[go: up one dir, main page]

WO2018212011A1 - Composition d'encre liquide, matière imprimée, et empilement de stratifiés - Google Patents

Composition d'encre liquide, matière imprimée, et empilement de stratifiés Download PDF

Info

Publication number
WO2018212011A1
WO2018212011A1 PCT/JP2018/017721 JP2018017721W WO2018212011A1 WO 2018212011 A1 WO2018212011 A1 WO 2018212011A1 JP 2018017721 W JP2018017721 W JP 2018017721W WO 2018212011 A1 WO2018212011 A1 WO 2018212011A1
Authority
WO
WIPO (PCT)
Prior art keywords
ink composition
liquid ink
parts
polyurethane resin
solvent
Prior art date
Legal status (The legal status 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 status listed.)
Ceased
Application number
PCT/JP2018/017721
Other languages
English (en)
Japanese (ja)
Inventor
朋美 進藤
富宏 大橋
敏生 渡邊
信吉 田口
川島　康成
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
DIC Graphics Corp
Original Assignee
DIC Graphics Corp
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 DIC Graphics Corp filed Critical DIC Graphics Corp
Priority to CN201880026335.7A priority Critical patent/CN110546215B/zh
Priority to JP2018554795A priority patent/JP6514835B2/ja
Publication of WO2018212011A1 publication Critical patent/WO2018212011A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M1/00—Inking and printing with a printer's forme
    • B41M1/26—Printing on other surfaces than ordinary paper
    • B41M1/30—Printing on other surfaces than ordinary paper on organic plastics, horn or similar materials
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins

Definitions

  • the present invention relates to a liquid ink composition for gravure inks and flexographic inks for soft packaging laminates.
  • the present invention relates to a liquid ink composition that facilitates recovery of a volatile solvent in the ink composition and has excellent ink transfer properties and laminate strength.
  • a solvent recovery and reuse type printing ink composition in which 95% or more of the volatile components contain two organic solvent components (see, for example, Patent Document 1). Also disclosed is an organic solvent-based printing ink composition in which an ester solvent containing ethyl acetate as a main component and an alcohol solvent containing n-propyl alcohol as a main component are used in a specific mass ratio range (for example, Patent Documents 2 and 3). Furthermore, a solvent recovery reusable printing ink composition comprising two or more solvents selected from hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents and glycol solvents is disclosed (for example, (See Patent Document 4). However, these are simplified and simplified solvent compositions to facilitate solvent recovery, and the basic properties such as ink transferability and laminate strength required for printing ink during printing are never enough. It can not be said.
  • An object of the present invention is to provide a liquid ink composition having both excellent ink transferability and laminate strength while facilitating recovery of a volatile solvent in the ink composition.
  • the present invention has been found to contain a liquid ink composition containing a polyurethane resin (A) having a specific physical property value using a specific reaction raw material and an organic solvent (B), and is effective in solving the problem. It was.
  • the present invention is a liquid ink composition containing a polyurethane resin (A) and an organic solvent (B), wherein the polyurethane resin (A) comprises an alkanolamine, a polyester polyol and / or a polyether polyol as a reaction raw material.
  • a liquid ink composition having a weight average molecular weight in the range of 30,000 to 70,000, a urea bond concentration of 0.8 mmol / g or less, and a hydroxyl value of 11.0 mgKOH / g or less About.
  • the present invention relates to a liquid ink composition in which the alkanolamine is an alkanolamine having two or more hydroxyl groups.
  • the present invention relates to a liquid ink composition in which the polyester polyol has a number average molecular weight of 3000 to 7000.
  • this invention relates to the liquid ink composition containing the vinyl chloride vinyl acetate copolymer resin (C) which further has a hydroxyl group.
  • the vinyl chloride vinyl acetate copolymer resin (C) having a hydroxyl group has a hydroxyl value of 50 to 200 mgKOH / g, and the content ratio of the vinyl chloride component in the copolymer resin is 80 to
  • the present invention relates to a liquid ink composition that is 95% by mass.
  • this invention relates to the liquid ink composition whose amine value of the said polyurethane resin (A) is 6.5 mgKOH / g or less.
  • the present invention provides the organic solvent (B) wherein the ester solvent (b-1) is 90% by mass or more of the total amount of the organic solvent (B) and the alcohol solvent (b-2) is the organic solvent (b-2).
  • the alcohol-based solvent (b-2) is one or more selected from the group consisting of methanol, ethanol, 1-propanol, 2-propanol, 1-butanol and 2-butanol. .
  • this invention relates to the printed matter formed by printing this liquid ink composition.
  • the present invention relates to a laminate laminate having a printed layer formed by printing the liquid ink composition.
  • liquid ink composition that can easily recover the volatile solvent in the ink composition and has both excellent ink transferability and laminate strength.
  • liquid ink is a low-grade ink used for a printing method in which ink is once attached to a plate and then transferred to a paper, such as a gravure printing method using a gravure plate or a flexographic printing method using a flexo plate. This refers to ink having a viscosity (approximately 1000 mPa ⁇ s or less), and representative examples include gravure ink or flexographic ink.
  • part means “part by mass”.
  • the liquid ink composition of the present invention is a liquid ink composition containing a polyurethane resin (A) and an organic solvent (B), wherein the polyurethane resin (A) is an alkanolamine, a polyester polyol and / or a polyether polyol. And a weight average molecular weight in the range of 30000 to 70000, a urea bond concentration of 0.8 mmol / g or less, and a hydroxyl value of 11.0 mgKOH / g or less. Is.
  • polyurethane resin (A) used in the liquid ink composition of the present invention it is essential to use alkanolamine and polyester polyol and / or polyether polyol as reaction raw materials.
  • the number average molecular weight of the polyester polyol is preferably 3000 to 7000.
  • the film of the polyurethane resin (A) tends to be hard and the adhesion to the polyester film tends to be lowered.
  • the number average molecular weight is larger than 7000, the polyurethane resin film tends to be brittle, and the blocking resistance of the ink film tends to be lowered.
  • the polyester polyol is less than 1 part by mass with respect to 100 parts by mass of the polyurethane resin (A), the solubility of the polyurethane resin (A) in ketones, esters, and alcohol-based solvents decreases, and thus a particularly high-performance barrier. The adhesion on the film tends to decrease.
  • the re-solubility of the ink film in the solvent is lowered, and the tone reproducibility of the printed matter tends to be lowered.
  • the ink film tends to be excessively soft and the anti-blocking tendency tends to be poor.
  • the number average molecular weight of the said polyester polyol shows the value measured on condition of the following by gel permeation chromatography (GPC) method.
  • Measuring device High-speed GPC device (“HLC-8220GPC” manufactured by Tosoh Corporation) Column: The following columns manufactured by Tosoh Corporation were connected in series. "TSKgel G5000" (7.8 mm ID x 30 cm) x 1 "TSKgel G4000” (7.8 mm ID x 30 cm) x 1 "TSKgel G3000” (7.8 mm ID x 30 cm) x 1 “TSKgel G2000” (7.8 mm ID ⁇ 30 cm) ⁇ 1 detector: RI (differential refractometer) Column temperature: 40 ° C Eluent: Tetrahydrofuran (THF) Flow rate: 1.0 mL / min Injection amount: 100 ⁇ L (tetrahydrofuran solution with a sample concentration of 0.4 mass%) Standard sample: A calibration curve was prepared using the following standard polystyrene.
  • polyester polyol what is obtained by a well-known esterification reaction with the compound and polybasic acid which have 2 or more of hydroxyl groups can be used, for example.
  • the compound having two or more hydroxyl groups is used as a chain extender.
  • ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6 -Glycols such as hexanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol; 2-methyl-1,5-pentanediol 3-methyl-1,5-pentanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2-butyl-2-ethyl-1,3-propanediol, 1, 2-propanediol, 2-methyl-1,3- Lopandiol, neopentyl glycol, 2-isopropyl-1,4-butane
  • chain extenders may be used alone or in combination of two or more.
  • the polybasic acid include succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, maleic anhydride, fumaric acid, 1,3-cyclopentanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, phthalate Acids, anhydrides of these acids, and the like can be used. These polybasic acids may be used alone or in combination of two or more.
  • the polyether polyol preferably has a number average molecular weight of 100 to 4000.
  • examples of the polyether polyol include polyether polyols of polymers or copolymers such as ethylene oxide, propylene oxide, and tetrahydrofuran.
  • known general-purpose materials such as polyethylene glycol, polypropylene glycol, and polytetramethylene glycol may be used, and polyethylene glycol is preferable.
  • the film of the polyurethane resin (A) tends to be hard, and the adhesion to the polyester film tends to be lowered.
  • the number average molecular weight is greater than 4000, the polyurethane resin film tends to be brittle, and the blocking resistance of the ink film tends to be lowered.
  • the polyester polyol is less than 1 part by mass with respect to 100 parts by mass of the polyurethane resin (A), the solubility of the polyurethane resin (A) in ketones, esters, and alcohol-based solvents decreases, and thus a particularly high-performance barrier. The adhesion on the film tends to decrease.
  • the re-solubility of the ink film in the solvent is lowered, and the tone reproducibility of the printed matter tends to be lowered.
  • the ink film tends to be excessively soft and the anti-blocking tendency tends to be poor.
  • the number average molecular weight of polyether polyol was measured on the same conditions by the gel permeation chromatography (GPC) method similarly to the said polyester polyol.
  • polyether polyol examples include polymer polyols such as methylene oxide, ethylene oxide, and tetrahydrofuran, or copolymer polyether polyols.
  • polyester polyol and / or a polyether polyol in a proportion of 1 to 50% by mass with respect to the total amount of the polyurethane resin (A).
  • diisocyanate compound used in the polyurethane resin (A) in the liquid ink composition of the present invention include various known aromatic diisocyanates, aliphatic diisocyanates, and alicyclic diisocyanates that are generally used in the production of polyurethane resins. It is done.
  • Examples of the chain extender used in the polyurethane resin (A) in the liquid ink composition of the present invention include ethylenediamine, propylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, isophoronediamine, dicyclohexylmethane-4,4′-diamine.
  • These chain extenders can be used alone or in admixture of two or more.
  • An alkanolamine is essential as a terminal blocking agent for the purpose of stopping the reaction used for the polyurethane resin (A) in the liquid ink composition of the present invention.
  • the alkanolamine include monoethanolamine, diethanolamine, and dipropanolamine.
  • amino acids such as glycine and L-alanine can be used as a supplementary reaction terminator.
  • end blockers can be used alone or in admixture of two or more.
  • an alkanolamine having two or more hydroxyl groups is used, the adhesiveness and laminate strength of the ink composition can be further improved.
  • the printed material printed with the liquid ink composition of the present invention is dry-laminated with a laminating adhesive, it reacts with the curing agent of the laminating adhesive Since the number of points increases, the laminate strength is improved.
  • the alkanolamine having two or more hydroxyl groups include diethanolamine and dipropanolamine.
  • the polyurethane resin (A) in the liquid ink composition of the present invention is obtained by, for example, reacting polyethylene glycol and a combination polyol with a diisocyanate compound in an excess ratio of an isocyanate group to obtain a prepolymer of a terminal isocyanate group.
  • Polymer is used in an appropriate solvent, that is, an ester solvent such as ethyl acetate, propyl acetate or butyl acetate, which is usually used as a solvent for gravure ink; a ketone solvent such as acetone, methyl ethyl ketone or methyl isobutyl ketone; methanol, ethanol In chain solvents such as alcohol solvents such as isopropyl alcohol and n-butanol; hydrocarbon solvents such as toluene, xylene, methylcyclohexane and ethylcyclohexane; Is prepared by a two-stage method in which a reaction is carried out with a terminal blocking agent, or a one-stage method in which polyethylene glycol and a combination polyol, diisocyanate compound, chain extender and / or terminal blocking agent are reacted at once in a suitable solvent.
  • an ester solvent such as ethyl acetate, propyl
  • the reaction is performed so that the total (equivalent ratio) of amino groups of the chain extender and / or end-capping agent is 1 / 0.9 to 1.3. It is preferable.
  • the equivalent ratio of isocyanate group to amino group is less than 1 / 1.3, the chain extender and / or the end-capping agent remain unreacted, the polyurethane resin turns yellow, or the odor after printing May occur.
  • the weight average molecular weight of the polyurethane resin (A) thus obtained is in the range of 30,000 to 70,000, more preferably in the range of 35,000 to 65,000.
  • the weight average molecular weight of the polyurethane resin is less than 30,000, the blocking resistance of the ink composition obtained, the strength of the printed film and the oil resistance tend to be low, and when it exceeds 70,000, There is a tendency for the viscosity of the resulting ink composition to increase and the gloss of the printed film to decrease.
  • the measurement of the weight average molecular weight (polystyrene conversion) by GPC (gel permeation chromatography) in this invention was performed on condition of the following using the Tosoh Corporation HLC8220 system.
  • Separation column 4 TSKgelGMH HR- N manufactured by Tosoh Corporation are used. Column temperature: 40 ° C. Moving layer: Tetrahydrofuran manufactured by Wako Pure Chemical Industries, Ltd. Flow rate: 1.0 ml / min. Sample concentration: 1.0% by weight. Sample injection volume: 100 microliters. Detector: differential refractometer. The viscosity was measured at 25 ° C. with a Tokimec B-type viscometer.
  • the urea bond concentration of the polyurethane resin (A) used in the liquid ink composition of the present invention is 0.8 mmol / g or less and the hydroxyl value is 11.0 mgKOH / g or less.
  • the urea bond concentration exceeds 0.8 mmol / g, the hardness of the composition increases more than necessary and the flexibility of the laminate tends to decrease, and the fluidity also deteriorates.
  • the highlight transferability of the printed matter also decreases due to a change in the viscosity of the ink.
  • the hydroxyl value exceeds 11.0 mgKOH / g the water resistance tends to decrease and the laminate strength after retort tends to decrease.
  • the urea bond concentration is more preferably in the range of 0.3 to 0.8 mmol / g, and the hydroxyl value is more preferably in the range of 0.5 to 10.0 mgKOH / g. preferable.
  • the relationship of urea bond concentration can be calculated by the following equation (1).
  • Urea binding concentration [(X1 / eq1 + X2 / eq2 + ... Xi / eqi)- ⁇ (W1 x OH1 + W2 x OH2 + ...
  • the amine value of the polyurethane resin (A) used in the liquid ink composition of the present invention is preferably 6.5 mgKOH / g or less.
  • the blocking resistance tends to be inferior.
  • the range of 1.0 to 5.0 mgKOH / g is more preferable, and 1.0 to 3.5 mgKOH / g is more preferable from the viewpoint of maintaining the plate fogging property, adhesiveness and extrusion laminate strength while maintaining good blocking resistance.
  • the content of the polyurethane resin (A) used in the liquid ink composition of the present invention in the ink is 5% by mass or more with respect to the total mass of the ink from the viewpoint of sufficient adhesion of the ink to the printing medium. From the viewpoint of the ink viscosity and the work efficiency during ink production and printing, it is preferably 50% by mass or less, and more preferably in the range of 10 to 40% by mass.
  • organic solvent (B) used in the liquid ink composition of the present invention various organic solvents can be used, for example, aromatic organic solvents such as toluene and xylene, ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone.
  • aromatic organic solvents such as toluene and xylene
  • ketones such as acetone, methyl ethyl ketone
  • methyl isobutyl ketone methyl isobutyl ketone.
  • Solvent, ester solvent such as ethyl acetate, n-propyl acetate, buty
  • the organic solvent (B) is prepared from the ester solvent (b-1) in the total amount of the organic solvent (B) from the viewpoint of easy adjustment of drying property at a suitable evaporation rate during printing and solubility of the polyurethane resin. 90% by mass or more, and 0.1% by mass or more of the alcoholic solvent (b-2) based on the total amount of the organic solvent (B), and the ester solvent (b-1) is ethyl acetate, n-propyl acetate, One or more selected from the group consisting of butyl acetate and propylene glycol monomethyl ether acetate, and the alcohol solvent (b-2) is selected from ethanol, 1-propanol, 2-propanol, 1-butanol and 2-butanol.
  • the waste solvent is less colored and easy to purify and more efficiently. Can be collected. If the ester solvent (b-1) / alcohol solvent (b-2) are used together under the above conditions, the water has a low azeotropic point, so that water mixed during printing can be easily removed. Further, it can be recovered as a mixed solvent at a high yield, and can be easily reused as a diluting solvent.
  • IPA 2-isopropyl isopropyl alcohol
  • NPAC normal propyl acetate
  • the purification process can be further simplified by selecting normal propyl alcohol (NPA) as the alcohol solvent (b-2).
  • a vinyl chloride vinyl acetate copolymer resin (C) may be added.
  • the vinyl chloride vinyl acetate copolymer resin (C) preferably has a hydroxyl group, the hydroxyl value is 50 to 200 mg KOH / g, and the content ratio of the vinyl chloride component in the copolymer resin is 80 to 95 mass. % Is preferable.
  • the vinyl chloride / vinyl acetate copolymer resin (C) is present, the cohesive strength of the ink film increases and the blocking resistance tends to be good. Furthermore, by using a blocking agent in combination, the improvement in blocking resistance is further improved.
  • the vinyl chloride-vinyl acetate copolymer resin having a hydroxyl group used in the liquid ink composition of the present invention can be obtained by two kinds of methods. One is obtained by copolymerizing vinyl chloride monomer, vinyl acetate monomer and vinyl alcohol in appropriate proportions. The other is obtained by copolymerizing vinyl chloride and vinyl acetate and then partially saponifying vinyl acetate.
  • the properties of the resin film and the resin dissolution behavior are determined by the monomer ratio of vinyl chloride, vinyl acetate and vinyl alcohol. That is, vinyl chloride imparts toughness and hardness of the resin coating, vinyl acetate imparts adhesion and flexibility, and vinyl alcohol imparts good solubility in polar solvents.
  • the resin has a proper monomer ratio. That is, the vinyl chloride content is preferably 80 to 95% by mass relative to the vinyl chloride vinyl acetate copolymer resin having a hydroxyl group. If it is less than 80% by mass, the toughness of the resin film is inferior and the blocking resistance is lowered. If it exceeds 95% by mass, the resin coating becomes too hard and the adhesiveness is lowered.
  • the hydroxyl value obtained from vinyl alcohol is preferably 50 to 200 mgKOH / g.
  • Examples of the resin used together as necessary in the liquid ink composition of the present invention include resins other than the polyurethane resin and vinyl chloride-vinyl acetate copolymer resin, such as chlorinated polypropylene resin, ethylene-vinyl acetate copolymer Combined resin, vinyl acetate resin, polyamide resin, acrylic resin, polyester resin, alkyd resin, polyvinyl chloride resin, rosin resin, rosin modified maleic acid resin, ketone resin, cyclized rubber, chlorinated rubber, butyral, petroleum resin, etc. Can be mentioned.
  • the combined resins can be used alone or in admixture of two or more.
  • the content of the combined resin is preferably 1 to 50% by mass, more preferably 2 to 40% by mass, based on the total mass of the ink.
  • Examples of the color pigment used in the liquid ink composition of the present invention include organic and inorganic pigments and dyes used in general inks, paints, and recording agents.
  • Organic pigments include azo, phthalocyanine, anthraquinone, perylene, perinone, quinacridone, thioindigo, dioxazine, isoindolinone, quinophthalone, azomethine azo, dictopyrrolopyrrole, isoindoline, etc.
  • Indigo ink is copper phthalocyanine
  • transparent yellow ink is C.I. I. Pigment No. Yellow83 is preferably used.
  • the inorganic pigment examples include carbon black, titanium oxide, zinc oxide, zinc sulfide, barium sulfate, calcium carbonate, chromium oxide, silica, bengara, aluminum, mica (mica), and the like. Further, a luster pigment (Metashine; Nippon Sheet Glass Co., Ltd.) having glass or block flake as a base material and coated with metal or metal oxide can be used. From the viewpoints of cost and coloring power, it is preferable to use titanium oxide for white ink, carbon black for black ink, aluminum for silver ink, and mica for pearl ink.
  • 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 is appropriately selected from the viewpoint of brightness and concentration.
  • the colorant is preferably contained in an amount sufficient to ensure the density and coloring power of the ink, that is, 1 to 50% by mass relative to the total mass of the ink.
  • a coloring agent can be used individually or in combination of 2 or more types.
  • a combination resin, extender pigment, pigment dispersant, leveling agent, antifoaming agent, wax, plasticizer, infrared absorber, ultraviolet absorber, fragrance, flame retardant and the like can also be included as necessary.
  • the resin alone can be dispersed, but a dispersant can also be used in combination in order to disperse the pigment stably.
  • a dispersant anionic, nonionic, cationic, amphoteric surfactants can be used.
  • a comb-structure polymer compound obtained by adding polyester to polyethyleneimine, or an alkylamine derivative of an ⁇ -olefin maleic acid polymer may be used.
  • Specific examples include Solsperz series (ZENECA), Ajisper series (Ajinomoto), and homogenol series (Kao).
  • BYK series Bic Chemie
  • EFKA series EFKA
  • the dispersant is preferably contained in the ink in an amount of 0.05% by mass or more based on the total mass of the ink from the viewpoint of the storage stability of the ink and 5% by mass or less from the viewpoint of the suitability for lamination.
  • the range is from 1 to 2% by mass.
  • the liquid ink composition of the present invention can be produced by dissolving and / or dispersing a resin, a color pigment or the like in an organic solvent. Specifically, it is possible to produce a pigment dispersion in which a pigment is dispersed in an organic solvent with a polyurethane resin, and to produce an ink by blending the obtained pigment dispersion with other compounds as necessary. it can.
  • 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.
  • 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 ink viscosity 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. preferable.
  • the said viscosity is a viscosity measured at 25 degreeC with the Tokimec B-type viscometer.
  • the viscosity of the ink can be adjusted by appropriately selecting the type and amount of raw materials used, for example, a polyurethane resin, a colorant, an organic solvent, and the like.
  • the viscosity of the ink can also be adjusted by adjusting the particle size and particle size distribution of the pigment in the ink.
  • the hue of the liquid ink composition of the present invention there are five basic colors of yellow, red, indigo, black, and white, depending on the type of pigment used, and red (orange) as a color outside the process gamut. There are three colors: grass (green) and purple. Further, transparent yellow, peony, vermilion, brown, gold, silver, pearl, almost transparent medium for adjusting color density (including extender pigments if necessary), etc. are prepared as base colors. The boil retort ink is appropriately selected in consideration of pigment migration and heat resistance.
  • the base ink of each hue is diluted with a diluting solvent to a viscosity and density suitable for gravure printing or flexographic printing, and is supplied alone or mixed to each printing unit.
  • the liquid ink composition of the present invention can be obtained as a printed matter and a coating by applying the printing and application to the various film and sheet-like substrates using the printing method described above, and drying and fixing by drying in an oven.
  • Film and sheet base materials include polyolefin resins such as polyethylene and polypropylene, polyester resins such as polyethylene terephthalate, polycarbonate and polylactic acid, polystyrene resins such as polystyrene, AS resin and ABS resin, nylon, polyamide and poly Examples include vinyl chloride, polyvinylidene chloride, cellophane, paper, aluminum, and composite materials thereof.
  • the base material may be subjected to vapor deposition coating treatment and / or polyvinyl alcohol coating treatment on the surface of metal oxide or the like, and may further be subjected to surface treatment such as corona treatment.
  • the usual extrusion lamination (extrusion laminating) method in which molten polyethylene resin is laminated on the printed surface of the printed material through various anchor coating agents such as imine, isocyanate, polybutadiene, and titanium, and urethane on the printed surface
  • the printing ink of the present invention was used by a known laminating process such as a dry laminating method in which an adhesive such as a system is applied and a plastic film is laminated, or a direct laminating method in which a molten polypropylene is directly pressed and laminated on a printing surface. Laminate laminate is obtained
  • the liquid ink composition of the present invention can easily separate and recover the ester / alcohol component when recovering the mixed solvent and generated VOC gas generated in the printing and drying processes as a liquid.
  • the hydroxyl value is the amount of hydroxyl group in 1 g of resin calculated by back titrating the remaining acid with alkali when the hydroxyl group in the polyurethane resin is acetylated with an excess of acetyl reagent. It is shown by the number of mg, and conforms to JISK0070.
  • the amine value indicates the number of mg of potassium hydroxide (KOH) equivalent to the equivalent amount of hydrochloric acid required to neutralize the amino group contained in 1 g of polyurethane resin.
  • a polyurethane resin solution having a solid content of 30%, a weight average molecular weight of 31,600, an amine value of 3.2 (mgKOH / g), a urea bond concentration of 0.8 mmol / g, and a hydroxyl value of 7.4 (mgKOH / g) X1) was obtained.
  • urethane prepolymer solution (A2) 13364.86 parts were added, and reacted at 45 ° C. for 4 hours.
  • Polyurethane resin solution (X2) having a solid content of 30%, a weight average molecular weight of 42,500, an amine value of 3.2 (mgKOH / g), a urea bond concentration of 0.7 mmol / g, and a hydroxyl value of 4.7 (mgKOH / g) Got.
  • A3 14.23 parts, 1.50 parts of diethanolamine, 396.00 parts of n-propyl acetate, 136.00 parts of n-propyl alcohol, and 424.71 parts of urethane prepolymer solution (A3) are added and reacted at 45 ° C. for 4 hours.
  • urethane prepolymer solution (A4) having an isocyanate group at the terminal.
  • 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane was added to a 1-liter four-necked flask equipped with a stirrer, a thermometer, a Dimroth type reflux condenser, and a nitrogen gas introduction tube.
  • urethane prepolymer solution 10.96 parts, 2.36 parts of diethanolamine, 413.00 parts of n-propyl acetate, 143.00 parts of n-propyl alcohol, and 449.55 parts of urethane prepolymer solution (A4) are added and reacted at 45 ° C. for 4 hours.
  • urethane prepolymer solution (A5) having an isocyanate group at the terminal.
  • 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane was added to a 1-liter four-necked flask equipped with a stirrer, a thermometer, a Dimroth type reflux condenser, and a nitrogen gas introduction tube.
  • urethane prepolymer solution (A6) having an isocyanate group at the terminal.
  • 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane was added to a 1-liter four-necked flask equipped with a stirrer, a thermometer, a Dimroth type reflux condenser, and a nitrogen gas introduction tube. 14.15 parts, diethanolamine 2.88 parts, n-propyl acetate 620.00 parts, n-propyl alcohol 215.00 parts, urethane prepolymer solution (A6) 680.11 parts are added and reacted at 45 ° C. for 4 hours.
  • urethane prepolymer solution (B2) having an isocyanate group at the terminal.
  • 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane was added to a 1-liter four-necked flask equipped with a stirrer, a thermometer, a Dimroth type reflux condenser, and a nitrogen gas introduction tube. 10.96 parts, 1.37 parts of monoethanolamine, 411.00 parts of n-propyl acetate, 142.00 parts of n-propyl alcohol, and 449.55 parts of urethane prepolymer solution (B2) are added at 45 ° C.
  • a polyurethane resin solution having a solid content of 30%, a weight average molecular weight of 31,800, an amine value of 3.2 (mgKOH / g), a urea bond concentration of 0.9 mmol / g, and a hydroxyl value of 7.4 (mgKOH / g) Y1) was obtained.
  • Example 1 Fastogen Blue FA5375 10.00 parts, vinyl chloride vinyl acetate copolymer resin 30.00 parts n-propyl acetate 15% solution (V1), n-propyl acetate / n-propyl alcohol mixed solvent (weight ratio 90/10) 10 0.000 part was stirred and mixed, and after kneading with a paint conditioner, 30.00 parts of polyurethane resin composition X1 and 20.00 parts of a mixed solvent of n-propyl acetate / n-propyl alcohol (weight ratio 90/10) were stirred. By mixing, an indigo ink composition was obtained. This was diluted with n-propyl acetate, and adjusted at 25 ° C.
  • Examples 2 to 7 were performed in the same procedure as in Example 1, Examples 8 to 14 were performed according to the formulation of Table 4, and Comparative Examples 1, 3 to 5 were performed according to the formulation of Table 5.
  • the ink was adjusted.
  • the time was adjusted to 16 seconds (manufactured by Fengsha).
  • Tables 3 to 5 show the ester / alcohol solvent ratio (mass ratio) in the final indigo ink.
  • the obtained liquid indigo ink is printed using a gravure printing machine (manufactured by DIC Engineering Co., Ltd.) equipped with a laser gravure plate having a plate depth of 35 ⁇ m, highlight transferability of printed matter, measurement of laminate strength, solvent recovery Efficiency was evaluated.
  • the evaluation results are shown in Tables 3-5. Evaluation was performed by the following method.
  • R-CPP ZK-75 50 ⁇ m manufactured by Toray Synthetic Film Co., Ltd.
  • the obtained laminate was formed into a bag having a size of 120 mm ⁇ 120 mm and filled with 70 g of pseudo food containing vinegar, salad oil, and meat sauce in a weight ratio of 1: 1: 1.
  • the prepared pouch was sterilized by steam retort at 135 ° C for 30 minutes, then the contents were taken out and the pouch was washed with water. went.
  • the produced laminate was made of PET substrate (F) / printing ink layer (I) / adhesive layer (Ad1) / aluminum foil (AL) / adhesive (Ad2) / R-CPP film from the PET film side of the substrate.
  • a biaxially stretched polyester film (PET film: E-5100, 12 ⁇ m thick, manufactured by Toyobo Co., Ltd.) was used. The larger the value, the higher the strength.
  • the abbreviations of the evaluation results in Tables 3 to 5 are as follows.
  • F Cut An abbreviation for FILM CUT, which represents that the film is broken before the laminate peels during measurement. The laminate strength is higher as it exceeds the film strength, indicating superiority.
  • the liquid ink composition of the present invention has excellent volatile solvent recovery efficiency due to less dissolution of the dissolved component of the pigment in the solvent, and also has excellent ink transferability and laminate strength. Can be combined.
  • the liquid ink composition of the present invention can be widely used in industrial products such as food packaging materials, sanitary products, cosmetics, and electronic parts as gravure inks and flexographic inks suitable for solvent recovery and reuse that facilitates recovery of the solvent used. .

Landscapes

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

Abstract

La présente invention aborde le problème de la fourniture d'une composition d'encre liquide qui facilite la récupération de solvants volatils dans la composition d'encre et qui a à la fois une excellente transférabilité d'encre et une excellente résistance de stratification. La présente invention concerne une composition d'encre liquide comprenant une résine de polyuréthane (A) et un solvant organique (B), et caractérisée en ce que la résine de polyuréthane (A) comprend, en tant que matériaux réactifs, une alcanolamine, un polyol de polyester et/ou un polyol de polyéther, a un poids moléculaire moyen en poids dans la plage de 30 000 à 70 000, une concentration de liaison urée de 0,8 mmol/g ou moins, et un indice d'hydroxyle de 11,0 mg de KOH/g ou moins.
PCT/JP2018/017721 2017-05-16 2018-05-08 Composition d'encre liquide, matière imprimée, et empilement de stratifiés Ceased WO2018212011A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
CN201880026335.7A CN110546215B (zh) 2017-05-16 2018-05-08 液体墨液组合物、印刷物和层压层叠体
JP2018554795A JP6514835B2 (ja) 2017-05-16 2018-05-08 リキッドインキ組成物、印刷物及びラミネート積層体

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2017097278 2017-05-16
JP2017-097278 2017-05-16

Publications (1)

Publication Number Publication Date
WO2018212011A1 true WO2018212011A1 (fr) 2018-11-22

Family

ID=64273661

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2018/017721 Ceased WO2018212011A1 (fr) 2017-05-16 2018-05-08 Composition d'encre liquide, matière imprimée, et empilement de stratifiés

Country Status (3)

Country Link
JP (1) JP6514835B2 (fr)
CN (1) CN110546215B (fr)
WO (1) WO2018212011A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2021066817A (ja) * 2019-10-24 2021-04-30 Ｄｉｃグラフィックス株式会社 リキッド印刷インキ、印刷物、及び包装材料
WO2022004082A1 (fr) * 2020-06-30 2022-01-06 サカタインクス株式会社 Composition d'encre d'impression stratifiée pour emballage souple
JP2023173861A (ja) * 2022-05-26 2023-12-07 サカタインクス株式会社 軟包装用印刷インキ組成物、印刷方法、印刷物及びラミネート積層体

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005040293A1 (fr) * 2003-10-24 2005-05-06 Daicel Chemical Industries, Ltd. Liant pour encre d'impression et composition d'encre d'impression
WO2012008339A1 (fr) * 2010-07-15 2012-01-19 Ｄｉｃグラフィックス株式会社 Encre d'impression
JP2012012419A (ja) * 2010-06-04 2012-01-19 Toyo Ink Sc Holdings Co Ltd 印刷インキバインダー用ポリウレタン樹脂および印刷インキ
WO2013146452A1 (fr) * 2012-03-28 2013-10-03 東洋インキＳｃホールディングス株式会社 Composition de résine de polyuréthane pour liant pour encre d'impression
JP5937285B1 (ja) * 2015-07-13 2016-06-22 Ｄｉｃグラフィックス株式会社 軟包装用ラミネートインキ組成物
JP2017039836A (ja) * 2015-08-19 2017-02-23 Ｄｉｃグラフィックス株式会社 軟包装用ラミネートインキ組成物
JP2017039835A (ja) * 2015-08-19 2017-02-23 Ｄｉｃグラフィックス株式会社 軟包装用ラミネートインキ組成物
JP6296257B1 (ja) * 2016-11-11 2018-03-20 東洋インキＳｃホールディングス株式会社 溶剤型ラミネート用グラビアインキ、印刷物、および積層体

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ITMI20020056A1 (it) * 2002-01-15 2003-07-15 Ausimont Spa Composizioni acquose di fosfati di perfluoropolieteri e loro uso per conferire oleorepellenza alla carta
JP5033463B2 (ja) * 2007-04-16 2012-09-26 サカタインクス株式会社 印刷物の製造方法、及びその印刷物の製造方法で利用する有機溶剤性印刷インキ組成物
JP5121288B2 (ja) * 2007-04-16 2013-01-16 サカタインクス株式会社 有機溶剤性印刷インキ組成物の印刷システム、及びその印刷システムで利用する有機溶剤性印刷インキ組成物
US20110027543A1 (en) * 2007-10-23 2011-02-03 Cognis Ip Management Gmbh Polyurethane resins for laminating inks
CN108864807B (zh) * 2013-11-11 2021-10-01 昭和电工材料株式会社 印刷油墨用粘合剂、印刷油墨及其应用以及印刷物

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005040293A1 (fr) * 2003-10-24 2005-05-06 Daicel Chemical Industries, Ltd. Liant pour encre d'impression et composition d'encre d'impression
JP2012012419A (ja) * 2010-06-04 2012-01-19 Toyo Ink Sc Holdings Co Ltd 印刷インキバインダー用ポリウレタン樹脂および印刷インキ
WO2012008339A1 (fr) * 2010-07-15 2012-01-19 Ｄｉｃグラフィックス株式会社 Encre d'impression
WO2013146452A1 (fr) * 2012-03-28 2013-10-03 東洋インキＳｃホールディングス株式会社 Composition de résine de polyuréthane pour liant pour encre d'impression
JP5937285B1 (ja) * 2015-07-13 2016-06-22 Ｄｉｃグラフィックス株式会社 軟包装用ラミネートインキ組成物
JP2017039836A (ja) * 2015-08-19 2017-02-23 Ｄｉｃグラフィックス株式会社 軟包装用ラミネートインキ組成物
JP2017039835A (ja) * 2015-08-19 2017-02-23 Ｄｉｃグラフィックス株式会社 軟包装用ラミネートインキ組成物
JP6296257B1 (ja) * 2016-11-11 2018-03-20 東洋インキＳｃホールディングス株式会社 溶剤型ラミネート用グラビアインキ、印刷物、および積層体

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2021066817A (ja) * 2019-10-24 2021-04-30 Ｄｉｃグラフィックス株式会社 リキッド印刷インキ、印刷物、及び包装材料
JP7361565B2 (ja) 2019-10-24 2023-10-16 Ｄｉｃグラフィックス株式会社 リキッド印刷インキ、印刷物、及び包装材料
WO2022004082A1 (fr) * 2020-06-30 2022-01-06 サカタインクス株式会社 Composition d'encre d'impression stratifiée pour emballage souple
JPWO2022004082A1 (fr) * 2020-06-30 2022-01-06
JP2023173861A (ja) * 2022-05-26 2023-12-07 サカタインクス株式会社 軟包装用印刷インキ組成物、印刷方法、印刷物及びラミネート積層体

Also Published As

Publication number Publication date
CN110546215A (zh) 2019-12-06
CN110546215B (zh) 2020-12-18
JP6514835B2 (ja) 2019-05-15
JPWO2018212011A1 (ja) 2019-06-27

Similar Documents

Publication Publication Date Title
JP7407159B2 (ja) 裏刷り用溶剤型グラビア印刷インキ組成物、印刷層、および積層体
JP5937285B1 (ja) 軟包装用ラミネートインキ組成物
JP4882206B2 (ja) 軟包装用ラミネートインキ組成物
JP6255124B1 (ja) リキッドインキ組成物、印刷物及びラミネート積層体
JP6317054B1 (ja) リキッドインキ組成物
JP5848837B1 (ja) 軟包装用ラミネート用インキ組成物
JP2015108057A (ja) 軟包装用ラミネート用インキ組成物
JP2019038897A (ja) リキッドインキ組成物
JP2019203066A (ja) リキッドインキ組成物
JP2019001932A (ja) リキッドインキ組成物
JP6514835B2 (ja) リキッドインキ組成物、印刷物及びラミネート積層体
JP2015108056A (ja) ラミネート用インキ組成物の製造方法
JP7129771B2 (ja) リキッドインキ組成物
JP2015227393A (ja) 軟包装用ラミネートインキ組成物
JP2019108443A (ja) 印刷インキ組成物
JP2017039836A (ja) 軟包装用ラミネートインキ組成物
JP7543890B2 (ja) リキッドインキ組成物、及び該リキッドインキ組成物を用いた印刷物並びに積層体
JP7073696B2 (ja) リキッドインキ組成物
JP2006070190A (ja) 印刷インキ及び包装材料
JP7423392B2 (ja) リキッド印刷インキ、印刷物、及び積層体
JP6903034B2 (ja) リキッドインキ組成物
JP2017039835A (ja) 軟包装用ラミネートインキ組成物
JP7608117B2 (ja) リキッドインキ組成物
JP5900668B2 (ja) 印刷インキ組成物
JP6346720B1 (ja) 軟包装用ラミネートインキ組成物

Legal Events

Date Code Title Description
ENP Entry into the national phase

Ref document number: 2018554795

Country of ref document: JP

Kind code of ref document: A

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

Ref document number: 18802226

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 18802226

Country of ref document: EP

Kind code of ref document: A1