CN114854247A - Aqueous flexographic printing ink composition - Google Patents
Aqueous flexographic printing ink composition Download PDFInfo
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- CN114854247A CN114854247A CN202210655490.3A CN202210655490A CN114854247A CN 114854247 A CN114854247 A CN 114854247A CN 202210655490 A CN202210655490 A CN 202210655490A CN 114854247 A CN114854247 A CN 114854247A
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- ink composition
- resin
- resistance
- rosin
- aqueous flexographic
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—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
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- 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
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/08—Printing inks based on natural resins
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- 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
Abstract
The present invention addresses the problem of providing a flexographic printing ink composition for paper containers and the like, which is excellent in physical properties such as coating film physical properties, resolubility, dew condensation resistance, and hexane resistance, and a flexographic printing ink composition for thin paper applications for food packaging, which is excellent in physical properties such as coating film physical properties such as water resistance, abrasion resistance, heat resistance, oil resistance, and rub resistance, and resolubility, even when a large amount of a carbon-neutralizable raw material is used. As a solution, an aqueous flexographic printing ink composition is provided, which is characterized by containing: a pigment, a pigment dispersing resin, a rosin resin emulsion having an acid value of 80 to 350mgKOH/g and/or a neutralized product of a rosin resin having an acid value of 80 to 350mgKOH/g, a styrene-acrylic resin emulsion having a glass transition temperature of-30 to 60 ℃ and an acid value of 30 to 80mgKOH/g, and an aqueous solvent.
Description
The application is a divisional application of an invention patent with the application date of 2018, 12 and 13, and the application number of 201880079510.9, and the invention name of the invention is 'aqueous flexographic printing ink composition'.
Technical Field
The invention relates to an aqueous flexographic printing ink composition and a flexographic printing method using the same.
Background
In the field of printing of packaging containers centered on corrugated paper for articles of daily use, industrial materials, and the like, aqueous flexographic printing is carried out. In recent years, efforts have been actively made to address the environment, and there is also a demand in the packaging industry to realize an ink that can reduce the emission of carbon dioxide (carbon neutralization) by using a raw material derived from a non-fossil fuel such as a raw material derived from a plant or an animal. The present applicant has proposed, on the premise of such a demand, the use of an aqueous polylactic acid resin dispersion obtained by dispersing a polylactic acid resin in an aqueous medium in the presence of a poly (ethylene oxide/propylene oxide) block polymer as a binder resin (see, for example, patent document 1). However, this method has problems of printability and insufficient coating film properties. Further, in the use of thin paper for food packaging, there is a problem that the coating film properties such as printability, water-resistant and rub-resistant properties, heat resistance, oil-resistant and rub-resistant properties are insufficient. Further, for example, when printing is performed on a paper food container, in an environment where the paper food container is used, that is, in an environment where water or oil is adhered, in addition to the above properties, dew condensation resistance and hexane resistance are required, but there is no printing ink composition having such properties. Further, if a large amount of a carbon-neutralizable raw material is used, there is a problem that the physical properties and printability of a conventional ink coating film are deteriorated.
Documents of the prior art
Patent document
Patent document 1: japanese laid-open patent publication No. 2008-013657
Disclosure of Invention
The present invention addresses the problem of providing a flexographic printing ink composition for paper containers and the like, which is excellent in physical properties such as coating film physical properties, resolubility, dew condensation resistance, and hexane resistance, and a flexographic printing ink composition for thin paper applications for food packaging, which is excellent in physical properties such as coating film physical properties such as water resistance, abrasion resistance, heat resistance, oil resistance, and rub resistance, and resolubility, even when a large amount of a carbon-neutralizable raw material is used.
The present inventors have found that the above problems can be solved by using the following aqueous flexographic ink composition, and have solved the present invention.
Namely, the present invention is that,
1. an aqueous flexographic ink composition comprising: a pigment, a pigment dispersing resin, a rosin resin having an acid value of 0mgKOH/g and/or 0 to 350mgKOH/g, a styrene-acrylic resin emulsion having a glass transition temperature of-30 to 60 ℃ and an acid value of 30 to 80mgKOH/g, and an aqueous solvent.
2. The aqueous flexographic printing ink composition according to claim 1, wherein the pigment-dispersing resin contains an alkali-soluble water-soluble resin.
3. The aqueous flexographic ink composition according to claim 1 or 2, wherein the pigment-dispersing resin contains a (ethylene oxide/propylene oxide) block polymer.
4. The aqueous flexographic printing ink composition according to any of claims 1 to 3, characterized in that the rosin-based resin is a rosin-based resin having an acid value of 0 to 200 mgKOH/g.
5. The aqueous flexographic printing ink composition according to any one of claims 1 to 4, wherein the carbon-neutralizable raw material component accounts for 10% by mass or more of the aqueous flexographic printing ink composition, and the solid content ratio of the rosin-based resin to the styrene-acrylic resin emulsion is 1: 0.8-1: a range of 3.5.
6. The aqueous flexographic printing ink composition according to any of claims 1 to 5, characterized by containing a wax resin fine particle dispersion having an average particle diameter of 1 to 10 μm.
7. A printing method comprising performing flexographic printing on a thin paper for food packaging using the aqueous flexographic printing ink composition according to any one of claims 1 to 6.
Detailed Description
The aqueous flexographic ink composition of the present invention will be described in detail below.
The aqueous flexographic printing ink composition of the present invention contains a carbon-neutralizable raw material component, and preferably contains 10 mass% or more of the carbon-neutralizable raw material component in the solid content of the aqueous flexographic printing ink composition. The aqueous flexographic ink composition of the present invention is used for printing on a paper container or the like, or a tissue paper for food packaging.
(pigments)
As the pigment used in the aqueous flexographic printing ink composition of the present invention, a pigment conventionally used in aqueous flexographic printing inks can be used. Specific examples of the inorganic pigment include colored pigments such as titanium oxide, red iron oxide, antimony red, cadmium yellow, cobalt blue, prussian blue, ultramarine, carbon black, and graphite. Further, as the organic pigment, oil-soluble azo pigments, insoluble azo pigments, azo lake pigments, condensed azo pigments, copper phthalocyanine pigments, condensed polycyclic pigments, and the like can be cited. The pigment may be used in 1 or more than 2.
The concentration of the pigment in the aqueous flexographic 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.
(resin for pigment Dispersion)
The pigment-dispersing resin used in the aqueous flexographic ink composition of the present invention is an alkali-soluble water-soluble resin, and a (ethylene oxide/propylene oxide) block polymer is preferably used in combination.
(alkali-soluble type water-soluble resin)
The alkali-soluble water-soluble resin as the pigment-dispersing resin is not particularly limited, and any resin may be used as long as it is a resin obtained by polymerizing a monomer having an unsaturated double bond, or a resin obtained by reacting functional groups with each other, which is used in a general aqueous flexographic ink composition.
Specifically, as preferable examples, various binder resins such as acrylic acid or methacrylic acid and an alkyl ester thereof, or a water-soluble acrylic resin obtained by copolymerizing a monomer component mainly comprising styrene or the like, a water-soluble styrene-acrylic resin, a water-soluble styrene-maleic resin, a water-soluble styrene-acrylic-maleic resin, a water-soluble polyurethane resin, a water-soluble polyester resin, and the like can be exemplified.
These alkali-soluble water-soluble resins are usually used as water-soluble resin varnishes by dissolving them in water in the presence of an alkali compound. Examples of the basic compound used for dissolving the alkali-soluble water-soluble resin in water include ammonia, organic amines, and alkali metal hydroxides. Specifically, the organic amine includes 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 and potassium hydroxide. Among them, from the viewpoint of improving dryness, dew condensation resistance and hexane resistance required for paper containers and the like, amines having a low boiling point and high volatility are preferable, and those having a boiling point of 150 ℃ or less, more preferably 100 ℃ or less, further preferably 50 ℃ or less, and particularly preferably 0 ℃ or less such as ammonia are preferable.
As such a resin, JONCRYL HPD-671 manufactured by BASF corporation and the like can be used. In addition, from the viewpoint of coating film physical properties and re-solubility required for thin paper applications and the like, volatile and nonvolatile basic compounds are preferably used.
The amount of the alkali-soluble water-soluble resin used 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 the pigment-dispersing resin, a (ethylene oxide/propylene oxide) block polymer contains two or more blocks, each block being 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 is reacted with propylene oxide to form a poly (propylene oxide/ethylene oxide/propylene oxide) block polymer, and as another approach, a polypropylene oxide polymer is reacted with ethylene oxide to form a poly (ethylene oxide/propylene oxide/ethylene oxide) block polymer.
The (ethylene oxide/propylene oxide) block polymer used in the present invention has a weight average molecular weight in the range of 5,000 to 100,000, and examples of commercially available products include Adeka Pluronic series manufactured by ADEKA corporation.
Further, the HLB value of the (ethylene oxide/propylene oxide) block polymer is preferably 8 to 20 in terms of the stability of the aqueous solvent.
The HLB value is a Balance between a hydrophilic portion and a lipophilic portion of a molecule (Hydrophile-Lipophile Balance) used in the field of surfactants, and can be obtained by applying Griffin formula (formula based on an experimental value obtained by measuring an emulsification efficiency with respect to a certain oil and a weight fraction of the hydrophilic portion) shown below.
[ Griffin formula ] HLB ═ 100/5 (x hydrophilic basis weight/(hydrophilic basis weight + hydrophobic weight)
The amount of the (ethylene oxide/propylene oxide) block polymer used is 0.5 to 10 parts by mass, preferably 0.5 to 8.0 parts by mass, per 100 parts by mass of the pigment.
The amount of the alkali-soluble water-soluble resin + (ethylene oxide/propylene oxide) block polymer used is preferably 10 to 30 parts by mass per 100 parts by mass of the pigment.
(rosin resin)
From the viewpoint of obtaining an aqueous flexographic ink composition excellent in physical properties of a coating film, re-solubility, dew condensation resistance, hexane resistance and the like, the rosin resin (hereinafter, the rosin resin is referred to as "rosin resin a") has an acid value of 80 to 350mgKOH/g, and may be either an emulsion or a water-soluble resin based on a volatile basic compound.
The rosin resin A emulsion having an acid value of 80 to 350mgKOH/g can be obtained by dispersing a rosin derivative such as a rosin ester or rosin in the presence of a low-molecular emulsifier or a high-molecular emulsifier comprising an acrylic copolymer, the rosin derivative being a material obtained by extraction from a plant or the like, or the rosin being fine particles in water. Specifically, HARIESTER SK370N manufactured by harlima chemical corporation, and the like can be exemplified.
The water-soluble rosin resin A emulsion preferably has an acid value of 100 to 300mgKOH/g, more preferably 120 to 270mgKOH/g, and still more preferably 150 to 250 mgKOH/g.
Specific examples of the water-soluble rosin-based resin A having an acid value of 80 to 350mgKOH/g include HARIMACK T-80, AS-5, HARIESTER MSR-4, TESPOL1150, 1154 and 1158 manufactured by Harlima chemical company, and MALKYD 31, 32 and 33 manufactured by Ishikawa chemical industry.
However, the water-soluble rosin-based resin a needs to be neutralized with a basic compound, and examples of the basic compound include ammonia and organic amines. Specifically, the organic amine may include alkylamines such as diethylamine, triethylamine, and ethylenediamine, and alkanolamines such as monoethanolamine, ethylethanolamine, diethylethanolamine, diethanolamine, and triethanolamine. Here, the boiling point of the highly volatile amine is preferably as low as possible from the viewpoint of dew condensation resistance and hexane resistance, and is 150 ℃ or lower, more preferably 100 ℃ or lower, further preferably 50 ℃ or lower, and particularly preferably 0 ℃ or lower.
The water-soluble rosin resin A preferably has an acid value of 100 to 300mgKOH/g, more preferably 120 to 270mgKOH/g, and still more preferably 150 to 250 mgKOH/g.
The content of the rosin-based resin a having an acid value of 80 to 350mgKOH/g in the aqueous flexographic ink composition of the present invention is preferably such that a carbon-neutralizable raw material component is contained in an amount of 10 mass% or more in the solid content of the aqueous flexographic ink composition. The carbon-neutralizable raw material component means a raw material component derived from a plant material.
From the viewpoint of obtaining an aqueous flexographic ink composition excellent in coating film properties such as water resistance and wear resistance, heat resistance, oil resistance and friction resistance, and properties such as re-solubility, the acid value of the rosin-based resin (hereinafter, the rosin-based resin is referred to as "rosin-based resin B") is 0mgKOH/g and/or 0 to 350mgKOH/g, and the rosin-based resin may be either an emulsion or a water-soluble resin. As such rosin-based resin B emulsion, a rosin derivative such as rosin ester or rosin, which is a material extracted from plants or the like, is dispersed in water as fine particles in the presence of a low-molecular-weight emulsifier. Specifically, HARIESTER SK218NS, SK370N, SK385NS and SK501NS manufactured by Harlima chemical company, Snowpack XW-2442, XW-2551, XW-2561, XW-2582, SE780G and 100G manufactured by Lauter chemical company, SUPER ESTER NS-121 and NS-100H, E-865NT manufactured by Mitsuwa chemical company, and the like can be exemplified.
The water-soluble rosin resin B is obtained by neutralizing a part or all of the acid value of a rosin resin having an acid value of 100 to 350mgKOH/g with a basic compound and dissolving the neutralized rosin resin in water. Specifically, TESPOL 150, 154, 158 manufactured by Hitachi chemical Co., Ltd, HARIMACK T-80, HARIESTER MSR-4, AS-5 manufactured by Harlima chemical Co., Ltd, MALKYD 31, 32, 33 manufactured by Mitsuka chemical Co., Ltd, and the like can be cited.
Examples of the basic compound include ammonia, organic amines, and alkali metal hydroxides. Specifically, the organic amine includes 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 and potassium hydroxide. Among them, volatile and nonvolatile basic compounds are preferably used from the viewpoint of the physical properties and re-solubility of the coating film.
Among the acid values of the rosin-based resin B, a rosin-based resin having an acid value of 0 to 200mgKOH/g is preferable, and when water resistance and abrasion resistance are required, a rosin-based resin B emulsion having an acid value of 0 to 100mgKOH/g is preferable.
The content of the rosin-based resin B in the aqueous flexographic ink composition of the present invention is preferably 10 mass% or more of a carbon-neutralizable raw material component in the solid content of the aqueous flexographic ink composition. The carbon-neutralizable raw material component means a raw material component derived from a plant material.
(styrene-acrylic resin emulsion)
The aqueous flexographic ink composition of the present invention may be formulated with a styrene-acrylic resin emulsion. As the styrene-acrylic resin emulsion, a styrene-acrylic resin emulsion having an acid value of 30 to 80mgKOH/g and a glass transition temperature of-30 to 60 ℃ which is produced by a known method can be used. The lower limit of the glass transition temperature range is preferably-20 ℃, more preferably-10 ℃, and the upper limit thereof is 40 ℃, more preferably 20 ℃.
Among such styrene-acrylic resin emulsions, in order to improve the printability by a water-soluble acrylic resin, preferably to improve the printability by a rosin-based resin, it is preferable to use a water-soluble acrylic resin obtained by neutralizing an acrylic resin having an acid value of 150 to 250mgKOH/g with a basic compound as a polymer emulsifier, and to copolymerize a styrene monomer and, if necessary, an alkyl ester of (meth) acrylic acid, and to form a film at ordinary temperature.
When a basic compound is used in the styrene-acrylic resin emulsion, examples of the basic compound include ammonia and organic amines. Specifically, the organic amine may include alkylamines such as diethylamine, triethylamine, and ethylenediamine, and alkanolamines such as monoethanolamine, ethylethanolamine, diethylethanolamine, diethanolamine, and triethanolamine. Among them, from the viewpoint of dew condensation resistance and hexane resistance, amines having a low boiling point and high volatility are preferable, and those having a boiling point of 150 ℃ or less, more preferably 100 ℃ or less, still more preferably 50 ℃ or less, and particularly preferably 0 ℃ or less such as ammonia are preferable.
As such a resin, JONCRYL 309 (glass transition temperature 2 ℃, solid content 46%) manufactured by BASF corporation, etc. can be used.
When the styrene-acrylic resin emulsion is used in an amount of 10 mass% or more of a raw material component capable of being neutralized by carbon in the solid content of the aqueous flexographic ink composition, the solid content ratio of the rosin-based resin to the styrene-acrylic resin emulsion is preferably 1: 0.8-1: a range of 3.5.
(wax resin Fine particle Dispersion)
In the aqueous flexographic printing ink composition of the present invention, a commercially available dispersion of wax fine particles having an average particle diameter of 1 to 10 μm, preferably 2 to 5 μm according to the Coulter counter method can be used for the purpose of improving the rub resistance of the coating film. The wax resin fine particle dispersion is preferably polyethylene wax, and specific examples thereof include CHEMIPEARL W100, W200, W300, W310, W306, W400, W410, W500, and W800 manufactured by mitsui chemical corporation. The amount of the wax resin microparticle dispersion to be added is preferably about 1 to 7% by mass in terms of solid content in 100% by weight of the aqueous flexographic ink composition, in view of the balance between the improvement in abrasion resistance and the adverse effect on hue in the physical properties of the coating film.
(aqueous solvent)
As the solvent used in the aqueous flexographic printing ink composition of the present invention, a water-soluble organic solvent is used in addition to water within a range that does not deteriorate the performance of the aqueous flexographic printing ink composition of the present invention.
As the water-soluble organic solvent, alcohol and polyhydric alcohol solvents are mentioned, and specifically, methanol, ethanol, propanol, butanol, hexanol, octanol, decanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monooctyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monopropyl ether, triethylene glycol monobutyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether, tripropylene glycol monopropyl ether, tripropylene glycol monobutyl ether, dibutylene glycol monoethyl ether, dipropylene glycol monopropyl ether, tripropylene glycol monobutyl ether, propylene glycol, Glycerin, and the like.
(additives)
In the aqueous flexographic printing ink composition of the present invention, various additives may be used as necessary.
Specifically, extender pigments such as calcium carbonate, kaolin, barium sulfate, aluminum hydroxide, clay and talc may be used for improving the drying property, inorganic fine particles and viscous resins (acrylic resin and vinyl acetate resin) may be used for imparting slip resistance, leveling agents may be used for improving leveling property, defoaming agents (SN defoaming agent 777# C, manufactured by sannopol corporation) may be used for imparting defoaming property, and various additives such as an alkaline compound such as caustic soda and a film-forming emulsion may be used for imparting redissolving property.
Next, the aqueous flexographic printing ink composition and the method for producing a printed matter according to the present invention will be described.
As a method for producing the aqueous flexographic ink composition of the present invention by a conventional method, a pigment-dispersing resin, and an aqueous solvent are mixed, and then kneaded by various kneading machines such as a bead Mill, a Pearl Mill, a sand Mill, a ball Mill, a vertical ball Mill (attritor), and a roll Mill, and further, predetermined materials such as a rosin-based resin emulsion and a styrene-acrylic resin emulsion, and additives as necessary are mixed.
Subsequently, if dilution is necessary at the time of printing, an aqueous solvent is further added to obtain an aqueous flexographic ink composition. Examples of a method for producing a printed matter using the aqueous flexographic printing ink composition include a method of printing on a paper or resin surface, particularly printing on a paper container such as a paper cup or a paper tray, a paper container having a surface covered with a resin layer, a food packaging tissue, or a material thereof using the aqueous flexographic printing ink composition by a flexographic printing machine.
In this case, the printed matter may be any of food packages such as packaging paper and paper bags, paper products such as paper containers having a resin layer such as polyolefin laminated on the surface thereof, paper products such as paper containers having a resin layer such as a resin coating layer of polyolefin on the surface thereof, paper products such as uncoated paper containers having no resin layer on the surface thereof, and the like.
A known method can be used for producing paper having a resin layer made of polyolefin or the like by lamination or coating.
Examples
The present invention will be described in further detail with reference to examples, but the present invention is not limited to these examples. Unless otherwise specified, "%" means "% by mass" and "part(s)" means "part(s) by mass". In addition, the numbers on the components of the respective materials in the table are also "parts by mass". The unit of the acid value is mgKOH/g.
(evaluation method)
(redissolution)
The aqueous flexographic printing ink composition was spread on a substrate using a 0.10mm Mayer Bar (Mayer Bar), dried, and then the same ink composition was dropped onto the coating film and wiped off, to evaluate the solubility of the dried coating film in the same ink composition.
Very good: after the rubbing off, no coating film remained on the plate and the substrate.
Very good: after the rubbing, a very small amount of coating film remained on the plate and the substrate.
O: after being wiped off, a small amount of coating film remains on the plate and the substrate.
Δ ≈ Δ: after the rubbing off, about half of the coating film remained on the plate and the substrate.
And (delta): a small amount of coating film can be wiped off the plate and the substrate.
X: the coating film could not be wiped off from the plate and the substrate.
(Hexane resistance)
The base paper was developed with a 200-wire hand-proofing machine (hand proofer) and immersed in a n-hexane bath for 2 hours at room temperature. After the immersion, the degree of coloring of n-hexane by the ink, peeling of the ink coating film, and whitening of the ink was evaluated.
Very good: no coloration, no peeling, and no whitening
Very good: a small amount of at least one of coloration, exfoliation, and whitening
Good: no coloration or peeling, and whitening of a part of the coating film
Good and Δ: no coloration or peeling, and whitening of the coating film
And (delta): no coloration, partial peeling of the coating film, and whitening of the coating film in most cases
X: coloring and most of the coating film comes off
(resistance to Water and abrasion)
The color developed on the base paper was developed with a 200-line hand proofing machine, and the developed color was evaluated using a chemical vibration type rubbing fastness testing machine.
Evaluation conditions were as follows: 200g × 2 times, contact paper: article for dripping 5 drops of water on bleached fine cotton cloth
Very good: the coating film was not removed.
O: a small amount of ink is attached to the contact paper. The ink of the color-developing substance is removed in a small amount.
Δ ≈ Δ: ink is thinly attached to the entire surface of the contact paper. The ink of the color-developing substance is removed in a small amount.
And (delta): ink is thinly attached to the entire surface of the contact paper. After the ink of the developed color material was removed, a part of the base paper was observed.
X: ink is densely attached to the whole surface of the contact paper. With regard to the color-developed material, the ink was also removed and most of the base paper was visible.
(abrasion resistance)
The color developed on the base paper was developed with a 200-line hand proofing machine, and the developed color was evaluated using a chemical vibration type rubbing fastness testing machine.
Evaluation conditions were as follows: 200g × 100 times, contact paper: bleached fine cotton cloth
Very good: the coating film was not removed.
Excellent: a very small amount of ink adheres to the contact paper. Ink of the color-developing substance is removed very little.
Good: a small amount of ink is attached to the contact paper. The ink of the color-developing substance is removed in a small amount.
Good and Δ: ink is thinly attached to the entire surface of the contact paper. The ink of the color-developing substance is removed in a small amount.
And (delta): ink is attached to the entire surface of the contact paper. After the ink of the developed color material was removed, a part of the base paper was observed.
X: ink is densely attached to the whole surface of the contact paper. With regard to the color-developed material, the ink was also removed and most of the base paper was visible.
(oil and wear resistance)
In the examples using rosin resin a, the base paper was developed with a 200-line hand proofing machine, and the developed color was evaluated using a chemical vibration type rubbing fastness testing machine.
In the examples using rosin resin B, the color developed on base paper (K Liner) was developed with a 200-line hand proofing machine, and the color developed was evaluated using a chemical vibration type rubbing fastness testing machine.
Evaluation conditions were as follows: 200g × 2 times, contact paper: article for dropping 5 drops of salad oil on bleached fine cotton cloth
Very good: the coating film was not removed.
Excellent: a very small amount of ink adheres to the contact paper. Ink of the color-developing substance is removed very little.
Good: a small amount of ink adheres to the contact paper. The ink of the color-developing substance is removed in a small amount.
Good and Δ: ink is thinly attached to the entire surface of the contact paper. The ink of the color-developing substance is removed in a small amount.
And (delta): ink is attached to the entire surface of the contact paper. After the ink of the developed color material was removed, a part of the base paper was observed.
X: ink is densely attached to the whole surface of the contact paper. With regard to the color-developed material, the ink was also removed and most of the base paper was visible.
The results of the test were the same for the article printed on the base paper (K Liner, uncoated paper) as for the article printed on the tissue paper (uncoated paper).
(alcohol resistance and abrasion resistance)
The color developed on the base paper was developed with a 200-line hand proofing machine, and the developed color was evaluated using a chemical vibration type rubbing fastness testing machine.
Evaluation conditions were as follows: 200g × 2 times, contact paper: article with 5 drops of 80% ethanol dropped on bleached fine cotton cloth
Alkali-soluble aqueous acrylic resin (solid content: 25% by mass) JONCRYL HPD-671, manufactured by BASF corporation
Poly (ethylene oxide/propylene oxide) block polymer: HLB value 14, Mw16000
Rosin emulsion (solid content 50% by mass, softening point 100 ℃ C., containing nonionic surfactant) HARIESTER SK218NS, manufactured by Harlima chemical Co., Ltd
Polyethylene wax (35 mass% solid content) CHEMIPEARL W-100, manufactured by Mitsui chemical Co., Ltd
Antifoaming agent SN antifoaming agent 777# C manufactured by Saint Novaco Co
(aqueous flexographic ink composition Using rosin-based resin A)
A mixture of a pigment (phthalocyanine blue, c.i. pigment blue 15: 3), an alkali-soluble water-based acrylic resin (JONCRYL HPD-671, manufactured by BASF corporation, solid content 25%), a poly (ethylene oxide/propylene oxide) block polymer ((EO/PO) block polymer, HLB value 14, Mw16000), dibutyl glycol, and water was kneaded and dispersed by a bead mill, and then a rosin-based resin a emulsion, an acrylic emulsion (styrene-acrylic resin emulsion), a polyethylene wax, and a defoaming agent were added to the mixture in such proportions as to achieve the proportions shown in table 1, and the mixture was mixed to obtain an aqueous flexographic printing ink composition.
The results of printing on polyethylene laminated paper obtained by laminating a polyethylene layer on the surface of a paper layer as a substrate are shown in table 2, and the results of printing on uncoated paper obtained by laminating a resin layer on the surface of a paper layer or not coated with a resin as a substrate are shown in table 3.
[ Table 1]
[ Table 2]
[ Table 3]
According to examples a1 to a10 which are examples according to the present invention, ink compositions excellent in re-solubility, hexane resistance, water resistance and abrasion resistance, oil resistance and abrasion resistance, and alcohol resistance and excellent in abrasion resistance, that is, printing applications for paper tableware such as paper cups and paper trays, can be obtained.
On the other hand, in comparative example a1 using rosin-based resin a having a low acid value, the hexane resistance was poor, and in comparative examples a2 and A3 using rosin-based resin a neutralized with a nonvolatile basic compound, the water resistance and abrasion resistance of the film were poor, and in comparative examples a4 and a5 using styrene-acrylic emulsion having an excessively high glass transition temperature, the water resistance and abrasion resistance and the alcohol resistance and abrasion resistance were poor.
(aqueous flexographic ink composition Using rosin-based resin B)
A mixture of a pigment (phthalocyanine blue, c.i. pigment blue 15: 3), an alkali-soluble water-soluble resin (JONCRYL HPD-671, manufactured by BASF, 25% solid content), (ethylene oxide/propylene oxide) block polymer ((EO/PO) block polymer, HLB value 14, Mw16000), dibutylethylene glycol, and water was kneaded and dispersed with a bead mill, and then, a rosin resin B, a styrene-acrylic resin emulsion, polyethylene wax, and a defoaming agent were added to the mixture in such a ratio as to achieve table 4, and the mixture was mixed to obtain an aqueous flexographic printing ink composition.
[ Table 4]
According to examples B1 to B14, which are examples consistent with the present invention, ink compositions excellent in re-solubility, water resistance, rub resistance, wear resistance, and oil resistance and wear resistance can be obtained. On the other hand, in comparative examples B1 and B2 in which styrene-acrylic resin emulsions having glass transition temperatures out of the range of the present invention were used, the water resistance and the abrasion resistance were poor and the abrasion resistance was not so good.
Further, according to examples B7 and B8, printing excellent in abrasion resistance and oil and abrasion resistance was possible.
Claims (7)
1. An aqueous flexographic ink composition comprising: a pigment, a pigment dispersing resin, a rosin resin having an acid value of 0mgKOH/g and/or 0 to 350mgKOH/g, a styrene-acrylic resin emulsion having a glass transition temperature of-30 to 60 ℃ and an acid value of 30 to 80mgKOH/g, and an aqueous solvent.
2. The aqueous flexographic ink composition according to claim 1, wherein the pigment-dispersing resin contains an alkali-soluble water-soluble resin.
3. The aqueous flexographic ink composition according to claim 1 or 2, wherein the pigment-dispersing resin contains a block polymer of ethylene oxide and/or propylene oxide.
4. The aqueous flexographic printing ink composition according to any of claims 1 to 3 wherein the rosin-based resin is a rosin-based resin having an acid value of 0 to 200 mgKOH/g.
5. The aqueous flexographic printing ink composition according to any one of claims 1 to 4, wherein the carbon-neutralizable raw material component accounts for 10% by mass or more of the aqueous flexographic printing ink composition, and the solid content ratio of the rosin-based resin to the styrene-acrylic resin emulsion is 1: 0.8-1: a range of 3.5.
6. The aqueous flexographic printing ink composition according to any of claims 1 to 5, characterized by containing a wax resin fine particle dispersion having an average particle diameter of 1 to 10 μm.
7. A printing method comprising flexographically printing on a food packaging tissue paper using the aqueous flexographic ink composition according to any one of claims 1 to 6.
Applications Claiming Priority (8)
| Application Number | Priority Date | Filing Date | Title |
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| JP2017240808 | 2017-12-15 | ||
| JP2017-240808 | 2017-12-15 | ||
| JP2018230410A JP7229744B2 (en) | 2017-12-15 | 2018-12-07 | Aqueous flexographic printing ink composition |
| JP2018230411A JP7229745B2 (en) | 2017-12-15 | 2018-12-07 | Aqueous flexographic printing ink composition |
| JP2018-230411 | 2018-12-07 | ||
| JP2018-230410 | 2018-12-07 | ||
| CN201880079510.9A CN111448268A (en) | 2017-12-15 | 2018-12-13 | Aqueous flexographic printing ink composition |
| PCT/JP2018/045801 WO2019117231A1 (en) | 2017-12-15 | 2018-12-13 | Aqueous flexographic printing ink composition |
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