JP5937285B1 - Laminated ink composition for flexible packaging - Google Patents

Abstract

PROBLEM TO BE SOLVED: To solve the problems of the present invention, in addition to being applicable to a wide variety of films, adhesion on various substrates, laminate strength before and after retorting, and suitability on various highly functional barrier films. An object is to provide an excellent laminate ink composition for soft packaging. A polyurethane resin (A) having a urea bond, a polyurethane resin (B) having no urea bond, a vinyl chloride vinyl acetate copolymer resin (C) having a hydroxyl group, a colorant (D), and an organic solvent (E) A laminate ink composition for soft packaging. [Selection figure] None

Description

  The present invention relates to a laminate ink composition for soft packaging. In particular, it is a gravure ink for laminating that can exhibit excellent adhesion performance on a printed laminating substrate, and a laminating ink composition for soft packaging for various films coated with inorganic or organic barrier coating materials. Related to things.

  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.
In addition, when a solvent having a slow drying rate is used in combination to improve ink transferability, it is difficult to achieve both blocking resistance and 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

  The present invention can be applied to a wide variety of films, as well as for flexible packaging having excellent adhesion on various substrates, laminate strength before and after retorting, and suitability on various high-performance barrier films. An object is to provide a laminate ink composition.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that in a flexible packaging laminate ink, a polyurethane resin (A) having a urea bond, a polyurethane resin (B) having no urea bond, a hydroxyl group It has been found that the inclusion of a vinyl chloride / vinyl acetate copolymer resin (C), a colorant (D), and an organic solvent (E) having an effective amount for solving the problems.

That is, the present invention relates to a polyurethane resin (A) containing a urea bond, a polyurethane resin (B) not containing a urea bond, a vinyl chloride vinyl acetate copolymer resin (C) having a hydroxyl group, a colorant (D), and an organic solvent. The present invention relates to a laminate ink composition for soft packaging, comprising (E) as an essential component.
The present invention also relates to a laminate ink composition for soft packaging, wherein the polyurethane resin (A) has a weight average molecular weight in the range of 10,000 to 100,000.
Moreover, this invention is a polyurethane resin from which the said polyurethane resin (A) uses the polyether polyol of the number average molecular weights 100-3500 as a raw material, The content rate of a polyether polyol is 1-30 weight with respect to a polyurethane resin. % Laminating ink composition for soft packaging.
The present invention also relates to a laminate ink composition for soft packaging, wherein the polyurethane resin (B) has a weight average molecular weight in the range of 10,000 to 100,000.
Moreover, this invention relates to the laminating ink composition for soft packaging whose softening temperature of the said polyurethane resin (B) is the range of 40-80 degreeC.
The present invention also relates to a laminate ink composition for soft packaging, wherein the polyurethane resin (B) is made from an aliphatic polyisocyanate and / or an alicyclic polyisocyanate.
The present invention also relates to a laminate ink composition for soft packaging, wherein the polyurethane resin (B) is made from polyester polyol.
In the present invention, the vinyl chloride vinyl acetate copolymer resin (C) 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. The present invention relates to a laminating ink composition for soft packaging which is in weight percent.
Furthermore, this invention relates to the laminate ink composition for soft packaging whose organic solvent (E) is an organic solvent which does not have an aromatic group.
In addition, the present invention relates to a printed matter obtained by printing the laminate ink composition for soft packaging.

  According to the present invention, for flexible packaging having a high laminate strength both before and after retorting on a wide range of films, including adhesiveness and blocking resistance on transparent deposited films, which have been increasing in recent years, and the aforementioned transparent deposited films. A laminate ink composition is obtained.

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

  The present invention relates to a polyurethane resin (A) having a urea bond, a polyurethane resin (B) having no urea bond, a vinyl chloride vinyl acetate copolymer resin (C) having a hydroxyl group, a colorant (D) and an organic solvent (E). Is a laminate ink composition for soft packaging.

  Specifically, the laminate ink composition for soft packaging of the present invention is prepared by using a binder resin containing the polyurethane resins (A) and (B) in advance in various organic solvents such as ethyl acetate, methyl ethyl ketone, toluene, IPA, and various additives. Mix. 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 polyurethane resin (A) having a urea bond used in the laminate ink composition for soft packaging of the present invention is used as a main resin, and the urea bond concentration in the resin solid content is 0.1-2. The range of 0 mmol / g is preferable, more preferably 0.3 to 1.5 mmol / g, and still more preferably 0.5 to 1.0 mmol / g.
The urea bond concentration here can be calculated by the following formula (1).
Urea binding concentration = {(X ₁ / M ₁ + X ₂ / M ₂ +... + X _i / M _i ) × 2− (W ₁ × OH ₁ + W ₂ × OH ₂ +... + W _i × OH _i ) / 56100} × 1000 / S Formula (1)
In the formula (1), the symbols are as follows.
X _1: the weight _{M 1} of a diisocyanate compound 1: molecular weight diisocyanate compound 1 _{X 2:} diisocyanate compound 2 weight _{M 2:} Molecular weight of the diisocyanate compound 2 _{X i:} the weight of the diisocyanate compound i _{M i:} diisocyanate compounds i molecular weight _{W 1} of : Weight OH _{1 of} polyol ₁ : Hydroxyl value W _{2 of} polyol 1: Weight OH _{2 of} polyol 2: Hydroxyl value W _{i of} polyol 2: Weight OH _{i of} polyol i: Hydroxyl value of polyol i S: Solid content of urethane resin weight

Furthermore, it is preferable to use 1 to 30% by mass of a polyether polyol having a number average molecular weight of 100 to 3500 as a raw material with respect to 100% by mass of the polyurethane resin (A). Although details will be described later, examples of the polyether polyol resin include polyether polyols of polymers or copolymers such as ethylene oxide, propylene oxide, and tetrahydrofuran. Specifically, a known general-purpose material such as a polyethylene glycol resin, a polypropylene glycol resin, or a polytetramethylene glycol resin may be used. By using the polyether polyol resin in the above-mentioned range, the adhesion 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 adhesiveness, blocking resistance and laminate strength on the high-performance barrier film, a polyethylene glycol resin is particularly preferable among the polyether polyol resins.
If the number average molecular weight of the polyether polyol resin, which is a constituent of the polyurethane resin (A) used in the soft packaging laminate ink composition of the present invention, is less than 100, the polyurethane resin (A) film tends to be hard. Adhesiveness to the polyester film is deteriorated. When the number average molecular weight is larger than 3500, the polyurethane resin (A) film tends to be brittle, so that the ink film has poor blocking resistance. When the polyether polyol resin is less than 1 part with respect to 100 parts of the polyurethane resin (A), the solubility of the urethane resin in ketones, esters, and alcohol solvents is deteriorated. Further, the re-solubility of the ink film in the solvent is deteriorated, and the tone reproducibility of the printed matter is inferior. Moreover, when it exceeds 30 parts, there exists a tendency for blocking resistance to be inferior.

  As the combined polyol used as needed for the polyurethane resin (A) used in the laminating ink composition for soft packaging of the present invention, various known polyols generally used in the production of polyurethane resins may be used. One or two or more may be used in combination. 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 soft packaging laminate ink composition of the present invention include various known aromatic diisocyanates, aliphatic diisocyanates, and alicyclic groups that are generally used in the production of polyurethane resins. And diisocyanate. 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 soft packaging laminate ink composition of the present invention include ethylenediamine, propylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, isophoronediamine, dicyclohexylmethane-4, In addition to 4'-diamine, 2-hydroxyethylethylenediamine, 2-hydroxyethylpropyldiamine, 2-hydroxyethylpropylenediamine, di-2-hydroxyethylethylenediamine, di-2-hydroxyethylenediamine, di-2-hydroxyethylpropylene Has a hydroxyl group in the molecule such as diamine, 2-hydroxypyrroleethylenediamine, di-2-hydroxypyrroleethylenediamine, di-2-hydroxypropylethylenediamine Amine can also 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 dialkylamines such as di-n-butylamine and alcohols such as ethanol and isopropyl alcohol. Furthermore, amino acids such as glycine and L-alanine can be used as a reaction terminator, particularly when it is desired to introduce a carboxyl group into the polyurethane resin. These end blockers can be used alone or in admixture of two or more.

  The polyurethane resin (A) used in the soft packaging laminating ink composition of the present invention is prepared by, for example, reacting polypropylene glycol and a combination polyol with a diisocyanate compound in an excess ratio of isocyanate groups, thereby prepolymer of terminal isocyanate groups. And the obtained prepolymer 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; acetone, methyl ethyl ketone, methyl isobutyl ketone Ketone solvents such as methanol, ethanol, isopropyl alcohol, alcohol solvents such as n-butanol, hydrocarbon solvents such as methylcyclohexane and ethylcyclohexane, or chain extenders among these solvents And / or by a two-stage method of reacting with an end-capping agent, or a one-step method of reacting polypropylene glycol and a combination polyol, diisocyanate compound, chain extender and / or end-capping agent at once in a suitable solvent. Manufactured. 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 laminating ink composition for soft packaging of the present invention in the ink is 4% based on the total weight of the ink from the viewpoint of sufficient adhesion of the ink to the printing medium. % To 25% by weight from the viewpoint of moderate ink viscosity and work efficiency at the time of ink production and printing, and more preferably in the range of 6 to 15% by weight.

  The urethane resin (A) used in the present invention can be used without particular limitation as long as it has the above-described composition. Among these, the active hydrogen-containing functional group in the polyurethane resin (A), for example, a hydroxyl group, primary, or A material containing a secondary amino group or the like is preferable because crosslinking of the polyurethane resin and the blocked isocyanate proceeds smoothly and the resulting printing ink layer becomes strong. In addition, even if the active hydrogen-containing functional group is not included in the urethane resin (A), if the ink layer is heated at a high temperature, the same result as in the case where the urethane resin (A) containing active hydrogen is used. Is obtained.

Next, the urethane resin (B) used in the present invention will be described.
The polyurethane resin (B) is an essential component for increasing moderate flexibility and 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 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.

  Examples of the compound having two or more hydroxyl groups include ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, diethylene glycol, triethylene glycol, and the like. Glycols such as ethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol; 2-methyl-1,5-pentanediol, 3-methyl-1, 5-pentanediol, 1,2-butanediol, 1,3-butanediol, 2-butyl-2-ethyl-1,3-propanediol, 1,2-propanediol, 2-methyl-1,3-propane Diol, neopentyl glycol, 2-i Propyl-1,4-butanediol, 2,4-dimethyl-1,5-pentanediol 2,4-diethyl-1,5-pentanediol, 2-ethyl-1,3-hexanediol, 2-ethyl-1 , 6-hexanediol, 3,5-heptanediol, glycol having a branched structure such as 2-methyl-1,8-octanediol; trimethylolpropane, trimethylolethane, pentaerythritol, sorbitol and the like can be used. These compounds 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. In addition, the number average molecular weight of the said polyester 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 polyisocyanate include 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 1-methyl-2,4-phenylene diisocyanate, 1-methyl-2,6-phenylene diisocyanate, 1-methyl-2, 5-phenylene diisocyanate, 1-methyl-2,6-phenylene diisocyanate, 1-methyl-3,5-phenylene diisocyanate, 1-ethyl-2,4-phenylene diisocyanate, 1-isopropyl-2,4-phenylene diisocyanate, 1 , 3-dimethyl-2,4-phenylene diisocyanate, 1,3-dimethyl-4,6-phenylene diisocyanate, 1,4-dimethyl-2,5-phenylene diisocyanate, diethylbenzene diisocyanate, diisopropylbenzene Zendiisocyanate, 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, 2,2′-diphenylmethane dii Soshi And aromatic polyisocyanates such as diphenylmethane-2,4-diisocyanate; tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, dodecamethylene diisocyanate, trimethylhexamethylene diisocyanate, 1,3-cyclopentylene diisocyanate, 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'-dicyclohexylmethane diisocyanate, 3,3'-di Aliphatic or alicyclic polyisocyanates such as methyl-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.

  Examples of the chain extender having two or more hydroxyl groups include ethylene glycol, diethylene recall, triethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, hexa Aliphatic polyols such as methylene glycol, saccharose, methylene glycol, glycerin, sorbitol; bisphenol A, 4,4′-dihydroxydiphenyl, 4,4′-dihydroxydiphenyl ether, 4,4′-dihydroxydiphenylsulfone, hydrogenated bisphenol A, A compound having a number average molecular weight in the range of 50 to 400 such as an aromatic polyol such as hydroquinone can be used. These chain extenders may be used alone or in combination of two or more. The number average molecular weight of the chain extender indicates a value obtained by measurement in the same manner as the number average molecular weight of the polyol.

  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.

  As a method for producing by solution polymerization, for example, the polyisocyanate is added after stirring the polyol, the organic solvent (E) described later, and a chain extender having two or more hydroxyl groups as necessary. 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 the flexibility and the laminate strength can be maintained at a high level. More preferably, it is in the range of ˜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 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 the flexibility and adhesion to the flexible packaging material and the laminate strength can be maintained at a high level. It is more preferable. 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 the flexibility and adhesion to the flexible packaging material and the laminate strength can be maintained at a high level, and 600 to A range of 800% is more preferable. 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 laminate ink composition for soft packaging of the present invention, the suitability of boiling and retort is further improved by adding the vinyl chloride-vinyl acetate copolymer resin (C) having a hydroxyl group.

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

  The vinyl chloride vinyl acetate copolymer resin having a hydroxyl group used in 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 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 flexible packaging, it is necessary to satisfy all of these properties: adhesiveness, anti-blocking, laminate strength, boil retort suitability, print suitability, so vinyl chloride vinyl acetate copolymer resin with hydroxyl groups is appropriate Monomer ratios exist. That is, 80 to 95 parts by weight of vinyl chloride is preferable with respect to 100 parts by weight of vinyl chloride vinyl acetate copolymer resin having a hydroxyl group. If it is less than 80 parts by weight, the resin film has poor toughness and the blocking resistance is lowered. If it exceeds 95 parts by weight, the resin coating becomes too hard and the adhesiveness is lowered. 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 boil and retort becomes poor.

  Examples of the colorant (D) used in 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 (E) used in the present invention will be described. In the soft packaging laminate ink composition of the present invention, for example, aromatic organic solvents, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, n-propyl acetate, butyl acetate, propylene glycol monomethyl ether acetate, etc. Examples include ester solvents, 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 laminate ink composition for soft packaging according to the present invention as needed include resins other than the polyurethane resin and vinyl chloride-vinyl acetate copolymer resin, for example, chlorinated polypropylene resin, ethylene-acetic acid Vinyl copolymer resin, vinyl acetate resin, polyamide resin, acrylic resin, polyester resin, alkyd resin, polyvinyl chloride resin, rosin resin, rosin modified maleic acid resin, ketone resin, cyclized rubber, chlorinated rubber, butyral, petroleum Examples thereof include resins. 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 weight, more preferably 2 to 15% by weight, based on the total weight of the ink.

  In the present invention, a combination resin, extender pigment, pigment dispersant, leveling agent, antifoaming agent, wax, plasticizer, infrared absorber, ultraviolet absorber, fragrance, flame retardant and the like can also be included as necessary. .

  In order to stably disperse the pigment in the organic solvent, it is possible to disperse the resin alone, but it is also possible to use a dispersant in order to disperse the pigment stably. 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 laminate ink composition for soft packaging 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. be able to. 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 ink composition of the present invention, there are five basic colors such as yellow, red, indigo, black, and white, depending on the type of colorant used, and red (orange) as the process gamut external color, There are three colors: grass (green) and 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, and 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 weight.
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: 1.0% by weight. Sample injection volume: 100 microliters. Detector: differential refractometer.
The viscosity was measured at 25 ° C. with a Tokimec B-type viscometer.

(Synthesis Example 1)
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 prepared 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 weight. 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-1 was obtained by stirring for a time. The obtained polyurethane resin solution A-1 has a resin solid content concentration of 30.4% by weight, a urea bond concentration = {(29.68 ÷ 222 × 2- (80 × 56.6 + 20 × 278) ÷ 56100) × 1000 / 137.76 = 0.64 mmol / g, and the weight average molecular weight (hereinafter referred to as Mw) of the resin solid content was 54,000.

(Synthesis Example 2)
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: 111 mgKOH / g) and isophorone diisocyanate (22.54 parts) were allowed to react at 90 ° C. for 10 hours under a nitrogen stream to produce a urethane prepolymer having an isocyanate group content of 2.84% by weight. Then, 66.0 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 7.25 parts of isophoronediamine, 0.27 parts of di-n-butylamine, 131.3 parts of ethyl acetate and 106.2 parts of isopropyl alcohol, The polyurethane resin solution A-2 was obtained by stirring for a time. The obtained polyurethane resin solution A-2 had a resin solid content concentration of 30.2% by weight, a urea bond concentration of 0.64 mmol / g by the same calculation method as in Synthesis Example 1, and a resin solid content Mw of 50,000. Met.

(Synthesis Example 3)
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 polypropylene glycol (hydroxyl value: 111 mgKOH / g) and isophorone diisocyanate (22.54 parts) were allowed to react at 90 ° C. for 10 hours under a nitrogen stream to produce a urethane prepolymer having an isocyanate group content of 2.84% by weight. Then, 66.0 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 7.25 parts of isophoronediamine, 0.27 parts of di-n-butylamine, 131.3 parts of ethyl acetate and 106.2 parts of isopropyl alcohol, The polyurethane resin solution A-3 was obtained by stirring for a time. The obtained polyurethane resin solution A-3 had a resin solid content concentration of 30.0% by weight, a urea bond concentration of 0.64 mmol / g by the same calculation method as in Synthesis Example 1, and a resin solid content Mw of 50,000. Met.

(Synthesis Example 4)
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 polytetramethylene glycol (hydroxyl value: 111 mgKOH / g) and 22.54 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 weight. 0 parts 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, 131.3 parts of ethyl acetate and 106.2 parts of isopropyl alcohol, The polyurethane resin solution A-4 was obtained by stirring for a period of time. The obtained polyurethane resin solution A-4 had a resin solid content concentration of 30.0% by weight, the urea bond concentration was 0.64 mmol / g by the same calculation method as in Synthesis Example 1, and the resin solid content Mw was 50,000. Met.

(Synthesis Example 5)
A four-necked flask equipped with a stirrer, a thermometer, a reflux condenser and a nitrogen gas inlet tube was charged with 100 parts of neopentyl glycol adipate diol (hydroxyl value: 56.6 mgKOH / g) and 20.22 parts of isophorone diisocyanate. After making it react at 90 degreeC under airflow for 10 hours and producing the urethane prepolymer with an isocyanate group content rate of 2.84 weight%, 64.7 parts of ethyl acetate was added to this, and it was set as the uniform solution of the urethane prepolymer. Next, the urethane prepolymer solution was added to a mixture consisting of 7.12 parts of isophoronediamine, 0.27 parts of di-n-butylamine, 128.8 parts of ethyl acetate and 104.2 parts of isopropyl alcohol, The polyurethane resin solution A-5 was obtained by stirring reaction for a period of time. The obtained polyurethane resin solution A-5 had a resin solid content concentration of 30.0% by weight, a urea bond concentration of 0.64 mmol / g, and a resin solid content Mw of 48,000 according to the same calculation method as in Synthesis Example 1. Met.

(Synthesis Example 6)
A four-necked flask equipped with a stirrer, thermometer, reflux condenser and nitrogen gas inlet tube was charged with 100 parts of neopentyl glycol adipate diol (hydroxyl value: 30.1 mg KOH / g) and 13.78 parts of isophorone diisocyanate, and nitrogen was added. After making it react at 90 degreeC under airflow for 10 hours and manufacturing the urethane prepolymer with an isocyanate group content rate of 2.60 weight%, 61.3 parts of ethyl acetate was added to this, and it was set as the uniform solution of the urethane prepolymer. Next, the urethane prepolymer solution was added to a mixture consisting of 6.06 parts of isophoronediamine, 0.45 parts of di-n-butylamine, 121.1 parts of ethyl acetate and 98.2 parts of isopropyl alcohol, A polyurethane resin solution A-6 was obtained by stirring for a period of time. The obtained polyurethane resin solution A-6 had a resin solid content concentration of 30.0% by weight, the urea bond concentration was 0.59 mmol / g by the same calculation method as in Synthesis Example 1, and the resin solid content Mw was 40,000. Met.

(Synthesis Example 7)
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 Example 8)
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 hydroxyl group used in combination with polyurethane resin (resin monomer composition is vinyl chloride / vinyl acetate / vinyl alcohol = 92/3/5, hydroxyl value (mgKOH) = 64 in weight%) acetic acid A 15% solution was made with ethyl, and this was made into a vinyl chloride resin solution (C-1).

[Example 1]
28 parts of the obtained polyurethane resin solution A-1, 3 parts of the polyurethane resin solution (B-1), 30 parts of vinyl chloride vinyl acetate copolymer resin solution C-1 having a hydroxyl group (15% solution), phthalocyanine blue A blue printing ink was prepared by kneading a mixture of 10 parts of pigment (FASTGEN Blue LA5380 manufactured by DIC Corporation) and 29 parts of ethyl acetate.
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 of 35 μm Film (W, X, Y, Z), corona-treated nylon film (hereinafter NY film: manufactured by Unitika Ltd., trade name emblem ON thickness 15 μm) and corona-treated polyester film (hereinafter PET film: manufactured by Toyobo Co., Ltd.) Name Ester E5102 (thickness: 12 μm) and dried at 40-50 ° C. to obtain a printed matter.
About the obtained printed matter, the adhesiveness to various barrier films, blocking resistance, and the lamination strength to NY film and PET film were measured and evaluated. The results are shown in Table 1. 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.
○: The printed film was not peeled off at all.
Δ: 50 to 80% of the printed film remained on the film.
X: 50% or less of the printed film remained in 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, the mixture is allowed to elapse for 12 hours in an environment of 40 ° C., and the ink is transferred to the non-printed surface after removal. The state of was visually evaluated in three stages.
○: No transfer is observed when the amount of ink transferred to the non-printing surface is 0%. Δ: Transfer is less than 20%. ×: Transfer amount is 20% or more. 3) Measurement of laminate strength (1) (PET film, NY film)
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 conducted a 90 ° peel test (measurement of laminate strength before retorting) at a pulling speed of 300 mm / min. It was. 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-degree peel test (measurement of laminate strength after the retort treatment) in the same manner as described above.
4) Measurement of 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, and then cut into a 15 mm width and subjected to a 90 ° peel test (measurement of laminate strength before retorting) at a pulling speed of 300 mm / min. .

[Examples 1 to 14, Comparative Examples 1 to 6]
Inks were prepared in the same manner as in Example 1, with Examples 1 to 14 having the composition shown in Tables 1 and 2, and Comparative Examples 1 to 6 having the composition shown in Table 3.

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 in the table is an abbreviation for FILM CUT and represents that the film is broken during measurement. The laminate strength is higher as it exceeds the film strength, indicating superiority.
Therefore, when laminating the ink composition for laminating soft packaging of the present invention on various films, it is excellent in adhesion and blocking resistance and lamination strength before and after retorting.

  The ink composition for laminating soft packaging according to the present invention exhibits high adhesiveness and block resistance, and has high lamination strength both before and after the retort treatment, even if it is a highly functional film subjected to a wide variety of barrier treatments. As an ink composition for laminating soft packaging having a wide variety of film configurations, it can be widely used for industrial products such as food packaging materials, sanitary products, cosmetics and electronic parts.

Claims (10)

  Contains a polyurethane resin (A) having a urea bond, a polyurethane resin (B) having no urea bond, a vinyl chloride vinyl acetate copolymer resin (C) having a hydroxyl group, a colorant (D) and an organic solvent (E). A laminate ink composition for soft packaging, characterized in that.   The laminate ink composition for soft packaging according to claim 1, wherein the polyurethane resin (A) has a weight average molecular weight in the range of 10,000 to 100,000.   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, and the content ratio of the polyether polyol is 1 to 30% by weight based on the polyurethane resin. Or the laminating ink composition for soft packaging of 2.   The laminate ink composition for flexible packaging according to any one of claims 1 to 3, wherein the polyurethane resin (B) has a weight average molecular weight in the range of 10,000 to 100,000.   The softening temperature of the said polyurethane resin (B) is the range of 40-80 degreeC, The laminate ink composition for soft packaging as described in any one of Claims 1-4.   The laminate ink composition for flexible packaging according to any one of claims 1 to 5, wherein the polyurethane resin (B) is made from an aliphatic polyisocyanate and / or an alicyclic polyisocyanate.   The laminate ink composition for flexible packaging according to any one of claims 1 to 6, wherein the polyurethane resin (B) is made from a polyester polyol as a raw material.   The hydroxyl value of the vinyl chloride vinyl acetate copolymer resin (C) having a hydroxyl group is 50 to 200 mg KOH / g, and the content ratio of the vinyl chloride component in the copolymer resin is 80 to 95% by weight. Item 8. The laminated ink composition for soft packaging according to any one of Items 1 to 7. The laminate ink composition for flexible packaging according to any one of claims 1 to 8, wherein the organic solvent ( E ) is an organic solvent having no aromatic group.
The printed matter formed by printing the laminate ink composition for soft packaging as described in any one of Claims 1-9.