JP6317054B1 - Liquid ink composition - Google Patents

Abstract

In addition to being able to be applied to a wide variety of films, the present invention can be applied to various substrates, adhesion strength, blocking resistance, laminate strength using dry laminate adhesive before and after retorting (hereinafter referred to as dry laminate strength). ) And polyethylene extrusion laminate strength, and a liquid ink composition excellent in suitability on various high-performance barrier films. A liquid ink composition comprising, as essential components, a polyurethane resin (A) having a urea bond, a polyurethane resin (B) having no urea bond, a colorant (C), and an organic solvent (D).

Description

  The present invention relates to a liquid ink composition that can be used as a laminate gravure ink or flexographic ink for soft packaging. In particular, the present invention relates to a liquid ink for laminating that can exhibit very excellent adhesion performance to a printed laminate base material, and to a liquid ink composition for various films coated with an inorganic or organic barrier coating material.

  Gravure inks and flexographic inks are widely used for the purpose of imparting cosmetic properties and functionality to a printing medium. When a gravure and flexographically printed material is used as a food packaging material among packaging materials, lamination is generally performed. In this case, various printed materials and laminating processes are used depending on the type of contents and the purpose of use.

Conventionally, a printing ink using a polyurethane resin as a binder has been widely used for such a laminated product because it has excellent adhesion to various printed materials, laminate strength of various laminated products, and suitability for boil retort. For example, JP-A-55-25453 discloses a printing ink composition for laminating mainly composed of a polymer polydiol, an organic diisocyanate, and a polyurethane polyurea resin soluble in an organic solvent obtained by reacting a diamine as a chain extender. Things are disclosed. Thereafter, various studies were made to improve the physical properties of the laminate. In a polyurethane resin obtained from a polymer diol and an organic diisocyanate in JP-A 63-161065, a polyester polyol obtained from 3-methyl-1,5-pentanediol and a dibasic acid is used as a polymer diol compound. It is exemplified that the property, hydrolysis resistance, and re-solubility are improved.
JP-A-6-41264 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. .
Japanese Patent Application Laid-Open No. 2000-273382 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.
Japanese Patent Application Laid-Open No. 2005-298618 describes a laminating ink composition for flexible packaging, which contains a polypropylene glycol-containing polyurethane resin and a vinyl chloride-vinyl acetate copolymer resin having a hydroxyl group as essential components.
JP-A-11-172184 and JP-A-2002-294129 describe a polyester-based urethane resin in which the range of urea bond concentration is specified as a printing ink binder for laminate cans. When used in the above, sufficient laminate strength cannot be obtained.
Japanese Patent Application Laid-Open Nos. 6-80921 and 11-279472 describe a polyurethane resin obtained by reacting a specific diol component with an organic diisocyanate and an amine chain extender. In this case, satisfactory laminate strength can be obtained. I can't.
However, with the recent diversification of packaging base materials, printing inks used for decoration or surface protection are required to have a high level of performance. There is nothing going on. In addition to anti-blocking properties, the market demands improvements in laminate strength before and after retorting on various base materials, and improvements in levels on films coated with the above inorganic and organic barrier coating agents. .
Furthermore, inks obtained with these polyurethane resins and organic solvents that do not contain aromatic organic solvents have poor resolubility and are a problem during gravure printing. The “fogging phenomenon” in which the ink cannot be scratched and becomes “fogging” is transferred to the printed matter, and the “grazing phenomenon” in which the ink is clogged in the gravure printing plate cell and the ink is difficult to transfer to the printed matter. It was difficult to obtain stable printability.
Also in flexographic printing, “ink re-dissolvability” is an important characteristic for reducing entanglement stains caused by drying of ink on a plate during long run printing.
In addition, when a solvent having a slow drying rate is used in combination with a gravure printing or flexographic printing in order to improve the ink transfer property to a film, it is difficult to achieve both blocking resistance accompanied by a print pattern and a residual solvent.

JP-A-55-25453 JP 63-161065 A JP-A-6-41264 JP 2000-273382 A JP 2005-298618 A JP-A-11-172184 JP 2002-294129 A JP-A-6-80921 JP-A-11-279472

  In addition to being able to be applied to a wide variety of films, the present invention can be applied to various substrates, adhesion strength, blocking resistance, laminate strength using dry laminate adhesive before and after retorting (hereinafter referred to as dry laminate strength). ) And polyethylene extrusion laminate strength, and a liquid ink composition excellent in suitability on various high-functional barrier films.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that in a liquid ink composition, a polyurethane resin (A) having a urea bond, a polyurethane resin (B) having no urea bond, and coloring It has been found that containing the agent (C) and the organic solvent (D) is effective in solving the problem.

  That is, the present invention includes a polyurethane resin (A) having a urea bond, a polyurethane resin (B) having no urea bond, a colorant (C) and an organic solvent (D) as essential components. The present invention relates to an ink composition.

  The present invention also relates to a liquid ink composition in which the polyurethane resin (A) having a urea bond uses a polyether polyol as a reaction raw material.

  The present invention also relates to a liquid ink composition in which the polyurethane resin (A) having a urea bond has a urethane bond concentration of 1.3 mmol / g or more and 2.5 mmol / g or less.

  In the present invention, the range of the absorbance ratio between the absorbance derived from the ether group and the absorbance derived from the carbonyl group obtained from the infrared absorption spectrum of the resin surface of the polyurethane resin (A) having a urea bond is 0.02 to 0. 10 liquid ink composition.

  Moreover, this invention relates to the liquid ink composition whose weight average molecular weights of the said polyurethane resin (A) are the ranges of 10,000-100,000.

  Moreover, this invention relates to the liquid ink composition whose weight average molecular weights of the said polyurethane resin (B) are the ranges of 10,000-100,000.

  Moreover, this invention relates to the liquid ink composition whose softening temperature of the said polyurethane resin (B) is the range of 40-80 degreeC.

  The present invention also relates to a liquid ink composition in which the polyurethane resin (B) is made from an aliphatic polyisocyanate and / or an alicyclic polyisocyanate.

  The present invention also relates to a liquid ink composition in which the polyurethane resin (B) is made from a polyester polyol.

  The present invention also relates to a liquid ink composition further containing a vinyl chloride vinyl acetate copolymer resin (E) having a hydroxyl group.

  In the present invention, the vinyl chloride vinyl acetate copolymer resin (E) having a hydroxyl group has a hydroxyl value of 50 to 200 mgKOH / g, and the content ratio of the vinyl chloride component in the copolymer resin is 80 to 95. It is related with the liquid ink composition which is the mass%.

  The present invention also relates to a liquid ink composition in which the organic solvent (D) is an organic solvent having no aromatic group.

  In addition, the present invention relates to a printed material obtained by printing the liquid ink composition.

  Furthermore, the present invention also provides a laminate obtained by processing a printed matter using the liquid ink composition and a substrate by a dry lamination or extrusion lamination method.

  According to the present invention, it has high dry laminate strength both before and after retorting on a wide range of films, including adhesiveness, blocking resistance on transparent deposited films, which have been increasing in recent years, and the aforementioned transparent deposited films. In addition, a liquid ink composition having a high polyethylene extrusion laminate strength can be obtained.

  The present invention will be described in detail. “Ink” used in the following description means “printing ink”. Further, “part” means “part by mass”.

  The present invention is a liquid ink composition comprising a polyurethane resin (A) having a urea bond, a polyurethane resin (B) having no urea bond, a colorant (C), and an organic solvent (D). .

  In the liquid ink composition of the present invention, specifically, the binder resin containing the polyurethane resins (A) and (B) is mixed in advance with various organic solvents such as ethyl acetate, methyl ethyl ketone, toluene and IPA, and various additives. A color pigment is added while stirring the solution with a dispersion stirrer and further stirred to obtain an ink composition in which the color pigment is sufficiently dispersed.

The urethane bond concentration of the urethane resin (A) used in the liquid ink composition of the present invention is preferably 1.3 mmol / g or more and 2.5 mmol / g or less, and more preferably 1.32 mmol / g or more. When the urethane bond concentration of the liquid ink composition of the present invention is 1.3 mmol / g or more and 2.5 mmol / g or less, the adhesiveness to various films and the blocking property accompanied by the print pattern back-off are improved. It is more preferable if it is 32 mmol / g or more.
When the urethane bond concentration is less than 1.3 mmol / g, the polyethylene extrusion laminate strength for the gravure printed product or the flexographic printed product using the liquid ink of the present invention tends to be lowered. On the other hand, when the urethane bond concentration exceeds 2.5 mmol / g, in gravure printing, the portion where the ink is not scratched by the doctor in a portion other than the image area becomes “fog” and is transferred to the printed matter. "Phenomenon" tends to occur. If the urethane bond concentration of the present invention is 1.3 mmol / g or more and 2.5 mmol / g or less, in addition to adhesiveness with various films and blocking property with print pattern back-off, it may become a problem in gravure printing. It also has antifogging.
Further, by setting the urethane bond concentration to 2.5 mmol / g or less, it is possible to suppress entanglement stains caused by drying of the ink on the plate during long run printing with a flexographic plate.
The urethane bond concentration can be calculated by the following formula (1).
Urethane bond concentration = {(W ₁ × OH ₁ + W ₂ × OH ₂ +... + W _i × OH _i ) × 1000} / ( 56100 × S) Formula (1)

In the formula (1), each is as follows.
When using multiple types of polyol, it calculates as polyol 1, polyol 2-polyol i, respectively.

W ₁ : Mass of polyol 1 OH ₁ : Hydroxyl value of polyol 1 W ₂ : Mass of polyol 2 OH ₂ : Hydroxyl value of polyol 2 W _i : Mass of polyol i OH _i : Hydroxyl value of polyol i S: Urethane resin solid Mass of minutes

Furthermore, the polyurethane resin (A) having a urea bond is obtained by using polyether polyol as a reaction raw material, and the absorbance derived from the ether group obtained from the infrared absorption spectrum of the resin surface and the absorbance derived from the carbonyl group. The range of the absorbance ratio is preferably 0.02 to 0.10. When the absorbance ratio of [absorption peak derived from the ether group] / [absorption peak derived from the carbonyl group] is less than 0.02, the solubility of the urethane resin in the ketone, ester and alcohol solvent decreases. Further, the re-solubility of the ink film in the solvent is deteriorated, and the tone reproducibility of the printed matter tends to be lowered. On the other hand, when the absorbance ratio exceeds 0.10, the ink film becomes too soft and the blocking resistance tends to be inferior.
In addition, it is preferable that the number average molecular weight of the said polyether polyol is 100-3500. In addition, the number average molecular weight of the said polyether polyol shows the value measured on condition of the following 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 connected in series.
"TSKgel G5000" (7.8 mm ID x 30 cm) x 1 "TSKgel G4000" (7.8 mm ID x 30 cm) x 1 "TSKgel G3000" (7.8 mm ID x 30 cm) x 1 “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 amount: 100 μL (tetrahydrofuran solution with a sample concentration of 0.4 mass%)
Standard sample: A calibration curve was prepared using the following standard polystyrene.

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

  Examples of the polyether polyol include polymer or copolymer polyether polyols such as ethylene oxide, propylene oxide, and tetrahydrofuran. Specifically, known general-purpose materials such as polyethylene glycol, polypropylene glycol, and polytetramethylene glycol may be used. By using the polyether polyol in the above-mentioned range, the adhesiveness particularly on the high-functional barrier film is greatly improved, and as a result, the blocking resistance and the laminate strength are excellent. In order to particularly improve the adhesion, blocking resistance and laminate strength on the high-functional barrier film, polyethylene glycol is particularly preferable among the polyether polyols.

  When the number average molecular weight of the polyether polyol, which is a component of the polyurethane resin (A) used in the liquid ink composition of the present invention, is less than 100, the polyurethane resin (A) film becomes hard, so that it adheres to the polyester film. Tend to decrease. When the number average molecular weight is larger than 3,500, the polyurethane resin (A) film tends to be brittle, and the blocking resistance of the ink film tends to be lowered.

  As the combined polyol used as necessary in the polyurethane resin (A) used in the liquid ink composition of the present invention, various known polyols generally used for the production of polyurethane resins can be used. Or you may use 2 or more types together. For example, polyether polyols (1) of polymers or copolymers such as methylene oxide, ethylene oxide, and tetrahydrofuran; 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, hexane Diol, Octanediol, 1,4-Butynediol, 1,4-Butylenediol, Diethylene glycol, Triethylene glycol, Dipropylene glycol, Glycerin, Trimethylolpropane, Trimethylolethane, 1,2,6-hexanetriol, 1, 2,4-butanetri Saturated or unsaturated low molecular polyols (2) such as alcohol, sorbitol, and pentaerythritol; these low molecular polyols (2) and adipic acid, phthalic acid, isophthalic acid, terephthalic acid, maleic acid, Dehydration condensation or polyhydric carboxylic acids such as fumaric acid, succinic acid, oxalic acid, malonic acid, glutaric acid, pimelic acid, speric acid, azelaic acid, sebacic acid, trimellitic acid, pyromellitic acid or their anhydrides Polyester polyols (3) obtained by polymerization; polyester polyols obtained by ring-opening polymerization of cyclic ester compounds, for example, lactones such as polycaprolactone, polyvalerolactone, and poly (β-methyl-γ-valerolactone) (4); the low molecular polyols (2) and the like, for example, dimethyl carbonate, Polycarbonate polyols obtained by reaction with phenyl carbonate, ethylene carbonate, phosgene, etc. (5); polybutadiene glycols (6); glycols obtained by adding ethylene oxide or propylene oxide to bisphenol A (7); 1 molecule Acrylic obtained by copolymerizing one or more hydroxyethyl, hydroxypropyl acrylate, acrylhydroxybutyl, etc., or their corresponding methacrylic acid derivatives, for example, with acrylic acid, methacrylic acid or its ester A polyol (8) etc. are mentioned.

  Among the polyester polyols (3), a polymer diol obtained from a diol (glycol) and a dibasic acid is a low molecular weight compound having up to 5 mol% of the diols having three or more hydroxyl groups. The polyols (2) can be substituted.

  Examples of the diisocyanate compound used in the polyurethane resin (A) in the liquid ink composition of the present invention include various known aromatic diisocyanates, aliphatic diisocyanates, and alicyclic diisocyanates that are generally used in the production of polyurethane resins. It is done. For example, 1,5-naphthylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 4,4′-diphenyldimethylmethane diisocyanate, 4,4′-dibenzyl isocyanate, dialkyldiphenylmethane diisocyanate, tetraalkyldiphenylmethane 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, lysine diisocyanate, cyclohexane-1 , 4-diisocyanate, xylylene diisocyanate, isophorone diisocyanate, Melyl diisocyanate, dicyclohexylmethane-4,4′-diisocyanate, 1,3-bis (isocyanatemethyl) cyclohexane, methylcyclohexane diisocyanate, norbornane diisocyanate, m-tetramethylxylylene diisocyanate, 4,4-diphenylmethane diisocyanate, tolylene diisocyanate Bis-chloromethyl-diphenylmethane-diisocyanate, 2,6-diisocyanate-benzyl chloride, dimerisocyanate obtained by converting a carboxyl group of dimer acid into an isocyanate group, and the like. These diisocyanate compounds can be used alone or in admixture of two or more.

Examples of the chain extender used in the polyurethane resin (A) in the liquid ink composition of the present invention include ethylenediamine, propylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, isophoronediamine, and dicyclohexylmethane-4,4′-diamine. 2-hydroxyethylethylenediamine, 2-hydroxyethylpropyldiamine, 2-hydroxyethylpropylenediamine, di-2-hydroxyethylethylenediamine, di-2-hydroxyethylenediamine, di-2-hydroxyethylpropylenediamine, 2- Amines having a hydroxyl group in the molecule, such as hydroxypropylethylenediamine, di-2-hydroxypropylethylenediamine, di-2-hydroxypropylethylenediamine, etc. Can be used. These chain extenders can be used alone or in admixture of two or more.
Moreover, a monovalent active hydrogen compound can also be used as a terminal blocking agent for the purpose of stopping the reaction. Examples of such compounds include alkylamines 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 blockers can be used alone or in admixture of two or more.

  The polyurethane resin (A) used in the liquid ink composition of the present invention is obtained, for example, by reacting polyethylene glycol and a combination polyol and a diisocyanate compound in an excess ratio of an isocyanate group to obtain a prepolymer of a terminal isocyanate group. The prepolymer obtained in an appropriate solvent, that is, an ester solvent such as ethyl acetate, propyl acetate or butyl acetate, which is usually used as a solvent for non-toluene gravure ink or flexo ink; acetone, methyl ethyl ketone, methyl isobutyl Among ketone solvents such as ketones; alcohol solvents such as methanol, ethanol, isopropyl alcohol and n-butanol; hydrocarbon solvents such as methylcyclohexane and ethylcyclohexane; A two-stage process of reacting with an extender and / or end-capping agent, or a single-stage reaction of polyethylene glycol and a combination polyol, diisocyanate compound, chain extender and / or end-capping agent at once in a suitable solvent of the above. Manufactured by the law. Among these methods, in order to obtain a uniform polyurethane resin (A), it is preferable to use a two-stage method. When the polyurethane resin (A) is produced by a two-stage method, the total (equivalent ratio) of amino groups of the chain extender and / or end-capping agent is 1 / 0.9 to 1.3. It is preferable to make it react. When the equivalent ratio of isocyanate group to amino group is less than 1 / 1.3, the chain extender and / or the end-capping agent remain unreacted, the polyurethane resin turns yellow, or the odor after printing 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, more preferably in the range of 15,000 to 80,000. When the weight average molecular weight of the polyurethane resin (A) is less than 10,000, there is a tendency that the blocking resistance of the ink composition obtained, the strength of the printed film, the oil resistance, etc. tend to be low, and it exceeds 100,000. In some cases, the viscosity of the resulting ink composition tends to be high and the gloss of the printed film tends to be low.
The content of the polyurethane resin (A) used in the liquid ink composition of the present invention in the ink is 4% by mass or more with respect to the total mass of the ink, from the viewpoint of sufficient adhesion of the ink to the printing medium. From the viewpoint of the ink viscosity and the work efficiency during ink production and printing, it is preferably 25% by mass or less, and more preferably in the range of 6-15% by mass.

Next, the urethane resin (B) having no urea bond used in the liquid ink composition of the present invention will be described.
The polyurethane resin (B) is an essential component for increasing moderate flexibility and particularly dry laminate strength, and does not have a urea bond.

  As the polyurethane resin (B), for example, those obtained by reacting polyol, polyisocyanate, and, if necessary, a chain extender having two or more hydroxyl groups can be used.

  Examples of the polyol include polyester polyol, polycaprolactone polyol, polyether polyol, polycarbonate polyol, polyacryl polyol, polybutadiene polyol, and the like. These polyols may be used alone or in combination of two or more. Among these, it is preferable to use a polyester polyol from the viewpoint of introducing an ester group into the polyurethane resin (B) to increase the polarity and further increase the dry laminate strength.

  As said polyester polyol, what is obtained by a well-known esterification reaction with the compound and polybasic acid which have 2 or more of hydroxyl groups can be used, for example.

  The compound having two or more hydroxyl groups is used as a chain extender. For example, ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6 -Glycols such as hexanediol, diethylene glycol, triethylene 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, 1,4-butanediol, 2-butyl-2-ethyl-1,3-propanediol, 1, 2-propanediol, 2-methyl-1,3- Lopandiol, neopentyl glycol, 2-isopropyl-1,4-butanediol, 2,4-dimethyl-1,5-pentanediol 2,4-diethyl-1,5-pentanediol, 2-ethyl-1,3- Glycols having a branched structure such as hexanediol, 2-ethyl-1,6-hexanediol, 3,5-heptanediol, 2-methyl-1,8-octanediol; trimethylolpropane, trimethylolethane, pentaerythritol, Aliphatic polyols such as sucrose, methylene glycol, glycerin, sorbitol; bisphenol A, 4,4′-dihydroxydiphenyl, 4,4′-dihydroxydiphenyl ether, 4,4′-dihydroxydiphenyl sulfone, hydrogenated bisphenol A, hydroquinone, etc. The number average molecular weight of such aromatic polyols can be used a compound in the range 50 to 400. These chain extenders may be used alone or in combination of two or more.

  Examples of the polybasic acid include succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, maleic anhydride, fumaric acid, 1,3-cyclopentanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, phthalate Acids, anhydrides of these acids, and the like can be used. These polybasic acids may be used alone or in combination of two or more.

  The number average molecular weight of the polyol is preferably in the range of 500 to 8,000, more preferably in the range of 800 to 5,000, and still more preferably in the range of 900 to 3,000. The number average molecular weight of the polyester polyol was measured by the gel permeation chromatography (GPC) method under the conditions described in paragraphs [0027] and [0028] as in the case of the polyurethane resin (A).

  Examples of the polyisocyanate used for producing the polyurethane resin (B) include 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 1-methyl-2,4-phenylene diisocyanate, and 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-2,4-phenylene diisocyanate, 1,3-dimethyl-4,6-phenylene diisocyanate, 1,4-dimethyl-2,5-phenylene diisocyanate, diethylben Diisocyanate, diisopropylbenzene diisocyanate, 1-methyl-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-2,4′-diisocyanate, biphenyl-4,4′-diisocyanate, 3-3′-dimethylbiphenyl-4,4′-diisocyanate, 4,4′-diphenylmethane diisocyanate Aromatic polyisocyanates such as 2,2′-diphenylmethane diisocyanate and diphenylmethane-2,4-diisocyanate; tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, dodecamethylene diisocyanate, trimethylhexamethylene diisocyanate, 1,3-cyclopent Range isocyanate, 1,3-cyclohexylene diisocyanate, 1,4-cyclohexylene diisocyanate, 1,3-di (isocyanatemethyl) cyclohexane, 1,4-di (isocyanatemethyl) cyclohexane, lysine diisocyanate, isophorone diisocyanate, 4,4 '-Dicyclohexylmethane diisocyanate, 2,4'-dicyclohexylmethane diisocyanate, 2,2'-dicyclohexyl Aliphatic or alicyclic polyisocyanates such as rumethane diisocyanate and 3,3'-dimethyl-4,4'-dicyclohexylmethane diisocyanate can be used. These polyisocyanates may be used alone or in combination of two or more. Among these, it is preferable to use an aliphatic polyisocyanate and / or an alicyclic polyisocyanate from the point that moderate flexibility is obtained, and from the point that the adhesive strength can be further improved by an excellent cohesive force. -It is more preferable to use hexamethylene diisocyanate.

  As a manufacturing method of the said polyurethane resin (B), the method of manufacturing by well-known solution polymerization, the extrusion molding by a twin-screw extruder, etc. is mentioned, for example.

  Examples of the method for producing by solution polymerization include, for example, the polyol, the organic solvent (D) described later, and, if necessary, a chain extender having two or more hydroxyl groups and stirring, and then adding the polyisocyanate. For example, the method of making a urethanation reaction in the range of 40-100 degreeC for 3 to 10 hours is mentioned.

  As a method of performing extrusion molding by the twin screw extruder, for example, the polyol and, if necessary, the chain extender having two or more hydroxyl groups, and the polyisocyanate in separate tanks of the twin screw extruder. A method of obtaining each of the pellet-shaped or sheet-shaped polyurethane resin (B) by putting them, heating them as necessary, kneading them with an extruder, and then extruding them from a die can be mentioned. When obtaining the said pellet-like polyurethane resin (B), the air hot cut system made into a pellet form in air, the underwater hot cut system made into a pellet form in water, etc. are employable.

  As a molar ratio [NCO / OH] of a hydroxyl group (derived from the polyol and the chain extender) and an isocyanate group (derived from the polyisocyanate) in producing the polyurethane resin (B). In any of the production methods, the range is preferably 0.8 to 1.2, and more preferably 0.9 to 1.1. Moreover, after the production of the urethane resin (B), an alcohol such as ethanol, methanol, or butanol may be added for the purpose of deactivating the remaining isocyanate group.

  The weight average molecular weight of the polyurethane resin (B) obtained by the above method is preferably in the range of 10,000 to 100,000 from the viewpoint that flexibility and particularly dry laminate strength can be maintained at a high level. More preferably, it is in the range of 5,000 to 90,000, and more preferably in the range of 50,000 to 85,000. In addition, the weight average molecular weight of the said polyurethane resin (B) shows the value obtained by measuring similarly to the number average molecular weight of the said polyol.

Moreover, as a softening temperature of the said polyurethane resin (B), it is preferable that it is the range of 40-80 degreeC from the point which obtains high dry lamination intensity | strength, and it is more preferable that it is the range of 40-60 degreeC. In addition, the softening temperature of the said polyurethane resin (B) shows the softening temperature obtained with the following measuring apparatus and conditions.
(Measurement device) Shimadzu flow tester CFT500D-2 (manufactured by Shimadzu Corporation)
(Die hole diameter) 1mm
(Die length) 1mm
(Conditions) Temperature rising method, temperature rising rate 3.0 ° C / min, preheating time 600s, load 98N

  The 100% modulus value of the polyurethane resin (B) is preferably in the range of 5 to 20 MPa, preferably in the range of 8 to 15 MPa, from the viewpoint that the flexibility and adhesion to the soft packaging material can be maintained at a high level. It is more preferable that The 100% modulus value of the polyurethane resin (B) is obtained by cutting a molded product of the polyurethane resin (B) into a length of 100 mm, a width of 5 mm, and a thickness of 1 mm. Using the machine “Autograph AG-I” (manufactured by Shimadzu Corporation), a tensile test was performed at a crosshead speed of 300 mm / min in an atmosphere with a distance between marked lines: 20 mm, a temperature of 23 ° C., and a humidity of 60%. 100% modulus value obtained in this case.

  The tensile strength of the polyurethane resin (B) is preferably in the range of 20 to 50 MPa, preferably in the range of 25 to 40 MPa, from the viewpoint that flexibility and adhesion to soft packaging materials and dry laminate strength can be maintained at a high level. More preferably. The tensile strength of the polyurethane resin (B) indicates a tensile strength obtained by performing the same tensile test as that for obtaining the 100% modulus value.

  The elongation at break of the polyurethane resin (B) is preferably in the range of 500 to 1,000% from the viewpoint that flexibility and adhesion to soft packaging materials and dry laminate strength can be maintained at a high level. 600 More preferably, it is in the range of ˜800%. In addition, the breaking elongation of the said polyurethane resin (B) shows the breaking elongation obtained by performing the same tensile test as the time of obtaining the said 100% modulus value.

  The solid content ratio of the polyurethane resin (A) having a urea bond and the polyurethane resin (B) having no urea bond is in the range of polyurethane resin (A): polyurethane resin (B) = 50: 50 to 99: 1. Is preferable, more preferably 60:40 to 99: 1, still more preferably 70:30 to 99: 1.

  Furthermore, in the liquid ink composition of the present invention, the suitability of boil and retort is further improved by adding the vinyl chloride vinyl acetate copolymer resin (E) having a hydroxyl group.

  The vinyl chloride vinyl acetate copolymer resin (E) having a hydroxyl group has a hydroxyl value of 50 to 200 mgKOH / g, and the content ratio of the vinyl chloride component in the copolymer resin is 80 to 95% by mass. Things are preferable.

  The vinyl chloride-vinyl acetate copolymer resin (E) having a hydroxyl group used in the liquid ink composition of the present invention can be obtained by two kinds of methods. One is obtained by copolymerizing vinyl chloride monomer, vinyl acetate monomer and vinyl alcohol in appropriate proportions. The other is obtained by copolymerizing vinyl chloride and vinyl acetate and then partially saponifying vinyl acetate. In the vinyl chloride vinyl acetate copolymer resin (E) 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 of the resin coating, vinyl acetate imparts adhesion and flexibility, and vinyl alcohol imparts good solubility in polar solvents.

  When used as a laminating ink for packaging, the adhesive, blocking resistance, dry laminating strength, extrusion laminating strength, boil retort suitability, printability, and all these properties must be satisfied. The polymer resin (E) has an appropriate monomer ratio. That is, the vinyl chloride is preferably 80 to 95 parts by mass with respect to 100 parts by mass of the vinyl chloride vinyl acetate copolymer resin (E) having a hydroxyl group. When it is less than 80 parts by mass, the resin film has poor toughness and the blocking resistance is lowered. If it exceeds 95 parts by mass, the resin coating becomes too hard and the adhesiveness decreases. The hydroxyl value obtained from vinyl alcohol is preferably 50 to 200 mgKOH / g. If it is less than 50 mgKOH / g, the solubility in a polar solvent is poor and the printability is poor. When it exceeds 200 mgKOH / g, the water resistance is lowered and the suitability for boiling and retort tends to be lowered.

  Examples of the colorant (C) used in the liquid ink composition of the present invention include organic and inorganic pigments and dyes used in general inks, paints, and recording agents. Organic pigments include azo, phthalocyanine, anthraquinone, perylene, perinone, quinacridone, thioindigo, dioxazine, isoindolinone, quinophthalone, azomethine azo, dictopyrrolopyrrole, isoindoline, etc. Pigments. Indigo ink is copper phthalocyanine, and transparent yellow ink is C.I. I. Pigment No Yellow 83 is preferably used.

Examples of the inorganic pigment include carbon black, titanium oxide, zinc oxide, zinc sulfide, barium sulfate, calcium carbonate, chromium oxide, silica, bengara, aluminum, mica (mica), and the like. Further, a luster pigment (Metashine; Nippon Sheet Glass Co., Ltd.) having glass or block flake as a base material and coated with metal or metal oxide can be used. From the viewpoints of cost and coloring power, it is preferable to use titanium oxide for white ink, carbon black for black ink, aluminum for silver ink, and mica for pearl ink. Aluminum is in the form of powder or paste, but is preferably used in the form of paste from the viewpoint of handling and safety, and whether to use leafing or non-leafing is appropriately selected from the viewpoint of brightness and concentration.
The colorant is preferably contained in an amount sufficient to ensure the density and coloring power 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 (D) used for the liquid ink composition of the present invention will be described. In the liquid ink composition of the present invention, for example, aromatic organic solvents, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, ester solvents such as ethyl acetate, n-propyl acetate, butyl acetate, propylene glycol monomethyl ether acetate, Examples thereof include alcohol solvents such as n-propanol, innopropanol, n-butanol, and propylene glycol monomethyl ether, and these can be used alone or in a mixture 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 liquid ink composition of the present invention as needed include resins other than the polyurethane resin and vinyl chloride-vinyl acetate copolymer resin, such as chlorinated polypropylene resin, ethylene-vinyl acetate copolymer. Combined resin, vinyl acetate resin, polyamide resin, acrylic resin, polyester resin, alkyd resin, polyvinyl chloride resin, rosin resin, rosin modified maleic acid resin, ketone resin, cyclized rubber, chlorinated rubber, butyral, petroleum resin, etc. Can be mentioned. The combined resins can be used alone or in admixture of two or more. The content of the combined resin is preferably 1 to 25% by mass, more preferably 2 to 15% by mass with respect to the total mass of the ink.

  In the liquid ink composition of the present invention, if necessary, a combination resin, extender pigment, pigment dispersant, leveling agent, antifoaming agent, wax, plasticizer, infrared absorber, ultraviolet absorber, aromatic agent, flame retardant, 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 can also be used in combination for further stably dispersing the pigment. As the dispersant, anionic, nonionic, cationic, amphoteric surfactants can be used. For example, a comb-structure polymer compound obtained by adding polyester to polyethyleneimine, or an alkylamine derivative of an α-olefin maleic acid polymer may be used. Specific examples include Solsperz series (ZENECA), Ajisper series (Ajinomoto), and homogenol series (Kao). Further, BYK series (Bic Chemie), EFKA series (EFKA), and the like 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 the storage stability of the ink and 5% by weight or less from the viewpoint of the suitability for lamination. .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, it is possible to produce a pigment dispersion in which a pigment is dispersed in an organic solvent with a polyurethane resin, and to produce an ink by blending the obtained pigment dispersion with other compounds 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 disperser, the filling rate of the grinding media, the dispersion treatment time, the discharge speed of the pigment dispersion, the viscosity of the pigment dispersion, and the like. can do. As a disperser, generally used, for example, a roller mill, a ball mill, a pebble mill, an attritor, a sand mill and the like can be used.
In the case where bubbles or unexpectedly large particles are included in the 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.

The 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 ink production or printing. preferable. In addition, the said viscosity is a viscosity measured at 25 degreeC with the 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 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.

  As the hue of the liquid ink composition of the present invention, there are five basic colors of yellow, red, indigo, black, and white depending on the type of colorant used, and red (orange) as the color outside the process gamut. , Grass (green), purple. Further, transparent yellow, peony, vermilion, brown, gold, silver, pearl, almost transparent medium for adjusting color density (including extender pigments if necessary), etc. are prepared as base colors. The boil retort ink is appropriately selected in consideration of pigment migration and heat resistance. The base ink of each hue is diluted with a diluting solvent to a viscosity and density suitable for gravure printing or flexographic printing, and is supplied alone or mixed to each printing unit.

  A polyester resin film is particularly preferable as a usable plastic film, but it is also widely used for various highly functional films in which an inorganic or organic barrier coating material is coated on the surface of other polypropylene, nylon, polyethylene resin films and the like. I can do it.

The present invention will be described more specifically with reference to examples. Hereinafter, both “parts” and “%” are based on mass.
In addition, the measurement of the weight average molecular weight (polystyrene conversion) by GPC (gel permeation chromatography) in this invention was performed on condition of the following using the Tosoh Corporation HLC8220 system.
Separation column: 4 TSKgelGMH _HR- N manufactured by Tosoh Corporation are used. Column temperature: 40 ° C. Moving layer: Tetrahydrofuran manufactured by Wako Pure Chemical Industries, Ltd. Flow rate: 1.0 ml / min. Sample concentration: 0.4% by mass. Sample injection volume: 100 microliters. Detector: differential refractometer.
The viscosity was measured at 25 ° C. with a Tokimec B-type viscometer.

<Calculation of Absorbance Ratio of [Absorption Peak Derived from Ether Group] / [Absorption Peak Derived from Carbonyl Group]>
Apparatus; Fourier transform infrared spectrophotometer Nicolet iS10 manufactured by Thermo SCIENTIFIC
Measurement conditions: 1-time reflection ATR (DuraScope), spectral resolution 4 cm-1, integration number 32 times, diamond and KRS5 crystal measurement sample; dry coating (film thickness 100 μm to 300 μm)
The spectrum obtained by the single reflection ATR measurement was subjected to second-order differential analysis, and absorption peaks derived from the carbonyl group based on the polyurethane resin (A) structure showed absorption near 1720 cm-1, absorption near 1740 cm-1, and ester. The absorbance ratio [1100 cm −1 / 1740 cm −1 + 1730 cm −1 + 1720 cm −1] was calculated as the ratio near the absorption peak 1100 cm −1 derived from the ether group to the total of the three absorptions near 1730 cm −1 based on the structure.

(Synthesis example 1) Polyurethane resin solution A
In a four-necked flask equipped with a stirrer, thermometer, reflux condenser and nitrogen gas inlet tube, 80 parts of neopentyl glycol adipate diol (hydroxyl value: 56.6 mgKOH / g) and 20 parts of polyethylene glycol (hydroxyl value: 278 mgKOH / g) and 29.68 parts of isophorone diisocyanate were added and reacted at 90 ° C. for 10 hours under a nitrogen stream to produce a urethane prepolymer having an isocyanate group content of 2.84% by mass. Then, 69.8 parts of ethyl acetate was added thereto. Was added to obtain a uniform solution of urethane prepolymer. Subsequently, the urethane prepolymer solution was added to a mixture consisting of 7.97 parts of isophoronediamine, 0.11 part of di-n-butylamine, 139.1 parts of ethyl acetate and 112.5 parts of isopropyl alcohol, The polyurethane resin solution A was obtained by stirring for a time. The obtained polyurethane resin solution A has a resin solid content concentration of 30.4% by mass, a resin solid content Mw of 54,000, and the urethane bond concentration is 1 by a calculation method according to the formula (1) described in paragraph [0012]. It was .31 mmol / g.
The absorbance ratio of [absorption peak derived from the ether group] / [absorption peak derived from the carbonyl group] = 0.06.

(Synthesis example 2) Polyurethane resin solution B
In a four-necked flask equipped with a stirrer, thermometer, reflux condenser and nitrogen gas inlet tube, 62 parts of neopentyl glycol adipate diol (hydroxyl value: 56.6 mgKOH / g) and 38 parts of polyethylene glycol (hydroxyl value: 160 mgKOH / g) and 24.50 parts of isophorone diisocyanate 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 1.68% by mass. Then, 67.0 parts of ethyl acetate was added thereto. Was added to obtain a uniform solution of urethane prepolymer. Next, the urethane prepolymer solution was added to a mixture consisting of 4.71 parts of isophoronediamine, 0.11 part of di-n-butylamine, 129.1 parts of ethyl acetate and 105.6 parts of isopropyl alcohol, A polyurethane resin solution B was obtained by stirring for a time. The obtained polyurethane resin solution B had a resin solid content concentration of 30.3% by mass, a resin solid content Mw of 54,000, and a urethane bond concentration of 1.32 mmol / g by the same calculation method as in Synthesis Example 1. there were.
The absorbance ratio of [absorption peak derived from the ether group] / [absorption peak derived from the carbonyl group] = 0.09.

(Synthesis Example 3) Polyurethane resin solution C
In a four-necked flask equipped with a stirrer, thermometer, reflux condenser and nitrogen gas introduction tube, 76 parts of neopentyl glycol adipate diol (hydroxyl value: 56.6 mgKOH / g) and 24 parts of polyethylene glycol (hydroxyl value: 278 mgKOH / g) and isophorone diisocyanate (31.58 parts) were reacted at 90 ° C. for 10 hours under a nitrogen stream to produce a urethane prepolymer having an isocyanate group content of 2.84% by mass. Was added to obtain a uniform solution of urethane prepolymer. Next, the urethane prepolymer solution was added to a mixture consisting of 8.08 parts of isophoronediamine, 0.11 part of di-n-butylamine, 141.1 parts of ethyl acetate and 114.2 parts of isopropyl alcohol, A polyurethane resin solution C was obtained by stirring for a period of time. The obtained polyurethane resin solution C had a resin solid content concentration of 30.4% by mass, a resin solid content Mw of 54,000, and a urethane bond concentration of 1.40 mmol / g by the same calculation method as in Synthesis Example 1. there were.
The absorbance ratio of [absorption peak derived from the ether group] / [absorption peak derived from the carbonyl group] = 0.07.

(Synthesis Example 4) Polyurethane resin solution D
In a four-necked flask equipped with a stirrer, thermometer, reflux condenser and nitrogen gas inlet tube, 75 parts of neopentyl glycol adipate diol (hydroxyl value: 224 mgKOH / g) and 25 parts of polyethylene glycol (hydroxyl value: 278 mgKOH / g) In addition, 58.74 parts of isophorone diisocyanate was charged and reacted at 90 ° C. for 10 hours under a nitrogen stream to produce a urethane prepolymer having an isocyanate group content of 2.80% by mass, and then 85.5 parts of ethyl acetate was added thereto. To obtain a uniform solution of urethane prepolymer. Next, the urethane prepolymer solution was added to a mixture consisting of 9.66 parts of isophoronediamine, 0.11 part of di-n-butylamine, 170.1 parts of ethyl acetate and 137.6 parts of isopropyl alcohol, The polyurethane resin solution D was obtained by stirring for a time. The obtained polyurethane resin solution D had a resin solid content concentration of 30.4% by mass, a resin solid content Mw of 54,000, and a urethane bond concentration of 2.50 mmol / g by the same calculation method as in Synthesis Example 1. there were. The absorbance ratio of [absorption peak derived from the ether group] / [absorption peak derived from the carbonyl group] = 0.06.

(Synthesis Example 5) Polyurethane resin solution E
In a four-necked flask equipped with a stirrer, thermometer, reflux condenser and nitrogen gas inlet tube, 77 parts of neopentyl glycol adipate diol (hydroxyl value: 140 mgKOH / g) and 23 parts of polypropylene glycol (hydroxyl value: 278 mgKOH / g) ) And 44.39 parts of isophorone diisocyanate were reacted at 90 ° C. for 10 hours under a nitrogen stream to produce a urethane prepolymer having an isocyanate group content of 2.73% by mass, and then 77.7 parts of ethyl acetate was added thereto. In addition, a uniform solution of urethane prepolymer was obtained. Next, the urethane prepolymer solution was added to a mixture consisting of 8.78 parts of isophoronediamine, 0.11 part of di-n-butylamine, 154.7 parts of ethyl acetate and 125.2 parts of isopropyl alcohol, The polyurethane resin solution E was obtained by stirring for a time. The obtained polyurethane resin solution E had a resin solid content concentration of 30.4% by mass, a resin solid content Mw of 54,000, and a urethane bond concentration of 2.00 mmol / g by the same calculation method as in Synthesis Example 1. there were. The absorbance ratio of [absorption peak derived from the ether group] / [absorption peak derived from the carbonyl group] = 0.06.

(Synthesis Example 6) Polyurethane resin solution F
In a four-necked flask equipped with a stirrer, thermometer, reflux condenser and nitrogen gas inlet tube, 77 parts of neopentyl glycol adipate diol (hydroxyl value: 140 mgKOH / g) and 23 parts of polytetramethylene glycol (hydroxyl value: 278 mgKOH / g) and 44.39 parts of isophorone diisocyanate 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 2.73% by mass. Then, 77.7 parts of ethyl acetate was added thereto. Was added to obtain a uniform solution of urethane prepolymer. Next, the urethane prepolymer solution was added to a mixture consisting of 8.78 parts of isophoronediamine, 0.11 part of di-n-butylamine, 154.7 parts of ethyl acetate and 125.2 parts of isopropyl alcohol, A polyurethane resin solution F was obtained by stirring for a period of time. The obtained polyurethane resin solution F had a resin solid content concentration of 30.4% by mass, a resin solid content Mw of 54,000, and a urethane bond concentration of 2.00 mmol / g by the same calculation method as in Synthesis Example 1. there were. The absorbance ratio of [absorption peak derived from the ether group] / [absorption peak derived from the carbonyl group] = 0.06.

(Synthesis Example 7) Polyurethane resin solution G
In a four-necked flask equipped with a stirrer, thermometer, reflux condenser and nitrogen gas inlet tube, 57 parts of neopentyl glycol adipate diol (hydroxyl value: 140 mgKOH / g) and 43 parts of polyethylene glycol (hydroxyl value: 160 mgKOH / g) In addition, 39.74 parts of isophorone diisocyanate was charged and reacted at 90 ° C. for 10 hours under a nitrogen stream to produce a urethane prepolymer having an isocyanate group content of 2.80% by mass, and then 75.2 parts of ethyl acetate was added thereto. To obtain a uniform solution of urethane prepolymer. Next, the urethane prepolymer solution was added to a mixture consisting of 8.49 parts of isophoronediamine, 0.11 part of di-n-butylamine, 149.7 parts of ethyl acetate and 121.1 parts of isopropyl alcohol, The polyurethane resin solution G was obtained by stirring for a time. The obtained polyurethane resin solution G had a resin solid content concentration of 30.4% by mass, a resin solid content Mw of 54,000, and a urethane bond concentration of 1.79 mmol / g by the same calculation method as in Synthesis Example 1. there were. The absorbance ratio of [absorption peak derived from the ether group] / [absorption peak derived from the carbonyl group] = 0.09.

(Synthesis Example 8) Polyurethane resin solution H
In a four-necked flask equipped with a stirrer, thermometer, reflux condenser and nitrogen gas inlet tube, 97 parts of neopentyl glycol adipate diol (hydroxyl value: 140 mgKOH / g) and 3 parts of polyethylene glycol (hydroxyl value: 160 mgKOH / g) And 39.74 parts of isophorone diisocyanate were added 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% by mass, and then 75.2 parts of ethyl acetate was added thereto. To obtain a uniform solution of urethane prepolymer. Next, the urethane prepolymer solution was added to a mixture consisting of 9.71 parts of isophoronediamine, 0.11 part of di-n-butylamine, 149.7 parts of ethyl acetate and 121.1 parts of isopropyl alcohol, A polyurethane resin solution H was obtained by stirring for a time. The obtained polyurethane resin solution H had a resin solid content concentration of 30.4% by mass, a resin solid content Mw of 54,000, and a urethane bond concentration of 1.69 mmol / g by the same calculation method as in Synthesis Example 1. there were. The absorbance ratio of [absorption peak derived from the ether group] / [absorption peak derived from the carbonyl group] = 0.03.

(Synthesis Example 9) Polyurethane resin solution I
In a four-necked flask equipped with a stirrer, thermometer, reflux condenser and nitrogen gas inlet tube, 77 parts of neopentyl glycol adipate diol (hydroxyl value: 224 mgKOH / g) and 28 parts of polyethylene glycol (hydroxyl value: 278 mgKOH / g) And 54.62 parts of isophorone diisocyanate were added and reacted at 90 ° C. for 10 hours under a nitrogen stream to produce a urethane prepolymer having an isocyanate group content of 1.21% by mass, and then 85.9 parts of ethyl acetate was added thereto. To obtain a uniform solution of urethane prepolymer. Next, the urethane prepolymer solution was added to a mixture consisting of 4.59 parts of isophoronediamine, 0.9 parts of di-n-butylamine, 164.5 parts of ethyl acetate and 134.8 parts of isopropyl alcohol, and 5 ° C. at 45 ° C. A polyurethane resin solution I was obtained by stirring for a period of time. The obtained polyurethane resin solution I had a resin solid content concentration of 30.4% by mass, a resin solid content Mw of 25,000, and a urethane bond concentration of 2.70 mmol / g by the same calculation method as in Synthesis Example 1. there were. The absorbance ratio of [absorption peak derived from the ether group] / [absorption peak derived from the carbonyl group] = 0.06.

(Synthesis Example 10) Polyurethane resin solution J
In a four-necked flask equipped with a stirrer, thermometer, reflux condenser and nitrogen gas inlet tube, 77 parts of neopentyl glycol adipate diol (hydroxyl value: 224 mgKOH / g) and 28 parts of polypropylene glycol (hydroxyl value: 278 mgKOH / g) And 54.62 parts of isophorone diisocyanate were added and reacted at 90 ° C. for 10 hours under a nitrogen stream to produce a urethane prepolymer having an isocyanate group content of 1.21% by mass, and then 85.9 parts of ethyl acetate was added thereto. To obtain a uniform solution of urethane prepolymer. Next, the urethane prepolymer solution was added to a mixture consisting of 4.59 parts of isophoronediamine, 0.9 parts of di-n-butylamine, 164.5 parts of ethyl acetate and 134.8 parts of isopropyl alcohol, and 5 ° C. at 45 ° C. A polyurethane resin solution J was obtained by stirring for a period of time. The obtained polyurethane resin solution J had a resin solid content concentration of 30.4 mass%, a resin solid content Mw of 25,000, and a urethane bond concentration of 2.70 mmol / g by the same calculation method as in Synthesis Example 1. there were. The absorbance ratio of [absorption peak derived from the ether group] / [absorption peak derived from the carbonyl group] = 0.06.

(Synthesis Example 11) Polyurethane resin solution K
In a four-necked flask equipped with a stirrer, thermometer, reflux condenser and nitrogen gas inlet tube, 77 parts of neopentyl glycol adipate diol (hydroxyl value: 224 mgKOH / g) and 28.0 parts of polytetramethylene glycol (hydroxyl value: 278 mg KOH / g) and 54.62 parts of isophorone diisocyanate were reacted at 90 ° C. for 10 hours under a nitrogen stream to produce a urethane prepolymer having an isocyanate group content of 1.21% by mass. 0 parts was added to make a uniform solution of urethane prepolymer. Next, the urethane prepolymer solution was added to a mixture consisting of 4.59 parts of isophoronediamine, 0.9 parts of di-n-butylamine, 164.5 parts of ethyl acetate and 134.8 parts of isopropyl alcohol, and 5 ° C. at 45 ° C. The polyurethane resin solution K was obtained by stirring for a time. The obtained polyurethane resin solution K had a resin solid content concentration of 30.4% by mass, a resin solid content Mw of 25,000, and a urethane bond concentration of 2.70 mmol / g by the same calculation method as in Synthesis Example 1. there were. The absorbance ratio of [absorption peak derived from the ether group] / [absorption peak derived from the carbonyl group] = 0.06.

(Synthesis example 12) Polyurethane resin solution L
In a four-necked flask equipped with a stirrer, thermometer, reflux condenser and nitrogen gas inlet tube, 47 parts of neopentyl glycol adipate diol (hydroxyl value: 140 mgKOH / g) and 53 parts of polyethylene glycol (hydroxyl value: 160 mgKOH / g) And 40.26 parts of isophorone diisocyanate were added and reacted at 90 ° C. for 10 hours under a nitrogen stream to produce a urethane prepolymer having an isocyanate group content of 2.82% by mass, and then 75.5 parts of ethyl acetate was added thereto. To obtain a uniform solution of urethane prepolymer. Next, the urethane prepolymer solution was added to a mixture consisting of 8.52 parts of isophorone diamine, 0.11 part of di-n-butylamine, 150.3 parts of ethyl acetate and 121.6 parts of isopropyl alcohol, and 5 ° C. at 45 ° C. The polyurethane resin solution L was obtained by stirring for a time. The obtained polyurethane resin solution L had a resin solid content concentration of 30.4 mass%, a resin solid content Mw of 54,000, and a urethane bond concentration of 1.80 mmol / g by the same calculation method as in Synthesis Example 1. there were. The absorbance ratio of [absorption peak derived from the ether group] / [absorption peak derived from the carbonyl group] = 0.14.

(Synthesis example 13) Polyurethane resin solution M
In a four-necked flask equipped with a stirrer, thermometer, reflux condenser and nitrogen gas inlet tube, 80 parts of neopentyl glycol adipate diol (hydroxyl value: 56.6 mgKOH / g) and 20 parts of neopentyl glycol adipate diol (hydroxyl value) : 109.8 mg KOH / g) and 22.49 parts of isophorone diisocyanate were reacted at 90 ° C. for 10 hours under a nitrogen stream to produce a urethane prepolymer having an isocyanate group content of 2.84% by mass. 65.96 parts of ethyl was added to make a uniform solution of urethane prepolymer. Next, the urethane prepolymer solution was added to a mixture consisting of 7.25 parts of isophoronediamine, 0.27 parts of di-n-butylamine, 131.2 parts of ethyl acetate, and 106.2 parts of isopropyl alcohol. The polyurethane resin solution M was obtained by stirring for a time. The obtained polyurethane resin solution M had a resin solid content concentration of 30.4% by mass, a resin solid content Mw of 50,000, and a urethane bond concentration of 0.92 mmol / g by the same calculation method as in Synthesis Example 1. there were. The absorbance ratio of [absorption peak derived from the ether group] / [absorption peak derived from the carbonyl group] = 0.00.

(Synthesis Example 14) Polyurethane resin solution N
In a four-necked flask equipped with a stirrer, thermometer, reflux condenser and nitrogen gas inlet tube, 35 parts of neopentyl glycol adipate diol (hydroxyl value: 56.6 mgKOH / g) and 65 parts of neopentyl glycol adipate diol (hydroxyl value) 109.8 mgKOH / g) and 27.62 parts of isophorone diisocyanate were reacted at 90 ° C. for 10 hours under a nitrogen stream to produce a urethane prepolymer having an isocyanate group content of 2.84% by mass. 68.7 parts of ethyl was added to make a uniform solution of urethane prepolymer. Next, the urethane prepolymer solution was added to a mixture consisting of 7.48 parts of isophoronediamine, 0.4 part of di-n-butylamine, 136.8 parts of ethyl acetate and 110.7 parts of isopropyl alcohol, and 5 ° C. at 45 ° C. A polyurethane resin solution N was obtained by stirring for a period of time. The obtained polyurethane resin solution N had a resin solid content concentration of 30.4 mass%, a weight average molecular weight of the resin solid content of 54,000, and the urethane bond concentration was 1.20 mmol /% by the same calculation method as in Synthesis Example 1. g. The absorbance ratio of [absorption peak derived from the ether group] / [absorption peak derived from the carbonyl group] = 0.00.

≪Synthesis of polyurethane resin (B-1) ≫
Polyester polyol-1 (polyester polyol obtained by reacting neopentyl glycol, 1,6-hexanediol and adipic acid, number average molecular weight; 2 in a reaction four-necked flask equipped with a stirrer, a reflux pipe, and a nitrogen introduction pipe; 2 ) Was added to 92.0 parts by mass and 400 parts by mass of normal propyl acetate and stirred, then 8.0 parts by mass of 1,6-hexamethylene diisocyanate and 100 ppm of tin octylate were added at 80 ° C. Was reacted for 3 hours to obtain a normal propyl acetate solution of the polyurethane resin (B-1). The obtained polyurethane resin (B-1) has a resin solid content concentration of 20.0% by mass, a weight average molecular weight of 86,000, a softening temperature of 45 ° C., a 100% modulus value of 10 MPa, a tensile strength of 30 MPa, and a breaking elongation. Was 850%.
The polyurethane resin (B-1) has a weight average molecular weight, a softening temperature, a 100% modulus value, a tensile strength, and a breaking elongation obtained by using an ethyl acetate solution of the polyurethane resin (B-1) as a polyethylene terephthalate film. The value measured using a 1 mm-thick film obtained by applying and drying at 80 ° C. for 5 minutes as a test specimen is shown.

≪Synthesis of polyurethane resin (B-2) ≫
Polyester polyol-1 (polyester polyol obtained by reacting neopentyl glycol, 1,6-hexanediol and adipic acid, number average molecular weight; 2 in a reaction four-necked flask equipped with a stirrer, a reflux pipe, and a nitrogen introduction pipe; 2 20.0 parts by weight of polyester polyol-2 (1,4-butanediol and adipic acid, number average molecular weight; 2,000) 80.0 parts by weight, and normal acetate After 435.3 parts by mass of propyl was charged and stirred, 8.82 parts by mass of 1,6-hexamethylene diisocyanate and 100 ppm of tin octylate were added and reacted at 80 ° C. for 3 hours to obtain a polyurethane resin ( A normal propyl acetate solution of B-2) was obtained. The obtained polyurethane resin (B-2) has a solid content concentration of 20.0%, a weight average molecular weight of 85,000, a softening temperature of 50 ° C., a 100% modulus value of 12 MPa, a tensile strength of 35 MPa, and a breaking elongation of It was 800%.
The polyurethane resin (B-2) has a weight average molecular weight, a softening temperature, a 100% modulus value, a tensile strength, and an elongation at break, using an ethyl acetate solution of the polyurethane resin (B-2) as a polyethylene terephthalate film. The value measured using a 1 mm-thick film obtained by applying and drying at 80 ° C. for 5 minutes as a test specimen is shown.

(Preparation of vinyl chloride vinyl acetate copolymer resin solution)
Vinyl chloride vinyl acetate copolymer resin having a hydroxyl group used in combination with a polyurethane resin (resin monomer composition in weight% vinyl chloride / vinyl acetate / vinyl alcohol = 92/3/5, hydroxyl value (mgKOH / g) = 64) Was made into a 15% solution with ethyl acetate, and this was made into a vinyl acetate resin solution (E-1).

≪Gravure ink / Production of printed matter≫
[Example 1]
28.2 parts of the obtained polyurethane resin solution A-1, 2.7 parts of polyurethane resin solution (B-1), 30 parts of vinyl chloride vinyl acetate copolymer resin solution E-1 having a hydroxyl group (15% solution) A mixture of 10 parts of phthalocyanine blue pigment (FASTGEN Blue LA5380 manufactured by DIC Corporation) and 29.1 parts of ethyl acetate was kneaded to prepare a blue printing ink.
The viscosity of the obtained printing ink was adjusted to 16 seconds (25 ° C.) with Zahn cup # 3 (manufactured by Kosei Co., Ltd.) with ethyl acetate, and various barriers shown in Table 1 were obtained using a gravure proofing machine equipped with a plate depth 25 μm Film (W, X, Y, Z), corona-treated nylon film (hereinafter “NY film”, manufactured by Unitika Ltd., trade name emblem ON thickness 15 μm), corona-treated biaxially oriented polypropylene film (hereinafter “OPP film: Toyobo”) Co., Ltd. P2161 (thickness: 20 μm)) and corona-treated polyester film (hereinafter PET film: Toyobo Co., Ltd., trade name: Ester E5102, thickness: 12 μm) and dried at 40-50 ° C. to obtain a printed matter It was.

  About the obtained gravure printed matter, the adhesiveness to various barrier films, blocking resistance, the measurement of the dry lamination strength to NY film and PET film, and the measurement of the polyethylene extrusion lamination strength were evaluated. The results are shown in Tables 6-10. The evaluation was performed by the following test method.

1) Adhesiveness (various barrier films)
After allowing the printed matter to stand for 1 day, a cellophane tape (12 mm width made by Nichiban) was attached to the printed surface, and the appearance of the printed film when it was rapidly peeled off was visually judged. The determination criteria were as follows. If it was more than △, it could be used.

A: The printed film was not peeled off at all.
○: 80% or more and less than 95% of the printed film remained on the film.
Δ: 70% to less than 80% of the printed film remained on the film.
X: Less than 70% of the printed film remained on the film.

2) Blocking resistance (various barrier films)
The film is overlapped so that the printed surface and the non-printed surface of the printed matter are in contact with each other, a load of 10 kgf / cm ² is applied, and the film is allowed to elapse for 12 hours in an environment of 40 ° C. The state of was visually evaluated in four stages. If it was more than △, it could be used.

A: No transfer is observed when the amount of ink transferred to the non-printed surface is 0%.
A: A slight transition of less than 5% is observed.
Δ: Transition of 5% or more to less than 20% is observed.
X: The transfer amount is 20% or more.

3) Measurement of laminate strength (1) (PET film, NY film)
The adhesive is diluted to an appropriate viscosity with an organic solvent, applied to a film, dried, and the laminate strength is measured by a dry laminating method in which the other film is pressed and bonded.
A non-stretched polypropylene film (hereinafter R-CPP: manufactured by Toray Synthetic Film Co., Ltd.) using a dry laminating machine (manufactured by DIC Engineering) with a urethane-based dry laminate adhesive Dick Dry LX-703VL / KR-90 (manufactured by DIC). ZK-75 50 μm) and aged at 40 ° C. for 5 days to obtain a laminate, cut into a 15 mm width and subjected to a 90 ° peel test (measurement of dry laminate strength before retorting) at a pulling speed of 300 mm / min. went. Furthermore, the obtained laminate was formed into a pouch having a size of 120 mm × 120 mm, and filled with 70 g of pseudo food, in which vinegar, salad oil, and meat sauce were mixed at a weight ratio of 1: 1: 1. The prepared pouch was subjected to a steam retort sterilization treatment at 120 ° C. for 30 minutes and then subjected to a 90 ° peel test (measurement of dry laminate strength after retort treatment) in the same manner as described above.

4) Measurement of dry laminate strength (2) (PET film)
An unstretched polypropylene film (hereinafter referred to as CPP: Toyobo Co., Ltd., Pyrene Film) by a dry laminating machine (manufactured by DIC Engineering) using an ether-based dry laminating adhesive Dick Dry LX-401A / SP-60 (manufactured by DIC Engineering) CPT1128 (30 μm) was laminated and aged at 40 ° C. for 3 days to obtain a laminate, then cut into a 15 mm width and subjected to a 90 ° peel test (measurement of dry laminate strength before retorting) at a pulling speed of 300 mm / min. It was.

5) Measurement of extrusion laminate strength (3) (OPP film only)
Extrusion lamination strength is measured by an extrusion laminating method, which is a polylamination that coats molten polyethylene on one side of the film.
After applying 0.1 g / m ^{2 of a} polyethyleneimine-based anchor coating agent to an OPP printed material, molten polyethylene is laminated at a thickness of 40 μm by an extrusion laminating machine to obtain a laminated product, and then the laminated film is 15 mm wide. And a 90 ° peel test (measurement of extrusion laminate strength) was performed at a pulling speed of 50 mm / min.
OPP film to be evaluated P2161 manufactured by Toyobo Co., Ltd. (thickness: 20 μm)

[Examples 1 to 20, Comparative Examples 1 to 14]
Inks were produced in the same manner as in Example 1, with Examples 1 to 20 having the composition shown in Tables 1 to 3, and Comparative Examples 1 to 14 having the compositions shown in Tables 4 and 5.
Examples 19 and 20 were prepared without adding the vinyl chloride-vinyl acetate copolymer resin solution E-1 (15% solution) having a hydroxyl group.

The evaluation results are shown in Tables 6-10.

評価対象のバリアフィルム
Ｔ：大日本印刷（株）製 アルミナ蒸着透明ＰＥＴフィルム ＩＢ−ＰＥＴ−ＰＵＢ（厚み：１２μｍ）
Ｕ：三菱樹脂（株）製 シリカ蒸着透明ＰＥＴフィルム テックバリア ＴＸ−Ｒ（厚み：１２μｍ）
Ｖ：尾池工業（株）製 シリカ蒸着透明ＰＥＴフィルム ＭＯＳ−ＴＥＢ（厚み：１２μｍ）
Ｗ：凸版印刷（株）製 酸化アルミニウム蒸着透明ＰＥＴフィルム ＧＬ−ＡＲＨ（厚み：１２μｍ）

Barrier film to be evaluated T: Dainippon Printing Co., Ltd. Alumina-deposited transparent PET film IB-PET-PUB (thickness: 12 μm)
U: manufactured by Mitsubishi Plastics, Inc. Silica-deposited transparent PET film, Tech Barrier TX-R (thickness: 12 μm)
V: manufactured by Oike Industry Co., Ltd. Silica-deposited transparent PET film MOS-TEB (thickness: 12 μm)
W: manufactured by Toppan Printing Co., Ltd. Aluminum oxide-deposited transparent PET film GL-ARH (thickness: 12 μm)

FC described in Examples 1 to 20 in the table is an abbreviation for FILM CUT, and represents that the film is broken before the laminate is peeled off during measurement. Therefore, in Examples 1 to 20, the N / 15 mm laminate strength between the PET film before retorting / unstretched polypropylene film R-CPP is FC (the film breaks before the laminate is peeled off during measurement). That is, it shows that the laminate strength exceeds the film strength and is excellent.
The liquid ink composition of the present invention has various dry barrier strengths before and after the retort treatment, which is the main purpose, and polyethylene extrusion laminate strength, while maintaining adhesion to a wide variety of barrier films and blocking resistance. A liquid ink composition having excellent suitability on a high-functional barrier film can be provided.

  The liquid ink composition of the present invention is a liquid that exhibits high adhesion and block resistance, and has high dry laminate strength both before and after retorting, even if it is a highly functional film subjected to a wide variety of barrier treatments. As an ink composition, it can be widely used for industrial products such as food packaging materials, sanitary products, cosmetics and electronic parts with various film configurations.

Claims (14)

A polyurethane resin (A) having a urea bond, no urea bond polyurethane resin (B), a Brighter Kid ink composition to contain a colorant (C) and the organic solvent (D), the urea bond A liquid ink composition, wherein the polyurethane resin (A) has a urethane bond concentration of 1.32 mmol / g or more and 2.5 mmol / g or less.
The liquid ink composition according to claim 1, wherein the polyurethane resin (A) having a urea bond uses a polyether polyol as a reaction raw material.
The range of the absorbance ratio between the absorbance derived from the ether group and the absorbance derived from the carbonyl group obtained from the infrared absorption spectrum of the resin surface of the polyurethane resin (A) having the urea bond is 0.02 to 0.10. The liquid ink composition according to claim 1 or 2 .
The liquid ink composition according to any one of claims 1 to 3 , wherein the polyurethane resin (A) has a weight average molecular weight in the range of 10,000 to 100,000.
The liquid ink composition according to any one of claims 1 to 4 , wherein the polyurethane resin (A) is a polyurethane resin using a polyether polyol having a number average molecular weight of 100 to 3500 as a raw material.
The liquid ink composition according to any one of claims 1 to 5 , wherein the polyurethane resin (B) has a weight average molecular weight in the range of 10,000 to 100,000.
The liquid ink composition according to any one of claims 1 to 6 , wherein a softening temperature of the polyurethane resin (B) is in a range of 40 to 80 ° C.
The liquid ink composition according to any one of claims 1 to 7 , wherein the polyurethane resin (B) is made from an aliphatic polyisocyanate and / or an alicyclic polyisocyanate.
The liquid ink composition according to any one of claims 1 to 8 , wherein the polyurethane resin (B) is made from a polyester polyol as a raw material.
Furthermore, the liquid ink composition of Claim 1 containing the vinyl chloride vinyl acetate copolymer resin (E) which has a hydroxyl group.
The hydroxyl value of the vinyl chloride vinyl acetate copolymer resin (E) having a hydroxyl group is 50 to 200 mgKOH / g, and the content ratio of the vinyl chloride component in the copolymer resin is 80 to 95% by mass. Item 11. The liquid ink composition according to any one of Items 1 to 10 .
The liquid ink composition according to any one of claims 1 to 11 , wherein the organic solvent (D) is an organic solvent having no aromatic group.
The printed matter formed by printing the liquid ink composition as described in any one of Claims 1-12.
A laminate obtained by processing the printed material according to claim 13 and a substrate by a dry lamination method or an extrusion lamination method.