JP2002069353A - Printing ink and laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a laminate excellent in reduction of neck-in in laminating and odor by using printing ink having sufficient laminate strength even when the temperature of melted polyethylene in extrusion laminating is low. SOLUTION: This printing ink comprises a compound dimer diamine represented by chemical formula (1).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention is useful as a printing ink, especially as a coating agent for various plastic films, plastic sheets or molded articles of synthetic resin, and is particularly suitable for gravure and flexographic printing, and printing. The present invention relates to a laminated product using ink.

[0002]

2. Description of the Related Art Gravure and flexographic printing are widely used for the purpose of imparting aesthetic and functional properties to a printing medium. When a gravure or flexo-printed printing medium is used as a packaging material, particularly a food packaging material, it is general to apply a laminating process. What is lamination?
This is a method of creating a laminate by laminating a sealant with a printing medium on which ink has been printed, and specifically includes extrusion lamination (extrusion lamination), dry lamination, and non-sol dry lamination. In recent years, in the extrusion lamination method, the melting temperature of polyethylene used for a sealant tends to be lowered from the viewpoint of neck-in during lamination and reduction of odor of a laminated product. However, when the temperature of the molten polyethylene is lowered during extrusion lamination, the adhesion between the polyethylene and the gravure-printed ink film is lowered, and there is a problem that sufficient lamination strength cannot be obtained.

[0003]

SUMMARY OF THE INVENTION The object of the present invention is to overcome the above-mentioned drawbacks which cannot be solved by existing printing inks according to the prior art. That is, by using a printing ink having sufficient lamination strength even when the temperature of the molten polyethylene during extrusion lamination is low,
An object of the present invention is to provide a laminated product excellent in reducing neck-in and odor during laminating.

[0004]

Means for Solving the Problems The inventors of the present invention have made intensive studies in view of the above-mentioned circumstances, and as a result, a printing ink containing a compound represented by the following chemical formula (1) was extruded and laminated in a low temperature region. The present inventors have found that the laminate has a sufficient lamination strength even in the case of the present invention, and have reached the present invention.

[0005]

Embedded image

That is, the present invention relates to a printing ink containing the compound represented by the chemical formula (1). Further, the present invention relates to a printed material, a printing ink film made of a printing ink containing the compound represented by the above chemical formula (1), and a laminated product obtained by laminating at least a sealant.

[0007]

Next, the printing ink of the present invention will be described in detail. In the following description, “ink” means “printing ink”. The compound represented by the chemical formula (1) to be blended in the ink of the present invention is dimer-diamine.

The content of the compound represented by the chemical formula (1) is 0.1% by weight or more based on the total weight of the ink from the viewpoint of obtaining sufficient lamination strength, and 1% by weight from the viewpoint of obtaining sufficient blocking resistance. The following is preferred. Chemical formula (1)
The compound shown in (1) may be compounded into the ink by a conventionally known method. For example, it can be blended at the time of ink production or blended with the ink immediately before printing. The above formula (1)
Is preferably a liquid at 25 ° C.

The ink of the present invention contains the compound represented by the chemical formula (1) and further has a function required as the ink, and thus can contain a resin (binder), an organic solvent, a colorant, and the like. In addition, if necessary, an extender, a pigment dispersant, a leveling agent, an antifoaming agent, a wax, a silane coupling agent, a plasticizer, an infrared absorber, an ultraviolet absorber, an aromatic agent, a flame retardant, and the like can be included.

Examples of the resin used in the ink of the present invention include resins used in general inks, paints, recording agents and the like. Examples of resins include:
Polyurethane resin, polyurethane-urea resin, vinyl chloride-vinyl acetate copolymer resin, chlorinated polypropylene resin, ethylene-vinyl acetate copolymer resin, vinyl acetate resin, polyamide resin, nitrocellulose 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 and the like can be mentioned. The resins can be used alone or in combination of two or more. The content of the resin is preferably 4 to 25% by weight, more preferably 6 to 20% by weight, based on the total weight of the ink.

Among the above resins, polyurethane urea resins are preferred from the viewpoint of general-purpose adhesiveness and suitability for boiling and retorting. Polyurethane urea resins are widely and generally used as resins for laminating inks. The content of the polyurethane / urea resin in the ink is 4% by weight or more from the viewpoint of sufficient adhesion of the ink to the printing medium, and 25% by weight from the viewpoint of appropriate ink viscosity and working efficiency during ink production and printing. % Or less, more preferably 6% or less.
The range of -20% by weight is preferred.

Polyurethane / urea resins can be prepared by a conventionally known method, for example, as described in JP-A-62-153366, JP-A-62-153267, JP-A-1-236289, JP-A-2-64173, Kaihei 2-641
No. 74, JP-A-2-64175 and the like. Specifically, it can be obtained by reacting a hydroxyl group-containing compound such as a polyol or a diol with an isocyanate compound in an excess of isocyanate to form an isocyanate-terminated prepolymer, and further reacting an amine compound with a prepolymer in excess of an amine.

Examples of hydroxyl group-containing compounds such as polyols and diols include ethylene oxide, propylene oxide,
Polyether polyols such as polymers or copolymers such as tetrahydrofuran; ethylene glycol, 1,2
-Propanediol, 1,3-propanediol, 1,
Saturated and unsaturated low molecular weight glycols such as 3-butanediol, 1,4-butanediol, neopentyl glycol, pentanediol, 3-methyl-1,5-pentanediol, hexanediol, 1,4-butynediol, diethylene glycol, triethylene glycol, and dipropylene glycol Glycidyl ethers such as n-butyl glycidyl ether, 2-ethylhexyl glycidyl ether, monocarboxylic acid glycidyl esters such as versatic acid glycidyl ester, and adipic acid, phthalic acid, isophthalic acid, terephthalic acid, maleic acid, Fumaric acid, succinic acid, oxalic acid, malonic acid, glutaric acid, pimelic acid, speric acid,
Polyester polyols obtained by dehydrating and condensing dibasic acids such as azelaic acid, sebacic acid and dimer acid or anhydrides thereof; polyester polyols obtained by ring-opening polymerization of cyclic ester compounds; other polycarbonate polyols and polybutadiene Various known high molecular weight diols generally used in the production of polyurethane, such as glycols and glycols obtained by adding ethylene oxide or propylene oxide to bisphenol A, may be mentioned.

When a high-molecular-weight diol obtained from a glycol and a dibasic acid is used among these high-molecular-weight diols, up to 5 mol% of the glycol can be replaced by the following various polyols. That is, it may be replaced with a polyol such as glycerin, trimethylolpropane, trimethylolethane, 1,2,6-hexanetriol, 1,2,4-butanetriol, sorbitol, and pentaethritol. These polyols may be used alone or in combination of two or more.

As the isocyanate compound, aromatic,
Various known aliphatic or alicyclic diisocyanates can be mentioned. For example, 1,5 naphthylene diisocyanate, 4,4 'diphenylmethane diisocyanate, 4,4' diphenyldimethyl methane diisocyanate, 4,4 'dibenzyl isocyanate, dialkyl diphenyl methane diisocyanate, tetraalkyl diphenyl methane diisocyanate, 1,3- Phenylene diisocyanate, 1,4-phenylene diisocyanate, tolylene diisocyanate, butane-1,
4-diisocyanate, hexamethylene diisocyanate, isopropylene diisocyanate, methylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, cyclohexane-1,4 diisocyanate, xylylene diisocyanate, isophorone diisocyanate, lysine diisocyanate, dicyclohexylmethane 4,4 Typical examples thereof include diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, methylcyclohexane diisocyanate, norbornane diisocyanate, m-tetramethylxylylene diisocyanate, and dimer isocyanate obtained by converting a carboxyl group of dimer acid into an isocyanate group. . These organic diisocyanate compounds may be used alone or in combination of two or more.

Examples of the amine compound include ethylenediamine, propylenediamine, hexamethylenediamine, triethylenetetramine, diethylenetriamine,
Isophoronediamine, dicyclohexylmethane-4
4'-diamine and the like. In addition, 2-hydroxyethylethylenediamine, 2-hydroxyethylpropyldiamine, di-2-hydroxyethylethylenediamine, di2-hydroxyethylpropylenediamine, 2-hydroxypropylethylenediamine, di2
Representative examples include diamines having a hydroxyl group in the molecule, such as -hydroxypropylethylenediamine, and the compound represented by the chemical formula (1).

Further, a monovalent active hydrogen compound may be used for the purpose of terminating the reaction. Such compounds include, for example, dialkylamines such as di-n-butylamine and alcohols such as ethanol and isopropyl alcohol. Further, particularly when a carboxyl group is to be introduced into a polyurethane resin, glycine, L-
Amino acids such as alanine can be used as a reaction terminator.

The weight average molecular weight of the polyurethane / urea resin is 10,000 or more from the viewpoints of water resistance, solvent resistance, boil resistance and retort suitability, ink resolubility, printing trouble (plate clogging and print suitability). 1) from the viewpoint of
It is preferably at most 00,000. More preferably, 2
It is in the range of from 000 to 80,000. The weight average molecular weight of the polyurethane / urea resin can be determined by gel permeation chromatography (GPC), a relational expression between the intrinsic viscosity of the polymer and the weight average molecular weight, or the like. The skeleton structure of the polyurethane-urea resin may be branched having a branch or linear. The terminal of the polyurethane urea resin is preferably an amine.

Examples of the organic solvent used in the ink of the present invention include hydrocarbon-based, ketone-based, ester-based, and alcohol-based organic solvents used in general inks, paints, and recording agents. . Specific examples include hydrocarbons such as toluene, methylcyclohexane and ethylcyclohexane, ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, esters such as ethyl acetate, n-propyl acetate and butyl acetate, methanol, ethanol and propanol. Alcohol-based organic solvents such as toluene and butanol can be used. From the viewpoint of reducing the amount of solvent remaining in the ink film after printing, a small amount of a high-boiling solvent can be used in combination. The organic solvents used in the ink of the present invention can be used alone or in combination of two or more.

Examples of the coloring agent used as needed in the ink of the present invention include organic and inorganic pigments used in general inks, paints and recording agents. Examples of organic pigments include azo, phthalocyanine, anthraquinone, perylene, perinone, quinacridone, thioindigo, dioxazine, isoindolinone, quinophthalone, azomethineazo, dictopyrrolopyrrole, and isoindoline. No.
It is preferable to use copper phthalocyanine for the indigo ink from the viewpoint of coloring power.

Examples of the inorganic pigment include carbon black, titanium oxide, zinc oxide, zinc sulfide, barium sulfate, calcium carbonate, chromium oxide, silica, and red iron oxide. It is preferable to use titanium oxide for the white ink and carbon black for the black ink from the viewpoint of coloring power.

The pigments can be used alone or as a mixture of two or more kinds for the purpose of adjusting the hue and density. The amount of the pigment is sufficient to secure the density and
Preferably, it is contained in the ink in an amount of 4 to 50% by weight based on the total weight of the ink.

In order to stably disperse the pigment in the organic solvent,
The resin can be dispersed alone, but a dispersant can also be used in combination to stably disperse the pigment. As the dispersant, an anionic, nonionic, cationic, amphoteric or other surfactant can be used. 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. 0.1 to 2% by weight.

The ink of the present invention can be produced by dissolving and / or dispersing the compound represented by the chemical formula (1), a resin, a colorant and the like in an organic solvent.
Specifically, a pigment dispersion in which a pigment is dispersed in an organic solvent with a resin is produced, and the resulting pigment dispersion is represented by the chemical formula (1).
An ink can be produced by blending the compound represented by the formula (1) and other compounds as required.

The particle size distribution of the pigment in the pigment dispersion is determined by the size of the grinding media of the disperser, the filling ratio of the grinding media,
It can be adjusted by appropriately adjusting the dispersion processing time, the discharge speed of the pigment dispersion, the viscosity of the pigment dispersion, and the like. As the disperser, a commonly used roller mill, ball mill, pebble mill, attritor, sand mill, or the like can be used. When bubbles or unexpectedly large particles are included in the ink, it is preferable to remove the ink by filtration or the like in order to reduce the quality of the printed matter. A conventionally known filter can be used.

The viscosity of the ink produced by the above method is 10 mPa · s from the viewpoint of preventing sedimentation of the pigment and dispersing it appropriately.
s or more, and preferably 1000 mPa · s or less from the viewpoint of workability efficiency during ink production or printing.
The viscosity is a viscosity measured at 25 ° C. with a Tokimec B-type viscometer. The viscosity of the ink can be adjusted by appropriately selecting the type and amount of raw materials used, for example, a urethane / urea resin, a coloring agent, an organic solvent, and the like. When a pigment is used as the colorant, the viscosity of the ink can be adjusted by adjusting the particle size and particle size distribution of the pigment in the ink.

Next, the laminated product of the present invention will be described. The laminated product of the present invention is a printing medium,
It comprises an ink, a sealant, and an anchor coat agent or an adhesive used for laminating the sealant, if necessary. Laminated product of the present invention,
It can be obtained by printing the ink of the present invention on a substrate by gravure printing or flexographic printing, and laminating the sealant by a method such as extrusion lamination (extrusion lamination), dry lamination, or non-sol dry lamination. I can do it. Further, a processed product obtained by printing an ink other than the present invention on a printing medium by the above method, printing the ink of the present invention last, and laminating by the above method can also be mentioned as the laminated product of the present invention.

Examples of the substrate to be used in the laminated product of the present invention include plastics and papers generally used for gravure printing or flexographic printing. Plastics include films or sheets that are uniaxially or biaxially stretched or unstretched, such as nylon, polyester, polypropylene, polyethylene, and the like, and these generally have surface treatments such as corona discharge treatment or low-temperature plasma treatment. It has been subjected. Further, a film or sheet made of cellophane, moisture-proof cellophane, vinyl chloride-based resin, vinylidene chloride-based resin, styrene-based resin, vinyl acetate-based resin, vinyl alcohol-based resin, polyamide, or the like, or a laminate thereof can also be used. .

Examples of the sealant used in the laminated product of the present invention include the plastic film or sheet, and aluminum foil. In particular, as the resin to be extruded (extrusion laminated), low-density polyethylene, linear low-density polyethylene, medium-density polyethylene, high-density polyethylene, ethylene-vinyl acetate copolymer or a saponified product thereof, ethylene-acrylic acid Copolymers, ethylene-ethyl acrylate copolymer, polypropylene and the like can be mentioned.

As the anchor coat agent or adhesive used as necessary in the laminated product of the present invention, there can be mentioned those which are widely and generally used for laminating. Examples of the anchor coating agent include polyisocyanate, polybutadiene, polyethyleneimine, and organic titanium. Examples of the adhesive include urethane-based and modified polyolefin-based adhesives.

The laminated product of the present invention is formed into a container such as a bag, and is used after being filled with food and drink, medical products, medical instruments and the like.

[0032]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples unless it departs from the technical idea of the present invention. In the following description, "part" represents "part by weight". In the examples, the viscosity was measured at 25 ° C. using a B-type viscometer manufactured by Tokimec Co., and the weight average molecular weight was measured using gel permeation chromatography (GPC) in terms of polystyrene.

<Synthesis Example 1> 100 parts of poly (1,2-propylene adipate) glycol having an average molecular weight of 2,000 and 22.7 parts of isophorone diisocyanate in 100 parts
The mixture was reacted at 6 ° C. for 6 hours to obtain a terminal isocyanate prepolymer, and 110 parts of toluene was further added thereto to obtain a solvent solution of the terminal isocyanate prepolymer. Next, as a compound represented by the chemical formula (1), dimer diamine “Versamine 551” (manufactured by Henkel Japan Ltd.,
Trade name) 12.9 parts, isophorone diamine 4.4 parts, di-n-butylamine 1.0 part, methyl ethyl ketone 11
To a mixture of 0 parts and 110 parts of isopropyl alcohol, the solvent solution of the terminal isocyanate prepolymer is gradually added at room temperature, and then reacted at 50 ° C. for 3 hours, solid content 30%, viscosity 350 mPa · s, weight A polyurethane urea resin having an average molecular weight of 40,000 was obtained.

Example 1 An ink of the present invention was produced from the following raw materials. -Titanium oxide 30.0 parts-Polyurethane urea resin of Synthesis Example 1 50.0 parts-Toluene 10.0 parts-Isopropyl alcohol 9.5 parts-Dimer diamine "Versamine 551" 0.5 parts Total 100.0 parts Above The mixture of the compositions was connected with a sand mill to obtain a white ink. The viscosity of the ink was about 200 mPa · s.

To 100 parts of the ink, toluene 35
And 15 parts of isopropyl alcohol, the viscosity of which was adjusted by a gravure rotary printing press equipped with a gravure plate having a depth of 35 μm, using a 15 μm thick corona discharge treated nylon film “Emblem” (trade name, manufactured by Unitika Ltd.) , Hereinafter abbreviated as NY) on the corona discharge treated surface at a printing speed of 100 m / min and dried at 40 to 50 ° C.
A film on which the ink of the present invention was printed (hereinafter abbreviated as print film) was obtained. The printed surface of the obtained printed film was superimposed on each other, and the printed surface and the non-printed surface were superimposed on each other, each having a load of 1 × 9.8 N / c.
After storage at m ² , 40 ° C. and 80% relative humidity for 24 hours, the anti-blocking property when peeled off was evaluated according to the following criteria, and the average value was obtained. 5: No blocking was observed at all. 4: There was resistance at the time of peeling, but no ink was removed. 3: A small area of the ink was partially removed, and the gloss of the printed surface was increased. 2: Blocking occurred in a large area. 1: Blocking occurred on the entire surface. Furthermore, a polyisocyanate-based anchor coating agent “EL-510 and CAT-RT8
0 "(manufactured by Toyo Morton Co., Ltd.) and a low-density polyethylene" Novatech LC606 "(manufactured by Nippon Polychem Co., Ltd.) as a sealant on the coated surface.
Was extruded at 315 ° C. or 305 ° C. to obtain a laminated product at each temperature. The melting temperature of low-density polyethylene is determined by the T
The temperature immediately below the die was measured with a contact thermometer (HL-100 manufactured by Anritsu Keiki Co., Ltd.). The lamination strength of the ink part of the roughly laminated product was measured.

Further, the laminated product obtained at a melting temperature of polyethylene of 315 ° C. is packed in a bag, and water / water is used as the content.
The oil was filled with 1/1 (weight ratio), and the mixture was boiled at 85 ° C. for 30 minutes to evaluate the appearance of the sack after treatment. Boil aptitude was evaluated for each of five test samples, and the appearance after the boiling test was evaluated according to the following criteria. ：: No abnormality was found in all five bags. Δ: Delamination or blister occurred in a part of 2 to 3 bags. ×: Delamination or blister occurred in all five bags.

Example 2 An ink of the present invention was produced from the following raw materials. -Phthalocyanine blue 10.0 parts -Polyurethane urea resin of Synthesis Example 1 50.0 parts -Toluene 25.0 parts -Isopropyl alcohol 14.5 parts -Dimer diamine "Versamine 551" 0.5 parts Total 100.0 parts Above Each mixture of the compositions was connected to each other with a sand mill to obtain a blue ink. The viscosity of the ink was about 250 mPa · s. The rough blue ink was evaluated by the method shown in Example 1.

Example 3 In the ink raw materials described in Example 1, "Supercron BX" (ethylene-vinyl acetate copolymer resin manufactured by Nippon Paper Industries Co., Ltd.) was used instead of the polyurethane-urea resin of Synthesis Example 1. , Product name) 25 copies,
A white ink was obtained by the method shown in Example 1 using 10 parts of "Supercron 803 MW" (chlorinated polypropylene resin, trade name, manufactured by Nippon Paper Industries Co., Ltd.) and further using 25 parts of toluene. The viscosity of the ink was about 300 mPa · s.
The roughly white ink was evaluated by the method shown in Example 1.

Example 4 In the raw materials of the ink described in Example 1, 30 parts of "Byron 200" (polyester resin, trade name, manufactured by Toyobo Co., Ltd.) instead of the polyurethane-urea resin of Synthesis Example 1 And 5 parts of a nitrocellulose resin (L cotton, 1/2 second). Further, 15 parts of ethyl acetate were used. A white ink was obtained by the method shown in Example 1.
The viscosity of the ink was about 190 mPa · s. The roughly white ink was evaluated by the method shown in Example 1.

Example 5 The amount of isopropyl alcohol in the ink raw materials described in Example 1 was 9.9.
Parts, and 0.1 part of the dimer diamine “Versamine 551”, a white ink was obtained by the method shown in Example 1. The viscosity of the ink was about 190 mPa · s. The roughly white ink was evaluated by the method shown in Example 1.

Example 6 In the ink raw materials described in Example 1, the amount of isopropyl alcohol was adjusted to 9.0.
Parts, and 1.0 part of the dimer diamine "Versamine 551" was used to obtain a white ink by the method shown in Example 1. The viscosity of the ink was about 210 mPa · s. The roughly white ink was evaluated by the method shown in Example 1.

Comparative Example 1 In the ink raw materials described in Example 1, the dimer diamine “Versamine 55” was used.
1) without using isopropyl alcohol
As a part, a white ink was obtained by the method shown in Example 1. The viscosity of the ink was about 190 mPa · s. The roughly white ink was evaluated by the method shown in Example 1.

Comparative Example 2 In the ink raw materials described in Example 2, the dimer diamine “Versamine 55” was used.
1) was not used and the amount of isopropyl alcohol was 15.0.
As a part, a white ink was obtained by the method shown in Example 1. The viscosity of the ink was about 260 mPa · s. The roughly white ink was evaluated by the method shown in Example 1.

(Comparative Example 3) The white ink was prepared in the same manner as in Example 1 except that the dimer diamine "Versamine 551" was not used in the raw materials of the ink used in Example 3 and the amount of isopropyl alcohol was 10.0 parts. I got The viscosity of the ink was about 300 mPa · s. The roughly white ink was evaluated by the method shown in Example 1.

(Comparative Example 4) The white ink was prepared in the same manner as in Example 1 except that the dimer diamine "Versamine 551" was not used and the amount of isopropyl alcohol was 10.0 parts in the raw materials of the ink used in Example 4. I got The viscosity of the ink was about 190 mPa · s. The roughly white ink was evaluated by the method shown in Example 1.

(Comparative Example 5) A white ink was obtained in the same manner as in Example 1 except that 0.5 parts of isophoronediamine was used in place of the dimer diamine "Versamine 551" in the raw materials of the ink used in Example 1. . The viscosity of the ink is about 20
It was 0 mPa · s. The roughly white ink was evaluated by the method shown in Example 1.

(Comparative Example 6) In the ink raw materials used in Example 1, 0.5 parts of dimer diol “Versa Dime 216” (trade name, manufactured by Henkel Japan Co., Ltd.) was used instead of dimer diamine “Versamine 551”. A white ink was obtained in the same manner as in Example 1. The viscosity of the ink was about 200 mPa · s. The roughly white ink was evaluated by the method shown in Example 1. Table 1 shows the evaluation results.

[0048]

[Table 1]

[0049]

Since the ink of the present invention contains the compound represented by the chemical formula (1), a laminated product using the same can be used for printing even when the extrusion laminating temperature is low. Since the adhesiveness between the body and the ink film and the sealant is good, it is possible to obtain a sufficient laminating strength. Therefore, it contributes to the neck-in during laminating and the reduction of the odor of the laminating product. Further, by using a polyurethane urea resin in the ink of the present invention, a processed product having excellent boil resistance can be obtained.

Continued on the front page F term (reference) 2H113 AA03 BA01 BA03 BB08 DA07 DA25 DA33 DA47 DA62 FA04 FA23 FA50 4J039 AD21 AE04 BA04 BA13 BA35 BC60 BE01 BE12 CA07 EA43 FA02 GA03 GA09

Claims (4)

[Claims] 1. A printing ink containing a compound represented by the following chemical formula (1). Embedded image 2. The printing ink according to claim 1, wherein the content of the compound represented by the following chemical formula (1) is 0.1 to 1% by weight. Embedded image 3. The printing ink according to claim 1, further comprising a polyurethane urea resin. 4. A laminated material comprising at least a printing medium, a printing ink film comprising the printing ink according to claim 1, and a sealant.