JP6365176B2 - Resin composition for printing ink - Google Patents

Description

  The present invention relates to a resin composition for printing ink. The present invention also relates to a printing ink, a printed matter, a laminate, a packaging material using the resin composition for printing ink, and a method for producing them.

  In recent years, with the diversification of packages and the advancement of packaging technology, plastic films are generally used as packaging materials. Accordingly, various printing inks for plastic films have been developed. In recent years, in particular, packaging materials have been required to have high functions (moisture resistance, oxygen barrier properties, heat resistance, retort resistance, etc.), and a laminate in which various plastic films are laminated as packaging materials having such functions. Such laminates are required to have excellent printability, adhesiveness, proper laminating properties, etc. with respect to the plastic film as the base material, and in particular, a laminate having an aluminum layer. In the case of a body, in addition to the above processing suitability, boil suitability, retort suitability, etc. are also required.

  Conventionally, as a printing ink for nylon, polyester, and other substrate films, a printing ink using a polyurethane resin as a binder has been widely used. However, general polyurethane resins distributed in the market have insufficient adhesiveness and laminating suitability for polyolefin films such as polyethylene films and polypropylene films. In order to improve this, an ink using a low chlorinated polyolefin as a binder has been proposed (Patent Document 1). However, in this case, although the adhesion to the polyolefin film is improved, the adhesion to the film such as nylon or polyester is not sufficient, and the boil suitability and retort suitability are insufficient.

  In addition, inks in which polybutadiene polyol, polyisoprene polyol, and polyolefin polyol typified by their hydride are introduced into the printing ink bainter skeleton have been proposed (Patent Documents 2 to 5). However, similarly to Patent Document 1, it has been difficult to achieve both the adhesion to the polyolefin film and the adhesion to the nylon film and the polyester film. In addition, the stability of the ink deteriorates over time, and when printing for a long time (long run), print defects are likely to occur due to doctor streaks, plate clogging, plate fog, impression cylinder dirt, trapping failure, etc. There was a problem that it was not possible. Therefore, there has been a demand for printing inks that can be used for various substrate films and various processing suitability.

JP-A-10-251594 JP-A-5-209146 Japanese Patent Laid-Open No. 5-86317 JP-A-7-126564 JP 2013-151653 A

  The problem to be solved by the present invention is excellent in the temporal stability of the ink, excellent adhesion to any of various plastic films such as polyolefin film, polyethylene terephthalate film, nylon film as a substrate (substrate), A resin composition for printing ink that has good laminating suitability, boiling suitability, and retort suitability, and excellent printing suitability for long runs, printing inks using the same, printed matter, laminates and packaging materials, and methods for producing them Is to provide.

  As a result of intensive studies, the present inventors have found that such problems can be solved, and have reached the present invention.

That is, the embodiment of the present invention includes at least a polyurethane resin (X), a polyester resin, a polyurethane resin, a polycarbonate resin, a polyamide resin, a vinyl acetate resin, a vinyl chloride resin, and nitrocellulose. A resin composition for printing ink comprising at least one binder resin (Y) selected from
In a total of 100% by mass of the polyurethane resin (X) and the binder resin (Y), the content of the polyurethane resin (X) is 1 to 50% by mass,
The polyurethane resin (X) obtained by reacting the polyol component (A) with the polyisocyanate component (B) and then reacting with the primary and / or secondary amine component (C) ( X)
The amino group content in the polyurethane-based resin (X) is 0.16 to 1.8 mmol / g,
The polyol component (A) contains at least a polydiene polyol and / or a hydrogenated polydiene polyol,
A printing ink resin composition comprising 10 to 80% by mass of a structural unit composed of a polydiene polyol and / or a hydrogenated polydiene polyol in 100% by mass of a polyurethane resin (X).
(However, the binder resin (Y) excludes the polyurethane resin (X).)

  In the embodiment of the present invention, the polyurethane resin (X) has a urethane (—NHCOO—) group content of 0.6 to 1.9 mmol / g and a urea (—NHCONH—) group content of 0. It is the said resin composition for printing inks which is 0.6-1.9 mmol / g.

  An embodiment of the present invention is a printing ink comprising the printing ink resin composition and a pigment.

  Moreover, the embodiment of the present invention is the method for producing the printing ink, in which the pigment is dispersed in the presence of the binder resin (Y) and then the polyurethane resin (X) is blended.

  Moreover, the embodiment of the present invention is a printed matter printed with the printing ink.

  Moreover, the embodiment of the present invention is a laminate in which a thermoplastic resin layer is disposed on one surface side of the printed matter.

  In addition, an embodiment of the present invention is a method for producing the laminate, in which a thermoplastic resin layer is laminated on one surface side of the printed matter by an extrusion laminating method.

  In addition, an embodiment of the present invention is the method for producing the laminate, in which an adhesive layer is formed on one surface side of the printed matter, and then a thermoplastic resin layer is laminated by a dry lamination method.

  Moreover, the embodiment of this invention is a packaging material obtained by heat-sealing the said laminated body.

  With the resin composition for printing ink of the present invention, the ink has excellent stability over time, and has excellent adhesion to any plastic film such as polyolefin film, polyethylene terephthalate film, nylon film, etc. It is possible to provide printing inks that are suitable for laminating, suitable for boil processing, and suitable for retort processing, and that are excellent for long-run printing. Thereby, the printed matter, laminated body, and packaging material which satisfy | fill the said appropriateness came to be able to be provided.

<Resin composition for printing ink>
The resin composition for printing ink used in the present invention reacts with the primary component and / or the secondary amine component (C) after reacting the polyol component (A) with the polyisocyanate component (B). A resin composition for printing ink comprising the obtained polyurethane resin (X) and a binder resin (Y) (however, the binder resin (Y) excludes the polyurethane resin (X)), The amino group content in the polyurethane-based resin (X) is 0.16 to 1.8 mmol / g, and the polyol component (A) contains at least a polydiene polyol and / or a hydrogenated polydiene polyol. 10 to 80% by mass of a structural unit composed of a polydiene polyol and / or a hydrogenated polydiene polyol is contained in 100% by mass of the resin (X).

<Polyurethane resin (X)>
The polyurethane-based resin (X) used in the present invention is prepared by reacting the polyol component (A) with the polyisocyanate component (B) to synthesize a urethane prepolymer, and then reacting the isocyanate group in the urethane prepolymer with 1 It can be obtained by reacting the primary amino group in the secondary amine component and / or the secondary amino group in the secondary amine component.

When synthesizing the urethane prepolymer, it is preferable to react the isocyanate (NCO) group equivalent in the polyisocyanate component (B) in an excess amount with respect to the hydroxyl equivalent in the polyol component (A). In this case, a urethane prepolymer having an isocyanate group at the end of the polymer chain is obtained. The equivalent ratio of the isocyanate group equivalent in the polyisocyanate component (B) to the hydroxyl equivalent in the polyol component (A) (hereinafter referred to as “NCO / OH ratio”) is preferably 1.01 to 3.00, more preferably The range is 1.30 to 2.50.
When the urethane prepolymer is reacted with the primary and / or secondary amine component (C), if the urethane prepolymer is a urethane prepolymer having an isocyanate group at the end of the polymer chain, the isocyanate in the urethane prepolymer It is preferable to react the total amount of the primary amino group equivalent in the primary amine component and / or the secondary amino group equivalent in the secondary amine component in an excess amount with respect to the (NCO) group equivalent. In this case, a polyurethane-based resin (X) having a urea (—NHCONH—) group generated by a reaction between an isocyanate group in the urethane prepolymer and an amino group in the amine component is obtained at the polymer chain end. .
Moreover, in the polysisonate component (B) with respect to the sum total of the hydroxyl group equivalent in the polyol component (A) and the primary amino group equivalent in the primary amine component and / or the secondary amino group equivalent in the secondary amine component. The equivalent ratio of isocyanate group equivalents (hereinafter referred to as “NCO / (OH + N) ratio”) is preferably in the range of 0.60 to 0.99, more preferably 0.65 to 0.90.

  The synthesis reaction of the polyurethane resin (X) used in the present invention is preferably performed in an organic solvent. Examples of the organic solvent include ester solvents such as ethyl acetate, propyl acetate, and butyl acetate, ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, ether solvents such as dioxane and tetrahydrofuran, n-hexane, cyclohexane, and methyl. Examples include aliphatic hydrocarbon solvents such as cyclohexane, aromatic hydrocarbon solvents such as toluene and xylene, alcohol solvents such as methanol, ethanol, and isopropanol. These may be used alone or in combination of two or more. From the viewpoint of solubility of the polyurethane resin (X), it is preferable to include an alcohol solvent or an ether solvent.

  The reaction temperature during the synthesis reaction is in the range of 20 to 180 ° C., preferably 40 to 120 ° C. when the polyol component (A) and the polyisocyanate component (B) are reacted. Moreover, when making it react with a primary and / or secondary amine component (C), it is 100 degrees C or less, Preferably it is the range of 0-80 degreeC.

  In the synthesis reaction, a known reaction catalyst may be used. Examples of known reaction catalysts include tertiary amine catalysts such as triethylamine and N-ethylmorpholine, tin catalysts such as dibutyltin dilaurate and dioctyltin dilaurate, and titanium catalysts such as tetrabutyl titanate. The amount of the reaction catalyst used is usually 0.1% by mass or less based on the polyurethane resin (X).

  In order to improve the adhesion to the polyolefin film, the polyol component (A) contains at least a polydiene polyol and / or a hydrogenated polydiene polyol, and in 100% by mass of the polyurethane resin (X), the polydiene polyol and / or It contains 10 to 80% by weight, more preferably 20 to 60% by weight, of a structural unit composed of hydrogenated polydiene polyol.

  The number average molecular weight of the polydiene polyol and / or hydrogenated polydiene polyol used in the present invention is preferably 500 to 5,000, more preferably 500 to 3,000, and still more preferably 500 from the viewpoint of adhesiveness. It is in the range of ~ 2,000. If the number average molecular weight of the polydiene polyol and / or hydrogenated polydiene polyol is lower than 500, the adhesion to the polyolefin film may be insufficient, and if it is higher than 5,000, the compatibility with the ink is deteriorated. There is a risk of doing. The number average molecular weight in the present invention means a value measured by gel permeation chromatography (GPC) using polyethylene glycol as a molecular weight standard and dimethylformamide as a solvent. As commercial products, NISSO PB G-1000, G-2000, G-3000 manufactured by Nippon Soda Co., Ltd., Poly bd R-15HT, R-45HT manufactured by Idemitsu Kosan Co., Ltd., Krasol LBH2000, LBH-P2000 manufactured by Clay Valley Co., Ltd. , LBH3000, LBH-P3000 (above polybutadiene polyol), NISSO PB GI-1000, GI-2000, GI-3000 manufactured by Nippon Soda Co., Ltd., Polytail H manufactured by Mitsubishi Chemical Corporation, Krasol HLBH-P2000 manufactured by Clay Valley, HLBH -P3000 (above hydrogenated polybutadiene polyol), Poly ip (polyisoprene polyol) manufactured by Idemitsu Kosan Co., Ltd., and Epol (hydrogenated polyisoprene polyol) manufactured by Idemitsu Kosan Co., Ltd.

  As the polyol component (A) used in the present invention, in addition to polydiene polyol and / or hydrogenated polydiene polyol, for example, aliphatic polyhydric alcohol, alicyclic polyhydric alcohol, aromatic polyhydric alcohol, etc. Examples thereof include polyhydric alcohols, polyester polyols, polyether polyols, polycarbonate polyols, and polylactone polyols. From the viewpoint of excellent solvent solubility, it is preferable to contain a polyether polyol as the polyol component (A). These may be used alone or in combination of two or more.

  Examples of the polyhydric alcohol include ethylene glycol, diethylene glycol, 1,3-propanediol, 1,4-butanediol, linear alkyl-containing diols such as 1,6-hexanediol, 1,2-propanediol, and neopenty. Branched alkyl-containing diols such as lenglycol, 3-methyl-1,5-pentanediol, 2,2-diethyl-1,3-propanediol, 1,4-bis (hydroxymethyl) cyclohexane, 2,2-bis (4- Alicyclic ring-containing diols such as hydroxycyclohexyl) propane, aromatic ring-containing diols such as xylylene glycol, bis (2-hydroxyethyl) benzene, and bis (hydroxyethoxy) benzene, glycerin, trimethylolpropane, trialkanolamine, pentaerythritol, Jig Serine, triglycerol, dipentaerythritol, sorbitol, sorbitan, polyhydric alcohols such as trihydric or higher such as sorbide like.

  The polyester polyol can be synthesized by an esterification reaction between a polybasic acid or an ester-forming derivative thereof and a polyhydric alcohol. Examples of the polybasic acid or an ester-forming derivative thereof include aliphatic dicarboxylic acids such as oxalic acid, succinic acid, adipic acid, sebacic acid, glutaric acid, azelaic acid, maleic acid and fumaric acid, and fatty acids such as cyclohexyldicarboxylic acid. Aromatic dicarboxylic acids such as cyclic dicarboxylic acids, terephthalic acid, isophthalic acid, etc., trivalent or higher polyvalent carboxylic acids such as trimellitic acid, pyromellitic acid, and their acid anhydrides, lower alkyl esters, acid halides, etc. Examples include ester-forming derivatives. These may be used alone or in combination of two or more. Examples of the polyhydric alcohol include those described above.

  Specific examples of the polyester polyol include, for example, polyethylene adipate polyol, polybutylene adipate polyol, polyhexamethylene adipate polyol, pohexamethylene isophthalate polyol, polyneopentylene adipate polyol, polyethylene propylene adipate polyol, polyethylene butylene adipate polyol, poly Butylene hexamethylene adipate polyol, poly (polyoxytetramethylene) adipate polyol, poly (3-methylpentylene adipate) polyol, polyethylene azelate polyol, polyethylene sebacate polyol, polybutylene azelate polyol, polybutylene sebacate polyol, poly Neopentylene terephthalate polyol, etc. . Examples of commercially available products include Kuraray Polyol P series and N series manufactured by Kuraray Co., Ltd., Sanester series manufactured by Sanyo Chemical Industries, Ltd., and Teslac series manufactured by Hitachi Chemical Co., Ltd.

  Examples of the polyether polyol include the aforementioned polyhydric alcohols and bisphenols (bisphenol A, bisphenol S, bisphenol F), alkylene oxide adducts such as dihydroxynaphthalene, polyethylene glycol, polypropylene glycol, polyethylene-propylene glycol, polyoxytetra Examples thereof include polymers obtained by ring-opening polymerization or ring-opening copolymerization of alkylene oxides such as methylene glycol, polyoxyhexamethylene glycol, and polyoxyoctamethylene glycol. Commercially available products include, for example, Sanix PP series, GP series, New Pole BPE series, Adeka polyether P series, BPX series, BA series made by Nippon Emulsifier, BA-P Series etc. are mentioned.

  The polycarbonate polyol can be obtained by reacting the aforementioned polyhydric alcohol with a carbonic acid diester such as dimethyl carbonate, diethyl carbonate, or diphenyl carbonate. Examples of the polycarbonate polyol used in the present invention include polyhexamethylene carbonate polyol, polypentamethylene carbonate polyol, polytetramethylene carbonate polyol, poly (tetramethylene / hexamethylene) carbonate polyol, and the like. Examples of the commercially available products include Kuraray polyol C series manufactured by Kuraray Co., Ltd., Duranor T series, G series manufactured by Asahi Kasei Chemicals Co., Ltd., and Plaxel CD series manufactured by Daicel Corporation.

  Examples of the polylactone polyol include those obtained by ring-opening polymerization of lactone monomers such as γ-butyrolactone, γ-valerolactone, and ε-caprolactone using the above-described polyhydric alcohol as an initiator. Examples of the polylactone polyol used in the present invention include polycaprolactone polyol and polyvalerolactone polyol. Examples of commercially available products include Plaxel H series manufactured by Daicel, and Polylite OD series manufactured by DIC.

  Examples of the polyisocyanate component (B) include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, 1,5-naphthalene diisocyanate, hexamethylene diisocyanate, bis ( 4-isocyanatocyclohexyl) Diisocyanate such as methane or hydrogenated diphenylmethane diisocyanate and compounds derived therefrom, that is, isocyanurate, adduct, biuret, uretdione, allophanate, and isocyanate residues of the diisocyanate Prepolymers (low polymers obtained from diisocyanates and polyols), or composites of these may be mentioned. These may be used alone or in combination of two or more.

  Examples of the primary and / or secondary amine component (C) include aliphatic monoamines such as monoethylamine, n-propylamine, diethylamine, di-n-propylamine, di-n-butylamine, cyclohexylamine, and N-methylcyclohexyl. Aliphatic monoamines such as amines, aromatic monoamines such as benzylamine and dibenzylamine, aliphatic monoamines containing hydroxyl groups such as monoethanolamine and diethanolamine, fats such as ethylenediamine, 1,2-propylenediamine and hexamethylenediamine Diamines, isophorone diamines, dicyclohexylmethane-4,4'-diamine, isopropylidene dicyclohexylene 4,4'-diamine, 1,4-diaminocyclohexane, 1,3-bisaminomethylcyclohexane, etc. Emissions, iminobispropylamine, aliphatic polyamines such as methyl iminobispropylamine. These may be used alone or in combination of two or more.

The polyurethane resin (X) used in the present invention has a urethane bond (—NHCOO—) and a urea bond (—NHCONH—). The polyurethane-based resin (X) used in the present invention has a urethane (—NHCOO—) group content in the range of 0.6 to 1.9 mmol / g from the viewpoint of obtaining high substrate adhesion. The urea (-NHCONH-) group content is preferably in the range of 0.6 to 1.9 mmol / g. As a more preferable range, the urethane group content is 0.8 to 1.7 mmol / g, and the urea group content is 0.8 to 1.7 mmol / g.
The urethane (—NHCOO—) group content and the urea (—NHCONH—) group content can be obtained by the following formulas, respectively.
Urethane (—NHCOO—) group content = total number of moles of hydroxyl groups in polyol component (A) × 1,000 / (blending amount of polyol component (A) + blending amount of polyisocyanate component (B) +1 grade and (Or blending amount of secondary amine component (C))
(However, NCO / OH ratio> 1)
Urea (—NHCONH—) group content = (sum of moles of isocyanate groups in polyisocyanate component (B) −sum of moles of hydroxyl groups in polyol (A)) × 1,000 / (polyol component (A ) + Amount of polyisocyanate component (B) + amount of primary and / or secondary amine component (C))
(However, NCO / (OH + N) <1)

  The polyurethane-based resin (X) used in the present invention can obtain further excellent substrate adhesiveness by introducing an amino group into the polyurethane-based resin (X). The amino group content is in the range of 0.16-1.8 mmol / g, more preferably in the range of 0.5-1.6 mmol / g. As a method for introducing an amino group into the polyurethane resin (X), a polyamine is used as the primary and / or secondary amine component (C), and a urethane prepolymer is synthesized so that NCO / OH <1. And a method in which the primary and / or secondary amine component (C) is reacted with the urethane prepolymer so that NCO / OH + N> 1. In addition, amino group content in this invention is calculated | required from amine value titration.

  In the present invention, by combining the polyurethane resin (X) and the binder resin (Y), which have excellent adhesion to the polyolefin film, excellent ink stability over time, long run suitability, and high adhesion to the polyolefin substrate are combined. Can have. Content of the polyurethane-type resin (X) used by this invention is 1-50 mass% in the total 100 mass% of polyurethane-type resin (X) and binder resin (Y), More preferably, it is 2- 30 mass%, More preferably, it is 5-25 mass%.

  The weight average molecular weight of the polyurethane-based resin (X) used in the present invention is preferably in the range of 4,000 to 25,000, more preferably 4,000 to 19,000, from the viewpoint of excellent adhesiveness. 000, more preferably 4,000 to 15,000, and particularly preferably 4,000 to 14,000. The weight average molecular weight in the present invention is a value measured by gel permeation chromatography (GPC) using polystyrene as a molecular weight standard and dimethylformamide as a developing solvent. A lithium halide salt such as lithium bromide is preferably used as an additive for preventing ion repulsion or association of the resin during measurement, and a tertiary amine such as triethylamine is preferably used to suppress adsorption of the resin to the column.

<Binder resin (Y)>
Binder resin (Y) used in the present invention is preferably a polyester resin, polyurethane resin, polycarbonate resin, polyamide resin, vinyl acetate resin, vinyl chloride resin, nitrocellulose resin, Those containing no polydiene and / or hydrogenated polydiene structure are preferably used.

  The polyester resin can be synthesized by an esterification reaction of the polybasic acid or an ester-forming derivative thereof and a polyhydric alcohol.

  The polyurethane resin includes a polyol component (A) used for the synthesis of the polyurethane resin (X) described above (however, the polyol component (A) does not include polydiene polyol and / or hydrogenated polydiene polyol) and polyisocyanate. It can be obtained by reacting the component (B) with a poly primary and / or secondary amine component (C) as required.

  The polycarbonate-based resin is obtained by a reaction between the aforementioned polyhydric alcohol and a carbonic acid diester.

  The polyamide-based resin can be obtained by subjecting the above-described polyhydric alcohol, polybasic acid, and polyvalent amine to salt formation and then an amidation reaction. As the polyvalent amine, compounds exemplified in the above-mentioned poly primary and / or secondary amine components can be used.

  The vinyl acetate resin can be obtained by polymerizing a vinyl acetate monomer alone or a vinyl acetate monomer and a polymerizable unsaturated monomer. Examples of the unsaturated monomer include n-butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, and lauryl (meth). Long chain (meth) acrylic monomers represented by alkyl (meth) acrylate monomers such as acrylate, tridecyl (meth) acrylate, stearyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate 1,4-butanediol mono (meth) acrylate, (poly) ethylene glycol mono (meth) acrylate and other hydroxyl group-containing (meth) acrylic monomers, (meth) acrylic acid, maleic acid, maleic anhydride, etc. Carboxyl Containing monomers, styrene, acrylonitrile, vinyl monomers such as vinyl chloride, ethylene, and the like. These may be used alone or in combination of two or more.

  The vinyl chloride resin is obtained by polymerizing a vinyl chloride monomer alone or a vinyl chloride monomer and a polymerizable unsaturated monomer. Examples of the unsaturated monomer include those described above.

  Nitrocellulose can be obtained by esterifying cellulose using a mixed acid of nitric acid and sulfuric acid. Nitrocellulose having a nitrogen content of 10 to 13% by mass is preferably used.

  The binder resin (Y) preferably contains a polyurethane resin from the viewpoint of excellent adhesiveness. The content of the polyurethane-based resin in the binder resin (Y) is preferably 30 to 100% by mass, and more preferably 50 to 100% by mass.

  The weight average molecular weight of the binder resin (Y) is preferably in the range of 20,000 to 100,000, and more preferably in the range of 30,000 to 100,000.

  The binder resin (Y) preferably contains at least one selected from polyester resins, polyurethane resins, vinyl acetate resins, vinyl chloride resins, and nitrocellulose from the viewpoint of excellent pigment dispersibility.

  In the present invention, a resin other than the polyurethane resin (X) and the binder resin (Y) may be used in combination as long as the effects of the present invention are not impaired. Examples of resins other than polyurethane resin (X) and binder resin (Y) include, for example, styrene maleic acid copolymer resins, chlorinated polyolefin resins, chlorosulfonated polyolefin resins, alkyd resins, phenol resins, and epoxy resins. Examples thereof include resins and rosin resins. These may be used alone or in combination of two or more. As a compounding quantity of resin other than polyurethane-type resin (X) and binder resin (Y), the range of 0-50 mass% is preferable with respect to a total of 100 mass% of polyurethane-type resin (X) and binder resin (Y). .

<Printing ink>
The printing ink of the present invention comprises the resin composition for printing ink of the present invention and a pigment.

  There is no restriction | limiting in particular as a pigment, The organic and inorganic pigment used for general printing ink can be used. For example, azo pigments, phthalocyanine pigments, perylene pigments, nitroso pigments, perinone pigments, carbon black, titanium black, zinc white, brown, aluminum, chromium oxide, iron black, cobalt blue, iron oxide yellow, viridian, zinc sulfide, Examples include lithopone, cadmium yellow, cadmium red, yellow lead, molybdate orange, zinc chromate, strontium chromate, white carbon, clay, talc, calcium carbonate, manganese violet and the like. These may be used alone or in combination of two or more.

  In the present invention, known additives such as pigment dispersants, leveling agents, antifoaming agents, slipping agents, antiblocking agents and the like used in general printing inks are used as necessary within the range not impairing the effects of the present invention. You may do it.

  The printing ink in which the polyurethane resin (X) of the present invention is used may be used in combination with a polyisocyanate curing agent. Examples of the polyisocyanate curing agent include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, 1,5-naphthalene diisocyanate, hexamethylene diisocyanate, bis (4 Diisocyanate such as isocyanate cyclohexyl) methane or hydrogenated diphenylmethane diisocyanate and compounds derived therefrom, that is, isocyanurate, adduct, biuret, uretdione, allophanate, and isocyanate residues of the diisocyanate. Examples thereof include polymers (low polymers obtained from diisocyanates and polyols), and composites thereof. These may be used alone or in combination of two or more. The addition amount of the polyisocyanate curing agent is preferably 0.5 to 10% by mass with respect to the main agent.

<Manufacturing method of printing ink>
The production method of the printing ink is not particularly limited, and includes a polyurethane resin (X), a binder resin (Y) and a pigment of the present invention, and, if necessary, a solvent, the above-mentioned additives, etc. It can be produced by kneading using a normal ink production apparatus such as a ball mill, an attritor or a sand mill. There are no particular restrictions on the manufacturing process, but in order to make the polyurethane resin (X) work as much as possible for adhesion to the base material, the polyurethane resin (X) is blended after dispersing the pigment in the presence of the binder resin (Y). Thus, it is preferable to produce a printing ink.

<Printing>
The printing method on the base material of the printing ink in which the polyurethane resin (X) of the present invention is used is a general printing method such as gravure printing, inkjet printing, offset printing, thermal transfer printing, and the like. It is done. Examples of the substrate include polyester film, nylon film, surface-treated or untreated polyethylene film, polypropylene film, polyvinyl acetal film, polyacetate film, polyvinyl chloride film, and films obtained by performing aluminum vapor deposition on these plastic films. Can be mentioned.

<Laminate>
The laminated body by which the thermoplastic resin layer is arrange | positioned at the one surface side of the printed matter of this invention can be manufactured. The thermoplastic resin layer may be in direct contact with the printed material or may be disposed via another layer. Further, the thermoplastic resin layer is not limited to one layer, and two or more layers may be laminated. For the purpose of the present invention, the thermoplastic resin layer is preferably disposed in direct contact with the printed surface of the printed matter. The method for forming the thermoplastic resin layer is not particularly limited. For example, a solution obtained by dissolving a thermoplastic resin in a solvent may be applied, or a film made of a thermoplastic resin may be laminated. Is preferred. Examples of laminating methods include various methods such as extrusion lamination and dry lamination. The temperature at the time of lamination is not particularly limited, and can be appropriately determined depending on the thermoplastic resin used.

<Thermoplastic resin layer>
A thermoplastic resin layer means the layer which has a thermoplastic resin as a main component. Although the thickness of a thermoplastic resin layer is not specifically limited, 5-200 micrometers is preferable and 5-100 micrometers is more preferable. The thermoplastic resin is not particularly limited as long as it can be laminated. For example, a low density polyethylene resin, a high density polyethylene resin, a medium density polyethylene resin, an ethylene-vinyl acetate copolymer, an ethylene-α-olefin copolymer, Examples thereof include resins such as ethylene-α, β-unsaturated carboxylic acid copolymers and ester compounds or ionic crosslinked products thereof, polypropylene resins, propylene-α-olefin copolymers, acid anhydride-modified polyolefins, and epoxy-modified polyolefins. These may be used alone or in a blend of two or more.

<Adhesive layer>
As the adhesive used for the adhesive layer, various adhesives can be selected according to various laminating methods, for example, urethane-based, polyester-based, polyether-based, epoxy-based, polyethyleneimine-based, polybutadiene-based, etc. A known adhesive can be used.

<Packaging material>
The packaging material of the present invention can be obtained by heat-sealing the laminate. Examples of the packaging material include packaging bags, sheets, trays, cases, vacuum pack packaging, lid materials, carton packaging, ampoule packaging, and the like. Three-sided sealing bags, four-sided sealing bags, pillow bags, etc. , Standing pouches, rocket packaging bags, etc.
The packaging material of the present invention has a particularly remarkable effect when it is used as a packaging bag. That is, when the packaging bag is filled with the contents containing water, oil and acid, and the retort treatment is performed, the quality of the contents is not deteriorated and a stable printing surface can be maintained. Therefore, the packaging material of the present invention can be filled and packaged with contents such as foods and drinks, liquid detergents, cosmetics, and chemical products.

  EXAMPLES The present invention will be described more specifically with reference to the following examples. However, the following examples do not limit the scope of rights of the present invention. Unless otherwise specified, “part” represents “part by mass” and “%” represents “% by mass”.

<Measurement of weight average molecular weight / number average molecular weight>
The weight average molecular weight and the number average molecular weight of the resin were measured by connecting Tosoh GPC (gel permeation chromatography) “HPC-8020” as a measuring device and Tosoh SUPER AW3000 as a column in series, and using triethylamine as an additive. Was measured at 40 ° C. using a dimethylformamide solution dissolved in 30 mM of lithium bromide and 10 mM of lithium bromide as an eluent. These average molecular weights were converted to standard polystyrene.

<Measurement of amino group content>
The amino group content in the resin was measured by preparing a solution in which 0.3 part of a resin sample was dissolved in 100 parts of tetrahydrofuran, and measuring by a potentiometric titration method using a 0.1 M hydrochloric acid solution.

<Calculation of urethane (-NHCOO-) group content>
The urethane (—NHCOO—) group content in the resin was determined from the following formula.
Urethane (—NHCOO—) group content = total number of moles of hydroxyl groups in polyol component (A) × 1,000 / (blending amount of polyol component (A) (g) + polyisocyanate component (B) Compounding amount (g) of +1 and / or secondary amine component (C) (g))

<Calculation of urea (-NHCONH-) group content>
The urea (—NHCONH—) group content in the resin was determined from the following formula.
Urea (—NHCONH—) group content = (sum of moles of isocyanate groups in polyisocyanate component (B) −sum of moles of hydroxyl groups in polyol (A)) × 1,000 / (polyol component (A ) Blending amount (g) + polyisocyanate component (B) blending amount (g) +1 and / or secondary amine component (C) blending amount (g))

Synthesis of <Polyurethane Resin (X-1) to (X-6)> and <Binder Resin (Y-1), (Y-2)> Polyurethane Resin (X) and Binder Resin (Y ) Was synthesized. Table 1 shows the blending amounts of the raw materials used for the synthesis and the physical properties of the obtained resin.

<Synthesis of polyurethane resin (X-1)>
Sanix PP-1000 (polyoxypropylene glycol, number average molecular weight 1,000, Sanyo Chemical Industries, Ltd.) as the polyol component (A) in a four-necked flask equipped with a stirrer, thermometer, reflux condenser, and nitrogen gas inlet tube 24.1 g, 46.1 g of NISSO-PB GI-2000 (hydrogenated polybutadiene polyol, number average molecular weight 2,300, manufactured by Nippon Soda Co., Ltd.) as the polyol component (A), and as the polyisocyanate component (B) 19.6 g of isophorone diisocyanate and 38.5 g of butyl acetate were charged and reacted at 90 ° C. for 6 hours while introducing nitrogen gas. Next, the reaction solution was cooled to 30 ° C. and then transferred to a dropping funnel, and the four-necked flask was washed with 11.4 g of butyl acetate and added to the dropping funnel. Next, a four-necked flask equipped with a separate stirrer, thermometer, reflux condenser, and nitrogen gas inlet tube was prepared, and 10.2 g of isophorone diamine as a secondary amine component (C), 80.1 g of butyl acetate, 93.3 g of isopropyl alcohol was added, the temperature was maintained at 30 ° C., and the temperature was maintained, and the reaction solution in the dropping funnel was added dropwise over 3 hours while stirring. After completion of the dropping, the dropping funnel was washed with 10.0 g of butyl acetate and added dropwise, and further stirred and reacted at 30 ° C. for 1 hour to obtain a polyurethane resin (X-1) solution. The obtained polyurethane resin (X-1) has a solid content of 30%, a weight average molecular weight of 23,000, a urethane group content of 0.88 mmol / g, a urea group content of 0.88 mmol / g, and an amino group. In the content of 0.32 mmol / g and 100% by mass of the polyurethane-based resin (X), the content of a constituent unit composed of a polydiene polyol and / or a hydrogenated polydiene polyol was 46.1%.

<Synthesis of polyurethane resin (X-2)>
In a four-necked flask equipped with a stirrer, thermometer, reflux condenser, and nitrogen gas inlet tube, Sanix PP-400 (polyoxypropylene glycol, number average molecular weight 400, manufactured by Sanyo Chemical Industries, Ltd.) as the polyol component (A) 18.9 g, 37.2 g of NISSO-PB G-2000 (polybutadiene polyol, number average molecular weight 2,100, manufactured by Nippon Soda Co., Ltd.) as the polyol component (A), and 28 of isophorone diisocyanate as the polyisocyanate component (B) 9.9 g and butyl acetate 36.4 g were charged, and the reaction was carried out at 90 ° C. for 6 hours while introducing nitrogen gas. Next, the reaction solution was cooled to 30 ° C. and then transferred to a dropping funnel, and the four-necked flask was washed with 10.2 g of butyl acetate and added to the dropping funnel. Next, a four-necked flask equipped with a separate stirrer, thermometer, reflux condenser, and nitrogen gas inlet tube was prepared, and 15.1 g of isophorone diamine, 83.3 g of butyl acetate as a secondary amine component (C), 93.3 g of isopropyl alcohol was added, the temperature was maintained at 30 ° C., and the temperature was maintained, and the reaction solution in the dropping funnel was added dropwise over 3 hours while stirring. After completion of the dropping, the dropping funnel was washed with 10.0 g of butyl acetate and added dropwise, and further stirred and reacted at 30 ° C. for 1 hour to obtain a polyurethane resin (X-2) solution. The obtained polyurethane resin (X-2) has a solid content of 30%, a weight average molecular weight of 18,000, a urethane group content of 1.3 mmol / g, a urea group content of 1.3 mmol / g, and an amino group. The content of 0.47 mmol / g of the polyurethane-based resin (X) was 100% by mass, and the content of the structural unit composed of polydiene polyol and / or hydrogenated polydiene polyol was 37.2%.

<Synthesis of polyurethane resin (X-3)>
Sanix PP-1000 (polyoxypropylene glycol, number average molecular weight 1000, manufactured by Sanyo Chemical Industries) as a polyol component (A) in a four-necked flask equipped with a stirrer, thermometer, reflux condenser, and nitrogen gas inlet tube As for the polyol component (A), 41.7 g of LBH-2000 (polybutadiene polyol, number average molecular weight 2,100, manufactured by Clay Valley) and NISSO-PB G-2000 (polybutadiene polyol, number average molecular weight) 20.0 g, manufactured by Nippon Soda Co., Ltd.), 18.8 g of 4,4′-dicyclohexylmethane diisocyanate as polyisocyanate component (B), 37.3 g of butyl acetate, and 90 ° C. while introducing nitrogen gas For 6 hours. Next, the reaction solution was cooled to 30 ° C. and then transferred to a dropping funnel, and the four-necked flask was washed with 10.7 g of butyl acetate and added to the dropping funnel. Next, a four-necked flask equipped with a separate stirrer, thermometer, reflux condenser, and nitrogen gas inlet tube was prepared, and 12.9 g of 4,4′-dicyclohexylmethanediamine as a secondary amine component (C), acetic acid 82.0 g of butyl and 93.3 g of isopropyl alcohol were added, the temperature was raised to 30 ° C., and the temperature was maintained, and the reaction solution in the dropping funnel was added dropwise over 3 hours while stirring. After completion of dropping, the dropping funnel was washed with 10.0 g of butyl acetate, and then the washing solution was added dropwise, and further reacted with stirring at 30 ° C. for 1 hour to obtain a polyurethane resin (X-3) solution. The obtained polyurethane resin (X-3) has a solid content of 30%, a weight average molecular weight of 16,000, a urethane group content of 0.72 mmol / g, a urea group content of 0.72 mmol / g, and an amino group. Content of 0.51 mmol / g and polyurethane-type resin (X) 100 mass% WHEREIN: Content of the structural unit which consists of a polydiene polyol and / or hydrogenated polydiene polyol was 61.7%.

<Synthesis of polyurethane resin (X-4)>
Sanix PP-1000 (polyoxypropylene glycol, number average molecular weight 1000, manufactured by Sanyo Chemical Industries) as a polyol component (A) in a four-necked flask equipped with a stirrer, thermometer, reflux condenser, and nitrogen gas inlet tube 20.3 g, 52.5 g of Krasol HLBH-3000 (hydrogenated polybutadiene polyol, number average molecular weight 3,100, manufactured by Clay Valley) as the polyol component (A), and 16 of isophorone diisocyanate as the polyisocyanate component (B) .6 g and 38.3 g of butyl acetate were charged and reacted at 90 ° C. for 6 hours while introducing nitrogen gas. Next, the reaction solution was cooled to 30 ° C. and then transferred to a dropping funnel, and the four-necked flask was washed with 11.3 g of butyl acetate and added to the dropping funnel. Next, a four-necked flask equipped with a separate stirrer, thermometer, reflux condenser and nitrogen gas inlet tube was prepared, and 10.6 g of isophorone diamine and 80.4 g of butyl acetate as the secondary amine component (C), 93.3 g of isopropyl alcohol was added, the temperature was maintained at 30 ° C., and the temperature was maintained, and the reaction solution in the dropping funnel was added dropwise over 3 hours while stirring. After completion of dropping, the dropping funnel was washed with 10.0 parts of butyl acetate and added dropwise, and further stirred and reacted at 30 ° C. for 1 hour to obtain a polyurethane resin (X-4) solution. The obtained polyurethane resin (X-4) has a solid content of 30%, a weight average molecular weight of 15,000, a urethane group content of 0.75 mmol / g, a urea group content of 0.75 mmol / g, and an amino group. The content was 0.50 mmol / g, and the content of polydiene polyol and / or hydrogenated polydiene polyol in the resin was 52.5%.

<Synthesis of polyurethane resin (X-5)>
Poly bd R-15HT (polybutadiene polyol, number average molecular weight 1,200, manufactured by Idemitsu Kosan Co., Ltd.) as a polyol component (A) is added to a four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen gas introduction tube. 61.6 g, 22.8 g of isophorone diisocyanate as a polyisocyanate component (B), and 36.2 g of butyl acetate were charged and reacted at 90 ° C. for 6 hours while introducing nitrogen gas. Next, the reaction solution was cooled to 30 ° C. and then transferred to a dropping funnel, and the four-necked flask was washed with 10.1 g of butyl acetate and added to the dropping funnel. Next, a four-necked flask equipped with a separate stirrer, thermometer, reflux condenser, and nitrogen gas inlet tube was prepared, and as the secondary amine component (C), 15.6 g of isophorone diamine, 83.7 g of butyl acetate, 93.3 g of isopropyl alcohol was added, the temperature was maintained at 30 ° C., and the temperature was maintained, and the reaction solution in the dropping funnel was added dropwise over 3 hours while stirring. After completion of dropping, the dropping funnel was washed with 10.0 g of butyl acetate and added dropwise, and further stirred and reacted at 30 ° C. for 1 hour to obtain a polyurethane resin (X-5) solution. The obtained polyurethane resin (X-5) has a solid content of 30%, a weight average molecular weight of 13,000, a urethane group content of 1.03 mmol / g, a urea group content of 1.03 mmol / g, and an amino group. In the content of 0.80 mmol / g and 100% by mass of the polyurethane-based resin (X), the content of the constituent unit composed of polydiene polyol and / or hydrogenated polydiene polyol was 61.6%.

<Synthesis of polyurethane resin (X-6)>
In a four-necked flask equipped with a stirrer, thermometer, reflux condenser, and nitrogen gas inlet tube, Sanix PP-200 (polyoxypropylene glycol, number average molecular weight 200, manufactured by Sanyo Chemical Industries, Ltd.) as the polyol component (A) 8.9 g, 38.2 g of NISSO-PB G-1000 (polybutadiene polyol, number average molecular weight 1,500, manufactured by Nippon Soda Co., Ltd.) as the polyol component (A), and 31 of isophorone diisocyanate as the polyisocyanate component (B) .2 g and 33.6 g of butyl acetate were charged and reacted at 90 ° C. for 6 hours while introducing nitrogen gas. Next, the reaction solution was cooled to 30 ° C. and then transferred to a dropping funnel, and the four-necked flask was washed with 8.6 g of butyl acetate and added to the dropping funnel. Next, a four-necked flask equipped with a separate stirrer, thermometer, reflux condenser and nitrogen gas inlet tube was prepared, and 21.7 g of isophorone diamine and 87.8 g of butyl acetate as the secondary amine component (C), 93.3 g of isopropyl alcohol was added, the temperature was maintained at 30 ° C., and the temperature was maintained, and the reaction solution in the dropping funnel was added dropwise over 3 hours while stirring. After completion of dropping, the dropping funnel was washed with 10.0 g of butyl acetate and added dropwise, and further stirred and reacted at 30 ° C. for 1 hour to obtain a polyurethane resin (X-6) solution. The obtained polyurethane resin (X-6) has a solid content of 30%, a weight average molecular weight of 9,000, a urethane group content of 1.40 mmol / g, a urea group content of 1.40 mmol / g, and an amino group. The content of the constituent unit consisting of polydiene polyol and / or hydrogenated polydiene polyol was 38.2% in a content of 1.15 mmol / g and 100% by mass of polyurethane-based resin (X).

<Synthesis of binder resin (Y-1)>
A four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen gas introduction tube was added to Kuraray polyol P-2010 (3-polymethyl-1,5-pentanediol / adipic acid polyester polyol, number average molecular weight 2, 000, manufactured by Kuraray Co., Ltd.), 75.6 g, isophorone diisocyanate 16.8 g, and ethyl acetate 39.6 g were charged and reacted at 90 ° C. for 6 hours while introducing nitrogen gas. Next, the reaction solution was cooled to 30 ° C. and then transferred to a dropping funnel, and the four-necked flask was washed with 12.0 g of ethyl acetate and added to the dropping funnel. Next, a four-necked flask equipped with a separate stirrer, thermometer, reflux condenser, and nitrogen gas introduction tube was prepared, and 7.6 parts of isophoronediamine, 78.4 g of ethyl acetate, and 93.3 g of isopropyl alcohol were charged. After raising the temperature to 30 ° C., the temperature was maintained, and the reaction solution in the dropping funnel was added dropwise over 3 hours with stirring. After completion of the dropping, the dropping funnel was dropped with 10.0 g of ethyl acetate, and the mixture was further reacted by stirring at 30 ° C. for 1 hour to obtain a binder resin (Y-1) solution. The obtained binder resin (Y-1) has a solid content of 30%, a weight average molecular weight of 40,000, a urethane group content of 0.76 mmol / g, a urea group content of 0.76 mmol / g, and an amino group content. The amount was 0.14 mmol / g.

<Synthesis of binder resin (Y-2)>
In a four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen gas inlet tube, 75.6 g of SANNICS PP-2000 (polyoxypropylene glycol, number average molecular weight 2,000, manufactured by Sanyo Chemical Industries, Ltd.) Then, 16.8 g of isophorone diisocyanate and 39.6 g of ethyl acetate were charged and reacted at 90 ° C. for 6 hours while introducing nitrogen gas. Next, the reaction solution was cooled to 30 ° C. and then transferred to a dropping funnel, and the four-necked flask was washed with 12.0 g of ethyl acetate and added to the dropping funnel. Next, a four-necked flask equipped with a separate stirrer, thermometer, reflux condenser, and nitrogen gas inlet tube was prepared, and 7.6 g of isophoronediamine, 78.4 g of ethyl acetate, and 93.3 g of isopropyl alcohol were charged. After raising the temperature to 0 ° C., the temperature was maintained, and the reaction solution in the dropping funnel was added dropwise over 3 hours with stirring. After completion of dropping, the dropping funnel was washed with 10.0 g of ethyl acetate and added dropwise, and the mixture was further reacted by stirring at 30 ° C. for 1 hour to obtain a binder resin (Y-2) solution. The obtained binder resin (Y-2) has a solid content of 30%, a weight average molecular weight of 40,000, a urethane group content of 0.76 mmol / g, a urea group content of 0.76 mmol / g, and an amino group content. The amount was 0.14 mmol / g.

<Preparation of resin composition for printing ink and printing ink>
According to the method shown below, the resin composition for printing inks and the printing ink were prepared. In Table 2, the compounding quantity of the material used for preparation of the resin composition for printing inks and printing ink, and the compounding quantity of the polyurethane-type resin (X) with respect to binder resin (Y) are shown.

<Example 1: Preparation of resin composition for printing ink (1) and printing ink (1)>
In a glass container, blend 60 g of the binder resin (Y-1) solution as the binder resin (Y) and 40 g of the polyurethane resin (X-1) solution as the polyurethane resin (X) until uniform using a disper. The resin composition for printing ink (1) was prepared by stirring. 25 g of phthalocyanine blue (Lionol Blue FG-7400 manufactured by Toyocolor Co., Ltd.) as a pigment, 57 g of ethyl acetate as a solvent, and 38 g of isopropyl alcohol are blended in the obtained resin composition for printing ink (1), and glass beads are mixed. The ink was kneaded with a paint shaker, and the printing beads (1) were prepared by removing the glass beads by filtration.

<Examples 2 to 7: Preparation of resin compositions for printing ink (2) to (7) and printing inks (2) to (7)>
Resin compositions for printing inks (2) to (7) and printing inks (2) to (7), except that the type and amount of resin were changed as described in Table 2, in the same manner as in Example 1. Were prepared respectively.

<Example 8: Preparation of resin composition for printing ink (8) and printing ink (8)>
A binder resin (Y-1) solution of 85 g as a binder resin (Y), 25 g of phthalocyanine blue (Lionol Blue FG-7400 manufactured by Toyocolor Co., Ltd.) as a pigment, 57 g of ethyl acetate as a solvent, and 38 g of isopropyl alcohol, After kneading with a glass shaker using a glass bead, 15 g of the polyurethane resin (X-1) solution is blended as the polyurethane resin (X), stirred until uniform using a dipper, and the glass beads are removed by filtration. Thus, a printing ink (8) was prepared.

<Comparative Examples 1 and 2: Preparation of Resin Compositions for Printing Inks (9) and (10) and Printing Inks (9) and (10)>
Resin compositions for printing ink (9), (10) and printing inks (9), (10), except that the type and amount of resin were changed as described in Table 2, in the same manner as in Example 1. Were prepared respectively.

<Stability of printing ink over time>
Immediately after the preparation of each of the printing inks (1) to (10), they were put in a glass sample bottle and sealed. Each ink viscosity at 25 ° C. was measured with a B-type viscometer before and after storage at 40 ° C. for 4 weeks. From the rate of change in viscosity over time (viscosity before storage / viscosity after storage (%)), evaluation was performed according to the following evaluation criteria.
(Evaluation criteria)
◯: Viscosity change rate is less than 15% (good)
X: Viscosity change rate is 15% or more (defect)

  The ink of Comparative Example 2 contains a hydrogenated polybutadiene polyol, which is a hydrogenated polydiene polyol, as the polyurethane resin (X). However, since the binder resin (Y) is not contained, the temporal stability of the ink is deteriorated. It became clear to do.

<Examples 9 to 16, Comparative Examples 3 and 4: Creation of Printed Material>
In order to evaluate adhesiveness, extrusion laminate strength, dry laminate strength, and boil suitability, printed materials were prepared by the following methods.

  An NBR (nitrile butadiene rubber) impression cylinder with a hardness of 80Hs, a blade thickness of 60 μm (a base thickness of 40 μm, a ceramic layer thickness of 10 μm), an electronic engraving with a chromium hardness of 1050 Hv manufactured by Toyo Prepress The plate (stylus angle 120 degrees, 250 lines / inch) was set on a gravure printing machine manufactured by Fuji Machine Industry Co., Ltd.

After rotating the plate at a doctor pressure of 2 kg / cm ² and a rotation speed of 100 m / min and idling for 15 minutes, as a base material, a corona-treated stretched polyolefin (OPP) film having a thickness of 20 μm (Pyrene P-2161 manufactured by Toyobo Co., Ltd.), Using a 12 μm thick corona-treated polyethylene terephthalate (PET) film (Toyobo Co., Ltd., Toyobo Ester Film E5100) and a 15 μm thick corona-treated nylon (NY) film (Unitika Emblem ON), a printing speed of 100 m / min, Printing inks (1) to (10) were printed at a printing pressure of 2 kg / cm ² and dried by blowing hot air at 60 ° C. to obtain printed matter.

  In addition, for the purpose of long run suitability evaluation, a corona-treated nylon having a base material of 15 μm in thickness is formed by the same printing method as above except that the rotation speed during idling is changed to 150 m / min and the printing speed is changed to 150 m / min. NY) 15,000 m was printed on a film (Emblem ON manufactured by Unitika Ltd.) to obtain a printed matter. In this way, printed matter (1)-(10) was obtained using printing ink (1)-(10).

<Evaluation of printed matter>
About the obtained printed matter, adhesiveness, extrusion laminate strength, dry laminate strength, boil suitability, and retort suitability were evaluated, respectively.

<Evaluation of adhesiveness>
About the printed matter, after leaving it to stand at 25 ° C. for 24 hours after printing, the cellophane tape (Cello tape (registered trademark) No. 405 manufactured by Nichiban Co., Ltd., width 24 mm, adhesive strength 3.93 N / 10 mm) is firmly attached to the printed surface with a fingertip. I let you. One minute after the tape was attached, the end of the tape was held, the end of the tape was held at an angle of 90 ° with respect to the printing surface, and the tape was reliably pulled off in 0.5 seconds. The ratio of the printing ink remaining on the substrate without peeling to the area where the tape was adhered (residual ink area%) was determined and evaluated according to the following evaluation criteria.
(Evaluation criteria)
A: The remaining ink area is 97% or more (very good)
◯: The remaining ink area is 80% or more and less than 97% (good)
Δ: Residual ink area is 70% or more and less than 80% (defect)
X: Residual ink area is less than 70% (very poor)

<Extruded laminate strength>
In the above printed matter, polyethyleneimine anchor coat agent (Olivene EL-420 manufactured by Toyo Morton Co., Ltd.) is used for printed matter using an OPP film as a substrate, and butadiene anchor coat is used for printed matter using a PET film and NY film as a substrate. An agent (EL451 manufactured by Toyo Morton Co., Ltd.) was applied to the printing surface so as to have a thickness of 0.1 μm. Next, low-density polyethylene (Novatech LC600, manufactured by Nippon Polychem Co., Ltd.), a thermoplastic resin as a sealant, was melted at a melting temperature of 315 ° C. on the coated surface of the anchor coating agent, and the line speed from the T die: 70 m / min, thickness The thickness was 20 μm, and the processing width was 620 mm, and extrusion lamination was performed to obtain a laminate (laminate). The laminate using the OPP film as the substrate was aged at 25 ° C. for 2 days, and the laminate using the PET film and the NY film as the substrate was aged at 40 ° C. for 2 days. After the aging, each laminate was cut out to a width of 15 mm, and the T-type peel strength was measured with an Intesco 2010 universal tensile tester. It can be said that the larger the numerical value, the better the evaluation result.

<Dry laminate strength>
A urethane adhesive (TM-250, CAT-RT80 manufactured by Toyo Morton Co., Ltd.) is applied to the printed surface of the printed matter to form an adhesive layer having a thickness of 5 μm, and further, a thermoplastic resin layer having a thickness of 30 μm. An unstretched polypropylene (CPP) film (Pyrene P-2161 manufactured by Toyobo Co., Ltd.) was laminated, and dry lamination was performed with a dry laminating machine to obtain a laminate (laminate). After aging at 40 ° C. for 3 days, the laminate was cut into a width of 15 mm, and the T-type peel strength was measured with an Intesco 2.01 million tensile tester. It can be said that the larger the numerical value, the better the evaluation result.

<Boil suitability and retort suitability>
The dry-laminated laminate was heat-sealed to form a four-sided type pouch (outer dimensions 120 mm × 190 mm, each seal width 10 mm) as a packaging material. Each sample pouch was filled and sealed with 150 g of a mixture of water / salad oil (Nisshin Salad Oil, Nisshin Oillio Group) / acetic acid = 1/1/1 (mass ratio), and hydrothermal retort treatment under the following conditions. Was given.
Boil suitability: The central temperature in the pouch was maintained at 100 ° C. for 30 minutes.
Retort suitability: The central temperature in the pouch was maintained at 120 ° C. for 30 minutes.
Evaluation was performed according to the following evaluation criteria.
(Evaluation criteria)
○: No change in the appearance of the laminate (good)
×: Change in the appearance of the laminate due to peeling or the like was observed (defect)

<Appropriate for long run>
Regarding the obtained printed matter of 100,000 m, the printed surface for 5 m from the start of printing and the printed matter for 5 m from the end of printing have the following evaluation criteria for the appearance of color unevenness, color loss, doctor streaks, etc. It was evaluated visually.
(Evaluation criteria)
○: No appearance defect (good).
X: Appearance defect exists (defect).

As shown in Table 3, since the printing ink (9) used in Comparative Example 3 did not contain the polyurethane resin (X), the adhesion to the OPP film was poor, and accompanying this, the extrusion laminate strength against the OPP It was revealed that the dry laminate strength was also significantly reduced.
In Comparative Example 4, since the printing ink (10) used does not contain the binder resin (Y), the temporal stability and long run suitability of the printing ink are remarkably lowered, and the adhesiveness to OPP is good, but NY and It was revealed that the adhesion to the PET substrate was poor.

On the other hand, it was revealed that the printing inks of Examples 1 to 8 shown in Table 3 satisfy all of adhesiveness, extrusion laminate strength, dry laminate strength, boil suitability and retort suitability.
Among these, the printing ink used in Examples 13, 14, and 16 has a preferred range of the weight average molecular weight of the polyurethane-based resin (X) contained, compared with the printing ink of Example 9, and Compared with the printing ink, the number average molecular weight of the polydiene polyol and / or hydrogenated polydiene polyol used in the contained polyurethane-based resin (X) is in a suitable range, and the printing inks of Examples 11 and 12 Compared with the printing ink of Example 15, the urethane (—NHCOO—) group content and urea (—NHCONH—) group content of the polyurethane-based resin (X) to be contained are suitable ranges. Since the binder resin (Y) to be contained is a polyurethane-based resin and the weight average molecular weight is in a suitable range, it has been clarified that excellent performance can be obtained. In particular, Example 16 was obtained by blending the polyurethane resin (X) after dispersing the pigment with the binder resin (Y), but compared with Examples 13 and 14, it was an extrusion laminate using an OPP film. It was revealed that excellent performance was obtained in strength and dry laminate strength.

  The resin composition for printing ink of the present invention exhibits excellent adhesion to various plastic films such as polyester film, nylon film and polyolefin film, and can obtain a printing ink having excellent temporal stability. It is useful for various inks and paints such as inks and flexographic inks, and is also useful as an additive resin in adhesives and coating agents because it has adhesiveness to various plastic films.

Claims (9)

At least one polyurethane resin (X) and at least one binder resin selected from the group consisting of polyester resins, polyurethane resins, polycarbonate resins, polyamide resins, vinyl acetate resins, vinyl chloride resins, and nitrocellulose. (Y) containing a resin composition for printing ink,
In a total of 100% by mass of the polyurethane resin (X) and the binder resin (Y), the content of the polyurethane resin (X) is 1 to 50% by mass,
The polyurethane resin (X) obtained by reacting the polyol component (A) with the polyisocyanate component (B) and then reacting with the primary and / or secondary amine component (C) ( X)
The amino group content in the polyurethane-based resin (X) is 0.16 to 1.8 mmol / g,
The polyol component (A) contains at least a polydiene polyol and / or a hydrogenated polydiene polyol,
A resin composition for printing ink, comprising 10 to 80% by mass of a structural unit comprising a polydiene polyol and / or a hydrogenated polydiene polyol in 100% by mass of a polyurethane resin (X).
(However, the binder resin (Y) excludes the polyurethane resin (X).)   The polyurethane resin (X) has a urethane (—NHCOO—) group content of 0.6 to 1.9 mmol / g and a urea (—NHCONH—) group content of 0.6 to 1.9 mmol / g. The resin composition for printing ink according to claim 1, wherein   A printing ink comprising the resin composition for printing ink according to claim 1 or 2 and a pigment.   4. The method for producing a printing ink according to claim 3, wherein the polyurethane resin (X) is blended after the pigment is dispersed in the presence of the binder resin (Y).   A printed matter printed with the printing ink according to claim 3.   A laminate comprising a thermoplastic resin layer disposed on one surface side of the printed matter according to claim 5.   The method for producing a laminate according to claim 6, wherein a thermoplastic resin layer is laminated on one surface side of the printed matter according to claim 5 by an extrusion laminating method.   The manufacturing method of the laminated body of Claim 6 which laminates | stacks a thermoplastic resin layer by the dry lamination method, after forming an adhesive bond layer in the one surface side of the printed matter of Claim 5. The packaging material obtained by heat-sealing the laminated body of Claim 6.