WO2018066699A1 - Laminate printing ink composition for soft packaging - Google Patents

Laminate printing ink composition for soft packaging Download PDF

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Publication number
WO2018066699A1
WO2018066699A1 PCT/JP2017/036511 JP2017036511W WO2018066699A1 WO 2018066699 A1 WO2018066699 A1 WO 2018066699A1 JP 2017036511 W JP2017036511 W JP 2017036511W WO 2018066699 A1 WO2018066699 A1 WO 2018066699A1
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WIPO (PCT)
Prior art keywords
mass
parts
diisocyanate
polyurethane resin
ink composition
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PCT/JP2017/036511
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French (fr)
Japanese (ja)
Inventor
小川　徹
淳一 原田
健太 赤坂
恭平 小林
Original Assignee
サカタインクス株式会社
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Application filed by サカタインクス株式会社 filed Critical サカタインクス株式会社
Priority claimed from JP2017195654A external-priority patent/JP7002905B2/en
Publication of WO2018066699A1 publication Critical patent/WO2018066699A1/en

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/102—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds

Definitions

  • the present invention relates to a laminating printing ink composition for soft packaging, and more particularly to a laminating printing ink composition for soft packaging having good printability, blocking resistance, impression cylinder stain, laminating suitability and the like.
  • Packaging materials using various plastic films are used for foods, confectionery, household goods, pet foods, and the like because of their functions such as design, economy, contents protection, and transportability. Further, many packaging materials are subjected to gravure printing or flexographic printing for the purpose of imparting design and message characteristics appealing to consumers. And in order to obtain packaging materials for applications, surface printing printed on the surface of the base material film of the packaging material, or applying an adhesive or anchor agent to the printed surface of the base material film of the packaging material as necessary, Back-printing is performed by laminating the film. In reverse printing, color ink and white ink are sequentially printed on various films such as polyester, nylon, and aluminum foil, and then a dry laminating process using an adhesive or an anchor coating agent is applied on the printed layer of the white ink.
  • a polyethylene film, a polypropylene film or the like is laminated for the purpose of heat sealing by the extrusion laminating process used.
  • the polyisocyanate used in the polyurethane resin of the laminate printing ink composition for soft packaging isophorone diisocyanate is mainly used in the examples and the like (see, for example, Patent Documents 1 and 2).
  • Patent Documents 1 and 2 Japanese Patent Documents 1 and 2
  • a laminate printing ink composition for soft packaging having higher performance has been demanded.
  • an object of the present invention is to provide a laminating printing ink composition for soft packaging which has better printability, blocking resistance, impression cylinder stain, laminating suitability, etc. than conventional laminating printing ink compositions for soft packaging. .
  • the present inventors have reacted polyisocyanate containing dicyclohexylmethane 4,4′-diisocyanate with a polymer polyol as a polyurethane resin of a binder resin.
  • the present inventors have found that the above-mentioned problems can be solved by using a polyurethane resin. That is, the present invention is as follows. 1. A laminate printing ink composition for soft packaging comprising a pigment, a binder resin and an organic solvent as main components, wherein the binder resin reacts a polyisocyanate containing dicyclohexylmethane 4,4′-diisocyanate with a polymer polyol.
  • a laminate printing ink composition for soft packaging wherein the polyurethane resin is a polyurethane resin satisfying the following conditions (1) to (3): Condition (1)
  • the weight ratio of polyisocyanate other than dicyclohexylmethane 4,4′-diisocyanate and dicyclohexylmethane 4,4′-diisocyanate is dicyclohexylmethane 4,4′-diisocyanate / dicyclohexylmethane 4,4′-diisocyanate.
  • Polyisocyanate other than nate 100/0 to 5/95.
  • Condition (2) The use ratio of the polyisocyanate and the polymer polyol is in the range where the equivalent ratio of isocyanate group: hydroxyl group (isocyanate index) is 1.2 to 2.3.
  • Condition (3) The polyurethane resin has an amine value. 2.
  • the laminate printing ink composition for soft packaging further comprises at least one selected from a vinyl chloride / vinyl acetate copolymer having a hydroxyl group, nitrified cotton and / or cellulose acetate propionate resin. 5.
  • the “polyurethane resin having a primary amino group and / or a secondary amino group at the terminal” refers to the primary amino group at the terminal of all or part of the main chain and side chain of the polyurethane resin. It means having a group and / or a secondary amino group.
  • the laminate printing ink composition for soft packaging of the present invention will be described in more detail.
  • the pigment various inorganic pigments and organic pigments generally used in printing ink can be used.
  • the inorganic pigment examples include colored pigments such as titanium oxide, bengara, antimony red, cadmium yellow, cobalt blue, bitumen, ultramarine, carbon black, graphite, silica, calcium carbonate, kaolin, clay, barium sulfate, aluminum hydroxide.
  • An extender such as talc, an aluminum paste containing aluminum particles surface-treated with an acrylic resin, and a pearl pigment such as mica whose surface is coated with titanium oxide, tin oxide and zirconium oxide.
  • the organic pigment examples include soluble azo pigments, insoluble azo pigments, azo lake pigments, condensed azo pigments, copper phthalocyanine pigments, and condensed polycyclic pigments.
  • the content of the pigment in the laminate printing ink composition for soft packaging of the present invention is preferably in the range of 5 to 60% by mass in the ink composition.
  • the content of the pigment in the laminate printing ink composition is less than the above range, the coloring power as the ink composition is lowered, and when it is more than the above range, the viscosity of the ink composition is increased and the printed matter is easily stained. Become.
  • ⁇ Binder resin> Polyurethane resin having an amine value of 1 to 13 mgKOH / g obtained by reacting a polyisocyanate containing dicyclohexylmethane 4,4′-diisocyanate and a polymer polyol
  • the polyurethane resin it is preferable to use a polyurethane resin having an amine value of 1 to 13 mgKOH / g in view of pigment dispersibility, adhesion, laminating suitability and the like.
  • polyisocyanates other than dicyclohexylmethane 4,4′-diisocyanate include aromatic diisocyanate compounds such as tolylene diisocyanate, alicyclic diisocyanate compounds such as 1,4-cyclohexane diisocyanate and isophorone diisocyanate, and fats such as hexamethylene diisocyanate.
  • aromatic diisocyanate compounds such as tolylene diisocyanate
  • alicyclic diisocyanate compounds such as 1,4-cyclohexane diisocyanate and isophorone diisocyanate
  • fats such as hexamethylene diisocyanate.
  • a group obtained by mixing an aromatic diisocyanate compound and an araliphatic diisocyanate compound such as ⁇ , ⁇ , ⁇ ′, ⁇ ′-tetramethylxylylene diisocyanate alone or in combination of two or more thereof can be used.
  • Dicyclohexylmethane-2,4′-diisocyanate which is an isomer of dicyclohexylmethane 4,4′-diisocyanate, can also be used. Especially, it is preferable to use isophorone diisocyanate from the point of a film physical property and printability.
  • polymer polyol examples include polyalkylene glycols such as polyethylene glycol and polypropylene glycol, polyether diol compounds such as alkylene oxide adducts such as ethylene oxide and propylene oxide of bisphenol A, adipic acid, sebacic acid, and phthalic anhydride 1 type or 2 types or more of dibasic acids such as ethylene glycol, propylene glycol, 1,4-butanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, etc.
  • polyalkylene glycols such as polyethylene glycol and polypropylene glycol
  • polyether diol compounds such as alkylene oxide adducts such as ethylene oxide and propylene oxide of bisphenol A, adipic acid, sebacic acid, and phthalic anhydride 1 type or 2 types or more of dibasic acids
  • dibasic acids such as ethylene glycol, propylene glycol, 1,4-butanedi
  • polyester diol compounds such as polyester diol compounds such as polyester diols and polycaprolactone diols obtained by condensation reaction with at least one species may be used alone or in combination of two or more.
  • polymer polyols it is preferable to use a polymer polyester polyol or a combination of a polyester polyol and a polyether polyol from the viewpoint of laminating suitability and the like.
  • alkane diols such as 1,4-pentanediol, 2,5-hexanediol, 3-methyl-1,5-pentanediol, ethylene glycol, propylene glycol, 1,4 -Low molecular diol compounds such as butanediol and 1,3-butanediol can be used alone or in combination of two or more.
  • the use ratio of the polyisocyanate and the polymer polyol is in a range where the equivalent ratio of isocyanate group / hydroxyl group (isocyanate index (II)) is 1.2 to 2.3.
  • the polyurethane resin can be obtained by reacting the polyisocyanate and the polymer polyol by a known method to obtain a prepolymer, and then reacting a chain extender and, if necessary, a reaction terminator by a known method.
  • the amine value having a primary amino group and / or a secondary amino group at the terminal containing the above-mentioned polymer polyol and organic polyisocyanate compound as components from the viewpoint of pigment dispersibility, adhesiveness, laminate suitability, etc.
  • a polyurethane resin having an amine value of 1 to 13 mgKOH / g is preferred.
  • a polyurethane resin having an amino group having a primary amino group and / or a secondary amino group at the terminal can be obtained by any of the following methods (1) to (4).
  • a chain extender is added to a urethane prepolymer having an isocyanate group at the terminal obtained by reacting a polymer polyol and a polyisocyanate to carry out chain extension to obtain a urethane prepolymer having an isocyanate group at the terminal.
  • a reaction stopper other than a polyamine compound whose terminal is a primary amino group and / or a secondary amino group is reacted, and then a polyamine compound whose both ends are a primary amino group and / or a secondary amino group
  • a chain extender is added to a urethane prepolymer having an isocyanate group at the terminal obtained by reacting a polymer polyol and a polyisocyanate to carry out chain extension, and a urethane prepolymer having an isocyanate group at the terminal is obtained.
  • a terminator a reaction terminator which is a polyamine compound whose both ends are a primary amino group and / or a secondary amino group, and another terminal is a primary amino group and / or a secondary amino group.
  • a chain extender is added to a urethane prepolymer having an isocyanate group at the terminal obtained by reacting a polymer polyol and a polyisocyanate to carry out chain extension to obtain a urethane prepolymer having an isocyanate group at the terminal.
  • reaction terminator which is a polyamine compound whose terminal is a primary amino group and / or secondary amino group, and has a primary amino group and / or secondary amino group at the terminal, and has an amine value
  • a method for obtaining a polyurethane resin (4) A urethane prepolymer having an isocyanate group at a terminal obtained by reacting a polymer diol and a polyisocyanate is reacted with a polyamine compound having both ends of a primary amino group and / or a secondary amino group to react with a chain.
  • chain extender used in the above (1) to (3) known chain extenders used in polyurethane resins as binders for ink can be used, and ethylenediamine, propylenediamine, tetramethylenediamine, hexamethylene Aliphatic diamines such as diamine, isophorone diamine, alicyclic diamines such as 4,4'-dicyclohexylmethane diamine, polyamines such as diethylenetriamine and triethylenetetratriamine, aromatic diamines such as toluylenediamine, xylenediamine Diamines having a hydroxyl group such as N- (2-hydroxyethyl) ethylenediamine, N- (2-hydroxyethyl) propylenediamine, N, N′-di (2-hydroxyethyl) ethylenediamine, Ethylene glycol Propylene glycol, 1,4-butanediol, neopentyl glycol, diethylene glycol, can be used, and
  • Examples of the reaction terminator used in the above methods (1) and (2) include polyamine compounds, monoamine compounds and / or monoalcohol compounds in which both ends are primary amino groups and / or secondary amino groups.
  • a reaction terminator can be illustrated.
  • Examples of the reaction terminator used in the above method (3) include polyamine compounds whose both ends are a primary amino group and / or a secondary amino group.
  • the above polyurethane resin having an amino group is a polyamine having both ends of a primary amino group and / or a secondary amino group so that the amine value is 1 to 13 mgKOH / g from the viewpoint of storage stability and pigment dispersibility.
  • the reaction is preferably stopped with a compound.
  • Polyamine compounds having a primary amino group and / or a secondary amino group at both ends include aliphatic diamines such as ethylenediamine, propylenediamine, tetramethylenediamine, hexamethylenediamine, isophoronediamine, 4,4′- Alicyclic diamines such as dicyclohexylmethanediamine, polyamines such as diethylenetriamine and triethylenetetratriamine, aromatic diamines such as toluylenediamine, araliphatic diamines such as xylenediamine, N- (2-hydroxyethyl) Examples include diamines having a hydroxyl group such as ethylenediamine and N- (2-hydroxyethyl) propylenediamine.
  • polyamines having primary amino groups such as diethylenetriamine and triethylenetetratriamine are preferable.
  • a reaction terminator used in combination with a polyamine compound having a primary amino group and / or a secondary amino group at both ends a monoamine compound which is a known reaction terminator utilized in a polyurethane resin as a binder for ink Monoalcohol compounds can be used, specifically, monoalkylamines such as n-propylamine and n-butylamine, dialkylamines such as di-n-butylamine, and alkanolamines such as monoethanolamine and diethanolamine. And monoalcohols such as ethanol.
  • a polyurethane resin of ⁇ 13 mg KOH / g can be obtained.
  • the polyurethane resin having an amine value having a primary amino group and / or a secondary amino group at the terminal in the laminated printing ink composition for soft packaging of the present invention has a mass average molecular weight of 5,000 to 60,000. It is preferably 10,000 to 60,000.
  • the content of the polyurethane resin having an amine value having a primary amino group and / or a secondary amino group at the terminal is preferably 5 to 20% by mass in the laminate printing ink composition for flexible packaging.
  • the binder resin that can be used together with the polyurethane resin is at least one of vinyl chloride / vinyl acetate copolymer, nitrified cotton, cellulose acetate propionate resin, and other binder resins.
  • Vinyl chloride / vinyl acetate copolymer In the case where it is difficult to disperse the pigment only with the polyurethane resin, a vinyl chloride / vinyl acetate copolymer is used in order to improve the adhesiveness and laminate suitability of a metal vapor deposition film or the like.
  • a copolymer of vinyl chloride monomer and vinyl acetate monomer conventionally used in gravure printing ink compositions can be used.
  • a vinyl chloride / vinyl acetate copolymer having a hydroxyl group and having 50 to 200 hydroxyl groups is preferable.
  • Such a vinyl chloride / vinyl acetate copolymer having a hydroxyl group can be obtained, for example, by saponifying a part of the acetate portion.
  • a structural unit based on the reaction site of vinyl chloride in the molecule (the following formula 1), vinyl acetate
  • the physical properties and dissolution behavior of the resin are determined by the ratio of the structural unit based on the reaction site (Formula 2 below) and the structural unit based on the saponification of the reaction site of Vinyl acetate (Formula 3 below). That is, the structural unit based on the reaction site of vinyl chloride gives toughness and hardness of the resin film, and the structural unit based on the reaction site of vinyl acetate provides adhesion and flexibility, and saponifies the reaction site of vinyl acetate.
  • the structural unit based on imparts good solubility of environmentally friendly inks in organic solvents.
  • Specific examples of the vinyl chloride / vinyl acetate copolymer having such a hydroxyl group include Solvein A, AL, TA5R, TA2, TA3, TAO, TAOL, C, CH, CN, manufactured by Nissin Chemical Industry Co., Ltd. CNL etc. can be mentioned.
  • the total content of a polyurethane resin having a primary amino group and / or a secondary amino group at the terminal and having an amine value of 1 to 13 mgKOH / g and a vinyl chloride / vinyl acetate copolymer is determined by a laminate printing ink for soft packaging.
  • the content is preferably 5 to 20% by mass.
  • the laminated printing ink composition for soft packaging of the present invention can be used in combination with nitrified cotton and cellulose acetate propionate resin.
  • the amount of nitrified cotton used is 0.1 to 2.0 mass% in the laminate printing ink composition for soft packaging, and the amount of cellulose acetate propionate resin used is in the laminate printing ink composition for soft packaging. 0.1 to 3.0% by mass is preferable.
  • nitrified cotton As the nitrified cotton, nitrified cotton conventionally used in gravure printing ink compositions can be used. Nitrified cotton is obtained as a nitrate ester obtained by reacting natural cellulose with nitric acid to replace the three hydroxyl groups in the 6-membered ring of anhydrous glucopyranose groups in the natural cellulose with nitrate groups. As the nitrified cotton used in the present invention, those having a nitrogen amount of 10 to 13% and an average degree of polymerization of 35 to 90 are preferably used. Specific examples include SS1 / 2, SS1 / 4, SS1 / 8, TR1 / 16, NC RS-2 (manufactured by KCNC, KOREA CNC LTD), and the like.
  • cellulose acetate propionate resin As the cellulose acetate propionate resin, cellulose acetate propionate resins conventionally used in gravure printing ink compositions can be used. Cellulose acetate propionate resin is obtained by triesterification of cellulose with acetic acid and propionic acid and then hydrolysis. In general, a resin having 0.6 to 2.5% by weight of acetyl groups, 42 to 46% by weight of propionate groups, and 1.8 to 5% by weight of hydroxyl groups is commercially available. Specific examples include cellulose acetate propionate manufactured by Kanto Chemical Co., Inc.
  • cellulose acetate butyrate resin, acrylic resin, polyamide resin, adhesive resin, and the like can be supplementarily added as other binder resins in consideration of cost as long as the performance does not deteriorate. it can.
  • organic solvent used in the laminate printing ink composition for flexible packaging examples include toluene, ketone organic solvents (for example, acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.), ester organic solvents (for example, methyl acetate, ethyl acetate, acetic acid). n-propyl, n-butyl acetate, isobutyl acetate, etc.), alcohol organic solvents (methanol, ethanol, n-propanol, isopropanol, butanol, etc.), hydrocarbon solvents (toluene, methylcyclohexane, etc.) can be used.
  • ketone organic solvents for example, acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.
  • ester organic solvents for example, methyl acetate, ethyl acetate, acetic acid.
  • additives such as a tackifier, a crosslinking agent, a lubricant, an anti-blocking agent, an antistatic agent, and a surfactant can be further added to the above-mentioned laminate printing ink composition for soft packaging.
  • the laminated printing ink composition for soft packaging of the present invention can be produced by using various dispersing / kneading apparatuses generally used for the various materials described above.
  • the viscosity is adjusted to 10 to 1000 mPa ⁇ s by adjusting the content of each solid material and the combination of the binder resin and the organic solvent.
  • the Zahn Cup No. 3 outflow time is 12-23 seconds / 25 ° C, high speed In printing, it is preferable to dilute with an organic solvent until the temperature reaches about 14 to 16 seconds / 25 ° C.
  • the substrate for printing is not particularly limited, and is a polyolefin film such as polyethylene or polypropylene, a polyester film such as polyethylene terephthalate (PET), polylactic acid or polycaprolactone, various printing plastic films such as nylon or vinylon, and various types thereof. It is intended for a film in which a barrier layer formed by coating a metal film and a barrier resin is laminated on a plastic film for printing.
  • the gist of the present invention may be a normal film or a heat-shrinkable film, and post-processing such as laminating or shrinking treatment can be performed after printing.
  • a printing plate to be used a conventional printing plate (an intaglio plate made by a normal gravure plate making method, the plate making method can be exemplified by engraving gravure etc.), a cell shallower than a conventional printing plate (shallow plate) A printed version can be used.
  • the laminate printing ink composition for soft packaging is printed using the printing plate, and the printed matter obtained by the method is further laminated by various laminating methods. It can be used for packaging bags, laminated cans, etc.
  • the laminating method for the packaging bag is an extrusion laminating method in which an anchor coating agent is applied to the surface of the printed material, and then a molten polymer is laminated, an adhesive is applied to the surface of the printed material, and then a film polymer is applied.
  • a dry laminating method can be used.
  • the above extrusion laminating method is a method of laminating a molten polymer by a known extrusion laminating machine after applying an anchor coating agent such as titanium, urethane, imine, polybutadiene or the like to the surface of the printed material as necessary. Furthermore, it can also be laminated in a sandwich with other materials using the molten resin as an intermediate layer.
  • an anchor coating agent such as titanium, urethane, imine, polybutadiene or the like
  • it can also be laminated in a sandwich with other materials using the molten resin as an intermediate layer.
  • the molten resin used in the extrusion laminating method conventionally used resins such as low density polyethylene, ethylene-vinyl acetate copolymer, and polypropylene can be used.
  • the dry laminating method is a method of applying a film-like polymer by a known dry laminating machine after applying an adhesive such as urethane or isocyanate to the surface of the printed material.
  • Polyethylene, unstretched polypropylene, etc. can be used as the film-like polymer used in the dry laminating method.
  • aluminum foil is placed between the base material and the plastic film to be bonded.
  • Can also be laminated. Such a laminated product can be used for boil and retort after bag making and filling the contents.
  • an adhesive can be applied to the surface of a printed material and then bonded to a metal plate.
  • an adhesive is applied to the surface of the printed material by known coating means such as spray coating, roll coating, gravure coating, etc., and dried at a temperature of 150 to 200 ° C.
  • the printed material can be bonded to the metal plate by bonding the printing substrate having the agent layer to the metal plate and laminating by heating at a temperature of about 100 to 250 ° C. for a short time.
  • the adhesive include a one-component or two-component polyester resin adhesive, a polyurethane resin adhesive, and an epoxy resin adhesive.
  • metal plate hot rolled steel plate, cold rolled steel plate, hot dip galvanized steel plate, electrogalvanized steel plate, iron-zinc alloy plated steel plate, zinc-aluminum alloy plated steel plate, nickel-zinc alloy plated steel plate, nickel-tin alloy plated Metal plates such as steel plates, tinplate, chrome-plated steel plates, aluminum-plated steel plates, turn-plated steel plates, nickel-plated steel plates, stainless steel, tin-free steel, aluminum plates, steel plates, titanium plates, etc.
  • these metal materials for example, those subjected to chemical conversion treatment such as phosphate treatment, chromate treatment, and composite oxide film treatment can be used.
  • the laminate can obtained by the present invention is excellent in the adhesiveness of the printed matter after the retort treatment.
  • ⁇ Production example of polyurethane resin varnish B> In a four-necked flask equipped with a stirrer, a condenser tube and a nitrogen gas inlet tube, 100 parts by mass of 3-methyl-1,5-pentylene adipatediol having an average molecular weight of 2000, 100 parts by mass of polypropylene glycol having an average molecular weight of 2000, and 41.8 parts by mass of hydrogenated MDI was charged and reacted at 100 to 105 ° C. for 6 hours while introducing nitrogen gas.
  • the mixture is allowed to cool to near room temperature, 405 parts by mass of ethyl acetate and 175 parts by mass of isopropyl alcohol are added, then 8.2 parts by mass of isophoronediamine is added to extend the chain, and 0.7 parts by mass of monoethanolamine is added and reacted. Thereafter, 0.65 parts by mass of isophoronediamine and 0.39 parts by mass of diethylenetriamine were added to stop the reaction, thereby obtaining a polyurethane resin varnish E (solid content 30% by mass, amine value 1.5).
  • ⁇ Production example of polyurethane resin varnish F> In a four-necked flask equipped with a stirrer, a condenser tube and a nitrogen gas inlet tube, 100 parts by mass of 3-methyl-1,5-pentylene adipatediol having an average molecular weight of 2000, 100 parts by mass of polypropylene glycol having an average molecular weight of 2000, and 17.6 parts by mass of isophorone diisocyanate and 21.0 parts by mass of hydrogenated MDI were charged and reacted at 100 to 105 ° C. for 6 hours while introducing nitrogen gas.
  • ⁇ Production example of polyurethane resin varnish G> In a four-necked flask equipped with a stirrer, a condenser tube and a nitrogen gas inlet tube, 100 parts by mass of 3-methyl-1,5-pentylene adipatediol having an average molecular weight of 2000, 100 parts by mass of polypropylene glycol having an average molecular weight of 2000, and 16.7 parts by mass of isophorone diisocyanate and 19.7 parts by mass of hydrogenated MDI were charged and reacted at 100 to 105 ° C. for 6 hours while introducing nitrogen gas.
  • the mixture was allowed to cool to near room temperature, 406 parts by mass of ethyl acetate and 175 parts by mass of isopropyl alcohol were added, then 9.2 parts by mass of isophoronediamine was added to extend the chain, and 0.7 parts by mass of monoethanolamine was further added to react.
  • the polyurethane resin varnish H solid content 30% by mass, amine value 0
  • ⁇ Production example of polyurethane resin varnish L> In a four-necked flask equipped with a stirrer, a condenser tube and a nitrogen gas inlet tube, 200 parts by mass of 3-methyl-1,5-pentylene adipate diol having an average molecular weight of 2,000, 8.8 parts by mass of isophorone diisocyanate, hydrogenated 31.3 parts by mass of MDI was charged and reacted at 100 to 105 ° C. for 6 hours while introducing nitrogen gas.
  • ⁇ Production example of polyurethane resin varnish M> In a four-necked flask equipped with a stirrer, a condenser tube and a nitrogen gas inlet tube, 200 parts by mass of 3-methyl-1,5-pentylene adipate diol having an average molecular weight of 2000, 26.5 parts by mass of isophorone diisocyanate, hydrogenated 10.4 parts by mass of MDI was charged and reacted at 100 to 105 ° C. for 6 hours while introducing nitrogen gas.
  • the mixture is allowed to cool to near room temperature, 405 parts by mass of ethyl acetate and 175 parts by mass of isopropyl alcohol are added, then 8.2 parts by mass of isophoronediamine is added to extend the chain, and 0.7 parts by mass of monoethanolamine is added and reacted. Thereafter, 0.65 parts by mass of isophoronediamine and 0.39 parts by mass of diethylenetriamine were added to stop the reaction, thereby obtaining a polyurethane resin varnish N (solid content 30% by mass, amine value 1.5).
  • ⁇ Production example of polyurethane resin varnish P> In a four-necked flask equipped with a stirrer, a condenser tube and a nitrogen gas inlet tube, 200 parts by mass of 3-methyl-1,5-pentylene adipate diol having an average molecular weight of 2000 and 16.7 parts by mass of isophorone diisocyanate, hydrogenated 19.7 parts by mass of MDI was charged and reacted at 100 to 105 ° C. for 6 hours while introducing nitrogen gas.
  • the mixture was allowed to cool to near room temperature, 406 parts by mass of ethyl acetate and 175 parts by mass of isopropyl alcohol were added, then 9.2 parts by mass of isophoronediamine was added to extend the chain, and 0.7 parts by mass of monoethanolamine was further added to react.
  • the polyurethane resin varnish Q (solid content 30% by mass, amine value 0) was obtained.
  • ink storage stability The white ink composition for soft packaging laminates of Examples 1 to 10, 12 to 18 and Comparative Examples 1 to 4 obtained above, and the indigo ink composition for soft packaging laminates of Examples 11 and 19 were used.
  • the storage stability of the ink was evaluated from the presence or absence of precipitation of the pigment when it was collected in a glass bottle and stored at an ambient temperature of 60 ° C. for 14 days. A: No sedimentation is observed, and the storage stability of the ink is good. B: Sedimentation is observed, and the storage stability of the ink is poor.
  • Print conditions for printing evaluation 1 With respect to 100 parts by mass of each of the white ink composition for soft packaging laminate of Examples 1 to 10, 12 to 18, and Comparative Examples 1 to 4, and the indigo color ink composition for soft packaging laminate of Examples 11 and 19, respectively. Furthermore, after diluting with a mixed solvent in accordance with the composition shown in Table 1 and adjusting the viscosity to 15 seconds with Zahn Cup No. 3 manufactured by Koiso Co., Ltd., a gravure printing machine equipped with an engraving plate (printing plate, Helio 175 line / inch) Then, printing was performed at a printing speed of 150 m / min on the treated surfaces of OPP, PET, and NY.
  • Print conditions for printing evaluation 2 With respect to 100 parts by mass of each of the white ink composition for soft packaging laminate of Examples 1 to 10, 12 to 18, and Comparative Examples 1 to 4, and the indigo color ink composition for soft packaging laminate of Examples 11 and 19, respectively. Furthermore, after diluting with a mixed solvent according to the composition shown in Table 1 and adjusting the viscosity to 15 seconds with Zahn Cup No. 3 made by Koiso Co., Ltd., a gravure printing machine equipped with an engraving plate (printing plate, helio 175 line / inch) Then, printing was performed at a printing speed of 100 m / min on the treated surfaces of OPP, PET, and NY.
  • PET Polyethylene terephthalate film with corona discharge treatment on one side, manufactured by Toyobo Co., Ltd., E-5101, thickness 12 ⁇ m
  • OPP Biaxially stretched polypropylene film, manufactured by Toyobo Co., Ltd. P-216 1.
  • Thickness 30 ⁇ m NY nylon film, manufactured by Toyobo Co., Ltd., N-1102, thickness 15 ⁇ m
  • ⁇ Printability (scratch)> Regarding the printability, the printability was evaluated from the ratio of the area of the blur caused by the clogged ink in the printing portion at the end of printing. In addition, only this evaluation was performed in printing evaluation 1 and 2, respectively. A: No blurring is observed B: Scratch is observed a little C: Many blurring is observed
  • the cellophane tape was affixed to the printed surface of each printed matter obtained, and the adhesiveness was evaluated from the ratio of the area where the ink film peeled off the adherend when peeled off. A: No peeling at all B: Peeling area is less than 20% C: Peeling area is at least 20%
  • This dry laminate is made into a bag, filled with a mixture of 90% by weight of water and 10% by weight of salad oil, sealed, and printed on PET when immersed in pressurized hot water at 135 ° C. for 60 minutes.
  • the suitability of retort was evaluated from the presence or absence of lami. Those printed on NY were subjected to the same test evaluation at 120 ° C. By this evaluation, the suitability for lamination can be confirmed.
  • B Pinhole shape or thin, short lami-floating
  • C Long streaky lami-floating over the entire surface
  • the ink storage stability and printability are excellent, the guide roll is not removed, and the adhesiveness, blocking resistance and retort suitability are excellent. It became.
  • Examples 5 and 13 slight blurring was observed when printing was performed at a printing speed of 100 m / min.
  • Comparative Examples 1 and 3 in which the polyurethane resin does not have an amine value, the adhesiveness, blocking resistance and retort suitability are inferior, and dicyclohexylmethane 4,4′-diisocyanate (hydrogenated) According to Comparative Examples 2 and 4 which did not use (MDI), the guide roll was taken out and the blocking resistance was also deteriorated.

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Abstract

The present invention addresses the problem of providing a laminate printing ink composition for soft packaging having superior suitability for printing, blocking resistance, impression drum staining, laminate suitability, and other characteristics relative to the conventional laminate printing ink composition for soft packaging. To solve this problem, the present invention provides a laminate printing ink composition for soft packaging, the composition having a pigment, a binder resin, and an organic solvent as main components thereof, wherein the binder resin is a polyurethane resin obtained by reacting a polymeric polyol and a polyisocyanate including dicyclohexylmethane-4,4'-diisocyanate, the polyurethane resin satisfying conditions (1) through (3). Condition (1): The mass ratio of dicyclohexylmethane-4,4'-diisocyanate and polyisocyanates other than dicyclohexylmethane-4,4'-diisocyanate (dicyclohexylmethane-4,4'-diisocyanate/polyisocyanates other than dicyclohexylmethane-4,4'-diisocyanate) is equal to 100/0 to 5/95. Condition (2): The usage ratio of the polyisocyanate and the polymeric polyol in terms of the equivalent ratio of isocyanate groups:hydroxyl groups (isocyanate index) is in the range of 1.2 to 2.3. Condition (3): The polyurethane resin has an amine value.

Description

軟包装用ラミネート印刷インキ組成物Laminate printing ink composition for flexible packaging
　本発明は、軟包装用ラミネート印刷インキ組成物に関し、より詳しくは、印刷適性、耐ブロッキング性、圧胴汚れ、ラミネート適性等が良好な軟包装用ラミネート印刷インキ組成物に関する。 The present invention relates to a laminating printing ink composition for soft packaging, and more particularly to a laminating printing ink composition for soft packaging having good printability, blocking resistance, impression cylinder stain, laminating suitability and the like.
　食品、菓子、生活雑貨、ペットフード等には意匠性、経済性、内容物保護性、輸送性などの機能から、各種プラスチックフィルムを使用した包装材料が使用されている。また、多くの包装材料には消費者へアピールする意匠性、メッセージ性の付与を意図してグラビア印刷やフレキソ印刷が施されている。
　そして用途の包装材料を得るために、包装材料の基材フィルムの表面に印刷される表刷り印刷、あるいは包装材料の基材フィルムの印刷面に必要に応じて接着剤やアンカー剤を塗布し、フィルムにラミネーション加工を施す裏刷り印刷が行われる。
　裏刷り印刷では、ポリエステル、ナイロン、アルミニウム箔等の各種フィルム上に色インキ、白インキを順次印刷後、該白インキの印刷層上に、接着剤を用いたドライラミネート加工や、アンカーコート剤を用いたエクストルージョンラミネート加工等によりヒートシールを目的にポリエチレンフィルムやポリプロピレンフィルム等が積層されている。
　この軟包装用ラミネート印刷インキ組成物のポリウレタン樹脂に使用されているポリイソシアネートとしては、実施例等を見ると、イソホロンジイソシアネートが主に使用されている（例えば、特許文献１及び２参照）。
　しかし、近年、より性能が高い軟包装用ラミネート印刷インキ組成物が要求されるようになってきている。 Packaging materials using various plastic films are used for foods, confectionery, household goods, pet foods, and the like because of their functions such as design, economy, contents protection, and transportability. Further, many packaging materials are subjected to gravure printing or flexographic printing for the purpose of imparting design and message characteristics appealing to consumers.
And in order to obtain packaging materials for applications, surface printing printed on the surface of the base material film of the packaging material, or applying an adhesive or anchor agent to the printed surface of the base material film of the packaging material as necessary, Back-printing is performed by laminating the film.
In reverse printing, color ink and white ink are sequentially printed on various films such as polyester, nylon, and aluminum foil, and then a dry laminating process using an adhesive or an anchor coating agent is applied on the printed layer of the white ink. A polyethylene film, a polypropylene film or the like is laminated for the purpose of heat sealing by the extrusion laminating process used.
As the polyisocyanate used in the polyurethane resin of the laminate printing ink composition for soft packaging, isophorone diisocyanate is mainly used in the examples and the like (see, for example, Patent Documents 1 and 2).
However, in recent years, a laminate printing ink composition for soft packaging having higher performance has been demanded.
特許第５８４８８３７号公報Japanese Patent No. 5848837 特開２０１６－０９４５４８号公報JP 2016-094548 A
　従って、本発明の目的は、従来の軟包装用ラミネート印刷インキ組成物より印刷適性、耐ブロッキング性、圧胴汚れ、ラミネート適性等が良好な軟包装用ラミネート印刷インキ組成物を提供することである。 Accordingly, an object of the present invention is to provide a laminating printing ink composition for soft packaging which has better printability, blocking resistance, impression cylinder stain, laminating suitability, etc. than conventional laminating printing ink compositions for soft packaging. .
　本発明者らは、上記課題を解決するために鋭意検討を行った結果、バインダー樹脂のポリウレタン樹脂として、ジシクロヘキシルメタン４，４’－ジイソシアナートを含むポリイソシアネートと高分子ポリオールとを反応させてなるポリウレタン樹脂を使用することにより、上記の課題を解決できることを見出し、本発明を完成させた。
　すなわち、本発明は、以下のとおりである。
１．顔料、バインダー樹脂及び有機溶剤を主成分とする軟包装用ラミネート印刷インキ組成物であって、バインダー樹脂が、ジシクロヘキシルメタン４，４’－ジイソシアナートを含むポリイソシアネートと高分子ポリオールとを反応させてなるポリウレタン樹脂であって、ポリウレタン樹脂が下記の条件（１）～（３）を満足するポリウレタン樹脂である軟包装用ラミネート印刷インキ組成物。
条件（１）
　ジシクロヘキシルメタン４，４’－ジイソシアナートとジシクロヘキシルメタン４，４’－ジイソシアナート以外のポリイソシアネートの質量比率が、ジシクロヘキシルメタン４，４’－ジイソシアナート／ジシクロヘキシルメタン４，４’－ジイソシアナート以外のポリイソシアネート＝１００／０～５／９５である。
条件（２）
　ポリイソシアネートと高分子ポリオールの使用比率は、イソシアネート基：水酸基の当量比率（イソシアネートインデックス）が、１．２～２．３となる範囲である。
条件（３）
　ポリウレタン樹脂がアミン価を有するものである。
２．ジシクロヘキシルメタン４，４’－ジイソシアナート以外のポリイソシアネートが、イソホロンジイソシアネートであることを特徴とする１記載の軟包装用ラミネート印刷インキ組成物。
３．ジシクロヘキシルメタン４，４’－ジイソシアナートとイソホロンジイソシアネートの質量比率が、ジシクロヘキシルメタン４，４’－ジイソシアナート／イソホロンジイソシアネート＝９５／５～１０／９０であり、高分子ポリオールがポリエステルポリオール又はポリエステルポリオールとポリエーテルポリオールとの併用である１又は２記載の軟包装用ラミネート印刷インキ組成物。
４．ポリウレタン樹脂は、末端に第１級アミノ基及び／又は第２級アミノ基を有するポリウレタン樹脂であることを特徴とする１～３のいずれかに記載の軟包装用ラミネート印刷インキ組成物。
５．軟包装用ラミネート印刷インキ組成物には、さらに、水酸基を有する塩化ビニル／酢酸ビニル共重合体、硝化綿及び／又はセルロースアセテートプロピオネート樹脂から選ばれる少なくとも１種を含有することを特徴とする１～４のいずれかに記載の軟包装用ラミネート印刷インキ組成物。
６．有機溶剤は、エステル系有機溶剤、及びアルコール系有機溶剤の混合溶剤である１～５のいずれかに記載の軟包装用ラミネート印刷インキ組成物。 As a result of intensive studies to solve the above problems, the present inventors have reacted polyisocyanate containing dicyclohexylmethane 4,4′-diisocyanate with a polymer polyol as a polyurethane resin of a binder resin. The present inventors have found that the above-mentioned problems can be solved by using a polyurethane resin.
That is, the present invention is as follows.
1. A laminate printing ink composition for soft packaging comprising a pigment, a binder resin and an organic solvent as main components, wherein the binder resin reacts a polyisocyanate containing dicyclohexylmethane 4,4′-diisocyanate with a polymer polyol. A laminate printing ink composition for soft packaging, wherein the polyurethane resin is a polyurethane resin satisfying the following conditions (1) to (3):
Condition (1)
The weight ratio of polyisocyanate other than dicyclohexylmethane 4,4′-diisocyanate and dicyclohexylmethane 4,4′-diisocyanate is dicyclohexylmethane 4,4′-diisocyanate / dicyclohexylmethane 4,4′-diisocyanate. Polyisocyanate other than nate = 100/0 to 5/95.
Condition (2)
The use ratio of the polyisocyanate and the polymer polyol is in the range where the equivalent ratio of isocyanate group: hydroxyl group (isocyanate index) is 1.2 to 2.3.
Condition (3)
The polyurethane resin has an amine value.
2. 2. The laminate printing ink composition for soft packaging according to 1, wherein the polyisocyanate other than dicyclohexylmethane 4,4′-diisocyanate is isophorone diisocyanate.
3. The mass ratio of dicyclohexylmethane 4,4′-diisocyanate and isophorone diisocyanate is dicyclohexylmethane 4,4′-diisocyanate / isophorone diisocyanate = 95/5 to 10/90, and the polymer polyol is polyester polyol or polyester The laminated printing ink composition for soft packaging according to 1 or 2, which is a combination of a polyol and a polyether polyol.
4). 4. The laminated printing ink composition for soft packaging according to any one of 1 to 3, wherein the polyurethane resin is a polyurethane resin having a primary amino group and / or a secondary amino group at the terminal.
5). The laminate printing ink composition for soft packaging further comprises at least one selected from a vinyl chloride / vinyl acetate copolymer having a hydroxyl group, nitrified cotton and / or cellulose acetate propionate resin. 5. A laminated printing ink composition for soft packaging according to any one of 1 to 4.
6). 6. The laminated printing ink composition for soft packaging according to any one of 1 to 5, wherein the organic solvent is a mixed solvent of an ester organic solvent and an alcohol organic solvent.
　従来の軟包装用ラミネート印刷インキ組成物より、印刷適性、耐ブロッキング性、圧胴汚れ、ラミネート適性等が良好な軟包装用ラミネート印刷インキ組成物を提供することができる。 It is possible to provide a laminate printing ink composition for soft packaging, which has better printability, blocking resistance, impression cylinder dirt, laminate suitability, etc. than conventional laminate printing ink compositions for soft packaging.
　本発明において、「末端に第１級アミノ基及び／又は第２級アミノ基を有するポリウレタン樹脂」とは、ポリウレタン樹脂の主鎖及び側鎖の全て又は一部の末端に、上記第１級アミノ基及び／又は第２級アミノ基を有することを意味する。
　以下、本発明の軟包装用ラミネート印刷インキ組成物についてより詳しく説明する。
＜顔料＞
　顔料としては、印刷インキで一般的に用いられている各種無機顔料、有機顔料等が使用できる。上記無機顔料としては、例えば、酸化チタン、ベンガラ、アンチモンレッド、カドミウムイエロー、コバルトブルー、紺青、群青、カーボンブラック、黒鉛等の有色顔料、シリカ、炭酸カルシウム、カオリン、クレー、硫酸バリウム、水酸化アルミニウム、タルク等の体質顔料、アクリル樹脂で表面処理したアルミニウム粒子を含有するアルミペースト、表面に酸化チタンと酸化スズと酸化ジルコニウムとがコーティングされたマイカ等のパール顔料を挙げることができる。上記有機顔料としては、例えば、溶性アゾ顔料、不溶性アゾ顔料、アゾレーキ顔料、縮合アゾ顔料、銅フタロシアニン顔料、縮合多環顔料等を挙げることができる。
　本発明の軟包装用ラミネート印刷インキ組成物における顔料の含有量は、インキ組成物中に、５～６０質量％の範囲であることが好ましい。ラミネート印刷インキ組成物中の顔料の含有量が上記の範囲より少なくなると、インキ組成物としての着色力が低下し、上記の範囲より多くなると、インキ組成物の粘度が高くなり、印刷物が汚れやすくなる。 In the present invention, the “polyurethane resin having a primary amino group and / or a secondary amino group at the terminal” refers to the primary amino group at the terminal of all or part of the main chain and side chain of the polyurethane resin. It means having a group and / or a secondary amino group.
Hereinafter, the laminate printing ink composition for soft packaging of the present invention will be described in more detail.
<Pigment>
As the pigment, various inorganic pigments and organic pigments generally used in printing ink can be used. Examples of the inorganic pigment include colored pigments such as titanium oxide, bengara, antimony red, cadmium yellow, cobalt blue, bitumen, ultramarine, carbon black, graphite, silica, calcium carbonate, kaolin, clay, barium sulfate, aluminum hydroxide. An extender such as talc, an aluminum paste containing aluminum particles surface-treated with an acrylic resin, and a pearl pigment such as mica whose surface is coated with titanium oxide, tin oxide and zirconium oxide. Examples of the organic pigment include soluble azo pigments, insoluble azo pigments, azo lake pigments, condensed azo pigments, copper phthalocyanine pigments, and condensed polycyclic pigments.
The content of the pigment in the laminate printing ink composition for soft packaging of the present invention is preferably in the range of 5 to 60% by mass in the ink composition. When the content of the pigment in the laminate printing ink composition is less than the above range, the coloring power as the ink composition is lowered, and when it is more than the above range, the viscosity of the ink composition is increased and the printed matter is easily stained. Become.
＜バインダー樹脂＞
（ジシクロヘキシルメタン４，４’－ジイソシアナートを含むポリイソシアネートと高分子ポリオールとを反応させてなる、アミン価が１～１３ｍｇＫＯＨ／ｇであるポリウレタン樹脂）
　ポリウレタン樹脂は、顔料分散性、接着性、ラミネート適性等からアミン価が１～１３ｍｇＫＯＨ／ｇのポリウレタン樹脂を使用することが好ましい。 <Binder resin>
(Polyurethane resin having an amine value of 1 to 13 mgKOH / g obtained by reacting a polyisocyanate containing dicyclohexylmethane 4,4′-diisocyanate and a polymer polyol)
As the polyurethane resin, it is preferable to use a polyurethane resin having an amine value of 1 to 13 mgKOH / g in view of pigment dispersibility, adhesion, laminating suitability and the like.
（ポリイソシアネート）
　ポリイソシアネートとしては、ジシクロヘキシルメタン４，４’－ジイソシアナート（水添ＭＤＩ）とジシクロヘキシルメタン４，４’－ジイソシアナート以外のポリイソシアネートの質量比率が、ジシクロヘキシルメタン４，４’－ジイソシアナート／ジシクロヘキシルメタン４，４’－ジイソシアナート以外のポリイソシアネート＝１００／０～５／９５、より好ましくは、８０／２０～２０／８０となるように使用する。
　ジシクロヘキシルメタン４，４’－ジイソシアナートの割合が、５より少ないと被膜物性が低下する傾向となる。
　ジシクロヘキシルメタン４，４’－ジイソシアナート以外のポリイソシアネートとしては、トリレンジイソシアネート等の芳香族ジイソシアネート化合物、１，４－シクロヘキサンジイソシアネート、イソホロンジイソシアネート等の脂環族ジイソシアネート化合物、ヘキサメチレンジイソシアネート等の脂肪族ジイソシアネート化合物、及び、α，α，α’，α’－テトラメチルキシリレンジイソシアネート等の芳香脂肪族ジイソシアネート化合物を、単独又は２種以上混合して得られたものを使用できる。ジシクロヘキシルメタン４，４’－ジイソシアナートの異性体であるジシクロヘキシルメタン－２，４’－ジイソシアネートも使用できる。なかでも、被膜物性及び印刷適性の点から、イソホロンジイソシアネートを使用することが好ましい。
　ジシクロヘキシルメタン４，４’－ジイソシアナートとイソホロンジイソシアネートの質量比率が、ジシクロヘキシルメタン４，４’－ジイソシアナート／イソホロンジイソシアネート＝９５／５～１０／９０となる範囲が好ましい。 (Polyisocyanate)
As the polyisocyanate, the weight ratio of dicyclohexylmethane 4,4′-diisocyanate (hydrogenated MDI) and polyisocyanate other than dicyclohexylmethane 4,4′-diisocyanate is dicyclohexylmethane 4,4′-diisocyanate. / Polyisocyanate other than dicyclohexylmethane 4,4′-diisocyanate = 100/0 to 5/95, more preferably 80/20 to 20/80.
When the proportion of dicyclohexylmethane 4,4′-diisocyanate is less than 5, the physical properties of the coating tend to be lowered.
Examples of polyisocyanates other than dicyclohexylmethane 4,4′-diisocyanate include aromatic diisocyanate compounds such as tolylene diisocyanate, alicyclic diisocyanate compounds such as 1,4-cyclohexane diisocyanate and isophorone diisocyanate, and fats such as hexamethylene diisocyanate. A group obtained by mixing an aromatic diisocyanate compound and an araliphatic diisocyanate compound such as α, α, α ′, α′-tetramethylxylylene diisocyanate alone or in combination of two or more thereof can be used. Dicyclohexylmethane-2,4′-diisocyanate, which is an isomer of dicyclohexylmethane 4,4′-diisocyanate, can also be used. Especially, it is preferable to use isophorone diisocyanate from the point of a film physical property and printability.
The mass ratio of dicyclohexylmethane 4,4′-diisocyanate and isophorone diisocyanate is preferably in the range of dicyclohexylmethane 4,4′-diisocyanate / isophorone diisocyanate = 95/5 to 10/90.
（高分子ポリオール）
　高分子ポリオール化合物としては、例えば、ポリエチレングリコール、ポリプロピレングリコール等のポリアルキレングリコール類、ビスフェノールＡのエチレンオキサイド、プロピレンオキサイド等アルキレンオキサイド付加物等のポリエーテルジオール化合物、アジピン酸、セバシン酸、無水フタル酸等の二塩基酸の１種又は２種以上と、エチレングリコール、プロピレングリコール、１，４－ブタンジオール、ネオペンチルグリコール、３－メチル－１，５－ペンタンジオール等のグリコール類の１種又は２種以上とを縮合反応させて得られるポリエステルジオール類、ポリカプロラクトンジオール類等のポリエステルジオール化合物等の各種高分子ジオール化合物を単独又は２種以上混合して使用できる。
　これらの高分子ポリオールの中でも、ラミネート適性等の点から、高分子ポリエステルポリオール又はポリエステルポリオールとポリエーテルポリオールとの併用したものを使用することが好ましい。
　さらに、上記高分子ジオール化合物に加えて、１，４－ペンタンジオール、２，５－ヘキサンジオール、３－メチル－１，５－ペンタンジオール等のアルカンジオールや、エチレングリコール、プロピレングリコール、１，４－ブタンジオール、１，３－ブタンジオール等の低分子ジオール化合物を単独又は２種以上混合して併用することもできる。
　また、上記ポリイソシアネートと上記高分子ポリオールの使用比率は、イソシアネート基／水酸基の当量比率（イソシアネートインデックス（Ｉ．Ｉ．））が、１．２～２．３となる範囲である。 (Polymer polyol)
Examples of the polymer polyol compound include polyalkylene glycols such as polyethylene glycol and polypropylene glycol, polyether diol compounds such as alkylene oxide adducts such as ethylene oxide and propylene oxide of bisphenol A, adipic acid, sebacic acid, and phthalic anhydride 1 type or 2 types or more of dibasic acids such as ethylene glycol, propylene glycol, 1,4-butanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, etc. Various polymer diol compounds such as polyester diol compounds such as polyester diols and polycaprolactone diols obtained by condensation reaction with at least one species may be used alone or in combination of two or more.
Among these polymer polyols, it is preferable to use a polymer polyester polyol or a combination of a polyester polyol and a polyether polyol from the viewpoint of laminating suitability and the like.
Further, in addition to the above polymer diol compounds, alkane diols such as 1,4-pentanediol, 2,5-hexanediol, 3-methyl-1,5-pentanediol, ethylene glycol, propylene glycol, 1,4 -Low molecular diol compounds such as butanediol and 1,3-butanediol can be used alone or in combination of two or more.
Further, the use ratio of the polyisocyanate and the polymer polyol is in a range where the equivalent ratio of isocyanate group / hydroxyl group (isocyanate index (II)) is 1.2 to 2.3.
（ポリウレタン樹脂）
　ポリウレタン樹脂は、上記ポリイソシアネートと上記高分子ポリオールを公知の方法で反応させプレポリマーを得た後、鎖伸長剤、必要に応じて反応停止剤を公知の方法で反応させたものが使用できる。
　なかでも、顔料分散性、接着性、ラミネート適性等の点から、上記高分子ポリオールと有機ポリイソシアネート化合物を成分として含有する末端に第１級アミノ基及び／又は第２級アミノ基を有するアミン価を有するポリウレタン樹脂、好ましくはアミン価が１～１３ｍｇＫＯＨ／ｇのポリウレタン樹脂が好ましい。
　末端に第１級アミノ基及び／又は第２級アミノ基を有するアミノ基を有するポリウレタン樹脂は、下記の（１）～（４）のいずれかの方法により得ることができる。 (Polyurethane resin)
The polyurethane resin can be obtained by reacting the polyisocyanate and the polymer polyol by a known method to obtain a prepolymer, and then reacting a chain extender and, if necessary, a reaction terminator by a known method.
Among these, from the viewpoint of pigment dispersibility, adhesiveness, laminate suitability, etc., the amine value having a primary amino group and / or a secondary amino group at the terminal containing the above-mentioned polymer polyol and organic polyisocyanate compound as components. A polyurethane resin having an amine value of 1 to 13 mgKOH / g is preferred.
A polyurethane resin having an amino group having a primary amino group and / or a secondary amino group at the terminal can be obtained by any of the following methods (1) to (4).
（１）高分子ポリオール及びポリイソシアネートを反応させてなる末端にイソシアネート基を有するウレタンプレポリマーに鎖伸長剤を加えて鎖伸長を行い、末端にイソシアネート基を有するウレタンプレポリマーを得た後、両末端が第１級アミノ基及び／又は第２級アミノ基であるポリアミン化合物以外の反応停止剤を反応させ、次いで、両末端が第１級アミノ基及び／又は第２級アミノ基であるポリアミン化合物である反応停止剤を反応させ、末端に第１級アミノ基及び／又は第２級アミノ基を有する、アミン価を有するポリウレタン樹脂を得る方法。
（２）高分子ポリオール及びポリイソシアネートを反応させてなる末端にイソシアネート基を有するウレタンプレポリマーに鎖伸長剤を加えて鎖伸長を行い、末端にイソシアネート基を有するウレタンプレポリマーを得た後、反応停止剤として、両末端が第１級アミノ基及び／又は第２級アミノ基であるポリアミン化合物である反応停止剤と、別の両末端が第１級アミノ基及び／又は第２級アミノ基であるポリアミン化合物である反応停止剤を同時に加えて反応させ、末端に第１級アミノ基及び／又は第２級アミノ基を有する、アミン価を有するポリウレタン樹脂を得る方法。
（３）高分子ポリオール及びポリイソシアネートを反応させてなる末端にイソシアネート基を有するウレタンプレポリマーに鎖伸長剤を加えて鎖伸長を行い、末端にイソシアネート基を有するウレタンプレポリマーを得た後、両末端が第１級アミノ基及び／又は第２級アミノ基であるポリアミン化合物である反応停止剤を反応させ、末端に第１級アミノ基及び／又は第２級アミノ基を有する、アミン価を有するポリウレタン樹脂を得る方法。
（４）高分子ジオール及びポリイソシアネートを反応させてなる末端にイソシアネート基を有するウレタンプレポリマーに、両末端が第１級アミノ基及び／又は第２級アミノ基であるポリアミン化合物を反応させて鎖伸長と反応停止を同時に行い、末端に第１級アミノ基及び／又は第２級アミノ基を有する、アミン価を有するポリウレタン樹脂を得る方法。 (1) A chain extender is added to a urethane prepolymer having an isocyanate group at the terminal obtained by reacting a polymer polyol and a polyisocyanate to carry out chain extension to obtain a urethane prepolymer having an isocyanate group at the terminal. A reaction stopper other than a polyamine compound whose terminal is a primary amino group and / or a secondary amino group is reacted, and then a polyamine compound whose both ends are a primary amino group and / or a secondary amino group A method for obtaining a polyurethane resin having an amine value, which is reacted with a reaction terminator and having a primary amino group and / or a secondary amino group at a terminal.
(2) A chain extender is added to a urethane prepolymer having an isocyanate group at the terminal obtained by reacting a polymer polyol and a polyisocyanate to carry out chain extension, and a urethane prepolymer having an isocyanate group at the terminal is obtained. As a terminator, a reaction terminator which is a polyamine compound whose both ends are a primary amino group and / or a secondary amino group, and another terminal is a primary amino group and / or a secondary amino group. A method of obtaining a polyurethane resin having an amine value having a primary amino group and / or a secondary amino group at a terminal by simultaneously adding a reaction terminator, which is a certain polyamine compound, to cause a reaction.
(3) A chain extender is added to a urethane prepolymer having an isocyanate group at the terminal obtained by reacting a polymer polyol and a polyisocyanate to carry out chain extension to obtain a urethane prepolymer having an isocyanate group at the terminal. Reaction with a reaction terminator, which is a polyamine compound whose terminal is a primary amino group and / or secondary amino group, and has a primary amino group and / or secondary amino group at the terminal, and has an amine value A method for obtaining a polyurethane resin.
(4) A urethane prepolymer having an isocyanate group at a terminal obtained by reacting a polymer diol and a polyisocyanate is reacted with a polyamine compound having both ends of a primary amino group and / or a secondary amino group to react with a chain. A method for obtaining a polyurethane resin having an amine value, wherein elongation and reaction termination are carried out at the same time to have a primary amino group and / or a secondary amino group at the terminal.
　上記（１）～（３）で使用する鎖伸長剤としては、インキ用バインダーとしてのポリウレタン樹脂で利用される既知の鎖伸長剤が利用可能であり、エチレンジアミン、プロピレンジアミン、テトラメチレンジアミン、ヘキサメチレンジアミン等の脂肪族ジアミン類、イソホロンジアミン、４，４’－ジシクロヘキシルメタンジアミン等の脂環式ジアミン類、ジエチレントリアミン、トリエチレンテトラトリアミン等のポリアミン類、トルイレンジアミン等の芳香族ジアミン類、キシレンジアミン等の芳香脂肪族ジアミン類、Ｎ－（２－ヒドロキシエチル）エチレンジアミン、Ｎ－（２－ヒドロキシエチル）プロピレンジアミン、Ｎ，Ｎ’－ジ（２－ヒドロキシエチル）エチレンジアミン等の水酸基を有するジアミン類、エチレングリコール、プロピレングリコール、１，４－ブタンジオール、ネオペンチルグリコール、ジエチレングリコール、トリエチレングリコール等のジオール化合物を例示することができる。
　上記（１）、（２）の方法で使用する反応停止剤としては、両末端が第１級アミノ基及び／又は第２級アミノ基であるポリアミン化合物、モノアミン化合物及び／又はモノアルコール化合物等の反応停止剤を例示できる。
　上記（３）の方法で使用する反応停止剤としては、両末端が第１級アミノ基及び／又は第２級アミノ基であるポリアミン化合物を例示できる。
　上記（４）の方法で使用する鎖伸長と反応停止を同時に行う化合物としては、上記鎖伸長剤だけでもよいし、鎖伸長剤と反応停止剤を併用してもよい。 As the chain extender used in the above (1) to (3), known chain extenders used in polyurethane resins as binders for ink can be used, and ethylenediamine, propylenediamine, tetramethylenediamine, hexamethylene Aliphatic diamines such as diamine, isophorone diamine, alicyclic diamines such as 4,4'-dicyclohexylmethane diamine, polyamines such as diethylenetriamine and triethylenetetratriamine, aromatic diamines such as toluylenediamine, xylenediamine Diamines having a hydroxyl group such as N- (2-hydroxyethyl) ethylenediamine, N- (2-hydroxyethyl) propylenediamine, N, N′-di (2-hydroxyethyl) ethylenediamine, Ethylene glycol Propylene glycol, 1,4-butanediol, neopentyl glycol, diethylene glycol, can be exemplified a diol compound such as triethylene glycol.
Examples of the reaction terminator used in the above methods (1) and (2) include polyamine compounds, monoamine compounds and / or monoalcohol compounds in which both ends are primary amino groups and / or secondary amino groups. A reaction terminator can be illustrated.
Examples of the reaction terminator used in the above method (3) include polyamine compounds whose both ends are a primary amino group and / or a secondary amino group.
As the compound that simultaneously performs chain extension and reaction termination used in the method (4), only the chain extender may be used, or a chain extender and a reaction terminator may be used in combination.
　上記アミノ基を有するポリウレタン樹脂は、保存安定性や顔料分散性の点からアミン価１～１３ｍｇＫＯＨ／ｇとなるように、両末端が第１級アミノ基及び／又は第２級アミノ基であるポリアミン化合物で反応停止されていることが好ましい。
　両末端に第１級アミノ基及び／又は第２級アミノ基を有するポリアミン化合物としては、エチレンジアミン、プロピレンジアミン、テトラメチレンジアミン、ヘキサメチレンジアミン等の脂肪族ジアミン類、イソホロンジアミン、４，４’－ジシクロヘキシルメタンジアミン等の脂環式ジアミン類、ジエチレントリアミン、トリエチレンテトラトリアミン等のポリアミン類、トルイレンジアミン等の芳香族ジアミン類、キシレンジアミン等の芳香脂肪族ジアミン類、Ｎ－（２－ヒドロキシエチル）エチレンジアミン、Ｎ－（２－ヒドロキシエチル）プロピレンジアミン等の水酸基を有するジアミン類等を例示できる。この中でも、ジエチレントリアミン、トリエチレンテトラトリアミン等の第１級アミノ基を有するポリアミンが好ましい。
　両末端に第１級アミノ基及び／又は第２級アミノ基を有するポリアミン化合物と併用される反応停止剤としては、インキ用バインダーとしてのポリウレタン樹脂で利用される既知の反応停止剤であるモノアミン化合物、モノアルコール化合物が利用可能であり、具体的には、ｎ－プロピルアミン、ｎ－ブチルアミン等のモノアルキルアミン類、ジ－ｎ－ブチルアミン等のジアルキルアミン類、モノエタノールアミン、ジエタノールアミン等のアルカノールアミン類、エタノール等のモノアルコール類を例示することができる。 The above polyurethane resin having an amino group is a polyamine having both ends of a primary amino group and / or a secondary amino group so that the amine value is 1 to 13 mgKOH / g from the viewpoint of storage stability and pigment dispersibility. The reaction is preferably stopped with a compound.
Polyamine compounds having a primary amino group and / or a secondary amino group at both ends include aliphatic diamines such as ethylenediamine, propylenediamine, tetramethylenediamine, hexamethylenediamine, isophoronediamine, 4,4′- Alicyclic diamines such as dicyclohexylmethanediamine, polyamines such as diethylenetriamine and triethylenetetratriamine, aromatic diamines such as toluylenediamine, araliphatic diamines such as xylenediamine, N- (2-hydroxyethyl) Examples include diamines having a hydroxyl group such as ethylenediamine and N- (2-hydroxyethyl) propylenediamine. Among these, polyamines having primary amino groups such as diethylenetriamine and triethylenetetratriamine are preferable.
As a reaction terminator used in combination with a polyamine compound having a primary amino group and / or a secondary amino group at both ends, a monoamine compound which is a known reaction terminator utilized in a polyurethane resin as a binder for ink Monoalcohol compounds can be used, specifically, monoalkylamines such as n-propylamine and n-butylamine, dialkylamines such as di-n-butylamine, and alkanolamines such as monoethanolamine and diethanolamine. And monoalcohols such as ethanol.
　本発明では、上記材料を用いて、公知のポリウレタン樹脂の製造方法を採用して末端に第１級アミノ基及び／又は第２級アミノ基を有するアミン価を有するポリウレタン樹脂、好ましくはアミン価１～１３ｍｇＫＯＨ／ｇのポリウレタン樹脂を得ることができる。
　そして、本発明の軟包装用ラミネート印刷インキ組成物における末端に第１級アミノ基及び／又は第２級アミノ基を有するアミン価を有するポリウレタン樹脂は、質量平均分子量が５０００～６００００であることが好ましく、１００００～６００００であることがより好ましい。
　また、末端に第１級アミノ基及び／又は第２級アミノ基を有するアミン価を有するポリウレタン樹脂の含有量は、軟包装用ラミネート印刷インキ組成物中に、５～２０質量％が好ましい。 In the present invention, a polyurethane resin having an amine value having a primary amino group and / or a secondary amino group at the terminal using the above-mentioned material and adopting a known method for producing a polyurethane resin, preferably an amine value of 1 A polyurethane resin of ˜13 mg KOH / g can be obtained.
The polyurethane resin having an amine value having a primary amino group and / or a secondary amino group at the terminal in the laminated printing ink composition for soft packaging of the present invention has a mass average molecular weight of 5,000 to 60,000. It is preferably 10,000 to 60,000.
The content of the polyurethane resin having an amine value having a primary amino group and / or a secondary amino group at the terminal is preferably 5 to 20% by mass in the laminate printing ink composition for flexible packaging.
（併用可能なバインダー樹脂）
　上記ポリウレタン樹脂と共に併用可能なバインダー樹脂としては、塩化ビニル／酢酸ビニル共重合体、硝化綿、セルロースアセテートプロピオネート樹脂及びその他のバインダー樹脂の１種以上である。
（塩化ビニル／酢酸ビニル共重合体）
　ポリウレタン樹脂だけでは、顔料分散が難しい場合、金属蒸着フィルム等の接着性やラミネート適性を向上させる場合に、塩化ビニル／酢酸ビニル共重合体を使用する。使用する塩化ビニル／酢酸ビニル共重合体としては、従来からグラビア印刷インキ組成物に使用されている塩化ビニルモノマーと酢酸ビニルモノマーの共重合体が使用できる。
　なかでも、環境に配慮したインキの有機溶剤系においては、水酸基を有する、５０～２００の水酸基を有する塩化ビニル／酢酸ビニル共重合体が好適である。この様な水酸基を有する塩化ビニル／酢酸ビニル共重合体は、例えば、酢酸エステル部分の一部をケン化することにより得ることができる。
　酢酸エステル部分の一部をケン化することにより得られた水酸基を有する塩化ビニル／酢酸ビニル共重合体の場合では、分子中の塩化ビニルの反応部位に基づく構成単位（下記式１）、酢酸ビニルの反応部位に基づく構成単位（下記式２）、および酢酸ビニルの反応部位のケン化に基づく構成単位（下記式３）の比率により樹脂の被膜物性や溶解挙動が決定される。
　即ち、塩化ビニルの反応部位に基づく構成単位は樹脂被膜の強靭さや硬さを付与し、酢酸ビニルの反応部位に基づく構成単位は接着性や柔軟性を付与し、酢酸ビニルの反応部位のケン化に基づく構成単位は環境に配慮したインキの有機溶剤系への良好な溶解性を付与する。
　式１　‐CH2-CHCl-
　式２　‐CH2-CH（OCOCH3）-
　式３　‐CH2-CH(OH)-
　このような水酸基を有する塩化ビニル／酢酸ビニル共重合体の具体例としては、日信化学工業（株）製のソルバインＡ、ＡＬ、ＴＡ５Ｒ、ＴＡ２、ＴＡ３、ＴＡＯ、ＴＡＯＬ、Ｃ、ＣＨ、ＣＮ、ＣＮＬ等を挙げることができる。
　末端に第１級アミノ基及び／又は第２級アミノ基を有するアミン価１～１３ｍｇＫＯＨ／ｇのポリウレタン樹脂と塩化ビニル／酢酸ビニル共重合体との合計の含有量は、軟包装用ラミネート印刷インキ組成物中に、５～２０質量％であることが好ましい。 (Binder resin that can be used in combination)
The binder resin that can be used together with the polyurethane resin is at least one of vinyl chloride / vinyl acetate copolymer, nitrified cotton, cellulose acetate propionate resin, and other binder resins.
(Vinyl chloride / vinyl acetate copolymer)
In the case where it is difficult to disperse the pigment only with the polyurethane resin, a vinyl chloride / vinyl acetate copolymer is used in order to improve the adhesiveness and laminate suitability of a metal vapor deposition film or the like. As the vinyl chloride / vinyl acetate copolymer to be used, a copolymer of vinyl chloride monomer and vinyl acetate monomer conventionally used in gravure printing ink compositions can be used.
Among these, in the organic solvent system of the ink in consideration of the environment, a vinyl chloride / vinyl acetate copolymer having a hydroxyl group and having 50 to 200 hydroxyl groups is preferable. Such a vinyl chloride / vinyl acetate copolymer having a hydroxyl group can be obtained, for example, by saponifying a part of the acetate portion.
In the case of a vinyl chloride / vinyl acetate copolymer having a hydroxyl group obtained by saponifying a part of the acetate portion, a structural unit based on the reaction site of vinyl chloride in the molecule (the following formula 1), vinyl acetate The physical properties and dissolution behavior of the resin are determined by the ratio of the structural unit based on the reaction site (Formula 2 below) and the structural unit based on the saponification of the reaction site of Vinyl acetate (Formula 3 below).
That is, the structural unit based on the reaction site of vinyl chloride gives toughness and hardness of the resin film, and the structural unit based on the reaction site of vinyl acetate provides adhesion and flexibility, and saponifies the reaction site of vinyl acetate. The structural unit based on imparts good solubility of environmentally friendly inks in organic solvents.
Formula 1 -CH2-CHCl-
Formula 2 -CH2-CH (OCOCH3)-
Formula 3 -CH2-CH (OH)-
Specific examples of the vinyl chloride / vinyl acetate copolymer having such a hydroxyl group include Solvein A, AL, TA5R, TA2, TA3, TAO, TAOL, C, CH, CN, manufactured by Nissin Chemical Industry Co., Ltd. CNL etc. can be mentioned.
The total content of a polyurethane resin having a primary amino group and / or a secondary amino group at the terminal and having an amine value of 1 to 13 mgKOH / g and a vinyl chloride / vinyl acetate copolymer is determined by a laminate printing ink for soft packaging. The content is preferably 5 to 20% by mass.
（硝化綿、セルロースアセテートプロピオネート樹脂）
　本発明の軟包装用ラミネート印刷インキ組成物には、耐ブロッキング性を向上させるために、硝化綿、セルロースアセテートプロピオネート樹脂を併用することができる。
　このとき、硝化綿の使用量は、軟包装用ラミネート印刷インキ組成中に、０．１～２．０質量％、セルロースアセテートプロピオネート樹脂の使用量は、軟包装用ラミネート印刷インキ組成中に、０．１～３．０質量％含有させることが好ましい。 (Nitrified cotton, cellulose acetate propionate resin)
In order to improve blocking resistance, the laminated printing ink composition for soft packaging of the present invention can be used in combination with nitrified cotton and cellulose acetate propionate resin.
At this time, the amount of nitrified cotton used is 0.1 to 2.0 mass% in the laminate printing ink composition for soft packaging, and the amount of cellulose acetate propionate resin used is in the laminate printing ink composition for soft packaging. 0.1 to 3.0% by mass is preferable.
＜硝化綿＞
　硝化綿としては、従来からグラビア印刷インキ組成物に使用されている硝化綿が使用できる。
　硝化綿としては、天然セルロースと硝酸を反応させて、天然セルロース中の無水グルコピラノース基の６員環中の３個の水酸基を、硝酸基に置換した硝酸エステルとして得られるものである。本発明に使用される硝化綿としては、窒素量１０～１３％、平均重合度３５～９０のものが好ましく用いられる。具体例としては、ＳＳ１／２、ＳＳ１／４、ＳＳ１／８、ＴＲ１／１６、ＮＣ ＲＳ－２、（ＫＣＮＣ、ＫＯＲＥＡ  ＣＮＣ  ＬＴＤ社製）等を挙げることができる。 <Nitrated cotton>
As the nitrified cotton, nitrified cotton conventionally used in gravure printing ink compositions can be used.
Nitrified cotton is obtained as a nitrate ester obtained by reacting natural cellulose with nitric acid to replace the three hydroxyl groups in the 6-membered ring of anhydrous glucopyranose groups in the natural cellulose with nitrate groups. As the nitrified cotton used in the present invention, those having a nitrogen amount of 10 to 13% and an average degree of polymerization of 35 to 90 are preferably used. Specific examples include SS1 / 2, SS1 / 4, SS1 / 8, TR1 / 16, NC RS-2 (manufactured by KCNC, KOREA CNC LTD), and the like.
＜セルロースアセテートプロピオネート樹脂＞
　セルロースアセテートプロピオネート樹脂としては、従来からグラビア印刷インキ組成物に使用されているセルロースアセテートプロピオネート樹脂が使用できる。
　セルロースアセテートプロピオネート樹脂は、セルロースを酢酸及びプロピオン酸でトリエステル化した後に加水分解して得られる。一般的にはアセチル基は０．６～２．５重量％、プロピオネート基は４２～４６重量％、水酸基は１．８～５重量％である樹脂が市販されている。具体例としては、関東化学(株)製のセルロースアセテートプロピオネート等を挙げることができる。 <Cellulose acetate propionate resin>
As the cellulose acetate propionate resin, cellulose acetate propionate resins conventionally used in gravure printing ink compositions can be used.
Cellulose acetate propionate resin is obtained by triesterification of cellulose with acetic acid and propionic acid and then hydrolysis. In general, a resin having 0.6 to 2.5% by weight of acetyl groups, 42 to 46% by weight of propionate groups, and 1.8 to 5% by weight of hydroxyl groups is commercially available. Specific examples include cellulose acetate propionate manufactured by Kanto Chemical Co., Inc.
＜他のバインダー樹脂＞
　さらに、本発明では、その他のバインダー樹脂として、性能が低下しない範囲で、さらにコストを考慮して、セルロースアセテートブチレート樹脂、アクリル樹脂、ポリアミド樹脂や粘着性樹脂等を補助的に添加することができる。 <Other binder resins>
Furthermore, in the present invention, cellulose acetate butyrate resin, acrylic resin, polyamide resin, adhesive resin, and the like can be supplementarily added as other binder resins in consideration of cost as long as the performance does not deteriorate. it can.
＜有機溶剤＞
　軟包装用ラミネート印刷インキ組成物に使用される有機溶剤としては、トルエン、ケトン系有機溶剤（例えば、アセトン、メチルエチルケトン、メチルイソブチルケトンなど）、エステル系有機溶剤（例えば、酢酸メチル、酢酸エチル、酢酸ｎ－プロピル、酢酸ｎ－ブチル、酢酸イソブチルなど）、アルコール系有機溶剤（メタノール、エタノール、ｎ－プロパノール、イソプロパノール、ブタノールなど）、炭化水素系溶剤（トルエン、メチルシクロヘキサンなど）が利用できる。
　なお、環境問題への対応と、インキの印刷適性や乾燥性などを考慮して、中でも印刷時の軟包装用ラミネート印刷インキ組成物の有機溶剤として、エステル系有機溶剤とアルコール系有機溶剤との混合溶剤を、エステル系有機溶剤／アルコール系有機溶剤＝５０／５０～９５／５の範囲、好ましくはエステル系有機溶剤／アルコール系有機溶剤＝６０／４０～８５／１５の範囲となるように使用することが好ましい。
　さらに、インキの印刷適性の点から、印刷時の軟包装用ラミネート印刷インキ組成物中に酢酸プロピルを５質量％以上、好ましくは１５質量％以上含有させることが好ましい。 <Organic solvent>
Examples of the organic solvent used in the laminate printing ink composition for flexible packaging include toluene, ketone organic solvents (for example, acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.), ester organic solvents (for example, methyl acetate, ethyl acetate, acetic acid). n-propyl, n-butyl acetate, isobutyl acetate, etc.), alcohol organic solvents (methanol, ethanol, n-propanol, isopropanol, butanol, etc.), hydrocarbon solvents (toluene, methylcyclohexane, etc.) can be used.
In consideration of environmental problems and the printability and drying properties of the ink, among the organic solvents for laminating printing ink compositions for soft packaging at the time of printing, ester organic solvents and alcoholic organic solvents The mixed solvent is used such that ester organic solvent / alcohol organic solvent = 50/50 to 95/5, preferably ester organic solvent / alcohol organic solvent = 60/40 to 85/15. It is preferable to do.
Furthermore, from the viewpoint of printing suitability of the ink, it is preferable to contain 5% by mass or more, preferably 15% by mass or more of propyl acetate in the laminated printing ink composition for soft packaging at the time of printing.
＜添加剤＞
　上記軟包装用ラミネート印刷インキ組成物には、さらに粘着付与剤、架橋剤、滑剤、耐ブロッキング剤、帯電防止剤、界面活性剤等の各種添加剤を添加することができる。 <Additives>
Various additives such as a tackifier, a crosslinking agent, a lubricant, an anti-blocking agent, an antistatic agent, and a surfactant can be further added to the above-mentioned laminate printing ink composition for soft packaging.
＜本発明の軟包装用ラミネート印刷インキ組成物の製造方法＞
　本発明の軟包装用ラミネート印刷インキ組成物は、上述の各種材料を従来一般的に使用されている各種の分散・混練装置を使用して製造することができる。
　そして、各固形分材料の含有量や、バインダー樹脂と有機溶剤との組み合わせなどを調整することにより、粘度を１０～１０００ｍＰａ・ｓとする。グラビア印刷時に使用する場合は、印刷時の雰囲気温度において、印刷条件に応じて適切な粘度となるように、具体的にはザーンカップ３号の流出秒数が１２～２３秒／２５℃、高速印刷では１４～１６秒／２５℃程度となるまで有機溶剤で希釈することが好ましい。 <Method for Producing Laminate Printing Ink Composition for Soft Packaging of the Present Invention>
The laminated printing ink composition for soft packaging of the present invention can be produced by using various dispersing / kneading apparatuses generally used for the various materials described above.
The viscosity is adjusted to 10 to 1000 mPa · s by adjusting the content of each solid material and the combination of the binder resin and the organic solvent. When using at the time of gravure printing, in order to obtain an appropriate viscosity according to the printing conditions at the atmospheric temperature during printing, specifically, the Zahn Cup No. 3 outflow time is 12-23 seconds / 25 ° C, high speed In printing, it is preferable to dilute with an organic solvent until the temperature reaches about 14 to 16 seconds / 25 ° C.
＜本発明の軟包装用ラミネート印刷インキ組成物を使用したグラビア印刷方法＞
　上記軟包装用ラミネート印刷インキ組成物を印刷する方法としては、一般的なグラビア印刷方式が利用できる。また、印刷用基材としては特に限定されず、ポリエチレン、ポリプロピレン等のポリオレフィンフィルム、ポリエチレンテレフタレート（ＰＥＴ）、ポリ乳酸、ポリカプロラクトン等のポリエステルフィルム、ナイロン、ビニロンといった各種印刷用プラスチックフィルムや、それら各種印刷用プラスチックフィルムに金属蒸着、バリア性樹脂をコーティングしたバリア層を積層したフィルムを対象とするものである。もちろん、本発明の主旨からして、通常のフィルムであっても、熱収縮フィルムであってもよく、印刷後にラミネートや収縮処理等の後加工を行うこともできる。
　また、使用する印刷版としては、従来の印刷版（通常のグラビア製版方式によって作られる凹版で、その製版方式は、彫刻グラビア等が例示できる）、従来の印刷版より浅いセルを形成（浅版化）した印刷版が利用できる。 <A gravure printing method using the laminate printing ink composition for soft packaging of the present invention>
As a method for printing the laminate printing ink composition for soft packaging, a general gravure printing method can be used. The substrate for printing is not particularly limited, and is a polyolefin film such as polyethylene or polypropylene, a polyester film such as polyethylene terephthalate (PET), polylactic acid or polycaprolactone, various printing plastic films such as nylon or vinylon, and various types thereof. It is intended for a film in which a barrier layer formed by coating a metal film and a barrier resin is laminated on a plastic film for printing. Of course, from the gist of the present invention, it may be a normal film or a heat-shrinkable film, and post-processing such as laminating or shrinking treatment can be performed after printing.
In addition, as a printing plate to be used, a conventional printing plate (an intaglio plate made by a normal gravure plate making method, the plate making method can be exemplified by engraving gravure etc.), a cell shallower than a conventional printing plate (shallow plate) A printed version can be used.
　上記グラビア印刷方法においては、上記軟包装用ラミネート印刷インキ組成物を、上記印刷版を用いて印刷することにより、さらに、上記の方法で得られた印刷物を、各種ラミネート加工法によりラミネート加工を施して、包装袋、ラミネート缶等に利用することができる。上記包装袋でのラミネート加工法としては、印刷物の表面にアンカーコート剤を塗工した後、溶融ポリマーを積層させる押し出しラミネート法、印刷物の表面に接着剤を塗工した後、フィルム状ポリマーを貼合させるドライラミネート法が利用できる。
　上記押し出しラミネート法は、印刷物の表面に必要に応じて、チタン系、ウレタン系、イミン系、ポリブタジエン系等のアンカーコート剤を塗工した後、既知の押し出しラミネート機によって、溶融ポリマーを積層させる方法であり、さらに溶融樹脂を中間層として、他の材料とサンドイッチ状に積層することもできる。
　上記押し出しラミネート法で使用する溶融樹脂としては、低密度ポリエチレン、エチレン－酢酸ビニル共重合体、ポリプロピレン等、従来使用されていた樹脂が使用できる。 In the gravure printing method, the laminate printing ink composition for soft packaging is printed using the printing plate, and the printed matter obtained by the method is further laminated by various laminating methods. It can be used for packaging bags, laminated cans, etc. The laminating method for the packaging bag is an extrusion laminating method in which an anchor coating agent is applied to the surface of the printed material, and then a molten polymer is laminated, an adhesive is applied to the surface of the printed material, and then a film polymer is applied. A dry laminating method can be used.
The above extrusion laminating method is a method of laminating a molten polymer by a known extrusion laminating machine after applying an anchor coating agent such as titanium, urethane, imine, polybutadiene or the like to the surface of the printed material as necessary. Furthermore, it can also be laminated in a sandwich with other materials using the molten resin as an intermediate layer.
As the molten resin used in the extrusion laminating method, conventionally used resins such as low density polyethylene, ethylene-vinyl acetate copolymer, and polypropylene can be used.
　また、上記ドライラミネート法は、印刷物の表面にウレタン系、イソシアネート系等の接着剤を塗工した後、既知のドライラミネート機によってフィルム状のポリマーを貼合する方法である。ドライラミネート法で使用するフィルム状のポリマーとしては、ポリエチレン、無延伸ポリプロピレン等が使用でき、特にレトルト用途で使用される包装材料では、基材と貼合されるプラスチックフィルムの間にアルミ箔をはさんでラミネートすることもできる。このようなラミネート加工物は、製袋して内容物を詰めた後、ボイル・レトルト用途に利用することもできる。 The dry laminating method is a method of applying a film-like polymer by a known dry laminating machine after applying an adhesive such as urethane or isocyanate to the surface of the printed material. Polyethylene, unstretched polypropylene, etc. can be used as the film-like polymer used in the dry laminating method. Especially in packaging materials used for retort applications, aluminum foil is placed between the base material and the plastic film to be bonded. Can also be laminated. Such a laminated product can be used for boil and retort after bag making and filling the contents.
　上記ラミネート缶用途でのラミネート加工法としては、印刷物表面に接着剤を塗工した後、金属板と貼り合わせる方法が利用できる。
　具体的には、印刷物の表面に、スプレーコーティング、ロールコーティング、グラビアコーティング等の公知の塗装手段にて接着剤を塗布し、１５０～２００℃の温度で乾燥させ、得られた印刷インキ層、接着剤層を有する印刷用基材を金属板と貼り合わせ、約１００～２５０℃の温度で短時間加熱ラミネートすることによって、印刷物を金属板と貼り合わせることができる。
　上記接着剤としては、例えば、１液型又は２液型のポリエステル樹脂系接着剤、ポリウレタン樹脂系接着剤、エポキシ樹脂系接着剤等が挙げられる。
　上記金属板としては、熱延鋼板、冷延鋼板、溶融亜鉛メッキ鋼板、電気亜鉛メッキ鋼板、鉄－亜鉛合金メッキ鋼板、亜鉛－アルミニウム合金メッキ鋼板、ニッケル－亜鉛合金メッキ鋼板、ニッケル－錫合金メッキ鋼板、ブリキ、クロムメッキ鋼板、アルミニウムメッキ鋼板、ターンメッキ鋼板、ニッケルメッキ鋼板等の各種メッキ鋼板、ステンレススチール、ティンフリースチール、アルミニウム板、鋼板、チタン板等の金属素材や、必要に応じて、これらの金属素材に、例えば、リン酸塩処理、クロメート処理、複合酸化膜処理等の化成処置を行ったもの等を用いることができる。
　本発明で得られたラミネート缶は、レトルト処理後の印刷物の接着性に優れたものとなる。 As a laminating method for use in the above-mentioned laminate can, an adhesive can be applied to the surface of a printed material and then bonded to a metal plate.
Specifically, an adhesive is applied to the surface of the printed material by known coating means such as spray coating, roll coating, gravure coating, etc., and dried at a temperature of 150 to 200 ° C. The printed material can be bonded to the metal plate by bonding the printing substrate having the agent layer to the metal plate and laminating by heating at a temperature of about 100 to 250 ° C. for a short time.
Examples of the adhesive include a one-component or two-component polyester resin adhesive, a polyurethane resin adhesive, and an epoxy resin adhesive.
As the above metal plate, hot rolled steel plate, cold rolled steel plate, hot dip galvanized steel plate, electrogalvanized steel plate, iron-zinc alloy plated steel plate, zinc-aluminum alloy plated steel plate, nickel-zinc alloy plated steel plate, nickel-tin alloy plated Metal plates such as steel plates, tinplate, chrome-plated steel plates, aluminum-plated steel plates, turn-plated steel plates, nickel-plated steel plates, stainless steel, tin-free steel, aluminum plates, steel plates, titanium plates, etc. As these metal materials, for example, those subjected to chemical conversion treatment such as phosphate treatment, chromate treatment, and composite oxide film treatment can be used.
The laminate can obtained by the present invention is excellent in the adhesiveness of the printed matter after the retort treatment.
　以下に実施例を挙げて本発明をさらに詳細に説明するが、本発明はこれらの実施例のみに限定されるものではない。なお、特に断りのない限り、「％」は「質量％」を意味し、「部」は「質量部」を意味する。
＜ポリエーテルポリオールとポリエステルポリオール使用系＞
ポリウレタン樹脂ワニスA：
　I.I.=1.6、IPDI/水添=50/50、アミン価が最適なもの
ポリウレタン樹脂ワニスB：
　I.I.=1.6、IPDI/水添=0/100、アミン価が最適なもの
ポリウレタン樹脂ワニスC：
　I.I.=1.6、IPDI/水添=25/75、アミン価が最適なもの
ポリウレタン樹脂ワニスD：
　I.I.=1.6、IPDI/水添=75/25、アミン価が最適なもの
ポリウレタン樹脂ワニスE：
　I.I.=1.6、IPDI/水添=50/50、アミン価が最適より小さいもの
ポリウレタン樹脂ワニスF：
　I.I.=1.6、IPDI/水添=50/50、アミン価が最適より大きいもの
ポリウレタン樹脂ワニスG：
　I.I.=1.5、IPDI/水添=50/50、アミン価が最適なもの
ポリウレタン樹脂ワニスH：
　I.I.=1.6、IPDI/水添=50/50、アミン価が０のもの
ポリウレタン樹脂ワニスI：
　I.I.=1.6、IPDI=100、アミン価が最適なもの The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. Unless otherwise specified, “%” means “% by mass”, and “part” means “part by mass”.
<System using polyether polyol and polyester polyol>
Polyurethane resin varnish A:
II = 1.6, IPDI / Hydrogenation = 50/50, Optimal amine value Polyurethane resin varnish B:
II = 1.6, IPDI / Hydrogenation = 0/100, Optimal amine value Polyurethane resin varnish C:
II = 1.6, IPDI / hydrogenation = 25/75, optimal amine value Polyurethane resin varnish D:
II = 1.6, IPDI / hydrogenation = 75/25, optimal amine value Polyurethane resin varnish E:
II = 1.6, IPDI / hydrogenation = 50/50, amine value is less than optimum polyurethane resin varnish F:
II = 1.6, IPDI / Hydrogenation = 50/50, Amine value greater than optimum Polyurethane resin varnish G:
II = 1.5, IPDI / hydrogenation = 50/50, optimal amine value Polyurethane resin varnish H:
Polyurethane resin varnish with II = 1.6, IPDI / hydrogenation = 50/50, 0 amine value:
II = 1.6, IPDI = 100, optimal amine value
＜ポリウレタン樹脂ワニスＡの製造例＞
　撹拌機、冷却管及び窒素ガス導入管を備えた四つ口フラスコに、平均分子量２０００の３－メチル－１，５－ペンチレンアジペートジオール１００質量部、平均分子量２０００のポリプロピレングリコール１００質量部、及びイソホロンジイソシアネート１７．６質量部、水添ＭＤＩ２１．０質量部を仕込み、窒素ガスを導入しながら１００～１０５℃で６時間反応させた。室温近くまで放冷し、酢酸エチル４００質量部、イソプロピルアルコール１７１質量部を加えた後、イソホロンジアミン８．２質量部を加えて鎖伸長させ、さらにモノエタノールアミン０．３５質量部を加え反応させ、その後、イソホロンジアミン１．３質量部、ジエチレントリアミン０．６質量部を加えて反応停止させてポリウレタン樹脂ワニスＡ（固形分３０質量％、アミン価３．２）を得た。 <Production example of polyurethane resin varnish A>
In a four-necked flask equipped with a stirrer, a condenser tube and a nitrogen gas inlet tube, 100 parts by mass of 3-methyl-1,5-pentylene adipatediol having an average molecular weight of 2000, 100 parts by mass of polypropylene glycol having an average molecular weight of 2000, and 17.6 parts by mass of isophorone diisocyanate and 21.0 parts by mass of hydrogenated MDI were charged and reacted at 100 to 105 ° C. for 6 hours while introducing nitrogen gas. After allowing to cool to near room temperature, 400 parts by mass of ethyl acetate and 171 parts by mass of isopropyl alcohol are added, then 8.2 parts by mass of isophoronediamine is added to extend the chain, and 0.35 parts by mass of monoethanolamine is further added and reacted. Thereafter, 1.3 parts by mass of isophoronediamine and 0.6 parts by mass of diethylenetriamine were added to stop the reaction, thereby obtaining a polyurethane resin varnish A (solid content: 30% by mass, amine value: 3.2).
＜ポリウレタン樹脂ワニスＢの製造例＞
　撹拌機、冷却管及び窒素ガス導入管を備えた四つ口フラスコに、平均分子量２０００の３－メチル－１，５－ペンチレンアジペートジオール１００質量部、平均分子量２０００のポリプロピレングリコール１００質量部、及び水添ＭＤＩ４１．８質量部を仕込み、窒素ガスを導入しながら１００～１０５℃で６時間反応させた。室温近くまで放冷し、酢酸エチル４１２質量部、イソプロピルアルコール１７７質量部を加えた後、イソホロンジアミン８．２質量部を加えて鎖伸長させ、さらにモノエタノールアミン０．３５質量部を加え反応させ、その後、イソホロンジアミン１．３質量部、ジエチレントリアミン０．６質量部を加えて反応停止させてポリウレタン樹脂ワニスＢ（固形分３０質量％、アミン価３．２）を得た。 <Production example of polyurethane resin varnish B>
In a four-necked flask equipped with a stirrer, a condenser tube and a nitrogen gas inlet tube, 100 parts by mass of 3-methyl-1,5-pentylene adipatediol having an average molecular weight of 2000, 100 parts by mass of polypropylene glycol having an average molecular weight of 2000, and 41.8 parts by mass of hydrogenated MDI was charged and reacted at 100 to 105 ° C. for 6 hours while introducing nitrogen gas. After cooling to near room temperature, 412 parts by mass of ethyl acetate and 177 parts by mass of isopropyl alcohol were added, then 8.2 parts by mass of isophorone diamine was added to extend the chain, and 0.35 parts by mass of monoethanolamine was further added and reacted. Thereafter, 1.3 parts by mass of isophoronediamine and 0.6 parts by mass of diethylenetriamine were added to stop the reaction, thereby obtaining a polyurethane resin varnish B (solid content: 30% by mass, amine value: 3.2).
＜ポリウレタン樹脂ワニスＣの製造例＞
　撹拌機、冷却管及び窒素ガス導入管を備えた四つ口フラスコに、平均分子量２０００の３－メチル－１，５－ペンチレンアジペートジオール１００質量部、平均分子量２０００のポリプロピレングリコール１００質量部、及びイソホロンジイソシアネート８．８質量部、水添ＭＤＩ３１．３質量部を仕込み、窒素ガスを導入しながら１００～１０５℃で６時間反応させた。室温近くまで放冷し、酢酸エチル４０９質量部、イソプロピルアルコール１７５質量部を加えた後、イソホロンジアミン８．２質量部を加えて鎖伸長させ、さらにモノエタノールアミン０．３５質量部を加え反応させ、その後、イソホロンジアミン１．３質量部、ジエチレントリアミン０．６質量部を加えて反応停止させてポリウレタン樹脂ワニスＣ（固形分３０質量％、アミン価３．２）を得た。 <Production example of polyurethane resin varnish C>
In a four-necked flask equipped with a stirrer, a condenser tube and a nitrogen gas inlet tube, 100 parts by mass of 3-methyl-1,5-pentylene adipatediol having an average molecular weight of 2000, 100 parts by mass of polypropylene glycol having an average molecular weight of 2000, and 8.8 parts by mass of isophorone diisocyanate and 31.3 parts by mass of hydrogenated MDI were charged and reacted at 100 to 105 ° C. for 6 hours while introducing nitrogen gas. After allowing to cool to near room temperature, 409 parts by mass of ethyl acetate and 175 parts by mass of isopropyl alcohol were added, then 8.2 parts by mass of isophoronediamine was added to extend the chain, and 0.35 parts by mass of monoethanolamine was further added and reacted. Thereafter, 1.3 parts by mass of isophoronediamine and 0.6 parts by mass of diethylenetriamine were added to stop the reaction, thereby obtaining a polyurethane resin varnish C (solid content: 30% by mass, amine value: 3.2).
＜ポリウレタン樹脂ワニスＤの製造例＞
　撹拌機、冷却管及び窒素ガス導入管を備えた四つ口フラスコに、平均分子量２０００の３－メチル－１，５－ペンチレンアジペートジオール１００質量部、平均分子量２０００のポリプロピレングリコール１００質量部、及びイソホロンジイソシアネート２６．５質量部、水添ＭＤＩ１０．４質量部を仕込み、窒素ガスを導入しながら１００～１０５℃で６時間反応させた。室温近くまで放冷し、酢酸エチル４０４質量部、イソプロピルアルコール１７３質量部を加えた後、イソホロンジアミン８．２質量部を加えて鎖伸長させ、さらにモノエタノールアミン０．３５質量部を加え反応させ、その後、イソホロンジアミン１．３質量部、ジエチレントリアミン０．６質量部を加えて反応停止させてポリウレタン樹脂ワニスＤ（固形分３０質量％、アミン価３．２）を得た。 <Production example of polyurethane resin varnish D>
In a four-necked flask equipped with a stirrer, a condenser tube and a nitrogen gas inlet tube, 100 parts by mass of 3-methyl-1,5-pentylene adipatediol having an average molecular weight of 2000, 100 parts by mass of polypropylene glycol having an average molecular weight of 2000, and 26.5 parts by mass of isophorone diisocyanate and 10.4 parts by mass of hydrogenated MDI were charged and reacted at 100 to 105 ° C. for 6 hours while introducing nitrogen gas. After allowing to cool to near room temperature, 404 parts by mass of ethyl acetate and 173 parts by mass of isopropyl alcohol are added, then 8.2 parts by mass of isophoronediamine is added to extend the chain, and 0.35 parts by mass of monoethanolamine is further added and reacted. Thereafter, 1.3 parts by mass of isophoronediamine and 0.6 parts by mass of diethylenetriamine were added to stop the reaction, thereby obtaining a polyurethane resin varnish D (solid content: 30% by mass, amine value: 3.2).
＜ポリウレタン樹脂ワニスＥの製造例＞
　撹拌機、冷却管及び窒素ガス導入管を備えた四つ口フラスコに、平均分子量２０００の３－メチル－１，５－ペンチレンアジペートジオール１００質量部、平均分子量２０００のポリプロピレングリコール１００質量部、及びイソホロンジイソシアネート１７．６質量部、水添ＭＤＩ２１．０質量部を仕込み、窒素ガスを導入しながら１００～１０５℃で６時間反応させた。室温近くまで放冷し、酢酸エチル４０５質量部、イソプロピルアルコール１７５質量部を加えた後、イソホロンジアミン８．２質量部を加えて鎖伸長させ、さらにモノエタノールアミン０．７質量部を加え反応させ、その後、イソホロンジアミン０．６５質量部、ジエチレントリアミン０．３９質量部を加えて反応停止させてポリウレタン樹脂ワニスＥ（固形分３０質量％、アミン価１．５）を得た。 <Production example of polyurethane resin varnish E>
In a four-necked flask equipped with a stirrer, a condenser tube and a nitrogen gas inlet tube, 100 parts by mass of 3-methyl-1,5-pentylene adipatediol having an average molecular weight of 2000, 100 parts by mass of polypropylene glycol having an average molecular weight of 2000, and 17.6 parts by mass of isophorone diisocyanate and 21.0 parts by mass of hydrogenated MDI were charged and reacted at 100 to 105 ° C. for 6 hours while introducing nitrogen gas. The mixture is allowed to cool to near room temperature, 405 parts by mass of ethyl acetate and 175 parts by mass of isopropyl alcohol are added, then 8.2 parts by mass of isophoronediamine is added to extend the chain, and 0.7 parts by mass of monoethanolamine is added and reacted. Thereafter, 0.65 parts by mass of isophoronediamine and 0.39 parts by mass of diethylenetriamine were added to stop the reaction, thereby obtaining a polyurethane resin varnish E (solid content 30% by mass, amine value 1.5).
＜ポリウレタン樹脂ワニスＦの製造例＞
　撹拌機、冷却管及び窒素ガス導入管を備えた四つ口フラスコに、平均分子量２０００の３－メチル－１，５－ペンチレンアジペートジオール１００質量部、平均分子量２０００のポリプロピレングリコール１００質量部、及びイソホロンジイソシアネート１７．６質量部、水添ＭＤＩ２１．０質量部を仕込み、窒素ガスを導入しながら１００～１０５℃で６時間反応させた。室温近くまで放冷し、酢酸エチル４０７質量部、イソプロピルアルコール１７５質量部を加えた後、イソホロンジアミン８．２質量部を加えて鎖伸長させ、その後イソホロンジアミン１．６質量部、ジエチレントリアミン１．０質量部を加えて反応停止させてポリウレタン樹脂ワニスＦ（固形分３０質量％、アミン価５．４）を得た。 <Production example of polyurethane resin varnish F>
In a four-necked flask equipped with a stirrer, a condenser tube and a nitrogen gas inlet tube, 100 parts by mass of 3-methyl-1,5-pentylene adipatediol having an average molecular weight of 2000, 100 parts by mass of polypropylene glycol having an average molecular weight of 2000, and 17.6 parts by mass of isophorone diisocyanate and 21.0 parts by mass of hydrogenated MDI were charged and reacted at 100 to 105 ° C. for 6 hours while introducing nitrogen gas. The mixture was allowed to cool to near room temperature, 407 parts by mass of ethyl acetate and 175 parts by mass of isopropyl alcohol were added, then 8.2 parts by mass of isophorone diamine was added to extend the chain, and then 1.6 parts by mass of isophorone diamine and 1.0 parts of diethylenetriamine were added. The reaction was stopped by adding parts by mass to obtain a polyurethane resin varnish F (solid content: 30% by mass, amine value: 5.4).
＜ポリウレタン樹脂ワニスＧの製造例＞
　撹拌機、冷却管及び窒素ガス導入管を備えた四つ口フラスコに、平均分子量２０００の３－メチル－１，５－ペンチレンアジペートジオール１００質量部、平均分子量２０００のポリプロピレングリコール１００質量部、及びイソホロンジイソシアネート１６．７質量部、水添ＭＤＩ１９．７質量部を仕込み、窒素ガスを導入しながら１００～１０５℃で６時間反応させた。室温近くまで放冷し、酢酸エチル４００質量部、イソプロピルアルコール１７２質量部を加えた後、イソホロンジアミン６．８質量部を加えて鎖伸長させ、さらにモノエタノールアミン０．３質量部を加え反応させ、その後、イソホロンジアミン１．２質量部、ジエチレントリアミン０．５質量部を加えて反応停止させてポリウレタン樹脂ワニスＧ（固形分３０質量％、アミン価３．２）を得た。 <Production example of polyurethane resin varnish G>
In a four-necked flask equipped with a stirrer, a condenser tube and a nitrogen gas inlet tube, 100 parts by mass of 3-methyl-1,5-pentylene adipatediol having an average molecular weight of 2000, 100 parts by mass of polypropylene glycol having an average molecular weight of 2000, and 16.7 parts by mass of isophorone diisocyanate and 19.7 parts by mass of hydrogenated MDI were charged and reacted at 100 to 105 ° C. for 6 hours while introducing nitrogen gas. After cooling to near room temperature, 400 parts by mass of ethyl acetate and 172 parts by mass of isopropyl alcohol are added, then 6.8 parts by mass of isophoronediamine is added to extend the chain, and 0.3 parts by mass of monoethanolamine is further added to react. Thereafter, 1.2 parts by mass of isophoronediamine and 0.5 parts by mass of diethylenetriamine were added to stop the reaction, thereby obtaining a polyurethane resin varnish G (solid content: 30% by mass, amine value: 3.2).
＜ポリウレタン樹脂ワニスＨの製造例＞
　撹拌機、冷却管及び窒素ガス導入管を備えた四つ口フラスコに、平均分子量２０００の３－メチル－１，５－ペンチレンアジペートジオール１００質量部、平均分子量２０００のポリプロピレングリコール１００質量部、及びイソホロンジイソシアネート１７．６質量部、水添ＭＤＩ２１．０質量部を仕込み、窒素ガスを導入しながら１００～１０５℃で６時間反応させた。室温近くまで放冷し、酢酸エチル４０６質量部、イソプロピルアルコール１７５質量部を加えた後、イソホロンジアミン９．２質量部を加えて鎖伸長させ、さらにモノエタノールアミン０．７質量部を加えて反応停止させ、ポリウレタン樹脂ワニスＨ（固形分３０質量％、アミン価０）を得た。 <Production example of polyurethane resin varnish H>
In a four-necked flask equipped with a stirrer, a condenser tube and a nitrogen gas inlet tube, 100 parts by mass of 3-methyl-1,5-pentylene adipatediol having an average molecular weight of 2000, 100 parts by mass of polypropylene glycol having an average molecular weight of 2000, and 17.6 parts by mass of isophorone diisocyanate and 21.0 parts by mass of hydrogenated MDI were charged and reacted at 100 to 105 ° C. for 6 hours while introducing nitrogen gas. The mixture was allowed to cool to near room temperature, 406 parts by mass of ethyl acetate and 175 parts by mass of isopropyl alcohol were added, then 9.2 parts by mass of isophoronediamine was added to extend the chain, and 0.7 parts by mass of monoethanolamine was further added to react. The polyurethane resin varnish H (solid content 30% by mass, amine value 0) was obtained.
＜ポリウレタン樹脂ワニスＩの製造例＞
　撹拌機、冷却管及び窒素ガス導入管を備えた四つ口フラスコに、平均分子量２０００の３－メチル－１，５－ペンチレンアジペートジオール１００質量部、平均分子量２０００のポリプロピレングリコール１００質量部、及びイソホロンジイソシアネート３５．２質量部を仕込み、窒素ガスを導入しながら１００～１０５℃で６時間反応させた。室温近くまで放冷し、酢酸エチル４０２質量部、イソプロピルアルコール１７２質量部を加えた後、イソホロンジアミン８．２質量部を加えて鎖伸長させ、さらにモノエタノールアミン０．３５質量部を加え反応させ、その後、イソホロンジアミン１．３質量部、ジエチレントリアミン０．６質量部を加えて反応停止させてポリウレタン樹脂ワニスＩ（固形分３０質量％、アミン価３．２）を得た。 <Production example of polyurethane resin varnish I>
In a four-necked flask equipped with a stirrer, a condenser tube and a nitrogen gas inlet tube, 100 parts by mass of 3-methyl-1,5-pentylene adipatediol having an average molecular weight of 2000, 100 parts by mass of polypropylene glycol having an average molecular weight of 2000, and 35.2 parts by mass of isophorone diisocyanate was charged and reacted at 100 to 105 ° C. for 6 hours while introducing nitrogen gas. After allowing to cool to near room temperature, 402 parts by mass of ethyl acetate and 172 parts by mass of isopropyl alcohol were added, and then 8.2 parts by mass of isophoronediamine was added to extend the chain, followed by addition of 0.35 parts by mass of monoethanolamine. Thereafter, 1.3 parts by mass of isophoronediamine and 0.6 parts by mass of diethylenetriamine were added to stop the reaction, thereby obtaining a polyurethane resin varnish I (solid content: 30% by mass, amine value: 3.2).
＜ポリエステルポリオール使用系＞
ポリウレタン樹脂ワニスJ：
　I.I.=1.6、IPDI/水添=50/50、アミン価が最適なもの
ポリウレタン樹脂ワニスK：
　I.I.=1.6、IPDI/水添=0/100、アミン価が最適なもの
ポリウレタン樹脂ワニスL：
　I.I.=1.6、IPDI/水添=25/75、アミン価が最適なもの
ポリウレタン樹脂ワニスM：
　I.I.=1.6、IPDI/水添=75/25、アミン価が最適なもの
ポリウレタン樹脂ワニスN：
　I.I.=1.6、IPDI/水添=50/50、アミン価が最適より小さいもの
ポリウレタン樹脂ワニスO：
　I.I.=1.6、IPDI/水添=50/50、アミン価が最適より大きいもの
ポリウレタン樹脂ワニスP：
　I.I.=1.5、IPDI/水添=50/50、アミン価が最適なもの
ポリウレタン樹脂ワニスQ：
　I.I.=1.6、IPDI/水添=50/50、アミン価が０のもの
ポリウレタン樹脂ワニスR：
　I.I.=1.6、IPDI=100、アミン価が最適なもの <Polyester polyol use system>
Polyurethane resin varnish J:
II = 1.6, IPDI / Hydrogenation = 50/50, Optimum amine value Polyurethane resin varnish K:
II = 1.6, IPDI / Hydrogenation = 0/100, Optimal amine value Polyurethane resin varnish L:
II = 1.6, IPDI / hydrogenation = 25/75, optimal amine value Polyurethane resin varnish M:
II = 1.6, IPDI / hydrogenation = 75/25, optimal amine value Polyurethane resin varnish N:
II = 1.6, IPDI / Hydrogenation = 50/50, Amine value is less than optimum Polyurethane resin varnish O:
II = 1.6, IPDI / Hydrogenation = 50/50, Amine value greater than optimum Polyurethane resin varnish P:
II = 1.5, IPDI / hydrogenation = 50/50, optimal amine value Polyurethane resin varnish Q:
Polyurethane resin varnish R with II = 1.6, IPDI / hydrogenation = 50/50, 0 amine number:
II = 1.6, IPDI = 100, optimal amine value
＜ポリウレタン樹脂ワニスＪの製造例＞
　撹拌機、冷却管及び窒素ガス導入管を備えた四つ口フラスコに、平均分子量２０００の３－メチル－１，５－ペンチレンアジペートジオール２００質量部、及びイソホロンジイソシアネート１７．６質量部、水添ＭＤＩ２１．０質量部を仕込み、窒素ガスを導入しながら１００～１０５℃で６時間反応させた。室温近くまで放冷し、酢酸エチル４００質量部、イソプロピルアルコール１７１質量部を加えた後、イソホロンジアミン８．２質量部を加えて鎖伸長させ、さらにモノエタノールアミン０．３５質量部を加え反応させ、その後、イソホロンジアミン１．３質量部、ジエチレントリアミン０．６質量部を加えて反応停止させてポリウレタン樹脂ワニスＪ（固形分３０質量％、アミン価３．２）を得た。 <Production example of polyurethane resin varnish J>
In a four-necked flask equipped with a stirrer, a condenser tube and a nitrogen gas inlet tube, 200 parts by mass of 3-methyl-1,5-pentylene adipate diol having an average molecular weight of 2000 and 17.6 parts by mass of isophorone diisocyanate, hydrogenated 21.0 parts by mass of MDI was charged and reacted at 100 to 105 ° C. for 6 hours while introducing nitrogen gas. After allowing to cool to near room temperature, 400 parts by mass of ethyl acetate and 171 parts by mass of isopropyl alcohol are added, then 8.2 parts by mass of isophoronediamine is added to extend the chain, and 0.35 parts by mass of monoethanolamine is further added and reacted. Thereafter, 1.3 parts by mass of isophoronediamine and 0.6 parts by mass of diethylenetriamine were added to stop the reaction, thereby obtaining a polyurethane resin varnish J (solid content: 30% by mass, amine value: 3.2).
＜ポリウレタン樹脂ワニスＫの製造例＞
　撹拌機、冷却管及び窒素ガス導入管を備えた四つ口フラスコに、平均分子量２０００の３－メチル－１，５－ペンチレンアジペートジオール２００質量部、及び水添ＭＤＩ４１．８質量部を仕込み、窒素ガスを導入しながら１００～１０５℃で６時間反応させた。室温近くまで放冷し、酢酸エチル４１２質量部、イソプロピルアルコール１７７質量部を加えた後、イソホロンジアミン８．２質量部を加えて鎖伸長させ、さらにモノエタノールアミン０．３５質量部を加え反応させ、その後、イソホロンジアミン１．３質量部、ジエチレントリアミン０．６質量部を加えて反応停止させてポリウレタン樹脂ワニスＫ（固形分３０質量％、アミン価３．２）を得た。 <Production example of polyurethane resin varnish K>
A four-necked flask equipped with a stirrer, a condenser tube and a nitrogen gas inlet tube was charged with 200 parts by mass of 3-methyl-1,5-pentylene adipate diol having an average molecular weight of 2000 and 41.8 parts by mass of hydrogenated MDI. The reaction was carried out at 100 to 105 ° C. for 6 hours while introducing nitrogen gas. After cooling to near room temperature, 412 parts by mass of ethyl acetate and 177 parts by mass of isopropyl alcohol were added, then 8.2 parts by mass of isophorone diamine was added to extend the chain, and 0.35 parts by mass of monoethanolamine was further added and reacted. Thereafter, 1.3 parts by mass of isophoronediamine and 0.6 parts by mass of diethylenetriamine were added to stop the reaction, thereby obtaining a polyurethane resin varnish K (solid content: 30% by mass, amine value: 3.2).
＜ポリウレタン樹脂ワニスＬの製造例＞
　撹拌機、冷却管及び窒素ガス導入管を備えた四つ口フラスコに、平均分子量２０００の３－メチル－１，５－ペンチレンアジペートジオール２００質量部、及びイソホロンジイソシアネート８．８質量部、水添ＭＤＩ３１．３質量部を仕込み、窒素ガスを導入しながら１００～１０５℃で６時間反応させた。室温近くまで放冷し、酢酸エチル４０９質量部、イソプロピルアルコール１７５質量部を加えた後、イソホロンジアミン８．２質量部を加えて鎖伸長させ、さらにモノエタノールアミン０．３５質量部を加え反応させ、その後、イソホロンジアミン１．３質量部、ジエチレントリアミン０．６質量部を加えて反応停止させてポリウレタン樹脂ワニスＬ（固形分３０質量％、アミン価３．２）を得た。 <Production example of polyurethane resin varnish L>
In a four-necked flask equipped with a stirrer, a condenser tube and a nitrogen gas inlet tube, 200 parts by mass of 3-methyl-1,5-pentylene adipate diol having an average molecular weight of 2,000, 8.8 parts by mass of isophorone diisocyanate, hydrogenated 31.3 parts by mass of MDI was charged and reacted at 100 to 105 ° C. for 6 hours while introducing nitrogen gas. After allowing to cool to near room temperature, 409 parts by mass of ethyl acetate and 175 parts by mass of isopropyl alcohol were added, then 8.2 parts by mass of isophoronediamine was added to extend the chain, and 0.35 parts by mass of monoethanolamine was further added and reacted. Thereafter, 1.3 parts by mass of isophoronediamine and 0.6 parts by mass of diethylenetriamine were added to stop the reaction, and a polyurethane resin varnish L (solid content 30% by mass, amine value 3.2) was obtained.
＜ポリウレタン樹脂ワニスＭの製造例＞
　撹拌機、冷却管及び窒素ガス導入管を備えた四つ口フラスコに、平均分子量２０００の３－メチル－１，５－ペンチレンアジペートジオール２００質量部、及びイソホロンジイソシアネート２６．５質量部、水添ＭＤＩ１０．４質量部を仕込み、窒素ガスを導入しながら１００～１０５℃で６時間反応させた。室温近くまで放冷し、酢酸エチル４０４質量部、イソプロピルアルコール１７３質量部を加えた後、イソホロンジアミン８．２質量部を加えて鎖伸長させ、さらにモノエタノールアミン０．３５質量部を加え反応させ、その後、イソホロンジアミン１．３質量部、ジエチレントリアミン０．６質量部を加えて反応停止させてポリウレタン樹脂ワニスＭ（固形分３０質量％、アミン価３．２）を得た。 <Production example of polyurethane resin varnish M>
In a four-necked flask equipped with a stirrer, a condenser tube and a nitrogen gas inlet tube, 200 parts by mass of 3-methyl-1,5-pentylene adipate diol having an average molecular weight of 2000, 26.5 parts by mass of isophorone diisocyanate, hydrogenated 10.4 parts by mass of MDI was charged and reacted at 100 to 105 ° C. for 6 hours while introducing nitrogen gas. After allowing to cool to near room temperature, 404 parts by mass of ethyl acetate and 173 parts by mass of isopropyl alcohol are added, then 8.2 parts by mass of isophoronediamine is added to extend the chain, and 0.35 parts by mass of monoethanolamine is further added and reacted. Thereafter, 1.3 parts by mass of isophoronediamine and 0.6 parts by mass of diethylenetriamine were added to stop the reaction, thereby obtaining a polyurethane resin varnish M (solid content 30% by mass, amine value 3.2).
＜ポリウレタン樹脂ワニスＮの製造例＞
　撹拌機、冷却管及び窒素ガス導入管を備えた四つ口フラスコに、平均分子量２０００の３－メチル－１，５－ペンチレンアジペートジオール２００質量部、及びイソホロンジイソシアネート１７．６質量部、水添ＭＤＩ２１．０質量部を仕込み、窒素ガスを導入しながら１００～１０５℃で６時間反応させた。室温近くまで放冷し、酢酸エチル４０５質量部、イソプロピルアルコール１７５質量部を加えた後、イソホロンジアミン８．２質量部を加えて鎖伸長させ、さらにモノエタノールアミン０．７質量部を加え反応させ、その後、イソホロンジアミン０．６５質量部、ジエチレントリアミン０．３９質量部を加えて反応停止させてポリウレタン樹脂ワニスＮ（固形分３０質量％、アミン価１．５）を得た。 <Production example of polyurethane resin varnish N>
In a four-necked flask equipped with a stirrer, a condenser tube and a nitrogen gas inlet tube, 200 parts by mass of 3-methyl-1,5-pentylene adipate diol having an average molecular weight of 2000 and 17.6 parts by mass of isophorone diisocyanate, hydrogenated 21.0 parts by mass of MDI was charged and reacted at 100 to 105 ° C. for 6 hours while introducing nitrogen gas. The mixture is allowed to cool to near room temperature, 405 parts by mass of ethyl acetate and 175 parts by mass of isopropyl alcohol are added, then 8.2 parts by mass of isophoronediamine is added to extend the chain, and 0.7 parts by mass of monoethanolamine is added and reacted. Thereafter, 0.65 parts by mass of isophoronediamine and 0.39 parts by mass of diethylenetriamine were added to stop the reaction, thereby obtaining a polyurethane resin varnish N (solid content 30% by mass, amine value 1.5).
＜ポリウレタン樹脂ワニスＯの製造例＞
　撹拌機、冷却管及び窒素ガス導入管を備えた四つ口フラスコに、平均分子量２０００の３－メチル－１，５－ペンチレンアジペートジオール２００質量部、及びイソホロンジイソシアネート１７．６質量部、水添ＭＤＩ２１．０質量部を仕込み、窒素ガスを導入しながら１００～１０５℃で６時間反応させた。室温近くまで放冷し、酢酸エチル４０７質量部、イソプロピルアルコール１７５質量部を加えた後、イソホロンジアミン８．２質量部を加えて鎖伸長させ、その後イソホロンジアミン１．６質量部、ジエチレントリアミン１．０質量部を加えて反応停止させてポリウレタン樹脂ワニスＯ（固形分３０質量％、アミン価５．４）を得た。 <Production example of polyurethane resin varnish O>
In a four-necked flask equipped with a stirrer, a condenser tube and a nitrogen gas inlet tube, 200 parts by mass of 3-methyl-1,5-pentylene adipate diol having an average molecular weight of 2000 and 17.6 parts by mass of isophorone diisocyanate, hydrogenated 21.0 parts by mass of MDI was charged and reacted at 100 to 105 ° C. for 6 hours while introducing nitrogen gas. The mixture was allowed to cool to near room temperature, 407 parts by mass of ethyl acetate and 175 parts by mass of isopropyl alcohol were added, then 8.2 parts by mass of isophorone diamine was added to extend the chain, and then 1.6 parts by mass of isophorone diamine and 1.0 parts of diethylenetriamine were added. The reaction was stopped by adding parts by mass to obtain a polyurethane resin varnish O (solid content 30% by mass, amine value 5.4).
＜ポリウレタン樹脂ワニスＰの製造例＞
　撹拌機、冷却管及び窒素ガス導入管を備えた四つ口フラスコに、平均分子量２０００の３－メチル－１，５－ペンチレンアジペートジオール２００質量部、及びイソホロンジイソシアネート１６．７質量部、水添ＭＤＩ１９．７質量部を仕込み、窒素ガスを導入しながら１００～１０５℃で６時間反応させた。室温近くまで放冷し、酢酸エチル４００質量部、イソプロピルアルコール１７２質量部を加えた後、イソホロンジアミン６．８質量部を加えて鎖伸長させ、さらにモノエタノールアミン０．３質量部を加え反応させ、その後、イソホロンジアミン１．２質量部、ジエチレントリアミン０．５質量部を加えて反応停止させてポリウレタン樹脂ワニスＰ（固形分３０質量％、アミン価３．２）を得た。 <Production example of polyurethane resin varnish P>
In a four-necked flask equipped with a stirrer, a condenser tube and a nitrogen gas inlet tube, 200 parts by mass of 3-methyl-1,5-pentylene adipate diol having an average molecular weight of 2000 and 16.7 parts by mass of isophorone diisocyanate, hydrogenated 19.7 parts by mass of MDI was charged and reacted at 100 to 105 ° C. for 6 hours while introducing nitrogen gas. After cooling to near room temperature, 400 parts by mass of ethyl acetate and 172 parts by mass of isopropyl alcohol are added, then 6.8 parts by mass of isophoronediamine is added to extend the chain, and 0.3 parts by mass of monoethanolamine is further added to react. Thereafter, 1.2 parts by mass of isophoronediamine and 0.5 parts by mass of diethylenetriamine were added to stop the reaction, thereby obtaining a polyurethane resin varnish P (solid content: 30% by mass, amine value: 3.2).
＜ポリウレタン樹脂ワニスＱの製造例＞
　撹拌機、冷却管及び窒素ガス導入管を備えた四つ口フラスコに、平均分子量２０００の３－メチル－１，５－ペンチレンアジペートジオール２００質量部、及びイソホロンジイソシアネート１７．６質量部、水添ＭＤＩ２１．０質量部を仕込み、窒素ガスを導入しながら１００～１０５℃で６時間反応させた。室温近くまで放冷し、酢酸エチル４０６質量部、イソプロピルアルコール１７５質量部を加えた後、イソホロンジアミン９．２質量部を加えて鎖伸長させ、さらにモノエタノールアミン０．７質量部を加えて反応停止させ、ポリウレタン樹脂ワニスＱ（固形分３０質量％、アミン価０）を得た。 <Production example of polyurethane resin varnish Q>
In a four-necked flask equipped with a stirrer, a condenser tube and a nitrogen gas inlet tube, 200 parts by mass of 3-methyl-1,5-pentylene adipate diol having an average molecular weight of 2000 and 17.6 parts by mass of isophorone diisocyanate, hydrogenated 21.0 parts by mass of MDI was charged and reacted at 100 to 105 ° C. for 6 hours while introducing nitrogen gas. The mixture was allowed to cool to near room temperature, 406 parts by mass of ethyl acetate and 175 parts by mass of isopropyl alcohol were added, then 9.2 parts by mass of isophoronediamine was added to extend the chain, and 0.7 parts by mass of monoethanolamine was further added to react. The polyurethane resin varnish Q (solid content 30% by mass, amine value 0) was obtained.
＜ポリウレタン樹脂ワニスＲの製造例＞
　撹拌機、冷却管及び窒素ガス導入管を備えた四つ口フラスコに、平均分子量２０００の３－メチル－１，５－ペンチレンアジペートジオール２００質量部、及びイソホロンジイソシアネート５．２質量部を仕込み、窒素ガスを導入しながら１００～１０５℃で６時間反応させた。室温近くまで放冷し、酢酸エチル４０２質量部、イソプロピルアルコール１７２質量部を加えた後、イソホロンジアミン８．２質量部を加えて鎖伸長させ、さらにモノエタノールアミン０．３５質量部を加え反応させ、その後、イソホロンジアミン１．３質量部、ジエチレントリアミン０．６質量部を加えて反応停止させてポリウレタン樹脂ワニスＲ（固形分３０質量％、アミン価３．２）を得た。 <Production example of polyurethane resin varnish R>
A four-necked flask equipped with a stirrer, a condenser tube and a nitrogen gas inlet tube was charged with 200 parts by weight of 3-methyl-1,5-pentylene adipate diol having an average molecular weight of 2000 and 5.2 parts by weight of isophorone diisocyanate. The reaction was carried out at 100 to 105 ° C. for 6 hours while introducing nitrogen gas. After allowing to cool to near room temperature, 402 parts by mass of ethyl acetate and 172 parts by mass of isopropyl alcohol were added, and then 8.2 parts by mass of isophoronediamine was added to extend the chain, followed by addition of 0.35 parts by mass of monoethanolamine. Thereafter, 1.3 parts by mass of isophoronediamine and 0.6 parts by mass of diethylenetriamine were added to stop the reaction, thereby obtaining a polyurethane resin varnish R (solid content: 30% by mass, amine value: 3.2).
＜軟包装用ラミネート用白色インキ組成物の製造例＞
　顔料（酸化チタンＲ－９６０、デュポン社製）、上記ポリウレタン樹脂ワニスＡ～Ｒ、塩化ビニル－酢酸ビニル系樹脂（ソルバインＴＡ－３、日信化学工業（株）製）を、レッドデビル社製のペイントコンディショナーを用いて混練し、さらに溶媒（該ペイントコンディショナーと溶媒を合わせて混合液とした。）を加えて、表１に示した実施例１～１０、１２～１８、比較例１～４の軟包装用ラミネート用白色インキ組成物を得た。 <Production Example of White Ink Composition for Laminating for Soft Packaging>
Pigment (titanium oxide R-960, manufactured by DuPont), polyurethane resin varnish A to R, vinyl chloride-vinyl acetate resin (Solvine TA-3, manufactured by Nissin Chemical Industry Co., Ltd.), manufactured by Red Devil Kneading was performed using a paint conditioner, and a solvent (the paint conditioner and the solvent were combined to form a mixed solution) was added, and Examples 1 to 10, 12 to 18 and Comparative Examples 1 to 4 shown in Table 1 were added. A white ink composition for laminating soft packaging was obtained.
＜軟包装用ラミネート用藍色インキ組成物の製造例＞
　顔料（フタロシアニンブルーＣ．Ｉ．Ｐｉｇｍｅｎｔ　Ｂｌｕｅ　１５：４）、ポリウレタン樹脂ワニスＡ、Ｊ、塩化ビニル－酢酸ビニル系樹脂（ソルバインＴＡ－３、日信化学工業（株）製）を、レッドデビル社製のペイントコンディショナーを用いて混練し、さらに溶媒（該ペイントコンディショナーと溶媒を合わせて混合液とした。）を加えて、表１に示した実施例１１、１９の軟包装用ラミネート用藍色インキ組成物を得た。 <Production Example of Indigo Ink Composition for Laminating for Soft Packaging>
Pigment (phthalocyanine blue CI Pigment Blue 15: 4), polyurethane resin varnish A, J, vinyl chloride-vinyl acetate resin (Solvine TA-3, manufactured by Nissin Chemical Industry Co., Ltd.), manufactured by Red Devil Kneading using a paint conditioner, and adding a solvent (a mixture of the paint conditioner and the solvent to obtain a mixed solution), and the indigo ink composition for soft packaging laminates of Examples 11 and 19 shown in Table 1 I got a thing.
（評価）
　上記で得られた実施例１～１０、１２～１８、比較例１～４の軟包装用ラミネート用白色インキ組成物、実施例１１、１９の軟包装用ラミネート用藍色インキ組成物の性能評価を下記方法にて行い、評価結果を表１に示す。 (Evaluation)
Performance evaluation of the white ink composition for soft packaging laminates of Examples 1 to 10, 12 to 18 and Comparative Examples 1 to 4 obtained above, and the blue ink composition for soft packaging laminates of Examples 11 and 19 Was performed by the following method, and the evaluation results are shown in Table 1.
＜インキ組成物の性能評価＞
（インキの保存安定性）
　上記で得られた実施例１～１０、１２～１８、比較例１～４の軟包装用ラミネート用白色インキ組成物、実施例１１、１９の軟包装用ラミネート用藍色インキ組成物の各々をガラス瓶に採取し、６０℃の雰囲気温度で１４日間保存した時の顔料の沈降の有無から、インキの保存安定性を評価した。
　Ａ：沈降が見られず、インキの保存安定性は良好である
　Ｂ：沈降が見られ、インキの保存安定性は不良である <Performance evaluation of ink composition>
(Ink storage stability)
The white ink composition for soft packaging laminates of Examples 1 to 10, 12 to 18 and Comparative Examples 1 to 4 obtained above, and the indigo ink composition for soft packaging laminates of Examples 11 and 19 were used. The storage stability of the ink was evaluated from the presence or absence of precipitation of the pigment when it was collected in a glass bottle and stored at an ambient temperature of 60 ° C. for 14 days.
A: No sedimentation is observed, and the storage stability of the ink is good. B: Sedimentation is observed, and the storage stability of the ink is poor.
（印刷評価１の印刷条件）
　実施例１～１０、１２～１８、比較例１～４の軟包装用ラミネート用白色インキ組成物、実施例１１、１９の軟包装用ラミネート用藍色インキ組成物の各々１００質量部に対し、さらに表１の配合にしたがって混合溶剤で希釈し、粘度を離合社製ザーンカップ３号で１５秒に調整した後、彫刻版（印刷刷版、ヘリオ１７５線／ｉｎｃｈ）を備えたグラビア印刷機にて、ＯＰＰ、ＰＥＴ、ＮＹの処理面に印刷速度１５０ｍ／分で印刷を行った。 (Printing conditions for printing evaluation 1)
With respect to 100 parts by mass of each of the white ink composition for soft packaging laminate of Examples 1 to 10, 12 to 18, and Comparative Examples 1 to 4, and the indigo color ink composition for soft packaging laminate of Examples 11 and 19, respectively. Furthermore, after diluting with a mixed solvent in accordance with the composition shown in Table 1 and adjusting the viscosity to 15 seconds with Zahn Cup No. 3 manufactured by Koiso Co., Ltd., a gravure printing machine equipped with an engraving plate (printing plate, Helio 175 line / inch) Then, printing was performed at a printing speed of 150 m / min on the treated surfaces of OPP, PET, and NY.
（印刷評価２の印刷条件）
　実施例１～１０、１２～１８、比較例１～４の軟包装用ラミネート用白色インキ組成物、実施例１１、１９の軟包装用ラミネート用藍色インキ組成物の各々１００質量部に対し、さらに表１の配合にしたがって混合溶剤で希釈し、粘度を離合社製ザーンカップ３号で１５秒に調整した後、彫刻版（印刷刷板、ヘリオ１７５線／ｉｎｃｈ）を備えたグラビア印刷機にて、ＯＰＰ、ＰＥＴ、ＮＹの処理面に印刷速度１００ｍ／分で印刷を行った。 (Printing conditions for printing evaluation 2)
With respect to 100 parts by mass of each of the white ink composition for soft packaging laminate of Examples 1 to 10, 12 to 18, and Comparative Examples 1 to 4, and the indigo color ink composition for soft packaging laminate of Examples 11 and 19, respectively. Furthermore, after diluting with a mixed solvent according to the composition shown in Table 1 and adjusting the viscosity to 15 seconds with Zahn Cup No. 3 made by Koiso Co., Ltd., a gravure printing machine equipped with an engraving plate (printing plate, helio 175 line / inch) Then, printing was performed at a printing speed of 100 m / min on the treated surfaces of OPP, PET, and NY.
＜フィルムについて＞
　ＰＥＴ：片面にコロナ放電処理を施したポリエチレンテレフタレートフィ
　　　　　ルム、東洋紡（株）製、Ｅ－５１０１、厚さ１２μｍ
　ＯＰＰ：二軸延伸ポリプロピレンフィルム、東洋紡（株）製  Ｐ－２１６
　　　　　１、厚さ３０μｍ
　ＮＹ：ナイロンフィルム、東洋紡（株）製、Ｎ－１１０２、厚さ１５μｍ <About film>
PET: Polyethylene terephthalate film with corona discharge treatment on one side, manufactured by Toyobo Co., Ltd., E-5101, thickness 12 μm
OPP: Biaxially stretched polypropylene film, manufactured by Toyobo Co., Ltd. P-216
1. Thickness 30μm
NY: nylon film, manufactured by Toyobo Co., Ltd., N-1102, thickness 15 μm
＜印刷適性（カスレ）＞
　印刷適性については、印刷終了時の印刷部分における、版にインキが詰まったことに起因するカスレの面積の割合から印刷適性を評価した。
　なお、この評価だけは、印刷評価１及び２それぞれにて行った。
　Ａ：カスレが全くみられない
　Ｂ：カスレが少しみられる
　Ｃ：カスレが多くみられる <Printability (scratch)>
Regarding the printability, the printability was evaluated from the ratio of the area of the blur caused by the clogged ink in the printing portion at the end of printing.
In addition, only this evaluation was performed in printing evaluation 1 and 2, respectively.
A: No blurring is observed B: Scratch is observed a little C: Many blurring is observed
＜ガイドロール取られ＞
　下記の方法から、印刷後、ガイドロールにインキが付着するかどうか（ガイドロール取られ）試験を行い、印刷適性を評価した。なお、一旦、ガイドロールに付着したインキが、印刷面に再転移して汚れが発生するため、「ガイドロール取られ」が発生する場合は、美粧印刷物を得るのに対して悪影響を及ぼす。
　グラビア印刷機のガイドロールによる印刷物インキ塗膜の脱落の有無を目視により評価した。
　Ａ：有るもの
　Ｃ：無いもの <Guide roll taken>
From the following method, after printing, whether or not ink adheres to the guide roll (guide roll was taken) was tested to evaluate printability. The ink once adhered to the guide roll is re-transferred to the printing surface and stains occur. Therefore, when “guide roll removal” occurs, it has an adverse effect on obtaining a cosmetic print.
The presence or absence of removal of the printed ink coating film by the guide roll of the gravure printing machine was visually evaluated.
A: Yes C: No
（接着性）
　得られた各印刷物の印刷面にセロファンテープを貼り付けて、剥がしたときにインキ被膜が被着体から剥がれる面積の比率から、接着性を評価した。
　Ａ：全く剥がれない
　Ｂ：剥がれる面積が２０％未満である
　Ｃ：剥がれる面積が２０％以上である (Adhesiveness)
The cellophane tape was affixed to the printed surface of each printed matter obtained, and the adhesiveness was evaluated from the ratio of the area where the ink film peeled off the adherend when peeled off.
A: No peeling at all B: Peeling area is less than 20% C: Peeling area is at least 20%
＜耐ブロッキング＞
　各印刷物の印刷面と、各フィルムのコロナ放電処理面とを重ね合わせ、３ｋｇ／ｃｍ２の荷重をかけて、温度４５℃で１日放置した。その後、インキ面とフィルム面を剥がし、インキ被膜のフィルム面への移行を評価した
　Ａ：抵抗なく剥がれてインキ被膜の移行が全くないもの
　Ｂ：抵抗はあるがインキ被膜の移行が全くないもの
　Ｃ：５０％未満のインキ被膜の移行が認められたもの
　Ｄ：５０～１００％のインキ被膜の移行が認められたもの <Blocking resistance>
The printed surface of each printed material and the corona discharge treated surface of each film were superposed and left to stand at a temperature of 45 ° C. for 1 day with a load of 3 kg / cm 2 . Then, the ink surface and the film surface were peeled off, and the transition of the ink coating to the film surface was evaluated. A: The coating was removed without resistance and there was no migration of the ink coating. B: The coating with resistance was not transferred at all. C : Less than 50% ink film transfer observed D: 50-100% ink film transfer recognized
（レトルト適性）
　ポリエチレンテレフタレート（ＰＥＴ）及びナイロン（ＮＹ）に印刷後１日経過した各印刷物に、固形分で２．０ｇ／ｍ２となる量のウレタン系接着剤（タケラックＡ－６１６／タケネートＡ－６５、三井化学ＳＫＣポリウレタン社製）を塗布した後、ドライラミネート機で無延伸ポリプロピレンフィルム（ＲＸＣ－２２、厚さ６０μｍ、三井化学東セロ社製）を貼り合わせ、４０℃で３日放置してドライラミネート物を得た。このドライラミネート物を製袋し、中に水９０重量％、サラダ油１０重量％の混合物を詰めて溶封後、ＰＥＴに印刷したものは１３５℃の加圧熱水中に６０分間浸漬した時のラミ浮きの有無からレトルト適性を評価した。ＮＹに印刷したものは１２０℃で同様の試験評価を行った。この評価によって、ラミネート適性を確認できる。
　Ａ：全くラミ浮きが見られないもの
　Ｂ：ピンホール状もしくは一部に細くて短いラミ浮きがみられるもの
　Ｃ：長い筋状のラミ浮きが全面にみられるもの (Retort suitability)
One day after printing on polyethylene terephthalate (PET) and nylon (NY), a urethane adhesive in an amount of 2.0 g / m 2 in solid content (Takelac A-616 / Takenate A-65, Mitsui) After application of Chemical SKC Polyurethane), an unstretched polypropylene film (RXC-22, thickness 60 μm, Mitsui Chemicals Tosero Co., Ltd.) is bonded with a dry laminating machine and left at 40 ° C. for 3 days to form a dry laminate. Obtained. This dry laminate is made into a bag, filled with a mixture of 90% by weight of water and 10% by weight of salad oil, sealed, and printed on PET when immersed in pressurized hot water at 135 ° C. for 60 minutes. The suitability of retort was evaluated from the presence or absence of lami. Those printed on NY were subjected to the same test evaluation at 120 ° C. By this evaluation, the suitability for lamination can be confirmed.
A: No lami-floating at all B: Pinhole shape or thin, short lami-floating C: Long streaky lami-floating over the entire surface
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　本発明に沿った実施例の軟包装用ラミネート印刷インキ組成物によれば、インキの保存安定性、印刷適性に優れ、ガイドロール取られが無く、接着性、耐ブロッキング性及びレトルト適性に優れる結果となった。
　なお実施例５及び１３については、印刷速度１００ｍ／分で印刷を行ったときにカスレが少し見られた。
　これに対して、ポリウレタン樹脂がアミン価を有しない比較例１及び３によれば、接着性、耐ブロッキング性及びレトルト適性に劣ることになり、ジシクロヘキシルメタン４，４’－ジイソシアナート（水添ＭＤＩ）を使用しなかった比較例２及び４によれば、ガイドロール取られが発生し、耐ブロッキング性も悪化した。 According to the laminated printing ink composition for soft packaging of examples according to the present invention, the ink storage stability and printability are excellent, the guide roll is not removed, and the adhesiveness, blocking resistance and retort suitability are excellent. It became.
In Examples 5 and 13, slight blurring was observed when printing was performed at a printing speed of 100 m / min.
On the other hand, according to Comparative Examples 1 and 3 in which the polyurethane resin does not have an amine value, the adhesiveness, blocking resistance and retort suitability are inferior, and dicyclohexylmethane 4,4′-diisocyanate (hydrogenated) According to Comparative Examples 2 and 4 which did not use (MDI), the guide roll was taken out and the blocking resistance was also deteriorated.

Claims (6)

  1. 　顔料、バインダー樹脂及び有機溶剤を主成分とする軟包装用ラミネート印刷インキ組成物であって、
    バインダー樹脂が、ジシクロヘキシルメタン４，４’－ジイソシアナートを含むポリイソシアネートと高分子ポリオールとを反応させてなるポリウレタン樹脂であって、ポリウレタン樹脂が下記の条件（１）～（３）を満足するポリウレタン樹脂である軟包装用ラミネート印刷インキ組成物。
    条件（１）
    　ジシクロヘキシルメタン４，４’－ジイソシアナートとジシクロヘキシルメタン４，４’－ジイソシアナート以外のポリイソシアネートの質量比率が、ジシクロヘキシルメタン４，４’－ジイソシアナート／ジシクロヘキシルメタン４，４’－ジイソシアナート以外のポリイソシアネート＝１００／０～５／９５である。
    条件（２）
    　ポリイソシアネートと高分子ポリオールの使用比率は、イソシアネート基：水酸基の当量比率（イソシアネートインデックス）が、１．２～２．３となる範囲である。
    条件（３）
    　ポリウレタン樹脂がアミン価を有するものである。     A laminating printing ink composition for soft packaging mainly comprising a pigment, a binder resin and an organic solvent,
    The binder resin is a polyurethane resin obtained by reacting a polyisocyanate containing dicyclohexylmethane 4,4′-diisocyanate and a polymer polyol, and the polyurethane resin satisfies the following conditions (1) to (3): A laminate printing ink composition for soft packaging, which is a polyurethane resin.
    Condition (1)
    The weight ratio of polyisocyanate other than dicyclohexylmethane 4,4′-diisocyanate and dicyclohexylmethane 4,4′-diisocyanate is dicyclohexylmethane 4,4′-diisocyanate / dicyclohexylmethane 4,4′-diisocyanate. Polyisocyanate other than nate = 100/0 to 5/95.
    Condition (2)
    The use ratio of the polyisocyanate and the polymer polyol is in the range where the equivalent ratio of isocyanate group: hydroxyl group (isocyanate index) is 1.2 to 2.3.
    Condition (3)
    The polyurethane resin has an amine value.
  2. 　ジシクロヘキシルメタン４，４’－ジイソシアナート以外のポリイソシアネートが、イソホロンジイソシアネートであることを特徴とする請求項１記載の軟包装用ラミネート印刷インキ組成物。 The laminated printing ink composition for soft packaging according to claim 1, wherein the polyisocyanate other than dicyclohexylmethane 4,4'-diisocyanate is isophorone diisocyanate.
  3. 　ジシクロヘキシルメタン４，４’－ジイソシアナートとイソホロンジイソシアネートの質量比率が、ジシクロヘキシルメタン４，４’－ジイソシアナート／イソホロンジイソシアネート＝９５／５～１０／９０であり、高分子ポリオールがポリエステルポリオール又はポリエステルポリオールとポリエーテルポリオールとの併用である請求項１又は２に記載の軟包装用ラミネート印刷インキ組成物。 The mass ratio of dicyclohexylmethane 4,4′-diisocyanate and isophorone diisocyanate is dicyclohexylmethane 4,4′-diisocyanate / isophorone diisocyanate = 95/5 to 10/90, and the polymer polyol is polyester polyol or polyester The laminate printing ink composition for soft packaging according to claim 1 or 2, wherein the composition is a combination of a polyol and a polyether polyol.
  4. 　ポリウレタン樹脂は、末端に第１級アミノ基及び／又は第２級アミノ基を有するポリウレタン樹脂であることを特徴とする請求項１～３のいずれかに記載の軟包装用ラミネート印刷インキ組成物。 The laminate printing ink composition for flexible packaging according to any one of claims 1 to 3, wherein the polyurethane resin is a polyurethane resin having a primary amino group and / or a secondary amino group at a terminal.
  5. 　軟包装用ラミネート印刷インキ組成物には、さらに、水酸基を有する塩化ビニル／酢酸ビニル共重合体、硝化綿及び／又はセルロースアセテートプロピオネート樹脂から選ばれる少なくとも１種を含有することを特徴とする請求項１～４のいずれかに記載の軟包装用ラミネート印刷インキ組成物。 The laminate printing ink composition for soft packaging further comprises at least one selected from a vinyl chloride / vinyl acetate copolymer having a hydroxyl group, nitrified cotton and / or cellulose acetate propionate resin. The laminate printing ink composition for soft packaging according to any one of claims 1 to 4.
  6. 　有機溶剤は、エステル系有機溶剤、及びアルコール系有機溶剤の混合溶剤である請求項１～５のいずれかに記載の軟包装用ラミネート印刷インキ組成物。 The laminate printing ink composition for soft packaging according to any one of claims 1 to 5, wherein the organic solvent is a mixed solvent of an ester organic solvent and an alcohol organic solvent.
PCT/JP2017/036511 2016-10-06 2017-10-06 Laminate printing ink composition for soft packaging WO2018066699A1 (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0463877A (en) * 1990-06-30 1992-02-28 Arakawa Chem Ind Co Ltd Binder for printing ink
JPH11323234A (en) * 1998-05-08 1999-11-26 Kuraray Co Ltd Binder for printing ink and printing ink composition containing the binder
JP2013116936A (en) * 2011-12-01 2013-06-13 Toyo Ink Sc Holdings Co Ltd Printing ink composition
JP2015108057A (en) * 2013-12-04 2015-06-11 Ｄｉｃグラフィックス株式会社 Ink composition for soft packaging laminate

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0463877A (en) * 1990-06-30 1992-02-28 Arakawa Chem Ind Co Ltd Binder for printing ink
JPH11323234A (en) * 1998-05-08 1999-11-26 Kuraray Co Ltd Binder for printing ink and printing ink composition containing the binder
JP2013116936A (en) * 2011-12-01 2013-06-13 Toyo Ink Sc Holdings Co Ltd Printing ink composition
JP2015108057A (en) * 2013-12-04 2015-06-11 Ｄｉｃグラフィックス株式会社 Ink composition for soft packaging laminate

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