WO2022130549A1 - Encre d'impression liquide, matière imprimée, et corps stratifié - Google Patents

Encre d'impression liquide, matière imprimée, et corps stratifié Download PDF

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Publication number
WO2022130549A1
WO2022130549A1 PCT/JP2020/047073 JP2020047073W WO2022130549A1 WO 2022130549 A1 WO2022130549 A1 WO 2022130549A1 JP 2020047073 W JP2020047073 W JP 2020047073W WO 2022130549 A1 WO2022130549 A1 WO 2022130549A1
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WO
WIPO (PCT)
Prior art keywords
ink
printing ink
titanium oxide
resin
liquid printing
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PCT/JP2020/047073
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English (en)
Japanese (ja)
Inventor
悠 片山
帆南美 山本
義道 河合
直 茂呂居
Original Assignee
Ｄｉｃグラフィックス株式会社
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Priority to PCT/JP2020/047073 priority Critical patent/WO2022130549A1/fr
Publication of WO2022130549A1 publication Critical patent/WO2022130549A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
    • C09D11/037—Printing inks characterised by features other than the chemical nature of the binder characterised by the pigment
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/102—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds

Definitions

  • the present invention relates to a liquid printing ink that can be used as a gravure ink or a flexographic ink.
  • Liquid printing inks such as gravure inks and flexographic inks are widely used for the purpose of imparting cosmeticity, functionality, and surface protection to an object to be printed.
  • this printed matter is used as a food packaging material among packaging materials, it is generally laminated.
  • various printed materials and laminating processes are used depending on the type of contents and the purpose of use.
  • printing inks using polyurethane resin as a binder have been widely used for such laminated products because they are excellent in adhesiveness to various objects to be printed, laminating strength of various laminated products, and boil retort suitability. ..
  • liquid printing inks are required to have adhesiveness to various packaging materials, laminating strength, and blocking resistance after film printing.
  • the part where the ink cannot be scratched by the doctor in the part other than the image line part becomes “fog” and transfers to the printed matter, "plate fog phenomenon", and the ink is clogged in the cell of the gravure printing plate.
  • it is also required to maintain good highlight transferability due to the "plate jam phenomenon” that does not easily transfer to printed matter, and further improvement is being attempted as an ink that satisfies all of these problems.
  • white ink mainly uses titanium oxide as a pigment, which is an inorganic pigment and has a high content in the ink. Is more difficult than inks that use organic pigments such as indigo ink. Further, since it has a hardness higher than that of an organic pigment, there is a problem that the doctor blade is severely worn when it is used as a gravure ink.
  • a composite particle containing titanium oxide particles, barium sulfate particles and / or calcium carbonate particles arranged around the titanium oxide particles, and the composite particles are coated with an aluminum compound.
  • a method of using a composite white pigment for gravure ink, which is larger than the size of one titanium oxide particle and is easily scraped by a doctor blade see, for example, Patent Document 1
  • a method of improving the printability of a gravure ink by using titanium oxide having a rutile crystal structure is known (see, for example, Patent Document 2, paragraph 0059).
  • neither method has been able to satisfy all of these problems.
  • the problems of the present invention are excellent adhesiveness to various packaging materials, laminating strength, blocking resistance after film printing, less likely to cause plate fog in gravure printing, hiding property, adhesiveness to film substrate, and resistance. It is an object of the present invention to provide a liquid printing ink having excellent blocking properties and laminating suitability.
  • liquid printing inks containing a binder resin, an organic solvent, and a colorant are liquid printing inks containing a binder resin, an organic solvent, and a colorant, and the oxidation obtained by the sulfuric acid method as the colorant. It has been found that a liquid printing ink containing titanium (A) and an inorganic filler (B) solves the above-mentioned problems.
  • the present invention is a liquid printing ink containing a binder resin, an organic solvent, and a colorant, and is characterized by containing titanium oxide (A) and an inorganic filler (B) obtained by a sulfuric acid method. Regarding liquid printing ink.
  • the present invention also relates to a liquid printing ink having a treated layer made of at least alumina and / or silica on the surface of the titanium oxide (A).
  • the present invention also relates to a liquid printing ink in which the Mohs hardness of the inorganic filler (B) is 1 to 5.
  • the present invention also relates to a liquid printing ink in which the inorganic filler (B) is a clay mineral.
  • the present invention also relates to a liquid printing ink in which the mass ratio of the titanium oxide (A) to the inorganic filler (B) is 99: 1 to 1:99.
  • the present invention also relates to a liquid printing ink in which the binder resin is a polyurethane urea resin having a weight average molecular weight of 15,000 to 100,000 and a urethane bond concentration of 1.2 mmol / g or more and 2.5 mmol / g or less. ..
  • the present invention also relates to a printed matter having a printed layer formed by printing the liquid printing ink on a substrate.
  • the present invention relates to a laminate in which an adhesive layer and a film layer are sequentially bonded to the printed layer of the printed matter.
  • the adhesiveness to various packaging materials, the laminating strength, and the blocking resistance after film printing are excellent, the phenomenon of plate fog is less likely to occur in gravure printing, the hiding property, the adhesiveness to the film substrate, and the blocking resistance. , And a liquid printing ink with excellent laminating suitability can be obtained.
  • the liquid printing ink refers to a liquid-like ink applied to a printing method using a printing plate, such as a gravure ink or a flexo ink, and is preferably a gravure ink or a flexo ink. Further, the liquid printing ink of the present invention does not contain an active energy curable component, that is, is an active energy ray non-reactive liquid ink.
  • the "inks” used in the following description all refer to “printing inks”. Further, "parts" all indicate “parts by mass”.
  • the liquid printing ink of the present invention is a white printing ink containing titanium oxide (A) and an inorganic filler (B) obtained by a sulfuric acid method as a white colorant.
  • titanium oxide (A) As the titanium oxide used in the present invention, known titanium oxide can be used without particular limitation on the production method, shape, crystal shape and particle size.
  • the titanium oxide particles may be produced by a chlorine method or a sulfuric acid method. Those manufactured by the sulfuric acid method are preferable in terms of suppressing wear of the doctor blade.
  • An example of a specific embodiment of the titanium oxide manufacturing process by the sulfuric acid method is as follows.
  • Dissolution step The dried and crushed ilmenite ore is dissolved with sulfuric acid to prepare a solution mainly of titanium sulfate (TIOSO 4 ) and ferrous sulfate (FeSO 4 ).
  • Cooling and separation steps The undiluted solution is cooled and crystallized ferrous sulfate (FeSO 4.7H 2 O) is separated by a centrifuge to obtain the undiluted solution.
  • Hydrolysis step The undiluted solution from which ferrous sulfate is separated is heated to separate it into titanium hydroxide (TIM (OH) 2 ) and sulfuric acid.
  • the crystal form of the titanium oxide particles may be rutile type, anatase type or brookite type.
  • the rutile type is preferable in that a higher hiding rate can be obtained.
  • the average particle size of the titanium oxide particles is preferably 0.1 to 1.0 ⁇ m, more preferably 0.1 to 0.5 ⁇ m, still more preferably 0.2 to 0, from the viewpoint of exhibiting high glossiness and hiding rate. It is 3 ⁇ m. If the average particle size of the titanium oxide particles is less than 0.1 ⁇ m, the concealment rate is lowered, and the doctor blade is likely to leave unscraped particles, which is likely to cause plate fog. Further, if the average particle size of the titanium oxide particles exceeds 1.0 ⁇ m, the hiding rate and glossiness may decrease.
  • the titanium oxide (A) preferably has a treated layer made of at least alumina and / or silica on the surface thereof.
  • silica is generally used for the purpose of adjusting the acid / base state of the titanium oxide surface and for imparting the durability of the obtained ink / paint film.
  • Alumina is used to improve the wetting of titanium oxide during dispersion.
  • the surface treatment method for titanium oxide include water-based treatment and vapor phase treatment. From the viewpoint of dispersion stability, the ratio of the treated amount of silica and the amount of treated alumina is preferably 35% by mass or more and 80% by mass or less.
  • the amount of the inorganic substance with respect to titanium oxide is not necessarily limited, but is generally 30 parts or less with respect to 100 parts of titanium oxide.
  • titanium oxide surface-treated with silica and alumina a commercially available product may be used, and for example, it is commercially available from a titanium oxide manufacturer such as Ishihara Sangyo Co., Ltd. or Tayca Corporation.
  • a titanium oxide manufacturer such as Ishihara Sangyo Co., Ltd. or Tayca Corporation.
  • varieties with a large amount of silica treated compared to the amount treated with alumina and varieties with a large amount of alumina treated compared to the amount treated with silica are commercially available, and titanium oxide whose amount treated with alumina falls within the above ratio range is also available. Can be done. It was
  • the mass ratio of each of the alumina and silica can be estimated from the amount of alumina and silica present together with titanium oxide on the surface of titanium oxide.
  • the abundance ratio of alumina and silica can be confirmed by analyzing and comparing the amounts of alumina or silica adsorbed on the surface of titanium oxide by fluorescent X-rays, ESCA or the like.
  • measurement by fluorescent X-ray is simple and highly accurate.
  • silica and alumina may be partially present as free particles, and the total amount can be measured by measuring with fluorescent X-rays.
  • an analysis method using a calibration curve using standard materials has been established. Therefore, the mass ratio of alumina and silica present on the surface of commercially available titanium oxide can be confirmed by measurement with fluorescent X-rays, and titanium oxide having various mass ratios can be used.
  • the inorganic filler (B) used in the present invention is not particularly limited, and is, for example, oxide-based ceramics such as alumina, silica, zirconia, magnesia, ceria, itria, zinc oxide, and iron oxide; silicon nitride, titanium nitride, boron nitride.
  • oxide-based ceramics such as alumina, silica, zirconia, magnesia, ceria, itria, zinc oxide, and iron oxide
  • silicon nitride titanium nitride, boron nitride.
  • Nitride-based ceramics such as silicon carbide, calcium carbonate, magnesium sulfate, aluminum sulfate, aluminum hydroxide, aluminum hydroxide, potassium titanate, talc, kaolinite, dikite, nacrite, halloysite, pyrophyllite, montmorillonite, seri.
  • Ceramics such as site, mica, amesite, bentonite, asbestos, zeolite, calcium silicate, magnesium silicate, diatomaceous earth, silica sand; glass fiber and the like can be mentioned. These may be used alone or in combination of two or more.
  • clay minerals such as kaolinite, halloysite, and montmorillonite are preferable, and kaolin (natural hydrous aluminum silicate) made from these clay minerals, for example, kaolinite (kaolin mineral), is also used. It can be preferably used.
  • kaolin wet kaolin and calcined kaolin formed by calcining the wet kaolin are known. In this embodiment, unbaked kaolin is particularly preferred.
  • the inorganic filler (B) preferably has an appropriate hardness, and specifically, the Mohs hardness is preferably in the range of 1 to 5. More preferably, the Mohs hardness is 1 to 3. It was
  • the average particle size of the inorganic filler is preferably more than 0.01 ⁇ m and 4.0 ⁇ m or less, more preferably more than 0.05 ⁇ m and 2.0 ⁇ m or less, and more than 0.1 ⁇ m and 1.0 ⁇ m.
  • Adjusting the average particle size of the inorganic filler to the above range is a method of adjusting the particle size of the inorganic filler and its distribution, for example, using an appropriate pulverizer such as a ball mill, a bead mill, or a jet mill to prepare the inorganic filler. Examples thereof include a method of pulverizing to reduce the particle size.
  • Examples of the shape of the inorganic filler include plate shape, scale shape, needle shape, columnar shape, spherical shape, polyhedral shape, and lump shape. A plurality of types of inorganic fillers having these shapes may be used in combination. It was
  • the inorganic filler may serve as a cushioning material. In that sense, the inorganic filler preferably has a Mohs hardness in the range of 1 to 5 as described above.
  • kaolin is the most effective inorganic filler that is used in combination with titanium oxide (A) to reduce the phenomenon of plate fog while maintaining high hiding power.
  • the content of titanium oxide (A) depends on the desired ink performance, but if it is a white ink that requires standard concealment and high plate fog, it is usually about 20 to 40% by mass with respect to the total mass of the ink. On the other hand, in the case of white ink for the purpose of very high concealment as a required performance, it is often designed with a content of about 40 to 60% by mass.
  • the titanium oxide (A) and the inorganic filler (B) are blended in a mass ratio of 99: 1 to 1:99, thereby contributing to the plate covering property and hiding property which are the effects of the present invention.
  • the mass ratio is preferably in the range of 99: 1 to 50:50, more preferably in the range of 99: 1 to 80:20.
  • the titanium oxide (A) and the inorganic filler (B) act as a white colorant, it is preferable that the titanium oxide (A) and the inorganic filler (B) are contained in the range of 20 to 75% by mass in total with respect to the total mass of the ink of the present invention. It is more preferably in the range of 20 to 60% by mass, and most preferably in the range of 30 to 50% by mass. In this range, it is possible to obtain an ink having a particularly excellent balance between plate fog and concealment.
  • a colorant can be added to the liquid printing ink of the present invention.
  • organic and inorganic pigments and dyes used in general inks, paints, recording agents and the like can be used.
  • Organic pigments include azo-based, phthalocyanine-based, anthraquinone-based, perylene-based, perinone-based, quinacridone-based, thioindigo-based, dioxazine-based, isoindoleinone-based, quinophthalone-based, azomethine-azo-based, dictopyrrolopyrrole-based, and isoindoline-based. Pigments can be mentioned.
  • the inorganic pigment examples include carbon black, red iron oxide, aluminum, mica (mica) and the like. Further, a bright pigment (Metashine; Nippon Sheet Glass Co., Ltd.), which is made of glass flakes or lumpy flakes as a base material and coated with a metal or a metal oxide, can be used. It is preferable to use carbon black for black ink, aluminum for gold and silver ink, and mica (mica) for pearl ink from the viewpoint of cost and coloring power.
  • aluminum is in the form of powder or paste, it is preferably used in the form of paste from the viewpoint of handleability and safety, and whether reefing or non-reefing is used is appropriately selected from the viewpoint of luminance and concentration.
  • the binder resin used in the present invention is not particularly limited as long as it is a binder resin used for liquid-like ink applied to a printing method using a printing plate, such as gravure ink or flexographic ink, but the present invention. It is preferable to use a polyurethane urea resin as the main binder resin because it is excellent in adhesiveness to a film substrate, blocking resistance, laminating suitability, highlight transfer property, and the like, which are problems.
  • a polyurethane urea resin having a weight average molecular weight of 15,000 to 100,000 and a urethane bond concentration in the range of 1.2 mmol / g or more and 2.5 mmol / g or less is preferable.
  • the structural unit derived from the polyether polyol is contained in an amount of 1 to 50% by mass, more preferably 1 to 30% by mass, in 100% by mass of the polyurethane urea resin.
  • the weight average molecular weight of the polyurethane urea resin is a value measured under the following conditions by a gel permeation chromatography (GPC) method.
  • Measuring device High-speed GPC device ("HLC-8220GPC" manufactured by Tosoh Corporation)
  • Column The following columns manufactured by Tosoh Corporation were connected in series and used.
  • TKgel G5000 (7.8 mm ID x 30 cm) x 1 "TSKgel G4000” (7.8 mm ID x 30 cm) x 1 "TSKgel G3000” (7.8 mm ID x 30 cm) x 1
  • Detector RI (Differential Refractometer) Column temperature: 40 ° C Eluent: Tetrahydrofuran (THF) Flow rate: 1.0 mL / min Injection amount: 100 ⁇ L (tetrahydrofuran solution with a sample concentration of 0.4% by mass) Standard sample: A calibration curve was prepared using the following standard polystyrene.
  • the urethane bond concentration of the urethane urea resin used in the liquid printing ink of the present invention is preferably 1.2 mmol / g or more and 2.5 mmol / g or less, and more preferably 1.3 mmol / g or more.
  • the urethane bond concentration of the liquid printing ink of the present invention is 1.2 mmol / g or more and 2.5 mmol / g or less, the adhesiveness to the film substrate and the blocking property accompanied by the set-off of the printed pattern are improved. It is more preferable if it is 3 mmol / g or more.
  • the urethane bond concentration is 1.2 mmol / g or more, the polyethylene extruded laminate strength for the gravure printed matter or the flexographic printed matter using the liquid printing ink of the present invention tends to be sufficiently maintained.
  • the urethane bond concentration is 2.5 mmol / g or less, in the case of gravure printing, the part where the ink cannot be scraped off by the doctor becomes "fog" in the part other than the image area and is transferred to the printed matter. The phenomenon that "the phenomenon of" occurs can be suppressed.
  • the urethane bond concentration of the present invention is 1.2 mmol / g or more and 2.5 mmol / g or less, it may cause problems in gravure printing in addition to adhesiveness to various films and blocking property accompanied by set-off of printed patterns. It also has "fog prevention”. Further, by setting the urethane bond concentration to 2.5 mmol / g or less, it is possible to suppress entanglement stains caused by the ink drying on the plate during long-run printing with a flexographic plate.
  • the urethane bond concentration can be calculated by the following formula (1).
  • Urethane bond concentration ⁇ (W1 x OH1 + W2 x OH2 + ... + Wi x OHi) x 1000 ⁇ / (56100 x S) Equation (1)
  • W1 Mass of polyol 1 OH1: Mass of polyol 1
  • W2 Mass of polyol 2
  • OH2 Mass of polyol 2
  • Wi Mass of polyol i OHi: Mass of polyol i hydroxyl value
  • S Mass of urethane resin solid content
  • polyether polyol examples include polymers such as ethylene oxide, propylene oxide and tetrahydrofuran, or polyether polyols of copolymers. Specifically, known general-purpose products such as polyethylene glycol, polypropylene glycol, and polytetramethylene glycol may be used.
  • polyether polyol in the above range, the adhesiveness is greatly improved especially on the high-performance barrier film, and as a result, the blocking resistance and the laminating strength are improved.
  • polyethylene glycol is particularly preferable in order to particularly improve the adhesiveness, blocking resistance and laminating strength on the high-performance barrier film.
  • the number average molecular weight of the polyether polyol is preferably 100 to 3500.
  • the number average molecular weight of the polyether polyol was measured under the above-mentioned conditions by the gel permeation chromatography (GPC) method as in the case of the polyurethane urea resin.
  • the number average molecular weight of the polyether polyol which is a constituent of the polyurethane urea resin used in the liquid printing ink of the present invention, is 100 or more, the film of the polyurethane urea resin does not become hard and can be applied to a film substrate such as a polyester film. Adhesiveness also tends to be maintained. When the number average molecular weight is 3500 or less, the blocking resistance of the ink film tends to be maintained without the polyurethane urea resin film becoming brittle.
  • polystyrene resin As the combined polyol used as necessary for the polyurethane urea resin used in the liquid printing ink of the present invention, various known polyols generally used for producing the polyurethane urea resin can be used, and one or two. You may use more than seeds together.
  • polyether polyols of polymers or copolymers such as methylene oxide, ethylene oxide, and tetrahydrofuran (1); ethylene glycol, 1,2-propanediol, 1,3-propanediol, 2-methyl-1,3.
  • polyester polyols (3) obtained by dehydration condensation or polymerization of the above; cyclic ester compounds such as polycaprolactone, polyvalerolactone, poly ( ⁇ -methyl- ⁇ -valerolactone) and other lactones are ring-open polymerized.
  • the high molecular weight diol obtained from the diols (glycols) and the dibasic acid is a low molecular weight having up to 5 mol% of the diols having three or more hydroxyl groups. It can be replaced with polyols (2).
  • diisocyanate compound used in the polyurethane urea resin in the liquid printing ink of the present invention examples include various known aromatic diisocyanates, aliphatic diisocyanates, and alicyclic diisocyanates generally used for producing polyurethane urea resins.
  • Examples of the chain extender used for the polyurethane urea resin in the liquid printing ink of the present invention include ethylenediamine, propylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, isophoronediamine, dicyclohexylmethane-4,4'-diamine and the like.
  • Examples of such compounds include alkylamines such as di-n-butylamine and alcohols such as ethanol and isopropyl alcohol. Further, especially when it is desired to introduce a carboxyl group into a polyurethane resin, amino acids such as glycine and L-alanine can be used as a reaction terminator. These terminal blockers can be used alone or in admixture of two or more.
  • the polyurethane urea resin used in the liquid printing ink of the present invention is, for example, a prepolymer obtained by reacting polyethylene glycol and a combined polyol with a diisocyanate compound at a ratio of an excess of isocyanate groups to obtain a prepolymer having terminal isocyanate groups.
  • a suitable solvent that is, an ester-based organic solvent such as ethyl acetate, propyl acetate, butyl acetate, which is usually used as a solvent for non-toluene gravure ink or flexo ink; acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.
  • Ketone-based solvents include alcohol-based organic solvents such as methanol, ethanol, isopropyl alcohol, n-butanol; hydrocarbon-based solvents such as methylcyclohexane and ethylcyclohexane; or chain extenders and / or in mixed solvents thereof. It is produced by a two-step method of reacting with a terminal-blocking agent, or a one-step method of reacting polyethylene glycol and a concomitant polyol, a diisocyanate compound, a chain extender and / or a terminal-blocking agent at one time in a suitable solvent among the above.
  • a two-step method is preferable in order to obtain a uniform polyurethane urea resin.
  • the reaction is performed so that the total (equivalent ratio) of the amino groups of the chain extender and / or the terminal blocker is 1 / 0.9 to 1.3. It is preferable to let it.
  • the equivalent ratio of isocyanate group to amino group is less than 1 / 1.3, the chain extender and / or terminal blocker remain unreacted, the polyurethane urea resin turns yellow, or the odor after printing. May occur.
  • the content of the polyurethane urea resin used in the liquid printing ink of the present invention in the ink is 4% by mass or more with respect to the total amount of solid ink from the viewpoint of sufficiently adhering the ink to the printed material, and has an appropriate ink viscosity. From the viewpoint of work efficiency during ink production and printing, it is preferably 25% by mass or less, and more preferably 6 to 15% by mass.
  • Vinyl chloride vinyl acetate copolymer resin (Vinyl chloride vinyl acetate copolymer resin) Further, in the liquid printing ink of the present invention, a vinyl chloride vinyl acetate copolymer resin may be used in combination with the polyurethane resin, which is preferable.
  • the vinyl chloride vinyl acetate copolymer resin may be known without particular limitation, but among them, a vinyl chloride vinyl acetate copolymer resin having a hydroxyl group is preferable, the hydroxyl value is 50 to 200 mgKOH / g, and the above-mentioned vinyl chloride acetate copolymer resin is used.
  • a vinyl chloride vinyl acetate copolymer resin having a hydroxyl group in which the content ratio of the vinyl chloride component in the copolymer resin is 80 to 95% by mass is still preferable.
  • the vinyl chloride vinyl acetate copolymer resin having a hydroxyl group used in the present invention can be obtained by two kinds of methods. One is obtained by copolymerizing a vinyl chloride monomer, a vinyl acetate monomer and a vinyl alcohol in an appropriate ratio. The other is obtained by copolymerizing vinyl chloride and vinyl acetate and then partially saponifying the vinyl acetate.
  • the properties of the resin film and the resin dissolving behavior are determined by the monomer ratios of vinyl chloride, vinyl acetate and vinyl alcohol. That is, vinyl chloride imparts toughness and hardness of the resin film, vinyl acetate imparts adhesiveness and flexibility, and vinyl alcohol imparts good solubility in polar solvents.
  • the monomer ratio of the vinyl chloride vinyl acetate copolymer resin having a hydroxyl group is, for example, blocking resistance when vinyl chloride is 80 to 95 parts by mass with respect to 100 parts by mass of the vinyl chloride vinyl acetate copolymer resin having a hydroxyl group. It is preferable that the adhesiveness is well-balanced. If it is 80 parts by mass or more, the toughness of the resin film can be maintained and blocking resistance can be ensured. If it is 95 parts by mass or less, the resin film does not become too hard and the adhesiveness does not easily decrease.
  • the hydroxyl value obtained from vinyl alcohol is preferably 50 to 200 mgKOH / g. When it is 50 mgKOH / g or more, the solubility in a polar solvent is good, and the printability is easily stable. If it is 200 mgKOH / g or less, the laminating suitability can be kept good. It was
  • the vinyl chloride vinyl acetate copolymer resin having a hydroxyl group is used in combination, it is preferably in the range of 1 to 30% with respect to the total resin solid content of the liquid printing ink.
  • chlorinated polypropylene resin a chlorinated polypropylene resin may be used in combination with the polyurethane resin.
  • the chlorinated polypropylene resin known ones can be used without particular limitation, but among them, when the degree of chlorination is 30 to 45% and the weight average molecular weight is 5000 to 50,000, the solubility in an organic solvent and the adhesion to the base film are obtained. It is preferable that the sex is well-balanced.
  • the degree of chlorination in the present invention is the weight% of chlorine atoms in the chlorinated polypropylene resin.
  • the chlorinated polypropylene resin When used in combination, it is preferably 0.1 to 3.0% by mass with respect to the total solid content of the liquid printing ink. In this range, it is possible to obtain an ink having a better balance between solubility in an organic solvent and adhesion to a base film.
  • the chlorinated polypropylene resin may be used in combination with the polyurethane resin, or may be used in combination with the polyurethane resin and a vinyl chloride vinyl acetate copolymer resin having a hydroxyl group.
  • examples of the resin used in combination with the liquid printing ink of the present invention as needed include ethylene-vinyl acetate copolymer resin, vinyl acetate resin, polyamide resin, acrylic resin, polyester resin, alkyd resin, and polyvinyl chloride.
  • examples thereof include resins, rosin-based resins, rosin-modified maleic acid resins, ketone resins, cyclized rubbers, rubber chlorides, butyral, and petroleum resins.
  • the combined resin can be used alone or in combination of two or more.
  • the content of the combined resin is preferably 1 to 25% by mass, more preferably 2 to 15% by mass, based on the total mass of the ink.
  • the liquid printing ink of the present invention includes, for example, aromatic organic solvents, ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone, and ester solvents such as ethyl acetate, n-propyl acetate, butyl acetate and propylene glycol monomethyl ether acetate.
  • aromatic organic solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone
  • ester solvents such as ethyl acetate, n-propyl acetate, butyl acetate and propylene glycol monomethyl ether acetate.
  • examples thereof include alcohol solvents such as n-propanol, inopropanol, n-butanol, and propylene glycol monomethyl ether, which can be used alone or in a mixture of two or more.
  • aromatic solvents such as toluene and xylene
  • Water may be added to the liquid printing ink of the present invention together with the organic solvent as a volatile component. By adding water, the dryness of the ink can be controlled, and especially in gravure printing, the characteristic gradation portion with a small amount of ink transfer can be clearly reproduced.
  • the amount of water added is preferably in the range of 0.3 to 10% by mass of the total amount of ink from the viewpoint of improving printability. When the amount of water added is 0.3% by mass or more, the reproducibility of the gradation portion tends to be good without deteriorating the effect of suppressing the drying of the ink, and the amount of water added is 10% by mass of the total amount of ink. If it is the following, it is possible to suppress the deterioration of ink stability. Further, by adding such water, it is possible to reduce the organic solvent component used, which leads to environmental friendliness. Water may be added to the organic solvent in advance as a water-containing organic solvent, or an appropriate amount may be added separately.
  • the present invention may further include a combined resin, extender pigment, pigment dispersant, leveling agent, defoaming agent, wax, plasticizer, infrared absorber, ultraviolet absorber, fragrance agent, flame retardant and the like, if necessary. ..
  • the resin In order to stably disperse the titanium oxide (A) and the inorganic filler (B) in an organic solvent, the resin alone can be dispersed, but a dispersant can also be used in combination to stably disperse the pigment.
  • a surfactant such as anionic, nonionic, cationic or zwitterionic can be used.
  • a comb-shaped structure polymer compound obtained by adding polyester to polyethyleneimine, an alkylamine derivative of an ⁇ -olefin maleic acid polymer, or the like can be mentioned. Specific examples thereof include the Sol Spurs series (ZENECA), the Azisper series (Ajinomoto), and the Homogenol series (Kao).
  • the dispersant is preferably contained in the ink in an amount of 0.05% by mass or more based on the total mass of the ink from the viewpoint of storage stability of the ink and 5% by mass or less from the viewpoint of laminating suitability, and more preferably 0. It is in the range of 1 to 2% by mass.
  • the liquid printing ink of the present invention can be produced by dissolving and / or dispersing the titanium oxide (A), the inorganic filler (B), the binder resin and the like in an organic solvent.
  • the particle size distribution of the pigment in the pigment dispersion is adjusted by appropriately adjusting the size of the pulverized media of the disperser, the filling rate of the pulverized media, the dispersion treatment time, the discharge rate of the pigment dispersion, the viscosity of the pigment dispersion, and the like. be able to.
  • the disperser commonly used, for example, a roller mill, a ball mill, a pebble mill, an attritor, a sand mill and the like can be used. If the ink contains air bubbles or unexpectedly coarse particles, it is preferable to remove them by filtration or the like in order to deteriorate the quality of the printed matter.
  • As the filter a conventionally known one can be used.
  • the viscosity of the ink produced by the above method may be in the range of 10 mPa ⁇ s or more from the viewpoint of preventing the pigment from settling and appropriately dispersing, and 1000 mPa ⁇ s or less from the viewpoint of workability efficiency during ink production and printing. preferable.
  • the viscosity is a viscosity measured at 25 ° C. with a B-type viscometer manufactured by Tokimec.
  • the viscosity of the ink can be adjusted by appropriately selecting the type and amount of the raw material used, for example, a polyurethane resin, a colorant, an organic solvent, and the like. Further, the viscosity of the ink can be adjusted by adjusting the particle size and the particle size distribution of the pigment in the ink.
  • the printed matter of the present invention is a printed matter having a printed layer formed by printing the liquid printing ink of the present invention on a substrate.
  • the liquid printing ink of the present invention has excellent adhesion to various substrates and can be used for printing on paper, synthetic paper, thermoplastic resin film, plastic products, steel plates, etc. It is useful as an ink for gravure printing using a gravure printing plate, or for flexographic printing using a flexographic printing plate with a resin plate, etc., but for an inkjet method that ejects ink from an inkjet nozzle without using a plate. It excludes ink.
  • the ink droplets ejected from the nozzle directly adhere to the substrate to form a printed matter
  • the printing ink is once adhered to and transferred to the printing plate or printing pattern. After that, only the ink is brought into close contact with the base material again, and if necessary, it is dried to obtain a printed matter.
  • the film thickness of the printing ink formed by the gravure printing method or the flexographic printing method using the liquid printing ink of the present invention is, for example, 10 ⁇ m or less, preferably 5 ⁇ m or less.
  • the base material examples include polyamide resins such as nylon 6, nylon 66, and nylon 46, polyethylene terephthalate (hereinafter sometimes referred to as PET), polyethylene naphthalate, polytrimethylene terephthalate, polytrimethylene naphthalate, and polybutylene terephthalate.
  • PET polyethylene terephthalate
  • polyester resins such as polybutylene naphthalate, polyhydroxycarboxylic acids such as polylactic acid, biodegradable resins such as aliphatic polyester resins such as poly (ethylene succinate) and poly (butylene succinate), polypropylene, polyethylene, etc.
  • Examples thereof include a film made of a thermoplastic resin such as a polyolefin resin, a polyimide resin, a polyarylate resin or a mixture thereof, and a laminate thereof.
  • a film made of polyester, polyamide, polyethylene and polypropylene can be preferably used.
  • These base films may be unstretched films or stretched films, and the production method thereof is not limited. Further, the thickness of the base film is not particularly limited, but usually it may be in the range of 1 to 500 ⁇ m.
  • the printed surface of the base film is preferably subjected to a corona discharge treatment, and silica, alumina, or the like may be vapor-deposited.
  • the liquid printing ink of the present invention can produce not only one printing layer but also a laminate having at least a first printing layer and a second printing layer on a plastic film in this order.
  • the liquid printing ink of the present invention wherein the first printing layer and the second printing layer contain a binder resin, an organic solvent, a colorant, titanium oxide (A) obtained by a sulfuric acid method, and an inorganic filler (B). It is characterized by being a printed layer formed from. Further, when the second printing layer is an overprint varnish, it may not contain a colorant, or various pigments may be used for coloring purposes, and a white pigment is preferable.
  • the coating film is flexible, has high adhesion to the plastic film, and has high followability due to deformation of the film base material.
  • the polyurethane urea resin is excellent in pigment dispersibility, resolubility during printing, and color development when the pigment is dispersed, and has good compatibility with the pigment.
  • the liquid printing ink of the present invention can form a laminate having a first printing layer and a third printing layer adjacent to the second printing layer in this order, for example, a polyurethane urea resin.
  • a laminate having this order can also be produced.
  • the first printing layer formed on the plastic film by the printing ink containing the polyurethane urea resin and the colorant can form a pattern by the colorant, and the second printed layer formed by the liquid printing ink containing the white pigment.
  • the white print layer and the third print layer can be used as a background of the pattern.
  • the third printing layer is an overprint varnish, it may not contain a colorant, or various coloring pigments may be used for coloring purposes, and a white pigment is preferable.
  • the weight average molecular weight (in terms of polystyrene) was measured by GPC (gel permeation chromatography) in the present invention using the HLC8220 system manufactured by Tosoh Corporation under the following conditions. Separation column: Uses 4 TSKgelGMHR-N manufactured by Tosoh Corporation. Column temperature: 40 ° C. Moving layer: Tetrahydrofuran manufactured by Wako Pure Chemical Industries, Ltd. Flow velocity: 1.0 ml / min. Sample concentration: 0.4% by mass. Sample injection volume: 100 microliters. Detector: Differential refractometer. The viscosity was measured at 25 ° C. with a Tokimec B-type viscometer.
  • the hydroxyl value is calculated by back-titrating the residual acid with an alkali when the hydroxyl group in the polyurethane resin is acetylated with an excess acetyl reagent, and the amount of the hydroxyl group in 1 g of the resin is potassium hydroxide (KOH). It is shown by the number of mg of, and is based on JISK0070. The average particle size was measured using a nanoparticle particle size distribution measuring device Nanotrac UPA EX-150 manufactured by Nikkiso Co., Ltd.
  • the target titanium oxide (A) and inorganic filler (B) are known general Mohs standard minerals (calcite as a mineral corresponding to Mohs hardness of 1 to 10) in order from 1. ), Gypsum, calcite, firefly stone, phosphorus ash stone, regular long stone, crystal, toppers, corundum, diamond) determines whether or not it is scratched.
  • urethane prepolymer solution 68.7 parts were added to make a uniform solution of urethane prepolymer.
  • the urethane prepolymer solution was added to a mixture consisting of 7.83 parts of isophorondiamine, 0.11 part of di-n-butylamine, 136.8 parts of ethyl acetate and 110.7 parts of isopropyl alcohol, and 5 at 45 ° C. The reaction was stirred for a time to obtain a polyurethane urea resin solution P-1.
  • the obtained polyurethane urea resin solution P-1 has a resin solid content concentration of 30.4% by weight, a resin solid content Mw of 54,000, and a urethane bond concentration of 1.20 mmol / by a calculation method according to the formula (1). It was g.
  • Urethane bond concentration ⁇ (W1 x OH1 + W2 x OH2 + ... + Wi x OHi) x 1000 ⁇ / (56100 x S) Equation (1)
  • W1 Mass of polyol 1 OH1: Mass of polyol 1
  • W2 Mass of polyol 2
  • OH2 Mass of polyol 2
  • Wi Mass of polyol i OHi: Mass of polyol i hydroxyl value
  • S Mass of urethane resin solid content
  • the polyurethane urea resin (137.76 parts in total) contains 11.4% by mass of polyethylene glycol (15.5 parts) as a polyether polyol.
  • a uniform solution of urethane prepolymer was prepared. Next, the urethane prepolymer solution was added to a mixture consisting of 9.66 parts of isophorondiamine, 0.11 part of di-n-butylamine, 170.1 parts of ethyl acetate and 137.6 parts of isopropyl alcohol, and 5 at 45 ° C. The reaction was stirred for a time to obtain a polyurethane urea resin solution P-2.
  • the obtained polyurethane urea resin solution P-2 has a resin solid content concentration of 30.4% by mass and a resin solid content of Mw of 54,000, and the urethane bond concentration is calculated by the same calculation method as in Synthesis Example 1. It was 50 mmol / g.
  • the polyurethane urea resin (total 168.51 parts) contains 14.8% by mass of polyethylene glycol (25 parts) as a polyether polyol.
  • chlorinated polypropylene resin As the chlorinated polypropylene, "Supercron 390S chlorine content 36%” manufactured by Nippon Paper Chemicals Co., Ltd. was used.
  • Example Comparative Example Liquid printing ink manufacturing method
  • the mixture mixed at the blending ratios shown in Table 1 was kneaded using a mighty mill (manufactured by Inoue Seisakusho Co., Ltd.), and Examples 1 to 13 were used.
  • the white inks described in Comparative Examples 1 to 6 were prepared, and the following evaluations were carried out for each of them.
  • Laminate strength is 5N / 15mm or more.
  • 4 Laminate strength is 4N / 15mm or more and less than 5N / 15mm.
  • 3 Laminate strength is 3N / 15mm or more and less than 4N / 15mm.
  • 2 Laminate strength is 2N / 15mm or more and less than 3N / 15mm.
  • 1 Laminate strength is less than 1N / 15mm.
  • Titanium oxide T Alumina silica-treated titanium oxide Titanium oxide U having a mass ratio of titanium oxide / alumina / silica (Ti / Al / Si) of 92/4/4 and a Mohs hardness of 7.0 obtained by the sulfuric acid method.
  • Alumina silica-treated titanium oxide titanium oxide V sulfuric acid method with a mass ratio of titanium oxide / alumina / silica (Ti / Al / Si) of 90/3/7 and a Mohs hardness of 7.0 obtained by the sulfuric acid method.
  • the aluminum oxide / alumina / silica (Ti / Al / Si) having a mass ratio of 97/3/0 and having a Mohs hardness of 7.0 was obtained by the alumina-treated titanium oxide titanium oxide W: chlorine method.
  • Titanium oxide / Alumina / Silica (Ti / Al / Si) mass ratio is 90/3/7
  • Alumina silica treated titanium oxide kaolin with Mohs hardness of 7.0 Particle size is 0.2
  • Calcium carbonate Average particle size is 0.5 ⁇ m
  • Mohs hardness is 3.0
  • Barium sulphate average particle size 0.7 ⁇ m
  • the liquid printing ink of the example was excellent in concealing property, plate fog property, adhesiveness, blocking property, and laminating property.
  • the inks containing no inorganic filler (Comparative Examples 1, 2, 3 and 4) or the inks containing an organic filler instead of the inorganic filler (Comparative Example 5) are both inferior in hiding property or plate fogability.
  • the result was.
  • the ink without the inorganic filler (Comparative Example 1) shows a high plate fog property of 8 but is inferior in concealment.
  • the inks (Examples 1, 9, and 13) in which the inorganic filler is used in combination have improved concealment while maintaining plate fog.
  • the ink without the inorganic filler shows a high concealing property of 0.23, but is inferior in plate fog.
  • the inks (Examples 3 and 11) in which the inorganic filler is used in combination have improved plate fogability while maintaining concealment.

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Abstract

L'objectif de la présente invention est de fournir une encre d'impression liquide qui présente une excellente adhérence à divers matériaux d'emballage, une excellente résistance à la stratification et une excellente résistance au blocage après l'impression d'un film ; et qui, lors de l'impression par gravure, ne tend pas à provoquer un phénomène de brouillard, et présente d'excellentes propriétés de masquage, d'adhérence à un substrat de film, de résistance au blocage et d'aptitude à la stratification. La présente invention concerne une encre d'impression liquide contenant une résine liante, un solvant organique et un agent colorant, l'encre d'impression liquide étant caractérisée en ce qu'elle contient une charge inorganique (B) et un oxyde de titane (A) obtenu par un procédé d'acide sulfurique.
PCT/JP2020/047073 2020-12-17 2020-12-17 Encre d'impression liquide, matière imprimée, et corps stratifié WO2022130549A1 (fr)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012184321A (ja) * 2011-03-04 2012-09-27 Toyo Ink Sc Holdings Co Ltd 水性白インキ組成物
WO2013187408A1 (fr) * 2012-06-13 2013-12-19 堺化学工業株式会社 Pigment blanc composite pour encre de gravure, et encre de gravure
WO2018003596A1 (fr) * 2016-06-27 2018-01-04 Ｄｉｃグラフィックス株式会社 Composition d'encre liquide
JP2019011435A (ja) * 2017-06-30 2019-01-24 東洋インキＳｃホールディングス株式会社 グラビアインキおよびその印刷物と積層体

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012184321A (ja) * 2011-03-04 2012-09-27 Toyo Ink Sc Holdings Co Ltd 水性白インキ組成物
WO2013187408A1 (fr) * 2012-06-13 2013-12-19 堺化学工業株式会社 Pigment blanc composite pour encre de gravure, et encre de gravure
WO2018003596A1 (fr) * 2016-06-27 2018-01-04 Ｄｉｃグラフィックス株式会社 Composition d'encre liquide
JP2019011435A (ja) * 2017-06-30 2019-01-24 東洋インキＳｃホールディングス株式会社 グラビアインキおよびその印刷物と積層体

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