JP5848837B1 - Laminating ink composition for flexible packaging - Google Patents

Abstract

The object of the present invention is to provide a laminate ink composition for flexible packaging that is excellent in polyethylene extrusion laminate strength and suitability on various high-performance films, as well as being applicable to a wide variety of films. The purpose is to do. A binder resin containing a polyurethane resin having a number average molecular weight of 15,000 to 100,000 and a urethane bond concentration of 0.6 mmol / g or more, a colorant and an organic solvent are contained as essential components. 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 polyethylene extrusion laminating that can exhibit very good adhesion performance to a printed laminate substrate, and is a flexible packaging laminate for various films coated with inorganic or organic barrier coating materials. The present invention relates to an ink composition.

Polyethylene extruded laminate films are widely used as food packaging materials. A polyethylene extruded laminate film is produced by melt-extruding polyethylene and laminating it onto a laminate base film such as a biaxially stretched polyester film, a biaxially stretched polyamide film, or a biaxially stretched polypropylene film. In particular, in the case of a biaxially stretched polypropylene base material, there is a tendency that the extrusion laminate strength tends to be insufficient. Therefore, a laminate ink having an excellent laminate strength is desired.
In recent years, among the films used for film packages, high-functional films imparted with various barrier properties tend to increase. These high-performance films have an inorganic or organic barrier coating applied on the surface, and when these high-performance films are used as gravure or flexographic printing, the adhesion between the film and the ink is inhibited. When stored in a wound state, the ink film moves to a non-printing surface (blocking phenomenon), often causing trouble. These high-performance films exist in a wide variety depending on the type of business and purpose, such as oxygen barriers that block air and water vapor barriers that block water vapor for food and electronic parts to prevent the contents from being altered. Also, there are many technically undisclosed ones, and the current situation is that it is difficult to cope with compared with general film printing.

For example, in Patent Document 1 (Japanese Patent Application Laid-Open No. 2005-298618), a specific polyurethane resin and a vinyl chloride vinyl acetate copolymer resin having a hydroxyl group are used in a specific ratio, thereby providing excellent adhesion to a wide variety of films. The laminate ink for soft packaging having blocking resistance, laminate strength and suitability for boil retort is exemplified, but the above-mentioned extrusion laminate strength is not sufficient.
Conventionally, such soft packaging laminate products have improved the high adhesion to the substrate and the laminate strength by adding a silane coupling agent to the printing ink with polyurethane resin as a binder. It is illustrated (for example, patent document 2: Unexamined-Japanese-Patent No. 2001-2971). However, while the types of high-performance films are diversified, the adhesiveness to the printing medium and the laminate strength are still not sufficient. It is desired that high adhesiveness and laminate strength can be maintained for a wider range of high-performance films.

JP 2005-298618 A JP 2001-2971 A

  The object of the present invention is to provide a laminate ink composition for flexible packaging that is excellent in polyethylene extrusion laminate strength and suitability on various highly functional films, as well as being applicable to a wide variety of films. To do.

  As a result of intensive studies to solve the above-mentioned problems, the inventors of the present invention contain a polyurethane resin having a specific molecular weight and urethane bond concentration, a colorant, and an organic solvent as essential components in a laminating ink for flexible packaging. It was found that doing this is effective in solving the problem.

That is, the present invention contains a binder resin containing a polyurethane resin having a weight average molecular weight of 15,000 to 100,000 and a urethane bond concentration of 0.6 mmol / g or more, a colorant, and an organic solvent as essential components. The present invention relates to a laminate ink composition for soft packaging.
The present invention also relates to a laminate ink composition for soft packaging, which contains 1 to 30% by weight of a polyether polyol resin in the polyurethane resin.
The present invention also relates to a laminate ink composition for soft packaging containing a vinyl chloride-vinyl acetate copolymer resin having a hydroxyl group.
Furthermore, in the present invention, the vinyl chloride vinyl acetate copolymer resin 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 weight. The present invention relates to a laminate ink composition for soft packaging.
Further, the present invention relates to a laminate ink composition for soft packaging containing cellulose acetate pyropionate.
The present invention also relates to a laminate ink composition for soft packaging, wherein the organic solvent is an organic solvent having no 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, a laminate ink composition for flexible packaging having excellent adhesion and blocking resistance to a wide variety of films can be 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 contains a binder resin containing a polyurethane resin, a colorant and an organic solvent, wherein the weight average molecular weight is 15,000 to 100,000 and the urethane bond concentration is 0.6 mmol / g or more. A laminating ink composition for soft packaging.

  Specifically, in the laminating ink composition for soft packaging of the present invention, the binder resin containing the polyurethane resin is preliminarily mixed with various organic solvents such as ethyl acetate, methyl ethyl ketone, toluene, 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 polyurethane resin used in the ink composition for a soft packaging laminate of the present invention contains 1 to 30 parts of a polyether polyol resin having a number average molecular weight of 100 to 3500 with respect to 100 parts of the polyurethane resin. preferable. 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 containing the polyether resin in the above 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 improved.
When the number average molecular weight of the polyether polyol resin, which is a component of the polyurethane resin used in the soft packaging laminate ink composition of the present invention, is less than 100, the polyurethane resin film tends to be hard and adheres to the polyester film. Becomes worse. When the number average molecular weight is larger than 3500, the polyurethane resin film tends to be brittle, and the blocking resistance of the ink film is deteriorated. When the polyether polyol resin is less than 1 part with respect to 100 parts of the polyurethane resin, the solubility of the urethane resin in ketones, esters, and alcohol solvents is deteriorated. In addition, 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 necessary for the polyurethane resin used in the soft packaging laminate ink composition of the present invention, various known polyols generally used in the production of polyurethane resins can be used. You may use a seed | species or 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, and 2-methyl-1,3-propane Diol, 2ethyl-2butyl-1,3-propanediol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, pentanediol, 3-methyl-1,5-pentanediol, hexanediol, octanediol 1,4-butynediol, 1,4-butylenediol, diethylene glycol, triethylene glycol, dipropylene glycol, glycerin, trimethylolpropane, trimethylolethane, 1,2,6-hexanetriol, 1,2,4- Butanetriol, Saturated or unsaturated low molecular polyols (2) such as rubitol and pentaerythritol; these low molecular polyols (2) and adipic acid, phthalic acid, isophthalic acid, terephthalic acid, maleic acid, fumaric acid, Dehydration condensation or polymerization of polycarboxylic acids such as 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 obtained (3); 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, dipheny Polycarbonate polyols obtained by reaction with carbonate, ethylene carbonate, phosgene, etc. (5); polybutadiene glycols (6); glycols obtained by adding ethylene oxide or propylene oxide to bisphenol A (7); in one molecule Acrylic polyol obtained by copolymerizing, for example, acrylic acid, methacrylic acid or an ester thereof with one or more hydroxyethyl, hydroxypropyl acrylate, acrylhydroxybutyl, etc., or their corresponding methacrylic acid derivatives, etc. (8).

  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 in the soft packaging laminate 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. Can be mentioned. 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.

The chain extender used in the polyurethane resin in the soft packaging laminate ink composition of the present invention includes ethylenediamine, propylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, isophoronediamine, dicyclohexylmethane-4,4'- Other than diamine, 2-hydroxyethylethylenediamine, 2-hydroxyethylpropyldiamine, 2-hydroxyethylpropylenediamine, di-2-hydroxyethylethylenediamine, di-2-hydroxyethylenediamine, di-2-hydroxyethylpropylenediamine, 2 -Amino having a hydroxyl group in the molecule, such as hydroxypropylethylenediamine, di-2-hydroxypropylethylenediamine, and di-2-hydroxypropylethylenediamine 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 used in the ink composition for laminating soft packaging of the present invention is, for example, by reacting polypropylene 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 obtained prepolymer is used 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; a ketone such as acetone, methyl ethyl ketone or methyl isobutyl ketone. Solvent solvents such as methanol, ethanol, isopropyl alcohol and n-butanol; hydrocarbon solvents such as methylcyclohexane and ethylcyclohexane; Or) produced by a two-stage method of reacting with an end-capping agent, or a one-stage method in which polypropylene glycol and a combination polyol, diisocyanate compound, chain extender and / or end-capping agent are reacted at once in a suitable solvent. The Among these methods, it is preferable to use a two-stage method in order to obtain a uniform polyurethane resin. Moreover, when producing a polyurethane resin by a two-stage method, it is made to react so that the total (equivalent ratio) of the amino group of a chain extender and / or terminal blocker may become a ratio of 1 / 0.9-1.3. It is preferable. 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 thus obtained is preferably in the range of 15,000 to 100,000, more preferably in the range of 15,000 to 80,000. When the weight average molecular weight of the polyurethane resin is less than 15,000, there is a tendency that the blocking resistance of the ink composition obtained, the strength of the printed film, the oil resistance, and the like tend to be low. The viscosity of the resulting ink composition tends to increase, and the gloss of the printed film tends to decrease.
The content of the polyurethane resin used in the laminating ink composition for soft packaging of the present invention in the ink is 4% by weight or more based on the total weight of the ink from the viewpoint of sufficient adhesion of the ink to the printing medium, From the viewpoint of appropriate ink viscosity and work efficiency during ink production and printing, it is preferably 25% by weight or less, and more preferably in the range of 6 to 15% by weight.

  The urethane resin used in the present invention can be used without any particular limitation as long as it has the above-described composition. Among these, active hydrogen-containing functional groups in the urethane resin, such as hydroxyl groups, primary, or secondary amino groups, etc. It is preferable because the crosslinking of urethane resin and blocked isocyanate proceeds smoothly and the resulting printing ink layer becomes strong. Even if the urethane resin does not contain an active hydrogen-containing functional group, if the ink layer is heated at a high temperature, the same result as that obtained when a urethane resin containing active hydrogen is used can be obtained.

The urethane bond concentration of the urethane resin used in the present invention is preferably 0.6 mmol / g or more and 2.5 mmol / g or less, and more preferably 0.6 mmol / g or more and 2.0 mmol / g or less. More preferred. When the urethane bond concentration is 0.6 mmol / g or more, the polyethylene extrusion laminate strength is particularly excellent. 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.
W ₁ : Weight of polyol 1
OH ₁ : hydroxyl value of polyol 1
W2: Weight of polyol 2
OH ₂ : hydroxyl value of polyol 2
W _i : Weight of polyol i
OH _i : hydroxyl value of polyol i
S: Weight of urethane resin solids

  In the soft packaging laminate ink composition of the present invention, an organic solvent other than the aromatic organic solvent can be used. For example, ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, ethyl acetate, n-propyl acetate, Examples include ester solvents such as butyl acetate and propylene glycol monomethyl ether acetate, and alcohol solvents such as n-propanol, inopropanol, n-butanol and propylene glycol monomethyl ether, and these may be used alone or in a mixture of two or more. Can do. In recent years, it is desirable not to use aromatic solvents such as toluene and xylene from the viewpoint of working environment.

  Furthermore, in the ink composition for laminating soft packaging of the present invention, a vinyl chloride-vinyl acetate copolymer resin having a hydroxyl group can be used.

  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 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.

  Examples of the colorant 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.

  When the printing ink of the present invention is used in combination with cellulose acetate propionate resin, the blocking resistance can be further improved. In the present invention, the inclusion of a polyether polyol resin in the polyurethane resin improves the adhesion to the substrate, resulting in improved blocking resistance. In addition to this, cellulose acetate pro The combined use of the pionate resin increases the hardness of the ink film and suppresses the transfer of ink to the non-printing surface in a state where the printing film is wound up. As addition amount of cellulose acetate propionate resin, it is preferable that it is 0.1 to 10 weight% in solid content. If it is less than 0.1% by weight, the expected blocking resistance is not improved, and if it exceeds 10% by weight, the storage stability in the ink is impaired.

The cellulose acetate propionate resin used in the present invention is obtained by hydrolysis after cellulose esterification with cellulose, acetic acid and propionic acid. Acetylation of 0.6 to 2.5% by weight, propionation of 42 to 46% by weight, and hydroxyl group of 1.8 to 5% are commercially available from Eastman Chemical.

  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 laminating 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 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) and grass (colors outside the process gamut) There are three colors, 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)
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 was obtained by stirring for a time. The obtained polyurethane resin solution A has a resin solid content concentration of 30.0% by weight, a resin solid content weight average molecular weight (hereinafter referred to as Mw) of 48,000, and a urethane bond concentration of {(100 × 56.6). ) × 1000} / (56100 × 127.61) = 0.79 mmol / g.

(Synthesis Example 2)
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: 109.8 mg KOH / g) and 29.50 parts of isophorone diisocyanate, and nitrogen was added. After reacting at 90 ° C. for 10 hours under an air stream to produce a urethane prepolymer having an isocyanate group content of 2.27% by weight, 70.99 parts of ethyl acetate was added thereto to obtain a uniform solution of the urethane prepolymer. Subsequently, the urethane prepolymer solution was added to a mixture consisting of 7.78 parts of isophoronediamine, 0.59 parts of di-n-butylamine, 141.7 parts of ethyl acetate and 114.5 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 30.9% by weight, a resin solid content Mw of 38,000, and the urethane bond concentration was 1.40 mmol / g by the same calculation method as in Synthesis Example 1. 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 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, 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 30.2% by weight, a resin solid content Mw of 50,000, and a urethane bond concentration of 0.93 mmol / g by the same calculation method as in Synthesis Example 1. 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 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 D was obtained by stirring for a time. The obtained polyurethane resin solution D had a resin solid content concentration of 30.0% by weight, a resin solid content Mw of 50,000, and a urethane bond concentration of 0.93 mmol / g by the same calculation method as in Synthesis Example 1. Met.

(Synthesis Example 5)
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 E was obtained by stirring for a time. The obtained polyurethane resin solution E had a resin solid content concentration of 30.0% by weight, a resin solid content Mw of 50,000, and a urethane bond concentration of 0.93 mmol / g by the same calculation method as in Synthesis Example 1. Met.

(Synthesis Example 6)
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, 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 weight, a resin solid content Mw of 54,000, and the urethane bond concentration was 1.31 mmol / g by the same calculation method as in Synthesis Example 1. Met.

(Synthesis Example 7)
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 mg KOH / 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 weight. 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 7.84 parts of isophoronediamine, 0.4 part of di-n-butylamine, 136.8 parts of ethyl acetate and 110.7 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 30.0% by weight, a weight average molecular weight of resin solid content of 45,000, and a urethane bond concentration of 1.20 mmol by the same calculation method as in Synthesis Example 1. / G.

(Synthesis Example 8)
In a four-necked flask equipped with a stirrer, thermometer, reflux condenser and nitrogen gas inlet tube, 84.5 parts of neopentyl glycol adipate diol (hydroxyl value: 56.6 mgKOH / g) and 15.5 parts of polyethylene glycol (hydroxyl group) (Valence: 278 mg KOH / g) and 27.55 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. 68.7 parts was added to make a uniform solution of urethane prepolymer. Next, the urethane prepolymer solution was added to a mixture consisting of 7.83 parts of isophoronediamine, 0.11 part of di-n-butylamine, 136.8 parts of ethyl acetate, and 110.7 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 weight, a resin solid content Mw of 54,000, and the urethane bond concentration was 1.20 mmol / g by the same calculation method as in Synthesis Example 1. Met.

(Synthesis Comparative Example 1)
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 I was obtained by stirring for a period of time. The obtained polyurethane resin solution I had a resin solid content concentration of 30.0% by weight, a resin solid content Mw of 40,000, and the urethane bond concentration was 0.45 mmol / g by the same calculation method as in Synthesis Example 1. Met.

(Synthesis Comparative Example 2)
In a four-necked flask equipped with a stirrer, thermometer, reflux condenser and nitrogen gas inlet tube, 90 parts of neopentyl glycol adipate diol (hydroxyl value: 21.2 mgKOH / g) and 10 parts of polyethylene glycol (hydroxyl value: 111 mgKOH / g) and 13.79 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 2.60% by weight. Was added to obtain a uniform solution of urethane prepolymer. Next, the urethane prepolymer solution was added to a mixture consisting of 6.06 parts of isophorone diamine, 0.45 parts of di-n-butylamine, 121.2 parts of ethyl acetate and 98.3 parts of isopropyl alcohol. 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 30.6% by weight, a resin solid content Mw of 70,000, and the urethane bond concentration was 0.45 mmol / g by the same calculation method as in Synthesis Example 1. Met.

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 prepared with ethyl, and this was made into a vinyl chloride resin solution K.

(Adjustment example 1)
Cellulose acetate propionate resin has an acetyl group content of 2.5% by weight, a propionyl group content of 45% by weight, a hydroxyl group content of 2.6% by weight, and a glass transition temperature of 142 ° C. “CAP-”. What dissolved 504-0.2 "in the following ratio was used. This was designated as CAP resin solution L.

Cellulose acetate propionate resin 20% by weight
Ethyl acetate 40%
Isopropyl alcohol 40%

[Example 7 ]
30 parts of the obtained polyurethane resin solution F , 30 parts of a vinyl acetate resin solution K having a hydroxyl group (15% solution), 10 parts of a phthalocyanine blue pigment (FASTGEN Blue LA5380 manufactured by DIC Corporation), 30 parts of ethyl acetate, The mixture was kneaded to create a blue printing ink.
The viscosity of the obtained printing ink was adjusted to 16 seconds (25 ° C.) with Zahn cup # 3 (manufactured by Kouaisha) with ethyl acetate, and shown in Tables 1 and 2 using a gravure proofing machine equipped with a 35 μm gravure printing plate. It printed on various barrier films (W, X, Y, Z) and a biaxially stretched polypropylene film (henceforth OPP), and dried at 40-50 degreeC, and the printed matter was obtained.
About the obtained printed matter, the adhesiveness to various barrier films, blocking resistance, the adhesiveness to an OPP film, and extrusion laminate strength were measured and evaluated. The results are shown in Table 1. The evaluation was performed by the following test method.
1) Adhesiveness (common to various barrier films and OPP films)
After leaving the printed matter for 1 day, a cellophane tape was applied 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 only)
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 observed when the amount of ink transferred to the non-printing surface is 0% Δ: Transfer is observed at a rate of less than 20% ×: Transfer is achieved at a rate of 20% or more 3) Extrusion laminate strength Measurement (OPP film only)
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 degree peel test was conducted at a pulling speed of 50 mm / min.

[Example 9, Comparative Examples 1 to 9 ]
Inks were prepared for Example 9 and Comparative Examples 1 to 9 in the same manner as Example 7 with the composition shown in Table 1.

In Examples 7 and 9 , both the adhesion to the barrier film and the OPP film and the blocking resistance to the barrier film were good results.

  The laminating ink composition for soft packaging according to the present invention exhibits high adhesiveness and block resistance even when it is a highly functional film subjected to various types of barrier treatments, and further exhibits high extrusion lamination on an OPP film. As an ink composition for laminate for soft packaging having strength, it can be widely used for industrial products such as food packaging materials, sanitary products, cosmetics and electronic parts.

Claims (6)

The binder resin having a weight average molecular weight containing a polyurethane resin 15,000 to 100,000 and the urethane bond concentration is less than 1.2 mmol / g or more 2.5 mmol / g, the soft packaging you a colorant and an organic solvent A laminating ink composition comprising 1 to 30% by weight of a polyether resin in the polyurethane resin. The ink composition for laminating for soft packaging according to claim 1, comprising a vinyl chloride vinyl acetate copolymer resin having a hydroxyl group. The hydroxyl value of the vinyl chloride-vinyl acetate copolymer resin having a hydroxyl group, a 50 to 200 / g, and in claim 2 content ratio of the vinyl chloride component in the copolymer resin is 80 to 95 parts by weight The laminating ink composition for soft packaging as described. Cellulose acetate propionate is contained, The laminate ink composition for flexible packaging as described in any one of Claims 1-3 characterized by the above-mentioned. The laminate ink composition for flexible packaging according to any one of claims 1 to 4 , wherein the organic solvent is an organic solvent having no aromatic group. A printed matter obtained by printing the laminating ink composition for soft packaging according to any one of claims 1 to 5 .