JP2019094407A - Liquid ink composition - Google Patents

Abstract

To provide a liquid ink composition having all of adhesion to diversified functional film substrates, laminate strength, retort resistance, and excellent printability.SOLUTION: The present invention provides a liquid ink composition containing a polyurethane resin (A) comprising polyester polyol as the reaction raw material and a polyvinyl chloride vinyl acetate copolymer resin (B), the polyester polyol comprising polycarboxylic acid with 7 or more carbon atoms and two or more carboxyl groups as the raw material.SELECTED DRAWING: None

Description

  The present invention relates to a liquid ink composition which can be used as a laminate gravure ink for flexible packaging or a flexo ink.

  Gravure ink and flexo ink are widely used for the purpose of imparting cosmetic property and functionality to a printing material. When a gravure or flexographic printed material is used as a food packaging material, particularly among packaging materials, lamination is generally applied. In this case, various printing materials and laminating processes are used according to the type of contents and the purpose of use.

Conventionally, for such a laminate, a printing ink containing a polyurethane resin as a binder has been widely used because of its excellent adhesion to various substrates, laminate strength of various laminates, and boil retort suitability.

For example, Patent Document 1 discloses a printing ink composition for lamination comprising, as a main binder resin, a polyurethane polyurea resin soluble in a high molecular weight diol, an organic diisocyanate and an organic solvent obtained by reacting a diamine as a chain extender. It is done. After that, various studies were made to improve the laminate physical properties. In Patent Document 2, in a polyurethane resin obtained from a high molecular weight diol and an organic diisocyanate, adhesiveness is obtained by using a polyester polyol obtained from 3-methyl-1,5-pentanediol and a dibasic acid as the high molecular weight diol compound. It is exemplified that the hydrolysis resistance and resolubility are improved.
Patent Document 3 discloses a polyurethane resin obtained by reacting a polyester polyol obtained by polycondensation of 2-butyl-2-ethyl-1,3-propanediol with a polycarboxylic acid with a polyisocyanate.
Patent Document 4 discloses a polyurethane resin obtained from a polyester diol obtained from 2,4-diethyl-1,5-pentanediol and a dicarboxylic acid and an organic diisocyanate compound.
Patent Document 5 describes a laminate ink composition for soft packaging, which comprises a polypropylene glycol-containing polyurethane resin and a vinyl chloride-vinyl acetate copolymer resin having a hydroxyl group as essential components.
Patent Document 6 and Patent Document 7 describe polyester-based urethane resins in which the range of urea bond concentration is specified as a printing ink binder for laminate cans.
Patent Documents 8 and 9 describe polyurethane resins obtained by reacting specific diol components with organic diisocyanates and amine chain extenders.

However, with the diversification of packaging substrates in recent years, printing inks used for decoration or surface protection are required to have high performance, so the above-mentioned laminate ink of the invention is sufficiently satisfactory. The present situation is that there is nothing to do.
Further, in recent years, in particular, the demand for environmentally friendly products for the purpose of global warming countermeasures and environmental load reduction is increasing. However, in the prior art, in addition to the basic printability, adhesion to various substrates, lamination strength, and retortability are simultaneously improved, and some of the raw materials of the liquid ink composition are derived from plants. It is not easy to satisfy the improvement of environmental responsiveness by incorporating ingredients.

Japanese Patent Application Laid-Open No. 55-25453 Japanese Patent Application Laid-Open No. 63-161065 JP-A-6-41264 JP, 2000-273382, A JP 2005-298618 A Unexamined-Japanese-Patent No. 11-172184 JP 2002-294129 A Japanese Patent Laid-Open No. 6-80921 Unexamined-Japanese-Patent No. 11-279472

  An object of the present invention is to provide a liquid ink composition that combines adhesion to various functional film substrates, lamination strength, retort resistance, and good printability.

  MEANS TO SOLVE THE PROBLEM As a result of repeating earnest research in order to solve the above-mentioned subject, the present inventors are polyurethane resin (A) and vinyl chloride vinyl acetate copolymer resin (B) which make polyester polyol a reaction raw material in liquid ink composition. It has been found that it is effective to solve the problem that in the liquid ink composition containing the polyester polyol, the polyester polyol has a polycarboxylic acid having 7 or more carbon atoms and two or more carboxyl groups as a raw material.

  That is, the present invention is a liquid ink composition comprising a polyurethane resin (A) using polyester polyol as a reaction raw material and a vinyl chloride / vinyl acetate copolymer resin (B), wherein said polyester polyol has 7 carbon atoms. The present invention relates to a liquid ink composition characterized by using, as a raw material, a polycarboxylic acid having two or more carboxyl groups as described above.

    The present invention further relates to a liquid ink composition containing water (C) in an amount of less than 10% by mass of the total amount of the composition.

  Moreover, this invention relates to the liquid ink composition which contains a polyether polyol as a structural component of the said polyurethane resin (A) 1-40 mass% with respect to the polyurethane resin (A) whole quantity.

  In addition, the present invention relates to a liquid ink composition in which the polyether polyol has a number average molecular weight of 100 to 3,500.

  The present invention further relates to a liquid ink composition containing a colorant (D) and an organic solvent (E).

  In addition, the present invention relates to a liquid ink composition in which the polycarboxylic acid is sebacic acid and / or a dimer acid.

  In the present invention, the vinyl chloride / vinyl acetate copolymer resin (B) has a hydroxyl group, the hydroxyl value is 50 to 200 mg equivalent KOH, and the content of the vinyl chloride component in the copolymer resin is The present invention relates to a liquid ink composition having 80 to 95% by mass.

  Further, the present invention relates to a liquid ink composition wherein the organic solvent (E) does not contain an aromatic group-free organic solvent and / or ketone solvent.

  The present invention also relates to a printed matter obtained by printing the liquid ink composition.

  In addition, the present invention relates to a laminate, which comprises the printed matter.

ADVANTAGE OF THE INVENTION By this invention, the liquid ink composition which combines the adhesiveness with respect to each functional film base material variously diversified, lamination strength, retort resistance, and favorable printability is obtained.

  The present invention will be described in detail. The term "ink" used in the following description refers to "printing ink". Moreover, all "parts" show a "mass part."

  The present invention is a liquid ink composition comprising a polyurethane resin (A) containing polyester polyol as a reactive raw material and a vinyl chloride / vinyl acetate copolymer resin (B), wherein said polyester polyol has 7 or more carbon atoms and It is a liquid ink composition characterized by using as a raw material a polycarboxylic acid having two or more carboxyl groups.

  Specifically, the liquid ink composition of the present invention comprises a polyurethane resin (A), a vinyl chloride / vinyl acetate copolymer resin (B), various organic solvents such as ethyl acetate, methyl ethyl ketone, toluene, IPA, and water depending on necessity. C) and various additives are mixed beforehand using a dispersion stirrer. Water may be added in advance to the organic solvent to form a water-containing organic solvent, or water may be separately added in a specific amount. If it is a varnish composition, a varnish composition can be obtained by adding and stirring various additives while stirring the said solution with a dispersion stirrer. If it is an ink composition, an ink composition will be obtained by adding a coloring agent (D) and fully disperse | distributing.

  The polyurethane resin (A) used in the liquid ink composition of the present invention is obtained by reacting a polyol, a polyisocyanate, a chain extender, and optionally a monovalent active hydrogen compound.

The polyester polyol, which is a reactive raw material of the polyurethane resin (A) used in the liquid ink composition of the present invention, essentially comprises a polycarboxylic acid having 7 or more carbon atoms and two or more carboxyl groups as a raw material, It is obtained by reacting with a compound having two or more hydroxyl groups.
The polyester polyol can further increase the laminate strength by introducing an ester group to increase the polarity, but using a polycarboxylic acid having 7 or more carbon atoms and two or more carboxyl groups as a raw material Therefore, it is possible to combine moderate flexibility and laminate strength.

  Examples of polycarboxylic acids having 7 or more carbon atoms and two or more carboxyl groups include aromatic dicarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, and anhydrides of these acids, pimelic acid and suberic acid Aliphatic dicarboxylic acids such as azelaic acid, sebacic acid and dimer acid, tricarboxylic acids such as trimellitic acid and its anhydride, benzenetetracarboxylic acid, benzenepentacarboxylic acid, benzenehexacarboxylic acid and anhydrides of these acids Can be used. These polybasic acids may be used alone or in combination of two or more. Among them, when sebacic acid or dimer acid is used, it is preferable in that adhesion to a wide variety of film substrates and high laminate strength can be obtained, and these may be used alone or in combination.

As the polyester polyol, other polyvalent carboxylic acids may be used if necessary, and various known polyvalent carboxylic acids generally used in the production of polyester polyols can be used, and one or two kinds can be used. The above may be used in combination. For example, adipic acid, maleic acid, fumaric acid, succinic acid, oxalic acid, malonic acid, glutaric acid and the like can be mentioned.

  Examples of the compound having two or more hydroxyl groups include ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, diethylene glycol, tri Glycols such as ethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol; 2-methyl-1,5-pentanediol, 3-methyl-1, 5-pentanediol, 1,2-butanediol, 1,3-butanediol, 2-butyl-2-ethyl-1,3-propanediol, 1,2-propanediol, 2-methyl-1,3-propane Diol, neopentyl glycol, 2-i Propyl-1,4-butanediol, 2,4-dimethyl-1,5-pentanediol 2,4-diethyl-1,5-pentanediol, 2-ethyl-1,3-hexanediol, 2-ethyl-1 A glycol having a branched structure such as 6, 6-hexanediol, 3,5-heptanediol, 2-methyl-1, 8-octanediol, etc .; trimethylolpropane, trimethylolethane, pentaerythritol, sorbitol, etc. can be used. These compounds may be used alone or in combination of two or more.

The number average molecular weight of the polyester polyol is preferably in the range of 500 to 8,000, more preferably in the range of 800 to 7,000, and still more preferably in the range of 900 to 6,000. .
In the present invention, the number average and weight average molecular weight show values measured under the following conditions by gel permeation chromatography (GPC) method.

Measuring device: High-speed GPC device ("HLC-8220GPC" manufactured by Tosoh Corporation)
Column: The following columns manufactured by Tosoh Corporation were used in series connection.
"TSKgel G5000" (7.8 mm ID × 30 cm) × 1 "TSK gel G 4000" (7.8 mm ID × 30 cm) × 1 "TSK gel G 3000" (7.8 mm ID × 30 cm) × 1 This "TSKgel G2000" (7.8 mm ID × 30 cm) × 1 detector: RI (differential refractometer)
Column temperature: 40 ° C
Eluent: Tetrahydrofuran (THF)
Flow rate: 1.0 mL / min Injection volume: 100 μL (tetrahydrofuran solution with a sample concentration of 0.4% by mass)
Standard sample: A calibration curve was prepared using the following standard polystyrene.

[Standard polystyrene]
Tosoh Corporation "TSKgel standard polystyrene A-500"
Tosoh Corporation "TSKgel standard polystyrene A-1000"
Tosoh Corporation "TSKgel standard polystyrene A-2500"
Tosoh Corporation "TSKgel standard polystyrene A-5000"
Tosoh Corporation "TSKgel standard polystyrene F-1"
Tosoh Corporation "TSKgel standard polystyrene F-2"
Tosoh Corporation "TSKgel standard polystyrene F-4"
Tosoh Corporation "TSKgel standard polystyrene F-10"
Tosoh Corporation "TSKgel standard polystyrene F-20"
Tosoh Corporation "TSKgel standard polystyrene F-40"
Tosoh Corporation "TSKgel standard polystyrene F-80"
Tosoh Corporation "TSKgel standard polystyrene F-128"
Tosoh Corporation "TSKgel standard polystyrene F-288"
Tosoh Corporation "TSKgel standard polystyrene F-550"

  Furthermore, it is more preferable if a polyether polyol is contained in the range of 1 to 40% by mass with respect to the polyurethane resin (A) as a component of the polyurethane resin (A). As polyether polyol, various well-known ether polyols generally used for manufacture of a polyurethane resin can be used, and 1 type or 2 or more types may be used together. Examples thereof include polyether polyols of polymers or copolymers of ethylene oxide, propylene oxide, tetrahydrofuran and the like, and the like. When the polyether polyol is 1% by mass or more based on 100% by mass of the polyurethane resin (A), the solubility of the urethane resin in ketones, esters and alcohol solvents is also good, and the solvent of the ink film is also preferable. It is difficult to reduce the resolubility in the ink, and the tone reproducibility of the printed matter does not easily deteriorate. Moreover, if it is 40 mass% or less, blocking resistance will not fall easily.

  Moreover, if the number average molecular weight of the said polyether polyol is 100-3500, it is more preferable. If the number average molecular weight of the polyether polyol is 100 or more, the film of the polyurethane resin (A) does not become hard, and the adhesion to the polyester film is unlikely to be reduced. If the number average molecular weight is 3,500 or less, the tendency of the polyurethane resin (A) film to become brittle can be suppressed, and the blocking resistance of the ink film tends to be difficult to reduce.

  As a combined polyol which is optionally used in the polyurethane resin (A) used in the liquid ink composition of the present invention, various known polyols generally used in the production of polyurethane resins can be used, and one kind of polyol can be used. Or you may use together 2 or more types. For example, ethylene glycol, 1,2-propanediol, 1,3-propanediol, 2-methyl-1,3-propanediol, 2-ethyl-2butyl-1,3-propanediol, 1,3-butanediol 1,4-butanediol, neopentyl glycol, pentanediol, 3-methyl-1,5 pentanediol, hexanediol, octanediol, 1,4-butynediol, 1,4-butylenediol, diethylene glycol, triethylene glycol Saturated or unsaturated low molecular weight polyols such as dipropylene glycol, glycerine, trimethylolpropane, trimethylolethane, 1,2,6-hexanetriol, 1,2,4-butanetriol, sorbitol, pentaethlytol (1), these low molecular weight (1) with 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, sebacic acid, trilic Polyester polyols (2) obtained by dehydration condensation or polymerization of a polybasic carboxylic acid such as mellitic acid or pyromellitic acid or an anhydride thereof; cyclic ester compounds such as polycaprolactone, polyvalerolactone, poly (β- (β-) Polyester polyols (3) obtained by ring-opening polymerization of lactones such as methyl-γ-valerolactone); the low molecular weight polyols (1) etc. and, for example, dimethyl carbonate, diphenyl carbonate, ethylene carbonate, phosgene etc. Polycarbonate polyol obtained by reaction with (4); polybutadiene glycols (5); glycols obtained by adding ethylene oxide or propylene oxide to bisphenol A (6); one or more of hydroxyethyl in one molecule, hydroxypropyl acrylate, acrylic hydroxy And acrylic polyol (7) obtained by copolymerizing, for example, butyl and the like or their corresponding methacrylic acid derivatives and the like with, for example, acrylic acid, methacrylic acid or an ester thereof.

  Examples of the diisocyanate compound used for the polyurethane resin (A) in the liquid ink composition of the present invention include various known aromatic diisocyanates, aliphatic diisocyanates, alicyclic diisocyanates and the like generally used in the production of polyurethane resins. Be For example, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 1-methyl-2,4-phenylene diisocyanate, 1-methyl-2,6-phenylene diisocyanate, 1-methyl-2,5-phenylene diisocyanate, 1 -Methyl-2,6-phenylene diisocyanate, 1-methyl-3,5-phenylene diisocyanate, 1-ethyl-2,4-phenylene diisocyanate, 1-isopropyl-2,4-phenylene diisocyanate, 1,3-dimethyl-2 2,4-phenylene diisocyanate, 1,3-dimethyl-4,6-phenylene diisocyanate, 1,4-dimethyl-2,5-phenylene diisocyanate, diethylbenzene diisocyanate, diisopropylbenzene diisocyanate, 1-methyl diisocyanate 3,5-diethylbenzene diisocyanate, 3-methyl-1,5-diethylbenzene-2,4-diisocyanate, 1,3,5-triethylbenzene-2,4-diisocyanate, naphthalene-1,4-diisocyanate, naphthalene-1 5-diisocyanate, 1-methyl-naphthalene-1,5-diisocyanate, naphthalene-2,6-diisocyanate, naphthalene-2,7-diisocyanate, 1,1-dinaphthyl-2,2'-diisocyanate, biphenyl-2,2 4'-diisocyanate, biphenyl-4,4'-diisocyanate, 3-3'-dimethylbiphenyl-4,4'-diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,2'-diphenylmethane diisocyanate, diphenylmethane-2, -Aromatic polyisocyanates such as diisocyanates; tetramethylene diisocyanate, hexamethylene diisocyanate, dodecamethylene diisocyanate, trimethylhexamethylene diisocyanate, 1,3-cyclopentylene diisocyanate, 1,3-cyclohexylene diisocyanate, 1,4-cyclohexylene diisocyanate 1,3-di (isocyanatomethyl) cyclohexane, 1,4-di (isocyanatomethyl) cyclohexane, lysine diisocyanate, isophorone diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, 2,4′-dicyclohexylmethane diisocyanate, 2,2 '-Dicyclohexylmethane diisocyanate, 3,3'-dimethyl-4,4'-dicyclohexylmethane Aliphatic or alicyclic polyisocyanates such as diisocyanate can be used. These polyisocyanates may be used alone or in combination of two or more. Among these, aliphatic polyisocyanates and / or alicyclic polyisocyanates are preferably used from the viewpoint that appropriate flexibility can be obtained, and isophorone diisocyanate and hexamethylene diisocyanate are used from the viewpoint that adhesion strength can be further improved. Is more preferred.

The chain extender used for the polyurethane resin (A) in the ink composition for laminates for soft packaging of the present invention includes ethylenediamine, propylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, isophoronediamine, dicyclohexylmethane-4, Other than 4'-diamine and the like, 2-hydroxyethylethylenediamine, 2-hydroxyethylpropyldiamine, 2-hydroxyethylpropylenediamine, di-2-hydroxyethylethylenediamine, di-2-hydroxyethylenediamine, di-2-hydroxyethylpropylene Diamine, 2-hydroxypyrrole ethylenediamine, di-2-hydroxypyrrole ethylenediamine, di-2-hydroxypropylethylenediamine, etc. have a hydroxyl group in the molecule Amines can also be used. These chain extenders can be used alone or in combination of two or more.
Moreover, a monovalent active hydrogen compound can also be used as an end capping agent for the purpose of terminating the reaction. Examples of such a compound include dialkylamines such as di-n-butylamine and alcohols such as ethanol and isopropyl alcohol. Furthermore, especially when it is desired to introduce a carboxyl group into the polyurethane resin, amino acids such as glycine and L-alanine can be used as the reaction terminator. These end capping agents can be used alone or in combination of two or more.

  The polyurethane resin (A) used in the liquid ink composition of the present invention is obtained by reacting a polyol, a polyisocyanate, a chain extender, and optionally a monovalent active hydrogen compound. For example, a polyester polyol and a combination polyol and a diisocyanate compound are reacted at a ratio of excess isocyanate groups to obtain a prepolymer of terminal isocyanate groups, and the resulting prepolymer is used in a suitable solvent, that is, a solvent for liquid ink 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; toluene, Hydrocarbon solvents such as xylene, methylcyclohexane, ethylcyclohexane, etc .; or a two-step method of reacting with a chain extender and / or an end blocker in these mixed solvents, or polyester polio Le and combination polyol, diisocyanate compound, a chain extender and (or) endblocker is produced by one-step process of reacting at a time in a suitable solvent of the above. Among these methods, in order to obtain a uniform polyurethane resin (A), the two-stage method is preferable. In addition, when the polyurethane resin (A) is produced by a two-step method, the total (equivalent ratio) of the amino groups of the chain extender and / or the end capping agent is 1 / 0.9 to 1.3. It is preferable to react with When the equivalent ratio of isocyanate group to amino group is smaller than 1 / 1.3, the chain extender and / or endblocker remain unreacted, yellowing of the polyurethane resin, odor after printing It may occur.

The weight average molecular weight of the polyurethane resin (A) thus obtained is preferably in the range of 10,000 to 100,000, and more preferably in the range of 15,000 to 95,000. If the weight average molecular weight of the polyurethane resin (A) is 10,000 or more, the blocking resistance of the resulting ink composition, the strength and oil resistance of the print film, and the like are hardly reduced, and if 100,000 or less The viscosity of the resulting ink composition does not become too high, and the gloss of the print film can be easily maintained. In addition, the weight average molecular weight of the said polyurethane resin (A) shows the value obtained by measuring similarly to the number average molecular weight of the said polyester polyol.
The content relative to the total amount of the polyurethane resin (A) used in the liquid ink composition of the present invention is 4% by mass or more based on the total amount of the composition from the viewpoint of sufficient adhesion of the ink to the printing material The content is preferably 25% by mass or less, and more preferably in the range of 6 to 15% by mass from the viewpoint of appropriate ink viscosity and working efficiency at the time of ink production and printing.

  Furthermore, in the liquid ink composition of the present invention, the retort resistance is further improved by making the vinyl chloride vinyl acetate copolymer resin (B) having a hydroxyl group essential in addition to the polyurethane resin (A).

  The vinyl chloride / vinyl acetate copolymer resin (B) having a hydroxyl group has a hydroxyl value of 50 to 200 mg KOH / g, and the content ratio of the vinyl chloride component in the copolymer resin is 80 to 95% by weight Is preferred.

  The vinyl chloride vinyl acetate copolymer resin which has a hydroxyl group used for this invention can be obtained by two types of methods. One is obtained by copolymerizing vinyl chloride monomer, vinyl acetate monomer and vinyl alcohol in appropriate proportions. The other is obtained by partially saponifying vinyl acetate after copolymerization of vinyl chloride and vinyl acetate. In the vinyl chloride / vinyl acetate copolymer resin having a hydroxyl group, the properties of the resin film and the resin dissolution behavior are determined by the monomer ratio of vinyl chloride, vinyl acetate and vinyl alcohol. That is, vinyl chloride imparts toughness and hardness to the resin film, vinyl acetate imparts adhesiveness and flexibility, and vinyl alcohol imparts good solubility in polar solvents.

  When the liquid ink composition of the present invention is used as a lamination ink for soft packaging, it is necessary to satisfy all the properties of adhesion, blocking resistance, lamination strength, boil retort aptitude, print aptitude, etc. The vinyl-vinyl acetate copolymer resin has a proper monomer ratio. That is, 80 to 95 parts by mass of vinyl chloride is preferable with respect to 100 parts by mass of vinyl chloride-vinyl acetate copolymer resin having a hydroxyl group. If it is 80 parts by mass or more, the toughness of the resin film can be maintained, and the blocking resistance can be ensured. If the amount is 95 parts by mass or less, the resin film does not become too hard, and the adhesiveness is unlikely to be reduced. The hydroxyl value obtained from vinyl alcohol is preferably 50 to 200 mg KOH / g. If it is 50 mg KOH / g or more, the solubility in polar solvents is good, and the printability tends to be stable. If the amount is 200 mg KOH / g or less, the boil and retort suitability can be well maintained without deterioration of water resistance.

You may add water (C) to the liquid ink composition of this invention with the said organic solvent as a volatile component. The addition of water (C) makes it possible to control the drying property of the ink, and in particular, in the case of gravure printing, the characteristic gradation portion with a small amount of ink transfer can be reproduced beautifully. The amount of the water (C) added is preferably in the range of 0.3 to 10% by mass of the total amount of the ink composition, from the viewpoint of improving the printability. If the addition amount of water is 0.3% by mass or more, the reproducibility of the gradation portion tends to be good without the drying suppression effect of the ink decreasing, and the addition amount of water is 10% of the total amount of the ink composition. If the content is less than or equal to the mass%, the decrease in the ink stability can be suppressed.
Moreover, it is also possible to reduce the organic solvent component to be used by adding such water (C), which leads to environmental protection. Water (C) may be added in advance to the organic solvent (D) to form a water-containing organic solvent, or a specific amount may be added separately.

  Examples of the colorant (D) used in the present invention include organic and inorganic pigments and dyes used in general inks, paints, recording agents and the like. Examples of organic pigments include azo pigments, phthalocyanine pigments, anthraquinone pigments, perylene pigments, perinone pigments, quinacridone pigments, thioindigo pigments, dioxazine pigments, isoindolinone pigments, quinophthalone pigments, azomethine azo pigments, dictopyrrolopyrrole pigments, and isoindoline pigments. And pigments. In light of cost and light resistance of copper phthalocyanine for transparent ink and light yellow ink for transparent yellow ink, C.I. I. It is preferable to use Pigment No Yellow 83.

Examples of the inorganic pigment include carbon black, titanium oxide, zinc oxide, zinc sulfide, barium sulfate, calcium carbonate, chromium oxide, silica, bengala, aluminum, mica (mica) and the like. Further, it is possible to use a bright pigment (Metashine; Nippon Sheet Glass Co., Ltd.) in which a metal flake or a metal oxide is coated on a glass flake or a massive flake as a base material. It is preferable to use titanium oxide for white ink, carbon black for black ink, aluminum for gold and silver ink, and mica for pearl ink from the viewpoint of cost and coloring power. Aluminum is in the form of powder or paste, but is preferably used in the form of paste in terms of handleability and safety, and whether leafing or non-leafing is used is appropriately selected in terms of brightness and density.
The colorant is preferably contained in an amount sufficient to secure the density and coloring strength of the ink, that is, in a proportion of 1 to 50% by weight based on the total weight of the ink. Moreover, a coloring agent can be used individually or in combination of 2 or more types.

  Next, the organic solvent (E) used in the present invention will be described. In the laminating ink composition for soft packaging of the present invention, for example, aromatic organic solvents, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, n-propyl acetate, butyl acetate, propylene glycol monomethyl ether acetate, etc. Alcohol solvents such as ester solvents, n-propanol, inopropanol, n-butanol and propylene glycol monomethyl ether are exemplified, and these can be used alone or in combination of two or more. In recent years, from the viewpoint of working environment, it is desirable not to use aromatic solvents such as toluene and xylene and solvents of ketones.

  Examples of the resin used in combination with the laminate ink composition for soft packaging of the present invention as needed include resins other than the above-mentioned polyurethane resin and vinyl chloride-vinyl acetate copolymer resin, such as chlorinated polypropylene resin, ethylene-acetic acid Vinyl copolymer resin, vinyl acetate resin, polyamide resin, acrylic resin, polyester resin, alkyd resin, polyvinyl chloride resin, rosin resin, rosin modified maleic resin, ketone resin, cyclized rubber, chlorinated rubber, butyral, petroleum Resin etc. can be mentioned. The combination resin can be used alone or in combination of two or more. The content of the combined resin is preferably 1 to 25% by weight, more preferably 2 to 15% by weight, based on the total weight of the ink.

  In the present invention, if necessary, combined resins, extender pigments, pigment dispersants, leveling agents, antifoaming agents, waxes, plasticizers, infrared absorbers, ultraviolet absorbers, fragrances, flame retardants, etc. can also be included. .

  In order to stably disperse the pigment in the organic solvent, the resin alone can be dispersed, but a dispersant may be used in combination to stably disperse the pigment. As the dispersing agent, surfactants such as anionic, nonionic, cationic and amphoteric surfactants can be used. For example, a comb structure polymer compound in which polyester is added to polyethyleneimine, or an alkylamine derivative of α-olefin maleic acid polymer is mentioned. Specifically, Solspars series (ZENECA), Azizpur series (Ajinomoto), Homogenol series (Kao), etc. can be mentioned. Also, BYK series (Bick Chemie), EFKA series (EFKA), etc. can be used as appropriate. The dispersant is preferably contained in the ink in an amount of 0.05% by weight or more based on the total weight of the ink from the viewpoint of storage stability of the ink and 5% by weight or less from the viewpoint of lamination suitability, more preferably 0 In the range of 1 to 2% by weight.

  The liquid ink composition of the present invention can be produced by dissolving and / or dispersing a resin, a colorant and the like in an organic solvent. Specifically, a pigment dispersion is produced by dispersing a pigment in an organic solvent using a polyurethane resin, and an ink is produced by blending the obtained pigment dispersion with another compound as necessary. it can.

The particle size distribution of the pigment in the pigment dispersion is adjusted by appropriately adjusting the size of the grinding media of the dispersing machine, the filling ratio of the grinding media, the dispersion treatment time, the discharge speed of the pigment dispersion, the viscosity of the pigment dispersion, etc. be able to. As a dispersing machine, a roller mill, a ball mill, a pebble mill, an attritor, a sand mill etc. can be used generally, for example.
In the case where air bubbles or unexpectedly large particles are contained in the ink, it is preferable to remove by filtration etc. in order to reduce the print quality. The filter can use a conventionally well-known thing.

The viscosity of the ink produced by the above method is in the range of 10 mPa · s or more from the viewpoint of preventing sedimentation of the pigment and appropriately dispersing it, and 1000 mPa · s or less from the viewpoint of the workability at the time of ink production or printing preferable. The above viscosity is a viscosity measured at 25 ° C. with a B-type viscometer manufactured by Tokimec.
The viscosity of the ink can be adjusted by appropriately selecting the type and amount of the raw material used, for example, a polyurethane resin, a colorant, an organic solvent and the like. The viscosity of the ink can also be adjusted by adjusting the particle size and particle size distribution of the pigment in the ink.

  Among the liquid ink compositions of the present invention, when a colorant (D) is used, yellow, red, amber, black, and white as basic colors of the process depending on the type of colorant (D) to be used. There are five colors, and there are three colors of red (orange), grass (green) and purple as process gamut outer color. Furthermore, transparent yellow, peony, mochi, tea, gold, silver, pearl, almost transparent medium for adjusting color density (including an extender pigment if necessary), etc. are prepared as base colors. The ink for boiling retort is appropriately selected in consideration of the migration property of the pigment and the heat resistance. The base ink of each color is diluted with a dilution solvent to a viscosity and concentration suitable for gravure printing or flexo printing, and supplied alone or mixed to each printing unit.

There is no particular limitation on the plastic film that can be used as a substrate, and for example, polyamide resin such as Ny6, nylon 66, nylon 46, polyethylene phthalate (PET), polyethylene naphthalate, polytrimethylene terephthalate, polytrimethylene naphthalate Such as polyester resins such as polybutylene terephthalate and polybutylene naphthalate, polyhydroxycarboxylic acids such as polylactic acid, aliphatic polyester resins such as poly (ethylene succinate) and poly (butylene succinate) Of thermoplastic resins such as thermoplastic resins, polyolefin resins such as polypropylene (PP) and polyethylene, polyimide resins, polyarylate resins or mixtures thereof, and laminates thereof, among which poly Ester, polyamide, polyethylene, of polypropylene film can be suitably used.
These films may be unstretched films or stretched films, and their production method is not limited. Further, the thickness of the base film is not particularly limited, but usually, it may be in the range of 1 to 500 μm.
Moreover, if the corona discharge treatment is carried out to the printing surface of a film, base material adhesiveness can be further improved and it is preferable. In addition, silica, alumina or the like may be vapor deposited.

The present invention will be more specifically described by way of examples. Hereinafter, “parts” and “%” are all based on mass.
The measurement of the weight average molecular weight (in terms of polystyrene) by GPC (gel permeation chromatography) in the present invention was carried out using an HLC 8220 system manufactured by Tosoh Corp. under the following conditions.
Separation column: Four Tosoh Co., Ltd. product TSKgelGMH _HR- N is used. Column temperature: 40 ° C. Moving bed: tetrahydrofuran manufactured by Wako Pure Chemical Industries, Ltd. Flow rate: 1.0 ml / min. Sample concentration: 1.0% by weight. Sample injection volume: 100 microliters. Detector: Differential refractometer.
The viscosity was measured at 25 ° C. with a Tokimec B-type viscometer.

[Synthesis of Polyurethane Resin (A)]
Synthesis Example 1 A-1
In a four-necked flask equipped with a stirrer, thermometer, reflux condenser and nitrogen gas inlet tube, 100 parts of polyester polyol made of neopentyl glycol and sebacic acid (hydroxyl value: 108 mg KOH / g) and isophorone diisocyanate 32.3. Parts are charged and reacted at 90.degree. C. for 10 hours under a nitrogen stream to produce a urethane prepolymer having an isocyanate group content of 3.08% by mass, and 71.2 parts of ethyl acetate is added thereto to make the urethane prepolymer uniform It was a solution. Next, the above urethane prepolymer solution is added to a mixture of 8.47 parts of isophorone diamine, 0.46 parts of di-n-butylamine, 143 parts of ethyl acetate and 115 parts of isopropyl alcohol, and the reaction is allowed to stir at 45 ° C for 5 hours. Thus, a polyurethane resin solution A-1 was obtained. The obtained polyurethane resin solution A-1 had a resin solid concentration of 29.9% by mass, and the resin solid content had a weight average molecular weight of 54,000.

Synthesis Example 2 A-2
In a four-necked flask equipped with a stirrer, thermometer, reflux condenser and nitrogen gas inlet tube, 100 parts (hydroxyl value: 122 mg KOH / g) of polyester polyol made from neopentyl glycol and dimer acid and hexamethylene diisocyanate 26. Three parts were charged and reacted at 90 ° C. for 10 hours under a nitrogen stream to produce a urethane prepolymer having an isocyanate group content of 3.07% by mass, to which 68 parts of ethyl acetate was added to make a uniform solution of the urethane prepolymer And Then, the above urethane prepolymer solution is added to a mixture of 8.09 parts of isophorone diamine, 0.38 parts of di-n-butylamine, 136 parts of ethyl acetate and 110 parts of isopropyl alcohol, and the reaction is allowed to stir at 45 ° C for 5 hours Thus, a polyurethane resin solution A-2 was obtained. The resulting polyurethane resin solution A-2 had a resin solid concentration of 30.1% by mass, and the resin solid content had a weight average molecular weight of 48,000.

Synthesis Example 3 A-3
In a four-necked flask equipped with a stirrer, thermometer, reflux condenser and nitrogen gas inlet tube, 100 parts (hydroxyl value: 122 mg KOH / g) of polyester polyol made from neopentyl glycol, sebacic acid and dimer acid and isophorone diisocyanate 41.4 parts is charged and reacted at 90 ° C. for 10 hours under a nitrogen stream to produce a urethane prepolymer having an isocyanate group content of 4.55% by mass, and 76.2 parts of ethyl acetate is added thereto to give a urethane prepolymer It was a homogeneous solution of the polymer. Then, the above urethane prepolymer solution is added to a mixture of 13.26 parts of isophorone diamine, 0.46 parts of di-n-butylamine, 159 parts of ethyl acetate and 127 parts of isopropyl alcohol, and the reaction is allowed to stir and react at 45 ° C for 5 hours. Thus, a polyurethane resin solution A-3 was obtained. The obtained polyurethane resin solution A-3 had a resin solid concentration of 30.1% by mass, and the resin solid content had a weight average molecular weight of 32,000.

Synthesis Example 4 A-4
In a four-necked flask equipped with a stirrer, thermometer, reflux condenser and nitrogen gas inlet tube, 95 parts (hydroxyl value: 35 mg KOH / g) of polyester polyol made from neopentyl glycol and sebacic acid and 5 parts of polyethylene glycol ( A hydroxyl value: 111 mg KOH / g) and 17.5 parts of isophorone diisocyanate are charged and reacted at 90 ° C. for 10 hours under a nitrogen stream to produce a urethane prepolymer having an isocyanate group content of 3.08% by mass, followed by acetic acid 63.2 parts of ethyl was added to make a uniform solution of urethane prepolymer. Then, the above urethane prepolymer solution is added to a mixture of 7.55 parts of isophorone diamine, 0.72 parts of di-n-butylamine, 127 parts of ethyl acetate and 103 parts of isopropyl alcohol, and the reaction is allowed to stir and react at 45 ° C for 5 hours. Thus, a polyurethane resin solution A-4 was obtained. The obtained polyurethane resin solution A-4 had a resin solid concentration of 30.1% by mass, and the resin solid content had a weight average molecular weight of 70,000.

Synthesis Example 5 A-5
In a four-necked flask equipped with a stirrer, thermometer, reflux condenser and nitrogen gas inlet tube, 90 parts (hydroxyl value: 20 mg KOH / g) of polyester polyol made of neopentyl glycol and sebacic acid and 10 parts of polyethylene glycol ( A hydroxyl value: 56 mg KOH / g) and 14.2 parts of isophorone diisocyanate are charged and reacted at 90 ° C. for 10 hours under a nitrogen stream to produce a urethane prepolymer having an isocyanate group content of 3.08% by mass, to which is then added acetic acid 61.5 parts of ethyl was added to make a uniform solution of urethane prepolymer. Then, the above urethane prepolymer solution is added to a mixture of 7.09 parts of isophorone diamine, 0.92 parts of di-n-butylamine, 124 parts of ethyl acetate and 100 parts of isopropyl alcohol, and the reaction is allowed to stir at 45 ° C for 5 hours Thus, a polyurethane resin solution A-5 was obtained. The obtained polyurethane resin solution A-5 had a resin solid concentration of 30.0% by mass, and the resin solid content had a weight average molecular weight of 60,000.

Synthesis Example 6 A-6
In a four-necked flask equipped with a stirrer, thermometer, reflux condenser and nitrogen gas inlet tube, 70 parts of polyester polyol made of neopentyl glycol and sebacic acid (hydroxyl value: 128 mg KOH / g) and polytetramethylene glycol 30 Parts (hydroxyl value: 278 mg KOH / g) and 42.5 parts of isophorone diisocyanate are charged and reacted at 90 ° C. for 10 hours under a nitrogen stream to produce a urethane prepolymer having an isocyanate group content of 2.15% by mass. Then, 76.8 parts of ethyl acetate was added to the mixture to obtain a uniform solution of urethane prepolymer. Next, the above urethane prepolymer solution is added to a mixture of 6.9 parts of isophorone diamine, 0.33 parts of di-n-butylamine, 150 parts of ethyl acetate and 122 parts of isopropyl alcohol, and the reaction is allowed to stir at 45 ° C for 5 hours. Thus, a polyurethane resin solution A-6 was obtained. The obtained polyurethane resin solution A-6 had a resin solid content concentration of 30.2% by mass, and the resin solid content had a weight average molecular weight of 95,000.

Synthesis Example 7 A-7
In a four-necked flask equipped with a stirrer, thermometer, reflux condenser and nitrogen gas inlet, 95 parts of polyester polyol (hydroxyl value: 122 mg KOH / g) and polyethylene glycol made from neopentyl glycol, sebacic acid and dimer acid as raw materials After 5 parts (hydroxyl value: 278 mg KOH / g) and 37.2 parts of isophorone diisocyanate are charged and reacted under a nitrogen stream at 90 ° C. for 10 hours to produce a urethane prepolymer having an isocyanate group content of 3.10% by mass, To this was added 73.9 parts of ethyl acetate to make a uniform solution of urethane prepolymer. Then, the urethane prepolymer solution is added to a mixture of 8.72 parts of isophorone diamine, 0.54 parts of di-n-butylamine, 148 parts of ethyl acetate and 120 parts of isopropyl alcohol, and the reaction is allowed to stir and react at 45 ° C for 5 hours. Thus, a polyurethane resin solution A-7 was obtained. The obtained polyurethane resin solution A-7 had a resin solid concentration of 30.1% by mass, and the resin solid content had a weight average molecular weight of 25,000.

(Composition Comparative Example 1) H-1
In a four-necked flask equipped with a stirrer, thermometer, reflux condenser and nitrogen gas inlet tube, 80 parts (hydroxyl value: 57 mg KOH / g) of polyester polyol made from neopentyl glycol and adipic acid, neopentyl glycol and adipine Charge 20 parts of polyester polyol (hydroxyl value: 110 mg KOH / g) and 22.5 parts of isophorone diisocyanate using acid as raw materials, react at 90 ° C. for 10 hours under nitrogen stream, urethane having isocyanate group content of 2.84 mass% After preparation of the prepolymer, 66 parts of ethyl acetate was added thereto to make a uniform solution of urethane prepolymer. Then, the above urethane prepolymer solution is added to a mixture of 7.25 parts of isophorone diamine, 0.27 parts of di-n-butylamine, 131 parts of ethyl acetate and 106 parts of isopropyl alcohol, and the reaction is allowed to stir and react at 45 ° C for 5 hours. Thus, a polyurethane resin solution H-1 was obtained. The obtained polyurethane resin solution H-1 had a resin solid concentration of 30.1% by mass, and the resin solid content had a weight average molecular weight of 30,000.

(Composition Comparative Example 2) H-2
In a four-necked flask equipped with a stirrer, thermometer, reflux condenser and nitrogen gas inlet, 97 parts (hydroxyl value: 140 mg KOH / g) of polyester polyol made from neopentyl glycol and adipic acid and 3 parts of polyethylene glycol ( A hydroxyl value of 160 mg KOH / g) and 39.7 parts of isophorone diisocyanate are charged and reacted at 90 ° C. for 10 hours under a nitrogen stream to produce a urethane prepolymer having an isocyanate group content of 3.23 mass%, and acetic acid is added thereto. 75.2 parts of ethyl was added to make a uniform solution of urethane prepolymer. Next, the urethane prepolymer solution is added to a mixture of 9.71 parts of isophorone diamine, 0.11 parts of di-n-butylamine, 152 parts of ethyl acetate and 122 parts of isopropyl alcohol, and the reaction is allowed to stir and react at 45 ° C for 5 hours. Thus, a polyurethane resin solution H-2 was obtained. The obtained polyurethane resin solution H-2 had a resin solid concentration of 30.0% by mass, and the resin solid content had a weight average molecular weight of 25,000.

(Preparation of vinyl chloride / vinyl acetate copolymer resin solution)
Acetic acid / vinyl acetate copolymer resin having a hydroxyl group to be used in combination with a polyurethane resin (vinyl chloride / vinyl acetate / vinyl alcohol = 92/3/5, hydroxyl value (mg KOH) = 64) in acetic acid with resin monomer composition in weight% It was made into a 15% solution with ethyl, and this was used as a salt and vinyl acetate resin solution (B-1).

Example 1
30 parts of the obtained polyurethane resin solution A, 30 parts of a vinyl acetate / vinyl acetate copolymer resin solution A-1 having a hydroxyl group (15% solution), 10 parts of a phthalocyanine blue pigment (manufactured by DIC Corporation FASTGEN Blue LA5380 A mixture of 27 parts of ethyl acetate and 3 parts of water was milled to form an amber-colored printing ink.

[Evaluation item 1: Adhesion to various films]
The viscosity of the obtained liquid black ink was adjusted to 16 seconds (25 ° C.) with ethyl acetate with Zahn cup # 3 (manufactured by Rigosha Co., Ltd.), and a gravure proofer equipped with a plate depth of 35 μm gravure plate is used in Tables 1 and 2 Various barrier films (W, X, Y, Z), biaxially stretched polyester film U (hereinafter, PET film, E-5100 manufactured by Toyobo Co., Ltd. 12 μm thick), corona-treated on one side, biaxially stretched polypropylene After leaving the printed matter prepared with Film V (hereinafter, OPP film, P2161 made by Toyobo Co., Ltd. P2161 thickness 20 μm) for 1 day, paste the cellophane tape (12 mm width made by Nichiban) on the printing surface and peel it off rapidly The appearance of the printed film was visually judged in the following five steps.

5: The printed film did not peel at all.
4: 70% or more and less than 90% of the printed film remained on the film.
3: 50% or more and less than 70% of the printed film remained on the film.
2: 30% or more and less than 50% of the printed film remained on the film.
1: Less than 30% of printing film remained.

Barrier film to be evaluated W: Dainippon Printing Co., Ltd. alumina-deposited transparent PET film IB-PET-PUB (thickness: 12 μm)
X: Mitsubishi Resins Co., Ltd. Silica vapor deposited transparent PET film Tech Barrier TX-R (thickness: 12 μm)
Y: Oike Kogyo Co., Ltd. silica vapor deposited transparent PET film MOS-TEB (thickness: 12 μm)
Z: Letterpress printing Co., Ltd. aluminum oxide vapor deposition transparent PET film GL-ARH (thickness: 12 μm)

[Evaluation item 2: Laminate strength PET / CPP, OPP / CPP]
Apply the above-mentioned printed matter to the ether-based dry lamination adhesive Dick Dry LX-401A / SP-60 (made by DIC) so that the coating weight will be 2.5 g / m ^2, and after drying, dry lamination machine (Musashino mechanical design A non-oriented polypropylene film (hereinafter, CPP: manufactured by Toyobo Co., Ltd. P1128 20 μm) is laminated by an office, and subjected to aging for 3 days at 40 ° C. to obtain a laminate. 90 ° peel test.
The larger the number, the stronger the laminate strength.

[Evaluation item 3: Printability, resistance to smearing, biaxially oriented polyester film (PET film)]
The viscosity of the obtained liquid black ink was diluted with a mixed organic solvent of ethyl acetate / isopropyl alcohol = 50/50, and diluted at 25 ° C. with a Zahn cup # 3 (manufactured by Rigosha Co., Ltd.) to be 16 seconds. A biaxially stretched polyester film U (Toyobo Co., Ltd.) corona-treated on one side using an MD-type gravure printer (manufactured by Fuji Machine Co., Ltd.) attached with a gravure plate having a plate depth of 25 μm. Printing was performed on the treated surface of E-5100 (12 μm thick) manufactured by E. K. Then, the degree of transfer of the ink to the printed portion of the printed matter (the degree of culling) was visually evaluated in the following three stages. In the castellation test, evaluation was made at a printing speed of 300 m / min with a circumference of 600 mmφ of a gravure plate.

○: no looseness has occurred.
:: A slight scuff has occurred.
X: Cassule occurs frequently.

[Evaluation item 4: Retort resistance]
Applying to the coating amount of a dry laminating adhesive Dick dry LX-500 / KW-75 (manufactured by DIC) of urethane on the PET film printed matter is 3.5 g / ^{m 2,} dried, dry laminator (( An aluminum foil (hereinafter, AL: manufactured by Toyo Aluminum Industry Co., Ltd., aluminum foil C, 15 μm) was laminated by Musashino Machine Design Office Co., Ltd. to obtain a laminate 1 of two layers. Next, an adhesive is similarly applied on the AL of the laminate 1, a non-oriented polypropylene film (hereinafter, R-CPP: Toray Synthetic Film ZK-93KM 50 μm) is laminated, and aging is performed at 40 ° C. for 5 days, A three-layer composite laminate 2 was obtained. Thereafter, the obtained laminate 2 was formed into a pouch of 120 mm × 120 mm in size, and 70 g of a simulated food compounded in water / salad oil = 1: 1 (weight ratio) was filled and sealed as a content. The prepared pouch was subjected to steam retort sterilization treatment at 135 ° C. for 30 minutes, and the degree of peeling was evaluated according to the following evaluation criteria.

○: There is no peeling.
Δ: Small blister-like exfoliation.
X: There is peeling on the entire surface regardless of size.

[Examples 1 to 9, Comparative Examples 1 to 4]
An ink was produced in the same procedure as Example 1 by the composition combination shown to Examples 1-9 shown to Tables 1 and 2 and comparative examples 1-3.
The evaluation results of each are also described.

  The liquid ink composition of the present invention combines adhesion to each of various functional film substrates, laminate strength, retort resistance, and good printability.

  The liquid ink composition of the present invention can be widely deployed in industrial products such as food packaging, sanitary cosmetics, electronic parts, and the like, for which demand for various film configurations is expected.

Claims (10)

A liquid ink composition comprising a polyurethane resin (A) containing polyester polyol as a reaction raw material and a vinyl chloride / vinyl acetate copolymer resin (B), wherein said polyester polyol has 7 or more carbon atoms and a carboxyl group. A liquid ink composition characterized by using a polycarboxylic acid having two or more as a raw material.
The liquid ink composition according to claim 1, further comprising less than 10% by mass of water (C).
The liquid ink composition according to claim 1 or 2, further comprising polyether polyol as a component of the polyurethane resin (A) in an amount of 1 to 40% by mass based on the total amount of the polyurethane resin (A).
The liquid ink composition according to any one of claims 1 to 3, wherein the polyether polyol has a number average molecular weight of 100 to 3,500.
The liquid ink composition according to any one of claims 1 to 4, further comprising a colorant (D) and an organic solvent (E).
The liquid ink composition according to any one of claims 1 to 5, wherein the polycarboxylic acid is sebacic acid and / or a dimer acid.
The vinyl chloride / vinyl acetate copolymer resin (B) has a hydroxyl group, the hydroxyl value is 50 to 200 mg equivalent KOH, and the content of the vinyl chloride component in the copolymer resin is 80 to 95% by mass The liquid ink composition according to any one of claims 1 to 6.
The liquid ink composition according to any one of claims 1 to 7, wherein the organic solvent (E) does not contain an organic solvent having no aromatic group and / or a ketone solvent.
The printed matter formed by printing the liquid ink composition as described in any one of Claims 1-8.
  A laminated laminate comprising the printed matter according to any one of claims 1 to 9.