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WO2019065267A1 - Procédé de production d'imprimés - Google Patents

Procédé de production d'imprimés Download PDF

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Publication number
WO2019065267A1
WO2019065267A1 PCT/JP2018/033954 JP2018033954W WO2019065267A1 WO 2019065267 A1 WO2019065267 A1 WO 2019065267A1 JP 2018033954 W JP2018033954 W JP 2018033954W WO 2019065267 A1 WO2019065267 A1 WO 2019065267A1
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WO
WIPO (PCT)
Prior art keywords
meth
printed matter
ink
water
acrylate
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2018/033954
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English (en)
Japanese (ja)
Inventor
島村　佳ノ助
剛啓 仁尾
友理 庄子
早紀 福井
正喜 保坂
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
DIC Corp
Original Assignee
DIC Corp
Dainippon Ink and Chemicals Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by DIC Corp, Dainippon Ink and Chemicals Co Ltd filed Critical DIC Corp
Priority to JP2019511506A priority Critical patent/JP6729797B2/ja
Publication of WO2019065267A1 publication Critical patent/WO2019065267A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
    • B41J2/00—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed
    • B41J2/005—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed characterised by bringing liquid or particles selectively into contact with a printing material
    • B41J2/01—Ink jet

Definitions

  • the present invention relates to a method of producing a printed matter.
  • packaging material and the like include a corrugated board in which a liner is adhered to one side or both sides of a core called a flute processed into a corrugated shape.
  • an aqueous emulsion resin having a glass transition temperature of 16 ° C. or more and an acid value of 10 mg KOH / g or more and a pigment are blended so as to have a solid content of 15% by weight or more
  • a method of printing on a cardboard using an ink composition for ink jet recording containing an amino alcohol as a stabilizer (see Patent Document 1), or a method of printing on the surface of the first liner of a single-faced corrugated sheet by an inkjet method (See Patent Document 2) is known.
  • the colored layer is generally a layer having low water absorbability in many cases, there is a problem that the aqueous ink is difficult to dry when printed on the surface of the colored layer using the aqueous ink. Therefore, when printing is carried out using aqueous ink on the surface of the corrugated board, color unevenness is likely to occur, and as a result, it may not be possible to form a clear printed matter of a level capable of securing high designability of the level required by the industry.
  • corrugated paperboards have different heat transfer rates during drying of the aqueous ink between the portion where the liner and the flute are in contact and the portion where the liner and the flute are not in contact. It is easy to make a difference. Due to the difference in the drying property, streak-like color unevenness caused by the contact area between the liner and the flute is easily generated, and as a result, it is difficult to further enhance the design of the printed material such as the packaging material. There was a case.
  • the problem to be solved by the present invention is the color of the printed image, even when printed using aqueous ink on the surface of a cardboard provided with a layer that does not absorb or hardly absorbs the solvent contained in the aqueous ink. It is providing the manufacturing method of the printed matter which can prevent generating of a nonuniformity.
  • the problem to be solved by the present invention is that even when printing is carried out using an aqueous ink on the surface of a corrugated board provided with a layer which does not absorb or hardly absorbs the solvent contained in the aqueous ink, It is an object of the present invention to provide a method for producing a printed matter which does not generate streak-like color unevenness caused by the flutes.
  • the solvent contained in the water-based ink is quickly absorbed by the liner or the like, and the coloring component in the water-based ink is rapidly fixed to the cardboard surface. Therefore, the color unevenness hardly occurs.
  • the present inventor has found that after the water-based ink is printed on the cardboard, the problem can be solved by applying a wind to the printing surface.
  • the present invention includes the step [1-1] of blowing the air to the printing surface after printing with a water-based ink on a cardboard (A) having a layer (a) having a water absorption amount of 15 g / m 2 or less.
  • the present invention relates to a method of producing a printed matter characterized in that the aqueous ink is dried by passing through 1).
  • the method for producing a printed matter of the present invention even when the water-based ink is printed on the surface of a corrugated board provided with a layer which does not or hardly absorbs the solvent in the water-based ink, It is possible to effectively suppress the occurrence of streak-like color unevenness caused.
  • the method for producing a printed matter according to the present invention comprises the steps [1-1] of printing on a cardboard (A) having a layer (a) having a water absorption of 15 g / m 2 or less with an aqueous ink and then blowing air on the printing surface The aqueous ink is dried by passing through the step [1].
  • the temperature of the blowing air is not particularly limited, but it is preferable to set the temperature of the printing surface to a temperature that can be adjusted to a range of 20 to 140 ° C., and set to a temperature that can be adjusted to a range of 40 to 90 ° C. It is more preferable to impart good drying property (reduction of tackiness) of the printed surface.
  • the solvent to be dried at the above temperature is mainly water, so by drying at the temperature within the above range, the improvement of the production efficiency of the printed matter by the improvement of the drying rate, the deterioration of the drying equipment due to high temperature, and cardboard (A) It is possible to realize the prevention of the color change and the reduction of energy loss.
  • the air blowing speed is not particularly limited, but is preferably in the range of 0.1 to 20 m / s on the surface of the printing surface, and more preferably in the range of 1 to 10 m / s. preferable.
  • the air blowing speed is not particularly limited, but is preferably in the range of 0.1 to 20 m / s on the surface of the printing surface, and more preferably in the range of 1 to 10 m / s. preferable.
  • the air blowing is performed in a direction approximately perpendicular to the printing surface of the corrugated board (A) to prevent the occurrence of bleeding and the like of the printed matter caused by the water-based ink flowing in the surface direction on the surface of the corrugated board (A). It is preferable to do. Specifically, the air blowing is preferably performed from the direction of -85 ° to + 85 ° with respect to the perpendicular direction of the printing surface of the cardboard (A), and the direction of the range of -45 ° to + 45 °. Is more preferable, the range of ⁇ 20 ° to + 20 ° is more preferable, and the range of ⁇ 10 ° to + 10 ° is particularly preferable.
  • the air blowing time is preferably short to improve the production efficiency of the printed matter, preferably 1 second to 1 minute, more preferably 1 second to 30 seconds, still more preferably 1 second to 5 seconds, particularly preferably 1 to 2 seconds.
  • the blowing temperature, the blowing direction, and the blowing speed in the blowing step [1-1] may be constant during the step [1] or may be changed as necessary.
  • the air blowing speed may be set to be slow and may be gradually changed.
  • the air blowing may be performed with the same air as the printed product manufacturing environment, or may be performed with air having a low content of dust and the like through a filter or the like.
  • the step [1] constituting the method for producing the printed matter of the present invention may be a step including other steps as necessary in addition to the blowing step [1-1].
  • a heating step [1-2] By combining the blowing step [1-1] and the heating step [1-2], generation of mottling (uneven color of mottled pattern) of printed matter can be more effectively prevented, and on the printing surface Good drying properties (reduction of tackiness) can be imparted.
  • the heating step [1-2] may be heating by radiant heat, and more specifically, a heating step using an infrared ray, a microwave or the like is preferable in order to prevent ignition and discoloration of the cardboard (A).
  • the heating step [1-2] takes a short time (approximately 10 seconds) within the above range, and the production efficiency of printed matter can be further improved.
  • Examples of the heating step [1-2] include a step of heating with infrared rays, microwaves and the like, and among them, the fact that it is a heating step using infrared rays is easy to be absorbed by water contained in the aqueous ink It is more preferable because the drying of the ink can be performed efficiently and uniformly.
  • the wavelength of the infrared ray is preferably 0.7 to 1000 ⁇ m in general, and it is effective that the infrared ray is easily absorbed by water contained in the aqueous ink, in the near infrared range of 0.8 to 4 ⁇ m. It is preferable because it can be dried.
  • a heating method using an infrared ray for example, a method using a radiation heater equipped with a halogen heater using a tungsten wire, a quartz tube heater using a nichrome wire, a carbon heater and the like can be mentioned.
  • the preferred method is to use a radiant heat dryer equipped with a high carbon heater.
  • the heating step [1-2] it is more preferable to carry out the heating step [1-2] in the range where the surface temperature of the printed matter is 150 ° C. or less, in order to further improve the production efficiency of the printed matter.
  • the heating step [1-2] may be performed after the blowing step [1-1] is finished, but the production time of the printed matter is shortened and the production efficiency is further enhanced. In order to improve, it is preferable to partially or entirely overlap the blowing step [1-1] and the heating step [1-2].
  • the step [1-1] of blowing air to the printing surface and the heating step is a method for producing a printed matter, characterized in that the aqueous ink is dried by passing through the step [1] including the step of partially overlapping with [1-2].
  • corrugated-cardboard (A) what has a layer (a) of 15 g / m ⁇ 2 > or less of water absorption amount is used.
  • the printing with the aqueous ink is applied to the surface of the layer (a) of the cardboard (A).
  • the said water absorption was determined by measuring and calculating with the following method.
  • any one of the surface of the layer (a) of the corrugated board (A) is used using an automatic scanning liquid absorption meter (manufactured by Kumagaya Riki Kogyo Co., Ltd., KM 500 win) under conditions of 23 ° C. and 50% relative humidity.
  • the amount of pure water absorbed in the layer (a) was measured within 100 ms from when pure water was brought into contact with the point.
  • the automatic scanning liquid absorption meter by preliminarily adjusting the load applied to the capillary height and liquid supply head, the water absorption of Oji Paper Co., Ltd. OK TOPCOAT + is 5 ml / m 2 It used what was calibrated.
  • the water absorption amount was measured by the same method as above with respect to any 19 points of the layer (a), and the average value of the water absorption amount of 19 points in total was defined as the water absorption amount in the present invention.
  • the measurement conditions are shown below.
  • the corrugated cardboard (A) has, for example, a liner on at least one surface of a flute and the layer (a) on the surface of the liner, or the layer as a liner on at least one surface of the flute ( Those having a) can be used.
  • the corrugated board (A) is usually classified according to the number of flute steps (number of waves) and the height of the flutes, and is A flute, B flute, C flute, E flute, F flute, G flute, delta flute Etc.
  • the liner examples include a liner in which a layer (a) is provided in advance on the surface of paper, and specifically, Maricoat (Hokuetsu Kishu Paper), suncoat, OK ball, UF coat, MF paper, MC coat (Oji Paper Co., Ltd.), JET Star (Nippon Paper Co., Ltd.), and the like.
  • Maricoat Hokuetsu Kishu Paper
  • OK ball OK ball
  • UF coat UF coat
  • MF paper MF paper
  • MC coat Oji Paper Co., Ltd.
  • JET Star Natural Paper Co., Ltd.
  • the layer formed for example by apply
  • Examples of the layer (a) include a layer containing a resin component such as a binder and an inorganic material such as calcium carbonate.
  • a printing method known in the related art can be applied, and among them, as the printing method, a printing method using an inkjet recording device is preferable.
  • a conventionally known method can be adopted. For example, from a surface (x) having an ink discharge port of an ink jet head, a perpendicular line of the surface (x) and a cardboard (A) It is preferable to apply an ink jet recording method in which the distance to the position (y) where the two intersect is 1 mm or more.
  • the distance (gap) from the surface (x) having the ink discharge port of the ink jet head to the position (y) where the perpendicular line assumed to the surface (x) intersects the cardboard (A) is preferably 2 mm or more More preferably, an inkjet recording apparatus having a configuration of 3 mm or more can be used.
  • the distance from the surface (x) to the position (y) where the assumed perpendicular to the surface (x) intersects with the cardboard (A) is large even if the cardboard (A) is large and it is easy to warp
  • the lower limit of the distance is 3 mm or more for producing printed matter without streaks even when the distance between the surface of the corrugated board (A) and the ink jet head is effectively prevented.
  • the upper limit of the distance is preferably 10 mm or less, and particularly preferably 5 mm or less.
  • aqueous ink As the aqueous ink used in the present invention, those known in the prior art can be used.
  • aqueous ink for example, in the case of printing by an inkjet recording method, it is preferable to use one having a lower viscosity limit of 1 mPa ⁇ s or more at 32 ° C., and it is preferable to use one having 2 mPa ⁇ s or more It is more preferable to use one having a viscosity of 3 mPa ⁇ s or more, more preferably to use one having a viscosity of 4 mPa ⁇ s or more, and one having an upper limit of viscosity at 20 ° C.
  • mPa ⁇ s or less Preferably 15 mPa ⁇ s or less, more preferably 12 mPa ⁇ s or less, preferably 9 mPa ⁇ s or less, and more preferably 8 mPa ⁇ s or less Is more preferable, and it is further preferable to use one having a viscosity of 7 mPa ⁇ s or less.
  • the water-based ink having the viscosity in the above-mentioned range has a sufficient volume for the droplets discharged from the ink jet head, so the perpendicular line of the surface (x) and the cardboard (from the surface (x) having the ink discharge port of the ink jet head Even if the distance to the position (y) where it intersects with A) is 2 mm or more, the displacement of the landing position on the cardboard (A) generated due to the flight bending is apparently reduced and the generation of streaks on the printed matter is effectively prevented. can do.
  • the aqueous ink which has the viscosity of the said range is further excellent in the storage stability and discharge stability point, it can be used conveniently, for example for printing by an inkjet system.
  • the viscosity of the aqueous ink refers to a value measured under the following conditions using a cone and plate (cone and plate) rotational viscometer corresponding to an E-type viscometer.
  • Measuring device TVE-25 type viscometer (manufactured by company, TVE-25 L)
  • Calibration standard solution JS20 Measurement temperature: 32 ° C
  • Rotation speed 10 to 100 rpm
  • Injection volume 1200 ⁇ L
  • the aqueous ink for example, in the case of printing by an inkjet recording method, it is preferable to use an ink having a lower limit of surface tension at 25 ° C.
  • the aqueous ink having the surface tension in the above-mentioned range is excellent in the wettability of the discharged droplets on the surface of the cardboard (A), and has a sufficient wetting and spreading after landing.
  • the distance from the surface (x) having the ink discharge port of the ink jet head to the position (y) where the perpendicular line of the surface (x) intersects the cardboard (A) is 2 mm or more It is possible to apparently reduce the deviation of the landing position on the cardboard (A) caused by the flight bending of the paper, and to effectively prevent the generation of streaks in the printed matter.
  • the surface tension of the aqueous ink refers to a value measured under the following conditions using an automatic surface tension meter to which Willhermi method is applied. According to the Will-Hermi method, static surface tension and dynamic surface tension can be measured, but the surface tension of the water-based ink in the present invention represents the value of static surface tension.
  • Measuring device Automatic surface tension meter (manufactured by Kyowa Interface Science Co., Ltd., CBVP-Z type) Measurement temperature: 25 ° C
  • Measuring element platinum plate
  • an aqueous ink containing, for example, a coloring material and a solvent such as an aqueous medium can be used.
  • aqueous ink it is preferable to use an aqueous ink further containing a binder resin in order to obtain a print having excellent scratch resistance, and to improve the setting property of the print, a urea bond is further added. It is more preferable to use an aqueous ink containing a compound having one.
  • aqueous ink it is preferable to use one in which the binder resin, the compound, the coloring material and the like are dissolved or dispersed in an aqueous medium which is a solvent.
  • binder resin examples include polyvinyl alcohol, gelatin, polyethylene oxide, polyvinyl pyrrolidone, acrylic resin, urethane resin, dextran, dextrin, carrageenan ( ⁇ , ⁇ , ⁇ , etc.), agar, pullulan, water-soluble polyvinyl butyral, hydroxy Ethylcellulose, carboxymethylcellulose and the like can be used alone or in combination.
  • acrylic resin is preferably used, and an acrylic resin having an amide group is preferably used.
  • the aqueous ink containing the binder resin can easily make the coagulated product water-based by circulating the water-based ink again in the discharge port. It is excellent in the property (redispersion property) which can be dispersed in ink. As a result, when discharging from the ink jet head, even if discharge is interrupted for a certain period of time and then started again, it is difficult to cause a flying bend of the discharge droplet or clogging of the discharge port, effectively generating streaks of printed matter It can be prevented.
  • acrylic resin which has the said amide group the polymer of the acrylic monomer which has an amide group, and another monomer as needed can be used.
  • acrylic monomer having an amide group examples include (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, and N-methylol (meth).
  • Acrylamide, N-isopropyl (meth) acrylamide, N-butyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N, N-dipropyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, diacetone (meth) acrylamide, hydroxyethyl (meth) acrylamide and the like can be used.
  • Examples of other resins that can be used for producing the acrylic resin include (meth) acrylic acid and alkali metal salts thereof, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, and 2-ethylhexyl ( (Meth) acrylic acid ester monomers such as meth) acrylate, benzyl (meth) acrylate and cyclohexyl (meth) acrylate, and acrylics having an amide group such as acrylamide and N, N-dimethyl (meth) acrylamide Acrylic monomers such as system monomers, (meth) acrylonitrile, 2-dimethylaminoethyl (meth) acrylate and glycidyl (meth) acrylate can be used.
  • Examples of other monomers that can be used for producing the acrylic resin include aromatic vinyl compounds such as styrene, ⁇ -methylstyrene, p-tert-butylstyrene, vinyl naphthalene, vinyl anthracene, vinyl sulfonic acid, styrene Vinylsulfonic acid compounds such as sulfonic acid, vinylpyridine compounds such as 2-vinylpyridine, 4-vinylpyridine, naphthylvinylpyridine, vinyltriethoxysilane, vinyltrimethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropyl Methyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, etc. It can be.
  • aromatic vinyl compounds
  • the other monomer it is preferable to use a monomer having an aromatic group such as styrene or benzyl (meth) acrylate in order to further improve the affinity to the pigment.
  • the acrylic resin having an amide group imparts the effect of improving the redispersibility to an aqueous ink, and is excellent in the dispersion stability in an aqueous medium.
  • the range of not more than 0.5% by mass or more and 5% by mass or more of the acrylic monomer having the amide group relative to the total amount of the monomers used for the production as the acrylic resin having the amide group Is preferably used in the range of 0.5% by mass to 4% by mass, and is preferably used in the range of 1.5% by mass to 3% by mass; It is particularly preferable to further improve the dispersion stability in an aqueous medium.
  • the acrylic resin it is possible to further improve the adhesion of the aqueous ink to a plastic that is difficult to absorb a solvent such as water contained in the aqueous ink, a highly hydrophobic coated paper, and art paper.
  • a solvent such as water contained in the aqueous ink, a highly hydrophobic coated paper, and art paper.
  • the content of THF insoluble component at 25 ° C is 20 mass The content is preferably less than 5%, more preferably less than 5% by mass, and most preferably not containing a THF insoluble component.
  • the acrylic resin it is preferable to use one having a number average molecular weight of 10,000 to 100,000 of an acrylic resin soluble in the THF, and having a number average molecular weight of 20,000 to 100,000. It is more preferred to use Further, as the acrylic resin, those having a weight average molecular weight of 30,000 to 1,000,000 are preferably used, and those having a weight average molecular weight of 50,000 to 1,000,000 are more preferable. preferable.
  • polyolefin can also be used as the binder resin.
  • the polymer or copolymer of the monomer which has an olefin type monomer as a main component is used.
  • the olefin monomer for example, ⁇ -olefins such as ethylene, propylene, butene, hexene, methyl butene, methyl pentene and methyl hexene, cyclic olefins such as norbornene and the like can be used.
  • Oxidized polyolefin can also be used as the polyolefin.
  • oxidized polyolefin for example, a polyolefin in which an oxygen atom is introduced into the molecule by thermal decomposition or chemical decomposition using an acid or an alkali component can be used.
  • the oxygen atom constitutes, for example, a carboxyl group having polarity.
  • the polyolefin it is preferable to use one having a melting point of 90 ° C. or more and 200 ° C. or less, and by using one having a melting point of 120 ° C. or more and less than 160 ° C. (A) It is possible to impart good settability that the aqueous ink on the surface does not peel off, and excellent abrasion resistance. In addition, the melting point of the said polyolefin points out the value measured by the melting point measuring apparatus based on JISK0064.
  • the polyolefin is preferably present in a state of being dissolved or dispersed in a solvent such as an aqueous medium as described above, and is more preferably in the form of an emulsion dispersed in a solvent such as an aqueous medium.
  • the polyolefin particles formed of the above-mentioned polyolefin preferably have an average particle diameter of 10 nm to 200 nm, and preferably 30 nm to 150 nm, for example, good ejection stability of the aqueous ink when printing by the inkjet recording method. It is more preferable from the viewpoint of achieving both good setting after printing and printing.
  • the average particle diameter of the said polyolefin shows the value measured by the dynamic-light-scattering method, using Nikkiso Co., Ltd. make Microtrac UPA particle size distribution analyzer.
  • the print density and the abrasion resistance of the printed matter may tend to be slightly reduced.
  • the binder resin prevents the generation of the streaks, improves the print density and the abrasion resistance of the printed matter, and provides 2% by mass to 7% by mass with respect to the total amount of the aqueous ink in order to impart good gloss. It is preferable to use in the range of 3% by mass to 6% by mass.
  • the aqueous ink containing the said binder resin of the said range can further improve the abrasion resistance of printed matter further by bridge
  • a compound having a urea bond can be used in combination with the binder resin.
  • the above-mentioned compound in combination with the above-mentioned binder resin, it is possible to impart good settability of printed matter and excellent scratch resistance.
  • Urea or a urea derivative can be used as the compound having a urea bond.
  • urea derivative for example, ethylene urea, propylene urea, diethyl urea, thiourea, N, N-dimethyl urea, hydroxyethyl urea, hydroxybutyl urea, ethylene thiourea, diethyl thiourea and the like are used singly or in combination of two or more. be able to.
  • the compound having a urea bond it is particularly preferable to use urea, ethylene urea or 2-hydroxyethyl urea, in order to obtain a printed product having a further excellent setting property.
  • the content of the compound having a urea bond is the total content of the ink in order to obtain a printed matter excellent in ejection stability and settability required when the aqueous ink used in the present invention is ejected by an inkjet recording method.
  • the amount is preferably 1% by mass to 20% by mass, more preferably 2% by mass to 15% by mass, and still more preferably 3% by mass to 10% by mass.
  • the binder resin and the compound having a urea bond are preferably used in such a range that their mass ratio [binder resin / compound having a urea bond] is 1/6 to 6/1, and 1/5 to 1 It is more preferable to use in the range of 1/1 in order to obtain the setting property improvement effect of the printed matter.
  • the urea and the urea derivative have a high moisturizing function and function as a wetting agent, drying and solidification of the aqueous ink at the ink discharge port of the ink jet head can be prevented, and excellent discharge stability can be ensured.
  • the distance from the surface (x) having the ink discharge port of the ink jet head to the position (y) where the perpendicular line of the surface (x) intersects the cardboard (A) is 2 mm or more, Has the effect of reducing the occurrence.
  • the urea and the urea derivative easily release water when heated, the aqueous ink is printed on the non-absorbent or non-absorbent cardboard (A), and then it is more excellent when heated and dried. It is possible to obtain a printed material having the set property.
  • aqueous ink one containing an aqueous medium as a solvent is used.
  • aqueous medium water can be used alone, or a mixed solvent of water and an organic solvent described later can be used.
  • pure water such as ion exchange water, ultrafiltered water, reverse osmosis water, distilled water or ultrapure water can be used as the water.
  • the aqueous medium is preferably used in the range of 1% by mass to 30% by mass, and in the range of 5% by mass to 25% by mass, based on the total amount of the aqueous ink, excellent in setability and excellent in ink jet system It is particularly preferable in order to obtain an aqueous ink capable of producing a clear print having high ejection stability required for ejection.
  • Examples of the organic solvent (F) include ketones such as acetone, methyl ethyl ketone, methyl butyl ketone and methyl isobutyl ketone; methanol, ethanol, 2-propanol, 2-methyl-1-propanol, 1-butanol, 2- Alcohols such as methoxyethanol; Ethers such as tetrahydrofuran, 1,4-dioxane, 1,2-dimethoxyethane; Dimethylformamide, N-methylpyrrolidone, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, Glycols such as polyethylene glycol and polypropylene glycol; Diols such as butanediol, pentanediol, hexanediol and their cognate diols; Glycol esters such as glycole; Diethylene glycol monoethyl, diethylene glycol monobutyl ether, di
  • a water-soluble organic solvent (f1) having a boiling point of 100 ° C. or more and 200 ° C. or less and a vapor pressure at 20 ° C. of 0.5 hPa or more It is preferable to use the above in order to achieve the quick-drying effect on the corrugated board (A) after the discharged droplets land on the surface of the corrugated board (A).
  • water-soluble organic solvent (f1) examples include 3-methoxy-1-butanol, 3-methyl-3-methoxy-1-butanol, 3-methoxy-3-methyl-1-butyl acetate, ethylene glycol monomethyl ether, Ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monoisobutyl ether, ethylene glycol t-butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether Ether acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol Lumpur diethyl ether, dipropylene glycol dimethyl ether, 4-methoxy-4-methyl-2-pentanone, ethyl lactate and the like, may be used in combination with one of the water
  • the water-soluble organic solvent (f1) As the water-soluble organic solvent (f1), maintenance of good dispersion stability of the aqueous ink, for example, deterioration due to the influence of the solvent contained in the aqueous ink of the ink discharge nozzle provided in the inkjet device is suppressed.
  • water-soluble organic solvent having a hydrogen bonding term of HSP in the above range examples include 3-methoxy-1-butanol, 3-methyl-3-methoxy-1-butanol, ethylene glycol monomethyl ether, ethylene glycol mono Ethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monoisobutyl ether, ethylene glycol t-butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether are preferable, and 3 is more preferable.
  • -Methoxy-1-butanol 3-methyl-3-methoxy-1-butanol.
  • the organic solvent (f3) is, for example, glycerin, diglycerin, polyglycerin, diglycerin fatty acid ester, polyoxypropylene (n) polyglyceryl ether represented by the general formula (1), or the general formula (2) Polyoxyethylene (n) polyglyceryl ether etc. can be used individually or in combination of 2 or more types.
  • n, o and p each independently represent an integer of 1 to 10.
  • the organic solvent (F) is preferably used in a range of 1% by mass to 30% by mass, and in a range of 5% by mass to 25% by mass, based on the total amount of the aqueous ink. It is particularly preferable in order to exhibit the effect of preventing drying and solidification of the aqueous ink at the ink discharge port.
  • the water-soluble organic solvent (f1), the propylene glycol (f2) and the organic solvent (f3) have a mass ratio [water-soluble solvent (f1) / propylene glycol (f2)], [propylene glycol (f2) /
  • the organic solvent (f3) is preferably used in the range of 1/25 to 1/1, 1/4 to 8/1, respectively, in the range of 1/20 to 1/1, 1/2 to 5/1. It is particularly preferable to use it because it is excellent in the setting property of the printed matter and has an effect of preventing the ink from drying and coagulating in the ink discharge port.
  • a colorant that can be used in the aqueous ink of the present invention, known pigments, dyes and the like can be used.
  • the coloring material it is preferable to use a pigment in order to produce a printed matter excellent in weather resistance and the like. Further, as the coloring material, it is also possible to use a coloring agent in which the pigment is coated with a resin.
  • the pigment is not particularly limited, and organic pigments or inorganic pigments generally used in aqueous gravure inks and aqueous inkjet recording inks can be used.
  • any of a non-acid treated pigment and an acid treated pigment can be used.
  • the inorganic pigment for example, iron oxide, carbon black produced by a method such as a contact method, a furnace method, or a thermal method can be used.
  • organic pigment examples include azo pigments (including azo lakes, insoluble azo pigments, condensed azo pigments, chelate azo pigments and the like), polycyclic pigments (for example, phthalocyanine pigments, perylene pigments, perinone pigments, anthraquinone pigments, quinacridone pigments, dioxazines Pigments, thioindigo pigments, isoindolinone pigments, quinofurarone pigments, etc., lake pigments (eg, basic dye type chelates, acid dye type chelates, etc.), nitro pigments, nitroso pigments, aniline black, etc. can be used.
  • azo pigments including azo lakes, insoluble azo pigments, condensed azo pigments, chelate azo pigments and the like
  • polycyclic pigments for example, phthalocyanine pigments, perylene pigments, perinone pigments, anthraquinone pigments, quinacridone pigments, dio
  • carbon black usable for black ink may be No. 4 manufactured by Mitsubishi Chemical Corporation. 2300, no. 2200 B, no. 900, no. 960, no. 980, no. 33, no. 40, No, 45, No. 45 L, no. 52, HCF88, MA7, MA8, MA100, etc., manufactured by Columbia Inc. Raven 5750, Raven 5250, Raven 5000, Raven 3500, Raven 1255, Raven 700 etc., Cabot Corp.
  • pigments that can be used for the yellow ink include C.I. I. Pigment yellow 1, 2, 12, 13, 14, 16, 17, 73, 74, 75, 83, 93, 95, 97, 98, 109, 110, 114, 120, 128, 129, 138, 150, 151, 151, 151 154, 155, 174, 180, 185 and the like.
  • pigments usable for cyan ink C.I. I. Pigment blue 1, 2, 3, 15, 15: 3, 15: 4, 16, 22, 60, 63, 66 and the like.
  • pigments that can be used for the white ink include sulfates of alkaline earth metals, carbonates, finely divided silicic acid, synthetic silicates, and other silicas, calcium silicate, alumina, alumina hydrate, Titanium oxide, zinc oxide, talc, clay and the like can be mentioned. These may be surface-treated.
  • the pigment is preferably treated to be well dispersed in an aqueous medium in order to stably exist in the aqueous ink.
  • a method of dispersing a pigment together with a pigment dispersant in an aqueous medium by a dispersing method described later ii) a dispersibility imparting group (hydrophilic functional group and / or a salt thereof) on the surface of the pigment
  • a method of dispersing and / or dissolving a self-dispersion pigment which is directly or indirectly bonded via an alkyl group, an alkyl ether group or an aryl group, to an aqueous medium.
  • the self-dispersion pigment for example, a pigment obtained by physically or chemically treating the pigment and binding (grafting) an active species having a dispersibility imparting group or a dispersibility imparting group to the surface of the pigment is used. be able to.
  • the self-dispersible pigment is, for example, a vacuum plasma treatment, an oxidation treatment with hypohalous acid and / or a hypohalite, an oxidation treatment with ozone, or a wet oxidation method in which the pigment surface is oxidized with an oxidant in water.
  • it can be produced by a method of bonding a carboxyl group through a phenyl group by bonding p-aminobenzoic acid to the pigment surface.
  • An aqueous ink containing a self-dispersion pigment does not need to contain the pigment dispersant, so there is almost no foaming or the like caused by the pigment dispersant, and it is easy to prepare an aqueous ink having excellent ejection stability.
  • the aqueous ink containing the self-dispersion pigment is easy to handle and can suppress a significant increase in viscosity due to the pigment dispersant, it is possible to contain more pigment, and a printed matter with high print density can be produced. It can be used for
  • Such commercial products can be used as the self-dispersion pigment, and such commercial products include Microjet CW-1 (trade name; manufactured by Orient Chemical Industries, Ltd.), CAB-O-JET 200, Examples include CAB-O-JET 300 (trade name; manufactured by Cabot Corporation).
  • the print density and the abrasion resistance of the printed matter may tend to be slightly reduced.
  • the coloring material prevents the generation of the streaks, maintains the excellent dispersion stability of the coloring material, and improves the print density and the abrasion resistance of the printed matter, relative to the total amount of the aqueous ink. It is preferably used in the range of 1% by mass to 20% by mass, and more preferably in the range of 2% by mass to 10% by mass.
  • the pigment dispersant can be suitably used when a pigment is used as the coloring material.
  • pigment dispersant examples include acrylic resins such as polyvinyl alcohols, polyvinyl pyrrolidones, acrylic acid-acrylic acid ester copolymers, styrene-acrylic acid copolymers, styrene-methacrylic acid copolymers, styrene-methacrylic acid Styrene-acrylic resin such as -acrylic acid ester copolymer, styrene- ⁇ -methylstyrene-acrylic acid copolymer, styrene- ⁇ -methylstyrene-acrylic acid-acrylic acid ester copolymer, styrene-maleic acid copolymer It is possible to use a combined resin of styrene-maleic anhydride copolymer, an aqueous resin of vinylnaphthalene-acrylic acid copolymer, and a salt of the aqueous resin.
  • acrylic resins such as polyvinyl alcohols, polyvin
  • pigment dispersant examples include: Azispar PB series manufactured by Ajinomoto Fine Techno Co., Ltd .; Disperbyk series manufactured by Big Chemie Japan Ltd .; EFKA series manufactured by BASF; SOLSPERSE series manufactured by Japan Lubrisol Co .; TEGO series etc. can be used.
  • the pigment dispersant it is possible to remarkably reduce coarse particles, and as a result, use a polymer (G) described later in order to impart good ejection stability required when ejecting an aqueous ink by an inkjet method. Is preferred.
  • the polymer (G) those having an anionic group can be used, and among them, the solubility in water is 0.1 g / 100 ml or less, and the inside of the basic compound of the anionic group is used. It is preferable to use a polymer having a number average molecular weight in the range of 1000 to 6000, which can form fine particles in water when the conversion ratio is 100%.
  • the solubility of the polymer (G) in water was defined as follows. That is, 0.5 g of polymer (G) whose particle diameter was adjusted in the range of 250 ⁇ m to 90 ⁇ m using sieves with openings of 250 ⁇ m and 90 ⁇ m was sealed in a bag processed with 400 mesh wire mesh to obtain a test piece (M) . Next, the test piece (M) was immersed in 50 ml of water and gently stirred at a temperature of 25 ° C. for 24 hours. After 24 hours, the test piece (M) was dried in a dryer set at 110 ° C. for 2 hours. The change in mass before and after immersing the test piece (M) in water was measured, and the solubility was calculated by the following equation.
  • Solubility (g / 100 ml) [(mass of test piece (M) before immersion in water (g))-(mass of test piece (M) after immersion in water (g)) ⁇ 2
  • the acid value of the polymer (G) is measured in advance by an acid value measurement method based on JIS test method K 0070-1992. Specifically, 0.5 g of the polymer (G) is dissolved in tetrahydrofuran, and titrated with a 0.1 M potassium hydroxide ethanol solution using phenolphthalein as an indicator to obtain an acid value. (2) Next, 1 g of the polymer (G) is added to 50 ml of water, and then the amount of 0.1 mol / L hydroxide required to neutralize 100% of the acid group of the polymer (G) is added.
  • the acid groups were neutralized 100% by the addition of aqueous potassium.
  • the solution obtained in the above (2) is subjected to ultrasonic waves in an ultrasonic cleaner (SSN Ultrasonic Cleaner US-102, 38 kHz self-oscillation) at a temperature of 25 ° C. for 2 hours. And leave for 24 hours at room temperature.
  • SSN Ultrasonic Cleaner US-102 38 kHz self-oscillation
  • Dynamic light scattering type particle size distribution measuring device manufactured by Nikkiso Co., Ltd., dynamic light scattering type particle size measurement, with a sample liquid obtained by sampling the liquid located 2 cm deep from the liquid surface after standing for 24 hours
  • the apparatus "Microtrack particle size distribution analyzer UPA-ST150" is used to confirm whether or not the fine particles exist by determining whether light scattering information can be obtained by the fine particle formation.
  • the particle diameter of the particles is preferably in the range of 5 nm to 1000 nm, and in the range of 7 nm to 700 nm. Is more preferable, and most preferably in the range of 10 nm to 500 nm. Further, the particle size distribution of the fine particles tends to be more excellent in the dispersion stability if the narrower the particle size distribution, but even if the particle size distribution is wide, it is possible to obtain an aqueous ink having a dispersion stability superior to the prior art. .
  • the particle size and the particle size distribution were measured using a dynamic light scattering particle size distribution measuring apparatus (a dynamic light scattering particle size measuring apparatus “Microtrac particle size distribution analyzer UPA-ST150” manufactured by Nikkiso Co., Ltd.).
  • the neutralization rate of the polymer (G) used in the present invention was determined by the following equation.
  • Neutralization rate (%) [(mass of basic compound (g) ⁇ 56 ⁇ 1000) / (acid value of polymer (G) (mg KOH / g) ⁇ equivalent of basic compound ⁇ mass of polymer (G) (G))] ⁇ 100
  • the acid value of the polymer (G) was measured based on JIS test method K 0070-1992. Specifically, it was determined by dissolving 0.5 g of the polymer (G) in tetrahydrofuran and titration with a 0.1 M potassium hydroxide ethanol solution using phenolphthalein as an indicator.
  • the number average molecular weight of the polymer (G) is preferably in the range of 1000 to 6000, more preferably 1300 to 5000, and it is preferably 1500 to 4500 that the color of the pigment or the like in the aqueous medium is It is more preferable from the viewpoint of obtaining an aqueous ink capable of effectively suppressing aggregation of the material and having good dispersion stability of the color material.
  • the said number average molecular weight be a value of polystyrene conversion measured by GPC (gel permeation chromatography), and let it be the value specifically, measured on condition of the following.
  • Measuring device High-speed GPC device ("HLC-8220GPC" manufactured by Tosoh Corporation) Column: The following columns manufactured by Tosoh Corporation were used in series connection.
  • TKgel G5000 (7.8 mm ID ⁇ 30 cm) ⁇ 1 "TSK gel G 4000” (7.8 mm ID ⁇ 30 cm) ⁇ 1 "TSK gel G 3000” (7.8 mm ID ⁇ 30 cm) ⁇ 1
  • the polymer (G) a polymer which is insoluble or poorly soluble in water in an unneutralized state and which forms fine particles in a 100% neutralized state can be used, and it is a hydrophilic group There is no particular limitation as long as the polymer has a hydrophobic group in one molecule in addition to a certain anionic group.
  • Such polymers include block polymers having a polymer block having a hydrophobic group and a polymer block having an anionic group.
  • the number of anionic groups and the solubility in water are not necessarily specified by the acid number or the number of anionic groups at the time of design of the polymer, and for example, polymers having the same acid number Even if the molecular weight is low, the solubility in water tends to be high, and the molecular weight is high, the solubility in water tends to be low. From this, in the present invention, the polymer (G) is specified by the solubility in water.
  • the polymer (G) may be a homopolymer, but is preferably a copolymer, and may be a random polymer, a block polymer, or an alternating polymer, among which a block polymer Is preferred.
  • the polymer may be a branched polymer but is preferably a linear polymer.
  • the polymer (G) is preferably a vinyl polymer from the freedom of design, and as a method of producing a vinyl polymer having the desired molecular weight and solubility characteristics in the present invention, living radical polymerization, living cationic polymerization It is preferable to manufacture by using "living polymerization", such as living anion polymerization.
  • the polymer (G) is preferably a vinyl polymer produced using a (meth) acrylate monomer as one of the raw materials, and as a method for producing such a vinyl polymer, living radical polymerization, living anion polymerization Living anionic polymerization is preferred from the viewpoint of designing the molecular weight of the block polymer and each segment more precisely.
  • the polymer (G) produced by living anionic polymerization is a polymer represented by the general formula (3).
  • a 1 represents an organolithium initiator residue
  • a 2 represents a polymer block of a monomer having an aromatic ring or a heterocycle
  • a 3 represents a polymer block containing an anionic group
  • n represents an integer of 1 to 5
  • B represents an aromatic group or an alkyl group.
  • a 1 represents an organolithium initiator residue.
  • organic lithium initiators include methyllithium, ethyllithium, propyllithium, butyllithium (n-butyllithium, sec-butyllithium, iso-butyllithium, tert-butyllithium etc.), pentyllithium, hexyllithium, Alkyl lithiums such as methoxymethyllithium and ethoxymethyllithium; phenyllithiums such as benzyllithium, ⁇ -methylstyryllithium, 1,1-diphenyl-3-methylpentyllithium, 1,1-diphenylhexyllithium and phenylethyllithium Alkenyllithium such as vinyllithium, allyllithium, propenyllithium and butenyllithium; ethynyllithium, butynyllithium, pentynyllithium, hexyn
  • the bond between the organic group and lithium is cleaved to form an active end on the organic group side, from which polymerization is initiated. Therefore, an organic group derived from organolithium is bonded to the end of the resulting polymer.
  • the organic group derived from organolithium bonded to the polymer terminal is referred to as an organolithium initiator residue.
  • the organolithium initiator acid group is a methyl group
  • the organolithium initiator acid group is a butyl group.
  • a 2 represents a polymer block having a hydrophobic group.
  • a 2 is another object to balance balance described above moderate solubility, it is preferably a high adsorption to the pigment group when in contact with the pigment, from the viewpoints,
  • a 2 is an aromatic ring or It is preferably a polymer block of a monomer having a heterocycle.
  • the polymer block of a monomer having an aromatic ring or a heterocycle is obtained by homopolymerizing or copolymerizing a monomer having an aromatic ring such as a styrene-based monomer or a monomer having a heterocycle such as a vinylpyridine-based monomer. It is a polymer block of homopolymer or copolymer obtained by
  • styrene As a monomer having an aromatic ring, styrene, p-tert-butyldimethylsiloxystyrene, o-methylstyrene, p-methylstyrene, p-tert-butylstyrene, p-tert-butoxystyrene, m-tert-butoxystyrene, Styrene-based monomers such as p-tert- (1-ethoxymethyl) styrene, m-chlorostyrene, p-chlorostyrene, p-fluorostyrene, ⁇ -methylstyrene, p-methyl- ⁇ -methylstyrene, and vinyl naphthalene And vinyl anthracene.
  • Styrene-based monomers such as p-tert- (1-ethoxymethyl) styrene, m-chlorostyrene, p-ch
  • examples of the monomer having a heterocycle include vinylpyridine-based monomers such as 2-vinylpyridine and 4-vinylpyridine. These monomers can be used alone or in combination of two or more.
  • a 3 represents a polymer block containing an anionic group.
  • a 3 is another object to provide a described above moderate solubility, there is a purpose of imparting dispersion stability in water when a pigment dispersion.
  • Anionic groups in the polymer block A for example, carboxyl group, sulfonic acid group or phosphoric acid group. Among them, a carboxyl group is preferable in view of its preparation and availability of monomer varieties.
  • two carboxyl groups may form an acid anhydride group which is dehydrated and condensed in a molecule or between molecules.
  • Method for introducing anionic groups of the A 3 is not particularly limited, for example, the case the anionic group is a carboxyl group, (meth) homopolymer obtained by copolymerizing a homopolymer or other monomers acrylic acid or It may be a polymer block (PB1) of a copolymer, or it may be a homo obtained by homopolymerizing or copolymerizing a (meth) acrylate having a renewable protecting group to an anionic group by deprotection.
  • the polymer block or the copolymer may be a polymer block (PB2) in which some or all of the renewable protecting groups for the anionic group are regenerated to an anionic group.
  • the A polymer block used in A 3 (meth) acrylic acid represents the general term for acrylic acid and methacrylic acid
  • (meth) acrylate represents the general term for acrylate and methacrylate.
  • (meth) acrylic acid and (meth) acrylate include (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, iso-propyl (meth) acrylate, (meth) Allyl acrylate, n-butyl (meth) acrylate, iso-butyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, n-amyl (meth) acrylate ( Meta) iso-amyl acrylate, n-hexyl (meth) acrylate, n-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-lauryl (meth) acrylate, n (meth) acrylate -Tridecyl, n-stearyl (meth) acrylate, phenyl (meth) acrylic
  • the active end of the living anion polymerization polymer immediately reacts with the group having such an active proton to deactivate it. Polymer can not be obtained.
  • living anionic polymerization it is difficult to directly polymerize a monomer having a group having an active proton, so polymerization is performed in a state in which the group having an active proton is protected, and then the protective group is deprotected to have an active proton. It is preferred to regenerate the group.
  • the polymer block A 3 it is preferable to use a monomer containing a (meth) acrylate having a renewable protecting group an anionic group by deprotection.
  • a monomer containing a (meth) acrylate having a renewable protecting group an anionic group by deprotection.
  • the carboxyl group can be regenerated by esterifying the carboxyl group and deprotecting by hydrolysis or the like as a subsequent step.
  • a protective group which can be converted to a carboxyl group a group having an ester bond is preferable, and, for example, a primary alkoxycarbonyl group such as methoxycarbonyl group, ethoxycarbonyl group, n-propoxycarbonyl group, n-butoxycarbonyl group Secondary alkoxycarbonyl groups such as isopropoxycarbonyl group, sec-butoxycarbonyl group; tertiary alkoxycarbonyl groups such as t-butoxycarbonyl group; phenylalkoxycarbonyl groups such as benzyloxycarbonyl group; ethoxyethyl carbonyl group etc. And the like.
  • usable monomers include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, sec -Butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, decyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate (lauryl (meta) ) Acrylates), tridecyl (meth) acrylate, pentadecyl (meth) acrylate, hexadecyl (meth) acrylate, heptadecyl (meth) acrylate, octa
  • (meth) acrylates can be used alone or in combination of two or more.
  • t-butyl (meth) acrylate and benzyl (meth) acrylate are preferably used because they are easy to convert to a carboxyl group.
  • t-butyl (meth) acrylate is more preferable in consideration of industrial availability.
  • B represents an aromatic group or an alkyl group having 1 to 10 carbon atoms.
  • n represents an integer of 1 to 5.
  • the reaction modifier is used to adjust the nucleophilicity, and then the (meth) acrylate monomer is polymerized.
  • B in the general formula (3) is a group derived from the reaction control agent. Specific examples of the reaction modifier include diphenylethylene, ⁇ -methylstyrene, p-methyl- ⁇ -methylstyrene and the like.
  • the living anion polymerization method can be carried out by batch method as used in conventional free radical polymerization by adjusting reaction conditions, and can also be mentioned a method of continuous polymerization by a microreactor.
  • the microreactor since the mixing property of the polymerization initiator and the monomer is good, the reaction starts simultaneously, the temperature is uniform, and the polymerization rate can be made uniform, so the molecular weight distribution of the produced polymer can be narrowed.
  • the growth end since the growth end is stable, it becomes easy to produce a block copolymer in which both components of the block are not mixed.
  • the controllability of the reaction temperature is good, it is easy to suppress the side reaction.
  • FIG. 3 is a schematic view of a microreactor.
  • a T-shaped micromixer M1 (Fig. 1) having a flow path capable of mixing a plurality of liquids from the tube reactors P1 and P2 (7 and 8 in Fig. 1) respectively with the first monomer and the polymerization initiator for initiating polymerization. It is introduced into 1) in 1 and living anion polymerization of the first monomer is carried out to form a first polymer in the T-shaped micro mixer M1 (step 1).
  • the obtained first polymer is transferred to a T-shaped micro mixer M2 (2 in FIG. 3), and the growth end of the obtained polymer is transferred to the tube reactor P3 (FIG. 3) in the mixer M2. Trap with the reaction modifier introduced from 9), and perform reaction adjustment (Step 2). At this time, it is possible to control the number of n in the general formula (3) according to the type and amount of use of the reaction modifier.
  • the first polymer subjected to reaction adjustment in the T-shaped micromixer M2 is transferred to the T-shaped micromixer M3 (3 in FIG. 3), and from the tube reactor P4 in the mixer M3. Living anionic polymerization is continuously performed on the introduced second monomer and the first polymer subjected to the reaction adjustment (step 3).
  • reaction is quenched with a compound having an active proton such as methanol to produce a block copolymer.
  • a monomer having an aromatic ring or a heterocyclic ring is used as the first monomer, and an organic is used as the initiator A polymer block of a monomer having an aromatic ring or a heterocyclic ring of the above A 2 by reaction with a lithium initiator (an organic group which is an organolithium initiator residue of the above A 1 at one end of the polymer block A 2 ) Get connected).
  • a lithium initiator an organic group which is an organolithium initiator residue of the above A 1 at one end of the polymer block A 2
  • a polymer block is reacted as the second monomer with a monomer containing a (meth) acrylate having a renewable protective group at the anionic group.
  • the hydrolysis reaction of an ester bond proceeds under both acidic and basic conditions, but the conditions are slightly different depending on the group having an ester bond.
  • the group having an ester bond is a primary alkoxycarbonyl group such as a methoxycarbonyl group or a secondary alkoxycarbonyl group such as an isopropoxycarbonyl group
  • a carboxyl group is obtained by hydrolysis under basic conditions. be able to.
  • metal hydroxides such as sodium hydroxide and potassium hydroxide, etc. are mentioned, for example.
  • a carboxyl group can be obtained by hydrolysis under acidic conditions.
  • mineral acids such as hydrochloric acid, a sulfuric acid, phosphoric acid, for example, Brested acids, such as trifluoroacetic acid; Lewis acids, such as trimethyl silyl triflate, etc. are mentioned.
  • the reaction conditions for hydrolysis under the acidic condition of t-butoxycarbonyl group are disclosed, for example, in “The Chemical Society of Japan, 5th Edition, Experimental Chemistry Lecture 16 Synthesis of Organic Compounds IV”.
  • a method using a cation exchange resin in place of the above-mentioned acid may also be mentioned.
  • the cation exchange resin include resins having an acid group such as a carboxyl group (—COOH) or a sulfo group (—SO 3 H) on the side chain of the polymer chain.
  • a cation exchange resin exhibiting strong acidity having a sulfo group in the side chain of the resin is preferable because it can accelerate the reaction.
  • the strong acidic cation exchange resin "Amberlite" etc. by Organo Ltd.
  • the amount of the cation exchange resin used is preferably in the range of 5 parts by mass to 200 parts by mass, and 10 parts by mass with respect to 100 parts by mass of the polymer represented by the general formula (3).
  • the range of ⁇ 100 parts by mass is more preferable.
  • the group having an ester bond is a phenylalkoxycarbonyl group such as a benzyloxycarbonyl group
  • it can be converted to a carboxyl group by performing a hydrogenation reduction reaction.
  • a phenyl alkoxy carbonyl group can be quantitatively regenerated to a carboxyl group by making it react using hydrogen gas as a reducing agent in presence of palladium catalysts, such as palladium acetate, under room temperature.
  • the polymer block is not a random copolymer in which the polymer block (A 2 ) and the polymer block (A 3 ) are randomly arranged and bonded. It is more advantageous to improve the stability of the aqueous pigment dispersion in which the pigment is dispersed in water by the polymer (G) if it is a block copolymer which is united to a certain length and bound regularly. is there.
  • the aqueous pigment dispersion is a raw material used for producing an aqueous ink, and is a liquid in which the pigment is dispersed in water at a high concentration using the polymer (G).
  • the number of monomers having an aromatic ring or a heterocyclic ring constituting the polymer block (A 2 ) is preferably in the range of 5 to 40, and in the range of 6 to 30 Is more preferred, and the range of 7 to 25 is most preferred.
  • the number of anionic groups constituting the polymer block (A 3 ) is preferably in the range of 3 to 20, more preferably in the range of 4 to 17, and most preferably in the range of 5 to 15.
  • Configure A 3 and the number of moles having an aromatic ring or a heterocyclic ring constituting the polymer block (A 2), the (A 3): molar ratio A 2 of the polymer block (A 2) and polymer blocks (A 3)
  • it is represented by the molar ratio of the number of moles of the anionic group, it is preferably 100: 7.5 to 100: 400.
  • the acid value of the polymer (G) represented by the general formula (3) is preferably 40 mg KOH / g to 400 mg KOH / g, more preferably 40 mg KOH / g to 300 mg KOH / g, and 40 mg KOH / g to 190 mg KOH / g.
  • the anionic group of the polymer (G) is preferably neutralized.
  • a basic compound which neutralizes the anionic group of the said polymer (G) all well-known and usual things can be used, for example, inorganic basicity, such as alkali metal hydroxides, such as sodium hydroxide and potassium hydroxide Substances and organic basic compounds such as ammonia, triethylamine and alkanolamines can be used.
  • inorganic basicity such as alkali metal hydroxides, such as sodium hydroxide and potassium hydroxide
  • organic basic compounds such as ammonia, triethylamine and alkanolamines
  • the amount of neutralization of the polymer (G) present in the aqueous pigment dispersion does not have to be 100% neutralized with respect to the acid value of the polymer.
  • the polymer (G) is preferably neutralized so as to have a neutralization rate of 20% to 200%, and more preferably 80% to 150%.
  • the aqueous ink used in the present invention may further contain, if necessary, a surfactant, a wetting agent (drying inhibitor), a penetrant, a preservative, a viscosity modifier, a pH modifier, a chelating agent, and a plasticizer, as required.
  • a surfactant such as an agent, an antioxidant, and a UV absorber can be used.
  • the surfactant can be used to improve the leveling properties of the aqueous ink by, for example, reducing the surface tension of the aqueous ink. Furthermore, after the aqueous ink discharged from the discharge port of the ink jet head lands on the cardboard (A), the surfactant wets and spreads well on the surface, thereby preventing the generation of streaks on the printed matter.
  • surfactant examples include various anionic surfactants, nonionic surfactants, cationic surfactants, amphoteric surfactants and the like, and among these, anionic surfactants, nonionic surfactants Activators are preferred.
  • anionic surfactant for example, alkyl benzene sulfonate, alkyl phenyl sulfonate, alkyl naphthalene sulfonate, higher fatty acid salt, sulfuric acid ester salt of higher fatty acid ester, sulfonate of higher fatty acid ester, higher alcohol ether Sulfuric acid esters and sulfonates, higher alkyl sulfosuccinates, polyoxyethylene alkyl ether carboxylates, polyoxyethylene alkyl ether sulfates, alkyl phosphates, polyoxyethylene alkyl ether phosphates, etc.
  • nonionic surfactant for example, polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, glycerin fatty acid ester , Polyoxyethylene glycerine fatty acid ester, polyglycerin fatty acid ester, sucrose fatty acid ester, polyoxyethylene alkylamine, polyoxyethylene fatty acid amide, fatty acid alkylolamide, alkylalkanolamide, acetylene glycol, oxyethylene adduct of acetylene glycol, Polyethylene glycol polypropylene glycol block copolymer etc can be used among them, as the nonionic surfactant, polyoxyethylene nonyl phenyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene dodecyl
  • acetylene glycol and oxyethylene adduct of acetylene glycol are preferably used as the nonionic surfactant, because the ink jet recording ink is in contact with the layer (z2) of the recording medium (Z).
  • the angle is small, the ink is easily wetted and spread on the surface of the recording medium (Z), and as a result, it is more preferable because a print having good whitening-free leveling properties can be obtained.
  • surfactants include silicone surfactants such as polysiloxane oxyethylene adducts; fluorosurfactants such as perfluoroalkyl carboxylates, perfluoroalkyl sulfonates and oxyethylene perfluoroalkyl ethers Agents; biosurfactants such as spicripolic acid, rhamnolipid, lysolecithin, etc. can also be used.
  • the surfactant is preferably used in an amount of 0.001% by mass to 2% by mass, and more preferably 0.001% by mass to 1.5% by mass, based on the total amount of the aqueous ink. Is more preferably used in the range of 0.5% by mass to 1.5% by mass.
  • the ink jet ink containing the surfactant in the above range is excellent in wettability of the discharged droplets on the surface of the cardboard (A), has sufficient wetting and spreading on the cardboard (A), and generates streaks of printed matter. It is preferable in achieving the effect of preventing.
  • a wetting agent which can be used for the said water-based ink, it can be used for the purpose of preventing drying of water-based ink.
  • the wetting agent is preferably used in the range of 3% by mass to 50% by mass with respect to the total amount of the aqueous ink.
  • the wetting agent one which is miscible with water and capable of preventing the clogging of the discharge port of the inkjet head is preferable.
  • ethylene glycol diethylene glycol, triethylene glycol, polyethylene glycol having a molecular weight of 2000 or less, dipropylene glycol, Tripropylene glycol, isopropylene glycol, isobutylene glycol, 1,4-butanediol, 1,3-butanediol, 1,5-pentanediol, 1,6-hexanediol, mesoerythritol, pentaerythritol and the like.
  • penetrants usable for the optional components include lower alcohols such as ethanol and isopropyl alcohol, ethylene oxide adducts of alkyl alcohols such as ethylene glycol hexyl ether and diethylene glycol butyl ether, and propylene oxide addition of alkyl alcohols such as propylene glycol propyl ether Things etc.
  • the content of the penetrant is preferably 3% by mass or less, more preferably 1% by mass or less, and still more preferably substantially non-containing with respect to the total amount of the aqueous ink.
  • the aqueous ink can be produced, for example, by mixing a binder resin, a compound having a urea bond, an aqueous medium, a coloring material and optionally, optional components such as the surfactant and the organic solvent (F).
  • a disperser such as a bead mill, an ultrasonic homogenizer, a high pressure homogenizer, a paint shaker, a ball mill, a roll mill, a sand mill, a sand grinder, a dyno mill, a disper mat, an SC mill, a nanomizer can be used.
  • a binder resin As the method for producing the aqueous ink, a binder resin, a compound having a urea bond, an aqueous medium, a coloring material and, if necessary, optional components such as the surfactant and the organic solvent (F), And mixing, stirring and the like.
  • aqueous ink for example, by mixing a pigment dispersant such as ⁇ 1> the polymer (G), a colorant such as the pigment, and a solvent as necessary.
  • a step of producing a colorant dispersion a containing a colorant at a high concentration, ⁇ 2> a step of producing a composition b by mixing a compound having the urea bond with a solvent according to need, ⁇ 3> By passing through a step of producing a composition c containing the binder resin and the aqueous medium, and a step of mixing ⁇ 4> the coloring material dispersion a, the composition b, and the composition c.
  • the method of manufacturing is mentioned.
  • the aqueous ink obtained by the above method is preferably subjected to centrifugation and filtration as necessary, in order to remove impurities mixed in the aqueous ink.
  • the pH of the aqueous ink of the present invention improves the storage stability and the ejection stability of the aqueous ink, and spreads when printed on a non-ink-absorbent or non-absorbent cardboard (A), the printing spread, the print density, and the scratch resistance Is preferably 7.0 or more, more preferably 7.5 or more, and still more preferably 8.0 or more.
  • the upper limit of the pH of the aqueous ink suppresses the deterioration of members (for example, an ink discharge port, an ink flow path, etc.) constituting the application or ejection device of the aqueous ink, and the influence when the ink adheres to the skin is In order to reduce the size, it is preferably 11.0 or less, more preferably 10.5 or less, and still more preferably 10.0 or less.
  • the polymer obtained in the above step is transferred to the T-shaped micro mixer M2 through the tube reactor R1 shown in FIG. 3, and the growth end of the polymer is introduced from the tube reactor P3. Trapped with methylstyrene ( ⁇ -MeSt)).
  • a tert-butyl methacrylate solution prepared by previously dissolving tert-butyl methacrylate in tetrahydrofuran is introduced from the tube reactor P4 shown in FIG. 3 into the T-shaped micromixer M3 and transferred through the tube reactor R2 with the trapped polymer A continuous living anionic polymerization reaction was performed. Thereafter, the block copolymer (PA-1) composition was prepared by quenching the living anionic polymerization reaction by supplying methanol.
  • the reaction temperature was set to 24 ° C. by immersing the entire microreactor shown in FIG. 3 in a constant temperature bath.
  • the resulting block copolymer (PA-1) composition is hydrolyzed by treatment with a cation exchange resin and then distilled off under reduced pressure, and the resulting solid is pulverized to obtain powdery product.
  • a polymer (P-1) was obtained.
  • Measuring device High-speed GPC device ("HLC-8220GPC" manufactured by Tosoh Corporation) Column: The following columns manufactured by Tosoh Corporation were used in series connection.
  • TKgel G5000 (7.8 mm ID ⁇ 30 cm) ⁇ 1 "TSK gel G 4000” (7.8 mm ID ⁇ 30 cm) ⁇ 1 "TSK gel G 3000” (7.8 mm ID ⁇ 30 cm) ⁇ 1
  • test piece (M) was obtained by sealing 0.5 g of a polymer whose particle diameter was adjusted in the range of 250 ⁇ m to 90 ⁇ m using sieves with openings of 250 ⁇ m and 90 ⁇ m, and sealing it in a bag obtained by processing a 400 mesh wire mesh.
  • the test piece (M) was immersed in 50 ml of water and allowed to stand under gentle stirring at a temperature of 25 ° C. for 24 hours. After 24 hours, the test piece (M) was dried in a dryer set at 110 ° C. for 2 hours. The change in mass before and after immersing the test piece (M) in water was measured, and the solubility was calculated by the following equation.
  • Solubility (g / 100 ml) [(mass of test piece (M) before immersion in water (g))-(mass of test piece (M) after immersion in water (g)) ⁇ 2
  • a dynamic light scattering particle size distribution measuring apparatus (dynamic light scattering particle size measurement manufactured by Nikkiso Co., Ltd.), using the liquid at a depth of 2 centimeters from the liquid surface as the sample liquid With the apparatus "Microtrack particle size distribution analyzer UPA-ST150", the presence or absence of the formation of fine particles was confirmed from the light scattering information of the particles, and when the fine particles were present, the volume average particle diameter was measured.
  • Table 1 shows the raw materials, reaction conditions, and physical properties of the polymer obtained in the synthesis example.
  • BuLi represents normal butyl lithium
  • St represents styrene
  • DPE represents 1,1-diphenylethylene
  • ⁇ -MeSt represents ⁇ -methylstyrene
  • tBMA represents tert-butyl methacrylate.
  • Aqueous Pigment Dispersion As a pigment, 150 parts by mass of phthalocyanine pigment Fastgen Blue Pigment (manufactured by DIC Corporation: CI Pigment 15: 3), 45 parts by mass of polymer (P-1), 150 parts by mass of triethylene glycol, 34 Twenty parts by mass of a mass% potassium hydroxide aqueous solution was charged in a 1.0 L intensive mixer (Nippon Eirich Co., Ltd.) and kneaded for 25 minutes at a rotor circumferential speed of 2.94 m / s and a pan circumferential speed of 1 m / s.
  • aqueous pigment dispersion (Y) having a pigment concentration of 15% by mass.
  • Example 1 The ink jet head KJ4B-YH manufactured by KYOCERA Corporation was filled with the aqueous ink (Y1), and the supply pressure was adjusted by setting the head difference of the ink subtank from the head nozzle plate surface to +35 cm and the negative pressure -5.0 kPa. .
  • the distance (gap) from the surface (x) having the ink discharge port of the ink jet head to the position (y) where the perpendicular line assumed to the surface (x) intersects the cardboard is set to 2 mm.
  • a 3 mm-thick B flute type having a liner provided with a layer having a water absorption amount of 5 g / m 2 on one side was used.
  • the driving conditions of the inkjet head were set to the standard voltage and standard temperature of the inkjet head, and the droplet size of the aqueous ink was set to 18 pL.
  • solid printing was performed at 600 ⁇ 600 dpi on the side corresponding to the layer of the corrugated board using a printer provided with the ink jet head.
  • the blowing temperature is 40 ° C and the blowing speed is 5 m / s at an angle of 90 ° to the cardboard conveyance direction and 60 ° from the perpendicular to the printing surface on the printed surface of the corrugated cardboard immediately after the above printing It blew.
  • the air blowing time was 1 second.
  • infrared rays ZKB1200 / 340G manufactured by Heraeus, carbon heaters 1000W ⁇ 7, output 100%
  • the heating and drying time was 1 second, and the temperature of the printing surface at the time of drying was 60.degree.
  • Example 2 Printed matter was obtained in the same manner as in Example 1 except that the temperature of the air blowing performed in Example 1 was changed to normal temperature. The temperature of the printing surface at the time of drying was 60.degree.
  • Example 3 Printed matter was obtained in the same manner as in Example 1 except that the temperature of the air blowing performed in Example 1 was normal temperature, the air blowing time was 30 seconds, and heating using an infrared ray was not performed.
  • Example 4 Printing and drying were performed in the same manner as in Example 1 except that a 5 mm-thick A-flute type having a liner provided with a layer having a water absorption amount of 10 g / m 2 was used as a cardboard on one side.
  • Example 5 Printing and drying were performed in the same manner as in Example 2 except that a 5 mm-thick A-flute type having a liner provided with a layer having a water absorption amount of 10 g / m 2 was used as a cardboard on one side.
  • Example 6 Printing and drying were performed in the same manner as in Example 3, except that a 5 mm-thick A-flute type having a liner provided with a layer having a water absorption amount of 10 g / m 2 was used as the cardboard on one side.
  • Example 1 (Comparative example 1) Printed matter was obtained in the same manner as in Example 1 except that the drying means was only infrared light and air blowing was not performed.
  • Example 2 Printed matter was obtained in the same manner as in Example 1 except that the air drying step was not performed, and natural drying was performed for 30 seconds in a windless environment.
  • Example 3 (Comparative example 3) Printed matter was obtained in the same manner as in Example 4 except that the drying means was only infrared light and air blowing was not performed.
  • Example 4 Printed matter was obtained in the same manner as in Example 4 except that the air drying step was not performed, and natural drying was performed for 30 seconds in a windless environment.
  • Example 1 in order to prevent the occurrence of color unevenness in the printed matter, it was effective to blow air on the printing surface.
  • the air blowing temperature was 40 ° C.
  • the tackiness was reduced and the drying time could be shortened.
  • the mottling of the printed matter could be reduced by adopting the heating and drying step using infrared rays together with the air blowing step.
  • Comparative Example 1 color unevenness was generated in the printed matter only by heat drying with infrared light without adopting the air blowing step, and tackiness remained immediately after drying.
  • Comparative Example 2 in the case of only natural drying without adopting the air-blowing process, the drying time tends to become longer due to the occurrence of mottling and the tackiness, so the productivity of printed matter is lowered.
  • a liner is formed on at least one side of the corrugated core and a cardboard having a layer having a water absorption of 15 g / m 2 or less on the liner is subjected to inkjet printing with an aqueous ink
  • a step of blowing air to the printing surface is essential, and furthermore, good drying property and good productivity of printed matter can be obtained.
  • it turned out that combined use of infrared rays drying is effective.
  • the fact that the drying property is good means that the drying time can be further shortened, and the good productivity means that the production time of the printed matter can be improved by being able to shorten the drying time.
  • T-shaped micro mixer M1 2 T-shaped micro mixer M2 3: T-shaped micro mixer M3 4: Tube reactor R1 5: Tube reactor R2 6: Tube reactor R3 7: Tube reactor P1 for precooling 8: Tube reactor P2 for precooling 9: Tube reactor P3 for precooling 10: Tube reactor P4 for precooling 11: lamination of layer (a) having a water absorption of 15 g / m 2 or less and a liner 12: flute 13: printed matter 14: printing surface 15: color unevenness in streaks

Landscapes

  • Ink Jet Recording Methods And Recording Media Thereof (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)
  • Ink Jet (AREA)

Abstract

La présente invention aborde le problème de la réalisation d'un procédé de fabrication d'imprimés, qui peut empêcher l'apparition d'une irrégularité de couleur, dans une image imprimée, provoquée par un étalement même lorsqu'une impression est effectuée à l'aide d'une encre aqueuse, sur la surface d'une plaque ondulée pourvue d'une couche qui n'absorbe pas ou absorbe difficilement un solvant contenu dans l'encre aqueuse. La présente invention concerne un procédé de fabrication d'imprimés, caractérisé par l'utilisation d'une encre aqueuse pour effectuer une impression sur une plaque ondulée (A) ayant une couche (a) présentant une quantité d'absorption de 15 g/m2 ou moins, puis le séchage de l'encre aqueuse par une étape [1] comprenant une étape [1-1] destinée à souffler de l'air sur une surface imprimée.
PCT/JP2018/033954 2017-09-27 2018-09-13 Procédé de production d'imprimés Ceased WO2019065267A1 (fr)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPWO2020012969A1 (ja) * 2018-07-10 2020-09-24 Dic株式会社 インクジェット印刷インク用プライマー、被記録媒体及び印刷システム
JP7794694B2 (ja) 2022-06-02 2026-01-06 株式会社日立産機システム 印字ドット乾燥装置、印字ドット乾燥方法、および印刷システム

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JPS60139442A (ja) * 1983-12-28 1985-07-24 味の素株式会社 強化段ボ−ル
JPS60184832A (ja) * 1984-12-28 1985-09-20 石崎産業株式会社 フイルム貼着段ボ−ルの製造方法
JP2009279870A (ja) * 2008-05-23 2009-12-03 Fujifilm Corp 画像形成方法
JP2015085576A (ja) * 2013-10-30 2015-05-07 花王株式会社 インクジェット記録方法
EP3081607A1 (fr) * 2015-04-15 2016-10-19 Agfa Graphics Nv Encres à jet d'encre à base de résine aqueuse
JP2017039922A (ja) * 2015-08-18 2017-02-23 花王株式会社 インクジェット記録用水系インク
WO2017061507A1 (fr) * 2015-10-06 2017-04-13 富士フイルム株式会社 Ensemble d'encres pour jet d'encre pour carton et procédé de formation d'image

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS60139442A (ja) * 1983-12-28 1985-07-24 味の素株式会社 強化段ボ−ル
JPS60184832A (ja) * 1984-12-28 1985-09-20 石崎産業株式会社 フイルム貼着段ボ−ルの製造方法
JP2009279870A (ja) * 2008-05-23 2009-12-03 Fujifilm Corp 画像形成方法
JP2015085576A (ja) * 2013-10-30 2015-05-07 花王株式会社 インクジェット記録方法
EP3081607A1 (fr) * 2015-04-15 2016-10-19 Agfa Graphics Nv Encres à jet d'encre à base de résine aqueuse
JP2017039922A (ja) * 2015-08-18 2017-02-23 花王株式会社 インクジェット記録用水系インク
WO2017061507A1 (fr) * 2015-10-06 2017-04-13 富士フイルム株式会社 Ensemble d'encres pour jet d'encre pour carton et procédé de formation d'image

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPWO2020012969A1 (ja) * 2018-07-10 2020-09-24 Dic株式会社 インクジェット印刷インク用プライマー、被記録媒体及び印刷システム
JP7794694B2 (ja) 2022-06-02 2026-01-06 株式会社日立産機システム 印字ドット乾燥装置、印字ドット乾燥方法、および印刷システム

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