WO2019117231A1 - Aqueous flexographic printing ink composition - Google Patents

Aqueous flexographic printing ink composition Download PDF

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Publication number
WO2019117231A1
WO2019117231A1 PCT/JP2018/045801 JP2018045801W WO2019117231A1 WO 2019117231 A1 WO2019117231 A1 WO 2019117231A1 JP 2018045801 W JP2018045801 W JP 2018045801W WO 2019117231 A1 WO2019117231 A1 WO 2019117231A1
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WO
WIPO (PCT)
Prior art keywords
flexographic printing
ink composition
printing ink
resin
water
Prior art date
Application number
PCT/JP2018/045801
Other languages
French (fr)
Japanese (ja)
Inventor
篤史 藤田
雄一 渋谷
智一 庄司
麻代 山岡
Original Assignee
サカタインクス株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP2018230411A external-priority patent/JP7229745B2/en
Application filed by サカタインクス株式会社 filed Critical サカタインクス株式会社
Priority to CN202210655490.3A priority Critical patent/CN114854247A/en
Priority to CN201880079510.9A priority patent/CN111448268A/en
Publication of WO2019117231A1 publication Critical patent/WO2019117231A1/en

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Classifications

    • 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
    • C09D11/106—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C09D11/107—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from unsaturated acids or derivatives thereof
    • 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
    • B41M1/02—Letterpress printing, e.g. book printing
    • B41M1/04—Flexographic printing
    • 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
    • C09D11/08—Printing inks based on natural resins
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W90/00—Enabling technologies or technologies with a potential or indirect contribution to greenhouse gas [GHG] emissions mitigation
    • Y02W90/10—Bio-packaging, e.g. packing containers made from renewable resources or bio-plastics

Definitions

  • the present invention relates to an aqueous flexographic printing ink composition and a flexographic printing method using the same.
  • the coating film properties such as printability, water and friction resistance, heat resistance, and oil and friction resistance are insufficient.
  • the coating film properties such as printability, water and friction resistance, heat resistance, and oil and friction resistance are insufficient.
  • the coating film properties such as printability, water and friction resistance, heat resistance, and oil and friction resistance are insufficient.
  • condensation resistance, hexane resistance Although needed, there were no printing ink compositions with that property.
  • the use of a large amount of carbon-neutral raw materials has a problem in that the conventional ink film properties and printability deteriorate.
  • the subject of the present invention is a paper container etc. excellent in physical properties such as coating film physical properties, re-solubility, condensation resistance, hexane resistance etc. even if it is an aqueous flexographic printing ink composition using many raw materials which can be carbon neutral
  • a flexographic printing ink composition for use in thin paper applications of food packages excellent in physical properties such as flexographic printing ink compositions for use as well as physical properties such as coating properties such as water abrasion resistance, heat resistance and oil rub resistance, and resolubility. It is to be.
  • the present inventors have found that the above-mentioned problems can be solved by using the following aqueous flexographic printing ink composition, and came to solve the present invention. That is, the present invention 1.
  • An aqueous flexographic printing ink composition comprising a styrene-acrylic resin emulsion having an acid value of 30 to 80 mg KOH / g at -30 to 60 ° C. and a solvent containing water. 2.
  • the carbon-neutralizable raw material component is 10% by mass or more in the aqueous flexographic printing ink composition, and the solid content ratio of the rosin resin to the styrene-acrylic resin emulsion is 1: 0.8 to 1: 3.5.
  • the aqueous flexographic printing ink composition as described in any one of 1 to 4 comprising a wax resin fine particle dispersion having an average particle size of 1 to 10 ⁇ m.
  • an aqueous flexographic printing ink composition containing a water-containing solvent 8. 7. The aqueous flexographic printing ink composition according to 7, wherein the pigment dispersion resin contains an alkali-soluble water-soluble resin. 9. 7. The aqueous flexographic printing ink composition as described in 7 or 8 in which the resin for pigment dispersion contains (ethylene oxide / propylene oxide) block polymer. 10. The aqueous flexographic printing ink composition according to any one of 7 to 9, wherein the rosin resin is a rosin resin having an acid value of 0 to 200 mg KOH / g. 11.
  • the carbon-neutralizable raw material component is 10% by mass or more in the aqueous flexographic printing ink composition, and the solid content ratio of the rosin resin to the styrene-acrylic resin emulsion is 1: 0.8 to 1: 3.5.
  • the aqueous flexographic printing ink composition of the present invention comprises a carbon neutralizable raw material component, and preferably contains 10% by mass or more of the carbon neutralizable raw material component in the solid content of the aqueous flexographic printing ink composition Is preferred.
  • water-based flexographic printing ink composition of this invention is printed on the thin paper use of a food package for paper containers etc. (Pigment)
  • a pigment used for the water-based flexographic printing ink composition of this invention what is conventionally used by water-based flexographic printing ink can be used.
  • examples of the inorganic pigment include colored pigments such as titanium oxide, bengala, antimony red, cadmium yellow, cobalt blue, bitumen, ultramarine, carbon black and graphite.
  • examples of the organic pigment include oil-soluble azo pigments, insoluble azo pigments, azo lake pigments, condensed azo pigments, copper phthalocyanine pigments, condensed polycyclic pigments and the like.
  • the pigment may be used alone or in combination of two or more.
  • the concentration of the pigment in the aqueous flexographic printing ink composition is 5 to 60% by mass, usually 6 to 35% by mass in the case of an organic pigment, and 30 to 60% by mass in the case of an inorganic pigment.
  • the resin for dispersing a pigment used in the aqueous flexographic printing ink composition of the present invention is an alkali-soluble water-soluble resin, and it is preferable to use a (ethylene oxide / propylene oxide) block polymer in combination.
  • Alkali-soluble type water-soluble resin As an alkali-soluble water-soluble resin which is a resin for pigment dispersion, a resin obtained by polymerizing a monomer having an unsaturated double bond, which is used in a common aqueous flexographic printing ink composition, or a reaction between functional groups Any resin can be used without particular limitation as long as it is obtained by Specifically, a water-soluble acrylic resin, a water-soluble styrene-acrylic resin, a water-soluble styrene-maleic acid resin, which is obtained by copolymerizing acrylic acid or methacrylic acid and its alkyl ester, or styrene as a main monomer component, Various binder resins such as water-soluble styrene-acrylic-maleic acid resins, water-soluble polyurethane resins, water-soluble polyester resins and the like can be exemplified as preferable examples.
  • alkali-soluble water-soluble resins are usually dissolved in water in the presence of a basic compound and used as a water-soluble resin varnish.
  • the basic compound used to dissolve the alkali-soluble water-soluble resin in water include ammonia, organic amines, alkali metal hydroxides and the like.
  • the organic amine include alkylamines such as diethylamine, triethylamine and ethylenediamine, and alkanolamines such as monoethanolamine, ethylethanolamine, diethylethanolamine, diethanolamine and triethanolamine.
  • alkali metal hydroxide include sodium hydroxide, potassium hydroxide and the like.
  • amines having a low boiling point and high volatility are preferable from the viewpoint of improving the drying property, condensation resistance and hexane resistance required for paper containers etc.
  • the boiling point is 150 ° C. or less, more preferably 100 ° C. or less, more preferably Is 50.degree. C. or less, particularly preferably 0.degree. C. or less such as ammonia.
  • a resin Joncryl HPD-671 or the like manufactured by BASF Corp. can be used.
  • the amount of the alkali-soluble water-soluble resin to be used relative to the pigment is 10 to 30 parts by mass, preferably 12 to 28 parts by mass, per 100 parts by mass of the pigment.
  • (Ethylene oxide / propylene oxide) block polymer As resin for pigment dispersion, (ethylene oxide / propylene oxide) block polymer contains 2 or more blocks, and each block is composed of polyethylene oxide or propylene oxide.
  • the (ethylene oxide / propylene oxide) block polymer can be synthesized by a known method. For example, a polyethylene oxide polymer can react with propylene oxide to form a poly (propylene oxide / ethylene oxide / propylene oxide) block polymer; alternatively, a polypropylene oxide polymer can react with ethylene oxide to form poly (ethylene oxide / propylene). Oxide / ethylene oxide) block polymers can be formed.
  • the (ethylene oxide / propylene oxide) block polymer that can be used in the present invention has a weight average molecular weight in the range of 5,000 to 100,000, and commercially available products include Adeka Pulronic Series manufactured by ADEKA Corporation, etc. Be From the viewpoint of the stability of the water-containing solvent, the (ethylene oxide / propylene oxide) block polymer preferably has an HLB value of 8 to 20.
  • the HLB value refers to the balance (Hydrophile-Lipophile Balance) of the hydrophilic portion and the lipophilic portion of the molecule, which is used in the field of surfactants, and the above-mentioned HLB value is as follows: It can be determined by applying the Griffin equation (an equation based on an experimental value determined from measurement of emulsification efficiency to a certain oil and a weight fraction of a hydrophilic portion).
  • the amount of the (ethylene oxide / propylene oxide) block polymer used relative to the pigment is 0.5 to 10 parts by mass, preferably 0.5 to 8.0 parts by mass based on 100 parts by mass of the pigment.
  • the total amount of the alkali-soluble water-soluble resin + (ethylene oxide / propylene oxide) block polymer to the pigment is preferably 10 to 30 parts by mass with respect to 100 parts by mass of the pigment.
  • rosin resin From the viewpoint of obtaining an aqueous flexographic printing ink composition excellent in physical properties such as coating film physical properties, re-solubility, condensation resistance and hexane resistance, a rosin resin (hereinafter, this rosin resin is referred to as "rosin resin A" And the acid value is 80 to 350 mg KOH / g, and may be either emulsion or water-soluble by volatile basic compounds.
  • Rosin-based resin A emulsions having an acid value of 80 to 350 mg KOH / g include rosin derivatives such as rosin esters and rosin, which are materials obtained by extraction from plants, etc., low molecular weight emulsifiers and acrylic copolymers What is obtained by dispersing in water as fine particles in the presence of a high molecular weight emulsifying agent can be used.
  • Harima Kasei Co., Ltd., Harrie star SK370N etc. can be illustrated.
  • the acid value is preferably 100 to 300 mg KOH / g, more preferably 120 to 270 mg KOH / g, and more preferably 150 to 250 mg KOH / g.
  • Specific examples of the water-soluble rosin-based resin A having an acid value of 80 to 350 mg KOH / g include Harima Chemicals, Harimac T-80, AS-5, Harrier MSR-4, Tespol 1150, 1154, 1158, Arakawa Chemical Industries, Ltd., Marquide 31, 32, 33 etc. can be illustrated.
  • the water-soluble rosin-based resin A needs to be neutralized with a basic compound
  • the basic compound include ammonia, organic amines and the like.
  • the organic amine include alkylamines such as diethylamine, triethylamine and ethylenediamine, and alkanolamines such as monoethanolamine, ethylethanolamine, diethylethanolamine, diethanolamine and triethanolamine.
  • the boiling point of the amine having high volatility is preferably as low as possible from the viewpoint of condensation resistance and hexane resistance, and the boiling point is 150 ° C. or less, more preferably 100 ° C. or less, still more preferably 50 ° C.
  • the acid value is preferably 100 to 300 mg KOH / g, more preferably 120 to 270 mg KOH / g, and still more preferably 150 to 250 mg KOH / g.
  • the content of the rosin resin A having an acid value of 80 to 350 mg KOH / g in the aqueous flexographic printing ink composition of the present invention is 10 mass% of the carbon neutralable raw material component in the solid content of the aqueous flexographic printing ink composition It is preferable to make it contain so that it becomes% or more.
  • the carbon neutral possible raw material component means a raw material component obtained by being derived from a vegetable material.
  • a rosin type resin (hereinafter referred to as rosin type resin
  • the acid value is 0 mg KOH / g and / or 0 to 350 mg KOH / g, and it may be any of emulsion and water solubility.
  • a rosin-based resin B emulsion a rosin derivative such as rosin ester or rosin comprising a material obtained by extraction from plants, etc. is dispersed in water as fine particles in the presence of a low molecular weight emulsifier.
  • the water-soluble rosin-based resin B one in which a part or all of the acid value of a rosin-based resin having an acid value of 100 to 350 mg KOH / g is neutralized with a basic compound and dissolved in water is used.
  • Tespol 150, 154, 158 manufactured by Hitachi Chemical Co., Ltd., Harimac T-80 manufactured by Harima Chemical Co., Ltd., Harrier MSR-4, AS-5, Marquid 31, 32, 33 manufactured by Arakawa Chemical Co., Ltd. can be exemplified.
  • a basic compound ammonia, an organic amine, an alkali metal hydroxide etc. are mentioned, for example.
  • the organic amine include alkylamines such as diethylamine, triethylamine and ethylenediamine, and alkanolamines such as monoethanolamine, ethylethanolamine, diethylethanolamine, diethanolamine and triethanolamine.
  • alkali metal hydroxide examples include sodium hydroxide, potassium hydroxide and the like. Among them, it is desirable to use volatile and non-volatile basic compounds from the viewpoint of coating physical properties and resolubility.
  • acid values of the rosin resin B preferred is a rosin resin having an acid value of 0 to 200 mg KOH / g, and when water and abrasion resistance is required, a rosin based on an acid value of preferably 0 to 100 mg KOH / g. Resin B emulsion.
  • the content of the rosin resin B in the aqueous flexographic printing ink composition of the present invention may be such that carbon neutral raw material components are contained in the solid content of the aqueous flexographic printing ink composition to be 10% by mass or more. preferable.
  • the carbon neutral possible raw material component means a raw material component obtained by being derived from a vegetable material.
  • a styrene-acrylic resin emulsion can be blended into the aqueous flexographic printing ink composition of the present invention.
  • a styrene-acrylic resin emulsion having an acid value of 30 to 80 mg KOH / g and a glass transition temperature of -30 to 60 ° C. manufactured by a known method can be used.
  • the lower limit of the temperature range of the glass transition temperature is preferably -20.degree. C., more preferably -10.degree. C., and the upper limit is 40.degree. C. more preferably 20.degree.
  • an acrylic resin having an acid value of 150 to 250 mg KOH / g is neutralized with a basic compound in order to improve the printability with a water-soluble acrylic resin, preferably a rosin resin.
  • a water-soluble acrylic resin preferably a rosin resin.
  • examples of the basic compound include ammonia and organic amines.
  • examples of the organic amine include alkylamines such as diethylamine, triethylamine and ethylenediamine, and alkanolamines such as monoethanolamine, ethylethanolamine, diethylethanolamine, diethanolamine and triethanolamine.
  • alkylamines such as diethylamine, triethylamine and ethylenediamine
  • alkanolamines such as monoethanolamine, ethylethanolamine, diethylethanolamine, diethanolamine and triethanolamine.
  • an amine having a low boiling point and high volatility is preferable from the viewpoint of condensation resistance and hexane resistance, and the boiling point is 150 ° C. or less, more preferably 100 ° C. or less, still more preferably 50 ° C. or less, particularly preferably ammonia or the like 0 ° C or less.
  • Joncryl 309 glass transition temperature: 2 ° C., solid content: 46%) manufactured by BASF, etc.
  • the amount of the styrene-acrylic resin emulsion used is a rosin resin and a styrene-acrylic resin when carbon neutral raw material components are contained in the solid content of the aqueous flexographic printing ink composition at 10% by mass or more.
  • the solid content ratio to the resin emulsion is preferably in the range of 1: 0.8 to 1: 3.5.
  • a wax fine particle dispersion having an average particle size of 1 to 10 ⁇ m, preferably 2 to 5 ⁇ m, according to a commercially available Coulter Counter method, is used for the purpose of improving the abrasion resistance of the coating.
  • the wax resin fine particle dispersion is preferably polyethylene wax, and specific examples thereof include Chemipearl W100, W200, W300, W310, W306, W400, W410, W500, W800 and the like manufactured by Mitsui Chemicals, Inc.
  • the addition amount of the wax resin fine particle dispersion is 1 to 7% by mass in terms of solid content in 100% by weight of the water-based flexographic printing ink composition in consideration of the balance between the improvement of the friction resistance in the coating film physical properties and the adverse effect on color. It is preferable to set it as a degree.
  • solvent containing water As a solvent to be used in the aqueous flexographic printing ink composition of the present invention, in addition to water, a water-soluble organic solvent is used insofar as the performance of the aqueous flexographic printing ink composition of the present invention does not deteriorate.
  • water-soluble organic solvents include alcohols and polyhydric alcohol solvents, specifically, methanol, ethanol, propanol, butanol, hexanol, octanol, decanol, ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene Glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monooctyl ether, diethylene glycol, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, triethylene glycol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triglycol Ethylene glycol monopropyl Ether, triethylene glycol monobutyl ether, propylene glycol, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether
  • additives can be used in the aqueous flexographic printing ink composition of the present invention as required.
  • an extender pigment such as calcium carbonate, kaolin, barium sulfate, aluminum hydroxide, clay, talc, etc., to impart anti-slip property, inorganic fine particles and adhesive resin (acrylic resin , Vinyl acetate resin), leveling agent for improving leveling ability, antifoaming agent (SN deformer 777 # C made by San Nopco) for imparting antifoaming properties, caustic soda for imparting resolubility, etc.
  • Various additives such as basic compounds and film-forming emulsions can be mentioned.
  • a method for producing the aqueous flexographic printing ink composition and the printed matter of the present invention will be described.
  • a method for producing the aqueous flexographic printing ink composition of the present invention by a conventional method, after mixing a pigment, a resin for dispersing a pigment, and a solvent containing water, various types of kneading machines such as bead mill, pearl mill, The mixture is milled using a sand mill, a ball mill, an attritor, a roll mill or the like, and further, predetermined materials such as a rosin resin emulsion, a styrene-acrylic resin emulsion, etc. and additives as required are mixed.
  • a solvent further containing water is added to obtain an aqueous flexographic printing ink composition.
  • a method of producing a printed matter using this aqueous flexographic printing ink composition printing on the surface of paper or resin, in particular, a paper container such as a paper cup, a paper container such as a paper tray, or the surface is covered with a resin layer
  • water-based flexographic printing ink composition can be illustrated to the paper-made container, the thin paper of a food package, or those materials.
  • the printed material includes a food package such as wrapping paper or paper bag, a paper product such as a paper container having a resin layer such as polyolefin by lamination on the surface, and a resin layer such as a resin coat layer such as polyolefin on the surface
  • a food package such as wrapping paper or paper bag
  • a paper product such as a paper container having a resin layer such as polyolefin by lamination on the surface
  • a resin layer such as a resin coat layer such as polyolefin on the surface
  • Any of paper products such as paper containers and paper products such as uncoated paper containers having no resin layer on the surface may be used.
  • the base paper was developed with a 200-line hand proofer, and the developed product was evaluated using a Gakushin-type friction fastness tester. Evaluation conditions: 200 g ⁇ 2 times, Paper: 5 drops of water dropped on Canaquin cloth ⁇ : No coating film removed. ⁇ : Ink adheres slightly to this paper. A slight amount of ink for the exhibition color. ⁇ : Ink thinly attached to the entire surface of the paper. Some of the ink on the exhibit is removed. :: Ink thinly attached to the entire surface of the paper. The ink of the exhibition color is removed, and part of the base paper is visible. X: Ink adheres to the entire surface of the paper. Ink is also removed for the exhibition color and most of the base paper can be seen.
  • the base paper was developed with a 200-line hand proofer, and the developed product was evaluated using a Gakushin-type friction fastness tester. Evaluation conditions: 200 g ⁇ 100 times, Paper: Canaquin cloth ⁇ : No coating film removed. ⁇ ⁇ : Ink adheres to this paper very slightly. Very little ink is taken from the exhibit. ⁇ : Ink adheres slightly to this paper. A slight amount of ink for the exhibition color is taken. ⁇ : The ink is lightly attached to the entire surface of the paper. A slight amount of ink for the exhibition color is taken. :: Ink adheres to the entire surface of the paper. I can take out the ink of the exhibition color and I can see a part of the base paper. X: Ink adheres strongly to the entire surface of the paper. Ink is also taken for the exhibition color, and most of the base paper is visible.
  • ⁇ The ink is lightly attached to the entire surface of the paper. A slight amount of ink for the exhibition color is taken. :: Ink adheres to the entire surface of the paper. I can take out the ink of the exhibition color and I can see a part of the base paper. X: Ink adheres strongly to the entire surface of the paper. Ink is also taken for the exhibition color, and most of the base paper is visible. Those printed on the base paper (K liner, uncoated paper) have the same results as those printed on thin paper (uncoated paper) as long as the test is conducted.
  • the base paper was developed with a 200-line hand proofer, and the developed product was evaluated using a Gakushin-type friction fastness tester. Evaluation conditions: 200 g ⁇ 2 times, Paper: 5 drops of 80% ethanol dropped on Kanakin cloth
  • Alkali-soluble aqueous acrylic resin solid content 25% by mass
  • Joncryl HPD-671 manufactured by BASF
  • poly (ethylene oxide / propylene oxide) block polymer HLB value 14
  • Mw 16000 Rosin emulsion solid content: 50% by mass, softening point: 100 ° C, containing nonionic surfactant
  • Haliester SK 218 NS Harima Chemicals Co., Ltd. polyethylene wax (solid content: 35% by mass)
  • Table 2 shows the result of printing on a polylaminated paper in which the paper layer surface is laminated with a polyethylene layer as a substrate, and the resin layer is not laminated on the paper layer surface and the resin is not coated.
  • the results of printing are shown in Table 3.
  • ink compositions excellent in resolubility, hexane resistance, water abrasion resistance, abrasion resistance, oil abrasion resistance and alcohol abrasion resistance that is, paper cups
  • the printing application to paper-made tableware etc., such as a paper plate could be obtained.
  • Comparative Example A1 in which the rosin resin A having a low acid value is used Comparative Examples A2 and A3 in which the rosin resin A which is inferior in hexane resistance and neutralized by a basic compound which is not volatile is used.
  • Comparative Examples A4 and A5 using a styrene-acrylic emulsion in which the film is inferior in water and abrasion resistance and the glass transition temperature is too high, the results are inferior in water and alcohol abrasion resistance.
  • Examples B1 to B14 which are examples according to the present invention, it was possible to obtain an ink composition excellent in resolubility, water and friction resistance, abrasion resistance, and oil resistance.
  • Comparative Examples B1 and B2 using a styrene-acrylic resin emulsion whose glass transition temperature is not within the range according to the present invention, it is particularly inferior in water and abrasion resistance and not so good in abrasion resistance.
  • Example B7 and B8 printing excellent also in abrasion resistance and oil abrasion resistance was able to be performed.

Abstract

The present invention addresses the problem of providing a flexographic printing ink composition which uses a large amount of carbon-neutral raw materials, wherein the flexographic printing ink composition is used for paper containers and has excellent physical properties such as coating properties, re-solubility, condensation resistance, and hexane resistance, or is used for thin paper used for food packaging and has excellent physical properties such as water and abrasion resistance, heat resistance, coating properties such as oil and friction resistance, and re-solubility. In order to resolve the problem, an aqueous flexographic printing ink composition containing: a pigment; a pigment dispersion resin; a rosin-based resin emulsion having an acid value of 80-350 mgKOH/g and/or a neutralized product of a volatile basic compound and a rosin-based resin having an acid vale of 80-350 mgKOH/g; a styrene-acrylic resin emulsion having a glass transition temperature of -30°C to 60°C and an acid value of 30-80 mgKOH/g; and a water-containing solvent is provided.

Description

水性フレキソ印刷インキ組成物Aqueous flexographic printing ink composition
　本発明は、水性フレキソ印刷インキ組成物及びそれを用いたフレキソ印刷方法に関する。 The present invention relates to an aqueous flexographic printing ink composition and a flexographic printing method using the same.
　生活用品や産業資材等の段ボールを中心とした包装容器の印刷分野においては、水性フレキソ凸版印刷が行われている。近年、環境に対する取り組みが活発化しており、包装業界においても、植物性由来及び動物性由来の原料等の化石燃料に由来しない原材料を使用して、二酸化炭素の排出量を削減（カーボンニュートラル）可能なインキを実現することが、要求されるようになってきている。本出願人は、この要求より前に、バインダー樹脂として、ポリ（エチレンオキサイド／プロピレンオキサイド）ブロックポリマーの存在下で、ポリ乳酸樹脂を水性媒体中に分散させてなるポリ乳酸樹脂水性分散液を使用することを提案した(例えば、特許文献１参照)。しかしながらこれでは印刷適性、塗膜物性が不十分であるという問題を有していた。さらに食品パッケージの薄紙用途では、印刷適性、耐水耐摩擦性、耐熱性、耐油耐摩擦性等の塗膜物性が不十分であるという問題を有していた。　さらに例えば紙製食品用容器への印刷を行う際には、紙製食品用容器が使用される環境、つまり、水や油が付着する環境では、上記の性質の他に耐結露性、耐ヘキサン性を必要とするが、その性質を備えた印刷インキ組成物は存在しなかった。また、カーボンニュートラル可能な原材料を多く使用すると、従来のインキ塗膜物性、印刷適性が低下するという問題を有していた。 In the printing field of packaging containers mainly made of cardboard such as household goods and industrial materials, aqueous flexographic letterpress printing is performed. In recent years, environmental efforts have become active, and in the packaging industry, carbon dioxide emissions can be reduced (carbon neutral) using raw materials not derived from fossil fuels such as plant-derived and animal-derived raw materials It has become necessary to realize various inks. Prior to this request, the applicant has used an aqueous dispersion of polylactic acid resin in which polylactic acid resin is dispersed in an aqueous medium in the presence of a poly (ethylene oxide / propylene oxide) block polymer as a binder resin. Proposed (see, for example, Patent Document 1). However, this has the problem that printability and film properties are insufficient. Furthermore, in the thin paper application of the food package, there is a problem that the coating film properties such as printability, water and friction resistance, heat resistance, and oil and friction resistance are insufficient. Further, for example, when printing on a paper food container, in an environment where the paper food container is used, that is, in an environment where water or oil adheres, in addition to the above-mentioned properties, condensation resistance, hexane resistance Although needed, there were no printing ink compositions with that property. In addition, the use of a large amount of carbon-neutral raw materials has a problem in that the conventional ink film properties and printability deteriorate.
特開２００８－０１３６５７号公報JP, 2008-013657, A
　本発明の課題は、カーボンニュートラル可能な原材料を多く使用した水性フレキソ印刷インキ組成物であっても、塗膜物性、再溶解性、耐結露性、耐ヘキサン性等の物性に優れる紙製容器等用のフレキソ印刷インキ組成物や、耐水耐摩性、耐熱性、耐油耐摩擦性等の塗膜物性、再溶解性等の物性に優れる食品パッケージの薄紙用途に使用されるフレキソ印刷インキ組成物を提供することである。 The subject of the present invention is a paper container etc. excellent in physical properties such as coating film physical properties, re-solubility, condensation resistance, hexane resistance etc. even if it is an aqueous flexographic printing ink composition using many raw materials which can be carbon neutral Provided is a flexographic printing ink composition for use in thin paper applications of food packages excellent in physical properties such as flexographic printing ink compositions for use as well as physical properties such as coating properties such as water abrasion resistance, heat resistance and oil rub resistance, and resolubility. It is to be.
　本発明者らは、下記の水性フレキソ印刷インキ組成物を使用することにより、上記課題を解決しうることを見出し、本発明を解決するに至った。
　すなわち、本発明は、
１．顔料、顔料分散用樹脂、酸価が８０～３５０ｍｇＫＯＨ／ｇのロジン系樹脂エマルジョン及び／又は酸価が８０～３５０ｍｇＫＯＨ／ｇのロジン系樹脂の揮発性塩基性化合物による中和物、ガラス転移温度が－３０～６０℃で酸価が３０～８０ｍｇＫＯＨ／ｇのスチレン－アクリル系樹脂エマルジョン、水を含有する溶剤を含有する水性フレキソ印刷インキ組成物。
２．顔料分散用樹脂がアルカリ可溶型水溶性樹脂を含有する１記載の水性フレキソ印刷インキ組成物。
３．顔料分散用樹脂が（エチレンオキサイド／プロピレンオキサイド）ブロックポリマーを含有する１又は２に記載の水性フレキソ印刷インキ組成物。
４．カーボンニュートラル可能な原材料成分が水性フレキソ印刷インキ組成物中１０質量％以上であり、且つロジン系樹脂とスチレン－アクリル系樹脂エマルジョンとの固形分比率が、１：０．８～１：３．５の範囲である１～３のいずれかに記載の水性フレキソ印刷インキ組成物。
５．平均粒子径が１～１０μｍのワックス樹脂微粒子分散体を含有する１～４のいずれかに記載の水性フレキソ印刷インキ組成物。
６．１～５のいずれかに記載の水性フレキソ印刷インキ組成物を使用して、紙製容器用の未コート紙、ポリラミ紙にフレキソ印刷することを特徴とする印刷方法。
７．顔料、顔料分散用樹脂、酸価が０ｍｇＫＯＨ／ｇ及び／又は０～３５０ｍｇＫＯＨ／ｇのロジン系樹脂、ガラス転移温度が－３０～６０℃で酸価が３０～８０ｍｇＫＯＨ／ｇのスチレン－アクリル系樹脂エマルジョン、水を含有する溶剤を含有する水性フレキソ印刷インキ組成物。
８．顔料分散用樹脂がアルカリ可溶型水溶性樹脂を含有する７記載の水性フレキソ印刷インキ組成物。
９．顔料分散用樹脂が（エチレンオキサイド／プロピレンオキサイド）ブロックポリマーを含有する７又は８に記載の水性フレキソ印刷インキ組成物。
１０．ロジン系樹脂が酸価０～２００ｍｇＫＯＨ／ｇのロジン系樹脂である７～９のいずれかに記載の水性フレキソ印刷インキ組成物。
１１．カーボンニュートラル可能な原材料成分が水性フレキソ印刷インキ組成物中１０質量％以上であり、かつロジン系樹脂とスチレン－アクリル系樹脂エマルジョンとの固形分比率が、１：０．８～１：３．５の範囲である７～１０のいずれかに記載の水性フレキソ印刷インキ組成物。
１２．平均粒子径が１～１０μｍのワックス樹脂微粒子分散体を含有する７～１１のいずれかに記載の水性フレキソ印刷インキ組成物。
１３．７～１２のいずれかに記載の水性フレキソ印刷インキ組成物を使用して、食品パッケージの薄紙にフレキソ印刷する印刷方法。 The present inventors have found that the above-mentioned problems can be solved by using the following aqueous flexographic printing ink composition, and came to solve the present invention.
That is, the present invention
1. Pigment, resin for dispersing the pigment, rosin resin emulsion having an acid value of 80 to 350 mg KOH / g, and / or neutralized product of volatile basic compound of rosin resin having an acid value of 80 to 350 mg KOH / g, glass transition temperature An aqueous flexographic printing ink composition comprising a styrene-acrylic resin emulsion having an acid value of 30 to 80 mg KOH / g at -30 to 60 ° C. and a solvent containing water.
2. The aqueous flexographic printing ink composition according to 1, wherein the pigment dispersion resin contains an alkali-soluble water-soluble resin.
3. The aqueous flexographic printing ink composition as described in 1 or 2, wherein the pigment dispersion resin contains (ethylene oxide / propylene oxide) block polymer.
4. The carbon-neutralizable raw material component is 10% by mass or more in the aqueous flexographic printing ink composition, and the solid content ratio of the rosin resin to the styrene-acrylic resin emulsion is 1: 0.8 to 1: 3.5. The aqueous flexographic printing ink composition according to any one of 1 to 3, which is in the range of
5. The aqueous flexographic printing ink composition as described in any one of 1 to 4 comprising a wax resin fine particle dispersion having an average particle size of 1 to 10 μm.
6. A printing method characterized by using the aqueous flexographic printing ink composition as described in any of 6.1 to 5 to flexo print on an uncoated paper for paper containers, a polylaminar paper.
7. Pigment, resin for dispersing pigment, rosin resin having an acid value of 0 mg KOH / g and / or 0 to 350 mg KOH / g, styrene-acrylic resin having a glass transition temperature of -30 to 60 ° C. and an acid value of 30 to 80 mg KOH / g An emulsion, an aqueous flexographic printing ink composition containing a water-containing solvent.
8. 7. The aqueous flexographic printing ink composition according to 7, wherein the pigment dispersion resin contains an alkali-soluble water-soluble resin.
9. 7. The aqueous flexographic printing ink composition as described in 7 or 8 in which the resin for pigment dispersion contains (ethylene oxide / propylene oxide) block polymer.
10. The aqueous flexographic printing ink composition according to any one of 7 to 9, wherein the rosin resin is a rosin resin having an acid value of 0 to 200 mg KOH / g.
11. The carbon-neutralizable raw material component is 10% by mass or more in the aqueous flexographic printing ink composition, and the solid content ratio of the rosin resin to the styrene-acrylic resin emulsion is 1: 0.8 to 1: 3.5. The aqueous flexographic printing ink composition according to any one of 7 to 10, which is in the range of
12. The aqueous flexographic printing ink composition according to any one of 7 to 11, which comprises a wax resin fine particle dispersion having an average particle size of 1 to 10 μm.
A printing method of flexographic printing on a food package thin paper using the aqueous flexographic printing ink composition according to any of 13.7 to 12.
　以下、本発明の水性フレキソ印刷インキ組成物について詳細に説明する。
　本発明の水性フレキソ印刷インキ組成物は、カーボンニュートラル可能な原材料成分を含むものであり、好ましくは、カーボンニュートラル可能な原材料成分を水性フレキソ印刷インキ組成物の固形分中に１０質量％以上含有させることが好ましい。また本発明の水性フレキソ印刷インキ組成物は、紙製容器等用、食品パッケージの薄紙用途に印刷される。
（顔料）
　本発明の水性フレキソ印刷インキ組成物に使用される顔料としては、従来から水性フレキソ印刷インキで使用されているものを使用できる。具体的には、無機顔料として、酸化チタン、ベンガラ、アンチモンレッド、カドミウムイエロー、コバルトブルー、紺青、群青、カーボンブラック、黒鉛等の有色顔料を挙げることができる。また、有機顔料として、油溶性アゾ顔料、不溶性アゾ顔料、アゾレーキ顔料、縮合アゾ顔料、銅フタロシアニン顔料、縮合多環顔料等を挙げることができる。上記顔料は、１種でも２種以上でも用いることができる。
　上記顔料の水性フレキソ印刷インキ組成物中での濃度は５～６０質量％であり、通常有機顔料の場合は、６～３５質量％、無機顔料の場合は、３０～６０質量％である。 Hereinafter, the aqueous flexographic printing ink composition of the present invention will be described in detail.
The aqueous flexographic printing ink composition of the present invention comprises a carbon neutralizable raw material component, and preferably contains 10% by mass or more of the carbon neutralizable raw material component in the solid content of the aqueous flexographic printing ink composition Is preferred. Moreover, the aqueous | water-based flexographic printing ink composition of this invention is printed on the thin paper use of a food package for paper containers etc.
(Pigment)
As a pigment used for the water-based flexographic printing ink composition of this invention, what is conventionally used by water-based flexographic printing ink can be used. Specifically, examples of the inorganic pigment include colored pigments such as titanium oxide, bengala, antimony red, cadmium yellow, cobalt blue, bitumen, ultramarine, carbon black and graphite. Further, examples of the organic pigment include oil-soluble azo pigments, insoluble azo pigments, azo lake pigments, condensed azo pigments, copper phthalocyanine pigments, condensed polycyclic pigments and the like. The pigment may be used alone or in combination of two or more.
The concentration of the pigment in the aqueous flexographic printing ink composition is 5 to 60% by mass, usually 6 to 35% by mass in the case of an organic pigment, and 30 to 60% by mass in the case of an inorganic pigment.
（顔料分散用樹脂）
　本発明の水性フレキソ印刷インキ組成物で使用する顔料分散用樹脂としては、アルカリ可溶型水溶性樹脂であり、さらに、（エチレンオキサイド／プロピレンオキサイド）ブロックポリマーを併用することが好ましい。 (Resin for pigment dispersion)
The resin for dispersing a pigment used in the aqueous flexographic printing ink composition of the present invention is an alkali-soluble water-soluble resin, and it is preferable to use a (ethylene oxide / propylene oxide) block polymer in combination.
（アルカリ可溶型水溶性樹脂）
　顔料分散用樹脂であるアルカリ可溶型水溶性樹脂としては、通常の水性フレキソ印刷インキ組成物で使用される不飽和二重結合を有するモノマーを重合させて得られる樹脂や、官能基同士の反応によって得られる樹脂等であれば特に制限なく使用できる。
　具体的には、アクリル酸あるいはメタクリル酸とそのアルキルエステル、あるいはスチレン等を主なモノマー成分として共重合した水溶性アクリル系樹脂、水溶性スチレン－アクリル系樹脂、水溶性スチレン－マレイン酸系樹脂、水溶性スチレン－アクリル－マレイン酸系樹脂、水溶性ポリウレタン系樹脂、水溶性ポリエステル系樹脂等の各種バインダー樹脂が好適な例として例示できる。 (Alkali-soluble type water-soluble resin)
As an alkali-soluble water-soluble resin which is a resin for pigment dispersion, a resin obtained by polymerizing a monomer having an unsaturated double bond, which is used in a common aqueous flexographic printing ink composition, or a reaction between functional groups Any resin can be used without particular limitation as long as it is obtained by
Specifically, a water-soluble acrylic resin, a water-soluble styrene-acrylic resin, a water-soluble styrene-maleic acid resin, which is obtained by copolymerizing acrylic acid or methacrylic acid and its alkyl ester, or styrene as a main monomer component, Various binder resins such as water-soluble styrene-acrylic-maleic acid resins, water-soluble polyurethane resins, water-soluble polyester resins and the like can be exemplified as preferable examples.
　これらのアルカリ可溶型水溶性樹脂は、通常、塩基性化合物の存在下で水中に溶解させて水溶性樹脂ワニスとして使用される。上記アルカリ可溶型水溶性樹脂を水中に溶解するために使用する塩基性化合物としては、例えば、アンモニア、有機アミン、アルカリ金属水酸化物等を挙げられる。具体的には、上記有機アミンとしては、ジエチルアミン、トリエチルアミン、エチレンジアミン等のアルキルアミン、モノエタノールアミン、エチルエタノールアミン、ジエチルエタノールアミン、ジエタノールアミン、トリエタノールアミン等のアルカノールアミン等を挙げることができる。上記アルカリ金属水酸化物としては、水酸化ナトリウム、水酸化カリウム等が挙げられる。その中でも紙製容器等で要求される乾燥性、耐結露性、耐ヘキサン性向上の点から沸点が低く揮発性が高いアミンが好ましく、沸点が１５０℃以下、より好ましくは１００℃以下、さらに好ましくは、５０℃以下、特に好ましくはアンモニア等の０℃以下のものである。
　このような樹脂として、ＢＡＳＦ社製、ジョンクリルＨＰＤ－６７１等を使用することができる。また、薄紙用途等で要求される塗膜物性及び再溶解性の点からは、揮発性及び不揮発性の塩基性化合物を使用することが望ましい。
　顔料に対するアルカリ可溶型水溶性樹脂の使用量は、顔料１００質量部に対して１０～３０質量部で、好ましくは１２～２８質量部である。 These alkali-soluble water-soluble resins are usually dissolved in water in the presence of a basic compound and used as a water-soluble resin varnish. Examples of the basic compound used to dissolve the alkali-soluble water-soluble resin in water include ammonia, organic amines, alkali metal hydroxides and the like. Specifically, examples of the organic amine include alkylamines such as diethylamine, triethylamine and ethylenediamine, and alkanolamines such as monoethanolamine, ethylethanolamine, diethylethanolamine, diethanolamine and triethanolamine. Examples of the alkali metal hydroxide include sodium hydroxide, potassium hydroxide and the like. Among them, amines having a low boiling point and high volatility are preferable from the viewpoint of improving the drying property, condensation resistance and hexane resistance required for paper containers etc., and the boiling point is 150 ° C. or less, more preferably 100 ° C. or less, more preferably Is 50.degree. C. or less, particularly preferably 0.degree. C. or less such as ammonia.
As such a resin, Joncryl HPD-671 or the like manufactured by BASF Corp. can be used. Moreover, it is desirable to use volatile and non-volatile basic compounds from the viewpoint of coating physical properties and resolubility required for thin paper applications and the like.
The amount of the alkali-soluble water-soluble resin to be used relative to the pigment is 10 to 30 parts by mass, preferably 12 to 28 parts by mass, per 100 parts by mass of the pigment.
（エチレンオキサイド／プロピレンオキサイド）ブロックポリマー
　顔料分散用樹脂として（エチレンオキサイド／プロピレンオキサイド）ブロックポリマーは、２以上のブロックを含み、それぞれのブロックは、ポリエチレンオキサイド又はプロピレンオキサイドで構成される。
（エチレンオキサイド／プロピレンオキサイド）ブロックポリマーは、公知の方法で合成することができる。例えば、ポリエチレンオキサイドポリマーがプロピレンオキサイドと反応し、ポリ（プロピレンオキサイド／エチレンオキサイド／プロピレンオキサイド）ブロックポリマーを形成でき、別の方法として、ポリプロピレンオキサイドポリマーがエチレンオキサイドと反応し、ポリ（エチレンオキサイド／プロピレンオキサイド／エチレンオキサイド）ブロックポリマーを形成することができる。
　なお、本発明で使用できる（エチレンオキサイド／プロピレンオキサイド）ブロックポリマーは、重量平均分子量が５，０００～１００，０００の範囲のものであり、市販品として、ＡＤＥＫＡ社製、アデカプルロニックシリーズ等が挙げられる。
　また、水を含有する溶剤の安定性の面から、（エチレンオキサイド／プロピレンオキサイド）ブロックポリマーのＨＬＢ値は８～２０であることが好ましい。 (Ethylene oxide / propylene oxide) block polymer As resin for pigment dispersion, (ethylene oxide / propylene oxide) block polymer contains 2 or more blocks, and each block is composed of polyethylene oxide or propylene oxide.
The (ethylene oxide / propylene oxide) block polymer can be synthesized by a known method. For example, a polyethylene oxide polymer can react with propylene oxide to form a poly (propylene oxide / ethylene oxide / propylene oxide) block polymer; alternatively, a polypropylene oxide polymer can react with ethylene oxide to form poly (ethylene oxide / propylene). Oxide / ethylene oxide) block polymers can be formed.
The (ethylene oxide / propylene oxide) block polymer that can be used in the present invention has a weight average molecular weight in the range of 5,000 to 100,000, and commercially available products include Adeka Pulronic Series manufactured by ADEKA Corporation, etc. Be
From the viewpoint of the stability of the water-containing solvent, the (ethylene oxide / propylene oxide) block polymer preferably has an HLB value of 8 to 20.
　ここで、ＨＬＢ値とは、界面活性剤の分野で利用されている、分子の親水性部分と親油性部分とのバランス（Hydrophile-Lipophile Balance）を表すものであり、上記ＨＬＢ値は、下記に示すグリフィン式（一定の油に対する乳化効率の測定から求めた実験値と親水部の重量分率に基づく式）を適用して求めることができる。
〔グリフィン式〕ＨＬＢ＝（１００／５）×親水基重量／（親水基重量＋疎水性重量）
　顔料に対する（エチレンオキサイド／プロピレンオキサイド）ブロックポリマーの使用量は、顔料１００質量部に対して０.５～１０質量部、好ましくは０．５～８．０質量部である。
　顔料に対してのアルカリ可溶型水溶性樹脂＋（エチレンオキサイド／プロピレンオキサイド）ブロックポリマーの合計使用量は、顔料１００質量部に対して１０～３０質量部であることが好ましい。 Here, the HLB value refers to the balance (Hydrophile-Lipophile Balance) of the hydrophilic portion and the lipophilic portion of the molecule, which is used in the field of surfactants, and the above-mentioned HLB value is as follows: It can be determined by applying the Griffin equation (an equation based on an experimental value determined from measurement of emulsification efficiency to a certain oil and a weight fraction of a hydrophilic portion).
[Griffin type] HLB = (100/5) x hydrophilic group weight / (hydrophilic group weight + hydrophobic weight)
The amount of the (ethylene oxide / propylene oxide) block polymer used relative to the pigment is 0.5 to 10 parts by mass, preferably 0.5 to 8.0 parts by mass based on 100 parts by mass of the pigment.
The total amount of the alkali-soluble water-soluble resin + (ethylene oxide / propylene oxide) block polymer to the pigment is preferably 10 to 30 parts by mass with respect to 100 parts by mass of the pigment.
（ロジン系樹脂）
　塗膜物性、再溶解性、耐結露性、耐ヘキサン性等の物性に優れる水性フレキソ印刷インキ組成物を得る観点からは、ロジン系樹脂（以下、このロジン系樹脂を「ロジン系樹脂Ａ」とする）としては、酸価が８０～３５０ｍｇＫＯＨ／ｇであり、エマルジョン及び揮発性塩基性化合物による水溶性の何れでもよい。
　酸価が８０～３５０ｍｇＫＯＨ／ｇのロジン系樹脂Ａエマルジョンとしては、植物から抽出する等して得られた材料からなる、ロジンエステル等のロジン誘導体や、ロジンを、低分子乳化剤やアクリル系共重合体からなる高分子乳化剤の存在下で、微細な粒子として水に分散させてなるものが利用できる。具体的には、ハリマ化成社製、ハリエスターＳＫ３７０Ｎ等が例示できる。
　水溶性ロジン系樹脂Ａエマルジョンの中でも、好ましくは酸価が１００～３００ｍｇＫＯＨ／ｇであり、さらに好ましくは酸価が１２０～２７０ｍｇＫＯＨ／ｇであり、より好ましくは１５０～２５０ｍｇＫＯＨ／ｇである。
　酸価が８０～３５０ｍｇＫＯＨ／ｇの水溶性ロジン系樹脂Ａとしては、具体的には、ハリマ化成社製、ハリマックＴ－８０、ＡＳ－５、ハリエスターＭＳＲ－４、テスポール１１５０、１１５４、１１５８、荒川化学工業社製、マルキード３１、３２、３３等を例示できる。
　但しこの水溶性ロジン系樹脂Ａは、塩基性化合物で中和されている必要があり、塩基性化合物としては、例えば、アンモニア、有機アミン等を挙げられる。具体的には、上記有機アミンとしては、ジエチルアミン、トリエチルアミン、エチレンジアミン等のアルキルアミン、モノエタノールアミン、エチルエタノールアミン、ジエチルエタノールアミン、ジエタノールアミン、トリエタノールアミン等のアルカノールアミン等を挙げることができる。尚、ここで揮発性が高いアミンの沸点は、耐結露性、耐ヘキサン性の点から低い程好ましく、沸点が１５０℃以下、より好ましくは１００℃以下、さらに好ましくは５０℃以下、特に好ましくは０℃以下のものである。
　水溶性ロジン系樹脂Ａの中でも、好ましくは酸価が１００～３００ｍｇＫＯＨ／ｇであり、さらに好ましくは酸価が１２０～２７０ｍｇＫＯＨ／ｇであり、より好ましくは１５０～２５０ｍｇＫＯＨ／ｇである。
　本発明の水性フレキソ印刷インキ組成物中の、酸価が８０～３５０ｍｇＫＯＨ／ｇのロジン系樹脂Ａの含有量は、カーボンニュートラル可能な原材料成分を水性フレキソ印刷インキ組成物の固形分中に１０質量％以上となるように含有させることが好ましい。なお、カーボンニュートラル可能な原材料成分とは、植物性の材料に由来して得た原材料成分を示す。 (Resin resin)
From the viewpoint of obtaining an aqueous flexographic printing ink composition excellent in physical properties such as coating film physical properties, re-solubility, condensation resistance and hexane resistance, a rosin resin (hereinafter, this rosin resin is referred to as "rosin resin A" And the acid value is 80 to 350 mg KOH / g, and may be either emulsion or water-soluble by volatile basic compounds.
Rosin-based resin A emulsions having an acid value of 80 to 350 mg KOH / g include rosin derivatives such as rosin esters and rosin, which are materials obtained by extraction from plants, etc., low molecular weight emulsifiers and acrylic copolymers What is obtained by dispersing in water as fine particles in the presence of a high molecular weight emulsifying agent can be used. Specifically, Harima Kasei Co., Ltd., Harrie star SK370N etc. can be illustrated.
Among the water-soluble rosin-based resin A emulsions, the acid value is preferably 100 to 300 mg KOH / g, more preferably 120 to 270 mg KOH / g, and more preferably 150 to 250 mg KOH / g.
Specific examples of the water-soluble rosin-based resin A having an acid value of 80 to 350 mg KOH / g include Harima Chemicals, Harimac T-80, AS-5, Harrier MSR-4, Tespol 1150, 1154, 1158, Arakawa Chemical Industries, Ltd., Marquide 31, 32, 33 etc. can be illustrated.
However, the water-soluble rosin-based resin A needs to be neutralized with a basic compound, and examples of the basic compound include ammonia, organic amines and the like. Specifically, examples of the organic amine include alkylamines such as diethylamine, triethylamine and ethylenediamine, and alkanolamines such as monoethanolamine, ethylethanolamine, diethylethanolamine, diethanolamine and triethanolamine. Here, the boiling point of the amine having high volatility is preferably as low as possible from the viewpoint of condensation resistance and hexane resistance, and the boiling point is 150 ° C. or less, more preferably 100 ° C. or less, still more preferably 50 ° C. or less, particularly preferably 0 ° C or less.
Among the water-soluble rosin resins A, the acid value is preferably 100 to 300 mg KOH / g, more preferably 120 to 270 mg KOH / g, and still more preferably 150 to 250 mg KOH / g.
The content of the rosin resin A having an acid value of 80 to 350 mg KOH / g in the aqueous flexographic printing ink composition of the present invention is 10 mass% of the carbon neutralable raw material component in the solid content of the aqueous flexographic printing ink composition It is preferable to make it contain so that it becomes% or more. In addition, the carbon neutral possible raw material component means a raw material component obtained by being derived from a vegetable material.
耐水耐摩性、耐熱性、耐油耐摩擦性等の塗膜物性、再溶解性等の物性に優れる水性フレキソ印刷インキ組成物を得る観点からは、ロジン系樹脂（以下、このロジン系樹脂を「ロジン系樹脂Ｂ」とする）として、酸価が０ｍｇＫＯＨ／ｇ及び／又は０～３５０ｍｇＫＯＨ／ｇであり、エマルジョン及び水溶性の何れでもよい。このようなロジン系樹脂Ｂエマルジョンとしては、植物から抽出する等して得られた材料からなる、ロジンエステル等のロジン誘導体やロジンを、低分子乳化剤の存在下で、微細な粒子として水に分散させてなるものが利用できる。具体的には、ハリマ化成社製　ハリエスターＳＫ２１８ＮＳ、ＳＫ３７０Ｎ、ＳＫ３８５ＮＳ、ＳＫ５０１ＮＳ、ＬＡＷＴＥＲ社製　Ｓｎｏｗｐａｃｋ　ＸＷ－２４４２、ＸＷ－２５５１、ＸＷ－２５６１、ＸＷ－２５８２、ＳＥ７８０Ｇ、１００Ｇ、荒川化学社製　スーパーエステル　ＮＳ－１２１、ＮＳ－１００Ｈ、Ｅ－８６５ＮＴ等が例示できる。
　水溶性ロジン系樹脂Ｂとしては、１００～３５０ｍｇＫＯＨ／ｇの酸価を有するロジン系樹脂の酸価の一部又は全部を塩基性化合物で中和して水中に溶解させたものを使用する。具体的には、日立化成社製　テスポール　１５０、１５４、１５８、ハリマ化成社製　ハリマックＴ－８０、ハリエスター　ＭＳＲ－４、ＡＳ－５、荒川化学社製のマルキード３１、３２、３３等が例示できる。
　塩基性化合物としては、例えば、アンモニア、有機アミン、アルカリ金属水酸化物等を挙げられる。具体的には、上記有機アミンとしては、ジエチルアミン、トリエチルアミン、エチレンジアミン等のアルキルアミン、モノエタノールアミン、エチルエタノールアミン、ジエチルエタノールアミン、ジエタノールアミン、トリエタノールアミン等のアルカノールアミン等を挙げることができる。上記アルカリ金属水酸化物としては、水酸化ナトリウム、水酸化カリウム等が挙げられる。その中でも塗膜物性及び再溶解性の点からは、揮発性及び不揮発性の塩基性化合物を使用することが望ましい。
　ロジン系樹脂Ｂの酸価の中でも好ましくは酸価が０～２００ｍｇＫＯＨ／ｇであるロジン系樹脂であり、耐水耐摩性が要求される場合は好ましくは酸価が０～１００ｍｇＫＯＨ／ｇであるロジン系樹脂Ｂエマルジョンである。
　本発明の水性フレキソ印刷インキ組成物中のロジン系樹脂Ｂの含有量は、カーボンニュートラル可能な原材料成分を水性フレキソ印刷インキ組成物の固形分中に１０質量％以上となるように含有させることが好ましい。なお、カーボンニュートラル可能な原材料成分とは、植物性の材料に由来して得た原材料成分を示す。 From the viewpoint of obtaining an aqueous flexographic printing ink composition which is excellent in physical properties such as coating resistance such as water and abrasion resistance, heat resistance and oil resistance, and resolubility, a rosin type resin (hereinafter referred to as rosin type resin The acid value is 0 mg KOH / g and / or 0 to 350 mg KOH / g, and it may be any of emulsion and water solubility. As such a rosin-based resin B emulsion, a rosin derivative such as rosin ester or rosin comprising a material obtained by extraction from plants, etc. is dispersed in water as fine particles in the presence of a low molecular weight emulsifier. You can use what you Specifically, Harima Chemical Co., Ltd. Harrier Star SK 218 NS, SK 370 N, SK 385 NS, SK 501 NS, LAWTER Snowpack XW-2442, XW-2551, XW-2561, XW-2582, SE 780 G, 100 G, Arakawa Chemical Co., Ltd. Super Ester NS -121, NS-100H, E-865NT, etc. can be exemplified.
As the water-soluble rosin-based resin B, one in which a part or all of the acid value of a rosin-based resin having an acid value of 100 to 350 mg KOH / g is neutralized with a basic compound and dissolved in water is used. Specifically, Tespol 150, 154, 158 manufactured by Hitachi Chemical Co., Ltd., Harimac T-80 manufactured by Harima Chemical Co., Ltd., Harrier MSR-4, AS-5, Marquid 31, 32, 33 manufactured by Arakawa Chemical Co., Ltd. can be exemplified. .
As a basic compound, ammonia, an organic amine, an alkali metal hydroxide etc. are mentioned, for example. Specifically, examples of the organic amine include alkylamines such as diethylamine, triethylamine and ethylenediamine, and alkanolamines such as monoethanolamine, ethylethanolamine, diethylethanolamine, diethanolamine and triethanolamine. Examples of the alkali metal hydroxide include sodium hydroxide, potassium hydroxide and the like. Among them, it is desirable to use volatile and non-volatile basic compounds from the viewpoint of coating physical properties and resolubility.
Among the acid values of the rosin resin B, preferred is a rosin resin having an acid value of 0 to 200 mg KOH / g, and when water and abrasion resistance is required, a rosin based on an acid value of preferably 0 to 100 mg KOH / g. Resin B emulsion.
The content of the rosin resin B in the aqueous flexographic printing ink composition of the present invention may be such that carbon neutral raw material components are contained in the solid content of the aqueous flexographic printing ink composition to be 10% by mass or more. preferable. In addition, the carbon neutral possible raw material component means a raw material component obtained by being derived from a vegetable material.
（スチレン－アクリル系樹脂エマルジョン）
　本発明の水性フレキソ印刷インキ組成物には、スチレン－アクリル系樹脂エマルジョンを配合することができる。そのようなスチレン－アクリル系樹脂エマルジョンとしては、公知の方法で製造される酸価３０～８０ｍｇＫＯＨ／ｇ、ガラス転移温度－３０～６０℃のスチレン－アクリル系樹脂エマルジョンが使用できる。ガラス転移温度の温度範囲の下限としては、好ましくは－２０℃、さらに好ましくは－１０℃であり、上限としては４０℃さらに好ましくは２０℃である。
　このようなスチレン－アクリル系樹脂エマルジョンのうち、水溶性アクリル系樹脂、好ましくはロジン系樹脂による印刷適性を向上させるために、酸価１５０～２５０ｍｇＫＯＨ／ｇのアクリル系樹脂を塩基性化合物で中和した水溶性アクリル系樹脂を高分子乳化剤として用いて、スチレン系モノマー、必要に応じて（メタ）アクリル酸のアルキルエステルを共重合して得られ、かつ常温で造膜するものが好適である。
　スチレン－アクリル系樹脂エマルジョンにおいても、塩基性化合物が使用されている場合は、塩基性化合物として例えば、アンモニア、有機アミン等を挙げられる。具体的には、上記有機アミンとしては、ジエチルアミン、トリエチルアミン、エチレンジアミン等のアルキルアミン、モノエタノールアミン、エチルエタノールアミン、ジエチルエタノールアミン、ジエタノールアミン、トリエタノールアミン等のアルカノールアミン等を挙げることができる。中でも、耐結露性、耐ヘキサン性の点から沸点が低く揮発性が高いアミンが好ましく、沸点が１５０℃以下、より好ましくは１００℃以下、さらに好ましくは、５０℃以下、特に好ましくはアンモニア等の０℃以下のものである。
　このような樹脂として、ＢＡＳＦ社製、ジョンクリル３０９（ガラス転移温度２℃、固形分４６％）等を使用することができる。
スチレン－アクリル系樹脂エマルジョンを配合する際の使用量は、カーボンニュートラル可能な原材料成分を水性フレキソ印刷インキ組成物の固形分中に１０質量％以上含有させる場合は、ロジン系樹脂とスチレン－アクリル系樹脂エマルジョンとの固形分比率が、１：０．８～１：３．５の範囲であることが好ましい。 (Styrene-acrylic resin emulsion)
A styrene-acrylic resin emulsion can be blended into the aqueous flexographic printing ink composition of the present invention. As such a styrene-acrylic resin emulsion, a styrene-acrylic resin emulsion having an acid value of 30 to 80 mg KOH / g and a glass transition temperature of -30 to 60 ° C. manufactured by a known method can be used. The lower limit of the temperature range of the glass transition temperature is preferably -20.degree. C., more preferably -10.degree. C., and the upper limit is 40.degree. C. more preferably 20.degree.
Among such styrene-acrylic resin emulsions, an acrylic resin having an acid value of 150 to 250 mg KOH / g is neutralized with a basic compound in order to improve the printability with a water-soluble acrylic resin, preferably a rosin resin. Those obtained by copolymerizing a styrene-based monomer and, if necessary, an alkyl ester of (meth) acrylic acid using the water-soluble acrylic resin as a polymer emulsifier, and forming a film at normal temperature are preferable.
Also in the styrene-acrylic resin emulsion, when a basic compound is used, examples of the basic compound include ammonia and organic amines. Specifically, examples of the organic amine include alkylamines such as diethylamine, triethylamine and ethylenediamine, and alkanolamines such as monoethanolamine, ethylethanolamine, diethylethanolamine, diethanolamine and triethanolamine. Among them, an amine having a low boiling point and high volatility is preferable from the viewpoint of condensation resistance and hexane resistance, and the boiling point is 150 ° C. or less, more preferably 100 ° C. or less, still more preferably 50 ° C. or less, particularly preferably ammonia or the like 0 ° C or less.
As such a resin, Joncryl 309 (glass transition temperature: 2 ° C., solid content: 46%) manufactured by BASF, etc. can be used.
The amount of the styrene-acrylic resin emulsion used is a rosin resin and a styrene-acrylic resin when carbon neutral raw material components are contained in the solid content of the aqueous flexographic printing ink composition at 10% by mass or more. The solid content ratio to the resin emulsion is preferably in the range of 1: 0.8 to 1: 3.5.
（ワックス樹脂微粒子分散体）
　本発明の水性フレキソ印刷インキ組成物には、塗膜の耐摩擦性を向上させる目的で市販のコールターカウンター法による平均粒子径１～１０μｍ、好ましくは２～５μｍのワックス微粒子分散体を使用する事ができる。ワックス樹脂微粒子分散体としては、好ましくは、ポリエチレンワックスで、具体的には、例えば、三井化学社製、ケミパールＷ１００、Ｗ２００、Ｗ３００、Ｗ３１０、Ｗ３０６、Ｗ４００、Ｗ４１０、Ｗ５００、Ｗ８００等が挙げられる。ワックス樹脂微粒子分散体の添加量は、塗膜物性における耐摩擦性向上と色相への悪影響のバランスを考慮して、水性フレキソ印刷インキ組成物１００重量％中、固形分換算で１～７質量％程度とすることが好ましい。 (Wax resin fine particle dispersion)
In the aqueous flexographic printing ink composition of the present invention, a wax fine particle dispersion having an average particle size of 1 to 10 μm, preferably 2 to 5 μm, according to a commercially available Coulter Counter method, is used for the purpose of improving the abrasion resistance of the coating. Can. The wax resin fine particle dispersion is preferably polyethylene wax, and specific examples thereof include Chemipearl W100, W200, W300, W310, W306, W400, W410, W500, W800 and the like manufactured by Mitsui Chemicals, Inc. The addition amount of the wax resin fine particle dispersion is 1 to 7% by mass in terms of solid content in 100% by weight of the water-based flexographic printing ink composition in consideration of the balance between the improvement of the friction resistance in the coating film physical properties and the adverse effect on color. It is preferable to set it as a degree.
（水を含有する溶剤）
　本発明の水性フレキソ印刷インキ組成物で使用する溶剤としては、水に加えて、本発明の水性フレキソ印刷インキ組成物の性能低下をきたさない範囲で、水溶性有機溶剤を使用する。
　水溶性有機溶剤としては、アルコールおよび多価アルコール系溶剤で、具体的には、メタノール、エタノール、プロパノール、ブタノール、ヘキサノール、オクタノール、デカノール、エチレングリコール、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、エチレングリコールモノプロピルエーテル、エチレングリコールモノブチルエーテル、エチレングリコールモノオクチルエーテル、ジエチレングリコール、ジエチレングリコールモノエチルエーテル、ジエチレングリコールモノプロピルエーテル、ジエチレングリコールモノブチルエーテル、トリエチレングリコール、トリエチレングリコールモノメチルエーテル、トリエチレングリコールモノエチルエーテル、トリエチレングリコールモノプロピルエーテル、トリエチレングリコールモノブチルエーテル、プロピレングリコール、プロピレングリコールモノエチルエーテル、プロピレングリコールモノプロピルエーテル、プロピレングリコールモノブチルエーテル、ジプロピレングリコール、ジピロピレングリコールモノメチルエーテル、ジプロピレングリコールモノエチルエーテル、ジプロピレングリコールモノプロピルエーテル、ジプロピレングリコールモノブチルエーテル、トリプロピレングリコール、トリプロピレングリコールモノメチルエーテル、トリプロピレングリコールモノエチルエーテル、トリプロピレングリコールモノプロピルエーテル、トリプロピレングリコールモノブチルエーテル、ジブチルグリコール、グリセリン等を添加することができる。 (Solvent containing water)
As a solvent to be used in the aqueous flexographic printing ink composition of the present invention, in addition to water, a water-soluble organic solvent is used insofar as the performance of the aqueous flexographic printing ink composition of the present invention does not deteriorate.
Examples of water-soluble organic solvents include alcohols and polyhydric alcohol solvents, specifically, methanol, ethanol, propanol, butanol, hexanol, octanol, decanol, ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene Glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monooctyl ether, diethylene glycol, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, triethylene glycol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triglycol Ethylene glycol monopropyl Ether, triethylene glycol monobutyl ether, propylene glycol, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol, dipyropyrene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono Propyl ether, dipropylene glycol monobutyl ether, tripropylene glycol, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether, tripropylene glycol monopropyl ether, tripropylene glycol monobutyl ether, dibutyl glycol, glycerin and the like can be added. .
（添加剤）
　本発明の水性フレキソ印刷インキ組成物には、必要に応じて各種添加剤を使用することができる。
　具体的には、乾燥性を向上させるために、炭酸カルシウム、カオリン、硫酸バリウム、水酸化アルミニウム、クレー、タルク等の体質顔料、防滑性を付与するために無機系微粒子及び粘着性樹脂（アクリル樹脂、酢酸ビニル樹脂）、レベリング性を向上させるためにレベリング剤、消泡性を付与するために消泡剤（サンノプコ社製、ＳＮデフォーマー７７７＃Ｃ）、再溶解性を付与するために苛性ソーダ等の塩基性化合物、造膜エマルジョン等の各種添加剤を挙げることができる。
　次に、本発明の水性フレキソ印刷インキ組成物及び印刷物の製造方法について説明する。
　本発明の水性フレキソ印刷インキ組成物を従来法で製造する方法としては、顔料と、顔料分散用樹脂と、水を含有する溶剤とを混合した後、各種練肉機、例えば、ビーズミル、パールミル、サンドミル、ボールミル、アトライター、ロールミル等を利用して練肉し、さらに、ロジン系樹脂エマルジョン、スチレン－アクリル系樹脂エマルジョン等の所定の材料及び必要に応じて添加剤を混合する。
　次いで、印刷時に希釈が必要な場合は、さらに水を含有する溶剤を加え水性フレキソ印刷インキ組成物を得る。この水性フレキソ印刷インキ組成物を用いた印刷物の製造方法としては、紙や樹脂の表面への印刷、特に、紙コップ、紙皿等の紙製容器等の紙器、又は表面が樹脂層で被覆された紙製容器、食品パッケージの薄紙又はそれらの材料に、上記水性フレキソ印刷インキ組成物を用いてフレキソ印刷機で印刷する方法が例示できる。
　このとき、被印刷物としては、包み紙や紙袋等の食品パッケージ、表面にラミネートによるポリオレフィン等の樹脂層を有する紙製容器等の紙製品、表面にポリオレフィン等の樹脂コート層等の樹脂層を有する紙製容器等の紙製品、及び表面に樹脂層を有しない未コートの紙製容器等の紙製品等の何れでも良い。
ラミネート又はコートによるポリオレフィン等の樹脂層を有する紙の製造方法は公知の手段を採用できる。 (Additive)
Various additives can be used in the aqueous flexographic printing ink composition of the present invention as required.
Specifically, in order to improve the drying property, an extender pigment such as calcium carbonate, kaolin, barium sulfate, aluminum hydroxide, clay, talc, etc., to impart anti-slip property, inorganic fine particles and adhesive resin (acrylic resin , Vinyl acetate resin), leveling agent for improving leveling ability, antifoaming agent (SN deformer 777 # C made by San Nopco) for imparting antifoaming properties, caustic soda for imparting resolubility, etc. Various additives such as basic compounds and film-forming emulsions can be mentioned.
Next, the method for producing the aqueous flexographic printing ink composition and the printed matter of the present invention will be described.
As a method for producing the aqueous flexographic printing ink composition of the present invention by a conventional method, after mixing a pigment, a resin for dispersing a pigment, and a solvent containing water, various types of kneading machines such as bead mill, pearl mill, The mixture is milled using a sand mill, a ball mill, an attritor, a roll mill or the like, and further, predetermined materials such as a rosin resin emulsion, a styrene-acrylic resin emulsion, etc. and additives as required are mixed.
Then, if dilution is necessary at the time of printing, a solvent further containing water is added to obtain an aqueous flexographic printing ink composition. As a method of producing a printed matter using this aqueous flexographic printing ink composition, printing on the surface of paper or resin, in particular, a paper container such as a paper cup, a paper container such as a paper tray, or the surface is covered with a resin layer The method of printing with a flexographic printing machine using the said aqueous | water-based flexographic printing ink composition can be illustrated to the paper-made container, the thin paper of a food package, or those materials.
At this time, the printed material includes a food package such as wrapping paper or paper bag, a paper product such as a paper container having a resin layer such as polyolefin by lamination on the surface, and a resin layer such as a resin coat layer such as polyolefin on the surface Any of paper products such as paper containers and paper products such as uncoated paper containers having no resin layer on the surface may be used.
A well-known means can be employ | adopted for the manufacturing method of paper which has resin layers, such as polyolefin by lamination or a coat.
　以下に、実施例を挙げて本発明を更に詳細に説明するが、本発明はこれらの実施例のみに限定されるものではない。なお、特に断りのない限り、「％」は「質量％」を意味し、「部」は「質量部」を意味するものである。また、表中の各材料の分量の数字についても「質量部」である。酸価の単位はｍｇＫＯＨ／ｇである。 Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited to these examples. In addition, unless there is particular notice, "%" means "mass%" and "part" means a "mass part." Moreover, it is a "mass part" also about the number of the quantity of each material in a table | surface. The unit of acid value is mg KOH / g.
（評価方法）
（再溶解性）
　水性フレキソ印刷インキ組成物を０．１０ｍｍメヤバーを用いて基材上に展色し、乾燥後、塗膜に同一のインキ組成物を滴下して拭き取り、乾燥塗膜の同一のインキ組成物への溶解性を評価した。
　　◎　：拭き取り後、版材及び基材に塗膜が全く残らない。
　　◎○：拭き取り後、版材及び基材に塗膜が極わずかに残る。
　　○　：拭き取り後、版材及び基材に塗膜がわずかに残る。
　　○△：拭き取り後、版材及び基材に塗膜が半分ほど残る。
　　△　：版材及び基材から、塗膜がわずかに拭き取れる。
　　×　：版材及び基材から、塗膜が全く拭き取れない。 (Evaluation method)
(Resolubility)
The aqueous flexographic printing ink composition is spread on a substrate using a 0.10 mm Mayer, and after drying, the same ink composition is dropped onto the coating film and wiped off, and the dried coating film is transferred to the same ink composition. The solubility was evaluated.
◎: After wiping off, no coating film remains on the printing plate and the substrate.
○ :: After wiping off, a very slight amount of coating film remains on the plate material and the substrate.
○: A slight amount of coating film remains on the printing plate and the substrate after wiping off.
△: about half of the coating remains on the printing plate and the substrate after wiping.
Δ: The coating film is slightly wiped off from the plate material and the substrate.
X: The coating film can not be wiped off from the plate material and the substrate at all.
（耐ヘキサン性）
　原紙に２００線ハンドプルーファーにて展色し、ノルマルヘキサン槽に室温で２時間浸漬した。浸漬後、インキによるノルマルヘキサンへの着色、インキ塗膜の脱落、白化度合を評価した。
　　◎　：着色、脱落、白化なし
　　◎○：着色、脱落、白化の少なくともいずれか一部わずかあり
　　〇　：着色、脱落はなく、塗膜の一部が白化
　　〇△：着色、脱落はなく、塗膜の大部分が白化
　　△　：着色はなく、塗膜の一部が脱落、塗膜の大部分が白化
　　×　：着色し、塗膜の大部分が脱落 (Hexane resistance)
The base paper was developed with a 200-line hand proofer and immersed in a normal hexane bath at room temperature for 2 hours. After immersion, the coloration to normal hexane with the ink, the dropout of the ink coating, and the whitening degree were evaluated.
:: No coloration, dropout, no whitening :: Coloring, dropout, whitening at least a little at least partially ○: No coloration, dropout, whitening of a part of the coating △: No coloration, dropout, coating film Most of the film is whitening :: There is no coloration, part of the coating film falls off, most of the coating film is whitening ×: Colored, and most of the coating film falls off
（耐水耐摩性）
　原紙に２００線ハンドプルーファーにて展色し、その展色物を、学振型摩擦堅牢度試験機を用いて評価した。
評価条件：２００ｇ×２回、当紙：カナキン布に水を５滴滴下したもの
　　◎　：塗膜取られなし。
　　○　：当紙にわずかにインキが付着。展色物のインキがわずかに取れて
　　　　　いるもの。
　　○△：当紙全面にインキ薄く付着。展色物のインキがわずかに取れてい
　　　　　るもの。
　　△　：当紙全面にインキ薄く付着。展色物のインキが取れ、一部原紙が
　　　　　見える。
　　×　：当紙全面にインキ濃く付着。展色物についてもインキが取れ、原
　　　　　紙の大部分が見える。 (Water and abrasion resistance)
The base paper was developed with a 200-line hand proofer, and the developed product was evaluated using a Gakushin-type friction fastness tester.
Evaluation conditions: 200 g × 2 times, Paper: 5 drops of water dropped on Canaquin cloth ◎: No coating film removed.
○: Ink adheres slightly to this paper. A slight amount of ink for the exhibition color.
△: Ink thinly attached to the entire surface of the paper. Some of the ink on the exhibit is removed.
:: Ink thinly attached to the entire surface of the paper. The ink of the exhibition color is removed, and part of the base paper is visible.
X: Ink adheres to the entire surface of the paper. Ink is also removed for the exhibition color and most of the base paper can be seen.
（耐摩性）
　原紙に２００線ハンドプルーファーにて展色し、その展色物を、学振型摩擦堅牢度試験機を用いて評価した。
評価条件：２００ｇ×１００回、当紙：カナキン布
　　◎　：塗膜取られなし。
　　◎○：当紙に極わずかにインキが付着。展色物のインキが極わずかに取
　　　　　れている。
　　〇　：当紙にわずかにインキが付着。展色物のインキがわずかに取れて
　　　　　いる。
　　〇△：当紙全面にインキが薄く付着。展色物のインキがわずかに取れて
　　　　　いる。
　　△　：当紙全面にインキが付着。展色物のインキが取れ、一部原紙が見
　　　　　える。
　　×　：当紙全面にインキが濃く付着。展色物についてもインキが取られ
　　　　　、原紙の大部分が見える。 (Abrasion resistance)
The base paper was developed with a 200-line hand proofer, and the developed product was evaluated using a Gakushin-type friction fastness tester.
Evaluation conditions: 200 g × 100 times, Paper: Canaquin cloth ◎: No coating film removed.
○ ○: Ink adheres to this paper very slightly. Very little ink is taken from the exhibit.
○: Ink adheres slightly to this paper. A slight amount of ink for the exhibition color is taken.
△: The ink is lightly attached to the entire surface of the paper. A slight amount of ink for the exhibition color is taken.
:: Ink adheres to the entire surface of the paper. I can take out the ink of the exhibition color and I can see a part of the base paper.
X: Ink adheres strongly to the entire surface of the paper. Ink is also taken for the exhibition color, and most of the base paper is visible.
（耐油耐摩性）
　ロジン樹脂Ａを使用した実施例では、原紙に２００線ハンドプルーファーにて展色し、その展色物を、学振型摩擦堅牢度試験機を用いて評価した。
ロジン樹脂Ｂを使用した実施例では、原紙（Ｋライナー）に２００線ハンドプルーファーにて展色し、その展色物を、学振型摩擦堅牢度試験機を用いて評価した。
評価条件：２００ｇ×２回、当紙：カナキン布にサラダ油を５滴滴下したもの
　　◎　：塗膜取られなし。
　　◎○：当紙に極わずかにインキが付着。展色物のインキが極わずかに取
　　　　　れている。
　　〇　：当紙にわずかにインキが付着。展色物のインキがわずかに取れて
　　　　　いる。
　　〇△：当紙全面にインキが薄く付着。展色物のインキがわずかに取れて
　　　　　いる。
　　△　：当紙全面にインキが付着。展色物のインキが取れ、一部原紙が見
　　　　　える。
　　×　：当紙全面にインキが濃く付着。展色物についてもインキが取られ
　　　　　、原紙の大部分が見える。
上記原紙（Ｋライナー、未コート紙）に印刷したものは、その試験を行う限りにおいて、薄紙（未コート紙）に印刷した場合と結果が共通する。 (Oil resistance)
In the example using the rosin resin A, a base paper was developed with a 200-line hand proofer, and the developed product was evaluated using a Gakushin-type friction fastness tester.
In the example using rosin resin B, a base paper (K liner) was developed with a 200-line hand proofer, and the developed product was evaluated using a Gakushin-type friction fastness tester.
Evaluation conditions: 200 g × 2 times, Paper: 5 drops of salad oil dropped on Kanakin cloth ◎: No coating film removed.
○ ○: Ink adheres to this paper very slightly. Very little ink is taken from the exhibit.
○: Ink adheres slightly to this paper. A slight amount of ink for the exhibition color is taken.
△: The ink is lightly attached to the entire surface of the paper. A slight amount of ink for the exhibition color is taken.
:: Ink adheres to the entire surface of the paper. I can take out the ink of the exhibition color and I can see a part of the base paper.
X: Ink adheres strongly to the entire surface of the paper. Ink is also taken for the exhibition color, and most of the base paper is visible.
Those printed on the base paper (K liner, uncoated paper) have the same results as those printed on thin paper (uncoated paper) as long as the test is conducted.
（耐アルコール耐摩性）
　原紙に２００線ハンドプルーファーにて展色し、その展色物を、学振型摩擦堅牢度試験機を用いて評価した。
評価条件：２００ｇ×２回、当紙：カナキン布に８０％エタノールを５滴滴下したもの (Alcohol resistance)
The base paper was developed with a 200-line hand proofer, and the developed product was evaluated using a Gakushin-type friction fastness tester.
Evaluation conditions: 200 g × 2 times, Paper: 5 drops of 80% ethanol dropped on Kanakin cloth
　アルカリ可溶性水性アクリル樹脂（固形分２５質量％）ジョンクリルＨＰＤ－６７１、ＢＡＳＦ社製
　ポリ(エチレンオキサイド／プロピレンオキサイド)ブロックポリマー
：ＨＬＢ値１４、Ｍｗ１６０００
　ロジンエマルジョン（固形分５０質量％、軟化点１００℃、ノニオン性界面活性剤含有）ハリエスターＳＫ２１８ＮＳ、ハリマ化成社製
　ポリエチレンワックス（固形分３５質量％）ケミパールＷ－１００、三井化学社製
　消泡剤ＳＮデフォーマー７７７♯Ｃ　サンノプコ社製 Alkali-soluble aqueous acrylic resin (solid content 25% by mass) Joncryl HPD-671, manufactured by BASF, poly (ethylene oxide / propylene oxide) block polymer: HLB value 14, Mw 16000
Rosin emulsion (solid content: 50% by mass, softening point: 100 ° C, containing nonionic surfactant): Haliester SK 218 NS, Harima Chemicals Co., Ltd. polyethylene wax (solid content: 35% by mass) Chemipearl W-100, Mitsui Chemicals Co., Ltd. SN deformer 777 # C made by Sannopco
（ロジン系樹脂Ａを使用した水性フレキソ印刷インキ組成物）
　顔料（フタロシアニンブルー、Ｃ．Ｉ．ピグメントブルー１５：３）、アルカリ可溶型水性アクリル樹脂（ジョンクリルＨＰＤ－６７１、ＢＡＳＦ社製、固形分２５％）、ポリ（エチレンオキサイド／プロピレンオキサイド）ブロックポリマー（（ＥＯ／ＰＯ）ブロックポリマー、ＨＬＢ値１４、Ｍｗ１６０００）、ジブチルグリコール、水の混合物をビーズミルで混練分散後、ロジン系樹脂Ａエマルジョン、アクリルエマルジョン（スチレン－アクリル系樹脂エマルジョン）、ポリエチレンワックス、消泡剤を表１の割合となるように加え混合して、水性フレキソ印刷インキ組成物を得た。
　基材として、紙層表面をポリエチレン層によりラミネートしてなるポリラミ紙に対して印刷した結果を表２に示し、紙層表面に樹脂層をラミネートせず、また樹脂をコーティングしない未コート紙に対して印刷した結果を表３に示す。 (Aqueous flexographic printing ink composition using rosin resin A)
Pigment (Phthalocyanine Blue, CI Pigment Blue 15: 3), Alkali-Soluble Aqueous Acrylic Resin (JONCRYL HPD-671, manufactured by BASF, solid content 25%), Poly (ethylene oxide / propylene oxide) block polymer A mixture of ((EO / PO) block polymer, HLB value 14, Mw 16000), dibutyl glycol and water is kneaded and dispersed with a bead mill, and then rosin resin A emulsion, acrylic emulsion (styrene-acrylic resin emulsion), polyethylene wax, eraser The foaming agents were added and mixed in the proportions in Table 1 to obtain an aqueous flexographic printing ink composition.
Table 2 shows the result of printing on a polylaminated paper in which the paper layer surface is laminated with a polyethylene layer as a substrate, and the resin layer is not laminated on the paper layer surface and the resin is not coated. The results of printing are shown in Table 3.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-I000002
 
 
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-I000002
 
 
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
　本発明に沿った例である実施例Ａ１～Ａ１０によれば、再溶解性、耐ヘキサン性、耐水耐摩性、耐摩性、耐油耐摩性及び耐アルコール耐摩性に優れたインキ組成物、つまり紙コップ、紙皿等の紙製食器等への印刷用途を得ることができた。
　これに対して、酸価が低いロジン系樹脂Ａを使用した比較例Ａ１では耐ヘキサン性に劣り、揮発性ではない塩基性化合物により中和されたロジン系樹脂Ａを使用した比較例Ａ２及びＡ３によれば皮膜が耐水耐摩性に劣り、ガラス転移温度が高すぎるスチレン－アクリルエマルジョンを使用した比較例Ａ４及びＡ５によれば、耐水耐摩性や耐アルコール耐摩性に劣る結果となった。 According to the examples A1 to A10 according to the present invention, ink compositions excellent in resolubility, hexane resistance, water abrasion resistance, abrasion resistance, oil abrasion resistance and alcohol abrasion resistance, that is, paper cups The printing application to paper-made tableware etc., such as a paper plate, could be obtained.
On the other hand, in Comparative Example A1 in which the rosin resin A having a low acid value is used, Comparative Examples A2 and A3 in which the rosin resin A which is inferior in hexane resistance and neutralized by a basic compound which is not volatile is used. According to Comparative Examples A4 and A5 using a styrene-acrylic emulsion in which the film is inferior in water and abrasion resistance and the glass transition temperature is too high, the results are inferior in water and alcohol abrasion resistance.
（ロジン系樹脂Ｂを使用した水性フレキソ印刷インキ組成物）
　顔料（フタロシアニンブルー、Ｃ．Ｉ．ピグメントブルー１５：３）、アルカリ可溶型水溶性樹脂（ジョンクリルＨＰＤ－６７１、ＢＡＳＦ社製、固形分２５％）、（エチレンオキサイド／プロピレンオキサイド）ブロックポリマー（（ＥＯ／ＰＯ）ブロックポリマー、ＨＬＢ値１４、Ｍｗ１６０００）、ジブチルグリコール、水の混合物をビーズミルで混練分散後、ロジン系樹脂Ｂ、スチレン－アクリル系樹脂エマルジョン、ポリエチレンワックス、消泡剤を表４の割合となるように加え混合して、水性フレキソ印刷インキ組成物を得た。 (Aqueous flexographic printing ink composition using rosin resin B)
Pigment (Phthalocyanine Blue, CI Pigment Blue 15: 3), Alkali-Soluble Water-Soluble Resin (JONCRYL HPD-671, manufactured by BASF, solid content 25%), (ethylene oxide / propylene oxide) block polymer After mixing and dispersing a mixture of (EO / PO) block polymer, HLB value 14, Mw 16000), dibutyl glycol and water with a bead mill, rosin resin B, styrene-acrylic resin emulsion, polyethylene wax, antifoaming agent are shown in Table 4 An aqueous flexographic printing ink composition was obtained by adding and mixing in proportions.
Figure JPOXMLDOC01-appb-T000005
  
Figure JPOXMLDOC01-appb-I000006
Figure JPOXMLDOC01-appb-T000005
  
Figure JPOXMLDOC01-appb-I000006
　本発明に沿った例である実施例Ｂ１～Ｂ１４によれば、再溶解性、耐水耐摩擦性、耐摩性及び耐油耐摩性に優れたインキ組成物を得ることができた。これに対してガラス転移温度が本発明中の範囲のものではないスチレン－アクリル系樹脂エマルジョンを使用した比較例Ｂ１及びＢ２によれば、特に耐水耐摩擦性に劣り、耐摩性もそれほど良好ではなかった。
　また実施例Ｂ７及びＢ８によれば、耐摩性及び耐油耐摩性にも優れた印刷を行うことができた。 According to Examples B1 to B14, which are examples according to the present invention, it was possible to obtain an ink composition excellent in resolubility, water and friction resistance, abrasion resistance, and oil resistance. On the other hand, according to Comparative Examples B1 and B2 using a styrene-acrylic resin emulsion whose glass transition temperature is not within the range according to the present invention, it is particularly inferior in water and abrasion resistance and not so good in abrasion resistance. The
Moreover, according to Example B7 and B8, printing excellent also in abrasion resistance and oil abrasion resistance was able to be performed.

Claims (13)

  1. 　顔料、顔料分散用樹脂、酸価が８０～３５０ｍｇＫＯＨ／ｇのロジン系樹脂エマルジョン及び／又は酸価が８０～３５０ｍｇＫＯＨ／ｇのロジン系樹脂の揮発性塩基性化合物による中和物、ガラス転移温度が－３０～６０℃で酸価が３０～８０ｍｇＫＯＨ／ｇのスチレン－アクリル系樹脂エマルジョン、水を含有する溶剤を含有する水性フレキソ印刷インキ組成物。 Pigment, resin for dispersing the pigment, rosin resin emulsion having an acid value of 80 to 350 mg KOH / g, and / or neutralized product of volatile basic compound of rosin resin having an acid value of 80 to 350 mg KOH / g, glass transition temperature An aqueous flexographic printing ink composition comprising a styrene-acrylic resin emulsion having an acid value of 30 to 80 mg KOH / g at -30 to 60 ° C. and a solvent containing water.
  2. 　顔料分散用樹脂がアルカリ可溶型水溶性樹脂を含有する請求項１記載の水性フレキソ印刷インキ組成物。 The aqueous flexographic printing ink composition according to claim 1, wherein the pigment dispersion resin contains an alkali-soluble water-soluble resin.
  3. 　顔料分散用樹脂が（エチレンオキサイド／プロピレンオキサイド）ブロックポリマーを含有する請求項１又は２に記載の水性フレキソ印刷インキ組成物。 The water-based flexographic printing ink composition according to claim 1 or 2, wherein the pigment dispersing resin contains (ethylene oxide / propylene oxide) block polymer.
  4. 　カーボンニュートラル可能な原材料成分が水性フレキソ印刷インキ組成物中１０質量％以上であり、且つロジン系樹脂とスチレン－アクリル系樹脂エマルジョンとの固形分比率が、１：０．８～１：３．５の範囲である請求項１～３のいずれかに記載の水性フレキソ印刷インキ組成物。 The carbon-neutralizable raw material component is 10% by mass or more in the aqueous flexographic printing ink composition, and the solid content ratio of the rosin resin to the styrene-acrylic resin emulsion is 1: 0.8 to 1: 3.5. The aqueous flexographic printing ink composition according to any one of claims 1 to 3, which is in the range of
  5. 　平均粒子径が１～１０μｍのワックス樹脂微粒子分散体を含有する請求項１～４のいずれかに記載の水性フレキソ印刷インキ組成物。 The aqueous flexographic printing ink composition according to any one of claims 1 to 4, which contains a wax resin fine particle dispersion having an average particle size of 1 to 10 μm.
  6. 　請求項１～５のいずれかに記載の水性フレキソ印刷インキ組成物を使用して、紙製容器用の未コート紙、ポリラミ紙にフレキソ印刷することを特徴とする印刷方法。 A printing method comprising: using the aqueous flexographic printing ink composition according to any one of claims 1 to 5, flexographic printing on an uncoated paper for a paper container and a polylaminated paper.
  7. 　顔料、顔料分散用樹脂、酸価が０ｍｇＫＯＨ／ｇ及び／又は０～３５０ｍｇＫＯＨ／ｇのロジン系樹脂、ガラス転移温度が－３０～６０℃で酸価が３０～８０ｍｇＫＯＨ／ｇのスチレン－アクリル系樹脂エマルジョン、水を含有する溶剤を含有する水性フレキソ印刷インキ組成物。 Pigment, resin for dispersing pigment, rosin resin having an acid value of 0 mg KOH / g and / or 0 to 350 mg KOH / g, styrene-acrylic resin having a glass transition temperature of -30 to 60 ° C. and an acid value of 30 to 80 mg KOH / g An emulsion, an aqueous flexographic printing ink composition containing a water-containing solvent.
  8. 　顔料分散用樹脂がアルカリ可溶型水溶性樹脂を含有する請求項７記載の水性フレキソ印刷インキ組成物。 The aqueous flexographic printing ink composition according to claim 7, wherein the pigment dispersion resin contains an alkali-soluble water-soluble resin.
  9. 　顔料分散用樹脂が（エチレンオキサイド／プロピレンオキサイド）ブロックポリマーを含有する請求項７又は８に記載の水性フレキソ印刷インキ組成物。 The water-based flexographic printing ink composition according to claim 7 or 8, wherein the pigment dispersion resin contains (ethylene oxide / propylene oxide) block polymer.
  10. 　ロジン系樹脂が酸価０～２００ｍｇＫＯＨ／ｇのロジン系樹脂である請求項７～９のいずれかに記載の水性フレキソ印刷インキ組成物。 The aqueous flexographic printing ink composition according to any one of claims 7 to 9, wherein the rosin resin is a rosin resin having an acid value of 0 to 200 mg KOH / g.
  11. 　カーボンニュートラル可能な原材料成分が水性フレキソ印刷インキ組成物中１０質量％以上であり、かつロジン系樹脂とスチレン－アクリル系樹脂エマルジョンとの固形分比率が、１：０．８～１：３．５の範囲である請求項７～１０のいずれかに記載の水性フレキソ印刷インキ組成物。 The carbon-neutralizable raw material component is 10% by mass or more in the aqueous flexographic printing ink composition, and the solid content ratio of the rosin resin to the styrene-acrylic resin emulsion is 1: 0.8 to 1: 3.5. The aqueous flexographic printing ink composition according to any one of claims 7 to 10, which is in the range of
  12. 　平均粒子径が１～１０μｍのワックス樹脂微粒子分散体を含有する請求項７～１１のいずれかに記載の水性フレキソ印刷インキ組成物。 The aqueous flexographic printing ink composition according to any one of claims 7 to 11, comprising a wax resin fine particle dispersion having an average particle size of 1 to 10 μm.
  13. 　請求項７～１２のいずれかに記載の水性フレキソ印刷インキ組成物を使用して、食品パッケージの薄紙にフレキソ印刷する印刷方法。 A printing method of flexographic printing on thin paper of a food package using the aqueous flexographic printing ink composition according to any one of claims 7 to 12.
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