WO2016060245A1 - Binder for printing inks, printing ink composition for packaging laminates, and printed material - Google Patents

Binder for printing inks, printing ink composition for packaging laminates, and printed material Download PDF

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Publication number
WO2016060245A1
WO2016060245A1 PCT/JP2015/079305 JP2015079305W WO2016060245A1 WO 2016060245 A1 WO2016060245 A1 WO 2016060245A1 JP 2015079305 W JP2015079305 W JP 2015079305W WO 2016060245 A1 WO2016060245 A1 WO 2016060245A1
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WO
WIPO (PCT)
Prior art keywords
binder
polyurethane resin
printing ink
polyol
organic solvent
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PCT/JP2015/079305
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French (fr)
Japanese (ja)
Inventor
英子 大井
典宏 福田
賢一 曽根
吉田　誠
Original Assignee
日立化成株式会社
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Publication date
Application filed by 日立化成株式会社 filed Critical 日立化成株式会社
Priority to CN201580046222.XA priority Critical patent/CN106795385A/en
Priority to JP2016554134A priority patent/JPWO2016060245A1/en
Priority to MYPI2017500008A priority patent/MY197623A/en
Priority to CN202311016096.6A priority patent/CN117004271A/en
Publication of WO2016060245A1 publication Critical patent/WO2016060245A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/102—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds

Definitions

  • the present invention relates to a binder for printing ink, a printing ink composition for packaging laminate, and a printed material.
  • plastic films have been used in various fields as packaging materials. Printing on such a plastic film is performed by gravure printing or flexographic printing. And with the diversification of packaging base materials, the performance required for printing inks and coating agents used for decoration or surface protection has become increasingly sophisticated.
  • printing ink for plastic film needs to have excellent printability, adhesion, blocking resistance, gloss, etc. for a wide variety of films.
  • packaging containers are used which are hygienically laminated so that the ink does not come into direct contact with the contents.
  • the laminating process the following two methods are used, that is, printing ink using various plastic films as a printing base material, and melted polyolefin or the like via an anchor coating agent on the surface (printing surface) of the formed printed film.
  • an extrusion laminating method for laminating and a dry laminating method for laminating a plastic film on the printed surface via an adhesive.
  • the laminating ink used in the laminating method should adhere well to printing substrates such as various plastic films, and must be excellent in terms of adhesion to the laminated plastic film, printability, and lamination strength. Furthermore, for the purpose of sterilization of the contents, when the boil treatment in which the laminated packaging container is immersed in hot water or retort treatment is performed, the boil does not cause the laminate to float or wrinkle during the treatment. Suitability and retort suitability are required.
  • a binder resin for laminating ink a polyurethane resin having an intramolecular urethane bond concentration as high as possible is used.
  • the ink's boilability and retort suitability tend to be poor.
  • the solubility in solvents such as methyl ethyl ketone, ethyl acetate, and isopropyl alcohol is reduced.
  • solvents such as methyl ethyl ketone, ethyl acetate, and isopropyl alcohol is reduced.
  • the solid matter of the ink accumulates in the plate, which is called plate clogging. There is a problem that printing failure occurs in some areas (decrease in printability).
  • the polyurethane resin skeleton is hardened to improve blocking resistance, and chlorinated polypropylene (PP) is added, so that boil suitability, retort suitability, laminate strength, print suitability, An ink having good adhesion and anti-blocking properties can be obtained.
  • PP chlorinated polypropylene
  • the use of an aromatic organic solvent or an organic solvent not containing a ketone organic solvent such as methyl ethyl ketone is being promoted from the viewpoint of the working environment (non-tolueneization, etc.).
  • an object of the present invention is for a printing ink for obtaining an ink having excellent printability, laminate strength, boilability, and retortability without requiring a ketone organic solvent or an aromatic organic solvent. It is to provide a binder. Moreover, the objective of this invention also includes providing the printing ink composition for packaging laminates which uses the binder for such printing ink, and the printed matter obtained from this.
  • the polyurethane resin is a polymer containing (A) a polyol, (B) dimethylolpropionic acid, (C) a diisocyanate compound, and (D) a chain extender.
  • This polyurethane resin is obtained by reacting at least (A) a polyol, (B) dimethylolpropionic acid, (C) a diisocyanate compound, and (D) a chain extender.
  • the polyol contains a polyester polyol having a number average molecular weight of 1000 to 6000.
  • the content of (B) dimethylolpropionic acid in the polyurethane resin is 0.01 to 5% by mass relative to the mass of the polyurethane resin.
  • the printability of the printing ink is improved. Further, when the content of dimethylolpropionic acid is within the above range, laminate strength, boil suitability, retort suitability, print suitability, and the like are improved.
  • the polyol may contain a polyether polyol (polyether) having a number average molecular weight of 200 to 4000.
  • the polyether polyol contained in the polyol may be one or more polyether polyols selected from the group consisting of polyethylene glycol, polypropylene glycol, and polytetramethylene ether glycol. These specific polyether polyols can contribute to further improvement in printability.
  • the following resins may be used in combination as subcomponents.
  • examples thereof include polyurethane resins, polyamides, nitrocellulose, poly (meth) acrylic acid esters, polyvinyl chloride, vinyl chloride vinyl acetate copolymers, rosin resins, and ketone resins other than those described above.
  • the present invention relates to a printing ink composition for packaging laminate containing the above printing ink binder, colorant and organic solvent as components.
  • the organic solvent in the printing ink composition for packaging laminate may contain substantially no aromatic organic solvent or ketone organic solvent.
  • the binder for printing ink is particularly suitable for a packaging laminate ink composition that does not contain an aromatic organic solvent or a ketone organic solvent. However, it is also possible to use the binder in an ink composition containing an aromatic organic solvent or a ketone organic solvent, and in that case, excellent characteristics can be exhibited.
  • Still another aspect of the present invention relates to a printed matter formed by printing the above-described packaging laminate ink composition.
  • This printed matter has a printed film containing a binder for printing ink and a colorant.
  • the present invention can provide a printing ink binder for obtaining ink excellent in printability, laminate strength, boilability and retortability. Since this binder is excellent in solubility in a solvent, it prevents plate clogging and hardly causes printing defects in image areas.
  • the binder for printing ink is a binder (binder resin) containing a polyurethane resin as a main component. Usually, 50 to 100% by mass of the entire binder is made of polyurethane resin.
  • the polyurethane resin in the binder may be a polymer obtained by reacting at least (A) a polyol, (B) dimethylolpropionic acid, (C) a diisocyanate compound, and (D) a chain extender. .
  • This polyurethane resin is derived from each of a polyol, dimethylolpropionic acid, a diisocyanate compound, and a chain extender.
  • the content of (B) dimethylolpropionic acid in the polyurethane resin may be 0.01 to 5% by mass relative to the mass of the polyurethane resin.
  • Polyol includes polyester polyol.
  • the polyester polyol is a polyester containing a diol, a dicarboxylic acid, and the like, and has a hydroxyl group at a terminal.
  • the number average molecular weight of the polyester polyol may be 1000 to 6000.
  • the number average molecular weight of each material may be a conversion value by standard polystyrene measured by gel permeation chromatography (GPC).
  • diol constituting the polyester polyol examples include ethylene glycol, diethylene glycol, dipropylene glycol, 1,4-butanediol, 1,6-hexanediol, triethylene glycol, 1- or 2-methyl-1,3-butylene glycol, 1- or 2-methyl-1,3-butylene glycol, 1- or 2-methyl-1,4-pentylene glycol, 2,4-diethyl-1,5-pentanediol, tripropylene glycol, 1,2- Propylene glycol, 1,3-butanediol, 1-, 2- or 3-methyl-1,5-pentanediol, 2-methyl-1,3-propanediol, ethylene oxide of bisphenol A, propylene oxide, ethylene Alkynes such as propylene oxide Emissions oxide adduct, neopentyl glycol, butyl ethyl propanediol.
  • 3-methyl-1,5-pentanediol and / or neopentyl glycol may be particularly selected.
  • 3-methyl-1,5-pentanediol and / or neopentyl glycol the effect according to the present invention can be exhibited more remarkably.
  • the polyester polyol may further contain a polyfunctional polyol.
  • the polyfunctional polyol include glycerin, trimethylolpropane, trimethylolethane, 1,2,6-hexanetriol, 1,2,4-butanol, sorbitol, and pentaerythritol. It is done.
  • dicarboxylic acid constituting the polyester polyol examples include adipic acid, succinic acid, sebacic acid, azelaic acid, fumaric acid, maleic acid, terephthalic acid, isophthalic acid, and combinations of two or more thereof.
  • adipic acid and / or sebacic acid may be specifically selected. By particularly selecting adipic acid and / or sebacic acid, the effect according to the present invention can be exhibited more remarkably.
  • the polyester polyol may contain an anhydride of dicarboxylic acid and / or an esterified product of a lower alcohol having 1 to 5 carbon atoms of dicarboxylic acid together with or in place of dicarboxylic acid.
  • the polyester polyol in the present embodiment can be obtained by the same method as a normal polyester production method.
  • a polyester polyol can be obtained by dehydrating condensation of a diol and a dicarboxylic acid or acid anhydride.
  • the polyol may contain a polyether polyol (polyether) having a number average molecular weight of 200 to 4000.
  • polyether polyols include polyoxyalkylene glycols such as polyethylene glycol (PEG), polypropylene glycol (PPG), and polytetramethylene ether glycol (PTMG), and alkylene oxide adducts of bisphenol A.
  • the alkylene oxide added to bisphenol A may be, for example, ethylene oxide, propylene oxide, or a combination thereof.
  • the printability can be further improved.
  • these glycols may have a number average molecular weight of 600 to 3,000.
  • the polyurethane resin is obtained by reacting (B) dimethylolpropionic acid (DMPA) with another monomer.
  • DMPA dimethylolpropionic acid
  • the content of dimethylolpropionic acid may be 0.01 to 5% by mass relative to the mass of the polyurethane resin.
  • the content of DMPA is 0.01% by mass or more, the pigment dispersibility of the printing ink is good. When the content is 5% by mass or less, the film (printed film) is not excessively hard, and good laminate strength, boil suitability, and retort suitability are easily obtained. That is, when the DMPA content is in the range of 0.01 to 5% by mass, effects such as improvement in laminate strength, suitability for boil, suitability for retort, and suitability for printing can be obtained. From the same viewpoint, the content of DMPA may be 0.05 to 4% by mass, or 0.1 to 3% by mass.
  • the diisocyanate compound constituting the polyurethane resin is a compound having two isocyanate groups, and can be various diisocyanates of aromatic, aliphatic or alicyclic.
  • isocyanate compounds include 1,5-naphthylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 4,4′-diphenyldimethylmethane diisocyanate, 4,4′-dibenzyl diisocyanate, dialkyldiphenylmethane diisocyanate, tetraalkyldiphenylmethane.
  • diisocyanate compounds may be used alone or in combination of two or more.
  • alicyclic diisocyanates particularly isophorone diisocyanate (IPDI)
  • IPDI isophorone diisocyanate
  • the (D) chain extender constituting the polyurethane resin can be arbitrarily selected from those usually used as the chain extender of polyurethane resins, and may be, for example, polyamine or glycol.
  • Examples of the chain extender include ethylene diamine, propylene diamine, hexamethylene diamine, triethylene tetramine, diethylene triamine, isophorone diamine, dicyclohexylmethane-4,4'-diamine, and dimer diamine.
  • chain extenders examples include 2-hydroxyethylethylenediamine, 2-hydroxyethylpropylenediamine, di-2-hydroxyethylethylenediamine, di-2-hydroxyethylpropylenediamine, 2-hydroxypropylethylenediamine, and di-2- Examples thereof include diamines having a hydroxyl group in the molecule such as hydroxypropylethylenediamine, glycols already exemplified as polyols constituting polyester polyols, and other glycols. These chain extenders may be used individually by 1 type, and may use 2 or more types together. Of these, isophoronediamine may be selected. By selecting isophorone diamine, the effect of the present invention can be more remarkably exhibited.
  • the chain extender is a diol having a tertiary amine structure such as methyldiethanolamine, methyldiisopropanolamine, phenyldiisopropanolamine, 4-methylphenyldiisopropanolamine, 4-methylphenyldiethanolamine, or a combination of two or more of these. There may be.
  • chain length terminator When synthesizing a polyurethane resin, a chain length terminator can be used as necessary.
  • chain length terminators include monoalcohols and monoamines.
  • monoalcohols include methanol, propanol, butanol, and 2-ethylhexanol.
  • monoamines include mono- or dialkylamines having 2 to 8 carbon atoms (butylamine, dibutylamine, etc.) and mono- or dialkanolamines having 2 to 6 carbon atoms (monoethanolamine, diethanolamine, propanolamine, etc.).
  • the polyurethane resin is produced by, for example, generating a urethane prepolymer having a urethane bond and an isocyanate group by reaction of a raw material mixture containing (A) polyol, (B) dimethylolpropionic acid and (C) diisocyanate compound, It can be synthesized by a method comprising producing a polyurethane resin by reaction of a polymer with (D) a chain extender.
  • the conditions for synthesis and the like can be set as appropriate according to conventional methods in the synthesis of polyurethane resins.
  • An ink composition according to an embodiment contains the binder for printing ink, a colorant, and an organic solvent.
  • This ink composition can be a packaging laminate ink composition used for forming a printed film of a packaging container produced by a laminating method.
  • the binder content (concentration of resin solids) in the ink composition is usually about 3 to 50% by mass relative to the mass of the ink composition.
  • the colorant in the ink composition can be appropriately selected from those usually used as colorants for printing inks.
  • Examples of colorants include pigments such as cyanine blue.
  • the content of the colorant in the ink composition is usually about 1 to 60% by mass with respect to the mass of the ink composition.
  • the organic solvent constituting the ink composition may be, for example, ethyl acetate, isopropyl alcohol, or a combination thereof.
  • the organic solvent may be substantially free of any aromatic organic solvent or ketone organic solvent. More specifically, the total content of the aromatic organic solvent and the ketone organic solvent in the organic solvent may be 0 to 1% by mass with respect to the mass of the organic solvent.
  • the printed matter has a base material and a printed film formed on the base material.
  • the printed film contains the printing ink binder and a colorant.
  • This printed matter may be a packaging container (particularly a food packaging container) further having a plastic film laminated on a base material while covering a printed film.
  • the printed film can be formed by a method including printing the ink composition on a substrate and removing the organic solvent from the printed ink composition.
  • the printing method is not particularly limited, and may be, for example, gravure printing or flexographic printing.
  • the thickness of the printed film is usually about 0.1 to 30 ⁇ m.
  • the substrate constituting the printed material, the plastic film to be laminated, the adhesive used for lamination, etc. are not particularly limited, and can be appropriately selected from commonly used materials.
  • part represents “part by mass”
  • % represents “% by mass”.
  • Synthesis Example 1 Synthesis of polyurethane resin A
  • a polyester polyol having a number average molecular weight of 3000 as component (A) (manufactured by Hitachi Chemical Polymer Co., Ltd., 3-methyl-1,5-pentanediol) Adipate) 300 parts
  • DMPA component dimethylolpropionic acid
  • IPDI component isophorone diisocyanate
  • polyurethane resin solution A With respect to this DMPA-modified polyurethane resin solution (hereinafter referred to as “polyurethane resin solution A”), the concentration (NV) of resin solids (polyurethane resin) is 30%, the viscosity is 500 mPa ⁇ s (25 ° C.), and the amine value is 0. 0.5 mg KOH / g. The content of DMPA in the DMPA-modified polyurethane resin was 0.4% when calculated from the amount of raw materials charged.
  • Example 1 Preparation of ink compositions (Examples 1 to 10 and Comparative Examples 1 to 3) Ink composition for evaluating color pigment dispersibility
  • Example 1 compared with 28 parts of the polyurethane resin solution of Synthesis Examples 1 to 12, 10 parts of cyanine blue, and 52 parts of a mixed solvent (ethyl acetate / isopropyl alcohol), a nitrocellulose solution (solvent) : Mixed solvent, concentration: 30%) 3.5 parts, and in Examples 2 to 10 and Comparative Examples 1 to 3, 10 parts of vinyl chloride vinyl acetate copolymer resin solution (solvent: ethyl acetate, concentration: 15%) Mixed. Each obtained mixture was dispersed for 3 hours using a pigment disperser (paint shaker).
  • a pigment disperser paintr
  • the viscosity of the obtained dispersion was adjusted using a mixed solvent.
  • An ink composition for evaluating color pigment dispersibility was obtained by adjusting the number of seconds measured in 3 to 15 seconds.
  • Example 1 a nitrocellulose solution was used for 35 parts of the polyurethane resin solution of Synthesis Examples 1 to 12, 35 parts of titanium white, and 20 parts of a mixed solvent (ethyl acetate / isopropyl alcohol). 3.5 parts of (solvent: mixed solvent, concentration: 30%) were used in Examples 2 to 10 and Comparative Examples 1 to 3 as a solution of vinyl chloride vinyl acetate copolymer resin (solvent: ethyl acetate, concentration: 15%) 10 The parts were mixed. Each obtained mixture was dispersed for 1 hour using a pigment disperser (paint shaker). Using the mixed solvent, the viscosity of the obtained dispersion was changed to Zahn Cup No.
  • a mixed solvent ethyl acetate / isopropyl alcohol
  • the number of seconds measured in 3 was adjusted to 15 seconds, and the ink compositions for evaluation (2) to (6) below were obtained.
  • Color Pigment Dispersibility The above ink composition was printed on a polyethylene terephthalate film (hereinafter abbreviated as “PET film”) to prepare a printed film having a coating film as a printed film.
  • the state of the coating film (printing film) of the obtained printing film was visually observed, and the color pigment dispersibility was determined according to the following criteria.
  • Color unevenness in the coating means that the dispersibility of the pigment is inferior.
  • A There is no color unevenness in the coating film.
  • B Color unevenness is present in a part of the coating film.
  • C Color unevenness occurs in the coating film.
  • Boil suitability test The above ink composition containing titanium white was printed on a PET film or NY film to obtain a printed material having a coating film as a printed film. After applying an isocyanate adhesive to the coating film, a 60 ⁇ m polyethylene film was laminated by a dry laminating machine to obtain a laminated product. Using this laminate, a bag was prepared, and a water / oil mixture was placed inside it to seal the bag. Next, the bag was heated in hot water at 95 ° C. for 30 minutes, and the floating state of the laminated product was observed. The suitability of the boil was evaluated based on the following criteria. “A”: There was no floating at all in the laminated product. “B”: Partial lifting occurred in the laminated product. “C”: Floating occurred on the entire surface of the laminated product.
  • the ink compositions of Examples 1 to 10 containing a polyurethane resin having a dimethylolpropionic acid content of 0.01 to 5% by mass as a binder have color pigment dispersibility, adhesiveness, and printability. It can be seen that the laminate strength, boil suitability, and retort suitability are all excellent.
  • the ink composition containing the printing ink binder of the present invention can have good color pigment dispersibility without using an aromatic organic solvent or a ketone organic solvent.
  • the ink composition containing the printing ink binder of the present invention is excellent in adhesiveness (laminate strength) and printability, and also excellent in boilability and retort suitability. Therefore, the printing ink binder used for food packaging containers and the like. As extremely useful.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)
  • Printing Methods (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Laminated Bodies (AREA)

Abstract

Disclosed is a binder for printing inks, which contains a polyurethane resin. The polyurethane resin is a polymer that contains (A) a polyol, (B) dimethylolpropionic acid, (C) a diisocyanate compound and (D) a chain extender. The polyol (A) contains a polyester polyol having a number average molecular weight of 1,000-6,000. The content of the dimethylolpropionic acid (B) in the polyurethane resin is 0.01-5% by mass relative to the mass of the polyurethane resin.

Description

印刷インキ用バインダー、包装ラミネート用印刷インキ組成物及び印刷物Binder for printing ink, printing ink composition for packaging laminate and printed matter
　本発明は、印刷インキ用バインダー、包装ラミネート用印刷インキ組成物及び印刷物に関する。 The present invention relates to a binder for printing ink, a printing ink composition for packaging laminate, and a printed material.
　近年、プラスチックフィルムは、包装用材料として様々な分野に用いられるようになっている。かかるプラスチックフィルムへの印刷は、グラビア印刷又はフレキソ印刷により行なわれている。そして、包装基材の多様化に伴い、装飾又は表面保護のために用いられる印刷インキ及びコーティング剤に求められる性能は益々高度になってきている。 In recent years, plastic films have been used in various fields as packaging materials. Printing on such a plastic film is performed by gravure printing or flexographic printing. And with the diversification of packaging base materials, the performance required for printing inks and coating agents used for decoration or surface protection has become increasingly sophisticated.
　例えば、プラスチックフィルム用印刷インキは、多種多様なフィルムに対する優れた印刷適性、接着性、耐ブロッキング性、及び光沢等を備えている必要がある。さらに、食品包装容器の分野においては、インキが内容物と直接触れることがないように衛生的にラミネート加工された包装容器が使用されている。 For example, printing ink for plastic film needs to have excellent printability, adhesion, blocking resistance, gloss, etc. for a wide variety of films. Furthermore, in the field of food packaging containers, packaging containers are used which are hygienically laminated so that the ink does not come into direct contact with the contents.
　一般にラミネート加工としては、次に挙げる２つの方法、すなわち、各種プラスチックフィルムを印刷基材としてインキを印刷し、形成された印刷膜の面（印刷面）にアンカーコート剤を介して溶融ポリオレフィン等を積層する押出しラミネート加工法、及び該印刷面に接着剤を介してプラスチックフィルムを積層するドライラミネート加工法がある。 In general, as the laminating process, the following two methods are used, that is, printing ink using various plastic films as a printing base material, and melted polyolefin or the like via an anchor coating agent on the surface (printing surface) of the formed printed film. There are an extrusion laminating method for laminating and a dry laminating method for laminating a plastic film on the printed surface via an adhesive.
　ラミネート加工法において使用されるラミネート用インキは、各種プラスチックフィルム等の印刷基材に良好に接着し、積層されるプラスチックフィルムとの接着性、印刷適性、ラミネート強度の点で優れていなければならない。さらに、内容物の殺菌処理を目的として、ラミネート加工された包装容器ごと熱水中に浸漬するボイル処理、又はレトルト処理が施される場合には、処理中にラミネートの浮き及びしわの生じないボイル適性及びレトルト適性が必要とされる。 The laminating ink used in the laminating method should adhere well to printing substrates such as various plastic films, and must be excellent in terms of adhesion to the laminated plastic film, printability, and lamination strength. Furthermore, for the purpose of sterilization of the contents, when the boil treatment in which the laminated packaging container is immersed in hot water or retort treatment is performed, the boil does not cause the laminate to float or wrinkle during the treatment. Suitability and retort suitability are required.
　以上のインキ性能のほとんどが、主にバインダー樹脂の性能に依存することが多い。そのため、それぞれ要求される性能に応じて、種々のバインダー樹脂が使用されている。一般に、ラミネート用インキのバインダー樹脂としては、ポリウレタン樹脂が使用されている（特許文献１～３参照）。 Most of the above ink performance often depends mainly on the performance of the binder resin. Therefore, various binder resins are used depending on the required performance. In general, a polyurethane resin is used as a binder resin for laminating ink (see Patent Documents 1 to 3).
特開２０１０－２７０２１５号公報JP 2010-270215 A 特開２０１０－２７０２１６号公報JP 2010-270216 A 特許第４８８２２０６号公報Japanese Patent No. 4882206
　一般に、ラミネート用インキのバインダー樹脂としては、分子内のウレタン結合濃度をできるだけ高くしたポリウレタン樹脂が使用されている。しかし、ウレタン結合濃度が高くなると、インキのボイル適性及びレトルト適性が不良となり易い。そのうえ、メチルエチルケトン、酢酸エチル、イソプロピルアルコール等の溶剤への溶解性が低下し、これら溶剤を用いた場合、版詰まりと言われる、版中にインキの固形分が堆積していく現象により、画線部の印刷不良が生じるという問題（印刷適性の低下）がある。 Generally, as a binder resin for laminating ink, a polyurethane resin having an intramolecular urethane bond concentration as high as possible is used. However, when the urethane bond concentration increases, the ink's boilability and retort suitability tend to be poor. In addition, the solubility in solvents such as methyl ethyl ketone, ethyl acetate, and isopropyl alcohol is reduced. When these solvents are used, the solid matter of the ink accumulates in the plate, which is called plate clogging. There is a problem that printing failure occurs in some areas (decrease in printability).
　トルエン等の芳香族系有機溶剤を使用する場合、ポリウレタン樹脂骨格を硬くして耐ブロッキングを向上させ、塩素化ポリプロピレン（ＰＰ）を添加することにより、ボイル適性、レトルト適性、ラミネート強度、印刷適性、接着性、耐ブロッキングが良好なインキが得られる。しかし、作業環境等の点から、芳香族系有機溶剤、又はメチルエチルケトン等のケトン系有機溶剤を含まない有機溶剤の使用が進められている（ノントルエン化など）。また、芳香族有機溶剤を含まない有機溶剤と、ポリウレタン樹脂とを含む従来のインキは、広範囲な種類のフィルムの要望に応えることは難しかった。 When using an aromatic organic solvent such as toluene, the polyurethane resin skeleton is hardened to improve blocking resistance, and chlorinated polypropylene (PP) is added, so that boil suitability, retort suitability, laminate strength, print suitability, An ink having good adhesion and anti-blocking properties can be obtained. However, the use of an aromatic organic solvent or an organic solvent not containing a ketone organic solvent such as methyl ethyl ketone is being promoted from the viewpoint of the working environment (non-tolueneization, etc.). In addition, it has been difficult for conventional inks containing an organic solvent not containing an aromatic organic solvent and a polyurethane resin to meet a wide variety of film demands.
　一側面において、本発明の目的は、ケトン系有機溶剤又は芳香族系有機溶剤を必要とせずに、優れた印刷適性、ラミネート強度、ボイル適性、及びレトルト適性を有するインキを得るための印刷インキ用バインダーを提供することである。また、本発明の目的は、係る印刷インキ用バインダーを使用した包装ラミネート用印刷インキ組成物及びこれから得られる印刷物を提供することも含む。 In one aspect, an object of the present invention is for a printing ink for obtaining an ink having excellent printability, laminate strength, boilability, and retortability without requiring a ketone organic solvent or an aromatic organic solvent. It is to provide a binder. Moreover, the objective of this invention also includes providing the printing ink composition for packaging laminates which uses the binder for such printing ink, and the printed matter obtained from this.
　本発明者らは、鋭意研究を重ねた結果、ケトン系有機溶剤又は芳香族系有機溶剤を含まない有機溶剤を使用した場合においても、ジメチロールプロピオン酸を含むポリウレタン樹脂が、優れた印刷適性、ラミネート強度、ボイル適性及びレトルト適性を有する印刷インキを得るために有効であることを見出した。本発明は、かかる知見に基づいて完成したものである。 As a result of intensive research, the inventors of the present invention, even when using an organic solvent that does not contain a ketone organic solvent or an aromatic organic solvent, polyurethane resin containing dimethylolpropionic acid has excellent printability, It has been found that it is effective for obtaining a printing ink having laminate strength, boilability and retortability. The present invention has been completed based on such findings.
　本発明の一側面は、ポリウレタン樹脂を主成分として含む印刷インキ用バインダーに関する。ポリウレタン樹脂が、（Ａ）ポリオール、（Ｂ）ジメチロールプロピオン酸、（Ｃ）ジイソシアネート化合物、及び（Ｄ）鎖伸長剤を含む重合体である。このポリウレタン樹脂は、少なくとも（Ａ）ポリオールと、（Ｂ）ジメチロールプロピオン酸と、（Ｃ）ジイソシアネート化合物と、(Ｄ)鎖伸長剤とを反応させて得られる。（Ａ）ポリオールが、数平均分子量１０００～６０００のポリエステルポリオールを含む。ポリウレタン樹脂における（Ｂ）ジメチロールプロピオン酸の含有量が、ポリウレタン樹脂の質量に対し０．０１～５質量％である。 One aspect of the present invention relates to a binder for printing ink containing a polyurethane resin as a main component. The polyurethane resin is a polymer containing (A) a polyol, (B) dimethylolpropionic acid, (C) a diisocyanate compound, and (D) a chain extender. This polyurethane resin is obtained by reacting at least (A) a polyol, (B) dimethylolpropionic acid, (C) a diisocyanate compound, and (D) a chain extender. (A) The polyol contains a polyester polyol having a number average molecular weight of 1000 to 6000. The content of (B) dimethylolpropionic acid in the polyurethane resin is 0.01 to 5% by mass relative to the mass of the polyurethane resin.
　バインダーがジメチロールプロピオン酸を含むポリウレタン樹脂を含むことによって、印刷インキの印刷適性が向上する。また、ジメチロールプロピオン酸の含有量が、前記の範囲内であることによって、ラミネート強度、ボイル適性、レトルト適性、及び印刷適性等が向上する。 ¡By including a polyurethane resin containing dimethylolpropionic acid in the binder, the printability of the printing ink is improved. Further, when the content of dimethylolpropionic acid is within the above range, laminate strength, boil suitability, retort suitability, print suitability, and the like are improved.
　（Ａ）ポリオールが、数平均分子量が２００～４０００のポリエーテルポリオール（ポリエーテル類）を含んでいてもよい。（Ａ）ポリオールに含まれるポリエーテルポリオールは、ポリエチレングリコール、ポリプロピレングリコール及びポリテトラメチレンエーテルグリコールからなる群より選ばれる1種以上のポリエーテルポリオールであってもよい。これら特定のポリエーテルポリオールは、印刷適性の更なる向上に寄与し得る。 (A) The polyol may contain a polyether polyol (polyether) having a number average molecular weight of 200 to 4000. (A) The polyether polyol contained in the polyol may be one or more polyether polyols selected from the group consisting of polyethylene glycol, polypropylene glycol, and polytetramethylene ether glycol. These specific polyether polyols can contribute to further improvement in printability.
　必要に応じて、ポリウレタン樹脂の他に、以下に示すような樹脂を副成分として併用し得る。その例としては、上記以外のポリウレタン樹脂、ポリアミド、ニトロセルロース、ポリ（メタ）アクリル酸エステル、ポリ塩化ビニル、塩化ビニル酢酸ビニル共重合体、ロジン系樹脂、及びケトン樹脂が挙げられる。 If necessary, in addition to the polyurethane resin, the following resins may be used in combination as subcomponents. Examples thereof include polyurethane resins, polyamides, nitrocellulose, poly (meth) acrylic acid esters, polyvinyl chloride, vinyl chloride vinyl acetate copolymers, rosin resins, and ketone resins other than those described above.
　別の側面において、本発明は、上記の印刷インキ用バインダー、着色剤及び有機溶剤を成分として含有する包装ラミネート用印刷インキ組成物に関する。 In another aspect, the present invention relates to a printing ink composition for packaging laminate containing the above printing ink binder, colorant and organic solvent as components.
　この包装ラミネート用印刷インキ組成物中の有機溶剤は、芳香族系有機溶剤又はケトン系有機溶剤のいずれも実質的に含まなくてもよい。上記の印刷インキ用バインダーは、芳香族系有機溶剤又はケトン系有機溶剤を含まない包装ラミネート用インキ組成物に対して特に好適である。ただし、当該バインダーを芳香族系有機溶剤又はケトン系有機溶剤を含むインキ組成物に使用することも可能であり、その場合も優れた特性が発揮され得る。 The organic solvent in the printing ink composition for packaging laminate may contain substantially no aromatic organic solvent or ketone organic solvent. The binder for printing ink is particularly suitable for a packaging laminate ink composition that does not contain an aromatic organic solvent or a ketone organic solvent. However, it is also possible to use the binder in an ink composition containing an aromatic organic solvent or a ketone organic solvent, and in that case, excellent characteristics can be exhibited.
　本発明の更なる別の側面は、上記の包装ラミネート用インキ組成物を印刷して形成される印刷物に関する。この印刷物は、印刷インキ用バインダーと着色剤とを含む印刷膜を有する。 Still another aspect of the present invention relates to a printed matter formed by printing the above-described packaging laminate ink composition. This printed matter has a printed film containing a binder for printing ink and a colorant.
　本発明は、印刷適性、ラミネート強度、ボイル適性及びレトルト適性に優れたインキを得るための印刷インキ用バインダーを提供することができる。このバインダーは、溶剤への溶解性に優れるため、版詰まりを抑制し、画線部の印刷不良を発生し難い。 The present invention can provide a printing ink binder for obtaining ink excellent in printability, laminate strength, boilability and retortability. Since this binder is excellent in solubility in a solvent, it prevents plate clogging and hardly causes printing defects in image areas.
　以下、本発明の実施形態について詳細に説明する。ただし、本発明は以下の実施形態に限定されるものではない。 Hereinafter, embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments.
　一実施形態に係る印刷インキ用バインダーは、ポリウレタン樹脂を主成分として含むバインダー（バインダー樹脂）である。通常、バインダー全体のうち５０～１００質量％がポリウレタン樹脂で構成される。 The binder for printing ink according to one embodiment is a binder (binder resin) containing a polyurethane resin as a main component. Usually, 50 to 100% by mass of the entire binder is made of polyurethane resin.
　バインダー中のポリウレタン樹脂は、少なくとも（Ａ）ポリオールと、（Ｂ）ジメチロールプロピオン酸と、（Ｃ）ジイソシアネート化合物と、(Ｄ)鎖伸長剤とを反応させて得られる重合体であってもよい。このポリウレタン樹脂は、ポリオール、ジメチロールプロピオン酸、ジイソシアネート化合物、及び鎖伸長剤のそれぞれに由来する。ポリウレタン樹脂における（Ｂ）ジメチロールプロピオン酸の含有量（ジメチロールプロピオン酸に由来する構成単位の含有量）が、ポリウレタン樹脂の質量に対し０．０１～５質量％であってもよい。 The polyurethane resin in the binder may be a polymer obtained by reacting at least (A) a polyol, (B) dimethylolpropionic acid, (C) a diisocyanate compound, and (D) a chain extender. . This polyurethane resin is derived from each of a polyol, dimethylolpropionic acid, a diisocyanate compound, and a chain extender. The content of (B) dimethylolpropionic acid in the polyurethane resin (content of structural units derived from dimethylolpropionic acid) may be 0.01 to 5% by mass relative to the mass of the polyurethane resin.
　（Ａ）ポリオールは、ポリエステルポリオールを含む。ポリエステルポリオールは、ジオール、及びジカルボン酸等を含むポリエステルであり、末端にヒドロキシル基を有する。 (A) Polyol includes polyester polyol. The polyester polyol is a polyester containing a diol, a dicarboxylic acid, and the like, and has a hydroxyl group at a terminal.
　ポリエステルポリオールの数平均分子量は、１０００～６０００であってもよい。本明細書において、各材料の数平均分子量は、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）により測定される、標準ポリスチレンによる換算値であってもよい。 The number average molecular weight of the polyester polyol may be 1000 to 6000. In this specification, the number average molecular weight of each material may be a conversion value by standard polystyrene measured by gel permeation chromatography (GPC).
　ポリエステルポリオールを構成するジオールとしては、エチレングリコール、ジエチレングリコール、ジプロピレングリコール、１，４－ブタンジオール、１，６－ヘキサンジオール、トリエチレングリコール、１－若しくは２－メチル－１，３－ブチレングリコール、１－若しくは２－メチル－１，３－ブチレングリコール、１－若しくは２－メチル－１，４－ペンチレングリコール、２，４－ジエチル－１，５－ペンタンジオール、トリプロピレングリコール、１，２－プロピレングリコール、１，３－ブタンジオ－ル、１－、２－若しくは３－メチル－１，５－ペンタンジオ－ル、２－メチル－１，３－プロパンジオール、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、エチレンプロピレンオキサイド等のアルキレンオキサイド付加物、ネオペンチルグリコール、ブチルエチルプロパンジオール等が挙げられる。これらのうち、３－メチル－１，５－ペンタンジオール、及び／又はネオペンチルグリコールを特に選択してもよい。３－メチル－１，５－ペンタンジオール及び／又はネオペンチルグリコールを選択することにより、本発明による効果がより一層顕著に奏され得る。 Examples of the diol constituting the polyester polyol include ethylene glycol, diethylene glycol, dipropylene glycol, 1,4-butanediol, 1,6-hexanediol, triethylene glycol, 1- or 2-methyl-1,3-butylene glycol, 1- or 2-methyl-1,3-butylene glycol, 1- or 2-methyl-1,4-pentylene glycol, 2,4-diethyl-1,5-pentanediol, tripropylene glycol, 1,2- Propylene glycol, 1,3-butanediol, 1-, 2- or 3-methyl-1,5-pentanediol, 2-methyl-1,3-propanediol, ethylene oxide of bisphenol A, propylene oxide, ethylene Alkynes such as propylene oxide Emissions oxide adduct, neopentyl glycol, butyl ethyl propanediol. Of these, 3-methyl-1,5-pentanediol and / or neopentyl glycol may be particularly selected. By selecting 3-methyl-1,5-pentanediol and / or neopentyl glycol, the effect according to the present invention can be exhibited more remarkably.
　ポリエステルポリオールは、多官能ポリオ－ルを更に含んでいてもよい。多官能ポリオールとしては、例えばグリセリン、トリメチロ－ルプロパン、トリメチロ－ルエタン、１，２，６－ヘキサントリオ－ル、１，２，４－ブタントリオ－ル、ソルビト－ル、及びペンタエリスリト－ルが挙げられる。 The polyester polyol may further contain a polyfunctional polyol. Examples of the polyfunctional polyol include glycerin, trimethylolpropane, trimethylolethane, 1,2,6-hexanetriol, 1,2,4-butanol, sorbitol, and pentaerythritol. It is done.
　ポリエステルポリオールを構成するジカルボン酸としては、アジピン酸、コハク酸、セバシン酸、アゼライン酸、フマル酸、マレイン酸、テレフタル酸、イソフタル酸、及びこれらの２種以上の組み合わせが挙げられる。これらのうち、アジピン酸及び／又はセバシン酸を特に選択してもよい。アジピン酸及び／又はセバシン酸を特に選択することにより、本発明による効果がより一層顕著に奏され得る。 Examples of the dicarboxylic acid constituting the polyester polyol include adipic acid, succinic acid, sebacic acid, azelaic acid, fumaric acid, maleic acid, terephthalic acid, isophthalic acid, and combinations of two or more thereof. Of these, adipic acid and / or sebacic acid may be specifically selected. By particularly selecting adipic acid and / or sebacic acid, the effect according to the present invention can be exhibited more remarkably.
　ポリエステルポリオールは、ジカルボン酸とともに、又はジカルボン酸に代えて、ジカルボン酸の無水物、及び／又はジカルボン酸の炭素数１～５の低級アルコールのエステル化物を含んでいてもよい。 The polyester polyol may contain an anhydride of dicarboxylic acid and / or an esterified product of a lower alcohol having 1 to 5 carbon atoms of dicarboxylic acid together with or in place of dicarboxylic acid.
　本実施形態におけるポリエステルポリオールは、通常のポリエステルの製造方法と同様の方法で得られる。例えば、ジオールとジカルボン酸若しくは酸無水物とを脱水縮合させることで、ポリエステルポリオールが得られる。 The polyester polyol in the present embodiment can be obtained by the same method as a normal polyester production method. For example, a polyester polyol can be obtained by dehydrating condensation of a diol and a dicarboxylic acid or acid anhydride.
　（Ａ）ポリオールは、数平均分子量が２００～４０００のポリエーテルポリオール（ポリエーテル類）を含んでいてもよい。ポリエーテルポリオールとして、例えば、ポリエチレングリコール（ＰＥＧ）、ポリプロピレングリコール（ＰＰＧ）、及びポリテトラメチレンエーテルグリコール（ＰＴＭＧ）等のポリオキシアルキレングリコール、並びに、ビスフェノールＡのアルキレンオキサイド付加物が挙げられる。ビスフェノールＡに付加するアルキレンオキサイドは、例えば、エチレンオキサイド、プロピレンオキサイド、又はこれらの組み合わせであってもよい。 (A) The polyol may contain a polyether polyol (polyether) having a number average molecular weight of 200 to 4000. Examples of polyether polyols include polyoxyalkylene glycols such as polyethylene glycol (PEG), polypropylene glycol (PPG), and polytetramethylene ether glycol (PTMG), and alkylene oxide adducts of bisphenol A. The alkylene oxide added to bisphenol A may be, for example, ethylene oxide, propylene oxide, or a combination thereof.
　（Ａ）ポリオールに含まれるポリエーテルポリオールが、ポリエチレングリコール、ポリプロピレングリコール及びポリテトラメチレンエーテルグリコールからなる群より選ばれる1種以上であると、印刷適性の更なる向上が図れる。同様の観点から、これらグリコールの数平均分子量が６００～３０００であってもよい。 (A) When the polyether polyol contained in the polyol is at least one selected from the group consisting of polyethylene glycol, polypropylene glycol and polytetramethylene ether glycol, the printability can be further improved. From the same viewpoint, these glycols may have a number average molecular weight of 600 to 3,000.
　ポリウレタン樹脂は、（Ｂ）ジメチロールプロピオン酸（ＤＭＰＡ）を他のモノマーと反応させて得られるものである。このポリウレタン樹脂を、本明細書では「ＤＭＰＡ変性ポリウレタン樹脂」ということがある。 The polyurethane resin is obtained by reacting (B) dimethylolpropionic acid (DMPA) with another monomer. This polyurethane resin is sometimes referred to herein as “DMPA-modified polyurethane resin”.
　（Ｂ）ジメチロールプロピオン酸の含有量は、ポリウレタン樹脂の質量に対して、０．０１～５質量％であってもよい。（Ｂ）ＤＭＰＡの含有量が０．０１質量％以上であれば、印刷インキの顔料分散性が良好である。この含有量が５質量％以下であれば、皮膜（印刷膜）が過度に硬くならず、良好なラミネート強度、ボイル適性、及びレトルト適性が得られ易い。すなわち、ＤＭＰＡの含有量が０．０１～５質量％の範囲内であることによって、ラミネート強度向上、ボイル適性、レトルト適性、及び印刷適性が向上する等の効果が得られる。同様の観点から、ＤＭＰＡの含有量は、０．０５～４質量％、又は０．１～３質量％であってもよい。 (B) The content of dimethylolpropionic acid may be 0.01 to 5% by mass relative to the mass of the polyurethane resin. (B) If the content of DMPA is 0.01% by mass or more, the pigment dispersibility of the printing ink is good. When the content is 5% by mass or less, the film (printed film) is not excessively hard, and good laminate strength, boil suitability, and retort suitability are easily obtained. That is, when the DMPA content is in the range of 0.01 to 5% by mass, effects such as improvement in laminate strength, suitability for boil, suitability for retort, and suitability for printing can be obtained. From the same viewpoint, the content of DMPA may be 0.05 to 4% by mass, or 0.1 to 3% by mass.
　ポリウレタン樹脂を構成する（Ｃ）ジイソシアネート化合物は、イソシアネート基を２つ有する化合物であり、芳香族、脂肪族又は脂環族の、各種のジイソシアネートであることができる。 (C) The diisocyanate compound constituting the polyurethane resin is a compound having two isocyanate groups, and can be various diisocyanates of aromatic, aliphatic or alicyclic.
　イソシアネート化合物の代表例としては、１，５－ナフチレンジイソシアネート、４，４’－ジフェニルメタンジイソシアネート、４，４’－ジフェニルジメチルメタンジイソシアネート、４，４’－ジベンジルジイソシアネート、ジアルキルジフェニルメタンジイソシアネート、テトラアルキルジフェニルメタンジイソシアネート、１，３－フェニレンジイソシアネート、１，４－フェニレンジイソシアネート、トリレンジイソシアネート、ブタン－１，４－ジイソシアネート、ヘキサメチレンジイソシアネート、イソプロピレンジイソシアネート、メチレンジイソシアネート、２，２，４－トリメチルヘキサメチレンジイソシアネート、２，４，４－トリメチルヘキサメチレンジイソシアネート、シクロヘキサン－１，４－ジイソシアネート、キシリレンジイソシアネート、イソホロンジイソシアネート、リジンジイソシアネート、ジシクロヘキシルメタン－４，４’－ジイソシアネート、１，３－ビス（イソシアネートメチル）シクロヘキサン、メチルシクロヘキサンジイソシアネート、ｍ－テトラメチルキシリレンジイソシアネート、及び、ダイマー酸のカルボキシル基をイソシアネート基に転化したダイマージイソシアネートが挙げられる。これらのジイソシアネート化合物は単独で用いてもよいし、２種類以上を併用してもよい。これらのうち、脂環式ジイソシアネート、特にイソホロンジイソシアネート（ＩＰＤＩ）を選択してもよい。脂環式ジイソシアネートを用いることで、本発明による効果がより一層顕著に奏され得る。 Representative examples of isocyanate compounds include 1,5-naphthylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 4,4′-diphenyldimethylmethane diisocyanate, 4,4′-dibenzyl diisocyanate, dialkyldiphenylmethane diisocyanate, tetraalkyldiphenylmethane. Diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, tolylene diisocyanate, butane-1,4-diisocyanate, hexamethylene diisocyanate, isopropylene diisocyanate, methylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, cyclohexane-1,4-diisocyanate , Xylylene diisocyanate, isophorone diisocyanate, lysine diisocyanate, dicyclohexylmethane-4,4′-diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, methylcyclohexane diisocyanate, m-tetramethylxylylene diisocyanate, and dimer acid The dimerized isocyanate which converted the carboxyl group of this into the isocyanate group is mentioned. These diisocyanate compounds may be used alone or in combination of two or more. Of these, alicyclic diisocyanates, particularly isophorone diisocyanate (IPDI), may be selected. By using the alicyclic diisocyanate, the effect of the present invention can be more remarkably exhibited.
　ポリウレタン樹脂を構成する（Ｄ）鎖伸長剤としては、ポリウレタン樹脂の鎖伸長剤として通常用いられているものから任意に選択することができ、例えばポリアミン、又はグリコールであってもよい。鎖伸長剤としては、例えば、エチレンジアミン、プロピレンジアミン、ヘキサメチレンジアミン、トリエチレンテトラミン、ジエチレントリアミン、イソホロンジアミン、ジシクロヘキシルメタン－４，４’－ジアミン、及びダイマージアミンが挙げられる。その他の鎖伸長剤の例として、２－ヒドロキシエチルエチレンジアミン、２－ヒドロキシエチルプロピレンジアミン、ジ－２－ヒドロキシエチルエチレンジアミン、ジ－２－ヒドロキシエチルプロピレンジアミン、２－ヒドロキシプロピルエチレンジアミン、及びジ－２－ヒドロキシプロピルエチレンジアミン等の分子内に水酸基を有するジアミン、ポリエステルポリオールを構成するポリオールとして既に例示したグリコール、及びそれ以外のグリコールが挙げられる。これら鎖伸長剤は１種を単独で用いてもよいし、２種類以上を併用してもよい。これらのうち、イソホロンジアミンを選択してもよい。イソホロンジアミンを選択することにより、本発明による効果がより一層顕著に奏され得る。 The (D) chain extender constituting the polyurethane resin can be arbitrarily selected from those usually used as the chain extender of polyurethane resins, and may be, for example, polyamine or glycol. Examples of the chain extender include ethylene diamine, propylene diamine, hexamethylene diamine, triethylene tetramine, diethylene triamine, isophorone diamine, dicyclohexylmethane-4,4'-diamine, and dimer diamine. Examples of other chain extenders include 2-hydroxyethylethylenediamine, 2-hydroxyethylpropylenediamine, di-2-hydroxyethylethylenediamine, di-2-hydroxyethylpropylenediamine, 2-hydroxypropylethylenediamine, and di-2- Examples thereof include diamines having a hydroxyl group in the molecule such as hydroxypropylethylenediamine, glycols already exemplified as polyols constituting polyester polyols, and other glycols. These chain extenders may be used individually by 1 type, and may use 2 or more types together. Of these, isophoronediamine may be selected. By selecting isophorone diamine, the effect of the present invention can be more remarkably exhibited.
　鎖伸長剤は、メチルジエタノールアミン、メチルジイソプロパノールアミン、フェニルジイソプロパノールアミン、４－メチルフェニルジイソプロパノールアミン、４－メチルフェニルジエタノールアミン等の３級アミン構造を有するジオール、又はこれらの２種類以上の組み合わせであってもよい。 The chain extender is a diol having a tertiary amine structure such as methyldiethanolamine, methyldiisopropanolamine, phenyldiisopropanolamine, 4-methylphenyldiisopropanolamine, 4-methylphenyldiethanolamine, or a combination of two or more of these. There may be.
　ポリウレタン樹脂を合成する際に、鎖長停止剤を必要に応じて用いることもできる。かかる鎖長停止剤としては、モノアルコール及びモノアミン等が挙げられる。モノアルコールの例は、メタノール、プロパノール、ブタノール、及び２－エチルヘキサノールを含む。モノアミンの例は、炭素数２～８のモノ若しくはジアルキルアミン（ブチルアミン、ジブチルアミン等）、及び、炭素数２～６のモノ若しくはジアルカノールアミン（モノエタノールアミン、ジエタノールアミン、プロパノールアミン等）を含む。 When synthesizing a polyurethane resin, a chain length terminator can be used as necessary. Examples of such chain length terminators include monoalcohols and monoamines. Examples of monoalcohols include methanol, propanol, butanol, and 2-ethylhexanol. Examples of monoamines include mono- or dialkylamines having 2 to 8 carbon atoms (butylamine, dibutylamine, etc.) and mono- or dialkanolamines having 2 to 6 carbon atoms (monoethanolamine, diethanolamine, propanolamine, etc.).
　ポリウレタン樹脂における、（Ａ）ポリオール、（Ｃ）ジイソシアネート化合物、及び（Ｄ）鎖伸長剤のそれぞれの含有量は、任意に調整できる。 The contents of (A) polyol, (C) diisocyanate compound, and (D) chain extender in the polyurethane resin can be arbitrarily adjusted.
　ポリウレタン樹脂は、例えば、（Ａ）ポリオール、（Ｂ）ジメチロールプロピオン酸及び（Ｃ）ジイソシアネート化合物を含む原料混合物の反応によって、ウレタン結合及びイソシアネート基を有するウレタンプレポリマーを生成させることと、ウレタンプレポリマーと（Ｄ）鎖伸長剤との反応によってポリウレタン樹脂を生成させることとを含む方法によって、合成することができる。合成の条件等は、ポリウレタン樹脂の合成における常法にしたがって適宜設定できる。 The polyurethane resin is produced by, for example, generating a urethane prepolymer having a urethane bond and an isocyanate group by reaction of a raw material mixture containing (A) polyol, (B) dimethylolpropionic acid and (C) diisocyanate compound, It can be synthesized by a method comprising producing a polyurethane resin by reaction of a polymer with (D) a chain extender. The conditions for synthesis and the like can be set as appropriate according to conventional methods in the synthesis of polyurethane resins.
　一実施形態に係るインキ組成物は、上記印刷インキ用バインダー、着色剤及び有機溶剤を含有する。このインキ組成物は、ラミネート加工法によって製造される包装容器の印刷膜を形成するために用いられる、包装ラミネート用インキ組成物であることができる。インキ組成物におけるバインダーの含有量（樹脂固形分の濃度）は、通常、インキ組成物の質量に対して３～５０質量％程度である。 An ink composition according to an embodiment contains the binder for printing ink, a colorant, and an organic solvent. This ink composition can be a packaging laminate ink composition used for forming a printed film of a packaging container produced by a laminating method. The binder content (concentration of resin solids) in the ink composition is usually about 3 to 50% by mass relative to the mass of the ink composition.
　インキ組成物中の着色剤は、印刷インキ用の着色剤として通常用いられるものから適宜選択することができる。着色剤の例としては、シアニンブルーのような顔料が挙げられる。インキ組成物における着色剤の含有量は、通常、インキ組成物の質量に対して１～６０質量％程度である。 The colorant in the ink composition can be appropriately selected from those usually used as colorants for printing inks. Examples of colorants include pigments such as cyanine blue. The content of the colorant in the ink composition is usually about 1 to 60% by mass with respect to the mass of the ink composition.
　インキ組成物を構成する有機溶剤は、例えば、酢酸エチル、イソプロピルアルコール又はこれらの組み合わせであってもよい。この有機溶剤は、芳香族系有機溶剤又はケトン系有機溶剤のいずれも実質的に含まなくてもよい。より具体的には、有機溶剤中の芳香族系有機溶剤及びケトン系有機溶剤の合計の含有量が、有機溶剤の質量に対して０～１質量％であってもよい。 The organic solvent constituting the ink composition may be, for example, ethyl acetate, isopropyl alcohol, or a combination thereof. The organic solvent may be substantially free of any aromatic organic solvent or ketone organic solvent. More specifically, the total content of the aromatic organic solvent and the ketone organic solvent in the organic solvent may be 0 to 1% by mass with respect to the mass of the organic solvent.
　一実施形態に係る印刷物は、基材と、基材上に形成された印刷膜とを有する。印刷膜は、上記印刷インキ用バインダーと、着色剤とを含む。この印刷物は、印刷膜を覆いながら基材上にラミネートされたプラスチックフィルムを更に有する包装容器（特に、食品用包装容器）であってもよい。印刷膜は、上記インキ組成物を基材に印刷することと、印刷されたインキ組成物から有機溶剤を除去することとを含む方法により、形成することができる。印刷の方法は特に限定されず、例えばグラビア印刷又はフレキソ印刷であってもよい。印刷膜の厚みは、通常、０.１～３０μｍ程度である。印刷物を構成する基材、ラミネートされるプラスチックフィルム、ラミネートに用いられる接着剤等は、特に制限されず、通常用いられる材料から適宜選択することができる。 The printed matter according to one embodiment has a base material and a printed film formed on the base material. The printed film contains the printing ink binder and a colorant. This printed matter may be a packaging container (particularly a food packaging container) further having a plastic film laminated on a base material while covering a printed film. The printed film can be formed by a method including printing the ink composition on a substrate and removing the organic solvent from the printed ink composition. The printing method is not particularly limited, and may be, for example, gravure printing or flexographic printing. The thickness of the printed film is usually about 0.1 to 30 μm. The substrate constituting the printed material, the plastic film to be laminated, the adhesive used for lamination, etc. are not particularly limited, and can be appropriately selected from commonly used materials.
　以下、本発明の好適な実施例について説明するが、本発明はこれらの実施例に限定されるものではない。以下、「部」は「質量部」を、「％」は「質量％」を表す。 Hereinafter, preferred examples of the present invention will be described, but the present invention is not limited to these examples. Hereinafter, “part” represents “part by mass”, and “%” represents “% by mass”.
合成例１（ポリウレタン樹脂Ａの合成）
　撹拌機、温度計及び窒素ガス導入管を備えた丸底フラスコに、（Ａ）成分として数平均分子量３０００のポリエステルポリオール（日立化成ポリマー(株)社製、３－メチル－１，５－ペンタンジオールのアジペート）３００部、（Ｂ）成分としてジメチロールプロピオン酸（ＤＭＰＡ、和光純薬工業(株)社）１．５部、及び（Ｃ）成分としてイソホロンジイソシアネート（ＩＰＤＩ、和光純薬工業(株)社）４９．４部を仕込んだ。これらを、窒素気流下、１０５℃で６時間反応させ、イソシアネート基含量２．６６％のプレポリマーを生成させた。そこに、酢酸エチル（和光純薬工業(株)社）２３４部を加えて、均一なウレタンプレポリマー溶液を得た。続いて（Ｄ）成分としてのイソホロンジアミン（ＩＰＤＡ、和光純薬工業(株)社）２０．１部、及びジ－ｎ－ブチルアミン（ＤＢＡ、和光純薬工業(株)社）１．７部と、有機溶剤としての酢酸エチル（和光純薬工業(株)社）３７５部及びイソプロピルアルコール（和光純薬工業(株)社）２６１部との混合物に、前記ウレタンプレポリマー溶液５８５部を加えた。得られた溶液を６０℃に加熱して、３時間の反応により、ジメチロールプロピオン酸を含むポリウレタン樹脂（ＤＭＰＡ変性ポリウレタン樹脂）の溶液を得た。このＤＭＰＡ変性ポリウレタン樹脂の溶液（以下、「ポリウレタン樹脂溶液Ａ」という）に関して、樹脂固形分（ポリウレタン樹脂）の濃度（ＮＶ）が３０％、粘度が５００ｍＰａ・ｓ（２５℃）、アミン価が０．５ｍｇＫＯＨ／ｇであった。ＤＭＰＡ変性ポリウレタン樹脂におけるＤＭＰＡの含有量は、原料の仕込み量から計算すると０．４％であった。 Synthesis Example 1 (Synthesis of polyurethane resin A)
In a round bottom flask equipped with a stirrer, a thermometer and a nitrogen gas introduction tube, a polyester polyol having a number average molecular weight of 3000 as component (A) (manufactured by Hitachi Chemical Polymer Co., Ltd., 3-methyl-1,5-pentanediol) Adipate) 300 parts, (B) component dimethylolpropionic acid (DMPA, Wako Pure Chemical Industries, Ltd.) 1.5 parts, and (C) component isophorone diisocyanate (IPDI, Wako Pure Chemical Industries, Ltd.) 49.4 parts were charged. These were reacted at 105 ° C. for 6 hours under a nitrogen stream to produce a prepolymer having an isocyanate group content of 2.66%. 234 parts of ethyl acetate (Wako Pure Chemical Industries, Ltd.) was added thereto to obtain a uniform urethane prepolymer solution. Subsequently, 20.1 parts of isophoronediamine (IPDA, Wako Pure Chemical Industries, Ltd.) as component (D), and 1.7 parts of di-n-butylamine (DBA, Wako Pure Chemical Industries, Ltd.) Then, 585 parts of the urethane prepolymer solution was added to a mixture of 375 parts of ethyl acetate (Wako Pure Chemical Industries, Ltd.) and 261 parts of isopropyl alcohol (Wako Pure Chemical Industries, Ltd.) as an organic solvent. The obtained solution was heated to 60 ° C., and a solution of a polyurethane resin (DMPA-modified polyurethane resin) containing dimethylolpropionic acid was obtained by a reaction for 3 hours. With respect to this DMPA-modified polyurethane resin solution (hereinafter referred to as “polyurethane resin solution A”), the concentration (NV) of resin solids (polyurethane resin) is 30%, the viscosity is 500 mPa · s (25 ° C.), and the amine value is 0. 0.5 mg KOH / g. The content of DMPA in the DMPA-modified polyurethane resin was 0.4% when calculated from the amount of raw materials charged.
（合成例２～１２）
　表１、表２に示す原料を用い、合成例１と同様にして、ポリウレタン樹脂溶液Ｂ～Ｌを得た。 (Synthesis Examples 2 to 12)
Using the raw materials shown in Tables 1 and 2, polyurethane resin solutions B to L were obtained in the same manner as in Synthesis Example 1.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
１．インキ組成物の調製
（実施例１～１０及び比較例１～３）
色顔料分散性評価用のインキ組成物
　合成例１～１２のポリウレタン樹脂溶液２８部、シアニンブルー１０部、混合溶剤（酢酸エチル／イソプロピルアルコール）５２部に対し、実施例１ではニトロセルロース溶液（溶媒：混合溶剤、濃度：３０％）３．５部を、実施例２～１０及び比較例１～３では塩化ビニル酢酸ビニル共重合樹脂の溶液（溶媒：酢酸エチル、濃度：１５％）を１０部混合した。
　得られた各混合物を、顔料分散機（ペイントシェイカー）を用いて３時間分散した。その後、得られた分散液の粘度を、混合溶剤を用いて、ザーンカップＮｏ．３で測定される秒数が１５秒となるように調整して、色顔料分散性評価用のインキ組成物を得た。
　インキ組成物の調製に用いた混合溶剤における混合比は、酢酸エチル／イソプロピルアルコール＝７／３（質量比）とした。 1. Preparation of ink compositions (Examples 1 to 10 and Comparative Examples 1 to 3)
Ink composition for evaluating color pigment dispersibility In Example 1, compared with 28 parts of the polyurethane resin solution of Synthesis Examples 1 to 12, 10 parts of cyanine blue, and 52 parts of a mixed solvent (ethyl acetate / isopropyl alcohol), a nitrocellulose solution (solvent) : Mixed solvent, concentration: 30%) 3.5 parts, and in Examples 2 to 10 and Comparative Examples 1 to 3, 10 parts of vinyl chloride vinyl acetate copolymer resin solution (solvent: ethyl acetate, concentration: 15%) Mixed.
Each obtained mixture was dispersed for 3 hours using a pigment disperser (paint shaker). Thereafter, the viscosity of the obtained dispersion was adjusted using a mixed solvent. An ink composition for evaluating color pigment dispersibility was obtained by adjusting the number of seconds measured in 3 to 15 seconds.
The mixing ratio in the mixed solvent used for preparing the ink composition was ethyl acetate / isopropyl alcohol = 7/3 (mass ratio).
その他の評価用のインキ組成物
　合成例１～１２のポリウレタン樹脂の溶液３５部、チタン白３５部、及び混合溶剤（酢酸エチル／イソプロピルアルコール）２０部に対して、実施例１ではニトロセルロースの溶液（溶媒：混合溶剤、濃度：３０％）３．５部を、実施例２～１０及び比較例１～３では塩化ビニル酢酸ビニル共重合樹脂の溶液（溶媒：酢酸エチル、濃度：１５％）１０部を混合した。
　得られた各混合物を、顔料分散機（ペイントシェイカー）を用いて１時間分散した。得られた分散液の粘度を、混合溶剤を用いて、ザーンカップＮｏ．３で測定される秒数が１５秒となるように調整して、下記（２）～（６）の評価用のインキ組成物を得た。
　インキ組成物の調製に用いた混合溶剤における混合比は、酢酸エチル／イソプロピルアルコール＝７／３（質量比）とした。 Other Evaluation Ink Composition In Example 1, a nitrocellulose solution was used for 35 parts of the polyurethane resin solution of Synthesis Examples 1 to 12, 35 parts of titanium white, and 20 parts of a mixed solvent (ethyl acetate / isopropyl alcohol). 3.5 parts of (solvent: mixed solvent, concentration: 30%) were used in Examples 2 to 10 and Comparative Examples 1 to 3 as a solution of vinyl chloride vinyl acetate copolymer resin (solvent: ethyl acetate, concentration: 15%) 10 The parts were mixed.
Each obtained mixture was dispersed for 1 hour using a pigment disperser (paint shaker). Using the mixed solvent, the viscosity of the obtained dispersion was changed to Zahn Cup No. The number of seconds measured in 3 was adjusted to 15 seconds, and the ink compositions for evaluation (2) to (6) below were obtained.
The mixing ratio in the mixed solvent used for preparing the ink composition was ethyl acetate / isopropyl alcohol = 7/3 (mass ratio).
２．評価
（１）色顔料分散性
　ポリエチレンテレフタレートフィルム（以下「ＰＥＴフィルム」と略す）に上記のインキ組成物を印刷して、印刷膜としての塗膜を有する印刷フィルムを作製した。得られた印刷フィルムの塗膜（印刷膜）の状態を目視観察し、以下の基準で色顔料分散性を判定した。塗膜に色むらがあることは、顔料の分散性が劣ることを意味する。
「Ａ」…塗膜に色むらがない。
「Ｂ」…塗膜の一部に色むらがある。
「Ｃ」…塗膜に色むらが生じている。 2. Evaluation (1) Color Pigment Dispersibility The above ink composition was printed on a polyethylene terephthalate film (hereinafter abbreviated as “PET film”) to prepare a printed film having a coating film as a printed film. The state of the coating film (printing film) of the obtained printing film was visually observed, and the color pigment dispersibility was determined according to the following criteria. Color unevenness in the coating means that the dispersibility of the pigment is inferior.
“A”: There is no color unevenness in the coating film.
“B”: Color unevenness is present in a part of the coating film.
“C”: Color unevenness occurs in the coating film.
（２）接着性
　ＰＥＴフィルム、又はナイロンフィルム（以下「ＮＹフィルム」と略す）に、チタン白を含有する上記のインキ組成物を印刷して、印刷膜としての塗膜を有する印刷フィルムを作製した。この印刷フィルムを２４時間放置後、塗膜にセロファンテープを貼り付け、これを急速に引き剥した。このときの塗膜の状態を観察して、以下の基準で塗膜の接着性を評価した。
「Ａ」…塗膜の８０％以上がフィルムに残る。
「Ｂ」…塗膜の５０～８０％がフィルムに残る。
「Ｃ」…塗膜の５０％以下がフィルムに残る。 (2) Adhesive The above ink composition containing titanium white was printed on a PET film or nylon film (hereinafter abbreviated as “NY film”) to produce a printed film having a coating film as a printed film. . The print film was allowed to stand for 24 hours, and a cellophane tape was then applied to the coating film, which was then quickly peeled off. The state of the coating film at this time was observed, and the adhesion of the coating film was evaluated according to the following criteria.
“A”: 80% or more of the coating film remains on the film.
“B”: 50 to 80% of the coating film remains on the film.
“C”: 50% or less of the coating film remains on the film.
（３）印刷適性
　小型グラビア印刷試験機を用いて、チタン白を含有する上記のインキ組成物をＰＥＴフィルムに印刷して、印刷パターン（印刷膜）を形成させた。その後、印刷パターンの状態、すなわち、版のドクター切れの状態及びセル詰りに関連する印刷パターンの欠落を目視で観察し、印刷適性を以下の基準で判定した。
「Ａ」…印刷適性が良好である。
「Ｂ」…印刷適性が不十分である。
「Ｃ」…印刷適性が極めて劣る。 (3) Printability The above ink composition containing titanium white was printed on a PET film using a small gravure printing tester to form a print pattern (printed film). Thereafter, the state of the printing pattern, that is, the state of the doctor running out of the plate and the lack of the printing pattern related to the cell clogging were visually observed, and the printability was determined according to the following criteria.
“A”: Good printability.
“B”: The printability is insufficient.
“C”: Printability is extremely poor.
（４）ドライ（ＤＬ）ラミネート強度
　チタン白を含有する上記のインキ組成物をＰＥＴフィルム又はＮＹフィルムに印刷して、印刷膜としての塗膜を有する印刷物を得た。塗膜に、ウレタン系接着剤を間に挟みながら、ドライラミネート機によって無延伸ポリプロピレンフィルム（ＣＰＰフィルム）を積層した。得られた積層体を、４０℃で２日間エージングした後（ラミネートから３日目）、１５ｍｍ幅に切断し、１８０°剥離強度を測定した。 (4) Dry (DL) laminate strength The above ink composition containing titanium white was printed on a PET film or NY film to obtain a printed material having a coating film as a printed film. An unstretched polypropylene film (CPP film) was laminated on the coating film by a dry laminating machine with a urethane adhesive interposed therebetween. The obtained laminate was aged at 40 ° C. for 2 days (third day after lamination), then cut to a width of 15 mm, and 180 ° peel strength was measured.
（５）ボイル適性試験
　チタン白を含有する上記のインキ組成物をＰＥＴフィルム又はＮＹフィルムに印刷して、印刷膜としての塗膜を有する印刷物を得た。塗膜にイソシアネート系接着剤を塗布した後、ドライラミネート機によって６０μｍのポリエチレンフィルムを積層し、ラミネート加工物を得た。このラミネート加工物を用いて袋を作製し、その内部に水／油の混合物を入れて、袋を密封した。次いで、袋を９５℃の熱水中で３０分間加熱し、ラミネート加工物の浮き状態を観察して、下記の基準に基づいてボイル適性を評価した。
「Ａ」：ラミネート加工物に全く浮きが無かった。
「Ｂ」：ラミネート加工物に部分的に浮きが生じた。
「Ｃ」：ラミネート加工物の全面で浮きが生じた。 (5) Boil suitability test The above ink composition containing titanium white was printed on a PET film or NY film to obtain a printed material having a coating film as a printed film. After applying an isocyanate adhesive to the coating film, a 60 μm polyethylene film was laminated by a dry laminating machine to obtain a laminated product. Using this laminate, a bag was prepared, and a water / oil mixture was placed inside it to seal the bag. Next, the bag was heated in hot water at 95 ° C. for 30 minutes, and the floating state of the laminated product was observed. The suitability of the boil was evaluated based on the following criteria.
“A”: There was no floating at all in the laminated product.
“B”: Partial lifting occurred in the laminated product.
“C”: Floating occurred on the entire surface of the laminated product.
（６）レトルト適性試験
　チタン白を含有する上記のインキ組成物の塗膜を、ＰＥＴフィルム、又はＮＹフィルムに印刷して、印刷物を得た。塗膜にイソシアネート系接着剤を塗布した後、ドライラミネート機によって６０μｍの無延伸ポリプロピレン（ＣＰＰ）フィルムを積層し、ラミネート加工物を得た。このラミネート加工物を用いて袋を作製し、その内部に水／油の混合物を入れて、袋を密封した。次いで、袋を１２０℃の加圧熱水中で３０分間加熱し、ラミネート加工物の浮き状態を観察して、下記の基準に基づいてレトルト適性を評価した。
「Ａ」：ラミネート加工物に全く浮きの無かった。
「Ｂ」：ラミネート加工物に部分的に浮きが生じた。
「Ｃ」：ラミネート加工物の全面で浮きが生じた。 (6) Retort suitability test The coating film of the ink composition containing titanium white was printed on a PET film or an NY film to obtain a printed matter. After applying an isocyanate adhesive to the coating film, a 60 μm unstretched polypropylene (CPP) film was laminated by a dry laminating machine to obtain a laminated product. Using this laminate, a bag was prepared, and a water / oil mixture was placed inside it to seal the bag. Subsequently, the bag was heated in 120 degreeC pressurized hot water for 30 minutes, the floating state of the laminated product was observed, and retort suitability was evaluated based on the following criteria.
“A”: There was no floating at all on the laminated product.
“B”: Partial lifting occurred in the laminated product.
“C”: Floating occurred on the entire surface of the laminated product.
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
　表中の評価結果の「ＡＢ」は、ＡとＢの中間的な評価であったことを意味する。表３、４に示したように、ジメチロールプロピオン酸の含有量が０．０１～５質量％の範囲ではないポリウレタン樹脂をバインダーとして含む比較例１～３のインキ組成物は、色顔料分散性、接着性、印刷適性、ボイル適性、及びレトルト適性のうちいずれかの点で十分な特性を示さなかった。 “AB” of the evaluation result in the table means that the evaluation was intermediate between A and B. As shown in Tables 3 and 4, the ink compositions of Comparative Examples 1 to 3 containing a polyurethane resin having a dimethylolpropionic acid content not in the range of 0.01 to 5% by mass as a binder have color pigment dispersibility. However, it did not show sufficient properties in any of adhesiveness, printability, boilability, and retortability.
　これに対し、ジメチロールプロピオン酸の含有量が０．０１～５質量％の範囲であるポリウレタン樹脂をバインダーとして含む実施例１～１０のインキ組成物は、色顔料分散性、接着性、印刷適性、ラミネート強度、ボイル適性、レトルト適性のいずれの点でも優れていることがわかる。 On the other hand, the ink compositions of Examples 1 to 10 containing a polyurethane resin having a dimethylolpropionic acid content of 0.01 to 5% by mass as a binder have color pigment dispersibility, adhesiveness, and printability. It can be seen that the laminate strength, boil suitability, and retort suitability are all excellent.
　従って、本発明の印刷インキ用バインダーを含むインキ組成物は、芳香族系有機溶剤又はケトン系有機溶剤を使用せずとも、良好な色顔料分散性を有することができる。また、本発明の印刷インキ用バインダーを含むインキ組成物は、接着性（ラミネート強度）、印刷適性に優れるとともに、ボイル適性及びレトルト適性にも優れるため、食品包装容器等に使用する印刷インキ用バインダーとして極めて有用である。
  Therefore, the ink composition containing the printing ink binder of the present invention can have good color pigment dispersibility without using an aromatic organic solvent or a ketone organic solvent. In addition, the ink composition containing the printing ink binder of the present invention is excellent in adhesiveness (laminate strength) and printability, and also excellent in boilability and retort suitability. Therefore, the printing ink binder used for food packaging containers and the like. As extremely useful.

Claims (6)

  1. 　ポリウレタン樹脂を含有する印刷インキ用バインダーであって、
    　前記ポリウレタン樹脂が、（Ａ）ポリオール、（Ｂ）ジメチロールプロピオン酸、（Ｃ）ジイソシアネート化合物、及び（Ｄ）鎖伸長剤を含む重合体であり、
    　前記（Ａ）ポリオールが、数平均分子量が１０００～６０００のポリエステルポリオールを含み、
    　前記ポリウレタン樹脂における、（Ｂ）ジメチロールプロピオン酸の含有量が、前記ポリウレタン樹脂の質量に対し０．０１～５質量％である、
    印刷インキ用バインダー。     A binder for printing ink containing a polyurethane resin,
    The polyurethane resin is a polymer containing (A) a polyol, (B) dimethylolpropionic acid, (C) a diisocyanate compound, and (D) a chain extender,
    The (A) polyol includes a polyester polyol having a number average molecular weight of 1000 to 6000,
    In the polyurethane resin, the content of (B) dimethylolpropionic acid is 0.01 to 5% by mass with respect to the mass of the polyurethane resin.
    Binder for printing ink.
  2. 　前記（Ａ）ポリオールが、数平均分子量が２００～４０００のポリエーテルポリオールを更に含む、請求項１に記載の印刷インキ用バインダー。 2. The printing ink binder according to claim 1, wherein the (A) polyol further comprises a polyether polyol having a number average molecular weight of 200 to 4,000.
  3. 　前記ポリエーテルポリオールが、ポリエチレングリコール、ポリプロピレングリコール及びポリテトラメチレンエーテルグリコールからなる群より選ばれる１種以上である、請求項２に記載の印刷インキ用バインダー。 The printing ink binder according to claim 2, wherein the polyether polyol is at least one selected from the group consisting of polyethylene glycol, polypropylene glycol and polytetramethylene ether glycol.
  4. 　請求項１～３のいずれか一項に記載の印刷インキ用バインダー、着色剤及び有機溶剤を含有する、包装ラミネート用印刷インキ組成物。 A printing ink composition for packaging laminate, comprising the printing ink binder according to any one of claims 1 to 3, a colorant, and an organic solvent.
  5. 　前記有機溶剤が芳香族系有機溶剤又はケトン系有機溶剤のいずれも実質的に含まない、請求項４に記載の包装ラミネート用印刷インキ組成物。 The printing ink composition for packaging laminate according to claim 4, wherein the organic solvent is substantially free of either an aromatic organic solvent or a ketone organic solvent.
  6. 　請求項１～３のいずれか一項に記載の印刷インキ用バインダーと着色剤とを含む印刷膜を有する、印刷物。 A printed matter comprising a printed film comprising the binder for printing ink according to any one of claims 1 to 3 and a colorant.
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2019001932A (en) * 2017-06-16 2019-01-10 Ｄｉｃグラフィックス株式会社 Liquid ink composition
WO2020180652A1 (en) * 2019-03-01 2020-09-10 Sun Chemical Corporation Microwavable solvent-based packaging ink composition
US20210292582A1 (en) * 2020-03-17 2021-09-23 Ricoh Company, Ltd. Ink, ink stored container, printing device, and printing method

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP7400562B2 (en) * 2020-03-11 2023-12-19 東洋インキＳｃホールディングス株式会社 Gravure or flexographic ink and its use
JP6915739B1 (en) * 2020-09-30 2021-08-04 東洋インキＳｃホールディングス株式会社 Gravure Ink-Hardener Set, Curable Gravure Ink, Printed Matter and Laminates

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010248466A (en) * 2009-03-25 2010-11-04 Toyo Ink Mfg Co Ltd Printing ink composition for laminate
WO2012008339A1 (en) * 2010-07-15 2012-01-19 Ｄｉｃグラフィックス株式会社 Printing ink
JP2013144732A (en) * 2012-01-13 2013-07-25 Dic Graphics Corp Printing ink
JP2014062138A (en) * 2009-03-25 2014-04-10 Toyo Ink Sc Holdings Co Ltd Printing ink composition for laminate
JP2014088465A (en) * 2012-10-29 2014-05-15 Dic Graphics Corp Polyurethane resin composition for ink and printing ink
WO2015068412A1 (en) * 2013-11-11 2015-05-14 日立化成株式会社 Binder for printing ink, laminate ink composition for soft packaging, and printed article

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2890977B2 (en) * 1992-04-28 1999-05-17 東洋インキ製造株式会社 Printing ink
JP2002363242A (en) * 2001-06-11 2002-12-18 Toyo Ink Mfg Co Ltd Polyurethane resin, printing ink composition and printed product
JP2003277669A (en) * 2002-03-25 2003-10-02 Toyo Ink Mfg Co Ltd Binder composition for printing ink
JP5251008B2 (en) * 2006-06-12 2013-07-31 東洋インキＳｃホールディングス株式会社 Solvent recovery reusable printing ink composition, diluting solvent, plastic sheet coating using the same, and laminate laminate thereof
JP5493798B2 (en) * 2009-12-11 2014-05-14 東洋インキＳｃホールディングス株式会社 Solvent type gravure ink

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010248466A (en) * 2009-03-25 2010-11-04 Toyo Ink Mfg Co Ltd Printing ink composition for laminate
JP2014062138A (en) * 2009-03-25 2014-04-10 Toyo Ink Sc Holdings Co Ltd Printing ink composition for laminate
WO2012008339A1 (en) * 2010-07-15 2012-01-19 Ｄｉｃグラフィックス株式会社 Printing ink
JP2013144732A (en) * 2012-01-13 2013-07-25 Dic Graphics Corp Printing ink
JP2014088465A (en) * 2012-10-29 2014-05-15 Dic Graphics Corp Polyurethane resin composition for ink and printing ink
WO2015068412A1 (en) * 2013-11-11 2015-05-14 日立化成株式会社 Binder for printing ink, laminate ink composition for soft packaging, and printed article

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2019001932A (en) * 2017-06-16 2019-01-10 Ｄｉｃグラフィックス株式会社 Liquid ink composition
WO2020180652A1 (en) * 2019-03-01 2020-09-10 Sun Chemical Corporation Microwavable solvent-based packaging ink composition
US11459472B2 (en) 2019-03-01 2022-10-04 Sun Chemical Corporation Microwavable solvent-based packaging ink composition
US20210292582A1 (en) * 2020-03-17 2021-09-23 Ricoh Company, Ltd. Ink, ink stored container, printing device, and printing method

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