CN104204020B - Polyurethane for printing ink binder resin combination - Google Patents

Polyurethane for printing ink binder resin combination Download PDF

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Publication number
CN104204020B
CN104204020B CN201380016733.8A CN201380016733A CN104204020B CN 104204020 B CN104204020 B CN 104204020B CN 201380016733 A CN201380016733 A CN 201380016733A CN 104204020 B CN104204020 B CN 104204020B
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China
Prior art keywords
printing
ink
urethane resin
solvent
resin composition
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CN201380016733.8A
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CN104204020A (en
Inventor
中川知子
志鹰基
小藤通久
野村雄史
幡野佑悟
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Toyo Ink Co Ltd
Artience Co Ltd
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Toyo Ink SC Holdings Co Ltd
Toyo Ink Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • 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
    • C08G18/08—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
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • 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
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    • 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
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    • 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
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    • 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
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    • 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
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • 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
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    • 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
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    • 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
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    • 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
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    • 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
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    • 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
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    • 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
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/03—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

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

Abstract

The invention provides a kind of polyurethane resin composition, it comprises: urethane resin and the mixed solvent containing ester series solvent and alcohol, this urethane resin is: the polyisocyanates and macromolecule polyol by making to comprise tolylene diisocyanate is carried out the carbamate prepolymer at end with isocyanate group reacted, react with organic diamine and alkanolamine further, control [NCO (all)]/[OH] and [NCO (TDI)]/[OH], the hydroxyl value of urethane resin, the ratio of organic diamine and alkanolamine and the urethane resin obtained.

Description

Polyurethane for printing ink binder resin combination
Technical field
The present invention relates to polyurethane resin composition and printing ink composition.
Background technology
All the time, as the solvent used in printing-ink, list the solvent of the stronger fragrant family of the dissolving power such as toluene and dimethylbenzene and the solvent of the ketone such as methylethylketone and methyl iso-butyl ketone (MIBK) system.But in recent years, from environmental preservation and the regulation aspect of earth scale, printing-ink industry is also required to consider environmental problem.Therefore, people expect and develop a kind of printing-ink eliminating the use ester/alcoholic solvent system of these aromatic series series solvents and ketone series solvent.Therefore, the printing-ink of a kind of ester/alcoholic solvent system being is is being researched and developed.But Comparatively speaking dissolving power is low for the solvent of ester/alcoholic solvent system and fragrant family and ketone system, and thus printing adaptability is poor.In addition, when improving the dissolving power of ester/alcoholic solvent, then other poor properties such as exudative, the resistance to adhesive of resistance to alcohol, problem is still many.
Such as, disclose in Japanese Unexamined Patent Publication 9-316156 publication, the polyurethane resin composition and the printing ink composition that employ '-diphenylmethane diisocyanate have excellent cementability for various plastic film.But, in these compositions, include the methylethylketone that requirement is got rid of in order to ensure printing adaptability.In addition, because [NCO]/[OH] is than low, thus in resistance to adhesive, also there is problem.
In addition, disclose in Japanese Unexamined Patent Publication 2003-221539 publication, containing ester/alcoholic solvent system in ink, improve the deliquescent research in ester/alcoholic solvent system.But, owing to the addition of hydroxycarboxylic acid in ink, thus produce the problem of residual solvent, in addition, water tolerance and the exudative difference of resistance to alcohol.
Prior art document
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 9-316156 publication
Patent documentation 2: Japanese Unexamined Patent Publication 2003-221539 publication
Summary of the invention
The problem solved is wanted in invention
The object of the present invention is to provide a kind of printing ink composition eliminating the aromatic organic solvent such as toluene and dimethylbenzene and the ketone such as methylethylketone and methyl iso-butyl ketone (MIBK) system organic solvent.In addition, the object of the present invention is to provide a kind of printing ink composition, it contains ester/alcoholic solvent system, there is the printing adaptabilities such as excellent forme albefaction (version か ぶ り), and also have the printing physical property such as the exudative and lamination physical property of cementability excellent for various plastic film, resistance to adhesive, resistance to alcohol concurrently.
For solving the method for problem
The present inventor etc. conduct in-depth research repeatedly in view of status, found that the following fact, to such an extent as to complete the present invention:
By using a kind of urethane resin, even if thus use the more weak ester/alcoholic solvent system of dissolving power, also can design the printing ink composition that can realize taking into account excellent printing adaptability and printing physical property; Described urethane resin comprises the polyisocyanates of tolylene diisocyanate and the alkanolamine as reaction terminating agent by using, and control the urethane resin of synthetic parameters.
First embodiment of the present invention relates to a kind of polyurethane resin composition, it is characterized in that, it is the polyurethane resin composition comprising urethane resin and mixed solvent, described urethane resin is the carbamate prepolymer at end with the isocyanate group polyisocyanates by making to comprise tolylene diisocyanate and macromolecule polyol being carried out reacting, the urethane resin that reacts is carried out with organic diamine and alkanolamine
Described polyurethane resin composition meets following (A) ~ (F).
(A) whole isocyanate group of polyisocyanates and hydroxyl mol ratio in the reaction [NCO (all)]/[OH] of macromolecule polyol are 1.8 ~ 2.3.
(B) isocyanate group of tolylene diisocyanate and hydroxyl mol ratio in the reaction [NCO (TDI)]/[OH] of macromolecule polyol are 1.0 ~ 2.1.
(C) hydroxyl value of urethane resin is 1.0 ~ 10.0mgKOH/g.
(D) the mol ratio d1/d2 of the mole number d1 of organic diamine and the mole number d2 of alkanolamine is 3 ~ 25.
(E) mixed solvent comprises ester series solvent and alcohol series solvent.
(F) macromolecule polyol comprises polyester glycol and polyether glycol.
Then, the second embodiment relates to a kind of polyurethane resin composition, it is characterized in that, in macromolecule polyol, previous polyesters glycol is 20 ~ 80 % by weight, and foregoing polyethers glycol is 80 ~ 20 % by weight.
Further, the 3rd embodiment relates to a kind of printing ink composition, it is characterized in that, the polyurethane resin composition containing the first or second embodiment.
The effect of invention
According to the present embodiment, even if use ester/alcoholic solvent system, a kind of printing ink composition possessing the printing physical property of excellent printing adaptability and excellence also can be provided.
Embodiment
Below, polyurethane for printing ink binder resin combination is described.About urethane resin, polyisocyanates and macromolecule polyol by making to comprise tolylene diisocyanate being carried out the carbamate prepolymer at end with isocyanate group reacted, carrying out reacting thus obtaining with the organic diamine as chainextender and the alkanolamine as reaction terminating agent.
For in the urethane resin of printing ink binder, when considering the dissolving power taken into account in ester/alcoholic solvent and the various printing physical property relative to various plastic film, what become important factor is the polyisocyanates of hard segment forming amino-formate bond, urea key.
In the present embodiment, the polyisocyanates used in urethane resin comprises tolylene diisocyanate (below, also can be expressed as TDI sometimes.)。Tolylene diisocyanate is preferably 2,4 toluene diisocyanate or 2,6-tolylene diisocyanate, also can be their mixture.
Tolylene diisocyanate owing to having an aromatic ring in molecule, thus compared with aliphatic isocyanates and alicyclic isocyanate, higher to the tolerance of alcohol.On the other hand, with as have two aromatic rings aromatic isocyanate '-diphenylmethane diisocyanate compared with, the aromatic ring of tolylene diisocyanate is one, and the dissolving power thus in ester/alcoholic solvent system is high.Therefore, tolylene diisocyanate, in the printing ink composition of ester/alcoholic solvent system, easily obtains printing adaptability and the exudative balances of resistance to alcohol such as forme albefaction.
In the present embodiment, during synthesis of carbamates prepolymer, [NCO (all)]/[OH] as the molar ratio of whole isocyanate group of whole polyisocyanates and the hydroxyl of macromolecule polyol is in the scope of 1.8 ~ 2.3.When [NCO (all)]/[OH] is more than 1.8, then hard segment Binding number is abundant, and resistance to adhesive, the exudative excellence of resistance to alcohol.When less than 2.3, then forme albefaction is excellent, and hard segment Binding number is appropriateness in addition, thus cementability, EL lamination strength excellence.
In the present embodiment, the scope of 1.0 ~ 2.1 is in as [NCO (TDI)]/[OH] of the isocyanate group of tolylene diisocyanate and the hydroxyl molar ratio in the reaction of macromolecule polyol.Generally speaking, aromatic isocyanate is compared with aliphatic isocyanates, alicyclic isocyanate, fast with the speed of response of hydroxyl, amino.Therefore, when [NCO (TDI)]/[OH] is less than 2.1, then speed of response is appropriateness, thus can synthesize uniform urethane resin.Further, intramolecular aromatic ring concentration is appropriateness, and thus forme albefaction is excellent.In addition, when [NCO (TDI)]/[OH] is more than 1.0, then the exudative excellence of resistance to alcohol.
Be explained, meet above-mentioned [NCO (all)]/[OH] and the scope of [NCO (TDI)]/[OH] if be in, then except tolylene diisocyanate also can and with other polyisocyanates.As other polyisocyanates, list normally used various known aliphatic isocyanates, alicyclic isocyanate in the manufacture of urethane resin.Such as, list butane-1, 4-vulcabond, hexamethylene diisocyanate, isopropylidene vulcabond, methylene diisocyanate, 2, 2, 4-trimethyl hexamethylene diisocyanate, lysinediisocyanate, hexanaphthene-1, 4-vulcabond, isophorone diisocyanate, dimer (fatty acid) yl diisocyanate (dimeryldiisocyanate), double-hexyl methane-4, 4 '-vulcabond, 1, two (isocyanatomethyl) hexanaphthene of 3-, methylcyclohexane diisocyanate, norcamphane vulcabond, and be the dipolymer vulcabond (dimerisocyanate) etc. that isocyanate group obtains by the converting carboxylate groups of dimeracid.Among other polyisocyanates, from the viewpoint of speed of response and the various physical property preferably isophorone diisocyanate of isocyanate group.
Further, in the mole number of whole isocyanate group 90 ~ 100% be tolylene diisocyanate and 10 ~ 0% for isophorone diisocyanate, resistance to alcohol is exudative excellent especially.In addition, similarly, in the mole number of whole isocyanate group 50 ~ 75% be tolylene diisocyanate and 50 ~ 25% for isophorone diisocyanate, and the solvent in printing ink composition contains the alcohol series solvent of more than 35% weight, forme albefaction is excellent especially.Be explained, the detailed content of mixed solvent contained in printing ink composition sees below.
Further, in order to obtain printing adaptability and the exudative balances of resistance to alcohol such as forme albefaction in ester/alcoholic solvent system, as important factor, the hydroxyl value of urethane resin is had.In the present embodiment, the hydroxyl value of urethane resin is 1.0 ~ 10.0mgKOH/g.When hydroxyl value is more than 1.0mgKOH/g, then cementability, EL lamination strength excellence, solvability is also significantly good in addition, and thus forme albefaction is excellent.When hydroxyl value is below 10.0mgKOH/g, then the exudative excellence of resistance to alcohol.
About the organic diamine as chainextender in present embodiment, such as, list quadrol, propylene diamine, hexanediamine, isophorone diamine, double-hexyl methane-4,4 '-diamines etc., list the amine that 2-hydroxyethylethylene diamine, 2-hydroxyethyl propylene diamine, 2-hydroxyethyl propylene diamine, two-2-hydroxyethylethylene diamine, two-2-hydroxy-ethylenediamines, two-2-hydroxyethyl propylene diamine, 2-hydroxy propylethylene diamine, two-2-hydroxy propylethylene diamine, two-2-hydroxy propylethylene diamine etc. have hydroxyl in molecule in addition.These chainextenders can be used alone or can be used in combination by two or more.Wherein, isophorone diamine is particularly preferably.
In the present embodiment, the mol ratio d1/d2 of the mole number d1 of the organic diamine of urethane resin and the mole number d2 of alkanolamine is 3 ~ 25.When d1/d2 is more than 3, then the exudative excellence of resistance to alcohol, the weight-average molecular weight of urethane resin is large in addition, and thus resistance to adhesive is also significantly good.When d1/d2 is less than 25, then cementability, EL lamination strength excellence, solvability is also significantly good in addition, and thus forme albefaction is excellent.
Be explained, when the use quantitative change as the alkanolamine of reaction terminating agent is many, then the weight-average molecular weight step-down of obtained urethane resin.In addition, owing to including hydroxyl in alkanolamine, when thus the use quantitative change of alkanolamine is many, then hydroxyl value becomes large.As alkanolamine, such as, list monoethanolamine, diethanolamine etc.They can be used alone or can be used in combination by two or more.Wherein, monoethanolamine is particularly preferably.
As macromolecule polyol, use various known polyester polyol and polyether glycol etc.Can use respectively a kind or also can and use two or more.As polyester polyol, such as, list: by ethylene glycol, 1,2-PD, 1,3-PD, 2 methyl isophthalic acids, 3 propylene glycol, 2 ethyl-2 butyl-1,3 propylene glycol, 1,3 butylene glycol, BDO, neopentyl glycol, pentanediol, 3-methyl isophthalic acid, 5 pentanediols, hexylene glycol, ethohexadiol, Isosorbide-5-Nitrae-butynediol, BDO, Diethylene Glycol, triethylene glycol, dipropylene glycol, glycerine, TriMethylolPropane(TMP), trimethylolethane, 1,2,6-hexanetriol, BT, sorbyl alcohol, saturated or the undersaturated low molecular polylol class such as tetramethylolmethane, with hexanodioic acid, phthalic acid, m-phthalic acid, terephthalic acid, toxilic acid, fumaric acid, succsinic acid, oxalic acid, propanedioic acid, pentanedioic acid, pimelic acid, suberic acid, nonane diacid, sebacic acid, trimellitic acid, the polycarboxylic acids such as Pyromellitic Acid or their acid anhydrides carry out dehydrating condensation or polymerization and the polyester polyols alcohols obtained, by by cyclic ester compounds, such as, polycaprolactone, poly-valerolactone, the polyester polyols alcohols etc. that lactone such as poly-(Beta-methyl-γ-valerolactones) is carried out ring-opening polymerization and obtained.As polyether glycol, such as, list polymkeric substance or the multipolymer of formaldehyde (methyleneoxide), oxyethane (ethyleneoxide), propylene oxide (propyleneoxide), tetrahydrofuran (THF) etc.In polyester polyol, in polyether glycol, all particularly preferably there is branched structure.
As macromolecule polyol, be preferably in polyester glycol be 20 ~ 80 % by weight scope and polyether glycol be 80 ~ 20 % by weight scope.When polyester glycol is below 80 % by weight, then forme albefaction is excellent.When polyether glycol is below 80 % by weight, then resistance to adhesive is excellent.
The amine value of the urethane resin in present embodiment is preferably 2.0 ~ 7.0mgKOH/g, is more preferably 3.0 ~ 6.0mgKOH/g.When amine value is more than 2.0mgKOH/g, then forme albefaction, cementability and EL lamination strength are excellent, and during below 7.0mgKOH/g, then resistance to adhesive is excellent.
The weight-average molecular weight of the urethane resin in present embodiment is preferably 10000 ~ 70000, is more preferably 15000 ~ 60000.When weight-average molecular weight is more than 10000, then resistance to adhesive is excellent, and thermotolerance is good in addition, and thus EL lamination strength is also excellent.When weight-average molecular weight is less than 70000, then forme albefaction, cementability and EL lamination strength are excellent.
The synthesis of the urethane resin in present embodiment manufactures by following prepolymer method.
1) macromolecule polyol and the temperature of the polyisocyanates comprising tolylene diisocyanate at 10 ~ 100 DEG C are reacted, be manufactured on the prepolymer that end has isocyanate group.When above-mentioned reaction, also can use as required for isocyanate group is inactive solvent.In addition, also polyurethane-reinforcement catalyzer can be used as required.
2) then, this prepolymer and the organic diamine as chainextender, the alkanolamine as reaction terminating agent are reacted at 10 ~ 80 DEG C and obtain urethane resin.
The solvent used in the polyurethane resin composition of present embodiment comprises the mixed solvent of ester series solvent and alcohol series solvent.As these solvents, preferably use following such known solvent.
As ester series solvent, such as, list ethyl acetate, n-propyl acetate, isopropyl acetate, isobutyl acetate, propylene glycol monoethyl ether acetate, propylene glycol methyl ether acetate etc.
As alcohol series solvent, list methyl alcohol, ethanol, n-propyl alcohol, Virahol, propyl carbinol, propylene glycol monoethyl, propylene glycol monomethyl ether etc.
Also catalyzer can be used in polyurethane-reinforcement reaction.As spendable catalyzer, such as, list the catalyzer of the tertiary amine such as triethylamine, xylidine system, the catalyzer etc. of the metal such as tin, zinc system.These catalyzer can use in the scope being 0.001 ~ 1 % by mole for polyvalent alcohol usually.
Also can using as reaction terminating agent alkanolamine with use together with the organic diamine of chainextender and carry out chain extending reaction.Or, also by chainextender to carry out chain extending reaction to a certain degree, then reaction terminating agent is added and stopped reaction individually.
In the printing ink composition of present embodiment, inorganic system tinting material and organic system tinting material can be used as tinting material.In white color agents, the titanium oxide of inorganic system tinting material can be used as, be more preferably the tinting material that surface of pigments is alkalescence.As inorganic system tinting material, beyond white color agents, also list the pigment such as carbon black, aluminium, mica (mica).Aluminium is powder or pasty state, but use from the viewpoint of treatability and the preferred of security with pasty state, about whether using floating (leafing) type or non-floating (non-leafing) type, suitably select from the viewpoint of brightness impression and concentration.On the other hand, as organic system tinting material, can enumerate and be used in pigment dyestuff in general ink, coating and recording agent etc. and organic dye.Such as list azo system, phthalocyanine system, anthraquinone Xi, perylene system, purple cyclic ketones (perinone) be, quinacridone, thioindigo (thioindigo) are, two piperazine system, isoindolinone (isoindolinone) are, quinophthalone system, azomethine azo system, pyrrolo-pyrrole-dione (diketo-pyrrolo-pyrrole) are, isoindoline system etc.
About tinting material, in order to ensure concentration, the tinting strength of printing-ink, preferably to measure fully, namely, the ratio being 1 ~ 50 % by weight relative to the gross weight of printing-ink comprises.In addition, these tinting materials can be used alone, or and use with two or more.
About the printing ink composition of present embodiment, by resin and tinting material etc. being dissolved and/or being scattered in organic solvent thus manufacturing.Specifically, manufacture the pigment dispersion by pigment and polyurethane resin composition and other compound are as required scattered in organic solvent and obtain, to in obtained pigment dispersion, further cooperation polyurethane resin composition and organic solvent and other compound as required, thus can ink be manufactured.
By urethane resin, pigment stabilizer is scattered in organic solvent, but in order to stably disperse further thus also can and use dispersion agent.As dispersion agent, the tensio-active agent of anionic property, nonionic, cationic, zwitter-ion etc. can be used.About dispersion agent, from the viewpoint of the storage stability of ink, relative to the gross weight of ink, be preferably contained in ink with more than 0.05 % by weight, and consider from the adaptive viewpoint of lamination, be preferably contained in ink with less than 5 % by weight.Further, more preferably with 0.1 ~ 2 % by weight scope and comprise.
About the size-grade distribution of the pigment in pigment dispersion, by suitably regulating the size of the crushing medium of dispersion machine, the filling ratio of crushing medium, dispersion treatment time, the velocity of discharge of pigment dispersion, the viscosity etc. of pigment dispersion, thus adjustment.As dispersion machine, the such as roller mill, ball mill, pebble mill (pebblemill), masher (attritor), sand mill etc. that usually use can be used.
The solvent used in the printing ink composition of present embodiment is the mixed solvent of ester series solvent and alcohol series solvent.As ester series solvent and alcohol series solvent, preferably use known solvent, object lesson is as shown in aforementioned.
In ink, comprising bubble, when not comprising big particle etc. with being contemplated to, in order to reduce the quality of print, thus removing preferably by filtration waits.Strainer can use always known strainer.
About the viscosity of the ink manufactured by preceding method, from the viewpoint of preventing the sedimentation of pigment, moderately disperseing the scope of preferably more than 10mPas, when manufacturing from the viewpoint of ink, printing time the scope of workability efficiency preferably below 1000mPas.Be explained, above-mentioned viscosity is the viscosity utilizing Tokimec Inc. Brookfield viscometer to obtain 25 DEG C of mensuration.
Printing ink composition can use in the known mode of printing such as intaglio printing, flexible printing.Such as, when for intaglio printing, with diluting solvent dilution until be suitable for viscosity and the concentration of intaglio printing, be supplied in each printing element individually or mixedly.Be preferably intaglio printing.
As the base material of applicable printing ink composition, such as list the base material comprising the membranaceous of following material or sheet, described material is: polystyrene resin, nylon, polymeric amide, polyvinyl chloride, polyvinylidene dichloride, cellulose film, paper, aluminium etc. or their matrix materials such as the polyester such as the polyolefine such as polyethylene, polypropylene, polyethylene terephthalate, polycarbonate, poly(lactic acid), polystyrene, AS resin, ABS resin.By using above-mentioned mode of printing coating and printing ink composite on base material, utilize baking oven carry out drying and fix, thus obtain print.For base material, the coating process evaporation of the evaporations such as metal oxide in surface being coated with process and/or pva coating etc. also can be implemented.Also the surface treatments such as corona treatment can be implemented to base material further.
If implement lamination process and slaking to print, then can obtain lamination duplexer.As lamination process method, list:
1) at the printing surface of obtained print, tackifier (anchorcoatagent) are coated with as required, then by extruding layer platen press stacked for molten resin,
2) coating adhesive, then carries out drying as required, and plastic film is carried out stacked dry lamination method etc.
As molten resin, such as, can use Low Density Polyethylene, polypropylene, vinyl-vinyl acetate copolymer etc.As caking agent, such as, list imines system, isocyanate-based, polyhutadiene system, titanic acid ester system etc.
Embodiment
Below, enumerate embodiment and describe embodiments of the present invention in detail, but the present invention is not limited to these embodiments.Below, about " part " and " % ", when annotating especially, represent " weight part " and " % by weight " respectively.
Be explained, hydroxyl value is by utilizing excessive acetylation reagent that the hydroxyl in resin is carried out acetylize, with alkali, back titration being carried out in remaining acid, the amount of hydroxyl groups in calculated resin 1g is scaled the mg number of potassium hydroxide thus the value obtained; And be the value recorded according to JISK0070.Amine value is: neutralize with in order to be carried out by the amino contained in resin 1g the mg number that necessary salt acid equivalent is the potassium hydroxide of identical amount.Acid number is: in order to the acidic group contained in resin 1g is carried out the mg number neutralizing necessary potassium hydroxide, and measuring method can be known method, generally speaking carries out according to JISK0070 (1996).About molecular weight, use GPC (gel permeation chromatography) device and determining molecular weight distributes, obtain in the mode of polystyrene conversion molecular weight.The measuring method of amine value is as shown in following.
[measuring method of amine value]
The sample of meticulous weighing 0.5 ~ 2g.Add neutral alcohol (BDG is neutral) 30mL in the sample that (sample size: Sg) goes out to meticulous weighing and dissolve.The tetrabromophenol sulfonphthalein as indicator is added, by the alcohol repellency hydrochloric acid soln of 0.2mol/L (titre: f) carry out titration in obtained solution.Be that the point of green color between Huang is set to terminal by the colour-change of solution, use titer (AmL) now to obtain amine value by (formula 1) below.
Calculating formula 1
Amine value=(A × f × 0.2 × 56.108)/S [mgKOH/g]
[synthesis example 1]
To in the four-hole boiling flask having stirrer, thermometer, reflux exchanger and nitrogen ingress pipe, add the PPA2000 (hydroxyl value 56.1mgKOH/g) 111.99 parts of molecular weight 2000, the PPG1000 (hydroxyl value 112.2mgKOH/g) 111.99 parts of molecular weight 1000, tolylene diisocyanate 52.65 parts, 0.03 part, 2 ethyl hexanoic acid tin (II), ethyl acetate 82.5 parts, 90 DEG C of reactions 3 hours under stream of nitrogen gas, obtain the solution 359.16 parts of terminal isocyanate prepolymer.Then, by isophorone diamine 21.74 parts, monoethanolamine 1.64 parts, Virahol 290 parts, ethyl acetate 327.47 parts mixing, to in the material be mixed to get, the solvent solution 359.16 parts of obtained terminal isocyanate prepolymer is at room temperature added lentamente, then 50 DEG C of reactions 1 hour, the polyurethane resin composition (PU01) of solids component 30.0%, weight-average molecular weight 30000, amine value 4.0mgKOH/g is obtained.
[synthesis example 2 ~ 26]
What utilize table 1 ~ 3 adds ratio, by the operation same with synthesis example 1, obtains polyurethane resin composition (PU02 ~ PU26).
[embodiment 1]
Titanium oxide (TITONER45M Sakai chemistry system) 30.00 parts, polyurethane resin composition (PU01) 10.00 parts, ethyl acetate/isopropyl alcohol mixed solvent (weight ratio 70/30) 10.00 parts are carried out being uniformly mixed and utilize sand mill to grind.Further, add polyurethane resin composition (PU01) 40.00 parts, ethyl acetate/isopropyl alcohol mixed solvent (weight ratio 70/30) 10.00 parts being uniformly mixed, obtain white printing ink composition (W01).Further, to in this white printing ink composition 100.00 parts, mix 40.00 parts be the diluting solvent 1 of ethyl acetate/Virahol=85/15 or the diluting solvent 2 of ethyl acetate/Virahol=50/50 of mixing 40.00 parts according to mass ratio range, made the white dilution printing-ink 1 and white dilution printing-ink 2 evaluated.
[embodiment 2 ~ 18] [comparative example 1 ~ 8]
Polyurethane resin composition (PU01) is changed to polyurethane resin composition (PU02) ~ (PU26) respectively, in addition, by operation similarly to Example 1, obtain white printing ink composition (W02 ~ 26).Be explained, the polyurethane resin composition used in each printing ink composition is as shown in table 4 ~ 6.In addition, by operation similarly to Example 1, to in obtained white printing ink composition 100.00 parts, mix 40.00 parts be the diluting solvent 1 of ethyl acetate/Virahol=85/15 or the diluting solvent 2 of ethyl acetate/Virahol=50/50 of mixing 40.00 parts according to mass ratio range, made the white dilution printing-ink 1 and white dilution printing-ink 2 evaluated.
Be explained, in synthesis example and embodiment, employ following raw material.
PPA2000: poly-(propylene adipic acid ester) glycol (number-average molecular weight 2000)
NPG2000: poly-(neopentyl glycol adipic acid ester) glycol (number-average molecular weight 2000)
PMPA2000: poly-(3-methyl isophthalic acid, 5-pentane adipic acid ester) glycol (number-average molecular weight 2000)
PPG1000: poly-(1,2-PD) (number-average molecular weight 1000)
TDI: tolylene diisocyanate
IPDI: isophorone diisocyanate
MDI: '-diphenylmethane diisocyanate
IPDA: isophorone diamine
MEA: monoethanolamine
DEA: diethanolamine
DBA: di-n-butyl amine
IPA: Virahol
HDA: hexanediamine
AEA:2-hydroxyethylethylene diamine
[forme albefaction]
The impression cylinder of rubber hardness 80Hs made at NBR (paracril), the thickness of the knife edge be the ceramic plating scraper of 60 μm (thickness of the thickness 40 μm of mother metal, one-sided ceramic layer 10 μm), the chromium hardness 1050Hv of prepress Co., Ltd. of Japan electronic engraving version (contact pilotage angle 120 degree, 200 lines/inch) Fuji Mechanical industry Co., Ltd.'s gravure printing machine on, be provided with white dilution printing-ink 1 or white dilution printing-ink 2.Then, with scraper pressure 2kg/cm 2, 100m/ minute speed of rotation carry out idle running 60 minutes, then on the corona treatment face of one side corona treatment OPP film " PylenP-2161 (Toyo Boseki K.K's system) ", with print speed 100m/ minute, squeegee pressure 2kg/cm2 prints, by the warm air drying of 60 DEG C, thus obtain print.This print is pasted on the paper of black, is attached to the amount of the ink of remaining white part (non-line portion) according to following benchmark visual valuation.
◎: the transfer not seeing ink in non-image portion completely.
Zero: the transfer slightly seeing ink in non-image portion.
Zero △: the transfer seeing ink at the small area in non-image portion.It is above is realistic scale.
△: the transfer seeing ink in the big area in non-image portion.
△ ×: the transfer seeing ink in the substantially entire surface in non-image portion.(△ with × the transfer amount of intermediate degree)
×: the transfer seeing ink in whole of non-image portion.
[resistance to adhesive]
Utilize the intaglio plate inspection machine having the dark 35 μm of intaglio plates of version, white is diluted printing-ink 1 and be printed in corona treatment OPP film (too pavilion FORFutamura#20) and 40 ~ 50 DEG C of dryings, obtain print.This print is sampled as 4cm × 4cm, be combined with the non-process face of the non-print film of the printing surface formed objects with this sample, 50 DEG C of pressurizations carrying out 10kgf 12 hours, observe the ink adhesion (transfer of ink) when having peeled off sample and opposing sense.
◎: do not see the transfer of ink from print completely, opposing sense when also not peeling off.
Zero: do not see the transfer of ink from print completely, but opposing sense when being provided with stripping.
Zero △: see the transfer of ink from print, but area is less than 10%.
It is above is realistic scale.
△: more than 10% and the area being less than 50% has found the transfer of ink from print.
×: the area more than 50% has found the transfer of ink from print.
[cementability]
The print being tested acquisition by resistance to adhesive attaches cellulose film adhesive tape (Nichiban system, width 12mm), carry out 5 severe friction with thumb, then cellulose film adhesive tape is pulled open lentamente, pull open suddenly from midway and have studied the degree of the stripping of ink epithelium.
◎: no matter be slowly pull open, or pull open suddenly, do not see the stripping of ink all completely.
Zero: slowly pull open the stripping also not seeing ink completely, but then see the stripping of ink at the area being less than 20% when pulling open suddenly.It is above is realistic scale.
△: slowly pull open the stripping also not seeing ink, but when pulling open suddenly then the area of more than 20% see the stripping of ink.
△ ×: the area slowly pulled open also till 50% degree sees the stripping of ink.
×: slowly pull open the stripping also seeing ink in major part.
[resistance to alcohol is exudative]
Utilize the intaglio plate inspection machine having the dark 35 μm of intaglio plates of version, white is diluted printing-ink 1 and be printed in corona treatment OPP film (too pavilion FORFutamura#20) and 40 ~ 50 DEG C of dryings, then apply Virahol online, 40 ~ 50 DEG C of dryings, observe outward appearances such as oozing out vestige.
◎: bad order does not occur on print.
Zero: on print, see some injustice.It is above is realistic scale.
△: see thinly on print and ooze out vestige.
×: clearly see on print and ooze out vestige.
[EL lamination strength]
Under the printing condition of forme blushing test, white is diluted the corona treatment face that printing-ink 1 is printed in base material, obtain print.Base material used herein is: polyethylene terephthalate (the being set to PET below) film " EsterfilmE5100 (Toyo Boseki K.K's system) spins in Japan " of the thickness 12 μm of polypropylene (the being set to OPP below) film " PylenP-2161 (Toyo Boseki K.K's system) " of the thickness 20 μm of one side corona treatment and one side corona treatment.Then, on printing surface, polymine system tackifier " OlivineEL-420 " (Morton Co., Ltd. of Japan system, trade(brand)name) is coated with.Further, on coated face, Low Density Polyethylene " NOVATECLC600 " (Japanese polychem Co., Ltd. system, trade(brand)name) is extruded as sealing agent melt temperature 315 DEG C, obtains lamination process thing.That is, lamination process thing is obtained by (extruding lamination (Extrusionlaminate, EL)).About the melt temperature of Low Density Polyethylene, contact thermometer (An Li gauge Co., Ltd. HL-100) is utilized to measure temperature immediately below the T-shaped mould of extruding layer press.Ink portion in this lamination process thing is carried out cutting with width 15mm, after the splitting of ink surface and molten resin layer, for stripping strength, utilizes INTESCO system 201 universal tensile testing machine and carried out the mensuration of stripping strength.Be explained, in the lamination process thing (OPP/ imines formation) employing OPP, more than 1.0N/15mm is set to realistic scale, in the lamination process thing (PET/ imines formation) employing PET, more than 1.5N/15mm is set to realistic scale.
Evaluation result is summarized in table 4 ~ 6.About the printing-ink of embodiment 1 ~ 18, compared with the printing ink composition of comparative example 1 ~ 8, can provide: in ester/alcoholic solvent system, show the printing adaptabilities such as excellent forme albefaction and the printing ink composition of the printing physical property such as the exudative and lamination adaptability of resistance to adhesive, cementability, resistance to alcohol can be guaranteed.
Table 1
Table 2
Table 3
Table 4
Table 5
Table 6

Claims (3)

1. a polyurethane resin composition, it is characterized in that, it is the polyurethane resin composition comprising urethane resin and mixed solvent, described urethane resin makes to comprise the carbamate prepolymer at end with isocyanate group that the polyisocyanates of tolylene diisocyanate and macromolecule polyol carry out reacting, the urethane resin that reacts is carried out with organic diamine and alkanolamine
Described polyurethane resin composition meets following (A) ~ (F),
(A) whole isocyanate group of polyisocyanates and hydroxyl mol ratio in the reaction [whole NCO]/[OH] of macromolecule polyol are 1.8 ~ 2.3,
(B) isocyanate group of tolylene diisocyanate and hydroxyl mol ratio in the reaction [NCO of tolylene diisocyanate]/[OH] of macromolecule polyol are 1.0 ~ 2.1,
(C) hydroxyl value of urethane resin is 1.0 ~ 10.0mgKOH/g,
(D) the mol ratio d1/d2 of the mole number d1 of organic diamine and the mole number d2 of alkanolamine is 3 ~ 25,
(E) mixed solvent comprises ester series solvent and alcohol series solvent,
(F) macromolecule polyol comprises polyester glycol and polyether glycol.
2. polyurethane resin composition according to claim 1, is characterized in that, in macromolecule polyol, described polyester glycol is 20 ~ 80 % by weight, and described polyether glycol is 80 ~ 20 % by weight.
3. a printing ink composition, is characterized in that, containing the polyurethane resin composition described in claim 1 or 2.
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