WO2018056293A1 - Ink composition for lamination printing on soft packaging - Google Patents

Ink composition for lamination printing on soft packaging Download PDF

Info

Publication number
WO2018056293A1
WO2018056293A1 PCT/JP2017/033847 JP2017033847W WO2018056293A1 WO 2018056293 A1 WO2018056293 A1 WO 2018056293A1 JP 2017033847 W JP2017033847 W JP 2017033847W WO 2018056293 A1 WO2018056293 A1 WO 2018056293A1
Authority
WO
WIPO (PCT)
Prior art keywords
mass
ink composition
parts
printing
soft packaging
Prior art date
Application number
PCT/JP2017/033847
Other languages
French (fr)
Japanese (ja)
Inventor
小川　徹
淳一 原田
裕一朗 本田
健太 赤坂
Original Assignee
サカタインクス株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
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 to JP2018540254A priority Critical patent/JP7008028B2/en
Publication of WO2018056293A1 publication Critical patent/WO2018056293A1/en

Links

Classifications

    • 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

Definitions

  • the present invention relates to a laminating printing ink composition for soft packaging, and more specifically, laminating printing ink for soft packaging having good printability, no blurring, adhesiveness, laminating strength, scratch resistance, and blocking resistance. Relates to the composition.
  • Packaging materials using various plastic films are used for foods, confectionery, household goods, pet foods and the like from the viewpoint of improving designability, economy, contents protection, transportability, and the like. Also, many other packaging materials are subjected to gravure printing and flexographic printing for the purpose of improving design and message characteristics for appealing to consumers. And in order to obtain these packaging materials, an adhesive or anchor agent is applied to the printed surface of the base film of the packaging material or the printing surface of the base material film of the packaging material, if 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.
  • the soft packaging laminate printing ink composition examples include, for example, a high-molecular polyester diol composed of a glycol component containing at least 50% 2-methyl-1,3-pentanediol and a dibasic acid component, a diisocyanate compound, a chain extension.
  • the soft packaging laminate printing ink composition examples include, for example, a high-molecular polyester diol composed of a glycol component containing at least 50% 2-methyl-1,3-pentanediol and a dibasic acid component, a diisocyanate compound, a chain extension.
  • a laminate ink composition for packaging using a binder mainly containing polyurethane obtained by reacting an agent see, for example, Patent Document 1).
  • the object of the present invention is to have superior performance to conventional ink compositions for laminating printing for soft packaging, in particular, good printability, no fading, adhesion, laminating strength, scratch resistance, and blocking resistance. It is to provide an ink composition for laminating printing for soft packaging.
  • a binder resin a glycol component in which 20% by mass or more of the glycol component is 2-methyl-1,3-propanediol, and an acid component
  • a high-molecular polyester diol comprising: an organic diisocyanate compound containing an alicyclic diisocyanate; a polyurethane resin having an amine value having a primary amino group and / or a secondary amino group at a terminal;
  • the inventors have found that the above-mentioned problems can be solved by using at least one selected from cellulose acetate propionate resin, cellulose acetate butyrate resin and vinyl chloride-vinyl acetate copolymer, and have completed the present invention.
  • An ink composition for laminating printing for soft packaging comprising a pigment, a binder resin and an organic solvent as main components, wherein the binder resin contains 2-methyl-1,3-propanediol in an amount of 20% by mass or more in the glycol component.
  • a high molecular polyester diol comprising a glycol component and an acid component, and an organic diisocyanate compound containing an alicyclic diisocyanate, and having an amine value having a primary amino group and / or a secondary amino group at the terminal.
  • An ink composition for laminate printing for flexible packaging comprising a polyurethane resin and at least one selected from nitrified cotton, cellulose acetate propionate resin, cellulose acetate butyrate resin, and vinyl chloride-vinyl acetate copolymer.
  • an ink composition for laminate printing for soft packaging that has superior performance to conventional ink compositions for laminate printing for soft packaging, especially excellent printability, no fading, and excellent adhesion, lamination strength, scratch resistance, and blocking resistance
  • An ink composition can be provided.
  • the anti-crying property to an adhesive agent is favorable.
  • the “polyurethane resin having an amine value having a primary amino group and / or a secondary amino group at the terminal” means the above-mentioned all or part of the main chain and side chain of the polyurethane resin. It means having a primary amino group and / or a secondary amino group.
  • the ink composition for laminating printing for soft packaging according to the present invention will be described in more detail.
  • the pigment various inorganic pigments and / or organic pigments generally used in printing inks 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 pigment content in the soft packaging laminate printing ink composition 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 ink composition for laminating printing is less than the above range, the coloring power as the ink composition is lowered, and when the content is more than the above range, the viscosity of the ink composition is increased and the printed matter becomes dirty. It becomes easy.
  • ⁇ Binder resin> Consisting of an organic diisocyanate compound containing a high molecular weight polyester diol composed of a glycol component in which 20% by mass or more of the glycol component is 2-methyl-1,3-propanediol and an acid component, and an alicyclic diisocyanate, and (Polyurethane resin having an amine value of 1 to 10 having a primary amino group and / or a secondary amino group at the terminal)
  • the content of the polyurethane resin in the ink composition of the present invention is preferably 20.0% by mass or less, more preferably 10% by mass or less.
  • glycol component 2-Methyl-1,3-propanediol is used in an amount of 20% by mass or more, preferably 50% by mass or more in the glycol component. If it is less than 20% by mass, the blocking resistance and scratch resistance tend to decrease, such being undesirable.
  • glycol components that can be used in combination include ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, and pentane.
  • Examples include various known and unsaturated glycols such as diol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, octanediol, 1,4-butynediol, and dipropylene glycol.
  • 1,6-hexanediol, neopentyl glycol and the like can be preferably used.
  • ⁇ Acid component As the acid component, known materials that can be used to obtain polyesters can be used. Specifically, adipic acid, maleic acid, phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, succinic acid, oxalic acid, malon Dibasic acids such as acid, pimelic acid, azelaic acid, sebacic acid and suberic acid, or acid anhydrides and dimer acids corresponding to these can be used.
  • adipic acid maleic acid, phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, succinic acid, oxalic acid, malon Dibasic acids such as acid, pimelic acid, azelaic acid, sebacic acid and suberic acid, or acid anhydrides and dimer acids corresponding to these can be used.
  • polyester polyol / polypropylene glycol 100/0 to 20/80, more preferably 100/0 To 20/50, more preferably 100/0 to 70/30.
  • polyalkylene glycols such as polymer polyester diols other than the above, polyethylene glycol, polypropylene glycol, etc., polyether diol compounds such as ethylene oxide of bisphenol A, alkylene oxide adducts such as propylene oxide, polycaprolactone diols, etc.
  • Polymer polyols such as polyester diol compounds such as can be used. Furthermore, as glycol components, alkanediols such as 1,4-pentanediol, 2,5-hexanediol, 3-methyl-1,5-pentanediol, ethylene glycol, propylene glycol, 1,4-butanediol, 1, A low molecular diol compound such as 3-butanediol can also be used in combination.
  • alkanediols such as 1,4-pentanediol, 2,5-hexanediol, 3-methyl-1,5-pentanediol, ethylene glycol, propylene glycol, 1,4-butanediol, 1,
  • a low molecular diol compound such as 3-butanediol can also be used in combination.
  • Organic diisocyanate compound examples include fats such as 1,4-cyclohexane diisocyanate, isophorone diisocyanate (IPDI), dicyclohexylmethane-4,4-diisocyanate (hydrogenated MDI), and the like. Aliphatic diisocyanate compounds such as cyclic diisocyanate compounds and hexamethylene diisocyanate are preferred.
  • An aromatic diisocyanate compound such as tolylene diisocyanate and an araliphatic diisocyanate compound such as ⁇ , ⁇ , ⁇ ′, ⁇ ′-tetramethylxylylene diisocyanate can be used in combination as long as the performance does not deteriorate.
  • polyurethane resin having an amine value having a primary amino group and / or a secondary amino group at the terminal containing the above-mentioned polymer polyester diol and the above-mentioned organic diisocyanate compound as components The polyurethane resin in the present invention can be obtained by any of the following methods (1) to (4).
  • reaction terminator which is a polyamine compound whose both ends are primary amino groups and / or secondary amino groups, and a polyamine compound whose both ends are other than primary amino groups and / or secondary amino groups.
  • reaction terminator After reacting a polymer diol and a polyisocyanate and adding a chain extender to a urethane prepolymer having an isocyanate group at the terminal to obtain a urethane prepolymer having an isocyanate group at the terminal
  • a reaction terminator which is a polyamine compound having both ends of a primary amino group and / or a secondary amino group is reacted, and a primary amino group and / or a secondary amino group is reacted at the end.
  • 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 a primary amino group and / or a secondary amino group at both terminals, to form a chain.
  • chain extender used in the above (1) to (3) a known chain extender used in a polyurethane resin as an ink binder 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 exemplified.
  • Examples of the reaction terminator used in the above method (3) include polyamine compounds in which 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.
  • the polyurethane resin is quenched with a polyamine compound having both primary and / or secondary amino groups so that the amine value is 1 to 10 in terms of storage stability and pigment dispersibility.
  • 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 that can be used in combination with a polyamine compound having a primary amino group and / or a secondary amino group at both ends, it is a known reaction terminator utilized in a polyurethane resin as a binder for ink.
  • Monoamine compounds and monoalcohol compounds can be used. Specifically, monoalkylamines such as n-propylamine and n-butylamine, dialkylamines such as di-n-butylamine, monoethanolamine, diethanolamine, etc. Examples thereof include alkanolamines and monoalcohols such as ethanol.
  • a polyurethane resin having an amine value of 1 to 10 having a primary amino group and / or a secondary amino group at the terminal can be obtained by using a known polyurethane resin production method using the above materials. it can.
  • the polyurethane resin having an amine number of 1 to 10 having a primary amino group and / or a secondary amino group at the end in the laminate printing ink composition for soft packaging of the present invention has a mass average molecular weight of 5000 to 60000. It is preferable that it is more preferably 30000 to 60000.
  • the ink composition for laminating printing for soft packaging of the present invention includes vinyl chloride-vinyl acetate copolymer, nitrified cotton, cellulose acetate propionate resin, and cellulose acetate butyrate resin.
  • the ink composition for laminating printing for soft packaging of the present invention includes vinyl chloride-vinyl acetate copolymer, nitrified cotton, and cellulose acetate propionate resin.
  • at least one selected from cellulose acetate butyrate resins can be used in combination.
  • the total amount of vinyl chloride-vinyl acetate copolymer, nitrified cotton, cellulose acetate propionate resin, and cellulose acetate butyrate resin is 0.1-25.
  • the amount of vinyl chloride-vinyl acetate copolymer used is 5 to 25.0% by mass in the laminate printing ink composition for soft packaging, and the amount of nitrified cotton used is in the laminate printing ink composition for flexible packaging.
  • the amount of cellulose acetate propionate resin and cellulose acetate butyrate resin used is preferably 0.1 to 3.0% by mass.
  • Vinyl chloride-vinyl acetate copolymer As the vinyl chloride-vinyl acetate copolymer, a copolymer of vinyl chloride monomer and vinyl acetate monomer conventionally used in gravure printing ink compositions can be used. Among them, in the organic solvent system of the ink having an environment-friendly composition, a vinyl chloride-vinyl acetate copolymer having a hydroxyl group, preferably having 50 to 200 hydroxyl groups, is suitable. 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 (formula 1 below), 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 such a vinyl chloride-vinyl acetate copolymer having 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.
  • a polyurethane resin having an amine number of 1 to 10 having a primary amino group and / or a secondary amino group at the terminal and a vinyl chloride-vinyl acetate copolymer in the laminate printing ink composition for soft packaging of the present invention The total content of is preferably 5.0 to 50.0% by mass, more preferably 5.0 to 40.0% by mass.
  • Nitrified cotton conventionally used for 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.
  • those having a nitrogen amount of 10 to 13% and an average degree of polymerization of 35 to 90 are preferable.
  • Specific examples include SS1 / 2, SS1 / 4, SS1 / 8, TR1 / 16, NC RS-2 (KCNC, manufactured by KOREA CNC LTD), and the like.
  • Cellulose acetate propionate resin As a cellulose acetate propionate resin, the cellulose acetate propionate resin conventionally used for the gravure printing ink composition can be used.
  • Cellulose acetate propionate resin is obtained by triesterifying cellulose with acetic acid and propionic acid, followed by hydrolysis.
  • a resin having 0.6 to 2.5% by mass for acetylation, 42 to 46% by mass for propionation, and 1.8 to 5% for a hydroxyl group is commercially available. Specific examples include cellulose acetate propionate resin manufactured by Kanto Chemical Co., Ltd.
  • Cellulose acetate butyrate resin is obtained by triesterification of cellulose with acetic acid and butyric acid, followed by hydrolysis. Generally, a resin having 2 to 30% by weight of acetylation, 17 to 53% by weight of butyrylation, and 1 to 5% of hydroxyl group is commercially available.
  • an acrylic resin, a polyamide resin, an adhesive resin, or the like can be supplementarily added as the other binder resin within a range where the performance by the ink composition of the present invention is not lowered and a price is not increased. it can.
  • organic solvents used in the ink composition for laminate printing 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, N-propyl acetate, n-butyl acetate, isobutyl acetate, etc.), alcohol organic solvents (eg, 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, N-propyl a
  • mixed organic solvents such as ester organic solvents and alcoholic organic solvents are used as organic solvents in the ink composition for laminate printing during printing.
  • propyl acetate in a printing ink composition for laminating at the time of printing of 5.0% by mass or more, preferably 15.0% by mass or more.
  • 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-described laminate printing ink composition for soft packaging.
  • the ink composition for laminating printing 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, the combination of the binder resin and the organic solvent, and the like.
  • 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.
  • ⁇ A gravure printing method using the ink composition for laminating printing for soft packaging of the present invention As a method for printing the soft packaging laminate printing ink composition, a general gravure printing method can be used.
  • the printing substrate is not particularly limited, and various printing plastic films such as polyolefin films such as polyethylene and polypropylene, polyester films such as polyethylene terephthalate, polylactic acid, and polycaprolactone, nylon, vinylon, barrier film, and vapor deposition film. It is intended for.
  • 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.
  • 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
  • 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. after processing.
  • 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 in which an anchor coating agent such as titanium-based, urethane-based, imine-based, or polybutadiene is applied to the surface of a printed material, and then a molten resin is laminated by a known extrusion laminating machine. Furthermore, a layer formed from a melted resin can be laminated as an intermediate layer with other materials.
  • an anchor coating agent such as titanium-based, urethane-based, imine-based, or polybutadiene is applied to the surface of a printed material, and then a molten resin is laminated by a known extrusion laminating machine. Furthermore, a layer formed from a melted resin can be laminated as an intermediate layer with other materials.
  • the melting 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 in which a urethane resin, an isocyanate adhesive, or the like is applied to the surface of a printed material, and then a film-like resin is bonded using a known dry laminating machine.
  • Polyethylene, unstretched polypropylene, etc. can be used as the film-like resin used in the dry laminating method.
  • an 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 a bag-like container for boil / retort after bag making and filling the contents.
  • an adhesive can be applied to the surface of the 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 using the ink composition for laminating printing for soft packaging according to the present invention is excellent in the adhesiveness of the printed matter after the retort treatment.
  • Polyester having an average molecular weight of 2000 obtained from 2-methyl-1,3-propanediol / 1,6-hexanediol 80/20 and adipic acid in a four-necked flask equipped with a stirrer, a cooling pipe and a nitrogen gas introduction pipe 200 parts by mass of diol and 35.2 parts by mass of isophorone diisocyanate were charged and reacted at 100 to 105 ° C. for 6 hours while introducing nitrogen gas.
  • Polyester having an average molecular weight of 2000 obtained from 2-methyl-1,3-propanediol / 1,6-hexanediol 40/60 and adipic acid in a four-necked flask equipped with a stirrer, a cooling pipe and a nitrogen gas introduction pipe 200 parts by mass of diol and 35.2 parts by mass of isophorone diisocyanate were charged and reacted at 100 to 105 ° C. for 6 hours while introducing nitrogen gas.
  • ⁇ 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, 200 parts by mass of polyester diol having an average molecular weight of 2000 obtained from 2-methyl-1,3-propanediol and adipic acid, and 33. 4 parts by mass 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, 396 parts by mass of ethyl acetate and 170 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 and reacted. Thereafter, 1.2 parts by mass of isophoronediamine and 0.5 parts by mass of diethylenetriamine were added to stop the reaction, and a polyurethane resin varnish F (solid content 30% by mass, amine value 3.2) was obtained.
  • ⁇ 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, 200 parts by mass of a polyester diol having an average molecular weight of 2000 obtained from 2-methyl-1,3-propanediol and adipic acid, and 35 of isophorone diisocyanate. 4 parts by mass were charged and reacted at 100 to 105 ° C. for 6 hours while introducing nitrogen gas.
  • ⁇ 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, 200 parts by mass of a polyester diol having an average molecular weight of 2000 obtained from 2-methyl-1,3-propanediol and adipic acid, and 35 of isophorone diisocyanate. 4 parts by mass 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, and 402 parts by mass of ethyl acetate and 172 parts by mass of isopropyl alcohol were added.
  • Polyester having an average molecular weight of 2000 obtained from 2-methyl-1,3-propanediol / 1,6-hexanediol 10/90 and adipic acid in a four-necked flask equipped with a stirrer, a cooling pipe and a nitrogen gas introduction pipe 200 parts by mass of diol and 35.2 parts by mass of isophorone diisocyanate were charged and reacted at 100 to 105 ° C. for 6 hours while introducing nitrogen gas.
  • ⁇ 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 a polyester diol having an average molecular weight of 2000 obtained from 2-methyl-1,3-propanediol and adipic acid, and 35 of isophorone diisocyanate. 4 parts by mass were charged and reacted at 100 to 105 ° C. for 6 hours while introducing nitrogen gas.
  • ⁇ Production example of polyurethane resin varnish K> In a four-necked flask equipped with a stirrer, a condenser tube and a nitrogen gas inlet tube, 200 parts by mass of a polyester diol having an average molecular weight of 2000 obtained from 3-methyl-1,5-pentanediol and adipic acid, and 35 of isophorone diisocyanate. 2 parts by mass were charged and reacted at 100 to 105 ° C. for 6 hours while introducing nitrogen gas.
  • ⁇ Production example of polyurethane resin varnish L> In a four-necked flask equipped with a stirrer, a cooling pipe and a nitrogen gas introduction pipe, 100 parts by mass of a polyester diol having an average molecular weight of 2000 obtained from 2-methyl-1,3-propanediol and adipic acid, an average of polyether polyol 100 parts by mass of polypropylene glycol having a molecular weight of 2000 and 35.2 parts by mass of isophorone diisocyanate were 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 cooling pipe and a nitrogen gas introduction pipe, 100 parts by mass of a polyester diol having an average molecular weight of 2000 obtained from 3-methyl-1,5-pentanediol and adipic acid, an average of polyether polyol 100 parts by mass of polypropylene glycol having a molecular weight of 2000 and 35.2 parts by mass of isophorone diisocyanate were charged and reacted at 100 to 105 ° C. for 6 hours while introducing nitrogen gas.
  • ⁇ Vinyl chloride-vinyl acetate copolymer> Solvein TA-3 (Nisshin Chemical Co., Ltd.) ⁇ Nitrocellulose solution> 20 parts of nitrocellulose (NC RS-2, manufactured by KOREA CNC) was dissolved in a mixed solvent consisting of 16 parts by mass of methylcyclohexane, 24 parts by mass of propyl acetate, 24 parts by mass of ethyl acetate and 16 parts by mass of isopropyl alcohol to obtain a solid content. A 20% nitrocellulose solution was obtained.
  • CAP Cellulose acetate propionate
  • a cellulose acetate propionate (CAP) solution having a solid content of 20% was obtained.
  • ⁇ Cellulose acetate butyrate solution (CAB)> Mixing 20 parts by weight of cellulose acetate butyrate (Kanto Chemical Co., Inc., number average molecular weight 70000, butyryl 35-39%), 20 parts by weight of isopropyl alcohol, 20 parts by weight of propyl acetate, and 40 parts by weight of ethyl acetate A cellulose acetate butyrate (CAB) solution having a solid content of 20% was obtained by dissolving in a solvent.
  • CAB cellulose acetate butyrate
  • PET Polyethylene terephthalate film with corona discharge treatment on one side, manufactured by Toyobo Co., Ltd., E-5101, thickness 12 ⁇ m
  • OPP Biaxially oriented polypropylene film, P-2161 manufactured by Toyobo Co., Ltd., thickness 30 ⁇ m NY: nylon film, manufactured by Toyobo Co., Ltd., N-1102, thickness 15 ⁇ m
  • Printability The printability was evaluated from the ratio of the area of the blur caused by the clogged ink in the printing part at the end of printing. A: No fading is observed B: Slight fading C: Many fading
  • 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%
  • laminating suitability As for laminating suitability, laminating suitability was evaluated from the retort suitability of each PET film printed matter and each NY film printed matter.
  • each PET film printed matter and each NY film printed matter are urethane adhesives (Takelac A-616 / Takenate A-65, manufactured by Mitsui Chemicals Polyurethanes) in an amount of 2.0 g / m 2 in solid content. Then, an unstretched polypropylene film (RXC-3, thickness 60 ⁇ m, manufactured by Mitsui Chemicals, Inc.) was pasted together with a dry laminator and left at 40 ° C. for 3 days to obtain a dry laminate.
  • urethane adhesives Takelac A-616 / Takenate A-65, manufactured by Mitsui Chemicals Polyurethanes
  • RXC-3 thickness 60 ⁇ m, manufactured by Mitsui Chemicals, Inc.
  • This dry laminate is made into a bag, filled with 90% by mass of water and 10% by mass of salad oil, sealed, and then retorted from the presence or absence of litter when immersed in pressurized hot water at 120 ° C. for 60 minutes. Suitability was evaluated. The evaluation criteria were the same as boil suitability.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)
  • Laminated Bodies (AREA)

Abstract

The present invention addresses the problem of providing an ink composition for lamination printing on soft packaging, the ink composition having superior performance to conventional ink compositions for lamination printing on soft packaging, and having good printability, adhesion, laminate strength, scratch resistance, and blocking resistance without exhibiting blurring. In order to solve the problem, an ink composition for lamination printing on soft packaging is provided, the ink composition containing a pigment, a binder resin, and an organic solvent as main components, wherein the binder resin contains: a polymeric polyester diol comprising an acidic component and a glycol component of which 20 mass% or more is 2-methyl-1,3-propanediol; a polyurethane resin which comprises an organic diisocyanate compound containing alicyclic diisocyanate, has a primary amino group and/or a secondary amino group at terminal ends thereof, and has an amine value; and at least one selected from among a nitrocellulose, a cellulose acetate propionate resin, a cellulose acetate butyrate resin, and a vinyl chloride-vinyl acetate copolymer.

Description

軟包装用ラミネート印刷用インキ組成物Laminated printing ink composition for flexible packaging
　本発明は、軟包装用ラミネート印刷用インキ組成物に関し、より詳しくは、良好な印刷適性、かすれがなく、接着性、ラミネート強度、耐スクラッチ性、耐ブロッキング性を有する軟包装用ラミネート印刷用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 specifically, laminating printing ink for soft packaging having good printability, no blurring, adhesiveness, laminating strength, scratch resistance, and blocking resistance. Relates to the composition.
　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、輸送性等向上の観点から、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、他の多くの包装資材も消費者に向けてアピールするための意匠性、メッセージ性の向上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。
　そしてこれら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を行って、ヒートシール性を有するポリエチレンフィルムやポリプロピレンフィルム等を積層している。
　この軟包装用ラミネート印刷用インキ組成物としては、例えば、２－メチル－１，３－ペンタンジオールを少なくとも５０％含有するグリコール成分及び二塩基酸成分からなる高分子ポリエステルジオール、ジイソシアネート化合物、鎖伸長剤を反応せしめて得られるポリウレタンを主として含有するバインダーを使用した包装用ラミネートインキ組成物が挙げられる（例えば、特許文献１参照）。 Packaging materials using various plastic films are used for foods, confectionery, household goods, pet foods and the like from the viewpoint of improving designability, economy, contents protection, transportability, and the like. Also, many other packaging materials are subjected to gravure printing and flexographic printing for the purpose of improving design and message characteristics for appealing to consumers.
And in order to obtain these packaging materials, an adhesive or anchor agent is applied to the printed surface of the base film of the packaging material or the printing surface of the base material film of the packaging material, if 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. The extrusion laminating process etc. which were used are performed and the polyethylene film, the polypropylene film, etc. which have heat-sealing property are laminated | stacked.
Examples of the soft packaging laminate printing ink composition include, for example, a high-molecular polyester diol composed of a glycol component containing at least 50% 2-methyl-1,3-pentanediol and a dibasic acid component, a diisocyanate compound, a chain extension. Examples thereof include a laminate ink composition for packaging using a binder mainly containing polyurethane obtained by reacting an agent (see, for example, Patent Document 1).
　近年、より性能が高い軟包装用ラミネート印刷用インキ組成物が要求されており、この要求に対して、３－メチル－１，５－ペンタンジオールからなるグリコール成分及び二塩基酸成分からなる高分子ポリエステルジオール、ジイソシアネート化合物、鎖伸長剤を反応せしめて得られるポリウレタンを主として含有するバインダーを使用した包装用ラミネートインキ組成物が提案されている（例えば、特許文献２参照）。 In recent years, there has been a demand for an ink composition for laminating printing for soft packaging with higher performance. In response to this demand, a polymer composed of a glycol component composed of 3-methyl-1,5-pentanediol and a dibasic acid component. A laminate ink composition for packaging using a binder mainly containing polyurethane obtained by reacting a polyester diol, a diisocyanate compound and a chain extender has been proposed (for example, see Patent Document 2).
特開平０６－１２８５２１号公報Japanese Patent Laid-Open No. 06-128521 特開２０１４－１０８５３４号公報JP 2014-108534 A
　本発明の目的は、従来の軟包装用ラミネート印刷用インキ組成物より優れた性能を有し、特に、良好な印刷適性、かすれがなく、接着性、ラミネート強度、耐スクラッチ性、耐ブロッキング性を有する軟包装用ラミネート印刷用インキ組成物を提供することである。 The object of the present invention is to have superior performance to conventional ink compositions for laminating printing for soft packaging, in particular, good printability, no fading, adhesion, laminating strength, scratch resistance, and blocking resistance. It is to provide an ink composition for laminating printing 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、バインダー樹脂として、グリコール成分中２０質量％以上が２－メチル－１，３－プロパンジオールであるグリコール成分と、酸成分とからなる高分子ポリエステルジオールと、脂環族ジイソシアネートを含有する有機ジイソシアネート化合物からなり、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と、硝化綿、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ブチレート樹脂及び塩化ビニル－酢酸ビニル共重合体から選ばれる少なくとも１種とを併用することにより、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ものである。
　すなわち、本発明は、
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用インキ組成物であって、前記バインダー樹脂は、グリコール成分中２０質量％以上が２－メチル－１，３－プロパンジオールであるグリコール成分と、酸成分とからなる高分子ポリエステルジオールと、脂環族ジイソシアネートを含有する有機ジイソシアネート化合物からなり、かつ末端に第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と、硝化綿、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ブチレート樹脂及び塩化ビニル－酢酸ビニル共重合体から選ばれる少なくとも１種とを含有する軟包装用ラミネート印刷用インキ組成物。
２．グリコール成分が、１，６－ヘキサンジオール、ネオペンチルグリコールから選ばれる少なくとも１種を含有する１記載の軟包装用ラミネート印刷用インキ組成物。
３．有機ジイソシアネート化合物が、イソホロンジイソシアネート及び／又はジシクロヘキシルメタン－４，４－ジイソシアネートである１又は２記載の軟包装用ラミネート印刷用インキ組成物。
４．高分子ポリエステルジオールのＯＨ基と有機ジイソシアネート化合物のＮＣＯ基の当量の比率が、ＮＣＯ基／ＯＨ基＝１．１～２．３であり、ポリウレタン樹脂の質量平均分子量が５０００～６００００である１～３のいずれかに記載の軟包装用ラミネート印刷用インキ組成物。
５．有機溶剤は、エステル系有機溶剤とアルコール系有機溶剤の混合溶剤である１～４のいずれかに記載の軟包装用ラミネート印刷用インキ組成物。 As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that as a binder resin, a glycol component in which 20% by mass or more of the glycol component is 2-methyl-1,3-propanediol, and an acid component A high-molecular polyester diol comprising: an organic diisocyanate compound containing an alicyclic diisocyanate; a polyurethane resin having an amine value having a primary amino group and / or a secondary amino group at a terminal; The inventors have found that the above-mentioned problems can be solved by using at least one selected from cellulose acetate propionate resin, cellulose acetate butyrate resin and vinyl chloride-vinyl acetate copolymer, and have completed the present invention. It is.
That is, the present invention
1. An ink composition for laminating printing for soft packaging comprising a pigment, a binder resin and an organic solvent as main components, wherein the binder resin contains 2-methyl-1,3-propanediol in an amount of 20% by mass or more in the glycol component. A high molecular polyester diol comprising a glycol component and an acid component, and an organic diisocyanate compound containing an alicyclic diisocyanate, and having an amine value having a primary amino group and / or a secondary amino group at the terminal. An ink composition for laminate printing for flexible packaging, comprising a polyurethane resin and at least one selected from nitrified cotton, cellulose acetate propionate resin, cellulose acetate butyrate resin, and vinyl chloride-vinyl acetate copolymer.
2. 2. The laminate printing ink composition for soft packaging according to 1, wherein the glycol component contains at least one selected from 1,6-hexanediol and neopentyl glycol.
3. The ink composition for laminating printing for soft packaging according to 1 or 2, wherein the organic diisocyanate compound is isophorone diisocyanate and / or dicyclohexylmethane-4,4-diisocyanate.
4). The equivalent ratio of the OH group of the high-molecular polyester diol and the NCO group of the organic diisocyanate compound is NCO group / OH group = 1.1 to 2.3, and the mass average molecular weight of the polyurethane resin is from 1 to 4. An ink composition for laminate printing for soft packaging according to any one of 3 above.
5). 5. The laminated packaging ink composition for soft packaging according to any one of 1 to 4, 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用インキ組成物より優れた性能を有する、特に、良好な印刷適性、かすれがなく、接着性、ラミネート強度、耐スクラッチ性、耐ブロッキング性に優れる軟包装用ラミネート印刷用インキ組成物を提供することができる。
　また、接着剤への耐泣き出し性が良好であることが好ましい。 For laminate printing for soft packaging that has superior performance to conventional ink compositions for laminate printing for soft packaging, especially excellent printability, no fading, and excellent adhesion, lamination strength, scratch resistance, and blocking resistance An ink composition can be provided.
Moreover, it is preferable that the anti-crying property to an adhesive agent is favorable.
　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アミン価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用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及び／又は有機顔料を使用できる。
　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用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。ラミネート印刷用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 an amine value having a primary amino group and / or a secondary amino group at the terminal” means the above-mentioned all or part of the main chain and side chain of the polyurethane resin. It means having a primary amino group and / or a secondary amino group.
Hereinafter, the ink composition for laminating printing for soft packaging according to the present invention will be described in more detail.
<Pigment>
As the pigment, various inorganic pigments and / or organic pigments generally used in printing inks 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 pigment content in the soft packaging laminate printing ink composition 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 ink composition for laminating printing is less than the above range, the coloring power as the ink composition is lowered, and when the content is more than the above range, the viscosity of the ink composition is increased and the printed matter becomes dirty. It becomes easy.
＜バインダー樹脂＞
（グリコール成分中２０質量％以上が２－メチル－１，３－プロパンジオールであるグリコール成分と、酸成分とからなる高分子ポリエステルジオールと、脂環族ジイソシアネートを含有する有機ジイソシアネート化合物からなり、かつ末端に第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１～１０のポリウレタン樹脂）
　本発明のインキ組成物におけるポリウレタン樹脂の含有量は、２０．０質量％以下が好ましく、さらに好ましくは１０質量％以下である。 <Binder resin>
(Consisting of an organic diisocyanate compound containing a high molecular weight polyester diol composed of a glycol component in which 20% by mass or more of the glycol component is 2-methyl-1,3-propanediol and an acid component, and an alicyclic diisocyanate, and (Polyurethane resin having an amine value of 1 to 10 having a primary amino group and / or a secondary amino group at the terminal)
The content of the polyurethane resin in the ink composition of the present invention is preferably 20.0% by mass or less, more preferably 10% by mass or less.
（高分子ポリエステルジオール）
グリコール成分
　２－メチル－１，３－プロパンジオールを、グリコール成分中２０質量％以上、好ましくは５０質量％以上となるように使用する。２０質量％未満であると、耐ブロッキング性、耐スクラッチ性が低下する傾向があるので好ましくない。
　併用可能なグリコール成分としては、エチレングリコール、ジエチレングリコール、トリエチレングリコール、１，２－プロパンジオール、１，３－プロパンジオール、１，３－ブタンジオール、１，４－ブタンジオール、ネオペンチルグリコール、ペンタンジオール、３－メチル－１，５－ペンタンジオール、１，６－ヘキサンジオール、オクタンジオール、１，４－ブチンジオール、ジプロピレングリコール等の飽和及び不飽和の各種公知のグリコール類が挙げられる。これらの中でも、１，６－ヘキサンジオール、ネオペンチルグリコール等が好適に使用できる。 (Polymer polyester diol)
Glycol component 2-Methyl-1,3-propanediol is used in an amount of 20% by mass or more, preferably 50% by mass or more in the glycol component. If it is less than 20% by mass, the blocking resistance and scratch resistance tend to decrease, such being undesirable.
Examples of glycol components that can be used in combination include ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, and pentane. Examples include various known and unsaturated glycols such as diol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, octanediol, 1,4-butynediol, and dipropylene glycol. Among these, 1,6-hexanediol, neopentyl glycol and the like can be preferably used.
＜酸成分＞
　酸成分としては、ポリエステルを得るために使用できる公知のものを使用でき、具体的には、アジピン酸、マレイン酸、フタル酸、無水フタル酸、イソフタル酸、テレフタル酸、コハク酸、しゅう酸、マロン酸、ピメリン酸、アゼライン酸、セバシン酸、スベリン酸等の二塩基酸もしくはこれらに対応する酸無水物やダイマー酸等を使用できる。 <Acid component>
As the acid component, known materials that can be used to obtain polyesters can be used. Specifically, adipic acid, maleic acid, phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, succinic acid, oxalic acid, malon Dibasic acids such as acid, pimelic acid, azelaic acid, sebacic acid and suberic acid, or acid anhydrides and dimer acids corresponding to these can be used.
（その他のグリコール成分）
　上記高分子ポリエステルジオール以外に、本発明による効果を阻害しない範囲（例えばポリエステルポリオールとその他のグリコール成分の割合が、ポリエステルポリオール／ポリプロピレングリコール＝１００／０～２０／８０、より好ましくは、１００／０～２０／５０、さらに好ましくは１００／０～７０／３０）で配合できる。
　その他のグリコール成分として、上記以外の高分子ポリエステルジオール、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、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高分子ポリオールを使用できる。
　更にグリコール成分として、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も併用することができる。 (Other glycol components)
In addition to the above-described high-molecular polyester diol, a range that does not impair the effects of the present invention (for example, the ratio of polyester polyol to other glycol component is polyester polyol / polypropylene glycol = 100/0 to 20/80, more preferably 100/0 To 20/50, more preferably 100/0 to 70/30).
As other glycol components, polyalkylene glycols such as polymer polyester diols other than the above, polyethylene glycol, polypropylene glycol, etc., polyether diol compounds such as ethylene oxide of bisphenol A, alkylene oxide adducts such as propylene oxide, polycaprolactone diols, etc. Polymer polyols such as polyester diol compounds such as can be used.
Furthermore, as glycol components, alkanediols such as 1,4-pentanediol, 2,5-hexanediol, 3-methyl-1,5-pentanediol, ethylene glycol, propylene glycol, 1,4-butanediol, 1, A low molecular diol compound such as 3-butanediol can also be used in combination.
[有機ジイソシアネート化合物]
　上記高分子ポリエステルジオールと反応させてバインダー樹脂を得るための有機ジイソシアネート化合物としては、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（ＩＰＤＩ）、ジシクロヘキシルメタン－４，４－ジイソシアネート（水添ＭＤＩ）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が好ましい。性能が低下しない範囲で、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、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が併用できる。　
　また、上記有機ジイソシアネート化合物と高分子ポリエステルジオールの使用比率は、イソシアネート基：水酸基の当量比（イソシアネートインデックス）が、通常、ＮＣＯ基／ＯＨ基＝１．１～２．３、より好ましくは１．３～２．０となる範囲である。 [Organic diisocyanate compound]
Examples of the organic diisocyanate compound for obtaining a binder resin by reacting with the above-mentioned polymer polyester diol include fats such as 1,4-cyclohexane diisocyanate, isophorone diisocyanate (IPDI), dicyclohexylmethane-4,4-diisocyanate (hydrogenated MDI), and the like. Aliphatic diisocyanate compounds such as cyclic diisocyanate compounds and hexamethylene diisocyanate are preferred. An aromatic diisocyanate compound such as tolylene diisocyanate and an araliphatic diisocyanate compound such as α, α, α ′, α′-tetramethylxylylene diisocyanate can be used in combination as long as the performance does not deteriorate.
The organic diisocyanate compound and the high-molecular polyester diol are used in an isocyanate group: hydroxyl group equivalent ratio (isocyanate index) of usually NCO group / OH group = 1.1 to 2.3, more preferably 1. The range is 3 to 2.0.
[上記高分子ポリエステルジオールと上記有機ジ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]
　本発明におけ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。
（１）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り、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１～１０のポリウレタン樹脂を得る方法。
（２）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り、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と、両末端が第１級アミノ基及び／又は第２級アミノ基以外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１～１０のポリウレタン樹脂を得る方法。
（３）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り、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１～１０の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、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１～１０のポリウレタン樹脂を得る方法。 [Polyurethane resin having an amine value having a primary amino group and / or a secondary amino group at the terminal containing the above-mentioned polymer polyester diol and the above-mentioned organic diisocyanate compound as components]
The polyurethane resin in the present invention can be obtained by any of the following methods (1) to (4).
(1) After reacting a polymer diol and a polyisocyanate and adding a chain extender to a urethane prepolymer having an isocyanate group at the terminal to obtain a urethane prepolymer having an isocyanate group at the terminal , A reaction terminator other than a polyamine compound in which both ends are a primary amino group and / or a secondary amino group are reacted, and then both ends are a primary amino group and / or a secondary amino group A method of obtaining a polyurethane resin having an amine value of 1 to 10 having a primary amino group and / or a secondary amino group at a terminal by reacting a reaction terminator which is a polyamine compound.
(2) After reacting a polymer diol and a polyisocyanate and adding a chain extender to a urethane prepolymer having an isocyanate group at the terminal to obtain a urethane prepolymer having an isocyanate group at the terminal A reaction terminator which is a polyamine compound whose both ends are primary amino groups and / or secondary amino groups, and a polyamine compound whose both ends are other than primary amino groups and / or secondary amino groups. A method of obtaining a polyurethane resin having an amine number of 1 to 10 having a primary amino group and / or a secondary amino group at the terminal by simultaneously adding a certain reaction terminator and reacting.
(3) After reacting a polymer diol and a polyisocyanate and adding a chain extender to a urethane prepolymer having an isocyanate group at the terminal to obtain a urethane prepolymer having an isocyanate group at the terminal As a reaction terminator, a reaction terminator which is a polyamine compound having both ends of a primary amino group and / or a secondary amino group is reacted, and a primary amino group and / or a secondary amino group is reacted at the end. To obtain a polyurethane resin having an amine number of 1 to 10 and
(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 a primary amino group and / or a secondary amino group at both terminals, to form a chain. A method of obtaining a polyurethane resin having an amine number of 1 to 10 having a primary amino group and / or a secondary amino group at the terminal by simultaneously extending and stopping the reaction.
　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を利用可能であり、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。 As the chain extender used in the above (1) to (3), a known chain extender used in a polyurethane resin as an ink binder 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.
　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が例示できる。
　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が例示できる。
　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。
　上記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１～１０になるように、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が例示される。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することができ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を利用可能であり、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等を例示することができる。 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 exemplified.
Examples of the reaction terminator used in the above method (3) include polyamine compounds in which 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.
The polyurethane resin is quenched with a polyamine compound having both primary and / or secondary amino groups so that the amine value is 1 to 10 in terms of storage stability and pigment dispersibility. Preferably it is.
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 that can be used in combination with a polyamine compound having a primary amino group and / or a secondary amino group at both ends, it is a known reaction terminator utilized in a polyurethane resin as a binder for ink. Monoamine compounds and monoalcohol compounds can be used. Specifically, monoalkylamines such as n-propylamine and n-butylamine, dialkylamines such as di-n-butylamine, monoethanolamine, diethanolamine, etc. Examples thereof include alkanolamines 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１～１０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用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１～１０の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、さらに３００００～６００００であることがより好ましい。 In the present invention, a polyurethane resin having an amine value of 1 to 10 having a primary amino group and / or a secondary amino group at the terminal can be obtained by using a known polyurethane resin production method using the above materials. it can.
The polyurethane resin having an amine number of 1 to 10 having a primary amino group and / or a secondary amino group at the end in the laminate printing ink composition for soft packaging of the present invention has a mass average molecular weight of 5000 to 60000. It is preferable that it is more preferably 30000 to 60000.
（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セルロースアセテートブチレート樹脂から選ばれる少なくとも１種）
　本発明の軟包装用ラミネート印刷用インキ組成物には、耐ブロッキング性、耐スクラッチ性、顔料分散性を向上させるために、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セルロースアセテートブチレート樹脂から選ばれる少なくとも1種を併用することができる。
　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セルロースアセテートブチレート樹脂の使用量は、軟包装用ラミネート印刷用インキ組成物中に、合計量で０．１～２５．０質量％含有させることが好ましい。塩化ビニル－酢酸ビニル共重合体の使用量は、軟包装用ラミネート印刷用インキ組成物中に、５～２５．０質量％、硝化綿の使用量は、軟包装用ラミネート印刷用インキ組成物中に、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及びセルロースアセテートブチレート樹脂の使用量は、０．１～３．０質量％が好ましい。 (At least one selected from vinyl chloride-vinyl acetate copolymer, nitrified cotton, cellulose acetate propionate resin, and cellulose acetate butyrate resin)
In order to improve blocking resistance, scratch resistance and pigment dispersibility, the ink composition for laminating printing for soft packaging of the present invention includes vinyl chloride-vinyl acetate copolymer, nitrified cotton, and cellulose acetate propionate resin. And at least one selected from cellulose acetate butyrate resins can be used in combination.
The total amount of vinyl chloride-vinyl acetate copolymer, nitrified cotton, cellulose acetate propionate resin, and cellulose acetate butyrate resin is 0.1-25. It is preferable to contain 0 mass%. The amount of vinyl chloride-vinyl acetate copolymer used is 5 to 25.0% by mass in the laminate printing ink composition for soft packaging, and the amount of nitrified cotton used is in the laminate printing ink composition for flexible packaging. In addition, the amount of cellulose acetate propionate resin and cellulose acetate butyrate resin used is preferably 0.1 to 3.0% by mass.
塩化ビニル－酢酸ビニル共重合体
　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を使用できる。
　中でも、環境に配慮した組成のインキの有機溶剤系においては、水酸基を有する、好ましくは、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。 Vinyl chloride-vinyl acetate copolymer As the vinyl chloride-vinyl acetate copolymer, a copolymer of vinyl chloride monomer and vinyl acetate monomer conventionally used in gravure printing ink compositions can be used.
Among them, in the organic solvent system of the ink having an environment-friendly composition, a vinyl chloride-vinyl acetate copolymer having a hydroxyl group, preferably having 50 to 200 hydroxyl groups, is suitable. Such a vinyl chloride-vinyl acetate copolymer having a hydroxyl group can be obtained, for example, by saponifying a part of the acetate portion.
　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。
　本発明の軟包装用ラミネート印刷用インキ組成物中において、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アミン価１～１０のポリウレタン樹脂と、塩化ビニル－酢酸ビニル共重合体の含有量は、合計で５．０～５０．０質量％であることが好ましく、さらに好ましくは５．０～４０．０質量％である。 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 (formula 1 below), 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 such a vinyl chloride-vinyl acetate copolymer having 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.
A polyurethane resin having an amine number of 1 to 10 having a primary amino group and / or a secondary amino group at the terminal and a vinyl chloride-vinyl acetate copolymer in the laminate printing ink composition for soft packaging of the present invention The total content of is preferably 5.0 to 50.0% by mass, more preferably 5.0 to 40.0% by mass.
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を使用できる。
　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のものが好ましい。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。 Nitrified cotton Nitrified cotton conventionally used for 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 preferable. Specific examples include SS1 / 2, SS1 / 4, SS1 / 8, TR1 / 16, NC RS-2 (KCNC, manufactured by 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を使用できる。
　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、加水分解して得られる。一般的にはアセチル化は０．６～２．５質量％、プロピオネート化は４２～４６質量％、水酸基は１．８～５％の樹脂が市販されている。具体例としては、関東化学株式会社製のセルロースアセテートプロピオネート樹脂等を挙げることができる。 Cellulose acetate propionate resin
As a cellulose acetate propionate resin, the cellulose acetate propionate resin conventionally used for the gravure printing ink composition can be used.
Cellulose acetate propionate resin is obtained by triesterifying cellulose with acetic acid and propionic acid, followed by hydrolysis. Generally, a resin having 0.6 to 2.5% by mass for acetylation, 42 to 46% by mass for propionation, and 1.8 to 5% for a hydroxyl group is commercially available. Specific examples include cellulose acetate propionate resin manufactured by Kanto Chemical Co., Ltd.
セルロースアセテートブチレート樹脂
　セルロースアセテートブチレート樹脂は、セルロースを酢酸および酪酸でトリエステル化した後、加水分解して得られる。一般的にはアセチル化は２～３０重量％、ブチリル化は１７～５３重量％、水酸基は１～５％の樹脂が市販されている。 Cellulose acetate butyrate resin Cellulose acetate butyrate resin is obtained by triesterification of cellulose with acetic acid and butyric acid, followed by hydrolysis. Generally, a resin having 2 to 30% by weight of acetylation, 17 to 53% by weight of butyrylation, and 1 to 5% of hydroxyl group is commercially available.
　更に、本発明では、その他のバインダー樹脂として、本発明のインキ組成物による性能が低下しない範囲、値段が上がらない範囲で、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。 Furthermore, in the present invention, an acrylic resin, a polyamide resin, an adhesive resin, or the like can be supplementarily added as the other binder resin within a range where the performance by the ink composition of the present invention is not lowered and a price is not increased. it can.
＜有機溶剤＞
　軟包装用ラミネート印刷用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等）、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、酢酸イソブチル等）、アルコール系有機溶剤（例えば、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、ブタノール等）、炭化水素系溶剤（トルエン、メチルシクロヘキサン等）を利用できる。
　なお、環境問題への対応と、インキの印刷適性や乾燥性等を考慮して、中でも印刷時のラミネート印刷用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有機溶剤を、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、印刷時のラミネート用印刷インキ組成物中に酢酸プロピルを５．０質量％以上、好ましくは１５．０質量％以上含有させることが好ましい。 <Organic solvent>
Examples of organic solvents used in the ink composition for laminate printing 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, N-propyl acetate, n-butyl acetate, isobutyl acetate, etc.), alcohol organic solvents (eg, methanol, ethanol, n-propanol, isopropanol, butanol, etc.), hydrocarbon solvents (toluene, methylcyclohexane, etc.) can be used. .
In addition, taking into account environmental issues, ink printability and drying properties, among others, mixed organic solvents such as ester organic solvents and alcoholic organic solvents are used as organic solvents in the ink composition for laminate printing during printing. The 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.
Furthermore, from the viewpoint of printing suitability of the ink, it is preferable to contain propyl acetate in a printing ink composition for laminating at the time of printing of 5.0% by mass or more, preferably 15.0% by mass or more.
＜添加剤＞
　上記軟包装用ラミネート印刷用インキ組成物には、更に粘着付与剤、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-described laminate printing ink composition for soft packaging.
＜本発明の軟包装用ラミネート印刷用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用インキ組成物は、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等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 ink composition for laminating printing 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, the combination of the binder resin and the organic solvent, and the like. 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用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用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を利用できる。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、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、バリア性フィルム、蒸着フィルムといった各種印刷用プラスチック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）した印刷版を利用できる。 <A gravure printing method using the ink composition for laminating printing for soft packaging of the present invention>
As a method for printing the soft packaging laminate printing ink composition, a general gravure printing method can be used. The printing substrate is not particularly limited, and various printing plastic films such as polyolefin films such as polyethylene and polypropylene, polyester films such as polyethylene terephthalate, polylactic acid, and polycaprolactone, nylon, vinylon, barrier film, and vapor deposition film. It is intended for. 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) Can be used.
　また、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用インキ組成物を、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を利用できる。
　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、溶融した樹脂を積層させる方法であり、更に溶融した樹脂から形成した層を中間層として、他の材料とサンドイッチ状に積層することもできる。 Further, 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. after processing. 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 in which an anchor coating agent such as titanium-based, urethane-based, imine-based, or polybutadiene is applied to the surface of a printed material, and then a molten resin is laminated by a known extrusion laminating machine. Furthermore, a layer formed from a melted resin can be laminated as an intermediate layer with other materials.
　上記押し出しラミネート法で使用する溶融する樹脂としては、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を使用できる。
　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樹脂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樹脂としては、ポリエチレン、無延伸ポリプロピレン等を使用でき、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・レトルト用途の袋状容器に利用することもできる。
　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を利用できる。 As the melting 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 in which a urethane resin, an isocyanate adhesive, or the like is applied to the surface of a printed material, and then a film-like resin is bonded using a known dry laminating machine. Polyethylene, unstretched polypropylene, etc. can be used as the film-like resin used in the dry laminating method. Especially in packaging materials used for retort applications, an 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 a bag-like container for boil / retort after bag making and filling the contents.
As a laminating method for the laminate can application, an adhesive can be applied to the surface of the printed material and then bonded to a metal plate.
　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理を行ったもの等を用いることができる。
　本発明の軟包装用ラミネート印刷用インキ組成物を使用して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。 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 using the ink composition for laminating printing for soft packaging according to 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、「部」は「質量部」を意味する。
＜ポリエステルポリオール単独系＞
ポリウレタン樹脂ワニスＡ：
I.I.=1.6、２－メチル－１，３－プロパンジオール=100％、IPDI、アミン価３．２
ポリウレタン樹脂ワニスＢ：
I.I.=1.6、２－メチル－１，３－プロパンジオール／１，６－ヘキサンジオール＝８０／２０、IPDI、アミン価３．２
ポリウレタン樹脂ワニスＣ：
I.I.=1.6、２－メチル－１，３－プロパンジオール／１，６－ヘキサンジオール＝４０／６０、IPDI、アミン価３．２
ポリウレタン樹脂ワニスＤ：
I.I.=1.6、２－メチル－１，３－プロパンジオール／３－メチル－１，５－ペンタンジオール＝８０／２０、IPDI、アミン価３．２
ポリウレタン樹脂ワニスＥ：
I.I.=1.6、水添ＭＤＩ、２－メチル－１，３－プロパンジオール=100％、水添MDI、アミン価３．２
ポリウレタン樹脂ワニスＦ：
I.I.=1.5、２－メチル－１，３－プロパンジオール=100％、IPDI、アミン価３．２
ポリウレタン樹脂ワニスＧ：
I.I.=1.6、２－メチル－１，３－プロパンジオール=100％、IPDI、アミン価１．５
ポリウレタン樹脂ワニスＨ：
I.I.=1.6、２－メチル－１，３－プロパンジオール=100％、IPDI、アミン価５．４
ポリウレタン樹脂ワニスＩ：
I.I.=1.6、２－メチル－１，３－プロパンジオール／１，６－ヘキサンジオール＝１０／９０、IPDI、アミン価３．２
ポリウレタン樹脂ワニスＪ：
I.I.=1.6、２－メチル－１，３－プロパンジオール=100％、IPDI、アミン価０
ポリウレタン樹脂ワニスＫ：
I.I.=1.6、３－メチル－１，５－ペンタンジオール＝100%、IPDI、アミン価３．２
＜ポリエステルポリオール／ポリエーテルポリオール＝５０/５０併用系＞
ポリウレタン樹脂ワニスＬ：
I.I.=1.6、２－メチル－１，３－プロパンジオール=100％、IPDI、アミン価３．２
ポリウレタン樹脂ワニスＭ：
I.I.=1.6、３－メチル－１，５－ペンタンジオール=100%、IPDI、アミン価３．２ 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 “mass%” and “part” means “mass part”.
<Polyester polyol single system>
Polyurethane resin varnish A:
II = 1.6, 2-methyl-1,3-propanediol = 100%, IPDI, amine value 3.2
Polyurethane resin varnish B:
II = 1.6, 2-methyl-1,3-propanediol / 1,6-hexanediol = 80/20, IPDI, amine value 3.2
Polyurethane resin varnish C:
II = 1.6, 2-methyl-1,3-propanediol / 1,6-hexanediol = 40/60, IPDI, amine value 3.2
Polyurethane resin varnish D:
II = 1.6, 2-methyl-1,3-propanediol / 3-methyl-1,5-pentanediol = 80/20, IPDI, amine value 3.2
Polyurethane resin varnish E:
II = 1.6, hydrogenated MDI, 2-methyl-1,3-propanediol = 100%, hydrogenated MDI, amine value 3.2
Polyurethane resin varnish F:
II = 1.5, 2-methyl-1,3-propanediol = 100%, IPDI, amine value 3.2
Polyurethane resin varnish G:
II = 1.6, 2-methyl-1,3-propanediol = 100%, IPDI, amine value 1.5
Polyurethane resin varnish H:
II = 1.6, 2-methyl-1,3-propanediol = 100%, IPDI, amine value 5.4
Polyurethane resin varnish I:
II = 1.6, 2-methyl-1,3-propanediol / 1,6-hexanediol = 10/90, IPDI, amine value 3.2
Polyurethane resin varnish J:
II = 1.6, 2-methyl-1,3-propanediol = 100%, IPDI, amine value 0
Polyurethane resin varnish K:
II = 1.6, 3-methyl-1,5-pentanediol = 100%, IPDI, amine value 3.2
<Polyester polyol / polyether polyol = 50/50 combined system>
Polyurethane resin varnish L:
II = 1.6, 2-methyl-1,3-propanediol = 100%, IPDI, amine value 3.2
Polyurethane resin varnish M:
II = 1.6, 3-methyl-1,5-pentanediol = 100%, IPDI, amine value 3.2
＜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２－メチル－１，３－プロパンジオールとアジピン酸から得られる平均分子量２０００のポリエステルジオール２００質量部、及びイソホロンジイソシアネートの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、更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, 200 parts by mass of a polyester diol having an average molecular weight of 2000 obtained from 2-methyl-1,3-propanediol and adipic acid, and 35 of isophorone diisocyanate. 2 parts by mass were 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 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２－メチル－１，３－プロパンジオール／１，６－ヘキサンジオール＝８０／２０とアジピン酸から得られる平均分子量２０００のポリエステルジオール２００質量部、及びイソホロンジイソシアネートの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、更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>
Polyester having an average molecular weight of 2000 obtained from 2-methyl-1,3-propanediol / 1,6-hexanediol = 80/20 and adipic acid in a four-necked flask equipped with a stirrer, a cooling pipe and a nitrogen gas introduction pipe 200 parts by mass of diol and 35.2 parts by mass of isophorone diisocyanate were 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 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 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２－メチル－１，３－プロパンジオール／１，６－ヘキサンジオール＝４０／６０とアジピン酸から得られる平均分子量２０００のポリエステルジオール２００質量部、及びイソホロンジイソシアネートの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、更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>
Polyester having an average molecular weight of 2000 obtained from 2-methyl-1,3-propanediol / 1,6-hexanediol = 40/60 and adipic acid in a four-necked flask equipped with a stirrer, a cooling pipe and a nitrogen gas introduction pipe 200 parts by mass of diol and 35.2 parts by mass of isophorone diisocyanate were 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 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 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２－メチル－１，３－プロパンジオール／３－メチル－１，５－ペンタンジオール＝８０／２０とアジピン酸から得られる平均分子量２０００のポリエステルジオール２００質量部、及びイソホロンジイソシアネートの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、更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>
Average obtained from 2-methyl-1,3-propanediol / 3-methyl-1,5-pentanediol = 80/20 and adipic acid in a four-necked flask equipped with a stirrer, condenser and nitrogen gas inlet tube 200 parts by mass of a polyester diol having a molecular weight of 2000 and 35.2 parts by mass of isophorone diisocyanate were 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 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２－メチル－１，３－プロパンジオールとアジピン酸から得られる平均分子量２０００のポリエステルジオール、及び水添ＭＤＩの４１．８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、更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Ｅ（固形分３０質量％、アミン価３．２）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, a polyester diol having an average molecular weight of 2000 obtained from 2-methyl-1,3-propanediol and adipic acid, and 41.8 masses of hydrogenated MDI 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, 412 parts by mass of ethyl acetate and 177 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 E (solid content: 30% by mass, amine value: 3.2).
＜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２－メチル－１，３－プロパンジオールとアジピン酸から得られる平均分子量２０００のポリエステルジオール２００質量部、及びイソホロンジイソシアネートの３３．４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３９６質量部、イソプロピルアルコール１７０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、更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Ｆ（固形分３０質量％、アミン価３．２）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, 200 parts by mass of polyester diol having an average molecular weight of 2000 obtained from 2-methyl-1,3-propanediol and adipic acid, and 33. 4 parts by mass 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, 396 parts by mass of ethyl acetate and 170 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 and reacted. Thereafter, 1.2 parts by mass of isophoronediamine and 0.5 parts by mass of diethylenetriamine were added to stop the reaction, and a polyurethane resin varnish F (solid content 30% by mass, amine value 3.2) was obtained.
＜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２－メチル－１，３－プロパンジオールとアジピン酸から得られる平均分子量２０００のポリエステルジオール２００質量部、及びイソホロンジイソシアネートの３５．４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４０１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、更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・BR>Eレタン樹脂ワニスＧ（固形分３０質量％、アミン価１．５）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, 200 parts by mass of a polyester diol having an average molecular weight of 2000 obtained from 2-methyl-1,3-propanediol and adipic acid, and 35 of isophorone diisocyanate. 4 parts by mass were charged and reacted at 100 to 105 ° C. for 6 hours while introducing nitrogen gas. After allowing to cool to near room temperature, 401 parts by mass of ethyl acetate and 172 parts by mass of isopropyl alcohol were added, then 8.2 parts by mass of isophoronediamine was added to extend the chain, and 0.7 parts by mass of monoethanolamine was further 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 poly-BR> E-retane resin varnish G (solid content 30% by mass, amine value 1.5).
＜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２－メチル－１，３－プロパンジオールとアジピン酸から得られる平均分子量２０００のポリエステルジオール２００質量部、及びイソホロンジイソシアネートの３５．４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、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Ｈ（固形分３０質量％、アミン価５．４）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, 200 parts by mass of a polyester diol having an average molecular weight of 2000 obtained from 2-methyl-1,3-propanediol and adipic acid, and 35 of isophorone diisocyanate. 4 parts by mass 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, and 402 parts by mass of ethyl acetate and 172 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 diethylene triamine were added. The reaction was stopped by adding parts by mass to obtain a polyurethane resin varnish H (solid content: 30% by mass, amine value: 5.4).
＜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２－メチル－１，３－プロパンジオール／１，６－ヘキサンジオール＝１０／９０とアジピン酸から得られる平均分子量２０００のポリエステルジオール２００質量部、及びイソホロンジイソシアネートの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、更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>
Polyester having an average molecular weight of 2000 obtained from 2-methyl-1,3-propanediol / 1,6-hexanediol = 10/90 and adipic acid in a four-necked flask equipped with a stirrer, a cooling pipe and a nitrogen gas introduction pipe 200 parts by mass of diol and 35.2 parts by mass of isophorone diisocyanate were 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 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 I (solid content: 30% by mass, amine value: 3.2).
＜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２－メチル－１，３－プロパンジオールとアジピン酸から得られる平均分子量２０００のポリエステルジオール２００質量部、及びイソホロンジイソシアネートの３５．４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４０１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９．２質量部を加えて鎖伸長させ、更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Ｊ（固形分３０質量％、アミン価０）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 a polyester diol having an average molecular weight of 2000 obtained from 2-methyl-1,3-propanediol and adipic acid, and 35 of isophorone diisocyanate. 4 parts by mass were charged and reacted at 100 to 105 ° C. for 6 hours while introducing nitrogen gas. After cooling to near room temperature, 401 parts by mass of ethyl acetate and 172 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 J (solid content 30% by mass, amine value 0) was obtained.
＜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３－メチル－１，５－ペンタンジオールとアジピン酸から得られる平均分子量２０００のポリエステルジオール２００質量部、及びイソホロンジイソシアネートの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、更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>
In a four-necked flask equipped with a stirrer, a condenser tube and a nitrogen gas inlet tube, 200 parts by mass of a polyester diol having an average molecular weight of 2000 obtained from 3-methyl-1,5-pentanediol and adipic acid, and 35 of isophorone diisocyanate. 2 parts by mass were 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 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 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２－メチル－１，３－プロパンジオールとアジピン酸から得られる平均分子量２０００のポリエステルジオール１００質量部、ポリエーテルポリオールである平均分子量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の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、更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 cooling pipe and a nitrogen gas introduction pipe, 100 parts by mass of a polyester diol having an average molecular weight of 2000 obtained from 2-methyl-1,3-propanediol and adipic acid, an average of polyether polyol 100 parts by mass of polypropylene glycol having a molecular weight of 2000 and 35.2 parts by mass of isophorone diisocyanate were 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 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, 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３－メチル－１，５－ペンタンジオールとアジピン酸から得られる平均分子量２０００のポリエステルジオール１００質量部、ポリエーテルポリオールである平均分子量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の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、更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 cooling pipe and a nitrogen gas introduction pipe, 100 parts by mass of a polyester diol having an average molecular weight of 2000 obtained from 3-methyl-1,5-pentanediol and adipic acid, an average of polyether polyol 100 parts by mass of polypropylene glycol having a molecular weight of 2000 and 35.2 parts by mass of isophorone diisocyanate were 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 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).
＜塩化ビニル－酢酸ビニル共重合体＞
　ソルバインＴＡ－３（日信化学（株）社製）
＜ニトロセルロース溶液＞
　ニトロセルロース（ＮＣ  ＲＳ－２、ＫＯＲＥＡ  ＣＮＣ社製）２０部を、メチルシクロヘキサン１６質量部、酢酸プロピル２４質量部、酢酸エチル２４質量部及びイソプロピルアルコール１６質量部からなる混合溶媒に溶解させて固形分２０％のニトロセルロース溶液を得た。
＜セルロースアセテートプロピオネート（ＣＡＰ）溶液＞
  セルロースアセテートプロピオネート（関東化学株式会社、数平均分子量２５０００、propionyl４３～４７％）２０質量部を、イソプロピルアルコール２０質量部、酢酸プロピル２０質量部、酢酸エチル４０質量を混合した混合溶剤中に溶解させ、固形分２０％のセルロースアセテートプロピオネート（ＣＡＰ）溶液を得た。
＜セルロースアセテートブチレート溶液（ＣＡＢ）＞
　セルロースアセテートブチレート（関東化学株式会社、数平均分子量７００００、ブチリル化（ｂｕｔｙｒｙｌ）３５～３９％）２０質量部を、イソプロピルアルコール２０質量部、酢酸プロピル２０質量部、酢酸エチル４０質量を混合した混合溶剤中に溶解させ、固形分２０％のセルロースアセテートブチレート（ＣＡＢ）溶液を得た。 <Vinyl chloride-vinyl acetate copolymer>
Solvein TA-3 (Nisshin Chemical Co., Ltd.)
<Nitrocellulose solution>
20 parts of nitrocellulose (NC RS-2, manufactured by KOREA CNC) was dissolved in a mixed solvent consisting of 16 parts by mass of methylcyclohexane, 24 parts by mass of propyl acetate, 24 parts by mass of ethyl acetate and 16 parts by mass of isopropyl alcohol to obtain a solid content. A 20% nitrocellulose solution was obtained.
<Cellulose acetate propionate (CAP) solution>
Dissolve 20 parts by mass of cellulose acetate propionate (Kanto Chemical Co., Inc., number average molecular weight 25000, propionyl 43-47%) in a mixed solvent in which 20 parts by mass of isopropyl alcohol, 20 parts by mass of propyl acetate and 40 parts by mass of ethyl acetate are mixed. Thus, a cellulose acetate propionate (CAP) solution having a solid content of 20% was obtained.
<Cellulose acetate butyrate solution (CAB)>
Mixing 20 parts by weight of cellulose acetate butyrate (Kanto Chemical Co., Inc., number average molecular weight 70000, butyryl 35-39%), 20 parts by weight of isopropyl alcohol, 20 parts by weight of propyl acetate, and 40 parts by weight of ethyl acetate A cellulose acetate butyrate (CAB) solution having a solid content of 20% was obtained by dissolving in a solvent.
＜軟包装用ラミネート用インキ組成物の製造例＞
　顔料（フタロシアニンブルーＣ．Ｉ．１５：４）、ポリウレタン樹脂ワニスＡ～Ｍ、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）、ニトロセルロース溶液、セルロースアセテートプロピオネート溶液、セルロースアセテートブチレート溶液を、レッドデビル社製のペイントコンデショナーを用いて混練し、更に溶媒を加えて、表１に示した実施例１～１４、比較例１～４の軟包装用ラミネート用インキ組成物を得た。 <Production Example of Laminating Ink Composition for Soft Packaging>
Pigment (phthalocyanine blue C.I.15: 4), polyurethane resin varnishes A to M, vinyl chloride-vinyl acetate resin (Solvine TA-3, manufactured by Nissin Chemical Industry Co., Ltd.), nitrocellulose solution, cellulose acetate pro The pionate solution and the cellulose acetate butyrate solution were kneaded using a paint conditioner manufactured by Red Devil, and further added with a solvent, for soft packaging of Examples 1 to 14 and Comparative Examples 1 to 4 shown in Table 1. A laminating ink composition was obtained.
（評価）
　上記で得られた実施例１～１４、比較例１～４の軟包装用ラミネート用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。
＜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１～１４、比較例１～４の軟包装用ラミネート用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。 (Evaluation)
The performance evaluation of the soft packaging laminating ink compositions of Examples 1 to 14 and Comparative Examples 1 to 4 obtained above was performed by the following method, and the evaluation results are shown in Table 1.
<Performance evaluation of ink composition>
(Ink storage stability)
Presence or absence of pigment precipitation when each of the ink compositions for laminating soft packaging of Examples 1 to 14 and Comparative Examples 1 to 4 obtained above was collected in a glass bottle and stored at an ambient temperature of 60 ° C. for 14 days. From this, the storage stability of the ink was evaluated.
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）
　実施例１～１４、比較例１～４の軟包装用ラミネート用インキ組成物の各々１００質量部に対し、更に表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（東谷製作所社製）にて、ＯＰＰ、ＰＥＴ、ＮＹの処理面に印刷速度１００ｍ／分で印刷を行った。 (Print evaluation)
Each 100 parts by mass of the soft packaging laminating ink compositions of Examples 1 to 14 and Comparative Examples 1 to 4 was further diluted with a mixed solvent in accordance with the composition shown in Table 1, and the viscosity was Zahn Cup No. 3 manufactured by Kouaisha. After adjusting to 15 seconds, a gravure printing machine (manufactured by Toya Seisakusho) equipped with an engraving plate (printing plate, Helio 175 line / inch), printing speed of 100 m / min on the treated surface of OPP, PET, NY The printing was done.
＜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、東洋紡社製、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－２１６１、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 oriented polypropylene film, P-2161 manufactured by Toyobo Co., Ltd., thickness 30 μm
NY: nylon film, manufactured by Toyobo Co., Ltd., N-1102, thickness 15 μm
（印刷適性）
　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かすれの面積の割合から印刷適性を評価した。
　　Ａ：かすれが全くみられない
　　Ｂ：かすれが少しみられる
　　Ｃ：かすれが多くみられる (Printability)
The printability was evaluated from the ratio of the area of the blur caused by the clogged ink in the printing part at the end of printing.
A: No fading is observed B: Slight fading C: Many fading
（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%
＜耐ブロッキング性＞
　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４０℃で１日放置した。その後、インキ面とフィルム面をはがし、インキ被膜のフィルム面への移行を評価した。
　　Ａ：抵抗なくはがれ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 matter and the corona discharge treated surface of each film were superposed and left to stand at a temperature of 40 ° C. for 1 day under a load of 3 kg / cm 2 . Thereafter, the ink surface and the film surface were peeled off, and the transition of the ink coating to the film surface was evaluated.
A: No peeling and no ink film transfer without resistance B: No resistance but no ink film transfer C: Less than 50% ink film transfer D: 50 to 100% ink A film that has been transferred
＜耐スクラッチ性＞
　印刷面を爪で１回擦り、塗膜の脱落から評価した。
　　Ａ：塗膜が脱落しないもの
　　Ｂ：塗膜が少し脱落するもの
　　Ｃ：塗膜が完全に脱落するもの <Scratch resistance>
The printed surface was rubbed once with a nail and evaluated from the removal of the coating film.
A: The coating film does not fall off B: The coating film falls off a little C: The coating film falls off completely
（ラミネート適性）
　ラミネート適性については、各ＰＥＴフィルム印刷物、各ＮＹフィルム印刷物のレトルト適性から、ラミネート適性を評価した。 (Lamination suitability)
As for laminating suitability, laminating suitability was evaluated from the retort suitability of each PET film printed matter and each NY film printed matter.
（レトルト適性）
　印刷後１日経過した各ＰＥＴフィルム印刷物、各ＮＹフィルム印刷物に、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－３、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質量％、サラダ油１０質量％の混合物を詰めて溶封後、１２０℃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。なお、評価の基準はボイル適性と同じとした。
　　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, each PET film printed matter and each NY film printed matter are urethane adhesives (Takelac A-616 / Takenate A-65, manufactured by Mitsui Chemicals Polyurethanes) in an amount of 2.0 g / m 2 in solid content. Then, an unstretched polypropylene film (RXC-3, thickness 60 μm, manufactured by Mitsui Chemicals, Inc.) was pasted together with a dry laminator and left at 40 ° C. for 3 days to obtain a dry laminate. This dry laminate is made into a bag, filled with 90% by mass of water and 10% by mass of salad oil, sealed, and then retorted from the presence or absence of litter when immersed in pressurized hot water at 120 ° C. for 60 minutes. Suitability was evaluated. The evaluation criteria were the same as boil suitability.
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
　本発明に沿った例である実施例１～１４の結果によれば、かすれがなく、接着性、ラミネート強度、耐ブロッキング性、耐スクラッチ性に優れる結果となった。
　これに対して、ポリエステルポリオールを構成するグリコール中の２－メチル－１．３－プロパンジオールの割合が低い比較例１によれば特に耐ブロッキング性に劣る結果となり、ポリウレタン樹脂のアミン価が０である比較例２によれば、耐ブロッキング性、接着性、耐スクラッチ性に劣る結果となった。
　またポリエステルポリオールを構成するグリコールの全てが３－メチル－１．５－ペンタンジオールである比較例３及び４によれば、特に耐ブロッキング性に劣る結果となった。
  According to the results of Examples 1 to 14, which are examples in accordance with the present invention, there was no blur and the results were excellent in adhesion, laminate strength, blocking resistance, and scratch resistance.
In contrast, Comparative Example 1 in which the proportion of 2-methyl-1.3-propanediol in the glycol constituting the polyester polyol is low resulted in particularly poor blocking resistance, and the polyurethane resin had an amine value of 0. According to a certain comparative example 2, the results were inferior in blocking resistance, adhesiveness and scratch resistance.
Further, according to Comparative Examples 3 and 4 in which all of the glycols constituting the polyester polyol were 3-methyl-1.5-pentanediol, the blocking resistance was particularly poor.

Claims (5)

  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用インキ組成物であって、前記バインダー樹脂は、グリコール成分中２０質量％以上が２－メチル－１，３－プロパンジオールであるグリコール成分と、酸成分とからなる高分子ポリエステルジオールと、脂環族ジイソシアネートを含有する有機ジイソシアネート化合物からなり、かつ末端に第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と、硝化綿、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ブチレート樹脂及び塩化ビニル－酢酸ビニル共重合体から選ばれる少なくとも１種とを含有する軟包装用ラミネート印刷用インキ組成物。 An ink composition for laminating printing for soft packaging comprising a pigment, a binder resin and an organic solvent as main components, wherein the binder resin contains 2-methyl-1,3-propanediol in an amount of 20% by mass or more in the glycol component. A high molecular polyester diol comprising a glycol component and an acid component, and an organic diisocyanate compound containing an alicyclic diisocyanate, and having an amine value having a primary amino group and / or a secondary amino group at the terminal. An ink composition for laminate printing for flexible packaging, comprising a polyurethane resin and at least one selected from nitrified cotton, cellulose acetate propionate resin, cellulose acetate butyrate resin, and vinyl chloride-vinyl acetate copolymer.
  2. 　グリコール成分が、１，６－ヘキサンジオール、ネオペンチルグリコールから選ばれる少なくとも１種を含有する請求項１記載の軟包装用ラミネート印刷用インキ組成物。 The laminate composition printing ink composition for soft packaging according to claim 1, wherein the glycol component contains at least one selected from 1,6-hexanediol and neopentyl glycol.
  3. 　有機ジイソシアネート化合物が、イソホロンジイソシアネート及び／又はジシクロヘキシルメタン－４，４－ジイソシアネートである請求項１又は２記載の軟包装用ラミネート印刷用インキ組成物。 The ink composition for laminating printing for soft packaging according to claim 1 or 2, wherein the organic diisocyanate compound is isophorone diisocyanate and / or dicyclohexylmethane-4,4-diisocyanate.
  4. 　高分子ポリエステルジオールのＯＨ基と有機ジイソシアネート化合物のＮＣＯ基の当量の比率が、ＮＣＯ基／ＯＨ基＝１．１～２．３であり、ポリウレタン樹脂の質量平均分子量が５０００～６００００である請求項１～３のいずれかに記載の軟包装用ラミネート印刷用インキ組成物。 The ratio of the equivalent of the OH group of the high-molecular polyester diol and the NCO group of the organic diisocyanate compound is NCO group / OH group = 1.1 to 2.3, and the mass average molecular weight of the polyurethane resin is 5000 to 60000. The laminate printing ink composition for soft packaging according to any one of 1 to 3.
  5. 　有機溶剤は、エステル系有機溶剤とアルコール系有機溶剤の混合溶剤である請求項１～４のいずれかに記載の軟包装用ラミネート印刷用インキ組成物。
          The laminate composition printing ink composition for flexible packaging according to any one of claims 1 to 4, wherein the organic solvent is a mixed solvent of an ester organic solvent and an alcohol organic solvent.
PCT/JP2017/033847 2016-09-20 2017-09-20 Ink composition for lamination printing on soft packaging WO2018056293A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2018540254A JP7008028B2 (en) 2016-09-20 2017-09-20 Laminate printing ink composition for flexible packaging

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2016-183226 2016-09-20
JP2016183226 2016-09-20

Publications (1)

Publication Number Publication Date
WO2018056293A1 true WO2018056293A1 (en) 2018-03-29

Family

ID=61690438

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2017/033847 WO2018056293A1 (en) 2016-09-20 2017-09-20 Ink composition for lamination printing on soft packaging

Country Status (2)

Country Link
JP (1) JP7008028B2 (en)
WO (1) WO2018056293A1 (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3514208A4 (en) * 2016-09-13 2020-05-06 Sakata INX Corporation Printing ink compositon for film and use thereof
JP2022139294A (en) * 2021-03-11 2022-09-26 東洋インキＳｃホールディングス株式会社 Organic solvent-based gravure ink, and printed matter and laminate using the same

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2016150943A (en) * 2015-02-16 2016-08-22 東洋インキＳｃホールディングス株式会社 Polyurethaneurea resin composition for gravure or flexographic printing ink
JP2016150941A (en) * 2015-02-16 2016-08-22 東洋インキＳｃホールディングス株式会社 Polyurethaneurea resin composition for gravure or flexographic printing ink
JP2016150942A (en) * 2015-02-16 2016-08-22 東洋インキＳｃホールディングス株式会社 Polyurethaneurea resin composition for gravure or flexographic printing ink

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2016150943A (en) * 2015-02-16 2016-08-22 東洋インキＳｃホールディングス株式会社 Polyurethaneurea resin composition for gravure or flexographic printing ink
JP2016150941A (en) * 2015-02-16 2016-08-22 東洋インキＳｃホールディングス株式会社 Polyurethaneurea resin composition for gravure or flexographic printing ink
JP2016150942A (en) * 2015-02-16 2016-08-22 東洋インキＳｃホールディングス株式会社 Polyurethaneurea resin composition for gravure or flexographic printing ink

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3514208A4 (en) * 2016-09-13 2020-05-06 Sakata INX Corporation Printing ink compositon for film and use thereof
JP2022139294A (en) * 2021-03-11 2022-09-26 東洋インキＳｃホールディングス株式会社 Organic solvent-based gravure ink, and printed matter and laminate using the same
JP7164779B2 (en) 2021-03-11 2022-11-02 東洋インキＳｃホールディングス株式会社 Organic solvent-based gravure ink, printed matter and laminate using the same

Also Published As

Publication number Publication date
JPWO2018056293A1 (en) 2019-07-25
JP7008028B2 (en) 2022-01-25

Similar Documents

Publication Publication Date Title
JP7407159B2 (en) Solvent-type gravure printing ink composition for back printing, printing layer, and laminate
JP6636483B2 (en) Printing ink composition for lamination for flexible packaging
JP6363941B2 (en) Gravure white ink composition
JP6545559B2 (en) PRINTING INK COMPOSITION FOR LAMINATE AND EASILY TREABLE LAMINATE
CN109476938B (en) Gravure ink for laminated body, printed matter, and laminated product
JP6666324B2 (en) Printing ink composition for lamination for flexible packaging
JP7008585B2 (en) Printing ink composition for laminating
WO2018110664A1 (en) Printing ink composition for soft packaging laminate
JP6688649B2 (en) Laminated ink composition for flexible packaging
JP7008028B2 (en) Laminate printing ink composition for flexible packaging
JP7002905B2 (en) Laminate printing ink composition for flexible packaging
JP6145207B1 (en) Printing ink composition for film and use thereof
JP6663929B2 (en) Organic solvent-based high solid ink composition for gravure printing and gravure printing method
JP7248498B2 (en) LAMINATE PRINTING INK COMPOSITION FOR FLEXIBLE PACKAGING
JP2021127429A (en) Print ink composition for laminate and easy-to-tear laminate
JP6997510B2 (en) Ink composition for organic solvent-based gravure printing
WO2018066699A1 (en) Laminate printing ink composition for soft packaging
JP7286891B1 (en) LAMINATE PRINTING INK COMPOSITION FOR FLEXIBLE PACKAGING
JP7372177B2 (en) Gravure printing ink composition for film, printing method, printed matter and laminate laminate
JP2023173862A (en) Printing ink composition for soft packaging laminate, printing method, printed matter and laminate
JP7461222B2 (en) Gravure printing ink composition for film, printing method, printed matter and laminate
JP7132148B2 (en) Gravure printing ink composition for film, printing method, printed matter and laminate
JP7338819B2 (en) Gravure printing ink composition for film, printing method, printed matter and laminate
JP7248497B2 (en) PRINTING INK COMPOSITION FOR FLEXIBLE PACKAGING LAMINATION
WO2021106367A1 (en) Printing ink composition for laminate for flexible packaging

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 17853063

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2018540254

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 17853063

Country of ref document: EP

Kind code of ref document: A1