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WO2013146452A1 - Polyurethane resin composition for printing ink binder - Google Patents

Polyurethane resin composition for printing ink binder Download PDF

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Publication number
WO2013146452A1
WO2013146452A1 PCT/JP2013/057772 JP2013057772W WO2013146452A1 WO 2013146452 A1 WO2013146452 A1 WO 2013146452A1 JP 2013057772 W JP2013057772 W JP 2013057772W WO 2013146452 A1 WO2013146452 A1 WO 2013146452A1
Authority
WO
WIPO (PCT)
Prior art keywords
polyurethane resin
printing ink
resin composition
solvent
alcohol
Prior art date
Application number
PCT/JP2013/057772
Other languages
French (fr)
Japanese (ja)
Inventor
知子 中川
志鷹　基
通久 小藤
雄史 野村
祐悟 幡野
Original Assignee
東洋インキＳｃホールディングス株式会社
東洋インキ株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 東洋インキＳｃホールディングス株式会社, 東洋インキ株式会社 filed Critical 東洋インキＳｃホールディングス株式会社
Priority to KR1020147029220A priority Critical patent/KR101588234B1/en
Priority to SG11201406055SA priority patent/SG11201406055SA/en
Priority to CN201380016733.8A priority patent/CN104204020B/en
Publication of WO2013146452A1 publication Critical patent/WO2013146452A1/en
Priority to PH12014502125A priority patent/PH12014502125A1/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
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
    • 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
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • 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
    • C08G18/2805—Compounds having only one group containing active hydrogen
    • C08G18/285—Nitrogen containing compounds
    • C08G18/2865—Compounds having only one primary or secondary amino group; Ammonia
    • 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
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3225—Polyamines
    • C08G18/3228—Polyamines acyclic
    • 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
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3225—Polyamines
    • C08G18/3234—Polyamines cycloaliphatic
    • 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
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3271—Hydroxyamines
    • 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
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3271—Hydroxyamines
    • C08G18/3275—Hydroxyamines containing two hydroxy groups
    • 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
    • C08G18/40—High-molecular-weight compounds
    • C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
    • C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
    • 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
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
    • C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
    • 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
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4825—Polyethers containing two hydroxy groups
    • 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
    • C08G18/6603—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
    • 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
    • C08G18/6603—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6614—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38
    • C08G18/6618—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3225 or polyamines of C08G18/38
    • 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
    • C08G18/6603—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6614—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38
    • C08G18/6622—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3271
    • 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
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
    • C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
    • C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
    • C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
    • 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
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
    • 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
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
    • C08G18/7621—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring being toluene diisocyanate including isomer mixtures
    • 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
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
    • C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
    • C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
    • 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
    • C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
    • C09D11/033—Printing inks characterised by features other than the chemical nature of the binder characterised by the solvent
    • 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 polyurethane resin composition and a printing ink composition.
  • examples of solvents used in printing inks include aromatic solvents having relatively strong dissolving power such as toluene and xylene, and ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone.
  • aromatic solvents having relatively strong dissolving power such as toluene and xylene
  • ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone.
  • JP-A-9-316156 discloses that a polyurethane resin composition and a printing ink composition using diphenylmethane diisocyanate have excellent adhesion to various plastic films.
  • these compositions contain methyl ethyl ketone, which is required to be excluded in order to ensure printability.
  • the [NCO] / [OH] ratio is low, there is also a problem in blocking resistance.
  • JP 2003-221539 discloses a study in which an ink contains an ester / alcohol solvent system to increase the solubility in the ester / alcohol solvent system.
  • a hydroxycarboxylic acid is added to the ink, a problem of a residual solvent occurs, and water resistance and alcohol bleed resistance are inferior.
  • An object of the present invention is to provide a printing ink composition that excludes aromatic organic solvents such as toluene and xylene and ketone organic solvents such as methyl ethyl ketone and methyl isobutyl ketone.
  • the present invention contains an ester / alcohol solvent system, has excellent printability such as plate fog, and has excellent adhesion, blocking resistance, alcohol bleed resistance and laminate physical properties to various plastic films.
  • An object of the present invention is to provide a printing ink composition having printing physical properties such as the above.
  • the present inventors have compared polyisocyanate containing tolylene diisocyanate, and further using a polyurethane resin that uses alkanolamine as a reaction terminator and has controlled synthesis parameters.
  • the present inventors have found that it is possible to design a printing ink composition that achieves both excellent printability and print physical properties even when using an ester / alcohol solvent system having a weak dynamic solubility.
  • the first embodiment of the present invention is a polyurethane formed by reacting a polyisocyanate containing tolylene diisocyanate and a polymer polyol, and reacting a urethane prepolymer having an isocyanate group at the terminal with an organic diamine and an alkanolamine.
  • a polyurethane resin composition containing a resin and a mixed solvent The present invention relates to a polyurethane resin composition having the following (A) to (F): (A) The molar ratio [NCO (total)] / [OH] in the reaction of all isocyanate groups of the polyisocyanate and hydroxyl groups of the polymer polyol is 1.8 to 2.3.
  • the molar ratio [NCO (TDI)] / [OH] in the reaction between the isocyanate group of tolylene diisocyanate and the hydroxyl group of the polymer polyol is 1.0 to 2.1.
  • the hydroxyl value of the polyurethane resin is 1.0 to 10.0 mgKOH / g.
  • the molar ratio d1 / d2 between the number of moles d1 of the organic diamine and the number of moles d2 of the alkanolamine is 3 to 25.
  • the mixed solvent includes an ester solvent and an alcohol solvent.
  • the polymer polyol is composed of a polyester diol and a polyether diol.
  • a second embodiment relates to a polyurethane resin composition characterized in that the polyester diol is 20 to 80% by weight and the polyether diol is 80 to 20% by weight in a polymer polyol. .
  • the third embodiment relates to a printing ink composition comprising the polyurethane resin composition of the first or second embodiment.
  • the polyurethane resin composition for printing ink binder is obtained by reacting a polyisocyanate containing tolylene diisocyanate with a polymer polyol, and reacting a urethane prepolymer having an isocyanate group at the terminal with an organic diamine as a chain extender and an alkanolamine as a reaction terminator. can get.
  • polyurethane resins used as printing ink binders when considering the compatibility between the solubility in ester / alcohol solvents and various printed physical properties for various plastic films, the important factors are the hard segments of urethane bonds and urea bonds. Is a polyisocyanate.
  • the polyisocyanate used in the polyurethane resin includes tolylene diisocyanate (hereinafter sometimes referred to as TDI).
  • Tolylene diisocyanate is preferably 2,4-tolylene diisocyanate or 2,6-tolylene diisocyanate, and may be a mixture thereof.
  • tolylene diisocyanate Since tolylene diisocyanate has one aromatic ring in the molecule, it has higher resistance to alcohol than aliphatic isocyanate and alicyclic isocyanate. On the other hand, as compared to diphenylmethane diisocyanate, which is an aromatic isocyanate having two aromatic rings, tolylene diisocyanate has a single aromatic ring and therefore has a higher solubility in an ester / alcohol solvent system. Therefore, tolylene diisocyanate tends to balance printing aptitude such as plate fog and alcohol bleeding resistance in an ester / alcohol solvent-based printing ink composition.
  • [NCO (total)] / [OH] which is the molar ratio of all isocyanate groups of all polyisocyanates to hydroxyl groups of the polymer polyol. It is in the range of 3.
  • [NCO (all)] / [OH] is 1.8 or more, the number of hard segment bonds is sufficient, and the blocking resistance and alcohol bleed resistance are excellent. If it is 2.3 or less, the plate fogging property is excellent, and since the number of hard segment bonds is moderate, the adhesiveness and EL laminate strength are excellent.
  • [NCO (TDI)] / [OH] which is the molar ratio in the reaction between the isocyanate group of tolylene diisocyanate and the hydroxyl group of the polymer polyol, is in the range of 1.0 to 2.1.
  • an aromatic isocyanate has a higher reaction rate with a hydroxyl group or an amino group than an aliphatic isocyanate or an alicyclic isocyanate. Therefore, when [NCO (TDI)] / [OH] is 2.1 or less, a uniform polyurethane resin can be synthesized because the reaction rate is moderate. Furthermore, since the concentration of the aromatic ring in the molecule is moderate, the plate fog is excellent. Further, when [NCO (TDI)] / [OH] is 1.0 or more, the alcohol bleed resistance is excellent.
  • polyisocyanates may be used in addition to tolylene diisocyanate as long as the above [NCO (all)] / [OH] and [NCO (TDI)] / [OH] are satisfied.
  • examples of other polyisocyanates include various known aliphatic isocyanates and alicyclic isocyanates that are generally used in the production of polyurethane resins.
  • Examples thereof include dicyclohexylmethane-4,4 ′ -diisocyanate, 1,3-bis (isocyanatemethyl) cyclohexane, methylcyclohexane diisocyanate, norbornane diisocyanate, and dimerized isocyanate obtained by converting the carboxyl group of dimer acid into an isocyanate group.
  • isophorone diisocyanate is preferable from the viewpoint of the reaction rate of the isocyanate group and various physical properties.
  • the alcohol bleeding resistance is particularly excellent.
  • 50 to 75% of the total number of isocyanate groups is tolylene diisocyanate and 50 to 25% is isophorone diisocyanate
  • the solvent in the printing ink composition is 35% by weight or more.
  • the plate fog is particularly excellent. The details of the mixed solvent contained in the printing ink composition will be described later.
  • the hydroxyl value of polyurethane resin is an important factor for balancing printing suitability such as plate fogging in an ester / alcohol solvent system and alcohol bleed resistance.
  • the hydroxyl value of the polyurethane resin is 1.0 to 10.0 mgKOH / g.
  • the hydroxyl value is 1.0 mgKOH / g or more, the adhesiveness and EL laminate strength are excellent, and the solubility is remarkably good, so that the plate fog is excellent.
  • the hydroxyl value is 10.0 mgKOH / g or less, the alcohol bleed resistance is excellent.
  • organic diamine as the chain extender in this embodiment examples include ethylenediamine, propylenediamine, hexamethylenediamine, isophoronediamine, dicyclohexylmethane-4,4 ′ -diamine, 2-hydroxyethylethylenediamine, 2-hydroxyethyl, and the like.
  • the molar ratio d1 / d2 between the number of moles d1 of the organic diamine of the polyurethane resin and the number of moles d2 of the alkanolamine is 3 to 25.
  • d1 / d2 is 3 or more, the alcohol bleed resistance is excellent, and since the weight average molecular weight of the polyurethane resin is large, the blocking resistance is remarkably good.
  • d1 / d2 is 25 or less, the adhesiveness and EL laminate strength are excellent, and the solubility is remarkably good, so that the plate covering property is excellent.
  • the weight average molecular weight of the polyurethane resin obtained will become low.
  • the alkanolamine contains a hydroxyl group, the hydroxyl value increases as the amount of alkanolamine used increases.
  • the alkanolamine include monoethanolamine and diethanolamine. These can be used alone or in admixture of two or more. Of these, monoethanolamine is particularly preferable.
  • polyester polyol various known polyester polyols, polyether polyols, and the like are used. You may use together 1 type, or 2 or more types, respectively.
  • polyester polyol include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 2methyl-1,3propanediol, 2ethyl-2butyl-1,3propanediol, and 1,3-butane.
  • polyether polyol examples include polymers or copolymers such as methylene oxide, ethylene oxide, propylene oxide, and tetrahydrofuran.
  • polyester polyols and polyether polyols those having a branched structure are particularly preferred.
  • the polymer polyol is preferably in the range of 20 to 80% by weight of polyester diol and 80 to 20% by weight of polyether diol.
  • the polyester diol is 80% by weight or less, the plate covering property is excellent.
  • the polyether diol is 80% by weight or less, the blocking resistance is excellent.
  • the amine value of the polyurethane resin in the present embodiment is preferably 2.0 to 7.0 mgKOH / g, more preferably 3.0 to 6.0 mgKOH / g.
  • the amine value is more than 2.0 mgKOH / g, the plate covering property, adhesiveness and EL laminate strength are excellent, and when it is 7.0 mgKOH / g or less, the blocking resistance is excellent.
  • the weight average molecular weight of the polyurethane resin in this embodiment is preferably 10,000 to 70,000, more preferably 15,000 to 60,000.
  • the weight average molecular weight is 10,000 or more, the blocking resistance is excellent, and since the heat resistance is good, the EL laminate strength is also excellent.
  • the weight average molecular weight is 70000 or less, the plate fogging property, adhesiveness and EL laminate strength are excellent.
  • the synthesis of the polyurethane resin in the present embodiment can be produced from the following prepolymer method.
  • a polymer polyol and polyisocyanate containing tolylene diisocyanate are reacted at a temperature of 10 to 100 ° C. to produce a prepolymer having an isocyanate group at the terminal.
  • a solvent inert to the isocyanate group may be used.
  • this prepolymer is reacted with an organic diamine as a chain extender and an alkanolamine as a reaction terminator at 10 to 80 ° C. to obtain a polyurethane resin.
  • the solvent used in the polyurethane resin composition of the present embodiment includes a mixed solvent of an ester solvent and an alcohol solvent.
  • the following known solvents are preferably used.
  • the ester solvent include ethyl acetate, n-propyl acetate, isopropyl acetate, isobutyl acetate, propylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, and the like.
  • the alcohol solvent include methanol, ethanol, n-propanol, isopropanol, n-butanol, propylene glycol monoethyl ether, propylene glycol monomethyl ether and the like.
  • a catalyst may be used for the urethanization reaction.
  • catalysts that can be used include tertiary amine catalysts such as triethylamine and dimethylaniline; metal catalysts such as tin and zinc. These catalysts are usually used in the range of 0.001 to 1 mol% based on the polyol.
  • a chain extension reaction may be carried out using an alkanolamine as a reaction terminator and an organic diamine as a chain extender together.
  • the chain extension reaction may be carried out to some extent with a chain extender, and then the reaction may be stopped by adding a reaction terminator alone.
  • an inorganic colorant and an organic colorant can be used as the colorant.
  • the white colorant titanium oxide, which is an inorganic colorant, can be used, and the pigment surface is more basic.
  • inorganic colorants include pigments such as carbon black, aluminum, and mica (mica) in addition to the white colorant.
  • Aluminum is in the form of powder or paste, but is preferably used in the form of paste from the viewpoint of handling and safety, and whether to use leafing or non-leafing depends on brightness and concentration. Is appropriately selected.
  • examples of the organic colorant include organic pigments and organic dyes used in general inks, paints, and recording agents.
  • Examples include azo, phthalocyanine, anthraquinone, perylene, perinone, quinacridone, thioindigo, dioxazine, isoindolinone, quinophthalone, azomethine azo, dictopyrrolopyrrole, and isoindoline.
  • the colorant is preferably contained in an amount sufficient to ensure the concentration and coloring power of the printing ink, that is, 1 to 50% by weight based on the total weight of the printing ink. These colorants can be used alone or in combination of two or more.
  • the printing ink composition of this embodiment can be produced by dissolving and / or dispersing a resin, a colorant, and the like in an organic solvent.
  • a pigment dispersion is prepared by dispersing a pigment, a polyurethane resin composition and, if necessary, another compound in an organic solvent, and the obtained polyurethane dispersion is further mixed with a polyurethane resin composition and an organic solvent.
  • an ink can be manufactured by mix
  • a dispersant may be used in combination for further stable dispersion.
  • the dispersant anionic, nonionic, cationic, amphoteric surfactants can be used.
  • the dispersant is preferably contained in the ink in an amount of 0.05% by weight or more based on the total weight of the ink from the viewpoint of the storage stability of the ink and 5% by weight or less from the viewpoint of the suitability for lamination. Further, it is more preferably contained in the range of 0.1 to 2% by weight.
  • the particle size distribution of the pigment in the pigment dispersion is adjusted by appropriately adjusting the size of the grinding media of the disperser, the filling rate of the grinding media, the dispersion treatment time, the discharge speed of the pigment dispersion, the viscosity of the pigment dispersion, and the like. be able to.
  • a disperser generally used, for example, a roller mill, a ball mill, a pebble mill, an attritor, a sand mill and the like can be used.
  • the solvent used in the printing ink composition of the present embodiment is a mixed solvent of an ester solvent and an alcohol solvent.
  • an ester solvent and the alcohol solvent a known solvent is preferably used, and specific examples are as described above.
  • the ink When air bubbles or unexpectedly large particles are included in the ink, it is preferably removed by filtration or the like in order to reduce the quality of the printed matter.
  • a conventionally well-known filter can be used.
  • the viscosity of the ink produced by the above method is in the range of 10 mPa ⁇ s or more from the viewpoint of preventing the pigment from settling and being appropriately dispersed, and 1000 mPa ⁇ s or less from the viewpoint of workability efficiency during ink production or printing. Is preferred.
  • the said viscosity is a viscosity measured at 25 degreeC with the Tokimec B-type viscometer.
  • the printing ink composition can be used in known printing methods such as gravure printing and flexographic printing.
  • gravure printing it is diluted with a diluting solvent to a viscosity and concentration suitable for gravure printing, and is supplied to each printing unit alone or mixed.
  • Gravure printing is preferable.
  • the substrate to which the printing ink composition can be applied examples include, for example, polyolefins such as polyethylene and polypropylene, polyesters such as polyethylene terephthalate, polycarbonate, and polylactic acid, polystyrene resins such as polystyrene, AS resin, and ABS resin, nylon, polyamide, and poly Examples thereof include vinyl chloride, polyvinylidene chloride, cellophane, paper, aluminum, etc., or a film or sheet made of a composite material thereof.
  • a printed matter can be obtained by applying a printing ink composition to a substrate using the printing method described above and fixing it by drying in an oven.
  • the substrate may be subjected to a vapor deposition coating process for depositing a metal oxide or the like on the surface and / or a coating process for coating polyvinyl alcohol or the like. Furthermore, the substrate may be subjected to a surface treatment such as a corona treatment.
  • a laminated laminate can be obtained.
  • a laminating method 1) An extrusion laminating method in which a molten resin is laminated after applying an anchor coating agent to the printed surface of the obtained printed matter, if necessary. 2) A dry laminating method in which a plastic film is laminated after applying an adhesive and then dried as necessary.
  • the molten resin for example, low density polyethylene, polypropylene, ethylene-vinyl acetate copolymer and the like can be used.
  • the adhesive include imine, isocyanate, polybutadiene, and titanate.
  • the hydroxyl value was acetylated with an excess of an acetylating reagent and the amount of hydroxyl group in 1 g of resin calculated by back titrating the remaining acid with alkali was converted to mg of potassium hydroxide.
  • the amine value is the number of mg of potassium hydroxide equivalent to the equivalent amount of hydrochloric acid required to neutralize the amino group contained in 1 g of resin.
  • the acid value is the number of mg of potassium hydroxide required to neutralize the acid group contained in 1 g of resin, and the measuring method may be a known method, generally according to JIS K0070 (1996). Done.
  • the molecular weight was determined as a polystyrene-converted molecular weight by measuring the molecular weight distribution using a GPC (gel permeation chromatography) apparatus. The method for measuring the amine value is as follows.
  • Example 1 30.00 parts of titanium oxide (TITONE R45M manufactured by Sakai Chemical Co., Ltd.), 10.00 parts of polyurethane resin composition (PU01), 10.00 parts of ethyl acetate / isopropyl alcohol mixed solvent (weight ratio 70/30) were stirred and mixed in a sand mill. I kneaded the meat. Furthermore, 40.00 parts of polyurethane resin composition (PU01) and 10.00 parts of ethyl acetate / isopropyl alcohol mixed solvent (weight ratio 70/30) were added and mixed by stirring to obtain a white printing ink composition (W01). .
  • Examples 2 to 18 [Comparative Examples 1 to 8]
  • White printing ink compositions (W02 to 26) were obtained in the same manner as in Example 1, except that the polyurethane resin composition (PU01) was changed to polyurethane resin compositions (PU02) to (PU26), respectively.
  • PPA2000 poly (1,2-propylene adipate) diol (number average molecular weight 2000)
  • NPG2000 poly (neopentyl adipate) diol (number average molecular weight 2000)
  • PMPA2000 poly (3-methyl-1,5-pentaneadipate) diol (number average molecular weight 2000)
  • PPG1000 poly (1,2-propylene glycol) (number average molecular weight 1000)
  • TDI tolylene diisocyanate
  • IPDI isophorone diisocyanate
  • MDI diphenylmethane diisocyanate
  • IPDA isophoronediamine
  • MEA monoethanolamine DEA: diethanolamine
  • DBA di-n-butylamine
  • IPA isopropyl alcohol
  • HDA hexamethylenediamine
  • AEA 2-hydroxyethylethylenediamine
  • An NBR (nitrile butadiene rubber) impression cylinder having a hardness of 80 Hs, a blade thickness of 60 ⁇ m (base material thickness of 40 ⁇ m, one side ceramic layer thickness of 10 ⁇ m), a chromium hardness of 1050 Hv manufactured by Toyo Prepress Co., Ltd.
  • White diluted printing ink 1 or white diluted printing ink 2 was set on a gravure printing machine manufactured by Fuji Machine Industry Co., Ltd. with an electronic engraving plate (stylus angle 120 °, 200 lines / inch).
  • ⁇ Slight ink transfer was observed in the non-image area.
  • ⁇ ⁇ Ink transfer was observed in a small area of the non-image area. More practical than that.
  • ⁇ Ink transfer was observed in a large area of the non-image area.
  • ⁇ ⁇ Ink transfer was observed on almost the entire non-image area. (The amount of transition is between ⁇ and ⁇ )
  • X Ink transfer was observed over the entire non-image area.
  • the white diluted printing ink 1 was printed on a corona-treated OPP film (Taiko FOR-Futamura # 20) by a gravure proofing machine equipped with a gravure plate having a plate depth of 35 ⁇ m and dried at 40 to 50 ° C. to obtain a printed matter.
  • This printed matter was sampled to 4 cm ⁇ 4 cm, and the unprinted surface of the unprinted film having the same size as the printed surface of this sample was combined and pressurized at 50 ° C. for 12 hours and 10 kgf, and the sample was peeled off.
  • the ink was removed (ink transfer) and the resistance was observed.
  • ⁇ No transfer of ink was observed from the printed matter, but there was a feeling of resistance during peeling.
  • ⁇ Ink transfer was observed from the printed matter, but the area was less than 10%. More practical than that.
  • ⁇ Ink transfer from the printed material was observed in an area of 10% or more and less than 50%.
  • X Ink transfer from the printed matter was observed in an area of 50% or more.
  • the white diluted printing ink 1 was printed on the corona-treated surface of the substrate under the printing conditions of the plate fog test to obtain a printed matter.
  • the base material used here is a polypropylene (hereinafter referred to as OPP) film having a thickness of 20 ⁇ m by single-sided corona treatment, “Pyrene P-2161 (manufactured by Toyobo Co., Ltd.)”, and polyethylene terephthalate having a thickness of 12 ⁇ m by single-sided corona treatment.
  • PET polypropylene
  • PET polyethylene terephthalate
  • PET A film “Toyobo Ester Film E5100 (manufactured by Toyobo Co., Ltd.)”.
  • a polyethyleneimine-based anchor coating agent “Olivein EL-420” (trade name, manufactured by Toyo Morton Co., Ltd.) was applied on the printed surface. Furthermore, the melt temperature of low density polyethylene “NOVATEC LC600” (manufactured by Nippon Polychem Co., Ltd., trade name) as a sealant was extruded on the coated surface at 315 ° C. to obtain a laminated product. That is, a laminate processed product was obtained by (Extension lamination (EL)). The melting temperature of the low density polyethylene was measured with a contact thermometer (HL-100, manufactured by Anritsu Keiki Co., Ltd.) at a temperature immediately below the T die of the extrusion laminating machine.
  • a contact thermometer HL-100, manufactured by Anritsu Keiki Co., Ltd.
  • the ink part in the laminated product was cut at a width of 15 mm and peeled between the ink surface and the molten resin layer, and the peel strength was measured with an Intesco 2.01 million tensile tester. It should be noted that a laminated product using OPP (OPP / imine structure) is 1.0 N / 15 mm or more, and a laminated product using PET (PET / imine structure) is 1.5 N / 15 mm or more.
  • the evaluation results are summarized in Tables 4-6.
  • the printing inks of Examples 1 to 18 showed excellent printability such as plate fog in an ester / alcohol solvent system as compared with the printing ink compositions of Comparative Examples 1 to 8, and anti-blocking property, adhesiveness, It is possible to provide a printing ink composition that can ensure printing property such as alcohol bleeding resistance and suitability for lamination.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
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  • Engineering & Computer Science (AREA)
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  • Inks, Pencil-Leads, Or Crayons (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

Provided is a polyurethane resin composition comprising: a polyurethane resin obtained by reacting an organic diamine and an alkanol amine with a urethane prepolymer that is made by reacting a polyisocyanate, including tolylene diisocyanate, with a high-molecular polyol and that has an isocyanate group at a terminal thereof, wherein [NCO (total)]/[OH], [NCO (TDI)]/[OH], the hydroxyl value of the polyurethane resin, and the ratio between the organic diamine and the alkanol amine are controlled; and a mixed solvent including an ester-based solvent and an alcohol.

Description

印刷インキバインダー用ポリウレタン樹脂組成物Polyurethane resin composition for printing ink binder
　本発明は、ポリウレタン樹脂組成物および印刷インキ組成物に関する。 The present invention relates to a polyurethane resin composition and a printing ink composition.
　従来から、印刷インキで使用される溶剤としては、トルエン及びキシレンなどの比較的溶解力の強い芳香族系の溶剤、及びメチルエチルケトン及びメチルイソブチルケトンなどのケトン系の溶剤が挙げられる。しかし近年、地球規模での環境保全及び法規制面から、印刷インキ業界へも、環境課題への配慮が要求されている。そこで、これらの芳香族系溶剤及びケトン系溶剤を排除した、エステル／アルコール溶剤系を用いる印刷インキが望まれている。そのため、エステル／アルコール溶剤系の印刷インキの研究開発が行われている。しかし、エステル／アルコール溶剤系は、芳香族系及びケトン系の溶剤と比較し、溶解力が低いため印刷適性が悪かった。また、エステル／アルコール溶剤の溶解力を上げると、耐アルコールブリード性や耐ブロッキング性などの他物性が劣り、未だに課題が多かった。 Conventionally, examples of solvents used in printing inks include aromatic solvents having relatively strong dissolving power such as toluene and xylene, and ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone. However, in recent years, due to environmental conservation and legal regulations on a global scale, the printing ink industry has been required to consider environmental issues. Therefore, a printing ink using an ester / alcohol solvent system in which these aromatic solvents and ketone solvents are excluded is desired. For this reason, research and development of printing inks based on ester / alcohol solvents are being carried out. However, the ester / alcohol solvent system was poor in printability because of its lower dissolving power than aromatic and ketone solvents. Moreover, when the dissolving power of the ester / alcohol solvent was increased, other physical properties such as alcohol bleed resistance and blocking resistance were inferior, and there were still many problems.
　例えば、特開平９－３１６１５６公報には、ジフェニルメタンジイソシアネートを使用したポリウレタン樹脂組成物および印刷インキ組成物が、各種プラスチックフィルムに対し、優れた接着性を有することが開示されている。しかし、これらの組成物は、印刷適性の確保のため、排除が求められているメチルエチルケトンを含む。また、［ＮＣＯ］／［ＯＨ］比が低いため、耐ブロッキング性にも課題がある。 For example, JP-A-9-316156 discloses that a polyurethane resin composition and a printing ink composition using diphenylmethane diisocyanate have excellent adhesion to various plastic films. However, these compositions contain methyl ethyl ketone, which is required to be excluded in order to ensure printability. Moreover, since the [NCO] / [OH] ratio is low, there is also a problem in blocking resistance.
　また、特開２００３－２２１５３９公報には、インキにエステル／アルコール溶剤系を含有し、エステル／アルコール溶剤系への溶解性を上げる検討が開示されている。しかし、インキ中にヒドロキシカルボン酸が添加されているため、残留溶剤の問題が発生し、また、耐水性及び耐アルコールブリード性が劣る。 JP 2003-221539 discloses a study in which an ink contains an ester / alcohol solvent system to increase the solubility in the ester / alcohol solvent system. However, since a hydroxycarboxylic acid is added to the ink, a problem of a residual solvent occurs, and water resistance and alcohol bleed resistance are inferior.
特開平９－３１６１５６公報JP-A-9-316156 特開２００３－２２１５３９公報JP 2003-221539 A
　本発明は、トルエン及びキシレンなどの芳香族有機溶剤、及びメチルエチルケトン及びメチルイソブチルケトンなどのケトン系有機溶剤を排除した印刷インキ組成物を提供することを目的とする。また、本発明は、エステル／アルコール溶剤系を含有し、優れた版かぶり性等の印刷適性を有し、かつ各種プラスチックフィルムに対し優れた接着性、耐ブロッキング性、耐アルコールブリード性およびラミネート物性等の印刷物性をも併せ持つ印刷インキ組成物を提供することを目的とする。 An object of the present invention is to provide a printing ink composition that excludes aromatic organic solvents such as toluene and xylene and ketone organic solvents such as methyl ethyl ketone and methyl isobutyl ketone. In addition, the present invention contains an ester / alcohol solvent system, has excellent printability such as plate fog, and has excellent adhesion, blocking resistance, alcohol bleed resistance and laminate physical properties to various plastic films. An object of the present invention is to provide a printing ink composition having printing physical properties such as the above.
　本発明者らは、前記状況を鑑み鋭意検討を重ねた結果、トリレンジイソシアネートを含むポリイソシアネート、さらに反応停止剤にアルカノールアミンを使用し、かつ合成パラメータを制御したポリウレタン樹脂を用いることで、比較的溶解力の弱いエステル／アルコール溶剤系を用いても、優れた印刷適性と印刷物性の両立を達成する印刷インキ組成物の設計を可能とすることを見出し、本発明に至った。 As a result of intensive studies in view of the above situation, the present inventors have compared polyisocyanate containing tolylene diisocyanate, and further using a polyurethane resin that uses alkanolamine as a reaction terminator and has controlled synthesis parameters. The present inventors have found that it is possible to design a printing ink composition that achieves both excellent printability and print physical properties even when using an ester / alcohol solvent system having a weak dynamic solubility.
　本発明の第一の実施形態は、トリレンジイソシアネートを含むポリイソシアネートと高分子ポリオールとを反応させてなる、末端にイソシアネート基を有するウレタンプレポリマーを、有機ジアミンおよびアルカノールアミンと反応させてなるポリウレタン樹脂、並びに混合溶剤を含むポリウレタン樹脂組成物であって、
　下記の（Ａ）～（Ｆ）であることを特徴とするポリウレタン樹脂組成物に関するものである。
（Ａ）ポリイソシアネートの全イソシアネート基と高分子ポリオールの水酸基との反応におけるモル比［ＮＣＯ（全）］／［ＯＨ］が、１．８～２．３である。
（Ｂ）トリレンジイソシアネートのイソシアネート基と高分子ポリオールの水酸基との反応におけるモル比［ＮＣＯ（ＴＤＩ）］／［ＯＨ］が、１．０～２．１である。
（Ｃ）ポリウレタン樹脂の水酸基価が１．０～１０．０ｍｇＫＯＨ／ｇである。
（Ｄ）有機ジアミンのモル数ｄ１とアルカノールアミンのモル数ｄ２とのモル比ｄ１／ｄ２が、３～２５である。
（Ｅ）混合溶剤が、エステル系溶剤とアルコール系溶剤とを含む。
（Ｆ）高分子ポリオールが、ポリエステルジオールとポリエーテルジオールとからなる。 The first embodiment of the present invention is a polyurethane formed by reacting a polyisocyanate containing tolylene diisocyanate and a polymer polyol, and reacting a urethane prepolymer having an isocyanate group at the terminal with an organic diamine and an alkanolamine. A polyurethane resin composition containing a resin and a mixed solvent,
The present invention relates to a polyurethane resin composition having the following (A) to (F):
(A) The molar ratio [NCO (total)] / [OH] in the reaction of all isocyanate groups of the polyisocyanate and hydroxyl groups of the polymer polyol is 1.8 to 2.3.
(B) The molar ratio [NCO (TDI)] / [OH] in the reaction between the isocyanate group of tolylene diisocyanate and the hydroxyl group of the polymer polyol is 1.0 to 2.1.
(C) The hydroxyl value of the polyurethane resin is 1.0 to 10.0 mgKOH / g.
(D) The molar ratio d1 / d2 between the number of moles d1 of the organic diamine and the number of moles d2 of the alkanolamine is 3 to 25.
(E) The mixed solvent includes an ester solvent and an alcohol solvent.
(F) The polymer polyol is composed of a polyester diol and a polyether diol.
　次に、第二の実施形態は、高分子ポリオール中に、前記ポリエステルジオールが２０～８０重量％、前記ポリエーテルジオール８０～２０重量％であることを特徴とするポリウレタン樹脂組成物に関するものである。 Next, a second embodiment relates to a polyurethane resin composition characterized in that the polyester diol is 20 to 80% by weight and the polyether diol is 80 to 20% by weight in a polymer polyol. .
　さらに、第三の実施形態は、第一または第二の実施形態のポリウレタン樹脂組成物を含有することを特徴とする印刷インキ組成物に関するものである。 Furthermore, the third embodiment relates to a printing ink composition comprising the polyurethane resin composition of the first or second embodiment.
　本実施形態によると、エステル／アルコール溶剤系を用いても、優れた印刷適性及び優れた印刷物性を保有する印刷インキ組成物を提供することを可能とする。 According to this embodiment, even if an ester / alcohol solvent system is used, it is possible to provide a printing ink composition having excellent printability and excellent print physical properties.
　以下、印刷インキバインダー用ポリウレタン樹脂組成物について説明する。ポリウレタン樹脂は、トリレンジイソシアネートを含むポリイソシアネートと高分子ポリオールとを反応させてなる、末端にイソシアネート基を有するウレタンプレポリマーに、鎖延長剤として有機ジアミン、反応停止剤としてアルカノールアミンを反応させて得られる。 Hereinafter, the polyurethane resin composition for printing ink binder will be described. The polyurethane resin is obtained by reacting a polyisocyanate containing tolylene diisocyanate with a polymer polyol, and reacting a urethane prepolymer having an isocyanate group at the terminal with an organic diamine as a chain extender and an alkanolamine as a reaction terminator. can get.
　印刷インキバインダーに用いるポリウレタン樹脂において、エステル／アルコール溶剤への溶解力と、種々のプラスチックフィルムに対する各種印刷物性の両立を考慮する場合、重要な因子となるのが、ウレタン結合、ウレア結合のハードセグメントを形成するポリイソシアネートである。 In polyurethane resins used as printing ink binders, when considering the compatibility between the solubility in ester / alcohol solvents and various printed physical properties for various plastic films, the important factors are the hard segments of urethane bonds and urea bonds. Is a polyisocyanate.
　本実施形態において、ポリウレタン樹脂で用いるポリイソシアネートは、トリレンジイソシアネートを含む（以下、ＴＤＩと表記されることもある。）。トリレンジイソシアネートは、２，４－トリレンジイソシアネートまたは、２，６－トリレンジイソシアネートが好ましく、これらの混合物であってもよい。 In this embodiment, the polyisocyanate used in the polyurethane resin includes tolylene diisocyanate (hereinafter sometimes referred to as TDI). Tolylene diisocyanate is preferably 2,4-tolylene diisocyanate or 2,6-tolylene diisocyanate, and may be a mixture thereof.
　トリレンジイソシアネートは分子内に芳香族環を一つ有するため、脂肪族イソシアネート及び脂環族イソシアネートと比較し、よりアルコールへの耐性が高い。一方で、芳香族環を二つ有する芳香族イソシアネートであるジフェニルメタンジイソシアネートと比較し、トリレンジイソシアネートは芳香族環が一つであるため、エステル／アルコール溶剤系への溶解力が高い。よって、トリレンジイソシアネートはエステル／アルコール溶剤系の印刷インキ組成物において、版かぶり性等の印刷適性と耐アルコールブリード性のバランスを取りやすい。 Since tolylene diisocyanate has one aromatic ring in the molecule, it has higher resistance to alcohol than aliphatic isocyanate and alicyclic isocyanate. On the other hand, as compared to diphenylmethane diisocyanate, which is an aromatic isocyanate having two aromatic rings, tolylene diisocyanate has a single aromatic ring and therefore has a higher solubility in an ester / alcohol solvent system. Therefore, tolylene diisocyanate tends to balance printing aptitude such as plate fog and alcohol bleeding resistance in an ester / alcohol solvent-based printing ink composition.
　本実施形態において、ウレタンプレポリマーを合成する際、全ポリイソシアネートの全イソシアネート基と高分子ポリオールの水酸基とのモル比率である［ＮＣＯ（全）］／［ＯＨ］が、１．８～２．３の範囲にある。［ＮＣＯ（全）］／［ＯＨ］が１．８以上だと、ハードセグメント結合数が十分で、耐ブロッキング性、耐アルコールブリード性が優れる。２．３以下だと、版かぶり性が優れ、またハードセグメント結合数が適度であるため接着性、ＥＬラミネート強度が優れる。 In this embodiment, when the urethane prepolymer is synthesized, [NCO (total)] / [OH], which is the molar ratio of all isocyanate groups of all polyisocyanates to hydroxyl groups of the polymer polyol, is 1.8-2. It is in the range of 3. When [NCO (all)] / [OH] is 1.8 or more, the number of hard segment bonds is sufficient, and the blocking resistance and alcohol bleed resistance are excellent. If it is 2.3 or less, the plate fogging property is excellent, and since the number of hard segment bonds is moderate, the adhesiveness and EL laminate strength are excellent.
　本実施形態において、トリレンジイソシアネートのイソシアネート基と高分子ポリオールの水酸基との反応におけるモル比率である［ＮＣＯ（ＴＤＩ）］／［ＯＨ］は、１．０～２．１の範囲にある。一般的に芳香族イソシアネートは、脂肪族イソシアネートや脂環族イソシアネートと比較し、水酸基やアミノ基との反応速度が速い。よって、［ＮＣＯ（ＴＤＩ）］／［ＯＨ］が２．１以下だと、反応速度が適度であるため均一なポリウレタン樹脂が合成できる。さらには、分子内の芳香族環濃度が適度であるため版かぶり性が優れる。また、［ＮＣＯ（ＴＤＩ）］／［ＯＨ］が１．０以上だと耐アルコールブリード性が優れる。 In this embodiment, [NCO (TDI)] / [OH], which is the molar ratio in the reaction between the isocyanate group of tolylene diisocyanate and the hydroxyl group of the polymer polyol, is in the range of 1.0 to 2.1. In general, an aromatic isocyanate has a higher reaction rate with a hydroxyl group or an amino group than an aliphatic isocyanate or an alicyclic isocyanate. Therefore, when [NCO (TDI)] / [OH] is 2.1 or less, a uniform polyurethane resin can be synthesized because the reaction rate is moderate. Furthermore, since the concentration of the aromatic ring in the molecule is moderate, the plate fog is excellent. Further, when [NCO (TDI)] / [OH] is 1.0 or more, the alcohol bleed resistance is excellent.
　なお、上記の［ＮＣＯ（全）］／［ＯＨ］および［ＮＣＯ（ＴＤＩ）］／［ＯＨ］を満たす範囲であれば、トリレンジイソシアネート以外に他のポリイソシアネートを併用してもよい。他のポリイソシアネートとしては、ポリウレタン樹脂の製造に一般的に用いられる各種公知の脂肪族イソシアネート、脂環族イソシアネートが挙げられる。例えば、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、リジ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、イソホロンジイソシアネート、ジメリールジイソシアネート、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、ノルボルナ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等があげられる。他のポリイソシアネートの中でも、イソシアネート基の反応速度および諸々の物性の観点からイソホロンジイソシアネートが好ましい。 In addition, other polyisocyanates may be used in addition to tolylene diisocyanate as long as the above [NCO (all)] / [OH] and [NCO (TDI)] / [OH] are satisfied. Examples of other polyisocyanates include various known aliphatic isocyanates and alicyclic isocyanates that are generally used in the production of polyurethane resins. For example, butane-1,4-diisocyanate, hexamethylene diisocyanate, isopropylene diisocyanate, methylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, cyclohexane-1,4-diisocyanate, isophorone diisocyanate, dimaryl diisocyanate, Examples thereof include dicyclohexylmethane-4,4 ′ -diisocyanate, 1,3-bis (isocyanatemethyl) cyclohexane, methylcyclohexane diisocyanate, norbornane diisocyanate, and dimerized isocyanate obtained by converting the carboxyl group of dimer acid into an isocyanate group. Among other polyisocyanates, isophorone diisocyanate is preferable from the viewpoint of the reaction rate of the isocyanate group and various physical properties.
　さらに、全イソシアネート基のモル数中の９０～１００％がトリレンジイソシアネート、及び１０～０％がイソホロンジイソシアネートである場合、耐アルコールブリード性に特に優れる。また、同様に全イソシアネート基のモル数中の５０～７５％がトリレンジイソシアネート、及び５０～２５％がイソホロンジイソシアネートである場合であって、印刷インキ組成物中の溶剤が、３５％重量以上のアルコール系溶剤を含有する場合は、版かぶり性に特に優れる。なお、印刷インキ組成物に含まれる混合溶剤の詳細については後述する。 Furthermore, when 90 to 100% of the total number of isocyanate groups is tolylene diisocyanate and 10 to 0% is isophorone diisocyanate, the alcohol bleeding resistance is particularly excellent. Similarly, when 50 to 75% of the total number of isocyanate groups is tolylene diisocyanate and 50 to 25% is isophorone diisocyanate, the solvent in the printing ink composition is 35% by weight or more. When an alcohol solvent is contained, the plate fog is particularly excellent. The details of the mixed solvent contained in the printing ink composition will be described later.
　さらに、エステル／アルコール溶剤系での版かぶり性等の印刷適性と、耐アルコールブリード性のバランスを取るために重要な因子として、ポリウレタン樹脂の水酸基価がある。本実施形態において、ポリウレタン樹脂の水酸基価は１．０～１０．０ｍｇＫＯＨ／ｇである。水酸基価が１．０ｍｇＫＯＨ／ｇ以上であると、接着性、ＥＬラミネート強度が優れ、また溶解性も著しく良好であるため版かぶり性が優れる。水酸基価が１０．０ｍｇＫＯＨ／ｇ以下だと、耐アルコールブリード性が優れる。 Furthermore, the hydroxyl value of polyurethane resin is an important factor for balancing printing suitability such as plate fogging in an ester / alcohol solvent system and alcohol bleed resistance. In this embodiment, the hydroxyl value of the polyurethane resin is 1.0 to 10.0 mgKOH / g. When the hydroxyl value is 1.0 mgKOH / g or more, the adhesiveness and EL laminate strength are excellent, and the solubility is remarkably good, so that the plate fog is excellent. When the hydroxyl value is 10.0 mgKOH / g or less, the alcohol bleed resistance is excellent.
　本実施形態における鎖延長剤としての有機ジアミンは、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、イソホロンジアミン、ジシクロヘキシルメタン－４，４’ －ジアミンなどの他、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ルジアミン、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－ヒドロキシピロピルエチレンジアミン、ジ－２－ヒドロキシピロピルエチレンジアミン、ジ－２－ヒドロキシプロピルエチレンジアミンなど分子内に水酸基を有するアミン類が挙げられる。これらの鎖伸長剤は単独で、または２種以上を混合して用いることができる。中でも、特にイソホロンジアミンが好ましい。 Examples of the organic diamine as the chain extender in this embodiment include ethylenediamine, propylenediamine, hexamethylenediamine, isophoronediamine, dicyclohexylmethane-4,4 ′ -diamine, 2-hydroxyethylethylenediamine, 2-hydroxyethyl, and the like. Propyldiamine, 2-hydroxyethylpropylenediamine, di-2-hydroxyethylethylenediamine, di-2-hydroxyethylenediamine, di-2-hydroxyethylpropylenediamine, 2-hydroxypropylethylenediamine, di-2-hydroxypropylethylenediamine, Examples include amines having a hydroxyl group in the molecule, such as di-2-hydroxypropylethylenediamine. These chain extenders can be used alone or in admixture of two or more. Of these, isophoronediamine is particularly preferable.
　本実施形態において、ポリウレタン樹脂の有機ジアミンのモル数ｄ１と、アルカノールアミンのモル数ｄ２とのモル比ｄ１／ｄ２は、３～２５である。ｄ１／ｄ２が３以上だと、耐アルコールブリード性が優れ、またポリウレタン樹脂の重量平均分子量が大きいため耐ブロッキング性も著しく良好である。ｄ１／ｄ２が２５以下だと、接着性、ＥＬラミネート強度が優れ、また溶解性も著しく良好であるため版かぶり性が優れる。 In this embodiment, the molar ratio d1 / d2 between the number of moles d1 of the organic diamine of the polyurethane resin and the number of moles d2 of the alkanolamine is 3 to 25. When d1 / d2 is 3 or more, the alcohol bleed resistance is excellent, and since the weight average molecular weight of the polyurethane resin is large, the blocking resistance is remarkably good. When d1 / d2 is 25 or less, the adhesiveness and EL laminate strength are excellent, and the solubility is remarkably good, so that the plate covering property is excellent.
　なお、反応停止剤であるアルカノールアミンの使用量が多くなると、得られるポリウレタン樹脂の重量平均分子量は低くなる。また、アルカノールアミンには水酸基が含まれているため、アルカノールアミンの使用量が多くなると、水酸基価は大きくなる。アルカノールアミンとしては、例えば、モノエタノールアミン、ジエタノールアミン等が挙げられる。これらは単独で、または２種以上を混合して用いることができる。中でも、特にモノエタノールアミンが好ましい。 In addition, when the usage-amount of alkanolamine which is a reaction terminator increases, the weight average molecular weight of the polyurethane resin obtained will become low. Further, since the alkanolamine contains a hydroxyl group, the hydroxyl value increases as the amount of alkanolamine used increases. Examples of the alkanolamine include monoethanolamine and diethanolamine. These can be used alone or in admixture of two or more. Of these, monoethanolamine is particularly preferable.
　高分子ポリオールとしては各種公知のポリエステルポリオール、及びポリエーテルポリオール等を用いる。それぞれ１種または２種以上を併用してもよい。ポリエステルポリオールとしては、例えば、エチレングリコール、１，２－プロパンジオール、１，３－プロパンジオール、２メチル－１，３プロパンジオール、２エチル－２ブチル－１，３プロパンジオール、１，３－ブタンジオール、１，４－ブタンジオール、ネオペンチルグリコール、ペンタンジオール、３－メチル－１，５ペンタンジオール、ヘキサンジオール、オクタンジオール、１，４－ブチンジオール、１，４－ブチレンジオール、ジエチレングリコール、トリエチレングリコール、ジプロピレングリコール、グリセリン、トリメチロールプロパン、トリメチロールエタン、１，２，６－ヘキサントリオール、１，２，４－ブタントリオール、ソルビトール、ペンタエスリトールなどの飽和または不飽和の低分子ポリオール類と、アジピン酸、フタル酸、イソフタル酸、テレフタル酸、マレイン酸、フマル酸、こはく酸、しゅう酸、マロン酸、グルタル酸、ピメリン酸、スペリン酸、アゼライン酸、セバシン酸、トリメリット酸、ピロメリット酸などの多価カルボン酸あるいはこれらの無水物とを脱水縮合または重合させて得られるポリエステルポリオール類、
　環状エステル化合物、例えばポリカプロラクトン、ポリバレロラクトン、ポリ（β－メチル－γ－バレロラクトン）等のラクトン類、を開環重合して得られるポリエステルポリオール類などが挙げられる。ポリエーテルポリオールとしては、例えば、酸化メチレン、酸化エチレン、酸化プロピレン、テトラヒドロフランなどの重合体または共重合体が挙げられる。ポリエステルポリオールにおいても、ポリエーテルポリオールにおいても分岐構造を持つものが特に好ましい。 As the polymer polyol, various known polyester polyols, polyether polyols, and the like are used. You may use together 1 type, or 2 or more types, respectively. Examples of the polyester polyol include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 2methyl-1,3propanediol, 2ethyl-2butyl-1,3propanediol, and 1,3-butane. Diol, 1,4-butanediol, neopentyl glycol, pentanediol, 3-methyl-1,5-pentanediol, hexanediol, octanediol, 1,4-butynediol, 1,4-butylenediol, diethylene glycol, triethylene Saturated or unsaturated low molecular weight polyols such as glycol, dipropylene glycol, glycerin, trimethylolpropane, trimethylolethane, 1,2,6-hexanetriol, 1,2,4-butanetriol, sorbitol, pentaesitol Kind , Adipic acid, phthalic acid, isophthalic acid, terephthalic acid, maleic acid, fumaric acid, succinic acid, oxalic acid, malonic acid, glutaric acid, pimelic acid, speric acid, azelaic acid, sebacic acid, trimellitic acid, pyromellitic acid Polyester polyols obtained by dehydration condensation or polymerization of polyhydric carboxylic acids such as these or their anhydrides,
Examples thereof include polyester polyols obtained by ring-opening polymerization of cyclic ester compounds such as lactones such as polycaprolactone, polyvalerolactone and poly (β-methyl-γ-valerolactone). Examples of the polyether polyol include polymers or copolymers such as methylene oxide, ethylene oxide, propylene oxide, and tetrahydrofuran. Of polyester polyols and polyether polyols, those having a branched structure are particularly preferred.
　高分子ポリオールとして、ポリエステルジオールが２０～８０重量％、及びポリエーテルジオール８０～２０重量％の範囲にあるのが好ましい。ポリエステルジオールが８０重量％以下だと版かぶり性が優れる。ポリエーテルジオールが８０重量％以下だと、耐ブロッキング性が優れる。 The polymer polyol is preferably in the range of 20 to 80% by weight of polyester diol and 80 to 20% by weight of polyether diol. When the polyester diol is 80% by weight or less, the plate covering property is excellent. When the polyether diol is 80% by weight or less, the blocking resistance is excellent.
　本実施形態におけるポリウレタン樹脂のアミン価は２．０～７．０ｍｇＫＯＨ／ｇが好ましく、より好ましくは３．０～６．０ｍｇＫＯＨ／ｇである。アミン価が２．０ｍｇＫＯＨ／ｇより以上だと、版かぶり性、接着性およびＥＬラミネート強度が優れ、７．０ｍｇＫＯＨ／ｇ以下だと耐ブロッキング性が優れる。 The amine value of the polyurethane resin in the present embodiment is preferably 2.0 to 7.0 mgKOH / g, more preferably 3.0 to 6.0 mgKOH / g. When the amine value is more than 2.0 mgKOH / g, the plate covering property, adhesiveness and EL laminate strength are excellent, and when it is 7.0 mgKOH / g or less, the blocking resistance is excellent.
　本実施形態におけるポリウレタン樹脂の重量平均分子量は１００００～７００００が好ましく、より好ましくは１５０００～６００００である。重量平均分子量が１００００以上だと耐ブロッキング性が優れ、また耐熱性が良好であるためＥＬラミネート強度も優れる。重量平均分子量が７００００以下だと、版かぶり性、接着性およびＥＬラミネート強度が優れる。 The weight average molecular weight of the polyurethane resin in this embodiment is preferably 10,000 to 70,000, more preferably 15,000 to 60,000. When the weight average molecular weight is 10,000 or more, the blocking resistance is excellent, and since the heat resistance is good, the EL laminate strength is also excellent. When the weight average molecular weight is 70000 or less, the plate fogging property, adhesiveness and EL laminate strength are excellent.
　本実施形態におけるポリウレタン樹脂の合成は、以下のプレポリマー法から製造することが出来る。
　１）高分子ポリオールとトリレンジイソシアネートを含むポリイソシアネートとを、１０～１００℃の温度で反応させ、末端にイソシアネート基を有するプレポリマーを製造する。上記の反応の際に、必要に応じイソシアネート基に対して不活性な溶媒を用いてもよい。また、必要に応じて、ウレタン化触媒を用いてもよい。
　２）次いで、このプレポリマーに鎖延長剤として有機ジアミン、反応停止剤としてアルカノールアミンを１０～８０℃で反応させてポリウレタン樹脂を得る。 The synthesis of the polyurethane resin in the present embodiment can be produced from the following prepolymer method.
1) A polymer polyol and polyisocyanate containing tolylene diisocyanate are reacted at a temperature of 10 to 100 ° C. to produce a prepolymer having an isocyanate group at the terminal. In the above reaction, if necessary, a solvent inert to the isocyanate group may be used. Moreover, you may use a urethanization catalyst as needed.
2) Next, this prepolymer is reacted with an organic diamine as a chain extender and an alkanolamine as a reaction terminator at 10 to 80 ° C. to obtain a polyurethane resin.
　本実施形態のポリウレタン樹脂組成物に使用される溶剤は、エステル系溶剤とアルコール系溶剤の混合溶剤を含む。これらの溶剤としては、以下の様な、公知の溶剤を使用することが好ましい。
　エステル系溶剤としては、例えば、酢酸エチル、酢酸ｎ－プロピル、酢酸イソプロピル、酢酸イソブチル、プロピレングリコールモノエチルエーテルアセテート、プロピレングリコールモノメチルエーテルアセテートなどが挙げられる。
　アルコール系溶剤としては、メタノール、エタノール、ｎ－プロパノール、イソプロパノール、ｎ－ブタノール、プロピレングリコールモノエチルエーテル、プロピレングリコールモノメチルエーテルなどが挙げられる。 The solvent used in the polyurethane resin composition of the present embodiment includes a mixed solvent of an ester solvent and an alcohol solvent. As these solvents, the following known solvents are preferably used.
Examples of the ester solvent include ethyl acetate, n-propyl acetate, isopropyl acetate, isobutyl acetate, propylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, and the like.
Examples of the alcohol solvent include methanol, ethanol, n-propanol, isopropanol, n-butanol, propylene glycol monoethyl ether, propylene glycol monomethyl ether and the like.
　ウレタン化反応には触媒を用いることもできる。使用できる触媒としては、例えば、トリエチルアミン、ジメチルアニリンなどの３級アミン系の触媒；スズ、亜鉛などの金属系の触媒などが挙げられる。これらの触媒は通常ポリオールに対して０．００１～１モル％の範囲で使用される。 A catalyst may be used for the urethanization reaction. Examples of catalysts that can be used include tertiary amine catalysts such as triethylamine and dimethylaniline; metal catalysts such as tin and zinc. These catalysts are usually used in the range of 0.001 to 1 mol% based on the polyol.
　反応停止剤であるアルカノールアミンと、鎖延長剤である有機ジアミンとは一緒に使用して鎖延長反応を行ってもよい。あるいは、鎖延長剤により、ある程度、鎖延長反応を行った後に、反応停止剤を単独に添加して反応を停止してもよい。 A chain extension reaction may be carried out using an alkanolamine as a reaction terminator and an organic diamine as a chain extender together. Alternatively, the chain extension reaction may be carried out to some extent with a chain extender, and then the reaction may be stopped by adding a reaction terminator alone.
　本実施形態の印刷インキ組成物には、着色剤として無機系着色剤および有機系着色剤を使用できる。白色着色剤には、無機系着色剤である酸化チタンを使用でき、顔料表面が塩基性であるものがより好ましい。無機系着色剤として、白色着色剤以外には、カーボンブラック、アルミニウム、マイカ（雲母）などの顔料が挙げられる。アルミニウムは粉末またはペースト状であるが、取扱い性および安全性の面からペースト状で使用するのが好ましく、リーフィング（ｌｅａｆｉｎｇ）またはノンリーフィング（ｎｏｎ-ｌｅａｆｉｎｇ）を使用するかは輝度感および濃度の点から適宜選択される。一方、有機系着色剤としては、一般のインキ、塗料、および記録剤などに使用されている有機顔料及び有機染料を挙げることができる。例えば、アゾ系、フタロシアニン系、アントラキノン系、ペリレン系、ペリノン系、キナクリドン系、チオインジゴ系、ジオキサジン系、イソインドリノン系、キノフタロン系、アゾメチンアゾ系、ジクトピロロピロール系、イソインドリン系などが挙げられる。 In the printing ink composition of the present embodiment, an inorganic colorant and an organic colorant can be used as the colorant. As the white colorant, titanium oxide, which is an inorganic colorant, can be used, and the pigment surface is more basic. Examples of inorganic colorants include pigments such as carbon black, aluminum, and mica (mica) in addition to the white colorant. Aluminum is in the form of powder or paste, but is preferably used in the form of paste from the viewpoint of handling and safety, and whether to use leafing or non-leafing depends on brightness and concentration. Is appropriately selected. On the other hand, examples of the organic colorant include organic pigments and organic dyes used in general inks, paints, and recording agents. Examples include azo, phthalocyanine, anthraquinone, perylene, perinone, quinacridone, thioindigo, dioxazine, isoindolinone, quinophthalone, azomethine azo, dictopyrrolopyrrole, and isoindoline.
　着色剤は、印刷インキの濃度・着色力を確保するのに充分な量、すなわち印刷インキの総重量に対して１～５０重量％の割合で含まれることが好ましい。また、これらの着色剤は単独で、または２種以上を併用して用いることができる。 The colorant is preferably contained in an amount sufficient to ensure the concentration and coloring power of the printing ink, that is, 1 to 50% by weight based on the total weight of the printing ink. These colorants can be used alone or in combination of two or more.
　本実施形態の印刷インキ組成物は、樹脂及び着色剤などを、有機溶剤中に溶解および／または分散することにより製造することができる。具体的には、顔料とポリウレタン樹脂組成物と必要に応じて他の化合物とを有機溶剤に分散させた顔料分散体を製造し、得られた顔料分散体に、さらにポリウレタン樹脂組成物と有機溶剤と必要に応じて他の化合物とを配合することにより、インキを製造することができる。 The printing ink composition of this embodiment can be produced by dissolving and / or dispersing a resin, a colorant, and the like in an organic solvent. Specifically, a pigment dispersion is prepared by dispersing a pigment, a polyurethane resin composition and, if necessary, another compound in an organic solvent, and the obtained polyurethane dispersion is further mixed with a polyurethane resin composition and an organic solvent. And an ink can be manufactured by mix | blending with another compound as needed.
　ポリウレタン樹脂により顔料を有機溶剤に安定的に分散させるが、さらに安定して分散させるには分散剤を併用することもできる。分散剤としては、アニオン性、ノニオン性、カチオン性、両イオン性などの界面活性剤を使用することができる。分散剤は、インキの保存安定性の観点から、インキの総重量に対して０．０５重量％以上、かつ、ラミネート適性の観点から、５重量％以下でインキ中に含まれることが好ましい。さらに、０．１～２重量％の範囲で含まれることがより好ましい。 Although the pigment is stably dispersed in the organic solvent by the polyurethane resin, a dispersant may be used in combination for further stable dispersion. As the dispersant, anionic, nonionic, cationic, amphoteric surfactants can be used. The dispersant is preferably contained in the ink in an amount of 0.05% by weight or more based on the total weight of the ink from the viewpoint of the storage stability of the ink and 5% by weight or less from the viewpoint of the suitability for lamination. Further, it is more preferably contained in the range of 0.1 to 2% by weight.
　顔料分散体における顔料の粒度分布は、分散機の粉砕メディアのサイズ、粉砕メディアの充填率、分散処理時間、顔料分散体の吐出速度、顔料分散体の粘度などを適宜調節することにより、調整することができる。分散機としては一般に使用される、例えば、ローラーミル、ボールミル、ペブルミル、アトライター、サンドミルなどを用いることができる。 The particle size distribution of the pigment in the pigment dispersion is adjusted by appropriately adjusting the size of the grinding media of the disperser, the filling rate of the grinding media, the dispersion treatment time, the discharge speed of the pigment dispersion, the viscosity of the pigment dispersion, and the like. be able to. As a disperser, generally used, for example, a roller mill, a ball mill, a pebble mill, an attritor, a sand mill and the like can be used.
　本実施形態の印刷インキ組成物に使用される溶剤は、エステル系溶剤とアルコール系溶剤の混合溶剤である。エステル系溶剤、およびアルコール系溶剤としては、公知の溶剤を使用することが好ましく、具体例は前述の通りである。 The solvent used in the printing ink composition of the present embodiment is a mixed solvent of an ester solvent and an alcohol solvent. As the ester solvent and the alcohol solvent, a known solvent is preferably used, and specific examples are as described above.
　インキ中に気泡や予期せずに粗大粒子などが含まれる場合は、印刷物の品質を低下させるため、濾過などにより取り除くことが好ましい。濾過器は従来公知のものを使用することができる。 When air bubbles or unexpectedly large particles are included in the ink, it is preferably removed by filtration or the like in order to reduce the quality of the printed matter. A conventionally well-known filter can be used.
　前記方法で製造されたインキの粘度は、顔料の沈降を防ぎ、適度に分散させる観点から１０ｍＰａ・ｓ以上、インキ製造時や印刷時の作業性効率の観点から１０００ｍＰａ・ｓ以下の範囲であることが好ましい。なお、上記粘度はトキメック社製Ｂ型粘度計で２５℃において測定された粘度である。 The viscosity of the ink produced by the above method is in the range of 10 mPa · s or more from the viewpoint of preventing the pigment from settling and being appropriately dispersed, and 1000 mPa · s or less from the viewpoint of workability efficiency during ink production or printing. Is preferred. In addition, the said viscosity is a viscosity measured at 25 degreeC with the Tokimec B-type viscometer.
　印刷インキ組成物は、グラビア印刷、フレキソ印刷などの既知の印刷方式で用いることができる。例えば、グラビア印刷に用いる場合は、グラビア印刷に適した粘度および濃度にまで希釈溶剤で希釈され、単独でまたは混合されて各印刷ユニットに供給される。好ましくは、グラビア印刷である。 The printing ink composition can be used in known printing methods such as gravure printing and flexographic printing. For example, when used for gravure printing, it is diluted with a diluting solvent to a viscosity and concentration suitable for gravure printing, and is supplied to each printing unit alone or mixed. Gravure printing is preferable.
　印刷インキ組成物を適用できる基材としては、例えば、ポリエチレン、ポリプロピレンなどのポリオレフィン、ポリエチレンテレフタレート、ポリカーボネート、ポリ乳酸などのポリエステル、ポリスチレン、ＡＳ樹脂、ＡＢＳ樹脂などのポリスチレン系樹脂、ナイロン、ポリアミド、ポリ塩化ビニル、ポリ塩化ビニリデン、セロハン、紙、アルミなど、もしくはこれらの複合材料からなるフィルム状もしくはシート状のものが挙げられる。上記の印刷方式を用いて基材に印刷インキ組成物を塗布し、オーブンによる乾燥によって定着させることで、印刷物を得ることができる。基材は、金属酸化物などを表面に蒸着する蒸着コート処理および／またはポリビニルアルコールなどをコートするコート処理が施されていても良い。さらに基材にコロナ処理などの表面処理が施されていても良い。 Examples of the substrate to which the printing ink composition can be applied include, for example, polyolefins such as polyethylene and polypropylene, polyesters such as polyethylene terephthalate, polycarbonate, and polylactic acid, polystyrene resins such as polystyrene, AS resin, and ABS resin, nylon, polyamide, and poly Examples thereof include vinyl chloride, polyvinylidene chloride, cellophane, paper, aluminum, etc., or a film or sheet made of a composite material thereof. A printed matter can be obtained by applying a printing ink composition to a substrate using the printing method described above and fixing it by drying in an oven. The substrate may be subjected to a vapor deposition coating process for depositing a metal oxide or the like on the surface and / or a coating process for coating polyvinyl alcohol or the like. Furthermore, the substrate may be subjected to a surface treatment such as a corona treatment.
　印刷物に、ラミネート加工を施しエージングすれば、ラミネート積層体が得られる。ラミネート加工法としては、
　１）得られた印刷物の印刷面に、必要に応じてアンカーコート剤を塗布後、溶融樹脂を積層する押し出しラミネート法、
　２）接着剤を塗布後、必要に応じて乾燥させ、プラスチックフィルムを積層するドライラミネート法等が挙げられる。
　溶融樹脂としては、例えば、低密度ポリエチレン、ポリプロピレン、エチレン－酢酸ビニル共重合体等が使用できる。接着剤としては、例えば、イミン系、イソシアネート系、ポリブタジエン系、チタネート系等が挙げられる。 If the printed material is laminated and aged, a laminated laminate can be obtained. As a laminating method,
1) An extrusion laminating method in which a molten resin is laminated after applying an anchor coating agent to the printed surface of the obtained printed matter, if necessary.
2) A dry laminating method in which a plastic film is laminated after applying an adhesive and then dried as necessary.
As the molten resin, for example, low density polyethylene, polypropylene, ethylene-vinyl acetate copolymer and the like can be used. Examples of the adhesive include imine, isocyanate, polybutadiene, and titanate.
　以下、実施例を挙げて本発明の実施形態を詳細に説明するが、本発明はこれら実施例に限定されるものではない。以下、「部」および「％」は、特に注釈の無い場合、それぞれ「重量部」および「重量％」を表す。 Hereinafter, embodiments of the present invention will be described in detail with reference to examples, but the present invention is not limited to these examples. Hereinafter, “parts” and “%” represent “parts by weight” and “% by weight”, respectively, unless otherwise specified.
　なお、水酸基価は、樹脂中の水酸基を過剰のアセチル化試薬にてアセチル化し、残存する酸をアルカリで逆滴定して算出した樹脂１ｇ中の水酸基量を、水酸化カリウムのｍｇ数に換算した値で、ＪＩＳ Ｋ００７０に従って行った値である。アミン価は、樹脂１ｇ中に含有するアミノ基を中和するのに必要とする塩酸の当量と同量の水酸化カリウムのｍｇ数である。酸価は、樹脂１ｇ中に含有する酸基を中和するのに必要とする水酸化カリウムのｍｇ数で、測定方法は既知の方法でよく、一般的にはＪＩＳ Ｋ００７０（１９９６年）に準じて行われる。分子量はＧＰＣ（ゲルパーミエーションクロマトグラフィー）装置を用いて分子量分布を測定し、ポリスチレン換算分子量として求めた。アミン価の測定方法は、下記の通りである。 The hydroxyl value was acetylated with an excess of an acetylating reagent and the amount of hydroxyl group in 1 g of resin calculated by back titrating the remaining acid with alkali was converted to mg of potassium hydroxide. This is a value obtained according to JIS K0070. The amine value is the number of mg of potassium hydroxide equivalent to the equivalent amount of hydrochloric acid required to neutralize the amino group contained in 1 g of resin. The acid value is the number of mg of potassium hydroxide required to neutralize the acid group contained in 1 g of resin, and the measuring method may be a known method, generally according to JIS K0070 (1996). Done. The molecular weight was determined as a polystyrene-converted molecular weight by measuring the molecular weight distribution using a GPC (gel permeation chromatography) apparatus. The method for measuring the amine value is as follows.
［アミン価の測定方法］
　試料を０．５～２ｇ精秤する。（試料量：Ｓｇ）精秤した試料に中性エタノール（ＢＤＧ中性）３０ｍＬを加え溶解させる。得られた溶液に指示薬としてブロモフェノールブルーを加え、０．２ｍｏｌ／Ｌエタノール性塩酸溶液（力価：ｆ）で滴定を行なう。溶液の色が、緑から黄の間の色に変化した点を終点とし、この時の滴定量（ＡｍＬ）を用い次の（式１）によりアミン価を求めた。 [Method for measuring amine value]
Weigh 0.5-2 g of sample accurately. (Sample amount: Sg) 30 mL of neutral ethanol (BDG neutral) is added to a precisely weighed sample and dissolved. Bromophenol blue is added to the obtained solution as an indicator, and titration is performed with a 0.2 mol / L ethanolic hydrochloric acid solution (titer: f). The point at which the color of the solution changed from green to yellow was taken as the end point, and the amine titer was determined by the following (Formula 1) using the titration amount (AmL) at this time.
計算式１
アミン価＝（Ａ×ｆ×０．２×５６．１０８）／Ｓ ［ｍｇＫＯＨ／ｇ］ Formula 1
Amine value = (A × f × 0.2 × 56.108) / S [mgKOH / g]
［合成例１］
　攪拌機、温度計、還流冷却器および窒素ガス導入管を備えた四つ口フラスコに、分子量２０００のＰＰＡ２０００（水酸基価５６．１ｍｇＫＯＨ／ｇ）１１１．９９部、分子量１０００のＰＰＧ１０００（水酸基価１１２．２ｍｇＫＯＨ／ｇ）１１１．９９部、トリレンジイソシアネート５２．６５部、２－エチルヘキサン酸スズ（II）０．０３部、酢酸エチル８２．５部を仕込み、窒素気流下に９０℃で３時間反応させ、末端イソシアネートプレポリマーの溶液３５９．１６部を得た。次いでイソホロンジアミン２１．７４部、モノエタノールアミン１．６４部、イソプロピルアルコール２９０部、酢酸エチル３２７．４７部を混合したものへ、得られた末端イソシアネートプレポリマーの溶剤溶液３５９．１６部を室温で徐々に添加し、次に５０℃で１時間反応させ、固形分３０．０％、重量平均分子量３００００、アミン価４．０ｍｇＫＯＨ／ｇのポリウレタン樹脂組成物（ＰＵ０１）を得た。 [Synthesis Example 1]
In a four-necked flask equipped with a stirrer, a thermometer, a reflux condenser and a nitrogen gas inlet tube, PPA2000 (hydroxyl value 56.1 mgKOH / g) with a molecular weight of 2000. / G) 111.99 parts, 52.65 parts of tolylene diisocyanate, 0.03 part of tin (II) 2-ethylhexanoate and 82.5 parts of ethyl acetate were allowed to react at 90 ° C. for 3 hours under a nitrogen stream. 359.16 parts of a terminal isocyanate prepolymer solution were obtained. Next, 359.16 parts of the solvent solution of the resulting terminal isocyanate prepolymer was mixed at room temperature with 21.74 parts of isophoronediamine, 1.64 parts of monoethanolamine, 290 parts of isopropyl alcohol, and 327.47 parts of ethyl acetate. The mixture was gradually added and then reacted at 50 ° C. for 1 hour to obtain a polyurethane resin composition (PU01) having a solid content of 30.0%, a weight average molecular weight of 30000, and an amine value of 4.0 mgKOH / g.
［合成例２～２６］
　表１～３の仕込み比にて、合成例１と同様の操作で、ポリウレタン樹脂組成物（ＰＵ０２～ＰＵ２６）を得た。 [Synthesis Examples 2 to 26]
Polyurethane resin compositions (PU02 to PU26) were obtained in the same manner as in Synthesis Example 1 with the charging ratios shown in Tables 1 to 3.
［実施例１］
　酸化チタン（ＴＩＴＯＮＥ Ｒ４５Ｍ 堺化学製）３０．００部、ポリウレタン樹脂組成物（ＰＵ０１）１０．００部、酢酸エチル／イソプロピルアルコール混合溶剤（重量比７０／３０）１０．００部を撹拌混合しサンドミルで練肉した。さらに、ポリウレタン樹脂組成物（ＰＵ０１）４０．００部、酢酸エチル／イソプロピルアルコール混合溶剤（重量比７０／３０）１０．００部を加えて攪拌混合し、白色印刷インキ組成物（Ｗ０１）を得た。さらに、この白色印刷インキ組成物１００．００部に、重量比で酢酸エチル／イソプロピルアルコール＝８５／１５の希釈溶剤１、または酢酸エチル／イソプロピルアルコール＝５０／５０の希釈溶剤２を、それぞれ４０．００部混合し、評価用の白色希釈印刷インキ１および白色希釈印刷インキ２とした。 [Example 1]
30.00 parts of titanium oxide (TITONE R45M manufactured by Sakai Chemical Co., Ltd.), 10.00 parts of polyurethane resin composition (PU01), 10.00 parts of ethyl acetate / isopropyl alcohol mixed solvent (weight ratio 70/30) were stirred and mixed in a sand mill. I kneaded the meat. Furthermore, 40.00 parts of polyurethane resin composition (PU01) and 10.00 parts of ethyl acetate / isopropyl alcohol mixed solvent (weight ratio 70/30) were added and mixed by stirring to obtain a white printing ink composition (W01). . Further, 100.00 parts of this white printing ink composition was diluted with 40% of dilution solvent 1 of ethyl acetate / isopropyl alcohol = 85/15 or dilution solvent 2 of ethyl acetate / isopropyl alcohol = 50/50, respectively, in a weight ratio. 00 parts were mixed to obtain white diluted printing ink 1 and white diluted printing ink 2 for evaluation.
［実施例２～１８］［比較例１～８］
　ポリウレタン樹脂組成物（ＰＵ０１）をそれぞれポリウレタン樹脂組成物（ＰＵ０２）～（ＰＵ２６）に変更した以外は、実施例１と同様の操作で、白色印刷インキ組成物（Ｗ０２～２６）を得た。なお、各々の印刷インキ組成物に用いるポリウレタン樹脂組成物は表４～６の通りである。また、実施例１と同様の操作で、得られた白色印刷インキ組成物１００．００部に、重量比で酢酸エチル／イソプロピルアルコール＝８５／１５の希釈溶剤１、または酢酸エチル／イソプロピルアルコール＝５０／５０の希釈溶剤２を、それぞれ４０．００部混合し、評価用の白色希釈印刷インキ１および白色希釈印刷インキ２とした。 [Examples 2 to 18] [Comparative Examples 1 to 8]
White printing ink compositions (W02 to 26) were obtained in the same manner as in Example 1, except that the polyurethane resin composition (PU01) was changed to polyurethane resin compositions (PU02) to (PU26), respectively. The polyurethane resin compositions used for each printing ink composition are shown in Tables 4-6. Further, by the same operation as in Example 1, 100.00 parts of the obtained white printing ink composition was diluted with a diluent 1 having a weight ratio of ethyl acetate / isopropyl alcohol = 85/15, or ethyl acetate / isopropyl alcohol = 50. 40.00 parts each of / 50 dilution solvent 2 was mixed to obtain white diluted printing ink 1 and white diluted printing ink 2 for evaluation.
　なお合成例及び実施例において下記の原料を用いた。
ＰＰＡ２０００：ポリ（１，２－プロピレンアジペート）ジオール（数平均分子量２０００）
ＮＰＧ２０００：ポリ（ネオペンチルアジペート）ジオール（数平均分子量２０００）
ＰＭＰＡ２０００：ポリ（３－メチル－１，５－ペンタンアジペート）ジオール（数平均分子量２０００）
ＰＰＧ１０００：ポリ（１，２－プロピレングリコール）（数平均分子量１０００）
ＴＤＩ：トリレンジイソシアネート
ＩＰＤＩ：イソホロンジイソシアネート
ＭＤＩ：ジフェニルメタンジイソシアネート
ＩＰＤＡ：イソホロンジアミン
ＭＥＡ：モノエタノールアミン
ＤＥＡ：ジエタノールアミン
ＤＢＡ：ジ－ｎ－ブチルアミン
ＩＰＡ：イソプロピルアルコール
ＨＤＡ：ヘキサメチレンジアミン
ＡＥＡ：２－ヒドロキシエチルエチレンジアミン In the synthesis examples and examples, the following raw materials were used.
PPA2000: poly (1,2-propylene adipate) diol (number average molecular weight 2000)
NPG2000: poly (neopentyl adipate) diol (number average molecular weight 2000)
PMPA2000: poly (3-methyl-1,5-pentaneadipate) diol (number average molecular weight 2000)
PPG1000: poly (1,2-propylene glycol) (number average molecular weight 1000)
TDI: tolylene diisocyanate IPDI: isophorone diisocyanate MDI: diphenylmethane diisocyanate IPDA: isophoronediamine MEA: monoethanolamine DEA: diethanolamine DBA: di-n-butylamine IPA: isopropyl alcohol HDA: hexamethylenediamine AEA: 2-hydroxyethylethylenediamine
［版かぶり性］
　ＮＢＲ（ニトリルブタジエンゴム）製のゴム硬度８０Ｈｓの圧胴、刃先の厚みが６０μｍ（母材の厚み４０μｍ、片側セラミック層の厚み１０μｍ）のセラミックメッキドクターブレード、東洋プリプレス株式会社製のクロム硬度１０５０Ｈｖの電子彫刻版（スタイラス角度１２０度、２００線／ｉｎｃｈ）の富士機械工業株式会社製グラビア印刷機に、白色希釈印刷インキ１または白色希釈印刷インキ２をセットした。次に、ドクター圧２ｋｇ／ｃｍ２、１００ｍ／分の回転速度で空転を６０分行った後、片面コロナ処理ＯＰＰフィルム「パイレンＰ－２１６１（東洋紡績株式会社製）」のコロナ処理面に、印刷速度１００ｍ／分、印圧２ｋｇ／ｃｍ２にて印刷し、６０℃の熱風で乾燥して、印刷物を得た。この印刷物を黒色の紙の上に貼り、余白部分（非画線部）に付着したインキの量を以下の基準で目視評価した。
◎ ：非画像部にインキの転移が全く認められなかった。
○ ：非画像部にインキの転移が僅かに認められた。
○△：非画像部の小面積にインキの転移が認められた。これ以上実用レベルである。
△ ：非画像部の大面積にインキの転移が認められた。
△× ：非画像部のほぼ全面にインキの転移が認められた。
　　　（△と×の中間程度の転移量である）
× ：非画像部全面にインキの転移が認められた。 [Plate fog]
An NBR (nitrile butadiene rubber) impression cylinder having a hardness of 80 Hs, a blade thickness of 60 μm (base material thickness of 40 μm, one side ceramic layer thickness of 10 μm), a chromium hardness of 1050 Hv manufactured by Toyo Prepress Co., Ltd. White diluted printing ink 1 or white diluted printing ink 2 was set on a gravure printing machine manufactured by Fuji Machine Industry Co., Ltd. with an electronic engraving plate (stylus angle 120 °, 200 lines / inch). Next, after idling for 60 minutes at a doctor pressure of 2 kg / cm 2 and a rotation speed of 100 m / min, printing is performed on the corona-treated surface of a single-sided corona-treated OPP film “Pyrene P-2161 (manufactured by Toyobo Co., Ltd.)”. Printing was performed at a speed of 100 m / min and a printing pressure of 2 kg / cm 2 and dried with hot air at 60 ° C. to obtain a printed matter. This printed matter was pasted on black paper, and the amount of ink attached to the blank portion (non-image area) was visually evaluated according to the following criteria.
A: No ink transfer was observed in the non-image area.
○: Slight ink transfer was observed in the non-image area.
○ Δ: Ink transfer was observed in a small area of the non-image area. More practical than that.
Δ: Ink transfer was observed in a large area of the non-image area.
Δ ×: Ink transfer was observed on almost the entire non-image area.
(The amount of transition is between △ and ×)
X: Ink transfer was observed over the entire non-image area.
［耐ブロッキング性］
　白色希釈印刷インキ１を、版深３５μｍグラビア版を備えたグラビア校正機によるコロナ処理ＯＰＰフィルム（太閤ＦＯＲ フタムラ ＃２０）に印刷して４０～５０℃で乾燥し、印刷物を得た。この印刷物を４ｃｍ×４ｃｍにサンプリングし、このサンプルの印刷面と同じ大きさの未印刷フィルムの非処理面とを合わせて、５０℃１２時間、１０ｋｇｆの加圧を行い、サンプルを剥離した時の、インキ取られ（インキの転移）及び抵抗感を観察した。
◎ ：印刷物からインキの転移が全く認められず、剥離時の抵抗感もなかった。
○ ：印刷物からインキの転移が全く認められなかったが、剥離時の抵抗感があった。
○△：印刷物からインキの転移が認められたが、面積にして１０％未満であった。
これ以上実用レベルである。
△ ：印刷物からインキの転移が、１０％以上５０％未満の面積で認められた。
× ：印刷物からインキの転移が、５０％以上の面積で認められた。 [Blocking resistance]
The white diluted printing ink 1 was printed on a corona-treated OPP film (Taiko FOR-Futamura # 20) by a gravure proofing machine equipped with a gravure plate having a plate depth of 35 μm and dried at 40 to 50 ° C. to obtain a printed matter. This printed matter was sampled to 4 cm × 4 cm, and the unprinted surface of the unprinted film having the same size as the printed surface of this sample was combined and pressurized at 50 ° C. for 12 hours and 10 kgf, and the sample was peeled off. The ink was removed (ink transfer) and the resistance was observed.
A: Ink transfer from the printed matter was not observed at all, and there was no resistance when peeled.
○: No transfer of ink was observed from the printed matter, but there was a feeling of resistance during peeling.
◯: Ink transfer was observed from the printed matter, but the area was less than 10%.
More practical than that.
Δ: Ink transfer from the printed material was observed in an area of 10% or more and less than 50%.
X: Ink transfer from the printed matter was observed in an area of 50% or more.
［接着性］
　耐ブロッキング性試験で得た印刷物にセロハンテープ（ニチバン製、幅１２ｍｍ）を貼り付け、親指で５回強く擦った後、セロハンテープを徐々に引き離し、途中から急激に引き離してインキ皮膜の剥離の程度を調べた。
◎ ：ゆっくり引き離しても、急激に引き離しても、全くインキの剥離が認められない。
○ ：ゆっくり引き離しても全くインキの剥離は認められないが、急激に引き離すとインキの剥離が２０％未満の面積で認められた。これ以上実用レベルである。
△ ：ゆっくり引き離してもインキの剥離は認められないが、急激に引き離すとインキの剥離が２０％以上の面積で認められた。
△×：ゆっくり引き離しても５０％程度までの面積のインキの剥離が認められた。
× ：ゆっくり引き離してもほとんどのインキの剥離が認められた。 [Adhesiveness]
Attaching cellophane tape (Nichiban, width 12 mm) to the printed matter obtained in the anti-blocking test, rubbing it strongly with the thumb 5 times, then gradually separating the cellophane tape, and then suddenly separating from the middle, the degree of peeling of the ink film I investigated.
A: No peeling of ink was observed even when pulled apart slowly or suddenly.
○: No peeling of the ink was observed even when it was slowly pulled away, but peeling of the ink was recognized in an area of less than 20% when pulled away rapidly. More practical than that.
Δ: Ink peeling was not observed even when pulled slowly, but ink peeling was observed in an area of 20% or more when pulled away abruptly.
Δ ×: Ink peeling with an area of up to about 50% was observed even when slowly separated.
X: Most ink peeling was recognized even if it pulled away slowly.
［耐アルコールブリード性］
　白色希釈印刷インキ１を、版深３５μｍグラビア版を備えたグラビア校正機により、コロナ処理ＯＰＰフィルム（太閤ＦＯＲ フタムラ ＃２０）に印刷して、４０～５０℃で乾燥し、次いでインラインにてイソプロピルアルコールを塗工、４０～５０℃で乾燥し、ブリード痕の跡など外観を観察した。
◎ ：印刷物に外観不良の発生はなかった。
○ ：印刷物に若干むらが認められた。これ以上実用レベルである。
△ ：印刷物に薄くブリード痕が認められた。
× ：印刷物にはっきりブリード痕が認められた。 [Alcohol bleed resistance]
White diluted printing ink 1 is printed on a corona-treated OPP film (Taiko FOR Futamura # 20) by a gravure proofing machine equipped with a 35 μm gravure printing plate, dried at 40-50 ° C., and then in-line isopropyl alcohol The film was coated and dried at 40 to 50 ° C., and the appearance such as bleed marks was observed.
A: There was no appearance defect on the printed matter.
○: Some unevenness was observed in the printed matter. More practical than that.
Δ: A thin bleed mark was observed on the printed matter.
X: Bleed marks were clearly observed on the printed matter.
［ＥＬラミネート強度］
　版かぶり性試験の印刷条件で、白色希釈印刷インキ１を、基材のコロナ処理面に印刷し、印刷物を得た。ここで用いた基材は、片面コロナ処理で厚み２０μｍのポリプロピレン（以下、ＯＰＰとする。）フィルム「パイレンＰ－２１６１（東洋紡績株式会社製）」、及び片面コロナ処理で厚み１２μｍのポリエチレンテレフタレート（以下、ＰＥＴとする。）フィルム「東洋紡エステルフィルムＥ５１００（東洋紡績株式会社製）」である。次に、印刷面上に、ポリエチレンイミン系アンカーコート剤「オリバインＥＬ－４２０」（東洋モートン株式会社製、商品名）を塗布した。さらに、塗布面上にシーラントとして低密度ポリエチレン「ノバテックＬＣ６００」（日本ポリケム株式会社製、商品名）の溶融温度を３１５℃にて押し出し、ラミネート加工物を得た。つまり、（Ｅｘｔｒｕｓｉｏｎ ｌａｍｉｎａｔｅ（ＥＬ））により、ラミネート加工物を得た。低密度ポリエチレンの溶融温度は、押し出しラミネート機のＴダイ直下における温度を接触式温度計（安立計器株式会社製ＨＬ－１００）にて測定した。該ラミネート加工物におけるインキ部を巾１５ｍｍで裁断し、インキ面と溶融樹脂層の層間で剥離させた後、剥離強度をインテスコ製２０１万能引張り試験機にて剥離強度の測定を行った。なお、ＯＰＰを用いたラミネート加工物（ＯＰＰ／イミン構成）では１．０Ｎ／１５ｍｍ以上、ＰＥＴを用いたラミネート加工物（ＰＥＴ／イミン構成）では１．５Ｎ／１５ｍｍ以上を実用レベルとする。 [EL laminate strength]
The white diluted printing ink 1 was printed on the corona-treated surface of the substrate under the printing conditions of the plate fog test to obtain a printed matter. The base material used here is a polypropylene (hereinafter referred to as OPP) film having a thickness of 20 μm by single-sided corona treatment, “Pyrene P-2161 (manufactured by Toyobo Co., Ltd.)”, and polyethylene terephthalate having a thickness of 12 μm by single-sided corona treatment. Hereinafter referred to as PET.) A film “Toyobo Ester Film E5100 (manufactured by Toyobo Co., Ltd.)”. Next, a polyethyleneimine-based anchor coating agent “Olivein EL-420” (trade name, manufactured by Toyo Morton Co., Ltd.) was applied on the printed surface. Furthermore, the melt temperature of low density polyethylene “NOVATEC LC600” (manufactured by Nippon Polychem Co., Ltd., trade name) as a sealant was extruded on the coated surface at 315 ° C. to obtain a laminated product. That is, a laminate processed product was obtained by (Extension lamination (EL)). The melting temperature of the low density polyethylene was measured with a contact thermometer (HL-100, manufactured by Anritsu Keiki Co., Ltd.) at a temperature immediately below the T die of the extrusion laminating machine. The ink part in the laminated product was cut at a width of 15 mm and peeled between the ink surface and the molten resin layer, and the peel strength was measured with an Intesco 2.01 million tensile tester. It should be noted that a laminated product using OPP (OPP / imine structure) is 1.0 N / 15 mm or more, and a laminated product using PET (PET / imine structure) is 1.5 N / 15 mm or more.
　評価結果を表４～６にまとめる。実施例１～１８の印刷インキは、比較例１～８の印刷インキ組成物と比較し、エステル／アルコール溶剤系において優れた版かぶり性等の印刷適性を示し、かつ耐ブロッキング性、接着性、耐アルコールブリード性、さらにラミネート適性等の印刷物性を確保できる、印刷インキ組成物を提供することができる。 The evaluation results are summarized in Tables 4-6. The printing inks of Examples 1 to 18 showed excellent printability such as plate fog in an ester / alcohol solvent system as compared with the printing ink compositions of Comparative Examples 1 to 8, and anti-blocking property, adhesiveness, It is possible to provide a printing ink composition that can ensure printing property such as alcohol bleeding resistance and suitability for lamination.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000006
Figure JPOXMLDOC01-appb-T000006

Claims (3)

  1. 　トリレンジイソシアネートを含むポリイソシアネートと高分子ポリオールとを反応させてなる末端にイソシアネート基を有するウレタンプレポリマーを、有機ジアミンおよびアルカノールアミンと反応させてなるポリウレタン樹脂、
    並びに混合溶剤を含むポリウレタン樹脂組成物であって、
    　下記の（Ａ）～（Ｆ）であることを特徴とするポリウレタン樹脂組成物。
    （Ａ）ポリイソシアネートの全イソシアネート基と高分子ポリオールの水酸基との反応におけるモル比［ＮＣＯ（全）］／［ＯＨ］が、１．８～２．３である。
    （Ｂ）トリレンジイソシアネートのイソシアネート基と高分子ポリオールの水酸基との反応におけるモル比［ＮＣＯ（ＴＤＩ）］／［ＯＨ］が、１．０～２．１である。
    （Ｃ）ポリウレタン樹脂の水酸基価が１．０～１０．０ｍｇＫＯＨ／ｇである。
    （Ｄ）有機ジアミンのモル数ｄ１とアルカノールアミンのモル数ｄ２とのモル比ｄ１／ｄ２が、３～２５である。
    （Ｅ）混合溶剤が、エステル系溶剤とアルコール系溶剤とを含む。
    （Ｆ）高分子ポリオールが、ポリエステルジオールとポリエーテルジオールとからなる。     A polyurethane resin obtained by reacting a urethane prepolymer having an isocyanate group at a terminal obtained by reacting a polyisocyanate containing tolylene diisocyanate and a polymer polyol with an organic diamine and an alkanolamine,
    A polyurethane resin composition comprising a mixed solvent,
    A polyurethane resin composition comprising the following (A) to (F):
    (A) The molar ratio [NCO (total)] / [OH] in the reaction of all isocyanate groups of the polyisocyanate and hydroxyl groups of the polymer polyol is 1.8 to 2.3.
    (B) The molar ratio [NCO (TDI)] / [OH] in the reaction between the isocyanate group of tolylene diisocyanate and the hydroxyl group of the polymer polyol is 1.0 to 2.1.
    (C) The hydroxyl value of the polyurethane resin is 1.0 to 10.0 mgKOH / g.
    (D) The molar ratio d1 / d2 between the number of moles d1 of the organic diamine and the number of moles d2 of the alkanolamine is 3 to 25.
    (E) The mixed solvent includes an ester solvent and an alcohol solvent.
    (F) The polymer polyol is composed of a polyester diol and a polyether diol.
  2. 　　高分子ポリオール中、前記ポリエステルジオールが２０～８０重量％、前記ポリエーテルジオールが８０～２０重量％であることを特徴とする請求項１記載のポリウレタン樹脂組成物。 2. The polyurethane resin composition according to claim 1, wherein the polyester diol is 20 to 80% by weight and the polyether diol is 80 to 20% by weight in the polymer polyol.
  3. 　請求項１または２記載のポリウレタン樹脂組成物を含有することを特徴とする印刷インキ組成物。 A printing ink composition comprising the polyurethane resin composition according to claim 1 or 2.
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JP2015199816A (en) * 2014-04-08 2015-11-12 東洋インキＳｃホールディングス株式会社 PTP packaging ink composition and laminate
JP2016094548A (en) * 2014-11-14 2016-05-26 サカタインクス株式会社 High solid ink composition for organic solvent gravure printing and gravure printing method
WO2018212011A1 (en) * 2017-05-16 2018-11-22 Ｄｉｃグラフィックス株式会社 Liquid ink composition, printed matter, and laminate stack
JPWO2018212011A1 (en) * 2017-05-16 2019-06-27 Ｄｉｃグラフィックス株式会社 Liquid ink composition, printed matter and laminate laminate

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KR101588234B1 (en) 2016-01-25
PH12014502125B1 (en) 2014-12-10
JP2013227465A (en) 2013-11-07
SG11201406055SA (en) 2014-11-27
MY169259A (en) 2019-03-19
PH12014502125A1 (en) 2014-12-10
JP5130553B1 (en) 2013-01-30
CN104204020A (en) 2014-12-10
KR20140139566A (en) 2014-12-05

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