, acetone, hexane, methyl ethyl ketone, cyclohexanone, diethylene glycol di-lower alkyl ether, or the like is used. Although not particularly limited thereto, n-propyl acetate is particularly preferable from the viewpoints of dispersion stability and low odor. Furthermore, the solvent which does not have an active hydrogen group from the reactivity of isocyanate is preferable.

  These polymerization solvents can be used as a mixture of two or more kinds, but are preferably used in the final application.

<Ethylenically unsaturated monomer (a2)>
As the ethylenically unsaturated monomer (a2), for example,
Methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, 2- Alkyl (meth) acrylates such as ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate, trimethylcyclohexyl (meth) acrylate, or isobornyl (meth) acrylate;
Aromatic (meth) acrylates such as phenyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, or phenoxydiethylene glycol (meth) acrylate;
Heterocyclic (meth) acrylates such as tetrahydrofurfuryl (meth) acrylate or oxetane (meth) acrylate;
Alkoxypolyalkylene glycol (meth) acrylates such as methoxypolypropylene glycol (meth) acrylate or ethoxypolyethylene glycol (meth) acrylate;
N-substituted type (meta) such as (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, diacetone (meth) acrylamide, or acryloylmorpholine ) Acrylamides;
Amino group-containing (meth) acrylates such as N, N-dimethylaminoethyl (meth) acrylate or N, N-diethylaminoethyl (meth) acrylate;
Nitriles such as (meth) acrylonitrile are exemplified.

In addition, as a monomer that can be used in combination with the acrylic monomer,
Styrenes such as styrene or α-methylstyrene;
Vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, or isobutyl vinyl ether;
Or fatty acid vinyls, such as vinyl acetate or vinyl propionate, etc. are mentioned.

  Moreover, a carboxyl group-containing ethylenically unsaturated monomer can be used in combination. As a carboxyl group-containing ethylenically unsaturated monomer, 1 type (s) or 2 or more types can be selected from acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, or crotonic acid.

<Polymerization conditions>
Among the ethylenically unsaturated monomers (a2) exemplified above, from the viewpoints of dispersibility and coating film resistance, lower alkyl (meth) acrylates (lower alkyl part has 1 to 4 carbon atoms), particularly methyl methacrylate. Are preferably used, and it is more preferable to use methyl methacrylate and n-butyl methacrylate or t-butyl methacrylate in combination from the viewpoint of affinity with the pigment carrier and the dispersion medium. When methyl methacrylate is used as the ethylenically unsaturated monomer (a2) and n-butyl methacrylate or t-butyl methacrylate is not used, the total amount of ethylenically unsaturated monomer (a2) is 100% by weight. The ratio of methyl methacrylate is preferably 30 to 100% by weight, and more preferably 50 to 100% by weight. Moreover, when methyl methacrylate and n-butyl methacrylate or t-butyl methacrylate are used in combination as the ethylenically unsaturated monomer (a2), the total of the two is the ethylenically unsaturated monomer (a2). 30) to 100% by weight, and more preferably 50 to 100% by weight. When methyl methacrylate is used as the ethylenically unsaturated monomer (a2), and when methyl methacrylate and n-butyl methacrylate or t-butyl methacrylate are used in combination, pigment dispersibility is better. It becomes. The copolymerization site of methyl methacrylate and n-butyl methacrylate or t-butyl methacrylate has high compatibility with the binder resin and the dispersion solvent while maintaining basic physical properties such as dispersibility and high versatility.

  The weight average molecular weight (Mw) in terms of polystyrene by GPC (gel permeation chromatography) of the vinyl polymer (A) having two hydroxyl groups in one terminal region is preferably 500 to 30,000, It is more preferably 1,000 to 15,000, and particularly preferably 1,000 to 8,000. When the weight average molecular weight is less than 500, the effect of steric repulsion by the solvent affinity part is reduced, and it becomes difficult to prevent aggregation of the pigment, and dispersion stability may be insufficient. On the other hand, if it exceeds 30,000, the absolute amount of the solvent affinity part may increase, and the dispersibility effect itself may decrease. Further, the viscosity of the dispersion may increase.

  When the weight average molecular weight is 500 to 30,000, it is advantageous to suppress an increase in the viscosity of the gravure ink by preventing aggregation of the pigment.

  The glass transition temperature (Tg) of the vinyl polymer (A) having two hydroxyl groups in one end region is preferably 50 to 200 ° C., more preferably 50 to 120 ° C., from the viewpoint that the resistance of the coating film is improved. .

  As the Tg of the vinyl polymer (A) having two hydroxyl groups in one end region, a value calculated by the following Fox formula was used. In addition, although the skeleton derived from the compound (a1) having two hydroxyl groups and one thiol group in the molecule is also present in the vinyl polymer (A), it is excluded from the following calculation for calculating the glass transition temperature. To do.

1 / Tg = W1 / Tg1 + W2 / Tg2 + ... + Wn / Tgn
W1 to Wn indicate the weight fraction of each monomer used, and Tg1 to Tgn indicate the glass transition temperature of each homopolymer obtained from each monomer (unit: absolute temperature “K”). Show.

The Tg of the main homopolymer used for the calculation is exemplified below.
Methyl methacrylate: 105 ° C (378K)
n-butyl methacrylate: 20 ° C. (293 K)
t-butyl methacrylate: 107 ° C. (380 K)
Lauryl methacrylate: -65 ° C (208K)
2-ethylhexyl methacrylate: -10 ° C (263K)
Cyclohexyl methacrylate: 66 ° C (339K)
n-butyl acrylate: -45 ° C (228K)
Ethyl acrylate: -20 ° C (253K)
Benzyl methacrylate: 54 ° C (327K)
Styrene: 100 ° C (373K)
<Diisocyanate (B)>
As the diisocyanate (B), known ones conventionally used in the synthesis of polyurethane and the like can be used. For example, diisocyanate (b1) having an aromatic group, diisocyanate (b2) having an aliphatic group , Diisocyanate (b3) having an aromatic group and an aliphatic group, or diisocyanate (b4) having an alicyclic group.

  Examples of the diisocyanate (b1) having an aromatic group include xylylene diisocyanate, 1,3-phenylene diisocyanate, 4,4′-diphenyl diisocyanate, 1,4-phenylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 2,4- Examples include tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4′-toluidine diisocyanate, naphthylene diisocyanate, or 1,3-bis (isocyanatomethyl) benzene.

  Examples of the diisocyanate (b2) having an aliphatic group include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), pentamethylene diisocyanate, 1,2-propylene diisocyanate, 2,3-butylene diisocyanate, and 1,3-butylene. Examples thereof include diisocyanate, dodecamethylene diisocyanate, and 2,4,4-trimethylhexamethylene diisocyanate.

  Examples of the diisocyanate (b3) having an aromatic group and an aliphatic group include ω, ω′-diisocyanate-1,3-dimethylbenzene, ω, ω′-diisocyanate-1,4-dimethylbenzene, ω, ω′-diisocyanate. Examples include -1,4-diethylbenzene, 1,4-tetramethylxylylene diisocyanate, or 1,3-tetramethylxylylene diisocyanate.

  Examples of the diisocyanate (b4) having an alicyclic group include 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate (IPDI), 1,3-cyclopentane diisocyanate, 1,3-cyclohexane diisocyanate, 1,4- Examples include cyclohexane diisocyanate, methyl-2,4-cyclohexane diisocyanate, or methyl-2,6-cyclohexane diisocyanate.

  As mentioned above, enumerated diisocyanate (B) is not necessarily limited to these, It can also be used in combination of 2 or more types.

  As the diisocyanate (B), 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate [also known as isophorone diisocyanate, IPDI] is preferable because it is hardly yellow-modified.

<Polyamine (C)>
The polyamine (C) is a compound having at least two primary and / or secondary amino groups, and is used for reacting with an isocyanate group to form a urea bond. A diamine (c1) is mentioned as such an amine.

As the diamine (c1) having two primary amino groups, a conventionally known chain extender can be used as a chain extender during the synthesis of polyurethane or the like. Specifically,
Ethylenediamine, propylenediamine [alias: 1,2-diaminopropane or 1,2-propanediamine], trimethylenediamine [alias: 1,3-diaminopropane or 1,3-propanediamine], tetramethylenediamine [alias: 1 , 4-diaminobutane], 2-methyl-1,3-propanediamine, pentamethylenediamine [alias: 1,5-diaminopentane], hexamethylenediamine [alias: 1,6-diaminohexane], 2,2- Aliphatic diamines such as dimethyl-1,3-propanediamine, 2,2,4-trimethylhexamethylenediamine, or tolylenediamine;
Cycloaliphatic diamines such as isophorone diamine or dicyclohexylmethane-4,4′-diamine; or
Examples thereof include aromatic diamines such as phenylenediamine and xylylenediamine.

In addition, as the diamine (c1) having two secondary amino groups, a conventionally used chain extender can be used as a chain extender during the synthesis of polyurethane or the like. Specifically,
N, N-dimethylethylenediamine, N, N-diethylethylenediamine, or N, N′-di-tert-butylethylenediamine can be used.

In addition, as the diamine (c1) having primary and secondary amino groups, a conventionally used chain extender can be used as a chain extender during the synthesis of polyurethane or the like. Specifically,
N-methylethylenediamine [alias: methylaminoethylamine], N-ethylethylenediamine [alias: ethylaminoethylamine], N-methyl-1,3-propanediamine [alias: N-methyl-1,3-diaminopropane or methylamino Propylamine], N, 2-methyl-1,3-propanediamine, N-isopropylethylenediamine [alias: isopropylaminoethylamine], N-isopropyl-1,3-diaminopropane [alias: N-isopropyl-1,3- Propanediamine or isopropylaminopropylamine], or N-lauryl-1,3-propanediamine [alias: N-lauryl-1,3-diaminopropane or laurylaminopropylamine].

  A polyamine is a compound having at least two primary and / or secondary amino groups, and the primary and / or secondary amine reacts with an isocyanate group to form a urea group. This urea group becomes a pigment adsorption site. When the polyamine (C) is a compound having two primary and / or secondary amino groups at both ends and further having a secondary and / or tertiary amino group at both ends, This is particularly preferable because the adsorptivity to the surface is improved.

  Examples of such polyamine (C) include polyamines having two primary and / or secondary amino groups at both ends as shown below, and further having secondary and / or tertiary amino groups at both ends. c2).

As polyamine (c2),
Methyliminobispropylamine [alias: N, N-bis (3-aminopropyl) methylamine], lauryliminobispropylamine [alias: N, N-bis (3-aminopropyl) laurylamine], iminobispropylamine [Alias: N, N-bis (3-aminopropyl) amine], N, N′-bisaminopropyl-1,3-propylenediamine, N, N′-bisaminopropyl-1,4-butylenediamine, etc. Can mention
Methyliminobispropylamine or lauryliminobispropylamine having two primary amino groups and one tertiary amino group is preferable because the reaction with diisocyanate is easily controlled.

  An iminobispropylamine having two primary amino groups and one secondary amino group is preferable because of its good adsorptivity to pigments.

  As the polyamine (C), a polymer (c3) having two or more primary and / or secondary amino groups can also be used.

  Examples of the polymer (c3) having a primary and / or secondary amino group include an ethylenically unsaturated monomer having a primary amino group and an ethylenically unsaturated monomer having a secondary amino group, such as vinylamine and allylamine. Homopolymers (so-called polyvinylamine and polyallylamine), copolymers thereof with other ethylenically unsaturated monomers, ring-opening polymers of ethyleneimine, and polycondensates of ethylene chloride and ethylenediamine Or a ring-opening polymer of oxazolidone-2 (so-called polyethyleneimine). The content of primary and / or secondary amino groups in the polymer is preferably 10 to 100% by weight, more preferably 20 to 100% by weight, in terms of monomer units, based on the polymer. If the content is 10% by weight or more, it is effective for preventing aggregation of pigments and suppressing an increase in viscosity.

As an ethylenically unsaturated monomer copolymerizable with an ethylenically unsaturated monomer having a primary amino group or an ethylenically unsaturated monomer having a secondary amino group, for example,
Unsaturated carboxylic acids such as (meth) acrylic acid, crotonic acid, itaconic acid, maleic acid or fumaric acid;
Aromatic vinyl compounds such as styrene, α-methylstyrene, p-hydroxystyrene, chloromethylstyrene, indene, or vinyltoluene;
(Meth) acrylic acid alkyl esters such as methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, or 2-ethylhexyl (meth) acrylate;
(Meth) acrylic acid alkylaryl esters such as benzyl (meth) acrylate;
(Meth) acrylic acid-substituted alkyl ester having a functional group such as glycidyl (meth) acrylate or 2-hydroxyethyl (meth) acrylate;
(Meth) acrylic acid-substituted alkyl ester having a tertiary amino group such as dimethylaminoethyl (meth) acrylate or dimethylaminopropyl (meth) acrylate;
Alkyl (meth) acrylamides such as (meth) acrylamide, dimethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, n-butyl (meth) acrylamide, tert-butyl (meth) acrylamide, or tert-octyl (meth) acrylamide ;
Substituted alkyl (meth) acrylamides such as dimethylaminoethyl (meth) acrylamide or dimethylaminopropyl (meth) acrylamide;
Diene compounds such as 1,3-butadiene or isoprene;
Polymerizable oligomers (macromonomers) such as one-end methacryloylated polymethyl methacrylate oligomer, one-end methacryloylated polystyrene oligomer, or one-end methacryloylated polyethylene glycol; or
And vinyl cyanide.

  The polymer having a primary and / or secondary amino group has a polystyrene-equivalent weight average molecular weight (Mw) by GPC (gel permeation chromatography), preferably 300 to 75,000, 300 to 20, 000 is more preferable, and 500 to 5,000 is particularly preferable. When the weight average molecular weight is 300 to 75,000, it is effective to suppress the increase in the viscosity of the gravure ink by preventing the aggregation of the pigment.

<Monoamine (D)>
As the amine compound constituting the dispersant, besides the polyamine (C), a monoamine (D) can also be used. The monoamine (D) is a monoamine compound having one primary amino group or secondary amino group in the molecule, and the monoamine (D) has a high molecular weight in the reaction of the diisocyanate (B) and the polyamine (C). It is used as a reaction terminator in order to suppress excessive conversion. The monoamine (D) may have a polar functional group other than the primary amino group or the secondary amino group in the molecule. Examples of such a polar functional group include a hydroxyl group, a carboxyl group, a sulfonic acid group, a phosphoric acid group, a cyano group, and a nitroxyl group.

As the monoamine (D), known compounds that have been conventionally used as a reaction terminator can be used during the synthesis of polyurethane and the like. Specifically,
Aminomethane, aminoethane, 1-aminopropane, 2-aminopropane, 1-aminobutane, 2-aminobutane, 1-aminopentane, 2-aminopentane, 3-aminopentane, isoamylamine, N-ethylisoamylamine, 1-amino Hexane, 1-aminoheptane, 2-aminoheptane, 2-octylamine, 1-aminononane, 1-aminodecane, 1-aminododecane, 1-aminotridecane, 1-aminohexadecane, stearylamine, aminocyclopropane, aminocyclobutane Aminocyclopentane, aminocyclohexane, aminocyclododecane, 1-amino-2-ethylhexane, 1-amino-2-methylpropane, 2-amino-2-methylpropane, 3-amino-1-propene, 3-amino Methyl heptane, -Isopropoxypropylamine, 3-butoxypropylamine, 3-isobutoxypropylamine, 2-ethylhexyloxypropylamine, 3-decyloxypropylamine, 3-lauryloxypropylamine, 3-myristoxypropylamine, 2 -Aminomethyltetrahydrofuran, dimethylamine, diethylamine, N-methylethylamine, N-methylisopropylamine, N-methylhexylamine, diisopropylamine, di-n-propylamine, di-n-butylamine, disec-butylamine, N-ethyl- 1,2-dimethylpropylamine, piperidine, 2-pipecoline, 3-pipecoline, 4-pipecoline, 2,4-lupetidine, 2,6-lupetidine, 3,5-lupetidine, 3-piperidinemethanol, pipecolinit Acid, isonipecotic acid, methyl isonipecotate, ethyl isonipecotate, 2-piperidine ethanol, 4-piperidine ethanol, 4-piperidine butyric acid hydrochloride, 4-piperidinol, pyrrolidine, 3-aminopyrrolidine, 3-pyrrolidinol, indoline, aniline, N-butylaniline, o-aminotoluene, m-aminotoluene, p-aminotoluene, o-benzylaniline, p-benzylaniline, 1-anilinonaphthalene, 1-aminoanthraquinone, 2 -Aminoanthraquinone, 1-aminoanthracene, 2-aminoanthracene, 5-aminoisoquinoline, o-aminodiphenyl, 4-aminodiphenyl ether, β-aminoethylbenzene, 2-aminobenzophenone, 4-aminobenzoph Non, o-aminoacetophenone, m-aminoacetophenone, p-aminoacetophenone, benzylamine, N-methylbenzylamine, 3-benzylaminopropionic acid ethyl ether, 4-benzylpiperidine, α-phenylethylamine, phenacylamine , P-methoxyphenethylamine, furfurylamine, p-aminoazobenzene, m-aminophenol, p-aminophenol, allylamine, 2-amino-2-methyl-propanol or diphenylamine.

  Among these, a monoamine compound having only a secondary amino group as an aliphatic amine is preferable because it improves the dispersibility of the dispersant.

As an aliphatic monoamine compound having only a secondary amino group,
Dimethylamine, diethylamine, N-methylethylamine, N-methylisopropylamine, N-methylhexylamine, diisopropylamine, di-n-propylamine, di-n-butylamine, disec-butylamine, N-ethyl-1,2-dimethyl Propylamine, Piperidine, 2-Pipecoline, 3-Pipecoline, 4-Pipecoline, 2,4-Lupetidine, 2,6-Lupetidine, 3,5-Lupetidine, 3-piperidinemethanol, 2-piperidineethanol, 4-piperidineethanol, 4-piperidinol, pyrrolidine, 3-aminopyrrolidine, 3-pyrrolidinol, etc. are mentioned.

  Further, since the tertiary amino group does not have an active hydrogen that reacts with the isocyanate group, the diamine having a primary or secondary amino group and a tertiary amino group is a reaction terminator in the same manner as the monoamine (D). A tertiary amino group having an effect of improving the pigment adsorbing ability can be introduced into the polymer terminal of the dispersant according to the present invention.

As a diamine having a primary or secondary amino group and a tertiary amino group,
Primary amino group such as N, N-dimethylethylenediamine, N, N-diethylethylenediamine, N, N-dimethyl-1,3-propanediamine, or N, N, 2,2-tetramethyl-1,3-propanediamine And a diamine having a tertiary amino group; or
Examples thereof include diamines having a secondary amino group and a tertiary amino group such as N, N, N′-trimethylethylenediamine.

  These amine compounds acting as a reaction terminator may be used alone or in combination of two or more. In addition, the active hydrogen of the urea bond after the primary amino group and the isocyanate group react with each other has low reactivity, and under the polymerization conditions of the dispersant of the present invention, it does not further react with the isocyanate group and the molecular weight does not increase. .

<Urethane prepolymer (E)>
The urethane prepolymer (E) is obtained by reacting the hydroxyl group of the vinyl polymer (A) having two hydroxyl groups in one end region with the isocyanate group of the diisocyanate (B).

  For example, when the number of moles of the vinyl polymer (A) is α and the number of moles of the diisocyanate (B) is β, when α / β = α / (α + 1), theoretically, two isocyanate groups are present in one end region. A urethane prepolymer having When α is a positive integer, the molecular weight increases as α increases. The actual structure control will be described later in detail.

  The weight average molecular weight (Mw) of the dispersant is preferably 1,000 to 100,000, more preferably 1,500 to 50,000, and particularly preferably 1,500 to 20,000. If the weight average molecular weight is less than 1,000, the stability of the gravure ink may be lowered. If the weight average molecular weight is more than 100,000, the interaction between the resins becomes strong and the viscosity of the gravure ink may be increased. Moreover, it is preferable that the amine value of the obtained dispersing agent is 1-100 mgKOH / g. If the amine value is less than 1 mg KOH / g, the pigment and the functional group that adsorbs may be insufficient, which may make it difficult to contribute to pigment dispersion. If the amine value exceeds 100 mg KOH / g, the isocyanate-based curing of the adhesive for dry lamination Reacts with most of the agent, reducing the retort suitability.

<Synthetic catalyst (F)>
At the time of synthesizing the urethane prepolymer (E), a known catalyst (F) conventionally used as a synthesis catalyst for polyurethane or the like can be used. For example, a tertiary amine compound or an organometallic compound is used. Can be mentioned.

As the tertiary amine compound, for example,
Examples include triethylamine, triethylenediamine, N, N-dimethylbenzylamine, N-methylmorpholine, diazabicycloundecene (DBU), and the like.

  Examples of organometallic compounds include tin compounds and non-tin compounds.

Examples of tin compounds include:
Dibutyltin dichloride, dibutyltin oxide, dibutyltin dibromide, dibutyltin dimaleate, dibutyltin dilaurate (DBTDL), dibutyltin diacetate, dibutyltin sulfide, tributyltin sulfide, tributyltin oxide, tributyltin acetate, triethyltin ethoxide, tributyl Examples thereof include tin ethoxide, dioctyl tin oxide, tributyltin chloride, tributyltin trichloroacetate, and 2-ethylhexanoic acid tin.

Examples of non-tin compounds include:
Titanium systems such as dibutyltitanium dichloride, tetrabutyltitanate, or butoxytitanium trichloride;
Lead systems such as lead oleate, lead 2-ethylhexanoate, lead benzoate or lead naphthenate;
Iron systems such as iron 2-ethylhexanoate or iron acetylacetonate;
Cobalt-based benzoate or cobalt 2-ethylhexanoate, etc .;
Zinc-based such as zinc naphthenate or zinc 2-ethylhexanoate; or
Zirconium-based compounds such as zirconium naphthenate can be mentioned.

  Among the above catalysts, dibutyltin dilaurate (DBTDL), tin 2-ethylhexanoate or the like is preferable in terms of reactivity and hygiene.

  Catalysts such as the tertiary amine compounds or organometallic compounds can be used alone or in combination depending on the case.

  The organometallic compound catalyst used in the synthesis of the urethane prepolymer (E) significantly accelerates the reaction even in the further reaction with the amine described later.

  Solvents used for this purpose include, for example, ethyl acetate, n-propyl acetate, n-butyl acetate, isobutyl acetate, toluene, xylene, acetone, hexane, methyl ethyl ketone, cyclohexanone, propylene glycol mono lower alkyl ether acetate, diethylene glycol mono Lower alkyl ether acetate, diethylene glycol di-lower alkyl ether, or the like is used, but is not particularly limited thereto.

  In view of the solubility of the urethane prepolymer (E), the boiling point of the solvent, etc., the solubility of the amine, in particular, ethyl acetate, n-propyl acetate, toluene, methyl ethyl ketone, diethylene glycol di-lower alkyl ether lower alkyl, or a mixed solvent thereof. preferable. Among these, n-propyl acetate is particularly preferable from the viewpoint of dispersion stability and low odor.

  Further, the concentration in the urethane prepolymer reaction system when using a solvent is preferably 30 to 95% by weight from the viewpoint of reaction control in terms of the solid content concentration of the urethane prepolymer, and from the viewpoint of viscosity control. More preferably, it is 40 to 90% by weight. If it is less than 30% by weight, the reaction becomes slow and unreacted substances may remain. If it exceeds 95% by weight, the reaction may partially proceed abruptly, and it is difficult to control the molecular weight or the like, which is not preferable.

  The amount of the dispersant used in the gravure ink of the present invention is preferably 3 to 12 parts by weight with respect to 100 parts by weight of the pigment, and if it is less than 3 parts by weight, the dispersion stability may deteriorate. When the amount is more than part by weight, the ink coating film resistance becomes weak, and the suitability for lamination deteriorates.

<Other dispersants>
The dispersant can be used in combination with a known dispersant other than the dispersant of the present invention in order to improve the dispersibility and storage stability of the pigment. Such known dispersants include hydroxyl group-containing carboxylic acid esters, salts of long chain polyaminoamides and high molecular weight acid esters, salts of high molecular weight polycarboxylic acids, salts of long chain polyaminoamides and polar acid esters, and high molecular weights. Unsaturated acid ester, polymer copolymer, modified polyurethane, modified polyacrylate, polyether ester type anionic activator, naphthalene sulfonic acid formalin condensate salt, aromatic sulfonic acid formalin condensate salt, polyoxyethylene alkyl phosphoric acid Esters, polyoxyethylene nonylphenyl ether, stearylamine acetate, and the like can be used.

  Specific examples of the other dispersants include “Anti-Terra-U (polyaminoamide phosphate)”, “Anti-Terra-203 / 204 (high molecular weight polycarboxylate)” manufactured by BYK Chemie, “Disperbyk- 101 (salt of long chain polyaminoamide and polar acid ester), 107 (hydroxyl group-containing carboxylic acid ester), 110, 111 (copolymer containing acid group), 130 (polyamide), 161, 162, 163, 164, 165, 166, 170, 180, or 182 (high molecular weight copolymer) "," Bykumen (high molecular weight unsaturated acid ester) "," BYK-P104, or P105 (high molecular weight unsaturated acid polycarboxylic acid) ", "P104S or 240S (mixture of high molecular weight unsaturated acid polycarboxylic acid and polysiloxane ", Or" Lactimon (a mixture of partial amides product and polysiloxanes with long chain amine and an unsaturated acid polycarboxylic acid) "can be mentioned.

  Further, “Efka CHEMICALS” “Efka 44, 46, 47, 48, 49, 54, 63, 64, 65, 66, 71, 701, 764, or 766”, “Efka Polymer 100 (modified polyacrylate), 150 (fat) Group-based modified polymer), 400, 401, 402, 403, 450, 451, 452, 453 (modified polyacrylate), or 745 (copper phthalocyanine-based) "," Kyoeisha Chemical Co., Ltd. "Floren TG-710 (urethane oligomer)" , “Flonon SH-290 or SP-1000”, “Polyflow No. 50E or No. 300 (acrylic copolymer)”, or “Disparon KS-860, 873SN, 874 (polymer) manufactured by Enomoto Kasei Co., Ltd. Dispersant), # 2150 (aliphatic polycarboxylic acid), or # 7004 ( Li ether ester type) "can be mentioned.

Furthermore, “Demol RN, N (Naphthalenesulfonic acid formalin condensate sodium salt), MS, C, SN-B (aromatic sulfonic acid formalin condensate sodium salt), or EP” manufactured by Kao Corporation, “Homogenol L-18 ( Polycarboxylic acid type polymer) "," Emulgen 920, 930, 931, 935, 950, or 985 (polyoxyethylene nonyl phenyl ether) "," Acetamine 24 (coconut amine acetate), or 86 (stearyl amine acetate) ""Solspers 5000 (phthalocyanine ammonium salt type), 13940 (polyesteramine type), 17000 (fatty acid amine type), 20000 or 24000" manufactured by Lubrizol, "Nikkor T106 (polyoxyethylene sorbitan monooleate) manufactured by Nikko Chemical Co., Ltd." ), MYS-IEX (polyoxyethylene monostearate), or Hexagline 4-0 (hexaglyceryl tetraoleate), or “Ajisper PB821 or PB822 (basic dispersant)” manufactured by Ajinomoto Fine-Techno Co., Ltd. It is done.
From the viewpoint of pigment dispersibility, the amount of these other dispersants used is preferably 50 parts by weight or less, more preferably 40 parts by weight or less with respect to 100 parts by weight of the dispersant. When the amount is more than 50 parts by weight, the resistance of the ink coating film may be deteriorated.
The dispersant used in the present invention has, as a pigment adsorbing site, a urethane bond and a urea bond, more preferably a primary and / or secondary and / or tertiary amino group in a polyurethane / urea main chain, and a solvent affinity. Since it has a structure having a polyacrylate chain in the side chain as a characteristic site, the balance between the pigment adsorption site and the solvent affinity site is good, and excellent dispersion stability is expressed in the solvent.

  On the other hand, the polyacrylate chain functioning as a solvent affinity site exhibits high ink coating film resistance after drying and curing.

  Furthermore, when adding a binder resin for the purpose of improving the properties of the ink coating film, the side-chain polyacrylic chain of the dispersant of the present invention used in the gravure ink of the present invention is excellent in compatibility with the binder resin. Therefore, the ink coating film physical properties can be improved without impairing the basic physical properties of the gravure ink.

  Moreover, the pigment contained in the gravure ink of this invention can use the various pigments used for printing ink and a coating material. The pigment used in the present invention is not particularly limited, and examples of the white inorganic pigment include titanium oxide, zinc oxide, zinc sulfide, barium sulfate, calcium carbonate, chromium oxide, and silica. In particular, it is preferable to use titanium oxide as a pigment for white ink from the viewpoint of coloring power, hiding power, chemical resistance, and weather resistance. Examples of inorganic pigments other than white are carbon black, aluminum, mica (mica), and the like. Also, chromatic organic pigments can be used.

<Pigment>
The organic pigment that can be used in the present invention is not particularly limited.
Soluble azo pigment, insoluble azo pigment, phthalocyanine pigment, halogenated phthalocyanine pigment, quinacridone pigment, isoindolinone pigment, isoindoline pigment, perylene pigment, perinone pigment, dioxazine pigment, anthraquinone pigment, dianthraquinonyl pigment, anthrapyrimidine pigment, Ansanthrone pigment, indanthrone pigment, flavanthrone pigment, pyranthrone pigment, diketopyrrolopyrrole pigment, etc.
A more specific example is indicated by the generic name of the color index.
Blue pigments such as Pigment Black 7, Pigment Blue 15, Pigment Blue 15: 1, Pigment Blue 15: 3, Pigment Blue 15: 4, Pigment Blue 15: 6, Pigment Blue 22, Pigment Blue 60, or Pigment Blue 64;
Green pigments such as CI Pigment Green 7, Pigment Green 36, or Pigment Green 58;
Pigment Red 9, Pigment Red 48, Pigment Red 49, Pigment Red 52, Pigment Red 53, Pigment Red 57, Pigment Red 97, Pigment Red 122, Pigment Red 123, Pigment Red 144, Pigment Red 146, Pigment Red 149, Pigment Red 166, Pigment Red 168, Pigment Red 177, Pigment Red 178, Pigment Red 179, Pigment Red 180, Pigment Red 185, Pigment Red 192, Pigment Red 202, Pigment Red 206, Pigment Red 207, Pigment Red 209, Pigment Red 215, Pigment Red 216, Pigment Red 217, Pigment Red 220, Pigment Head 221, Pigment Red 223, Pigment Red 224, Pigment Red 226, Pigment Red 227, Pigment Red 228, Pigment Red 238, Pigment Red 240, Pigment Red 242, a red pigment such as Pigment Red 254 or Pigment Red 255;
A purple pigment such as Pigment Violet 19, Pigment Violet 23, Pigment Violet 29, Pigment Violet 30, Pigment Violet 37, Pigment Violet 40, or Pigment Violet 50;
Pigment Yellow 12, Pigment Yellow 13, Pigment Yellow 14, Pigment Yellow 17, Pigment Yellow 20, Pigment Yellow 24, Pigment Yellow 74, Pigment Yellow 83, Pigment Yellow 86, Pigment Yellow 93, Pigment Yellow 94, Pigment Yellow 95, Pigment Yellow 109, Pigment Yellow 110, Pigment Yellow 117, Pigment Yellow 120, Pigment Yellow 125, Pigment Yellow 128, Pigment Yellow 137, Pigment, Yellow 138, Pigment Yellow 139, Pigment Yellow 147, Pigment Yellow 148, Pigment Yellow 150, Pigment Yellow 151 , Pigment Yellow 153, Pigment I Low 154, Pigment Yellow 155, Pigment Yellow 166, Pigment Yellow 168, Pigment Yellow 180, Pigment Yellow 185, or yellow pigments such as CI Pigment Yellow 213;
Pigment Orange 13, Pigment Orange 36, Pigment Orange 37, Pigment Orange 38, Pigment Orange 43, Pigment Orange 51, Pigment Orange 55, Pigment Orange 59, Pigment Orange 61, Pigment Orange 64, Pigment Orange 71, or Pigment Orange 74, etc. Orange pigment; or
Examples thereof include brown pigments such as Pigment Brown 23, Pigment Brown 25, and Pigment Brown 26.

  The pigment concentration used in the gravure ink of the present invention is preferably 1 to 50 parts by weight with respect to the total weight of the gravure ink. When the amount is less than 1 part by weight, there is no coloring power. These pigments can be used alone or in combination of two or more.

<Dye derivative>
Next, the pigment derivative having an acidic substituent that can be used in the present invention will be described. The dye derivative having an acidic substituent that can be used in the present invention is selected from the group of dye derivatives represented by the following general formula (1), the following general formula (2), and the following general formula (3). There may be mentioned at least one dye derivative.

General formula (1):
PZ ¹
[In the general formula (1), P represents azo, benzimidazolone, phthalocyanine, quinacridone, anthraquinone, dioxazine, diketopyrrolopyrrole, quinophthalone, isoindolinone, isoindoline, perylene. Z ¹ is a sulfonic acid group or a carboxyl group, which is a kind of organic dye residue selected from the group, perinone, flavanthrone, pyranthrone, and anthrapyrimidine. ]
General formula (2):
(PZ ² ) [N ⁺ (R ¹ , R ² , R ³ , R ⁴ )]
(In general formula (2), P represents azo, benzimidazolone, phthalocyanine, quinacridone, anthraquinone, dioxazine, diketopyrrolopyrrole, quinophthalone, isoindolinone, isoindoline, perylene. R ¹ is an alkyl group having 5 to 20 carbon atoms, R ² , R ³ , and R ¹ is an organic dye residue selected from the group consisting of a perine, perinone, flavanthrone, pyranthrone, and anthrapyrimidine R ⁴ are each independently a hydrogen atom or an alkyl group having a carbon number of 1 to 20, Z ² is SO ₃ ^- or COO ^- and is).
General formula (3):
(P−Z ² ) M ⁺ / l
(In the general formula (3), P represents azo, benzimidazolone, phthalocyanine, quinacridone, anthraquinone, dioxazine, diketopyrrolopyrrole, quinophthalone, isoindolinone, isoindoline, perylene. Is an organic pigment residue selected from the group consisting of perylene, flavanthrone, pyranthrone, and anthrapyrimidine, and M is a sodium atom, potassium atom, calcium atom, barium atom, strontium atom or aluminum atom, l Is the valence of M, and Z ² is SO ₃ ⁻ or COO ⁻ .)
The amount of the pigment derivative used in the gravure ink of the present invention is preferably 3 to 10 parts by weight with respect to 100 parts of the pigment. If the amount is less than 3 parts by weight, the aging stability of the remaining meat tends to be inferior. If the amount is more than 10 parts by weight, the aging stability of the raw ink tends to be inferior, and the plate fogging property and laminate physical properties may be lowered.

The particle size distribution of the pigment in the gravure ink can be adjusted by appropriately adjusting the grinding media size of the disperser, the filling rate of the grinding media, the dispersion processing time, the discharge speed, the viscosity, and the like. As the disperser, for example, a commonly used roller mill, ball mill, pebble mill, attritor, sand mill and the like can be used.
<Binder resin>
Various resins can be selected as the binder resin used in the present invention depending on the application and the substrate. Examples of resins used include polyurethane / urea resins, vinyl chloride-vinyl acetate copolymer resins, chlorinated polypropylene resins, polyamide resins, polynitrocellulose resins, and these resins may be used alone or in combination of two or more. The content is preferably 5 to 25% by weight based on the total weight of the ink.

  Furthermore, in the printing ink for laminating, polyurethane / urea resin can be used as the main binder among the resins used in the printing ink composition of the present invention because of storage stability over time, stability on printing press, suitability for laminating, and the like. Most preferred. In the present invention, mention may be made of polyurethane / urea resins used in general inks, paints, recording agents and the like.

  The polyurethane / urea resin used in the binder resin of the present invention can be synthesized using various commonly used polyols. A polyol may use together 1 type, or 2 or more types.

  The polyurethane / urea resin is prepared by reacting a polyol and a polyisocyanate with an inert solvent for an isocyanate group, if necessary, and further using a urethanization catalyst if necessary at a temperature of 10 to 150 ° C. A prepolymer method obtained by producing a prepolymer having a group and then reacting this prepolymer with a chain extender, or a one-shot method obtained by reacting an organic polyol compound, a polyisocyanate compound and a chain extender in one step It can manufacture by a well-known method.

Examples of the polyol include polymer polyols such as methylene oxide, ethylene oxide, and tetrahydrofuran, or copolymer polyether polyols (1);
Ethylene glycol, 1,2-propanediol, 1,3-propanediol, 2methyl-1,3-propanediol, 2ethyl-2butyl-1,3propanediol, 1,3-butanediol, 1,4-butane Diol, neopentyl glycol, pentanediol, 3-methyl-1,5-pentanediol, hexanediol, octanediol, 1,4-butynediol, 1,4-butylenediol, diethylene glycol, triethylene glycol, polypropylene glycol, dipropylene Saturated or unsaturated low molecular polyols (2) such as glycol, glycerin, trimethylolpropane, trimethylolethane, 1,2,6-hexanetriol, 1,2,4-butanetriol, sorbitol, pentaesitol ;
These low molecular weight polyols (2), adipic acid, phthalic acid, isophthalic acid, terephthalic acid, maleic acid, fumaric acid, succinic acid, oxalic acid, malonic acid, glutaric acid, pimelic acid, speric acid, azelaic acid, Polyester polyols (3) obtained by dehydration condensation or polymerization of polycarboxylic acids such as sebacic acid, trimellitic acid, pyromellitic acid or their anhydrides;
Polyester polyols (4) obtained by ring-opening polymerization of lactones such as cyclic ester compounds such as polycaprolactone, polyvalerolactone, poly (β-methyl-γ-valerolactone);
Polycarbonate polyols (5) obtained by reaction of the low molecular polyols (2) and the like with, for example, dimethyl carbonate, diphenyl carbonate, ethylene carbonate, phosgene and the like;
Polybutadiene glycols (6); glycols obtained by adding ethylene oxide or propylene oxide to bisphenol A (7); one or more hydroxyethyl, hydroxypropyl acrylate, acrylic hydroxybutyl, etc. in one molecule, or An acrylic polyol (8) obtained by copolymerizing these corresponding methacrylic acid derivatives and the like, for example, acrylic acid, methacrylic acid or an ester thereof; an oxirane compound such as ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran, etc. Examples thereof include polyether polyol (9) obtained by polymerizing water, ethylene glycol, propylene glycol, trimethylolpropane, glycerin and other low molecular weight polyols as initiators. In particular, the polyether polyol is preferably polypropylene glycol, and the polyester polyol is preferably a polymer of 3-methyl-1,5-pentanediol and adipic acid.

  The polyisocyanate used in the polyurethane / urea resin can be used in the same manner as various diisocyanates used in the dispersant. These diisocyanate compounds can be used alone or in admixture of two or more.

  Examples of the chain extender used in the polyurethane / urea resin include ethylenediamine, propylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, isophoronediamine, dicyclohexylmethane-4,4′-diamine, and the like. Hydroxyethylethylenediamine, 2-hydroxyethylpropyldiamine, 2-hydroxyethylpropylenediamine, di-2-hydroxyethylethylenediamine, di-2-hydroxyethylenediamine, di-2-hydroxyethylpropylenediamine, 2-hydroxypyrroleethylenediamine, di Amines having a hydroxyl group in the molecule, such as 2-hydroxypropylethylenediamine and di-2-hydroxypropylethylenediamine, can also be used. These chain extenders can be used alone or in admixture of two or more. Considering reactivity and solubility, isophoronediamine is preferable.

  A monovalent active hydrogen compound can also be used as a terminal terminator for the purpose of terminating the reaction. Examples of such compounds include dialkylamines such as di-n-butylamine and alcohols such as ethanol and isopropyl alcohol. Furthermore, amino acids such as glycine and L-alanine can be used as a reaction terminator, particularly when it is desired to introduce a carboxyl group into the polyurethane resin. These end terminators can be used alone or in admixture of two or more.

  In the production of the prepolymer, the amount of polyol and polyisocyanate is such that the NCO / OH ratio, which is the ratio of the equivalent of the isocyanate group of polyisocyanate (F) to the equivalent of the hydroxyl group of the organic polyol compound, is 1.1 to 3.0. It is preferable to be in the range. When this ratio is less than 1.1, there is a tendency that sufficient alkali resistance cannot be obtained, and when it is more than 3.0, the solubility of the resulting prepolymer tends to be lowered.

  Moreover, it is preferable from the surface of reaction control to use a solvent for reaction. As the solvent that can be used, those that dissolve the polyurethane adhesive composition are preferable. For example, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ethers such as dioxane and tetrahydrofuran; aromatic hydrocarbons such as toluene and xylene And the like; esters such as ethyl acetate and n-propyl acetate; and halogenated hydrocarbons such as chlorobenzene and perchlene. These may be used alone or in combination as a mixed solvent.

  Furthermore, a catalyst can also be used for this urethanation reaction. Examples of catalysts that can be used include tertiary amine catalysts such as triethylamine and dimethylaniline; metal catalysts such as tin and zinc. These catalysts are usually used in the range of 0.001 to 1 mol% with respect to the polyol compound.

  The prepolymer having an isocyanate group at the terminal obtained above and the chain extender diol, diamine, triol, etc. are reacted at 10 to 80 ° C. to obtain a high molecular weight polyurethane resin containing an active hydrogen group at the terminal. It is done.

  When using an end-stopper, the end-stopper and chain extender may be used together to carry out a chain extension reaction. Thus, an end termination reaction may be performed. On the other hand, the molecular weight can be controlled without using a terminal terminator, but in this case, a method of adding a prepolymer to a solution containing a chain extender is preferable in terms of reaction control.

  End terminators are used to control molecular weight. As the amount used increases, the molecular weight of the resulting polyurethane / urea resin decreases. This varies depending on the reactivity of the chain extender and the terminal terminator with respect to the prepolymer. In general, the ratio of the amino group or hydroxyl group equivalent of the chain extender to the equivalent of the amino group or hydroxyl group of the terminal terminator is 0. A range of 5 to 5.0 is preferred. When this ratio exceeds 5.0, the polymer has a high molecular weight, so that the suitability for dry lamination tends to deteriorate. When it is less than 0.5, the molecular weight and the initial adhesive force tend to decrease.

  Further, the ratio of the total equivalent of the amino group and the hydroxyl group of the chain extender and the terminal terminator to the equivalent of the isocyanate group in the prepolymer is 1.1 to 3.0, preferably 1.5 to 2.0. To react. When this ratio is large and the amount of chain extender or terminal terminator used is large, they remain unreacted and odor tends to remain.

<Solvent>
Generally used organic solvents can be widely used for the gravure ink of the present invention. There is no particular limitation as long as it is an organic solvent in which the dispersant of the present invention is dissolved or uniformly dispersed.

Specific examples of organic solvents include
Alcohols such as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, or n-butyl alcohol;
Acetone, methyl ethyl ketone, methyl-n-propyl ketone, methyl isopropyl ketone, methyl-n-butyl ketone, methyl isobutyl ketone, methyl-n-amyl ketone, methyl isoamyl ketone, diethyl ketone, ethyl-n-propyl ketone, ethyl isopropyl ketone, ethyl Ketones such as n-butyl ketone, ethyl isobutyl ketone, di-n-propyl ketone, diisobutyl ketone, cyclohexanone, methylcyclohexanone, or isophorone;
Esters such as methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, hexyl acetate, octyl acetate, methyl lactate, propyl lactate, or butyl lactate;
Lactones such as γ-butyrolactone or ε-caprolactone;
Glycols such as ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, or dipropylene glycol;
Ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether , Propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl Ether, dipropylene glycol dipropyl ether, tripropylene glycol monomethyl ether, or glycol ethers such as tetraethylene glycol dimethyl ether;
Ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol Glycol acetates such as monobutyl ether acetate or dipropylene glycol monomethyl ether acetate;
saturated hydrocarbons such as n-hexane, isohexane, n-nonane, isononane, dodecane, or isododecane;
Unsaturated hydrocarbons such as 1-hexene, 1-heptene, or 1-octene;
Cyclic saturated hydrocarbons such as cyclohexane, cycloheptane, cyclooctane, cyclodecane, or decalin;
Cyclic unsaturated hydrocarbons such as cyclohexene, cycloheptene, cyclooctene, 1,1,3,5,7-cyclooctatetraene, or cyclododecene;
(N-alkyl) pyrrolidones such as N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, or 2-pyrrolidone;
N-alkyloxazolidinones such as N-methyl-2-oxazolidinone; or
Aromatic hydrocarbons such as benzene, toluene, xylene and the like.

  These organic solvents can be used alone or in combination of two or more, but are preferably used in gravure inks.

  The gravure ink of the present invention comprises a pigment, the dispersant, a binder resin, an organic solvent, a dye derivative as necessary, a plasticizer, a surface conditioner, an ultraviolet light inhibitor, a light stabilizer, an antioxidant, an antistatic agent, Various additives such as an antiblocking agent, an antifoaming agent, a viscosity modifier, a wax, a surfactant, and a leveling agent can be used.

  The gravure ink viscosity produced by the above method is in the range of 10 mPa · s or more from the viewpoint of preventing the pigment from settling and being appropriately dispersed, and 1000 mPa · s or less from the viewpoint of workability efficiency during gravure ink production or printing. It is preferable. In addition, the said viscosity is a viscosity measured at 25 degreeC with the Tokimec B-type viscometer.

  The viscosity of the gravure ink can be adjusted by appropriately selecting the type and amount of raw materials used, for example, pigments, resins, organic solvents and the like. Also, the viscosity can be adjusted by adjusting the particle size and particle size distribution of the pigment.

  In the case where bubbles or unexpectedly coarse particles are included in the gravure ink, it is preferably removed by filtration or the like in order to reduce the quality of the printed matter. A conventionally well-known filter can be used.

EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to these Examples. In addition, the part and% in an Example and a comparative example represent a weight part and weight%. In addition, a hydroxyl group is the number of mg of potassium hydroxide required in order to neutralize the hydroxyl group contained in 1g of resin, and is the value performed according to JISK0070. The amine value is the number of mg of potassium hydroxide equivalent to the equivalent amount of hydrochloric acid required to neutralize the amino group contained in 1 g of resin. The method for measuring the amine value was as described below. The molecular weight is a molecular weight in terms of polystyrene when a TSKgel column (manufactured by Tosoh Corporation) is used, GPC (manufactured by Tosoh Corporation, HLC-8320GPC), and DMF is used as a developing solvent. The method for measuring the amine value is as follows.
[Method for measuring amine value]
Weigh 0.5-2 g of sample accurately. (Sample amount: Sg) 30 mL of neutral ethanol (BDG neutral) is added to a precisely weighed sample and dissolved. The obtained solution is titrated with a 0.2 mol / L ethanolic hydrochloric acid solution (titer: f). The point at which the color of the solution changed from green to yellow was taken as the end point, and the amine value was determined by the following (Formula 1) using the titration amount (AmL) at this time.
(Formula 1) Amine number = (A × f × 0.2 × 56.108) / S
<Synthesis of vinyl polymer (A)>
A reaction vessel equipped with a gas introduction tube, a thermometer, a condenser, and a stirrer was charged with 500 parts of methyl methacrylate, 11 parts of thioglycerol, and 511 parts of n-propyl acetate and replaced with nitrogen gas. The inside of the reaction vessel was heated to 90 ° C., and 0.50 part of AIBN [2,2′-azobis (isobutyronitrile)] was added, followed by reaction for 7 hours. After confirming that 95% had reacted by solid content measurement, it was cooled to room temperature, and the solid content of vinyl polymer (A-1) having a weight average molecular weight of 9,500 and having two free hydroxyl groups in one end region A 50% solution was obtained.

<Synthesis of polyurethane / urea-based basic dispersant (F-1)>
In a reaction vessel equipped with a gas introduction tube, a thermometer, a condenser, and a stirrer, 1022 parts of a 50% solid solution of vinyl polymer (A-1), 45.2 parts of isophorone diisocyanate, and n-propyl acetate 45. 1 part and 0.11 g of dibutyltin dilaurate as a catalyst were charged and replaced with nitrogen gas. The reaction vessel was heated to 100 ° C. and reacted for 3 hours, and then cooled to 40 ° C. to obtain a colorless transparent solution. A reaction vessel equipped with a gas inlet tube, a thermometer, a condenser, and a stirrer was charged with a mixed solution of 11.1 parts of methyliminobispropylamine, 6.6 parts of dibutylamine, and 304.6 parts of n-propyl acetate. The mixture was heated to ° C. and 112.4 parts of a colorless and transparent solution (B-1) was added dropwise over 30 minutes. After further reaction for 1 hour, the reaction was terminated by cooling to room temperature. The solid content was adjusted to 40% to obtain a colorless and transparent solution of polyurethane / urea basic dispersant (F-1). The weight average molecular weight of the dispersant (F-1) was 43,200, and the amine value was 9.0 mgKOH / g.

<Synthesis of polyurethane / urea basic dispersant (F-2 to F-6)>
In the same manner as in the method for synthesizing the polyurethane / urea basic dispersant (F-1), an amine value of 0.5, 1.0, 40.0, 100.0, 200.0 mgKOH / g (F-2, F-3, F-4, F-5, F-6) polyurethane / urea basic dispersants were synthesized.
<Synthesis of binder resin (polyurethane / urea resin)>
[Synthesis Example 1]
2. In a reaction vessel equipped with a gas introduction tube, a thermometer, a condenser, and a stirrer, 54.719 parts of polyester diol having a number average molecular weight of 2000 obtained from adipic acid and 3-methyl-1,5-pentanediol, isophorone diisocyanate; 989 parts, 0.010 part of stannous 2-ethylhexylate and 10.0 parts of n-propyl acetate were reacted at 85 ° C. for 3 hours under a nitrogen stream, and then 10.0 parts of n-propyl acetate was added and cooled. 78.718 parts of a solvent solution of an isocyanate prepolymer was obtained. Subsequently, 1.031 parts of isophoronediamine, 0.261 parts of di-n-butylamine, 30.4 parts of n-propyl acetate and 19.6 parts of isopropyl alcohol were mixed with a solvent solution of the obtained terminal isocyanate prepolymer. 718 parts are gradually added at room temperature and then reacted at 50 ° C. for 1 hour to obtain a polyurethane / urea resin solution (G) having a solid content of 30%, a weight average molecular weight of 60000, and an amine value of 3.0 mgKOH / g. It was.
<Other binder resin adjustment>
Vinyl chloride-vinyl acetate copolymer (Solvine TA5R manufactured by Nissin Chemical Co., Ltd.), polynitrocellulose (1 / 8H, manufactured by Asahi Kasei Co., Ltd.), polyamide resin (Sunamide 550H, manufactured by Air Products), chlorinated polypropylene Each resin solution (H, I, J, K) was prepared by mixing and dissolving in 30 parts of each resin and 70 parts of n-propyl acetate using a resin (Supercron 813A, manufactured by Nippon Paper Industries Co., Ltd.).
Phthalocyanine-based acidic derivative (A): General formula (5) shown in the following general formula (5):
_{P- [SO 3 H · H 2} N (CH 2) 11 CH 3]
(In general formula (5), P is a copper phthalocyanine residue.)
Azo-based acidic derivative (A): represented by the following general formula (6).
General formula (6):
P- (SO ₃ H)
(In general formula (6), P is an azo pigment residue.)
Azo-based acidic derivative (B): shown in the following general formula (7).
General formula (7):
P- (COONa)
(In General Formula (7), P is an azo pigment residue.)
[Example 1]
C. I. 12 parts of Pigment Yellow 14; 1.8 parts of the polyurethane / urea-based basic dispersant solution (F-1, amine value 9 mgKOH / g) (6 parts with respect to 100 parts of pigment); azo-based acidic derivative (A) 0.6 parts (5 parts with respect to 100 parts of pigment) and 10 parts of a mixed solvent of n-propyl acetate / isopropyl alcohol (weight ratio 72/28) were stirred and mixed with a sand mill, and then polyurethane / 38.7 parts of urea resin solution (G) and 36.9 parts of the mixed solvent were mixed to obtain yellow / raw ink (G-1). To 100 parts of the obtained yellow / raw ink (G-1), 50 parts of a toluene / isopropyl alcohol mixed solvent (weight ratio 90/10) was added and mixed as a diluent solvent to obtain yellow / diluted ink (G-2). It was.
[Examples 2 to 4]
Using an amine value of 1.0, 40.0, 100.0 mg KOH / g (F-3, F-4, F-5) for the polyurethane / urea basic dispersant, as in Example 1, Yellow / raw ink (H-1, I-1, J-1) and yellow / diluted ink (H-2, I-2, J-2) were obtained.
[Examples 5 to 8]
Using vinyl chloride-vinyl acetate copolymer resin (H), nitrocellulose resin (I), polyamide resin (J), and chlorinated polypropylene resin (K) as the binder resin, yellow / raw Inks (K-1, L-1, M-1, N-1) and yellow / diluted inks (K-2, L-2, M-2, N-2) were obtained.
[Example 9]
Black / raw ink (O-1) and black / diluted ink (O) were used in the same manner as in Example 1 using carbon black (Regal 99R, manufactured by Cabot) as the pigment, and phthalocyanine-based acidic derivative (A) as the pigment derivative. -2) was obtained.
[Example 10]
Using carbon black (Regal 99R, manufactured by Cabot Corporation) as a pigment, without using a pigment derivative, black / raw ink (P-1) and black / diluted ink (P-2) were used in the same manner as in Example 1. Obtained.
[Examples 11 to 13]
Example 1 with 100 parts by weight of the polyurethane / urea basic dispersant (F-1, amine value 9 mgKOH / g) as 1, 12, 24 parts per 100 parts by weight of pigment Similarly, yellow / raw ink (Q-1, R-1, S-1) and yellow / diluted ink (Q-2, R-2, S-2) were obtained.
[Examples 14 to 17]
Yellow / raw ink (T-1, U-1, V-) in the same manner as in Example 1 with the blending amount of the azo acid derivative (B) being 0, 1, 3, 15 parts relative to 100 parts of pigment. 1, W-1) and yellow / diluted ink (T-2, U-2, V-2, W-2).
[Comparative Examples 1 and 2]
Without using the polyurethane / urea basic dispersant, yellow / raw ink (X-1), yellow / diluted ink (X-2), black / raw ink (Y-1) A black / diluted ink (Y-2) was obtained.
[Comparative Examples 3 and 4]
Using 100 parts of pigment, 6 parts of polyurethane / urea basic dispersant having an amine number of 0.5 and 200.0 mg KOH / g, yellow / raw ink (Z-1, AA- 1) and a yellow / diluted ink (Z-2, AA-2) were obtained.
[Comparative Examples 5 to 7]
Polyamide-polycaprolactone basic dispersant (Ajisper PB-821, Ajinomoto Fine Techno Co.), polyamide-polyester basic dispersant (Solsperse 20000, Lubrizol Co.), polycarboxylic acid component Using an acid agent (homogenol L-18, manufactured by Kao Corporation), yellow raw ink (AB-1, AC-1, AD-1) and yellow diluted ink (AB-2, AC-) as in Example 1. 2, AD-2) was obtained.

For the raw inks G-1 to AD-1 of Examples 1 to 17 and Comparative Examples 1 to 7, (1) the amount of residue was evaluated as a measure of storage stability over time. In addition, for gravure diluted inks G-2 to AD-2, (2) Separation and (3) Precipitation as a measure of storage stability with time, (4) On-machine stability (plate fog) as a measure of dispersibility, and laminate suitability (5) Retort suitability was evaluated as a measure of each.
(1) Residue amount: The gravure printing ink was stored at 40 ° C. for 2 weeks and then filtered through a nylon filter cloth (350 mesh). Visually evaluate the amount of residue.

<Evaluation criteria>
A: There is almost no residue and it is good.
○: Almost good with only a small amount of residue.
X: The amount of residue is very large, and a large lump is formed.
(2) Separation: After storing the gravure diluted ink at 40 ° C. for 2 weeks, the difference in density between the supernatant and the supernatant of the liquid is evaluated from the ink adhesion by inserting a spatula.
<Evaluation criteria>
A: The diluted ink adheres at a uniform concentration, and the concentration in the liquid is uniform and good.
○: Diluted ink adheres with very slight density unevenness but is generally good.
Δ: Diluted ink adheres to the spatula in a striped pattern, and the concentration in the liquid is not uniform.
X: There is a large density difference between the upper and lower sides of the diluted ink, and since the liquid surface is transparent, it hardly adheres to the spatula.
(3) Precipitation: After storing the gravure diluted ink at 40 ° C. for 2 weeks, the amount of precipitation is visually evaluated from scraping the bottom with a spatula.
<Evaluation criteria>
(Double-circle): There is no deposit and it is good.
○: There is no obvious precipitate, but the concentration at the bottom is slightly high and thick.
X: A large amount of hard precipitate is generated on the entire bottom surface.
(4) On-machine stability (plate cover): NBR (nitrile butadiene rubber) rubber cylinder 80Hs impression cylinder, blade tip thickness 60μm (base material thickness 40μm, one side ceramic layer thickness 10μm) Blade, an electronic engraving plate with a chrome hardness of 1050 Hv (stylus angle 120 degrees, 250 lines / inch) manufactured by Toyo Prepress Co., Ltd., and the dilute ink obtained in Example 1-14 and Comparative Example 1-5 The plate is idled at a doctor pressure of 2 kg / cm ² and a rotation speed of 100 m / min for 60 minutes, and then a single-sided corona-treated PET film “E-5100 (manufactured by Toyobo Co., Ltd.)” On the corona-treated surface, printing was performed at a printing speed of 100 m / min at a printing pressure of 2 kg / cm ² and drying with hot air at 60 ° C. to obtain a printed matter. During printing, a viscosity controller is used to appropriately replenish each dilution solvent to maintain a certain viscosity.

<Evaluation criteria>
A: No ink transfer was observed in the non-image area.
○: Ink transfer was slightly observed in the non-image area.
X: Ink transfer was observed over the entire non-image area.
(5) Retort suitability: Using a dry laminating machine (manufactured by Fuji Machine Industry Co., Ltd.), printed matter and aluminum foil, CPP film “ZK-93K” (manufactured by Toray Synthetic Film Co., Ltd.) prepared by the above method. A laminate was obtained using a dry laminate adhesive TM-250HV / CAT-RT86 (manufactured by Toyo Morton Co., Ltd.). The laminate was cut into 20 × 12 cm, and a bag was made by heat-sealing the three sides (temperature: 190 ° C., pressure: 2 kgf, time: 1 second), and 1: 1: 1 soup (ketchup: vinegar: An evaluation sample was prepared by filling water = weight ratio 1: 1: 1) and heat-sealing the remainder. The sample was subjected to a retort treatment at 120 ° C./30 minutes using a retort sterilizer (Flavor Ace, manufactured by Nisaka Seisakusho).

<Evaluation criteria>
Filled with 1: 1: 1 soup (ketchup: vinegar: water = 1: 1: 1 by weight), and after retort treatment at 120 ° C./30 minutes, the presence or absence of delamination was visually evaluated, and the adhesive strength was measured and evaluated.
○: There is no delamination and the adhesive strength is generally good.
○ △: Good with no delamination, although the adhesive strength is slightly reduced, but is generally good.
X: Delamination occurs and the adhesive strength is greatly reduced.

The compositions and evaluation results are shown in Tables 1 and 2.

  From Examples 1 to 4 and Comparative Examples 1 and 2, the storage stability over time is improved by the polyurethane / urea basic dispersant.

  From Examples 1 to 4 and Comparative Examples 3 and 4, the polyurethane / urea-based basic dispersant is improved in storage stability with time and on-machine stability when the amine value is 1 to 100 mgKOH / g. The balance with aptitude was also good. On the other hand, when the amine value was 0.5 mgKOH / g, the effect of the dispersant was low, and when the amine value was 200 mgKOH / g, the retort suitability was lowered.

  From Example 1 and Comparative Examples 5 to 7, the performance is greatly improved only when the main chain of the basic dispersant has a polyurethane / urea structure and the side chain has an acrylic structure, and this characteristic structure has a great influence. doing.

  From Example 1 and Examples 5-8, it is effective also in the general binder resin used with gravure ink. In particular, when the binder resin is a polyurethane / urea resin, the plate fog is optimal. Examples 9 and 10 are effective in carbon black as an inorganic pigment and have a wide range of pigment selectivity. Furthermore, from Examples 11 to 13, the dispersant is preferably 3 to 12 parts by weight with respect to 100 parts by weight of the pigment. Even if the pigment derivative having an acidic group is not contained, the performance is improved. However, by adding 3 to 10 parts by weight with respect to 100 parts by weight of the pigment, the acid-base interaction with the dispersant becomes stronger, and the dispersion effect Increased further.

Claims (4)

The urethane prepolymer (E) having two isocyanate groups in one end region obtained by reacting the hydroxyl group of the vinyl polymer (A) having two hydroxyl groups in one end region with the isocyanate group of diisocyanate (B) Dispersants, pigments, polyurethane / urea resins, and vinyl chlorides obtained by reacting isocyanate groups with primary and / or secondary amino groups of amine compounds containing polyamine (C) and having an amine value of 1 to 100 mgKOH / g -A gravure ink comprising one or more binder resins selected from vinyl acetate copolymer resins, polynitrocellulose resins, polyamide resins, and chlorinated polypropylene resins, and a solvent. The gravure ink according to claim 1, wherein the dispersant is used in an amount of 3 to 12 parts by weight based on 100 parts by weight of the pigment. The gravure ink contains at least one dye derivative selected from the group of dye derivatives having an acidic substituent represented by the following general formula (1), the following general formula (2), and the following general formula (3). The gravure ink according to claim 1, wherein the pigment derivative is used in an amount of 3 to 10 parts by weight based on 100 parts by weight of the pigment.
General formula (1):
PZ ¹
(In general formula (1), P represents azo, benzimidazolone, phthalocyanine, quinacridone, anthraquinone, dioxazine, diketopyrrolopyrrole, quinophthalone, isoindolinone, isoindoline, perylene. Z ¹ is a sulfonic acid group or a carboxyl group, which is a kind of organic dye residue selected from the group, perinone, flavanthrone, pyranthrone, and anthrapyrimidine.
General formula (2):
(PZ ² ) [N ⁺ (R ¹ , R ² , R ³ , R ⁴ )]
(In general formula (2), P represents azo, benzimidazolone, phthalocyanine, quinacridone, anthraquinone, dioxazine, diketopyrrolopyrrole, quinophthalone, isoindolinone, isoindoline, perylene. R ¹ is an alkyl group having 5 to 20 carbon atoms, R ² , R ³ , and R ¹ is an organic dye residue selected from the group consisting of a perine, perinone, flavanthrone, pyranthrone, and anthrapyrimidine R ⁴ are each independently a hydrogen atom or an alkyl group having a carbon number of 1 to 20, Z ² is SO ₃ ^- or COO ^- and is).
General formula (3):
(P−Z ² ) M ⁺ / l
(In the general formula (3), P represents azo, benzimidazolone, phthalocyanine, quinacridone, anthraquinone, dioxazine, diketopyrrolopyrrole, quinophthalone, isoindolinone, isoindoline, perylene. Is an organic pigment residue selected from the group consisting of perylene, flavanthrone, pyranthrone, and anthrapyrimidine, and M is a sodium atom, potassium atom, calcium atom, barium atom, strontium atom or aluminum atom, l Is the valence of M, and Z ² is SO ₃ ⁻ or COO ⁻ .) The gravure ink according to any one of claims 1 to 3, wherein the polyurethane / urea resin is obtained by reacting a polyester polyol, a polyether polyol, a low molecular polyol, a polyisocyanate, a chain extender, and a terminal terminator.