WO2019065267A1 - Method for manufacturing printed matter - Google Patents

Method for manufacturing printed matter 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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WIPO (PCT)
Prior art keywords
meth
printed matter
ink
acrylate
polymer
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PCT/JP2018/033954
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French (fr)
Japanese (ja)
Inventor
島村　佳ノ助
剛啓 仁尾
友理 庄子
早紀 福井
正喜 保坂
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Dic株式会社
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Application filed by Dic株式会社 filed Critical Dic株式会社
Priority to JP2019511506A priority Critical patent/JP6729797B2/en
Publication of WO2019065267A1 publication Critical patent/WO2019065267A1/en

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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

Abstract

The present invention addresses the problem of providing a method for manufacturing printed matter, which can prevent the occurrence of color unevenness, in a printed image, caused by bleeding even when printing is performed using an aqueous ink, on the surface of a corrugated board provided with a layer which does not absorb or hardly absorbs a solvent contained in the aqueous ink. The present invention relates to a method for manufacturing printed matter, characterized by using an aqueous ink to perform printing on a corrugated board (A) having a layer (a) having an absorption amount of 15 g/m2 or less, and then drying the aqueous ink through a step [1] including a step [1-1] for blowing air onto a printed surface.

Description

印刷物の製造方法Production method of printed matter
　本発明は、印刷物の製造方法に関するものである。 The present invention relates to a method of producing a printed matter.
　産業界では、水性インクを用いて包装材料や広告宣伝媒体へ印刷する方式が検討されている。前記包装材料等としては、例えば波形状に加工されたフルートと呼ばれる中芯の片面または両側にライナーが接着された段ボールが挙げられる。 In the industry, methods of printing on packaging materials and advertising media using water-based inks are being considered. Examples of the 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.
　前記段ボールに印刷する方法としては、例えばガラス転移点１６℃以上でありかつ酸価１０ｍｇＫＯＨ／ｇ以上の水性エマルジョン樹脂と顔料とを、固形分量が１５重量％以上となるように配合すると共に、分散安定剤としてアミノアルコールを配合したインクジェット記録用インク組成物を用い段ボールに印刷する方法（特許文献１参照。）や、片面段ボールシートの第１ライナーの表面に対して、インクジェット方式により印刷を行う方法が（特許文献２参照。）が知られている。 As a method of printing on the corrugated cardboard, for example, 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.
　一方、段ボールを用いた包装材料には、近年、高意匠性が求められている。例えば家電製品の包装材料としては、従来の茶色の段ボールのほかに、高意匠性を付与する観点から、白色等の着色層が設けられた段ボールが使用される場合がある。また、前記着色層の表面には、意匠性をより一層高めるうえで、包装される製品の写真や、製造メーカーのハウスマーク等のカラー画像が印刷される場合もある。 On the other hand, in recent years, high designability is required for packaging materials using cardboard. For example, as packaging materials for home electric appliances, in addition to conventional brown corrugated cardboard, corrugated cardboard provided with a colored layer such as white may be used from the viewpoint of imparting high designability. Further, on the surface of the colored layer, in order to further enhance the design, a photograph of the product to be packaged or a color image such as a house mark of a manufacturer may be printed.
　しかし、前記着色層は、一般に吸水性の低い層である場合が多いため、前記着色層の表面に水性インクを用いて印刷した場合に水性インクが乾燥しにくいという課題がある。そのため、前記段ボールの表面に水性インクを用いて印刷すると色ムラが発生しやすく、その結果、産業界が求めるレベルの高意匠性を確保可能なレベルの鮮明な印刷物を形成できない場合があった。 However, since 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.
　とりわけ、段ボールは、ライナーとフルートとが接触した部分と、ライナーとフルートとが接触していない部分とで、水性インクが乾燥する際の熱の移動量が異なるため、水性インクの乾燥性にも違いが生じやすい。前記乾燥性に違いが生じることで、前記ライナーとフルートとの接触部位に起因したスジ状の色ムラが発生しやすく、その結果、包装材料等の印刷物の意匠性をより一層高めることが困難な場合があった。 In particular, 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.
特開２０１１－１２２２６号公報JP, 2011-12226, A 特開２００８－１２８４２号公報JP, 2008-12842, A
　本発明が解決しようとする課題は、水性インクに含まれる溶媒を吸収しないまたは吸収しにくい層が設けられた段ボールの表面に、水性インクを用いて印刷した場合であっても、印刷画像の色ムラの発生を防止可能な印刷物の製造方法を提供することである。 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.
　また、本発明が解決しようとする課題は、水性インクに含まれる溶媒を吸収しないまたは吸収しにくい層が設けられた段ボールの表面に、水性インクを用いて印刷した場合であっても、段ボールを構成するフルートに起因したスジ状の色むらを発生させない印刷物の製造方法を提供することである。 Further, 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.
　吸水性の高いライナーまたは層を有する段ボールの表面に、水性インクを印刷した場合、水性インクに含まれる溶媒はすみやかに前記ライナー等に吸収され、水性インク中の着色成分が段ボール表面にすみやかに固定されるため、前記色ムラは発生しにくい。 When the water-based ink is printed on the surface of a cardboard having a highly water-absorbent liner or layer, 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.
　一方、前記したような水性インク中の溶媒を吸収しないまたは吸収しにくいライナーまたは層が設けられた段ボールに水性インクを印刷した場合、水性インクに含まれる溶媒が前記ライナー等に吸収されにくく、水性インク中の着色成分が前記表面で一時的に滞留しやすくなるため、色ムラが生じやすくなると考えられる。 On the other hand, when the water-based ink is printed on a corrugated board provided with a liner or layer which does not or hardly absorbs the solvent in the water-based ink as described above, the solvent contained in the water-based ink is hardly absorbed by the liner etc. Since the coloring component in the ink tends to be temporarily retained on the surface, it is considered that color unevenness tends to occur.
　そこで、本発明者は、前記段ボールに水性インクを印刷した後、その印刷面に風を当てることによって、前記課題を解決できることを見出した。 Thus, 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.
　すなわち、本発明は、吸水量１５ｇ／ｍ２以下の層（ａ）を有する段ボール（Ａ）に、水性インクで印刷を施した後、印刷面に送風する工程［１－１］を含む工程［１］を経ることによって前記水性インクを乾燥させることを特徴とする印刷物の製造方法に関するものである。 That is, 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).
　本発明の印刷物の製造方法であれば、水性インク中の溶媒を吸収しないまたは吸収しにくい層が設けられた段ボールの表面に水性インクを印刷した場合であっても、段ボールを構成するフルート等に起因したスジ状の色ムラの発生を効果的に抑制することができる。 According to 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.
ポリマー（Ｇ）の製造で使用するマイクロリアクターの模式図である。It is a schematic diagram of the microreactor used in manufacture of a polymer (G). 段ボール（Ａ）を側面からみた模式図である。It is the model which saw the cardboard (A) from the side. 印刷物の斜視図である。It is a perspective view of printed matter.
　本発明の印刷物の製造方法は、吸水量１５ｇ／ｍ２以下の層（ａ）を有する段ボール（Ａ）に、水性インクで印刷を施した後、印刷面に送風する工程［１－１］を含む工程［１］を経ることによって前記水性インクを乾燥させることを特徴とする。 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].
　本発明では、前記段ボール（Ａ）に水性インクで印刷を施した後、その印刷面に風を当てる。これにより、前記色ムラの原因と考えられる段ボール（Ａ）表面の乾燥性の差を小さくすることができ、その結果、前記色ムラを低減できると考えられる。 In the present invention, after printing the cardboard (A) with an aqueous ink, wind is applied to the printing surface. As a result, it is possible to reduce the difference in the drying property of the surface of the cardboard (A) which is considered to be the cause of the color unevenness, and as a result, it is considered that the color unevenness can be reduced.
　前記送風する風の温度は、特に制限は無いが、印刷面の温度を２０～１４０℃の範囲に調整可能な温度に設定することが好ましく、４０～９０℃の範囲に調整可能な温度に設定することが、印刷面の良好な乾燥性（タック感の低減）を付与するうえでより好ましい。前記温度で乾燥させる溶媒は、主に水であるため、前記範囲内の温度で乾燥させることによって、乾燥速度の向上による印刷物の生産効率の向上と、高温による乾燥設備の劣化や段ボール（Ａ）の変色の防止と、エネルギーロスの低減とを実現することができる。 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.
　送風温度を前記した範囲に設定する方法としては、例えば赤外線やマイクロ波等で加熱可能な装置を使用する方法が挙げられる。 As a method of setting blowing temperature to the above-mentioned range, the method of using the apparatus which can be heated by infrared rays, a microwave, etc. is mentioned, for example.
　前記送風速度は、特に制限は無いが、印刷面の表面での速度が０．１～２０ｍ／ｓとなる範囲に設定することが好ましく、１～１０ｍ／ｓとなる範囲に設定することがより好ましい。送風速度を前記範囲内に設定することによって、水性インクの乾燥性の違いに起因した色ムラの発生を防止でき、かつ、送風速度が速すぎることによって水性インクが段ボール（Ａ）の表面で面方向に流れることに起因した印刷物のにじみ等の発生を防止することができる。 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. By setting the blowing speed within the above range, it is possible to prevent the occurrence of color unevenness due to the difference in the drying property of the water-based ink, and the water speed is too fast. It is possible to prevent the occurrence of bleeding and the like of the printed matter caused by flowing in the direction.
　前記送風は、前記段ボール（Ａ）の印刷面に対して、およそ垂直方向から行うことが、水性インクが段ボール（Ａ）の表面で面方向に流れることに起因した印刷物のにじみ等の発生を防止するうえで好ましい。具体的には、前記送風は、前記段ボール（Ａ）の印刷面の垂線方向に対して、－８５°～＋８５°の範囲の方向から行うことが好ましく、－４５°～＋４５°の範囲の方向から行うことがより好ましく、－２０°～＋２０°の範囲がさらに好ましく、－１０°～＋１０°の範囲が特に好ましい。 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.
　前記送風時間は、印刷物の製造効率を向上するうえで短い方が好適であり、好ましくは１秒～１分、より好ましくは１秒～３０秒、さらに好ましくは１秒～５秒、特に好ましくは１秒～２秒である。 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.
　前記送風工程［１－１］における送風温度、送風方向及び送風速度は、前記工程［１］の間、一定であってもよく、必要に応じて変化させてもよい。例えば前記送風する工程［１－１］の初期においては送風速度を遅く設定し、次第に速く変化させるなどしてもよい。 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. For example, at the initial stage of the air blowing step [1-1], the air blowing speed may be set to be slow and may be gradually changed.
　前記送風は、印刷物の製造環境と同じ空気で行ってもよく、フィルター等を通した埃等の含有量が少ない空気で行ってもよい。 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.
　本発明の印刷物の製造方法を構成する工程［１］は、前記送風工程［１－１］の他に必要に応じて他の工程を含む工程であっても良い。 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].
　前記その他の工程としては、例えば加熱工程［１－２］を採用することが好ましい。前記送風工程［１－１］と前記加熱工程［１－２］とを組み合わせることによって、印刷物のモットリング（まだら模様の色ムラ）の発生をより一層効果的に防止でき、かつ、印刷面の良好な乾燥性（タック感の低減）を付与することができる。 As the other steps, for example, it is preferable to adopt 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.
　前記加熱工程［１－２］は、輻射熱による加熱が挙げられ、より具体的には、赤外線やマイクロ波等を用いた加熱工程が、段ボール（Ａ）の発火や変色を防止するうえで好ましい。 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).
　前記加熱工程［１－２］であることが、吸水量が１５ｇ／ｍ２以下の層（ａ）を有する段ボール（Ａ）に水性インクを印刷した場合であっても、短時間（およそ１０秒以内）で乾燥させることができ、印刷物の生産効率をより一層向上できるため好ましい。 Even if the aqueous ink is printed on a cardboard (A) having a layer (a) having a water absorption of 15 g / m 2 or less, 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.
　前記加熱工程［１－２］としては、例えば赤外線、マイクロ波等によって加熱する工程が挙げられ、なかでも、赤外線を用いた加熱工程であることが、水性インクに含まれる水に吸収されやすいためインクの乾燥を効率的かつ均一に行うことができるためより好ましい。 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.
　前記赤外線の波長は、一般的な０．７～１０００μｍであることが好ましく、０．８～４μｍの近赤外領域であることが、赤外線が水性インクに含まれる水に吸収されやすく、効果的に乾燥することができるため好ましい。 The wavelength of the infrared ray is preferably 0.7 to 1000 μm 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 μm. It is preferable because it can be dried.
　赤外線を用いた加熱方法としては、例えばタングステン線を用いたハロゲンヒーター、ニクロム線を用いた石英管ヒーター、カーボンヒーター等を備えた放射熱型乾燥機を使用する方法が挙げられ、なかでも放射率の高いカーボンヒーターを備えた放射熱型乾燥機を使用する方法が好ましい。 As 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.
　前記加熱工程［１－２］は、印刷物の表面温度が１５０℃以下となる範囲で行うことが、印刷物の生産効率をより一層向上させるうえでより好ましい。 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.
　前記工程［１］では、前記送風工程［１－１］を終了した後に、前記加熱工程［１－２］を実施してもよいが、印刷物の製造時間を短縮し、その生産効率をより一層向上するうえで、前記送風工程［１－１］と前記加熱工程［１－２］の一部または全部を重複させることが好ましい。具体的には、吸水量１５ｇ／ｍ２以下の層（ａ）を有する段ボール（Ａ）に、水性インクで印刷を施した後、印刷面に送風する工程［１－１］と前記加熱する工程［１－２］との一部が重複する工程を含む工程［１］を経ることによって前記水性インクを乾燥させることを特徴とする印刷物の製造方法であることが好ましい。 In the step [1], 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]. Specifically, after a cardboard (A) having a layer (a) having a water absorption amount of 15 g / m 2 or less is printed with an aqueous ink, the step [1-1] of blowing air to the printing surface and the heating step Preferably, the method 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].
　次に、本発明の印刷物の製造方法で使用する段ボール（Ａ）について説明する。 Next, the cardboard (A) used in the method for producing a printed matter of the present invention will be described.
　前記段ボール（Ａ）としては、吸水量１５ｇ／ｍ２以下の層（ａ）を有するものを使用する。前記水性インクによる印刷は、前記ダンボール（Ａ）の前記層（ａ）の表面に施される。 As said 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).
　本発明の印刷物の製造方法によれば、前記層（ａ）の吸水量が１５ｇ／ｍ２以下、さらには１０ｇ／ｍ２以下である段ボールに対しても、にじみに起因した印刷画像の色ムラがなく、かつ、段ボールを構成するフルートに起因したスジ状の色ムラがない印刷物を製造することができる。 According to the printed material production method of the present invention, the color unevenness of the printed image water absorption 15 g / m 2 or less, even for more or less 10 g / m 2 cardboard, due to bleeding of the layer (a) It is possible to produce a printed material free of streaks and uneven color due to the flutes constituting the corrugated board.
　なお、前記吸水量は、以下の方法で測定し算出することによって決定した。 In addition, the said water absorption was determined by measuring and calculating with the following method.
　はじめに、２３℃、相対湿度５０％の条件下、自動走査吸液計（熊谷理機工業（株）社製、ＫＭ５００ｗｉｎ）を用い、前記段ボール（Ａ）の層（ａ）の表面の任意の１点に、純水を接触させた時から１００ｍ秒以内に、前記層（ａ）に吸収された純水の量を測定した。なお、前記自動走査吸液計は、そのキャピラリー高さ及び給液ヘッド部へかかる荷重をあらかじめ調整することで、王子製紙（株）製ＯＫトップコート＋の前記吸水量が５ｍｌ／ｍ２となるようにキャリブレーションしたものを使用した。 First, 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. Incidentally, 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.
　前記層（ａ）の任意の１９点に対し、上記と同様の方法で吸水量を測定し、合計１９点の吸水量の平均値を、本発明でいう吸水量とした。測定条件を以下に示す。 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.
　［Ｓｐｉｒａｌ Ｍｅｔｈｏｄ］
Ｃｏｎｔａｃｔ　Ｔｉｍｅ：０．０１０～１．０（ｓｅｃ）
Ｐｉｔｃｈ：７（ｍｍ）
Ｌｅｎｃｔｈ　ｐｅｒ　ｓａｍｐｌｉｎｇ：１８０（ｄｅｇｒｅｅ）
Ｓｔａｒｔ　Ｒａｄｉｕｓ：２０（ｍｍ）
Ｅｎｄ　Ｒａｄｉｕｓ：６０（ｍｍ）
Ｍｉｎ　Ｃｏｎｔａｃｔ　Ｔｉｍｅ：１０（ｍｓ）
Ｍａｘ　Ｃｏｎｔａｃｔ　Ｔｉｍｅ：１０００（ｍｓ）
Ｓａｍｐｌｉｎｇ　Ｐａｔｔｅｒｎ：５０
Ｎｕｍｂｅｒ　ｏｆ　ｓａｍｐｌｉｎｇ　ｐｏｉｎｔｓ：１９
［Ｓｑｕａｒｅ　Ｈｅａｄ］
Ｓｌｉｔ　Ｓｐａｎ：１（ｍｍ）
Ｗｉｄｔｈ：５（ｍｍ）  [Spiral Method]
Contact Time: 0.010 to 1.0 (sec)
Pitch: 7 (mm)
Lencth per sampling: 180 (degree)
Start Radius: 20 (mm)
End Radius: 60 (mm)
Min Contact Time: 10 (ms)
Max Contact Time: 1000 (ms)
Sampling Pattern: 50
Number of sampling points: 19
[Square Head]
Slit Span: 1 (mm)
Width: 5 (mm)
　前記段ボール（Ａ）としては、例えばフルートの少なくとも一方の面にライナーを有し、前記ライナーの表面に前記層（ａ）を有するもの、または、前記フルートの少なくとも一方の面にライナーとして前記層（ａ）を有するものを使用することができる。 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.
　前記段ボール（Ａ）は、通常、フルートの段の数（波の数）や段の高さによって分類されており、Ａフルート、Ｂフルート、Ｃフルート、Ｅフルート、Ｆフルート、Ｇフルート、デルタフルート等が挙げられる。 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.
　前記ライナーとしては、例えば紙の表面に予め層（ａ）が設けられたライナーが挙げられ、具体的には、マリコート（北越紀州製紙）、サンコート、ＯＫボール、ＵＦコート、ＭＦ用紙、ＭＣコート（王子製紙）、ＪＥＴスター（日本製紙）等が挙げられる。 Examples of the liner 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.
　前記段ボール（Ａ）を構成する層（ａ）としては、例えばコート剤を塗布し乾燥させることで形成された層や、フィルムまたはシートからなる層が挙げられる。 As a layer (a) which comprises the said corrugated-cardboard (A), the layer formed, for example by apply | coating and drying a coating agent, and the layer which consists of a film or a sheet | seat are mentioned.
　前記層（ａ）としては、例えばバインダー等の樹脂成分と、炭酸カルシウム等の無機物を含有する層が挙げられる。 Examples of the layer (a) include a layer containing a resin component such as a binder and an inorganic material such as calcium carbonate.
　前記段ボール（Ａ）に水性インクを印刷する方法としては、従来知られた印刷法を適用でき、なかでも、前記印刷方法としては、インクジェット記録装置を用いた印刷法であることが好ましい。 As a method of printing the aqueous ink on the corrugated paperboard (A), 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.
　前記インクジェット記録装置を用いた印刷法としては、従来知られた方法を採用できるが、例えばインクジェットヘッドのインク吐出口を有する面（ｘ）から、前記面（ｘ）の垂線と段ボール（Ａ）とが交わる位置（ｙ）までの距離が１ｍｍ以上であるインクジェット記録法を適用することが好ましい。 As a printing method using the ink jet recording apparatus, 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.
　インクジェットヘッドのインク吐出口を有する面（ｘ）から、前記面（ｘ）に対して仮定した垂線と、段ボール（Ａ）とが交わる位置（ｙ）までの距離（ギャップ）は、好ましくは２ｍｍ以上、より好ましくは３ｍｍ以上である構成を備えたインクジェット記録装置を使用することができる。 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.
　前記面（ｘ）から、前記面（ｘ）に対して仮定した垂線と、段ボール（Ａ）とが交わる位置（ｙ）までの距離は、段ボール（Ａ）が大きく、反りやすいものであっても、前記段ボール（Ａ）の表面と前記インク吐出口とが接触することを防止し、前記インク吐出口の損傷や、前記インク吐出口が備える場合の多い撥水機能の低下に起因したインク吐出不良を効果的に防止するとともに、段ボール（Ａ）の表面とインクジェットヘッドとの距離が長い場合であっても、スジを有さない印刷物を製造するうえで、前記距離の下限は３ｍｍ以上であることが好ましく、前記距離の上限は、１０ｍｍ以下であることが好ましく、５ｍｍ以下であることが特に好ましい。 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 An ink discharge failure caused by damage to the ink discharge port or deterioration of the water repellent function often provided in the ink discharge port, to prevent the surface of the cardboard (A) from coming into contact with the ink discharge port. 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.
（水性インク）
　本発明で使用する水性インクとしては、従来知られたものを使用することができる。 (Water-based ink)
As the aqueous ink used in the present invention, those known in the prior art can be used.
　前記水性インクとしては、例えばインクジェット記録法で印刷する場合であれば、３２℃における粘度の下限が１ｍＰａ・ｓ以上のものを使用することが好ましく、２ｍＰａ・ｓ以上のものを使用することが好ましく、３ｍＰａ・ｓ以上のものを使用することがより好ましく、４ｍＰａ・ｓ以上のものを使用することがさらに好ましく、かつ、３２℃における粘度の上限が２０ｍＰａ・ｓ以下のものを使用することが好ましく、１５ｍＰａ・ｓ以下のものを使用することが好ましく、１２ｍＰａ・ｓ以下のものを使用することが好ましく、９ｍＰａ・ｓ以下のものを使用することが好ましく、８ｍＰａ・ｓ以下のものを使用することがより好ましく、７ｍＰａ・ｓ以下のものを使用することがさらに好ましい。 As the 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. of 20 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.
　前記範囲の粘度を有する水性インクは、インクジェットヘッドからの吐出液滴が十分な体積を有するため、前記インクジェットヘッドのインク吐出口を有する面（ｘ）から、前記面（ｘ）の垂線と段ボール（Ａ）とが交わる位置（ｙ）までの距離が２ｍｍ以上であっても、飛行曲がりによって発生する段ボール（Ａ）上の着弾位置のズレを見かけ上軽減し、印刷物のスジ発生を効果的に防止することができる。 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.
　また、前記範囲の粘度を有する水性インクは、保存安定性及び吐出安定性の点でより一層優れることから、例えばインクジェット方式での印刷に好適に使用することができる。 Moreover, since 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.
　前記水性インクの粘度は、Ｅ型粘度計に相当する円錐平板形（コーン・プレート形）回転粘度計を使用し、下記条件にて測定した値を指す。
測定装置：ＴＶＥ－２５形粘度計（社製、ＴＶＥ－２５　Ｌ）
校正用標準液：ＪＳ２０
測定温度：３２℃
回転速度：１０～１００ｒｐｍ
注入量：１２００μＬ
　また、前記水性インクとしては、例えばインクジェット記録法で印刷する場合であれば、２５℃における表面張力の下限が２０ｍＮ／ｍ以上のものを使用することが好ましく、２５ｍＮ／ｍ以上のものを使用することがより好ましく、２８ｍＮ／ｍ以上のものを使用することがさらに好ましく、かつ、２５℃における表面張力の上限が４０ｍＮ／ｍ以下のものを使用することが好ましく、３５ｍＮ／ｍ以下のものを使用することがより好ましく、３２ｍＮ／ｍ以下のものを使用することがさらに好ましい。 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 μL
Further, as 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. of 20 mN / m or more, and 25 mN / m or more It is more preferable to use one having a viscosity of 28 mN / m or more, and one having an upper limit of surface tension at 25 ° C. of 40 mN / m or less, preferably 35 mN / m or less It is more preferable to use one having a viscosity of 32 mN / m or less.
　前記範囲の表面張力を有する水性インクは、吐出液滴の段ボール（Ａ）表面での濡れ性良好であり、着弾後十分な濡れ広がりを有する。その結果、インクジェットヘッドのインク吐出口を有する面（ｘ）から、前記面（ｘ）の垂線と段ボール（Ａ）とが交わる位置（ｙ）までの距離が２ｍｍ以上であっても、吐出液滴の飛行曲がりによって発生する段ボール（Ａ）上の着弾位置のズレを見かけ上軽減し、印刷物におけるスジの発生を効果的に防止することができる。 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. As a result, even if 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.
　前記水性インクの表面張力は、ウィルへルミ法を適用した自動表面張力計を使用し、下記条件にて測定した値を指す。前記ウィルへルミ法によれば、静的表面張力及び動的表面張力を測定可能であるが、本発明でいう上記水性インクの表面張力は、静的表面張力の値を表す。
測定装置：自動表面張力計（協和界面科学（株）社製、ＣＢＶＰ－Ｚ型）
測定温度：２５℃
測定子：白金プレート
　前記水性インクとしては、例えば色材と、水性媒体等の溶媒とを含有する水性インクを使用することができる。なかでも、前記水性インクとしては、耐擦過性に優れた印刷物を得るうえで、さらにバインダー樹脂を含有する水性インクを使用することが好ましく、印刷物のセット性を向上させるうえで、さらに尿素結合を有する化合物を含有する水性インクを使用することがより好ましい。 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 As the aqueous ink, an aqueous ink containing, for example, a coloring material and a solvent such as an aqueous medium can be used. Among them, as the 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.
　前記水性インクとしては、前記バインダー樹脂、前記化合物及び前記色材等が、溶媒である水性媒体に溶解または分散した状態で存在するものを使用することが好ましい。 As the 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.
　前記バインダー樹脂としては、例えばポリビニルアルコール、ゼラチン、ポリエチレンオキサイド、ポリビニルピロリドン、アクリル系樹脂、ウレタン系樹脂、デキストラン、デキストリン、カラーギーナン（κ、ι、λ等）、寒天、プルラン、水溶性ポリビニルブチラール、ヒドロキシエチルセルロース、カルボキシメチルセルロース等を１種もしくは数種併用して使用することができる。なかでも、前記バインダー樹脂としては、アクリル系樹脂を使用することが好ましく、アミド基を有するアクリル系樹脂を使用することが好ましい。 Examples of the binder resin include polyvinyl alcohol, gelatin, polyethylene oxide, polyvinyl pyrrolidone, acrylic resin, urethane resin, dextran, dextrin, carrageenan (κ, ι, λ, etc.), agar, pullulan, water-soluble polyvinyl butyral, hydroxy Ethylcellulose, carboxymethylcellulose and the like can be used alone or in combination. Among them, as the binder resin, an acrylic resin is preferably used, and an acrylic resin having an amide group is preferably used.
　前記バインダー樹脂を含有する水性インクは、乾燥による溶媒蒸発に伴いインク吐出口のインクが凝固した場合であっても、前記吐出口に再び水性インクが流通することによって、前記凝固物が容易に水性インク中に分散できる性質（再分散性）に優れる。その結果、インクジェットヘッドから吐出する際、吐出を一定時間中断した後、再度開始した場合であっても、吐出液滴の飛行曲がりあるいは吐出口の閉塞を引き起こしにくく、印刷物のスジ発生を効果的に防止することができる。 Even when the ink in the ink discharge port coagulates due to the evaporation of the solvent due to drying, 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.
　前記アミド基を有するアクリル系樹脂としては、アミド基を有するアクリル系単量体と必要に応じてその他の単量体との重合体を使用することができる。 As 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.
　前記アミド基を有するアクリル系単量体としては、例えば、（メタ）アクリルアミド、Ｎ－メチル（メタ）アクリルアミド、Ｎ－エチル（メタ）アクリルアミド、Ｎ－プロピル（メタ）アクリルアミド、Ｎ－メチロール（メタ）アクリルアミド、Ｎ－イソプロピル（メタ）アクリルアミド、Ｎ－ブチル（メタ）アクリルアミド、Ｎ，Ｎ－ジメチル（メタ）アクリルアミド、Ｎ，Ｎ－ジエチル（メタ）アクリルアミド、Ｎ，Ｎ－ジプロピル（メタ）アクリルアミド、Ｎ，Ｎ－ジメチルアミノプロピル（メタ）アクリルアミド、ジアセトン（メタ）アクリルアミド、ヒドロキシエチル（メタ）アクリルアミド等を使用することができる。 Examples of the acrylic monomer having an amide group 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.
　前記アクリル系樹脂の製造に使用可能なその他の樹脂としては、例えば（メタ）アクリル酸やそのアルカリ金属塩、メチル（メタ）アクリレート、エチル（メタ）アクリレート、ブチル（メタ）アクリレート、２－エチルヘキシル（メタ）アクリレート、ベンジル（メタ）アクリレート、シクロへキシル（メタ）アクリレート等の（メタ）アクリル酸エステル系単量体、アクリルアマイド、Ｎ，Ｎ－ジメチル(メタ)アクリルアマイド等のアミド基を有するアクリル系単量体、（メタ）アクリロニトリル、２－ジメチルアミノエチル（メタ）アクリレート、グリシジル（メタ）アクリレート等のアクリル系単量体を使用することができる。 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.
　前記アクリル系樹脂の製造に使用可能なその他の単量体としては、例えばスチレン、α－メチルスチレン、ｐ－ｔｅｒｔ－ブチルスチレン、ビニルナフタレン、ビニルアントラセン等の芳香族ビニル化合物、ビニルスルホン酸、スチレンスルホン酸などのビニルスルホン酸化合物、２－ビニルピリジン、４－ビニルピリジン、ナフチルビニルピリジン等のビニルピリジン化合物、ビニルトリエトキシシラン、ビニルトリメトキシシラン、ｐ－スチリルトリメトキシシラン、３－メタクリロキシプロピルメチルジメトキシシラン、３－メタクリロキシプロピルトリメトキシシラン、３－メタクリロキシプロピルメチルジエトキシシラン、３－メタクリロキシプロピルトリエトキシシラン、３－アクリロキシプロピルトリメトキシシラン等を使用することができる。 Examples of other monomers that can be used for producing the acrylic resin include aromatic vinyl compounds such as styrene, α-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.
　前記その他の単量体としては、スチレンやベンジル（メタ）アクリレート等の芳香族基を有する単量体を使用することが、顔料との親和性をより一層向上させるうえで好ましい。 As 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.
　前記アミド基を有するアクリル系樹脂としては、水性インクに再分散性の向上という効果を付与し、かつ、水性媒体中での分散安定性に優れる。前記アミド基を有するアクリル系樹脂としては、その製造に使用する前記単量体の全量に対して、前記アミド基を有するアクリル系単量体を０．５質量％以上５質量％を超えない範囲で使用することが好ましく、０．５質量％～４質量％の範囲で使用することがより好ましく、１．５質量％～３質量％の範囲で使用することが、水性インクの再分散性及び水性媒体中での分散安定性をより一層向上させるうえで特に好ましい。 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.
　また、前記アクリル系樹脂としては、水性インク中に含まれる水等の溶媒を吸収しにくいプラスチックや疎水性の高いコート紙やアート紙への水性インクの付着性をより一層向上させるうえで、ゲルパーミエーションクロマトグラフィーによる分子量測定時の展開溶媒であるテトラヒドロフラン（ＴＨＦ）に不溶で分子量の測定が困難な成分を含有するものであってもよいが、２５℃におけるＴＨＦ不溶成分の含有率が２０質量％未満であるものが好ましく、５質量％未満であるものがよりも好ましく、ＴＨＦ不溶成分を含有しないものが最も好ましい。 Further, as 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. Although it may contain a component which is insoluble in tetrahydrofuran (THF), which is a developing solvent for molecular weight measurement by permeation chromatography, and whose measurement of molecular weight is difficult, 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.
　前記アクリル系樹脂としては、前記ＴＨＦに溶解するアクリル系樹脂の、数平均分子量が１０，０００～１００，０００のものを使用することが好ましく、数平均分子量が２０，０００～１００，０００のものを使用することがより好ましい。また、前記アクリル系樹脂としては、重量平均分子量が３０，０００～１，０００，０００であるものを使用することが好ましく、重量平均分子量が５０，０００～１，０００，０００であるものがより好ましい。 As 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.
　前記バインダー樹脂としては、例えばポリオレフィンを使用することもできる。 For example, polyolefin can also be used as the binder resin.
　前記ポリオレフィンとしては、オレフィン系モノマーを主成分とするモノマーの重合体又は共重合体を使用する。前記オレフィン系モノマーとしては、例えばエチレン、プロピレン、ブテン、ヘキセン、メチルブテン、メチルペンテン、メチルへキセン等のα－オレフィン、ノルボネン等の環状オレフィン等を使用することができる。前記ポリオレフィンとしては、酸化ポリオレフィンを使用することもできる。 As said polyolefin, the polymer or copolymer of the monomer which has an olefin type monomer as a main component is used. As the olefin monomer, for example, α-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.
　前記酸化ポリオレフィンとしては、例えば、ポリオレフィンを、熱分解や酸やアルカリ成分を用いた化学的分解などにより、分子内に酸素原子が導入されたものを使用することができる。前記酸素原子は、例えば、極性を有するカルボキシル基等を構成する。 As the 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.
　前記ポリオレフィンとしては、融点が９０℃以上２００℃以下であるものを使用することが好ましく、１２０℃以上１６０℃未満であるものを使用することによって、印刷直後に印刷物を重ね合わせた場合でも、段ボール（Ａ）表面の水性インクが剥離しない良好なセット性と、優れた耐擦過性を付与することができる。なお、前記ポリオレフィンの融点は、ＪＩＳ　Ｋ　００６４に準拠した融点測定装置によって測定した値を指す。 As 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.
　前記ポリオレフィンは、前記したとおり水性媒体等の溶媒中に溶解または分散した状態で存在することが好ましく、水性媒体等の溶媒中に分散したエマルジョンの状態であることがより好ましい。 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.
　その場合、前記ポリオレフィンによって形成されるポリオレフィン粒子は、平均粒子径１０ｎｍ～２００ｎｍであることが好ましく、３０ｎｍ～１５０ｎｍであることが、例えばインクジェット記録法で印刷する際に水性インクの良好な吐出安定性と印刷後の良好なセット性とを両立するうえでより好ましい。なお、前記ポリオレフィンの平均粒子径は、日機装社製マイクロトラックＵＰＡ粒度分布計を用い、動的光散乱法で測定した値を示す。 In that case, 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. In addition, 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.
　本発明において、前記スジの発生を防止すべく、水性インクの組成を過度に変更しようとすると、印刷物の印字濃度や耐擦過性が若干、低下する傾向がみられる場合がある。前記バインダー樹脂は、前記スジの発生を防止するとともに、印刷物の印字濃度や耐擦過性を向上させ、良好な光沢を付与する上で、前記水性インクの全量に対して２質量％～７質量％の範囲で使用することが好ましく、３質量％～６質量％の範囲で使用することがより好ましい。また、上記範囲の前記バインダー樹脂を含有する水性インクは、印刷後の加熱工程を経て前記バインダー樹脂が架橋し強固な被膜を形成することで、印刷物の耐擦過性をより一層向上させることができる。また、印刷物に水を滴下した場合あるいは水を含んだ布等でこすった場合でも、段ボール（Ａ）の表面の水性インクが剥離しない良好な耐水性を付与することができる。 In the present invention, when the composition of the aqueous ink is excessively changed in order to prevent the generation of the streaks, 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. Moreover, the aqueous ink containing the said binder resin of the said range can further improve the abrasion resistance of printed matter further by bridge | crosslinking the said binder resin and forming a firm film through the heating process after printing. . Further, even when water is dropped onto a printed matter or when it is rubbed with a cloth or the like containing water, it is possible to impart good water resistance so that the aqueous ink on the surface of the cardboard (A) does not peel off.
　本発明で使用する水性インクとしては、前記バインダー樹脂とともに尿素結合を有する化合物を組み合わせ使用することができる。前記化合物を前記バインダー樹脂と組み合わせ使用することによって、印刷物の良好なセット性と、優れた耐擦過性を付与することができる。 As the aqueous ink used in the present invention, a compound having a urea bond can be used in combination with the binder resin. By using 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.
　前記尿素結合を有する化合物としては、尿素または尿素誘導体を使用することができる。 Urea or a urea derivative can be used as the compound having a urea bond.
　前記尿素誘導体としては、例えばエチレン尿素、プロピレン尿素、ジエチル尿素、チオ尿素、Ｎ，Ｎ－ジメチル尿素、ヒドロキシエチル尿素、ヒドロキシブチル尿素、エチレンチオ尿素、ジエチルチオ尿素等を、単独または２種以上組み合わせ使用することができる。 As the 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.
　なかでも、前記尿素結合を有する化合物としては、尿素、エチレン尿素または２－ヒドロキシエチル尿素を使用することが、より一層優れたセット性を備えた印刷物を得るうえで特に好ましい。 Among them, as 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.
　前記尿素結合を有する化合物の含有量は、本発明で使用する水性インクをインクジェット記録方式で吐出する場合に求められる吐出安定性や、セット性に優れた印刷物を得るうえで、前記インクの全量に対して１質量％～２０質量％であることが好ましく、２質量％～１５質量％であることがより好ましく、３質量％～１０質量％であることがさらに好ましい。 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.
　前記バインダー樹脂と前記尿素結合を有する化合物とは、それらの質量割合［バインダー樹脂／尿素結合を有する化合物］が１／６～６／１となる範囲で使用することが好ましく、１／５～１／１の範囲で使用することが、印刷物のセット性向上効果を奏するうえでより好ましい。 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.
　また、前記尿素及び尿素誘導体は、保湿機能が高く湿潤剤として機能するため、インクジェットヘッドのインク吐出口における水性インクの乾燥や凝固を防止し、優れた吐出安定性を確保することができる。その結果、インクジェットヘッドのインク吐出口を有する面（ｘ）から、前記面（ｘ）の垂線と段ボール（Ａ）とが交わる位置（ｙ）までの距離が２ｍｍ以上であっても、印刷物のスジ発生を軽減する効果がある。 Further, since 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. As a result, even if 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.
　一方、前記尿素及び尿素誘導体は、加熱されると水を放出しやすいため、前記非吸収性または難吸収性の段ボール（Ａ）に水性インクを印刷後、加熱乾燥を行った場合、より一層優れたセット性を備えた印刷物を得ることができる。 On the other hand, since 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.
　前記水性インクとしては、溶媒として水性媒体を含有するものを使用する。 As the aqueous ink, one containing an aqueous medium as a solvent is used.
　前記水性媒体としては、水を単独、または、水と後述する有機溶剤との混合溶媒を使用することができる。 As the aqueous medium, water can be used alone, or a mixed solvent of water and an organic solvent described later can be used.
　前記水としては、具体的にはイオン交換水、限外濾過水、逆浸透水、蒸留水等の純水または超純水を使用することができる。 Specifically, pure water such as ion exchange water, ultrafiltered water, reverse osmosis water, distilled water or ultrapure water can be used as the water.
　前記水性媒体は、前記水性インク全量に対し１質量％～３０質量％の範囲で使用することが好ましく、５質量％～２５質量％の範囲で使用することが、セット性に優れ、インクジェット方式で吐出する場合に求められる高い吐出安定性を備えた、鮮明な印刷物を製造可能な水性インクを得るうえで特に好ましい。 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.
　前記有機溶剤（Ｆ）としては、例えば、アセトン、メチルエチルケトン、メチルブチルケトン、メチルイソブチルケトン、等のケトン類；メタノール、エタノール、２－プロパノール、２－メチル－１－プロパノール、１－ブタノール、２－メトキシエタノール等のアルコール類；テトラヒドロフラン、１，４－ジオキサン、１，２－ジメトキシエタン等のエーテル類；ジメチルホルムアミド、Ｎ－メチルピロリドン、エチレングリコール、ジエチレングリコール、トリエチレングリコール、テトラエチレングリコール、プロピレングリコール、ポリエチレングリコール、ポリプロピレングリコール等のグリコール類；ブタンジオール、ペンタンジオール、ヘキサンジオールおよびこれらと同族のジオール等のジオール類；ラウリン酸プロピレングリコール等のグリコールエステル；ジエチレングリコールモノエチル、ジエチレングリコールモノブチルエーテル、ジエチレングリコールモノヘキシルエーテル、プロピレングリコールエーテル、ジプロピレングリコールエーテル、および、トリエチレングリコールエーテルを含むセロソルブ等のグリコールエーテル類；メタノール、エタノール、イソプロピルアルコール、１－プロパノール、２－プロパノール、１－ブタノールや２－ブタノール等のブチルアルコール、ペンチルアルコール、およびこれらと同族のアルコールなどのアルコール類；スルホラン；γ－ブチロラクトン等のラクトン類；Ｎ－（２－ヒドロキシエチル）ピロリドン等のラクタム類などを、単独または２種以上組み合わせ使用することができる。 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, diethylene glycol monohexyl ether, propylene glycol ether, dipropylene glycol ether, and glycol ethers such as cellosolve including triethylene glycol ether; methanol, ethanol, isopropyl alcohol Alcohols such as 1-propanol, 2-propanol, butyl alcohol such as 1-butanol or 2-butanol, pentyl alcohol, and alcohols similar to these; sulfolane; lactones such as γ-butyrolactone; N- (2- Lactams such as hydroxyethyl) pyrrolidone and the like can be used alone or in combination of two or more.
　また、前記有機溶剤（Ｆ）としては、前記したものの他に、沸点が１００℃以上２００℃以下であり、かつ、２０℃での蒸気圧が０．５ｈＰａ以上である水溶性有機溶剤（ｆ１）を使用することが、吐出液滴が段ボール（Ａ）の表面に着弾した後、段ボール（Ａ）上で速乾効果を奏するうえで好ましい。 Further, as the organic solvent (F), 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).
　前記水溶性有機溶剤（ｆ１）としては、例えば３－メトキシ－１－ブタノール、３－メチル－３－メトキシ－１－ブタノール、３－メトキシ－３－メチル－１－ブチルアセテート、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、エチレングリコールモノプロピルエーテル、エチレングリコールモノブチルエーテル、エチレングリコールモノイソブチルエーテル、エチレングリコール－ｔ－ブチルエーテル、プロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル、プロピレングリコールモノプロピルエーテル、プロピレングリコールモノメチルエーテルアセテート、ジエチレングリコールジメチルエーテル、ジエチレングリコールメチルエチルエーテル、ジエチレングリコールジエチルエーテル、ジプロピレングリコールジメチルエーテル、４－メトキシ－４－メチル－２－ペンタノン、エチルラクテート等が挙げられ、これらのものを２種以上組み合わせ使用することができる。 Examples of the water-soluble organic solvent (f1) 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 two or more.
　なかでも、前記水溶性有機溶剤（ｆ１）としては、水性インクの良好な分散安定性の維持や、例えばインクジェット装置が備えるインク吐出ノズルの、前記水性インクに含まれる溶剤の影響による劣化を抑制するうえで、ＨＳＰ（ハンセン溶解度パラメータ）の水素結合項δＨが６～２０の範囲であるような水溶性有機溶剤を使用することが好ましい。 Among them, 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. In addition, it is preferable to use a water-soluble organic solvent in which the hydrogen bonding term δ H of HSP (Hansen solubility parameter) is in the range of 6 to 20.
　前記範囲のＨＳＰの水素結合項を有する水溶性有機溶剤としては、具体的には、３－メトキシ－１－ブタノール、３－メチル－３－メトキシ－１－ブタノール、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、エチレングリコールモノプロピルエーテル、エチレングリコールモノブチルエーテル、エチレングリコールモノイソブチルエーテル、エチレングリコール－ｔ－ブチルエーテル、プロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル、プロピレングリコールモノプロピルエーテルが好ましく、より好ましくは３－メトキシ－１－ブタノール、３－メチル－３－メトキシ－１－ブタノールである。 Specific examples of the water-soluble organic solvent having a hydrogen bonding term of HSP in the above range 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.
　前記水性媒体と組み合わせ使用可能な有機溶剤としては、前記した水溶性有機溶剤（ｆ１）のほかに、または、前記水溶性有機溶剤（ｆ１）とともに、プロピレングリコール（ｆ２）と、グリセリン、グリセリン誘導体、ジグリセリン及びジグリセリン誘導体からなる群より選ばれる１種以上の有機溶剤（ｆ３）とを組み合わせ使用することが、段ボール（Ａ）上での水性インク速乾効果と、インク吐出口における水性インクの乾燥や凝固を防止する効果を両立するうえで好ましい。 Examples of the organic solvent which can be used in combination with the aqueous medium include propylene glycol (f2), glycerin and glycerin derivatives, in addition to the above-mentioned water-soluble organic solvent (f1) or together with the water-soluble organic solvent (f1) The combination of one or more organic solvents (f3) selected from the group consisting of diglycerin and diglycerin derivatives and the use thereof in combination with the aqueous ink quick drying effect on the cardboard (A) and the aqueous ink at the ink discharge port It is preferable in achieving both the effect of preventing drying and coagulation.
　前記有機溶剤（ｆ３）としては、例えばグリセリン、ジグリセリン、ポリグリセリン、ジグリセリン脂肪酸エステル、一般式（１）で表されるポリオキシプロピレン（ｎ）ポリグリセリルエーテル、一般式（２）で表されるポリオキシエチレン（ｎ）ポリグリセリルエーテル等を、単独または２種以上組み合わせ使用することができる。 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.
　なかでも、前記有機溶剤（ｆ３）としては、グリセリン及びｎ＝８～１５のポリオキシプロピレン（ｎ）ポリグリセリルエーテルを使用することが、印刷物のセット性に優れ、インク吐出口における水性インクの乾燥や凝固を防止する効果を奏するうえで特に好ましい。 Above all, using glycerin and a polyoxypropylene (n) polyglyceryl ether of n = 8 to 15 as the organic solvent (f3) is excellent in the setting property of the printed matter, and drying of the aqueous ink at the ink discharge port or It is particularly preferable in achieving the effect of preventing coagulation.
Figure JPOXMLDOC01-appb-C000001
Figure JPOXMLDOC01-appb-C000001
　一般式（１）及び一般式（２）中のｍ、ｎ、ｏ及びｐは、各々独立して１～１０の整数を示す。 In the general formula (1) and the general formula (2), m, n, o and p each independently represent an integer of 1 to 10.
　前記有機溶剤（Ｆ）としては、前記水性インク全量に対し１質量％～３０質量％の範囲で使用することが好ましく、５質量％～２５質量％の範囲で使用することが、印刷物のセット性に優れ、インク吐出口における水性インクの乾燥や凝固を防止する効果を奏するうえで特に好ましい。 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.
　前記水溶性有機溶剤（ｆ１）とプロピレングリコール（ｆ２）と前記有機溶剤（ｆ３）とは、それらの質量割合［水溶性溶剤（ｆ１）／プロピレングリコール（ｆ２）］、［プロピレングリコール（ｆ２）／有機溶剤（ｆ３）］がそれぞれ１／２５～１／１、１／４～８／１の範囲で使用することが好ましく、１／２０～１／１、１／２～５／１の範囲で使用することが、印刷物のセット性に優れ、インク吐出口におけるインクの乾燥や凝固を防止する効果を奏するうえで特に好ましい。 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.
　本発明の水性インクで使用可能な色材としては、公知慣用の顔料や染料等を使用することができる。なかでも、前記色材としては、耐候性等に優れた印刷物を製造するうえで、顔料を使用することが好ましい。また、前記色材としては、前記顔料が樹脂で被覆された着色剤を使用することもできる。 As a colorant that can be used in the aqueous ink of the present invention, known pigments, dyes and the like can be used. Among them, as 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.
　前記顔料としては、特に限定はなく、水性グラビアインクや水性インクジェット記録用インクにおいて通常使用される有機顔料または無機顔料を使用することができる。 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.
　また、前記顔料としては、未酸性処理顔料、酸性処理顔料のいずれも使用することができる。 Moreover, as said pigment, any of a non-acid treated pigment and an acid treated pigment can be used.
　前記無機顔料としては、例えば、酸化鉄や、コンタクト法、ファーネス法またはサーマル法等の方法で製造されたカーボンブラック等を使用することができる。 As 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.
　前記有機顔料としては、例えばアゾ顔料（アゾレーキ、不溶性アゾ顔料、縮合アゾ顔料、キレートアゾ顔料などを含む）、多環式顔料（例えば、フタロシアニン顔料、ペリレン顔料、ペリノン顔料、アントラキノン顔料、キナクリドン顔料、ジオキサジン顔料、チオインジゴ顔料、イソインドリノン顔料、キノフラロン顔料など）、レーキ顔料（例えば、塩基性染料型キレート、酸性染料型キレートなど）、ニトロ顔料、ニトロソ顔料、アニリンブラック等を使用することができる。 Examples of the organic pigment 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.
　前記顔料のうち、ブラックインクに使用可能なカーボンブラックとしては、三菱化学株式会社製のＮｏ．２３００、Ｎｏ．２２００Ｂ、Ｎｏ．９００、Ｎｏ．９６０、　Ｎｏ．９８０、Ｎｏ．３３、Ｎｏ．４０、Ｎｏ，４５、Ｎｏ．４５Ｌ、Ｎｏ．５２、ＨＣＦ８８、ＭＡ７、ＭＡ８、ＭＡ１００、等が、コロンビア社製のＲａｖｅｎ５７５０、Ｒａｖｅｎ５２５０、Ｒａｖｅｎ５０００、Ｒａｖｅｎ３５００、Ｒａｖｅｎ１２５５、Ｒａｖｅｎ７００等、キャボット社製のＲｅｇａｌ　４００Ｒ、Ｒｅｇａｌ　３３０Ｒ、Ｒｅｇａｌ　６６０Ｒ、Ｍｏｇｕｌ　Ｌ、Ｍｏｇｕｌ　７００、Ｍｏｎａｒｃｈ８００、Ｍｏｎａｒｃｈ８８０、Ｍｏｎａｒｃｈ９００、Ｍｏｎａｒｃｈ１０００、Ｍｏｎａｒｃｈ１１００、Ｍｏｎａｒｃｈ１３００、Ｍｏｎａｒｃｈ１４００等、デグサ社製のＣｏｌｏｒ　Ｂｌａｃｋ　ＦＷ１、同ＦＷ２、同ＦＷ２Ｖ、同ＦＷ１８、同ＦＷ２００、同Ｓ１５０、同Ｓ１６０、同Ｓ１７０、Ｐｒｉｎｔｅｘ　３５、同Ｕ、同Ｖ、同１４００Ｕ、Ｓｐｅｃｉａｌ　Ｂｌａｃｋ　６、同５、同４、同４Ａ、ＮＩＰＥＸ１５０、ＮＩＰＥＸ１６０、ＮＩＰＥＸ１７０、ＮＩＰＥＸ１８０等を使用することができる。 Among the above pigments, 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. Regal 400R, Regal 330R, Regal 660R, Mogul L, Mogul 700, Monarch 800 , Monarch 880, Monarch 900, Monarch 1000, Monarch 1100, Monarch 1300, Monarch 1400 etc., Degussa's Color Black FW1, FW2, FW2 V, FW18, FW200, S150, S150, S160, Printex 35, U, etc. V, 1400U, Special Bl ck 6, Special Black 5, Special Black 4, it is possible to use the same 4A, NIPEX150, NIPEX160, NIPEX170, NIPEX180 like.
　また、イエローインクに使用可能な顔料の具体例としては、Ｃ．Ｉ．ピグメントイエロー１、２、１２、１３、１４、１６、１７、７３、７４、７５、８３、９３、９５、９７、９８、１０９、１１０、１１４、１２０、１２８、１２９、１３８、１５０、１５１、１５４、１５５、１７４、１８０、１８５等が挙げられる。 In addition, specific examples of the pigment 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.
　また、マゼンタインクに使用可能な顔料の具体例としては、Ｃ．Ｉ．ピグメントレッド５、７、１２、４８（Ｃａ）、４８（Ｍｎ）、５７（Ｃａ）、５７：１、１１２、１２２、１２３、１４６、１６８、１７６、１８４、１８５、２０２、２０９、２６９、２８２等、Ｃ．Ｉ．ピグメントバイオレット１９等が挙げられる。 In addition, as specific examples of pigments that can be used for magenta ink, C.I. I. Pigment red 5, 7, 12, 48 (Ca), 48 (Mn), 57 (Ca), 57: 1, 112, 122, 123, 146, 168, 176, 184, 185, 202, 209, 269, 282 , Etc., C.I. I. Pigment violet 19 and the like.
　また、シアンインクに使用可能な顔料の具体例としては、Ｃ．Ｉ．ピグメントブルー１、２、３、１５、１５：３、１５：４、１６、２２、６０、６３、６６等が挙げられる。 Further, as specific examples of 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.
　また、白インクに使用可能な顔料の具体例としては、アルカリ土類金属の硫酸塩、炭酸塩、微粉ケイ酸、合成珪酸塩、等のシリカ類、ケイ酸カルシウム、アルミナ、アルミナ水和物、酸化チタン、酸化亜鉛、タルク、クレイ等があげられる。これらは、表面処理されていてもよい。 Further, specific examples of the pigment 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.
　前記顔料は、水性インク中に安定に存在させるために、水性媒体に良好に分散させるための処理がされていることが好ましい。 The pigment is preferably treated to be well dispersed in an aqueous medium in order to stably exist in the aqueous ink.
　前記処理としては、例えば
（ｉ）顔料を顔料分散剤と共に、後述する分散方法で水性媒体中に分散させる方法
（ｉｉ）顔料の表面に分散性付与基（親水性官能基および／またはその塩）を直接またはアルキル基、アルキルエーテル基またはアリール基等を介して間接的に結合させた自己分散型顔料を水性媒体に分散および／または溶解させる方法が挙げられる。 As the treatment, for example, (i) 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 And 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.
　前記自己分散型顔料としては、例えば、顔料に物理的処理または化学的処理を施し、分散性付与基または分散性付与基を有する活性種を顔料の表面に結合（グラフト）させたものを使用することができる。前記自己分散型顔料は、例えば、真空プラズマ処理、次亜ハロゲン酸および／または次亜ハロゲン酸塩による酸化処理、またはオゾンによる酸化処理等や、水中で酸化剤により顔料表面を酸化する湿式酸化法や、ｐ－アミノ安息香酸を顔料表面に結合させることによりフェニル基を介してカルボキシル基を結合させる方法によって製造することができる。 As 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. Alternatively, 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.
　自己分散型顔料を含有する水性インクは、前記顔料分散剤を含む必要がないため、顔料分散剤に起因する発泡等がほとんどなく、吐出安定性に優れた水性インクを調製しやすい。また、自己分散型顔料を含有する水性インクは、取り扱いが容易で、顔料分散剤に起因する大幅な粘度上昇が抑えられるため顔料をより多く含有することが可能となり、印字濃度の高い印刷物の製造に使用することができる。 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. In addition, since 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
　自己分散型顔料としては、市販品を利用することも可能であり、そのような市販品としては、マイクロジェットＣＷ－１（商品名；オリヱント化学工業（株）製）、ＣＡＢ－Ｏ－ＪＥＴ２００、ＣＡＢ－Ｏ－ＪＥＴ３００（以上商品名；キヤボット社製）が挙げられる。 Commercially available 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).
　本発明において、前記スジの発生を防止すべく、水性インクの組成を過度に変更しようとすると、印刷物の印字濃度や耐擦過性が若干、低下する傾向がみられる場合がある。前記色材は、前記スジの発生を防止するとともに、色材の優れた分散安定性を維持し、かつ、印刷物の印字濃度や耐擦過性を向上させるうえで、前記水性インクの全量に対して１質量％～２０質量％の範囲で使用することが好ましく、２質量％～１０質量％の範囲で使用することがより好ましい。 In the present invention, when the composition of the aqueous ink is excessively changed in order to prevent the generation of the streaks, 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.
（顔料分散剤）
　前記顔料分散剤は、前記色材として顔料を使用する場合に、好適に使用することができる。 (Pigment dispersant)
The pigment dispersant can be suitably used when a pigment is used as the coloring material.
　前記顔料分散剤としては、例えばポリビニルアルコール類、ポリビニルピロリドン類、アクリル酸－アクリル酸エステル共重合体などのアクリル樹脂、スチレン－アクリル酸共重合体、スチレン－メタクリル酸共重合体、スチレン－メタクリル酸－アクリル酸エステル共重合体、スチレン－α－メチルスチレン－アクリル酸共重合体、スチレン－α－メチルスチレン－アクリル酸－アクリル酸エステル共重合体などのスチレン－アクリル樹脂、スチレン－マレイン酸共重合体、スチレン－無水マレイン酸共重合体、ビニルナフタレン－アクリル酸共重合体の水性樹脂、及び、前記水性樹脂の塩を使用することができる。前記顔料分散剤としては、味の素ファインテクノ（株）製品）のアジスパーＰＢシリーズ、ビックケミー・ジャパン（株）のＤｉｓｐｅｒｂｙｋシリーズ、ＢＡＳＦ社製のＥＦＫＡシリーズ、日本ルーブリゾール株式会社製のＳＯＬＳＰＥＲＳＥシリーズ、エボニック社製のＴＥＧＯシリーズ等を使用することができる。 Examples of the pigment dispersant 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-α-methylstyrene-acrylic acid copolymer, styrene-α-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. Examples of the pigment dispersant 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.
　前記顔料分散剤としては、粗大粒子を著しく低減でき、その結果、水性インクをインクジェット方式で吐出する場合に求められる良好な吐出安定性を付与するうえで、後述するポリマー（Ｇ）を使用することが好ましい。 As 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.
　前記ポリマー（Ｇ）としては、アニオン性基を有するものを使用することができ、なかでも、水への溶解度が０．１ｇ／１００ｍｌ以下であり、かつ、前記アニオン性基の塩基性化合物による中和率を１００％にしたときに水中で微粒子を形成可能な、数平均分子量が１０００～６０００の範囲内のポリマーを使用することが好ましい。 As 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%.
　前記ポリマー（Ｇ）の水への溶解度は、次のように定義した。すなわち、目開き２５０μｍおよび９０μｍの篩を用い２５０μｍ～９０μｍの範囲に粒子径を整えたポリマー（Ｇ）０．５ｇを、４００メッシュ金網を加工した袋に封入したものを試験片（Ｍ）とした。次に、前記試験片（Ｍ）を水５０ｍｌに浸漬し、２５℃の温度下で２４時間緩やかに攪拌放置した。２４時間後、前記試験片（Ｍ）を１１０℃に設定した乾燥機で２時間乾燥させた。前記試験片（Ｍ）を水に浸漬する前後の質量の変化を測定し、次式により溶解度を算出した。 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 μm to 90 μm using sieves with openings of 250 μm and 90 μm 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.
　溶解度（ｇ／１００ｍｌ）＝［（水に浸漬する前の試験片（Ｍ）の質量（ｇ））－（水に浸漬した後の試験片（Ｍ）の質量（ｇ））］×２ 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
　また、本発明において、アニオン性基の塩基性化合物による中和率を１００％にしたときに水中で微粒子を形成するか否かは、次のように判断した。
（１）ポリマー（Ｇ）の酸価を、予め、ＪＩＳ試験方法Ｋ　００７０－１９９２に基づく酸価測定方法により測定する。具体的には、テトラヒドロフランにポリマー（Ｇ）０．５ｇを溶解させ、フェノールフタレインを指示薬として、０．１Ｍ水酸化カリウムエタノール溶液で滴定し酸価を求める。
（２）次に、水５０ｍｌに対して、ポリマー（Ｇ）を１ｇ添加した後、前記ポリマー（Ｇ）が有する酸基を１００％中和するために必要な量の０．１ｍｏｌ／Ｌ水酸化カリウム水溶液を加えることによって、前記酸基を１００％中和した。
（３）次に、前記（２）で得た液を、２５℃の温度下で、２時間超音波洗浄器（株式会社エスエヌディ超音波洗浄器ＵＳ－１０２、３８ｋＨｚ自励発振）中で超音波を照射させた後２４時間室温で放置する。 Further, in the present invention, it was judged as follows whether or not to form fine particles in water when the neutralization ratio of the anionic group by the basic compound was 100%.
(1) 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.
(3) Next, 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.
（４）２４時間放置後、液面から２センチメートルの深部にある液をサンプリングしたサンプル液を、動的光散乱式粒子径分布測定装置（日機装株式会社製、動的光散乱式粒子径測定装置「マイクロトラック粒度分布計ＵＰＡ－ＳＴ１５０」）を用い、微粒子形成による光散乱情報が得られるか判定することにより、微粒子が存在するか確認する。 (4) 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.
　本発明で使用するポリマー（Ｇ）が形成する微粒子の水中で安定をより一層向上させるために、前記微粒子の粒子径は、５ｎｍ～１０００ｎｍの範囲であることが好ましく、７ｎｍ～７００ｎｍの範囲であることがより好ましく、１０ｎｍ～５００ｎｍの範囲であることが最も好ましい。また、前記微粒子の粒度分布は、狭いほうがより分散安定性に優れる傾向にあるが、粒度分布が広い場合であっても、従来よりも優れた分散安定性を備えた水性インクを得ることができる。なお、前記粒子径及び粒度分布は、動的光散乱式粒子径分布測定装置（日機装株式会社製動的光散乱式粒子径測定装置「マイクロトラック粒度分布計ＵＰＡ－ＳＴ１５０」）を用い測定した。 In order to further improve the stability of the particles formed by the polymer (G) used in the present invention in water, 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.).
　本発明で使用するポリマー（Ｇ）の中和率は、以下の式により決定した。 The neutralization rate of the polymer (G) used in the present invention was determined by the following equation.
中和率（％）＝［（塩基性化合物の質量（ｇ）×５６×１０００）／（前記ポリマー（Ｇ）の酸価（ｍｇＫＯＨ／ｇ）×塩基性化合物の当量×ポリマー（Ｇ）の質量（ｇ））］×１００ 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
　また、前記ポリマー（Ｇ）の酸価は、ＪＩＳ試験方法Ｋ　００７０－１９９２に基づいて測定した。具体的には、テトラヒドロフランにポリマー（Ｇ）０．５ｇを溶解させ、フェノールフタレインを指示薬として、０．１Ｍ水酸化カリウムエタノール溶液で滴定することにより求めた。 Further, 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.
　前記ポリマー（Ｇ）の数平均分子量は１０００～６０００の範囲のものを使用することが好ましく、１３００～５０００であることがより好ましく、１５００～４５００であることが、水性媒体中における顔料等の色材の凝集等を効果的に抑制でき、前記色材の良好な分散安定性を備えた水性インクを得るうえでより好ましい。 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.
　なお、前記数平均分子量は、ＧＰＣ（ゲルパーミネーションクロマトグラフィー）によって測定されるポリスチレン換算の値とし、具体的には以下の条件で測定した値とする。 In addition, let 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.
（数平均分子量（Ｍｎ）の測定方法）
　ゲル・パーミエーション・クロマトグラフィー（ＧＰＣ）法により、下記の条件で測定した。 (Method of measuring number average molecular weight (Mn))
It measured on condition of the following by gel permeation chromatography (GPC) method.
測定装置：高速ＧＰＣ装置（東ソー株式会社製「ＨＬＣ－８２２０ＧＰＣ」）
カラム：東ソー株式会社製の下記のカラムを直列に接続して使用した。 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.
　「ＴＳＫｇｅｌ　Ｇ５０００」（７．８ｍｍＩ．Ｄ．×３０ｃｍ）×１本
　「ＴＳＫｇｅｌ　Ｇ４０００」（７．８ｍｍＩ．Ｄ．×３０ｃｍ）×１本
　「ＴＳＫｇｅｌ　Ｇ３０００」（７．８ｍｍＩ．Ｄ．×３０ｃｍ）×１本
　「ＴＳＫｇｅｌ　Ｇ２０００」（７．８ｍｍＩ．Ｄ．×３０ｃｍ）×１本
検出器：ＲＩ（示差屈折計）
カラム温度：４０℃
溶離液：テトラヒドロフラン
流速：１．０ｍＬ／分
注入量：１００μＬ（試料濃度０．４質量％のテトラヒドロフラン溶液）
標準試料：下記の標準ポリスチレンを用いて検量線を作成した。 "TSKgel 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 This "TSKgel G2000" (7.8 mm ID × 30 cm) × 1 detector: RI (differential refractometer)
Column temperature: 40 ° C
Eluent: Tetrahydrofuran Flow rate: 1.0 mL / min Injection volume: 100 μL (tetrahydrofuran solution with a sample concentration of 0.4% by mass)
Standard sample: A calibration curve was prepared using the following standard polystyrene.
（標準ポリスチレン）
　東ソー株式会社製「ＴＳＫｇｅｌ　標準ポリスチレン　Ａ－５００」
　東ソー株式会社製「ＴＳＫｇｅｌ　標準ポリスチレン　Ａ－１０００」
　東ソー株式会社製「ＴＳＫｇｅｌ　標準ポリスチレン　Ａ－２５００」
　東ソー株式会社製「ＴＳＫｇｅｌ　標準ポリスチレン　Ａ－５０００」
　東ソー株式会社製「ＴＳＫｇｅｌ　標準ポリスチレン　Ｆ－１」
　東ソー株式会社製「ＴＳＫｇｅｌ　標準ポリスチレン　Ｆ－２」
　東ソー株式会社製「ＴＳＫｇｅｌ　標準ポリスチレン　Ｆ－４」
　東ソー株式会社製「ＴＳＫｇｅｌ　標準ポリスチレン　Ｆ－１０」
　東ソー株式会社製「ＴＳＫｇｅｌ　標準ポリスチレン　Ｆ－２０」
　東ソー株式会社製「ＴＳＫｇｅｌ　標準ポリスチレン　Ｆ－４０」
　東ソー株式会社製「ＴＳＫｇｅｌ　標準ポリスチレン　Ｆ－８０」
　東ソー株式会社製「ＴＳＫｇｅｌ　標準ポリスチレン　Ｆ－１２８」
　東ソー株式会社製「ＴＳＫｇｅｌ　標準ポリスチレン　Ｆ－２８８」
　東ソー株式会社製「ＴＳＫｇｅｌ　標準ポリスチレン　Ｆ－５５０」 (Standard polystyrene)
Tosoh Corporation "TSKgel standard polystyrene A-500"
Tosoh Corporation "TSKgel standard polystyrene A-1000"
Tosoh Corporation "TSKgel standard polystyrene A-2500"
Tosoh Corporation "TSKgel standard polystyrene A-5000"
Tosoh Corporation "TSKgel standard polystyrene F-1"
Tosoh Corporation "TSKgel standard polystyrene F-2"
Tosoh Corporation "TSKgel standard polystyrene F-4"
Tosoh Corporation "TSKgel standard polystyrene F-10"
Tosoh Corporation "TSKgel standard polystyrene F-20"
Tosoh Corporation "TSKgel standard polystyrene F-40"
Tosoh Corporation "TSKgel standard polystyrene F-80"
Tosoh Corporation "TSKgel standard polystyrene F-128"
Tosoh Corporation "TSKgel standard polystyrene F-288"
Tosoh Corporation "TSKgel standard polystyrene F-550"
　前記ポリマー（Ｇ）としては、水に対し、未中和の状態では不溶もしくは難溶性であり、且つ１００％中和された状態では微粒子を形成するポリマーを使用することができ、親水性基であるアニオン性基のほかに疎水性基を１分子中に有するポリマーであるならば、特に限定はされない。 As 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.
　このようなポリマーとして、疎水性基を有するポリマーブロックとアニオン性基を有するポリマーブロックとを有するブロックポリマーがあげられる。ポリマー（Ｇ）において、前記アニオン性基の数と水への溶解度は、必ずしも酸価や、ポリマー設計時のアニオン性基の数で特定されるものではなく、例えば同一の酸価を有するポリマーであっても、分子量の低いものは水への溶解度が高くなる傾向にあり、分子量の高いものは水への溶解度は下がる傾向にある。このことから、本発明においては、ポリマー（Ｇ）を水への溶解度で特定している。 Such polymers include block polymers having a polymer block having a hydrophobic group and a polymer block having an anionic group. In the polymer (G), 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.
　前記ポリマー（Ｇ）は、ホモポリマーでも良いが、共重合体であることが好ましく、ランダムポリマーであってもブロックポリマーであっても、交互ポリマーであっても良いが、なかでもブロックポリマーであることが好ましい。また、ポリマーは分岐ポリマーであっても良いが、直鎖ポリマーであることが好ましい。 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.
　また、前記ポリマー（Ｇ）は設計の自由度からビニルポリマーであることが好ましく、本発明において所望される分子量や、溶解度特性を有するビニルポリマーを製造する方法としては、リビングラジカル重合、リビングカチオン重合、リビングアニオン重合といった、「リビング重合」を用いることにより製造することが好ましい。 Further, 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.
　なかでも、前記ポリマー（Ｇ）は（メタ）アクリレートモノマーを原料の１つとして用い製造されるビニルポリマーであることが好ましく、そのようなビニルポリマーの製造方法としては、リビングラジカル重合、リビングアニオン重合が好ましく、さらにブロックポリマーの分子量や各セグメントをより精密に設計できる観点からリビングアニオン重合が好ましい。 Among them, 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.
　リビングアニオン重合によって製造される前記ポリマー（Ｇ）は、具体的には、一般式（３）で表されるポリマーである。 Specifically, the polymer (G) produced by living anionic polymerization is a polymer represented by the general formula (3).
Figure JPOXMLDOC01-appb-C000002
Figure JPOXMLDOC01-appb-C000002
　一般式（３）中、Ａ１は有機リチウム開始剤残基を表し、Ａ２は芳香環または複素環を有するモノマーのポリマーブロックを表し、Ａ３はアニオン性基を含むポリマーブロックを表し、ｎは１～５の整数を表し、Ｂは芳香族基またはアルキル基を表す。 In 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, and B represents an aromatic group or an alkyl group.
　一般式（３）中、Ａ１は有機リチウム開始剤残基を表す。有機リチウム開始剤として具体的にはメチルリチウム、エチルリチウム、プロピルリチウム、ブチルリチウム（ｎ－ブチルリチウム、ｓｅｃ－ブチルリチウム、ｉｓｏ－ブチルリチウム、ｔｅｒｔ－ブチルリチウムなど）、ペンチルリチウム、へキシルリチウム、メトキシメチルリチウム、エトシキメチルリチウムなどのアルキルリチウム；ベンジルリチウム、α－メチルスチリルリチウム、１，１－ジフェニル－３－メチルペンチルリチウム、１，１－ジフェニルヘキシルリチウム、フェニルエチルリチウムなどのフェニルアルキレンリチウム；ビニルリチウム、アリルリチウム、プロペニルリチウム、ブテニルリチウムなどのアルケニルリチウム；エチニルリチウム、ブチニルリチウム、ペンチニルリチウム、ヘキシニルリチウムなどのアルキニルリチウム；フェニルリチウム、ナフチルリチウムなどのアリールリチウム；２－チエニルリチウム、４－ピリジルリチウム、２－キノリルリチウムなどのヘテロ環リチウム；トリ（ｎ－ブチル）マグネシウムリチウム、トリメチルマグネシウムリチウムなどのアルキルリチウムマグネシウム錯体などが挙げられる。 In general formula (3), A 1 represents an organolithium initiator residue. Specific examples of 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, α-methylstyryllithium, 1,1-diphenyl-3-methylpentyllithium, 1,1-diphenylhexyllithium and phenylethyllithium Alkenyllithium such as vinyllithium, allyllithium, propenyllithium and butenyllithium; ethynyllithium, butynyllithium, pentynyllithium, hexynyllithium and the like Aryllithiums such as phenyllithium and naphthyllithium; heterocyclic lithiums such as 2-thienyllithium, 4-pyridyllithium and 2-quinolyllithium; alkyls such as tri (n-butyl) magnesiumlithium and trimethylmagnesiumlithium Lithium magnesium complex etc. are mentioned.
　有機リチウム開始剤は、有機基とリチウムとの結合が開裂し有機基側に活性末端が生じ、そこから重合が開始される。従って得られるポリマー末端には有機リチウム由来の有機基が結合している。本発明においては、該ポリマー末端に結合した有機リチウム由来の有機基を、有機リチウム開始剤残基と称する。例えばメチルリチウムを開始剤として使用したポリマーであれば、有機リチウム開始剤酸基はメチル基となり、ブチルリチウムを開始剤として使用したポリマーであれば、有機リチウム開始剤酸基はブチル基となる。 In the organic lithium initiator, 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. In the present invention, the organic group derived from organolithium bonded to the polymer terminal is referred to as an organolithium initiator residue. For example, in the case of a polymer using methyllithium as an initiator, the organolithium initiator acid group is a methyl group, and in the case of a polymer using butyllithium as an initiator, the organolithium initiator acid group is a butyl group.
　前記一般式（３）中、Ａ２は疎水性基を有するポリマーブロックを表す。Ａ２は、前述の通り適度な溶解性のバランスのバランスを取る目的の他、顔料と接触したときに顔料への吸着の高い基であることが好ましく、その観点から、Ａ２は芳香環または複素環を有するモノマーのポリマーブロックであることが好ましい。
芳香環または複素環を有するモノマーのポリマーブロックとは、具体的には、スチレン系モノマー等の芳香族環を有するモノマーや、ビニルピリジン系モノマー等の複素環を有するモノマーを単独重合または共重合して得たホモポリマーまたはコポリマーのポリマーブロックである。 In the general formula (3), 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.
Specifically, 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
　芳香環を有するモノマーとしては、スチレン、ｐ－ｔｅｒｔ－ブチルジメチルシロキシスチレン、ｏ－メチルスチレン、ｐ－メチルスチレン、ｐ－ｔｅｒｔ－ブチルスチレン、ｐ－ｔｅｒｔ－ブトキシスチレン、ｍ－ｔｅｒｔ－ブトキシスチレン、ｐ－ｔｅｒｔ－（１－エトキシメチル）スチレン、ｍ－クロロスチレン、ｐ－クロロスチレン、ｐ－フロロスチレン、α－メチルスチレン、ｐ－メチル－α－メチルスチレン、などのスチレン系モノマーや、ビニルナフタレン、ビニルアントラセンなどがあげられる。 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, α-methylstyrene, p-methyl-α-methylstyrene, and vinyl naphthalene And vinyl anthracene.
　また、複素環を有するモノマーとしては、２－ビニルピリジン、４－ビニルピリジンなどのビニルピリジン系モノマーがあげられる。これらのモノマーは単独でまたは２種以上を混合して用いることができる。 Further, 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.
　前記一般式（３）中、Ａ３はアニオン性基を含むポリマーブロックを表す。Ａ３は、前述の通り適度な溶解性を与える目的の他、顔料分散体となったときに水中で分散安定性を付与する目的がある。
前記ポリマーブロックＡ３におけるアニオン性基は、例えば、カルボキシル基、スルホン酸基または燐酸基等があげられる。なかでも、カルボキシル基がその調製やモノマー品種の豊富さ入手し易さから好ましい。また２つのカルボキシル基が分子内または分子間において脱水縮合した酸無水基となっていてもよい。 In the general formula (3), 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 3, 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. In addition, two carboxyl groups may form an acid anhydride group which is dehydrated and condensed in a molecule or between molecules.
　前記Ａ３のアニオン性基の導入方法は特に限定はなく、例えば該アニオン性基がカルボキシル基の場合は、（メタ）アクリル酸を単独重合もしくは他のモノマーと共重合させて得たホモポリマーまたはコポリマーのポリマーブロック（ＰＢ１）であってもよいし、脱保護をすることによりアニオン性基に再生可能な保護基を有する（メタ）アクリレートを単独重合もしくは他のモノマーと共重合させて得たホモポリマーまたはコポリマーの、該アニオン性基に再生可能な保護基の一部または全てがアニオン性基に再生されたポリマーブロック（ＰＢ２）であってもよい。 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.
　なお、前記ポリマーブロックＡ３で使用する（メタ）アクリル酸とは、アクリル酸とメタクリル酸の総称を表し、（メタ）アクリレートとは、アクリレートとメタクリレートとの総称を表す。 Incidentally, the A polymer block used in A 3 (meth) acrylic acid represents the general term for acrylic acid and methacrylic acid, and (meth) acrylate represents the general term for acrylate and methacrylate.
　（メタ）アクリル酸や（メタ）アクリレートとしては、具体的には、（メタ）アクリル酸、（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸ｉｓｏ－プロピル、（メタ）アクリル酸アリル、（メタ）アクリル酸ｎ－ブチル、（メタ）アクリル酸ｉｓｏ－ブチル、（メタ）アクリル酸ｓｅｃ－ブチル、（メタ）アクリル酸ｔｅｒｔ－ブチル、（メタ）アクリル酸ｎ－アミル、（メタ）アクリル酸ｉｓｏ－アミル、（メタ）アクリル酸ｎ－ヘキシル、（メタ）アクリル酸ｎ－オクチル、（メタ）アクリル酸２－エチルヘキシル、（メタ）アクリル酸ｎ－ラウリル、（メタ）アクリル酸ｎ－トリデシル、（メタ）アクリル酸ｎ－ステアリル、（メタ）アクリル酸フェニル、（メタ）アクリル酸ベンジル、（メタ）アクリル酸シクロヘキシル、（メタ）アクリル酸４－ｔｅｒｔ－ブチルシクロヘキシル、（メタ）アクリル酸イソボルニル、（メタ）アクリル酸トリシクロデカニル、（メタ）アクリル酸ジシクロペンタジエニル、（メタ）アクリル酸アダマンチル、（メタ）アクリル酸グリシジル、(メタ)アクリル酸テトラヒドロフルフリル、(メタ)アクリル酸２－メトキシエチル、(メタ)アクリル酸２－エトキシエチル、（メタ）アクリル酸ジメチルアミノエチル、（メタ）アクリル酸ジエチルアミノエチル、（メタ）アクリル酸トリフルオロエチル、（メタ）アクリル酸テトラフルオロプロピル、（メタ）アクリル酸ペンタフルオロプロピル、（メタ）アクリル酸オクタフルオロペンチル、（メタ）アクリル酸ペンタデカフルオロオクチル、（メタ）アクリル酸ヘプタデカフルオロデシル、Ｎ，Ｎ－ジメチル（メタ）アクリルアミド、（メタ）アクリロイルモルホリン、（メタ）アクリロニトリル、ポリエチレングリコール（メタ）アクリレート、ポリプロピレングリコール（メタ）アクリレート、ポリエチレングリコール－ポリプロピレングリコール（メタ）アクリレート、ポリエチレングリコール－ポリブチレングリコール（メタ）アクリレート、ポリプロピレングリコール－ポリブチレングリコール（メタ）アクリレート、メトキシポリエチレングリコール（メタ）アクリレート、エトキシポリエチレングリコール（メタ）アクリレート、ブトキシポリエチレングリコール（メタ）アクリレート、オクトキシポリエチレングリコール（メタ）アクリレート、ラウロキシポリエチレングリコール（メタ）アクリレート、ステアロキシポリエチレングリコール（メタ）アクリレート、フェノキシポリエチレングリコール（メタ）アクリレート、メトキシポリプロピレングリコール（メタ）アクリレート、オクトキシポリエチレングリコール－ポリプロピレングリコール（メタ）アクリレートなどのポリアルキレンオキサイド基含有（メタ）アクリレート等があげられる。これらのモノマーは単独でまたは２種以上を混合して用いることができる。 Specific examples of (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) acrylate, benzyl (meth) acrylate, (meth) acrylate Cyclohexyl methacrylate, 4-tert-butylcyclohexyl acrylate, isobornyl (meth) acrylate, tricyclodecanyl (meth) acrylate, dicyclopentadienyl (meth) acrylate, adamantyl (meth) acrylate Glycidyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, (meth) acrylic Acid diethylaminoethyl, (meth) acrylate trifluoroethyl, (meth) acrylate tetrafluoropropyl, (meth) acrylate pentafluoropropyl, (meth) acrylate octafluoropentyl, (meth) acrylate pentadecafluorooctyl, (Meth) acrylic Heptadecafluorodecyl, N, N-dimethyl (meth) acrylamide, (meth) acryloyl morpholine, (meth) acrylonitrile, polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, polyethylene glycol-polypropylene glycol (meth) acrylate, Polyethylene glycol-polybutylene glycol (meth) acrylate, polypropylene glycol-polybutylene glycol (meth) acrylate, methoxy polyethylene glycol (meth) acrylate, ethoxy polyethylene glycol (meth) acrylate, butoxy polyethylene glycol (meth) acrylate, octoxy polyethylene glycol (Meth) acrylate, lauroxy polyethylene glycol ( Polyalkylene oxide group-containing (meth) acrylates such as meta) acrylate, stearoxy polyethylene glycol (meth) acrylate, phenoxy polyethylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, octoxy polyethylene glycol-polypropylene glycol (meth) acrylate An acrylate etc. are mention | raise | lifted. These monomers can be used alone or in combination of two or more.
　リビングアニオン重合法においては、使用するモノマーがアニオン性基等の活性プロトンを持つ基を有するモノマーの場合、リビングアニオン重合ポリマーの活性末端が直ちにこれら活性プロトンを持つ基と反応し失活するため、ポリマーが得られない。リビングアニオン重合では活性プロトンを持つ基を有するモノマーをそのまま重合することは困難であるため、活性プロトンを持つ基を保護した状態で重合し、その後、保護基を脱保護することで活性プロトンを持つ基を再生することが好ましい。 In the living anion polymerization method, when the monomer used is a monomer having a group having an active proton such as an anionic group, 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. In 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.
　このような理由から、前記ポリマーブロックＡ３においては、脱保護をすることによりアニオン性基に再生可能な保護基を有する（メタ）アクリレートを含むモノマーを用いることが好ましい。該モノマーを使用することで、重合時には前述の重合の阻害を防止できる。また保護基により保護されたアニオン性基は、ブロックポリマーを得た後に脱保護することにより、アニオン性基に再生することが可能である。 For this reason, in 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. By using the monomer, the above-mentioned inhibition of the polymerization can be prevented during the polymerization. Moreover, the anionic group protected by the protecting group can be regenerated to an anionic group by deprotecting after obtaining the block polymer.
　例えばアニオン性基がカルボキシル基の場合、カルボキシル基をエステル化し、後工程として加水分解等で脱保護することによりカルボキシル基を再生することができる。この場合のカルボキシル基に変換可能な保護基としてはエステル結合を有する基が好ましく、例えば、メトキシカルボニル基、エトキシカルボニル基、ｎ－プロポキシカルボニル基、ｎ－ブトキシカルボニル基等の第１級アルコキシカルボニル基；イソプロポキシカルボニル基、ｓｅｃ－ブトキシカルボニル基等の第２級アルコキシカルボニル基；ｔ－ブトキシカルボニル基等の第３級アルコキシカルボニル基；ベンジルオキシカルボニル基等のフェニルアルコキシカルボニル基；エトキシエチルカルボニル基等のアルコキシアルキルカルボニル基などが挙げられる。 For example, when the anionic group is a carboxyl group, the carboxyl group can be regenerated by esterifying the carboxyl group and deprotecting by hydrolysis or the like as a subsequent step. In this case, as 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.
　アニオン性基がカルボキシル基の場合、使用できるモノマーとしては、メチル（メタ）アクリレート、エチル（メタ）アクリレート、ｎ－プロピル（メタ）アクリレート、イソプロピル（メタ）アクリレート、ｎ－ブチル（メタ）アクリレート、ｓｅｃ－ブチル（メタ）アクリレート、イソブチル（メタ）アクリレート、ｔ－ブチル（メタ）アクリレート、２－エチルヘキシル（メタ）アクリレート、デシル（メタ）アクリレート、ウンデシル（メタ）アクリレート、ドデシル（メタ）アクリレート（ラウリル（メタ）アクリレート）、トリデシル（メタ）アクリレート、ペンタデシル（メタ）アクリレート、ヘキサデシル（メタ）アクリレート、ヘプタデシル（メタ）アクリレート、オクタデシル（メタ）アクリレート（ステアリル（メタ）アクリレート）、ノナデシル（メタ）アクリレート、イコサニル（メタ）アクリレート等のアルキル（メタ）アクリレート；ベンジル（メタ）アクリレート等のフェニルアルキレン（メタ）アクリレート；エトキシエチル（メタ）アクリレート等のアルコキシアルキル（メタ）アクリレートなどが挙げられる。これらの（メタ）アクリレートは、１種で用いることも２種以上併用することもできる。また、これらの（メタ）アクリレートのなかでも、ｔ－ブチル（メタ）アクリレート、ベンジル（メタ）アクリレートを用いると、カルボキシル基への変換反応が容易であることから好ましい。また、工業的に入手のしやすさを考慮すると、ｔ－ブチル（メタ）アクリレートがより好ましい。 When the anionic group is a carboxyl group, 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, octadecyl (meth) acrylate (stearyl (meth) acrylate ) Acrylates) Alkyl (meth) acrylates such as nonadecyl (meth) acrylate and icosanyl (meth) acrylate; phenyl alkylene (meth) acrylates such as benzyl (meth) acrylate; alkoxyalkyl (meth) such as ethoxyethyl (meth) acrylate An acrylate etc. are mentioned. These (meth) acrylates can be used alone or in combination of two or more. Among these (meth) acrylates, t-butyl (meth) acrylate and benzyl (meth) acrylate are preferably used because they are easy to convert to a carboxyl group. Also, t-butyl (meth) acrylate is more preferable in consideration of industrial availability.
　一般式（３）中、Ｂは芳香族基または炭素原子数１～１０のアルキル基を表す。またｎは１～５の整数を表す。 In the general formula (3), B represents an aromatic group or an alkyl group having 1 to 10 carbon atoms. And n represents an integer of 1 to 5.
　リビングアニオン重合法においては、（メタ）アクリレートモノマーを求核性の強いスチレン系ポリマーの活性末端に直接重合しようとした場合、カルボニル炭素への求核攻撃により、ポリマー化できない場合がある。このため、前記Ａ1－Ａ2に（メタ）アクリレートモノマーの重合を行う際には反応調整剤を使用し、求核性を調整した後、（メタ）アクリレートモノマーを重合することが行われる。一般式（３）におけるＢは該反応調整剤に由来する基である。反応調整剤としては、具体的にはジフェニルエチレンやα－メチルスチレン、ｐ－メチル－α－メチルスチレン等があげられる。 In the living anionic polymerization method, when it is attempted to directly polymerize the (meth) acrylate monomer to the active end of the strongly nucleophilic styrenic polymer, the polymer may not be polymerized due to nucleophilic attack on the carbonyl carbon. Therefore, when the (meth) acrylate monomer is polymerized to A 1 -A 2 , a 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, α-methylstyrene, p-methyl-α-methylstyrene and the like.
　リビングアニオン重合法は、反応条件を整えることにより、従来のフリーラジカル重合で用いられるようなバッチ方式により実施できる他、マイクロリアクターによる連続的に重合する方法を挙げることもできる。マイクロリアクターは、重合開始剤とモノマーの混合性が良好であるため、反応が同時に開始し、温度が均一で重合速度を揃えることができるため、製造される重合体の分子量分布を狭くできる。また同時に、成長末端が安定であるためブロックの両成分が混じりあわないブロック共重合体を製造することが容易になる。また、反応温度の制御性が良好であるため副反応を抑えることが容易である。 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. In 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. At the same time, since the growth end is stable, it becomes easy to produce a block copolymer in which both components of the block are not mixed. In addition, since the controllability of the reaction temperature is good, it is easy to suppress the side reaction.
　マイクロリアクターを使用したリビングアニオン重合の一般的な方法を、マイクロリアクターの模式図である図３を参照しながら説明する。
第一のモノマーと重合を開始させる重合開始剤とを、それぞれチューブリアクターＰ１及びＰ２（図１中７及び８）から、複数の液体を混合可能な流路を備えるＴ字型マイクロミキサーＭ１（図１中１）に導入し、Ｔ字型マイクロミキサーＭ１内で、第一のモノマーをリビングアニオン重合し第一の重合体を形成する（工程１）。 A general method of living anionic polymerization using a microreactor is described with reference to FIG. 3, which 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).
　次に、得られた第一の重合体をＴ字型マイクロミキサーＭ２（図３中２）に移動させ、同ミキサーＭ２内で、得られた重合体の成長末端を、チューブリアクターＰ３（図３中９）から導入された反応調整剤によりトラップし、反応調節を行う（工程２）。
なお、このとき反応調整剤の種類や使用量により、前記一般式（３）におけるｎの数をコントロールすることが可能である。 Next, 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.
　次に、前記Ｔ字型マイクロミキサーＭ２内の反応調節を行った第一の重合体を、Ｔ字型マイクロミキサーＭ３（図３中３）に移動させ、同ミキサーＭ３内で、チューブリアクターＰ４から導入された第二のモノマーと、前記反応調節を行った第一の重合体とを、連続的にリビングアニオン重合を行う（工程３）。 Next, 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).
　その後メタノール等活性プロトンを有する化合物で反応をクエンチすることで、ブロック共重合体を製造する。 Thereafter, the reaction is quenched with a compound having an active proton such as methanol to produce a block copolymer.
　本発明の一般式（３）で表されるポリマー（Ｇ）を、前記マイクロリアクターで製造する場合は、前記第一のモノマーとして芳香環または複素環を有するモノマーを使用し、前記開始剤として有機リチウム開始剤により反応させることで、前記Ａ２の芳香環または複素環を有するモノマーのポリマーブロック（該ポリマーブロックＡ２の片末端には前記Ａ１の有機リチウム開始剤残基である有機基が結合している）を得る。
次に、反応調整剤を使用して成長末端の反応性を調整した後、前記アニオン性基に再生可能な保護基を有する（メタ）アクリレートを含むモノマーを前記第二のモノマーとして反応させポリマーブロックを得る。 When the polymer (G) represented by the general formula (3) of the present invention is produced in the microreactor, 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).
Next, after adjusting the reactivity of the growth end using a reaction modifier, 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. Get
　この後、加水分解等の脱保護反応によりアニオン性基に再生することにより、前記Ａ３即ちアニオン性基を含むポリマーブロックが得られる。 Thereafter, by reproducing the anionic group by deprotection reaction such as hydrolysis, polymer blocks containing the A 3 i.e. anionic groups are obtained.
　前記アニオン性基に再生可能な保護基のエステル結合を、加水分解等の脱保護反応によりアニオン性基に再生させる方法を詳細に述べる。 The method for regenerating the ester bond of the renewable protecting group to the anionic group to an anionic group by a deprotection reaction such as hydrolysis is described in detail.
　エステル結合の加水分解反応は、酸性条件下でも塩基性条件下でも進行するが、エステル結合を有する基によって条件がやや異なる。例えばエステル結合を有する基がメトキシカルボニル基等の第１級アルコキシカルボニル基又はイソプロポキシカルボニル基等の第２級アルコキシカルボニル基の場合は、塩基性条件下で加水分解を行うことでカルボキシル基を得ることができる。この際、塩基性条件下とする塩基性化合物としては、例えば、水酸化ナトリウム、水酸化カリウム等の金属水酸化物などが挙げられる。 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. For example, in the case where 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. Under the present circumstances, as a basic compound made into basic conditions, metal hydroxides, such as sodium hydroxide and potassium hydroxide, etc. are mentioned, for example.
　また、エステル結合を有する基が、ｔ－ブトキシカルボニル基等の第３級アルコキシカルボニル基の場合は、酸性条件下で加水分解を行うことにより、カルボキシル基を得ることができる。この際、酸性条件下とする酸性化合物としては、例えば、塩酸、硫酸、リン酸等の鉱酸；トリフルオロ酢酸等のブレステッド酸；トリメチルシリルトリフラート等のルイス酸などが挙げられる。ｔ－ブトキシカルボニル基の酸性条件下で加水分解の反応条件については、例えば、「日本化学会編第５版　実験化学講座１６　有機化合物の合成ＩＶ」に開示されている。 When the group having an ester bond is a tertiary alkoxycarbonyl group such as t-butoxycarbonyl group, a carboxyl group can be obtained by hydrolysis under acidic conditions. Under the present circumstances, as an acidic compound made into 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”.
　さらに、ｔ－ブトキシカルボニル基をカルボキシル基に変換する方法として、上記の酸に代えて、陽イオン交換樹脂を用いた方法も挙げられる。前記陽イオン交換樹脂としては、例えば、ポリマー鎖の側鎖にカルボキシル基（－ＣＯＯＨ）、スルホ基（－ＳＯ３Ｈ）等の酸基を有する樹脂が挙げられる。これらの中でも、当該樹脂の側鎖にスルホ基を有する強酸性を示す陽イオン交換樹脂が、反応の進行を速くできることから好ましい。本発明で使用できる陽イオン交換樹脂の市販品としては、例えば、オルガノ株式会社製強酸性陽イオン交換樹脂「アンバーライト」等が挙げられる。この陽イオン交換樹脂の使用量は、効果的に加水分解できることから、前記一般式（３）で表されるポリマー１００質量部に対し、５質量部～２００質量部の範囲が好ましく、１０質量部～１００質量部の範囲がより好ましい。 Furthermore, as a method of converting a t-butoxycarbonyl group into a carboxyl group, a method using a cation exchange resin in place of the above-mentioned acid may also be mentioned. Examples of 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. Among these, 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. As a commercial item of the cation exchange resin which can be used by this invention, the strong acidic cation exchange resin "Amberlite" etc. by Organo Ltd. are mentioned, for example. 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.
　また、エステル結合を有する基が、ベンジルオキシカルボニル基等のフェニルアルコキシカルボニル基の場合は、水素化還元反応を行うことにより、カルボキシル基に変換できる。この際、反応条件としては、室温下、酢酸パラジウム等のパラジウム触媒の存在下で、水素ガスを還元剤として用いて反応させることにより定量的にフェニルアルコキシカルボニル基をカルボキシル基に再生できる。 When 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. Under the present circumstances, as reaction conditions, 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.
　上記のように、エステル結合を有する基の種類によってカルボキシル基への変換の際の反応条件が異なるため、例えばＡ３の原料としてｔ－ブチル（メタ）アクリレートとｎ－ブチル（メタ）アクリレートを用い共重合して得られたポリマーは、ｔ－ブトキシカルボニル基とｎ－ブトキシカルボニル基とを有することになる。ここで、ｔ－ブトキシカルボニル基が加水分解する酸性条件下では、ｎ－ブトキシカルボニル基は加水分解しないことから、ｔ－ブトキシカルボニル基のみを選択的に加水分解してカルボキシル基へ脱保護が可能となる。したがって、Ａ３の原料モノマーであるアニオン性基に再生可能な保護基を有する（メタ）アクリレートを含むモノマーを適宜選択することにより親水ブロック（Ａ３）の酸価の調整が可能となる。 As described above, since the reaction conditions during the conversion of the type of group to the carboxyl group are different with, for example, t- butyl as a raw material of A 3 (meth) acrylate and n- butyl (meth) acrylate with an ester bond The polymer obtained by copolymerization will have t-butoxycarbonyl group and n-butoxycarbonyl group. Here, since the n-butoxycarbonyl group is not hydrolyzed under the acidic conditions where the t-butoxycarbonyl group is hydrolyzed, only the t-butoxycarbonyl group can be selectively hydrolyzed to be deprotected to the carboxyl group. It becomes. Therefore, it is possible to the acid value of the adjustment of the hydrophilic block (A 3) by appropriately selecting a monomer containing a (meth) acrylate having a renewable protecting group an anionic group which is a raw material monomer of A 3.
　また、前記一般式（３）で表されるポリマー（Ｇ）において、ポリマーブロック（Ａ２）とポリマーブロック（Ａ３）がランダムに配列して結合したランダム共重合体でなく、前記ポリマーブロックがある程度の長さのまとまりとなって規則的に結合したブロック共重合体であるほうが、前記顔料が前記ポリマー（Ｇ）によって水中に分散された水性顔料分散体の安定性を向上させるうえで有利である。水性顔料分散体は、水性インクの製造に使用する原料であり、前記顔料を前記ポリマー（Ｇ）を用いて高濃度で水中に分散させた液体である。ポリマーブロック（Ａ２）とポリマーブロック（Ａ３）のモル比Ａ２：Ａ３は、１００：１０～１００：５００の範囲であることが好ましく、Ａ２：Ａ３＝１００：１０～１００：４５０であることが、例えばインクジェット方式で水性インクを吐出する際に求められる良好な吐出安定性を維持することができ、かつ、より一層、発色性などに優れた印刷物を製造可能な水性インクを得るうえでより好ましい。 In the polymer (G) represented by the general formula (3), 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 molar ratio A 2 : A 3 of the polymer block (A 2 ) to the polymer block (A 3 ) is preferably in the range of 100: 10 to 100: 500, and A 2 : A 3 = 100: 10 to 100: For example, it is possible to maintain good discharge stability required when discharging an aqueous ink by, for example, an inkjet method, and to obtain an aqueous ink capable of producing a printed material further excellent in color development and the like. More preferable for obtaining.
　また、前記一般式（３）で表されるポリマー（Ｇ）において、ポリマーブロック（Ａ２）を構成する芳香環または複素環を有するモノマー数は５～４０の範囲が好ましく、６～３０の範囲がなお好ましく、７～２５の範囲が最も好ましい。またポリマーブロック（Ａ３）を構成するアニオン性基の数は、３～２０の範囲が好ましく、４～１７の範囲がなお好ましく、５～１５の範囲が最も好ましい。
前記ポリマーブロック（Ａ２）とポリマーブロック（Ａ３）のモル比Ａ２：Ａ３を、ポリマーブロック（Ａ２）を構成する芳香環または複素環を有するモル数と、（Ａ３）を構成するアニオン性基のモル数のモル比で表した場合は１００：７．５～１００：４００が好ましい。 Further, in the polymer (G) represented by the general formula (3), 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) When 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.
　また、前記一般式（３）で表されるポリマー（Ｇ）の酸価は４０ｍｇＫＯＨ／ｇ～４００ｍｇＫＯＨ／ｇが好ましく、４０ｍｇＫＯＨ／ｇ～３００ｍｇＫＯＨ／ｇでより好ましく、４０ｍｇＫＯＨ／ｇ～１９０ｍｇＫＯＨ／ｇであることが、例えばインクジェット方式で水性インクを吐出する際に求められる良好な吐出安定性を維持することができ、かつ、耐擦過性等の点でより一層優れた印刷物を製造可能な水性インクを得るうえでより好ましい。 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. For example, it is possible to maintain a good discharge stability required when discharging an aqueous ink by an inkjet method, and obtain an aqueous ink capable of producing a printed material having even more excellent in the abrasion resistance and the like. And more preferred.
　前記ポリマー（Ｇ）のアニオン性基は中和されていることが好ましい。 The anionic group of the polymer (G) is preferably neutralized.
　前記ポリマー（Ｇ）のアニオン性基を中和する塩基性化合物としては、公知慣用のものがいずれも使用出来、例えば、水酸化ナトリウム、水酸化カリウム等のアルカリ金属水酸化物等の無機塩基性物質や、アンモニア、トリエチルアミン、アルカノールアミンの様な有機塩基性化合物を用いることができる。 As 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.
　前記水性顔料分散体中に存在する前記ポリマー（Ｇ）の中和量は、ポリマーの酸価に対して１００％中和されている必要はない。具体的には、前記ポリマー（Ｇ）の中和率が２０％～２００％になるように中和されることが好ましく、８０％～１５０％がなお好ましい。 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. Specifically, the polymer (G) is preferably neutralized so as to have a neutralization rate of 20% to 200%, and more preferably 80% to 150%.
　本発明で使用する水性インクは、前記成分のほかに必要に応じて、界面活性剤、湿潤剤（乾燥抑止剤）、浸透剤、防腐剤、粘度調整剤、ｐＨ調整剤、キレート化剤、可塑剤、酸化防止剤、紫外線吸収剤等のその他の添加剤を含有するものを使用することができる。 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. Those containing other additives such as an agent, an antioxidant, and a UV absorber can be used.
　前記界面活性剤は、水性インクの表面張力を低下させるなどすることで水性インクのレベリング性を向上させるうえで使用することができる。さらに、前記界面活性剤は、インクジェットヘッドの吐出口から吐出された水性インクが段ボール（Ａ）に着弾後、表面で良好に濡れ広がらせることで、印刷物のスジ発生を防止することができる。 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.
　前記界面活性剤としては、各種のアニオン性界面活性剤、ノニオン性界面活性剤、カチオン性界面活性剤、両性界面活性剤などが挙げられ、これらの中では、アニオン性界面活性剤、ノニオン性界面活性剤が好ましい。 Examples of the surfactant include various anionic surfactants, nonionic surfactants, cationic surfactants, amphoteric surfactants and the like, and among these, anionic surfactants, nonionic surfactants Activators are preferred.
　アニオン性界面活性剤としては、例えば、アルキルベンゼンスルホン酸塩、アルキルフェニルスルホン酸塩、アルキルナフタレンスルホン酸塩、高級脂肪酸塩、高級脂肪酸エステルの硫酸エステル塩、高級脂肪酸エステルのスルホン酸塩、高級アルコールエーテルの硫酸エステル塩及びスルホン酸塩、高級アルキルスルホコハク酸塩、ポリオキシエチレンアルキルエーテルカルボン酸塩、ポリオキシエチレンアルキルエーテル硫酸塩、アルキルリン酸塩、ポリオキシエチレンアルキルエーテルリン酸塩等が挙げられ、これらの具体例として、ドデシルベンゼンスルホン酸塩、イソプロピルナフタレンスルホン酸塩、モノブチルフェニルフェノールモノスルホン酸塩、モノブチルビフェニルスルホン酸塩、ジブチルフェニルフェノールジスルホン酸塩などを挙げることができる。 As the 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. Specific examples of these include dodecyl benzene sulfonate, isopropyl naphthalene sulfonate, monobutyl phenyl phenol mono sulfonate, mono butyl biphenyl sulfonate, dibutyl phenyl phenol disulf Such as phosphate salt can be mentioned.
　ノニオン性界面活性剤としては、例えば、ポリオキシエチレンアルキルエーテル、ポリオキシエチレンアルキルフェニルエーテル、ポリオキシエチレン脂肪酸エステル、ソルビタン脂肪酸エステル、ポリオキシエチレンソルビタン脂肪酸エステル、ポリオキシエチレンソルビトール脂肪酸エステル、グリセリン脂肪酸エステル、ポリオキシエチレングリセリン脂肪酸エステル、ポリグリセリン脂肪酸エステル、ショ糖脂肪酸エステル、ポリオキシエチレンアルキルアミン、ポリオキシエチレン脂肪酸アミド、脂肪酸アルキロールアミド、アルキルアルカノールアミド、アセチレングリコール、アセチレングリコールのオキシエチレン付加物、ポリエチレングリコールポリプロピレングリコールブロックコポリマー等を使用することができる。なかでも前記ノニオン性界面活性剤としては、ポリオキシエチレンノニルフェニルエーテル、ポリオキシエチレンオクチルフェニルエーテル、ポリオキシエチレンドデシルフェニルエーテル、ポリオキシエチレンアルキルエーテル、ポリオキシエチレン脂肪酸エステル、ソルビタン脂肪酸エステル、ポリオキシエチレンソルビタン脂肪酸エステル、脂肪酸アルキロールアミド、アセチレングリコール、アセチレングリコールのオキシエチレン付加物、ポリエチレングリコールポリプロピレングリコールブロックコポリマーを使用することが好ましい。なかでも、前記ノニオン性界面活性剤としては、アセチレングリコール、アセチレングリコールのオキシエチレン付加物を使用することが、被記録媒体（Ｚ）の前記層（ｚ２）に対するインクジェット記録用インクの液滴の接触角が小さくなり、被記録媒体（Ｚ）の表面でインクが濡れ広がりやすくなり、その結果、白スジのないレベリング性が良好な印刷物を得られるためより好ましい。 As a 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 usedAmong them, as the nonionic surfactant, polyoxyethylene nonyl phenyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene dodecyl phenyl ether, polyoxyethylene alkyl ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, polyoxy acid Preference is given to using ethylene sorbitan fatty acid esters, fatty acid alkylolamides, acetylene glycols, oxyethylene adducts of acetylene glycols, polyethylene glycol polypropylene glycol block copolymers. Among them, 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.
　その他の界面活性剤としては、ポリシロキサンオキシエチレン付加物のようなシリコーン系界面活性剤；パーフルオロアルキルカルボン酸塩、パーフルオロアルキルスルホン酸塩、オキシエチレンパーフルオロアルキルエーテルのようなフッ素系界面活性剤；スピクリスポール酸、ラムノリピド、リゾレシチンのようなバイオサーファクタント等も使用することができる。 Other 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.
　前記界面活性剤としては、水を主溶媒とする水性インクに前記界面活性剤が溶解した状態を安定的に維持するうえで、ＨＬＢが４～２０の範囲であるものを使用することが好ましい。 In order to stably maintain the state in which the surfactant is dissolved in an aqueous ink containing water as a main solvent, it is preferable to use one having an HLB in the range of 4 to 20 as the surfactant.
　前記界面活性剤としては、前記水性インクの全量に対し、０．００１質量％～２質量％の範囲で使用することが好ましく、０．００１質量％～１．５質量％の範囲で使用することがより好ましく、０．５質量％～１．５質量％の範囲で使用することが好ましい。上記範囲の前記界面活性剤を含有するインクジェットインクは、吐出液滴の段ボール（Ａ）表面での濡れ性良好であり、段ボール（Ａ）上で十分な濡れ広がりを有し、印刷物のスジ発生を防止する効果を奏するうえで好ましい。 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.
　また、前記水性インクに使用可能な湿潤剤としては、水性インクの乾燥を防止することを目的として使用することができる。湿潤剤は、前記水性インクの全量に対して３質量％～５０質量％の範囲で使用することが好ましい。 Moreover, as 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.
　湿潤剤としては、水との混和性がありインクジェットヘッドの吐出口の閉塞防止効果が得られるものが好ましく、例えば、エチレングリコール、ジエチレングリコール、トリエチレングリコール、分子量２０００以下のポリエチレングリコール、ジプロピレングリコール、トリプロピレングリコール、イソプロピレングリコール、イソブチレングリコール、１，４－ブタンジオール、１，３－ブタンジオール、１，５－ペンタンジオール、１，６－ヘキサンジオール、メソエリスリトール、ペンタエリスリトール等が挙げられる。 As 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. For example, 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.
　前記任意成分に使用可能な浸透剤としては、例えばエタノール、イソプロピルアルコール等の低級アルコール、エチレングリコールヘキシルエーテルやジエチレングリコールブチルエーテル等のアルキルアルコールのエチレンオキシド付加物やプロピレングリコールプロピルエーテル等のアルキルアルコールのプロピレンオキシド付加物等が挙げられる。前記浸透剤の含有量は、水性インクの全量に対して３質量％以下であることが好ましく、１質量％以下であることがより好ましく、実質的に含有しないことがさらに好ましい。 Examples of 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.
（水性インクの製造方法）
　水性インクは、例えばバインダー樹脂、尿素結合を有する化合物、水性媒体、色材及び必要に応じて前記界面活性剤や有機溶剤（Ｆ）などの任意成分を混合することによって製造することができる。 (Method of producing water-based 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).
　前記混合の際には、例えば、ビーズミル、超音波ホモジナイザー、高圧ホモジナイザー、ペイントシェーカー、ボールミル、ロールミル、サンドミル、サンドグラインダー、ダイノーミル、ディスパーマット、ＳＣミル、ナノマイザー等の分散機を使用することができる。 In the mixing, for example, 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.
　前記水性インクの製造方法としては、より具体的にはバインダー樹脂、尿素結合を有する化合物、水性媒体、色材及び必要に応じて前記界面活性剤や有機溶剤（Ｆ）などの任意成分を、一括して混合し、攪拌などすることによって製造する方法が挙げられる。 More specifically, 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.
　また、前記とは別の水性インクの製造方法としては、例えば＜１＞前記ポリマー（Ｇ）等の顔料分散剤と、前記顔料等の色材と必要に応じて溶媒等とを混合することで色材を高濃度で含有する色材分散体ａを製造する工程、＜２＞前記尿素結合を有する化合物と必要に応じて溶媒とを混合することによって組成物ｂを製造する工程、＜３＞前記バインダー樹脂と前記水性媒体等とを含有する組成物ｃを製造する工程、ならびに、＜４＞前記色材分散体ａと前記組成物ｂと前記組成物ｃとを混合する工程を経ることによって製造する方法が挙げられる。 In addition, as a method of producing an aqueous ink different from the above, 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.
　前記方法で得られた水性インクは、必要に応じて遠心分離処理や濾過処理を行うことが、水性インク中に混入した不純物を除去するうえで好ましい。 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.
　本発明の水性インクのｐＨは、水性インクの保存安定性及び吐出安定性を向上させ、インク非吸収性または難吸収性の段ボール（Ａ）に印刷した際の濡れ広がり、印字濃度、耐擦過性を向上させるうえで、好ましくは７．０以上、より好ましくは７．５以上、更により好ましくは８．０以上である。前記水性インクのｐＨの上限は、水性インクの塗布または吐出装置を構成する部材（例えば、インク吐出口、インク流路等）の劣化を抑制し、かつ、インクが皮膚に付着した場合の影響を小さくするうえで、好ましくは１１．０以下、より好ましくは１０．５以下、更により好ましくは１０．０以下である。 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.
　以下、本発明を実施例によってさらに詳細に説明する。 Hereinafter, the present invention will be described in more detail by way of examples.
（ポリマー（Ｐ－１）の調製方法）
（合成例１）
　ＢｕＬｉのヘキサン溶液と、スチレンを予めテトラヒドロフランに溶解したスチレン溶液とを図３に示すチューブリアクターＰ１及びＰ２から、Ｔ字型マイクロミキサーＭ１に導入し、リビングアニオン重合させることによって重合体を得た。 (Method of preparing polymer (P-1))
Synthesis Example 1
A hexane solution of BuLi and a styrene solution in which styrene was previously dissolved in tetrahydrofuran were introduced from the tube reactors P1 and P2 shown in FIG. 3 into a T-shaped micromixer M1 and living anion polymerization was performed to obtain a polymer.
　次に、前記工程で得られた重合体を図３に示すチューブリアクターＲ１を通じてＴ字型マイクロミキサーＭ２に移動させ、前記重合体の成長末端を、チューブリアクターＰ３から導入した反応調整剤（α－メチルスチレン（α－ＭｅＳｔ））によりトラップした。 Next, 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 (α-MeSt)).
　次いで、ｔｅｒｔ－ブチルメタクリレートを予めテトラヒドロフランに溶解したｔｅｒｔ－ブチルメタクリレート溶液を図３に示すチューブリアクターＰ４からＴ字型マイクロミキサーＭ３に導入し、チューブリアクターＲ２を通じて移動させた前記トラップされた重合体と、連続的なリビングアニオン重合反応を行った。その後、メタノールを供給することによって前記リビングアニオン重合反応をクエンチすることによってブロック共重合体（ＰＡ－１）組成物を製造した。 Then, 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.
　前記ブロック共重合体（ＰＡ－１）組成物を製造する際、図３に示すマイクロリアクター全体を恒温槽に埋没させることで、反応温度を２４℃に設定した。 When the block copolymer (PA-1) composition was produced, the reaction temperature was set to 24 ° C. by immersing the entire microreactor shown in FIG. 3 in a constant temperature bath.
　前記方法で得られたブロック共重合体（ＰＡ－１）を構成するモノマーのモル比は、（ＢｕＬｉ／スチレン／α－メチルスチレン／ｔｅｒｔ－ブチルメタクリレート）＝１．０／１２．０／１．３／８．１であった。 The molar ratio of the monomers constituting the block copolymer (PA-1) obtained by the above method is (BuLi / styrene / α-methylstyrene / tert-butyl methacrylate) = 1.0 / 12.0 / 1. It was 3 / 8.1.
　得られたブロック共重合体（ＰＡ－１）組成物を、陽イオン交換樹脂で処理することで加水分解した後、減圧下で留去し、得られた固体を粉砕することによって、粉状のポリマー（Ｐ－１）を得た。 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.
　得られたポリマー（Ｐ－１）の物性値は以下のように測定した。 Physical properties of the obtained polymer (P-1) were measured as follows.
（数平均分子量（Ｍｎ）の測定方法）
　ゲル・パーミエーション・クロマトグラフィー（ＧＰＣ）法により、下記の条件で測定した。 (Method of measuring number average molecular weight (Mn))
It measured on condition of the following by gel permeation chromatography (GPC) method.
測定装置：高速ＧＰＣ装置（東ソー株式会社製「ＨＬＣ－８２２０ＧＰＣ」）
カラム：東ソー株式会社製の下記のカラムを直列に接続して使用した。 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.
　「ＴＳＫｇｅｌ　Ｇ５０００」（７．８ｍｍＩ．Ｄ．×３０ｃｍ）×１本
　「ＴＳＫｇｅｌ　Ｇ４０００」（７．８ｍｍＩ．Ｄ．×３０ｃｍ）×１本
　「ＴＳＫｇｅｌ　Ｇ３０００」（７．８ｍｍＩ．Ｄ．×３０ｃｍ）×１本
　「ＴＳＫｇｅｌ　Ｇ２０００」（７．８ｍｍＩ．Ｄ．×３０ｃｍ）×１本
検出器：ＲＩ（示差屈折計）
カラム温度：４０℃
溶離液：テトラヒドロフラン
流速：１．０ｍＬ／分
注入量：１００μＬ（試料濃度０．４質量％のテトラヒドロフラン溶液）
標準試料：下記の標準ポリスチレンを用いて検量線を作成した。 "TSKgel 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 This "TSKgel G2000" (7.8 mm ID × 30 cm) × 1 detector: RI (differential refractometer)
Column temperature: 40 ° C
Eluent: Tetrahydrofuran Flow rate: 1.0 mL / min Injection volume: 100 μL (tetrahydrofuran solution with a sample concentration of 0.4% by mass)
Standard sample: A calibration curve was prepared using the following standard polystyrene.
（標準ポリスチレン）
　東ソー株式会社製「ＴＳＫｇｅｌ　標準ポリスチレン　Ａ－５００」
　東ソー株式会社製「ＴＳＫｇｅｌ　標準ポリスチレン　Ａ－１０００」
　東ソー株式会社製「ＴＳＫｇｅｌ　標準ポリスチレン　Ａ－２５００」
　東ソー株式会社製「ＴＳＫｇｅｌ　標準ポリスチレン　Ａ－５０００」
　東ソー株式会社製「ＴＳＫｇｅｌ　標準ポリスチレン　Ｆ－１」
　東ソー株式会社製「ＴＳＫｇｅｌ　標準ポリスチレン　Ｆ－２」
　東ソー株式会社製「ＴＳＫｇｅｌ　標準ポリスチレン　Ｆ－４」
　東ソー株式会社製「ＴＳＫｇｅｌ　標準ポリスチレン　Ｆ－１０」
　東ソー株式会社製「ＴＳＫｇｅｌ　標準ポリスチレン　Ｆ－２０」
　東ソー株式会社製「ＴＳＫｇｅｌ　標準ポリスチレン　Ｆ－４０」
　東ソー株式会社製「ＴＳＫｇｅｌ　標準ポリスチレン　Ｆ－８０」
　東ソー株式会社製「ＴＳＫｇｅｌ　標準ポリスチレン　Ｆ－１２８」
　東ソー株式会社製「ＴＳＫｇｅｌ　標準ポリスチレン　Ｆ－２８８」
　東ソー株式会社製「ＴＳＫｇｅｌ　標準ポリスチレン　Ｆ－５５０」 (Standard polystyrene)
Tosoh Corporation "TSKgel standard polystyrene A-500"
Tosoh Corporation "TSKgel standard polystyrene A-1000"
Tosoh Corporation "TSKgel standard polystyrene A-2500"
Tosoh Corporation "TSKgel standard polystyrene A-5000"
Tosoh Corporation "TSKgel standard polystyrene F-1"
Tosoh Corporation "TSKgel standard polystyrene F-2"
Tosoh Corporation "TSKgel standard polystyrene F-4"
Tosoh Corporation "TSKgel standard polystyrene F-10"
Tosoh Corporation "TSKgel standard polystyrene F-20"
Tosoh Corporation "TSKgel standard polystyrene F-40"
Tosoh Corporation "TSKgel standard polystyrene F-80"
Tosoh Corporation "TSKgel standard polystyrene F-128"
Tosoh Corporation "TSKgel standard polystyrene F-288"
Tosoh Corporation "TSKgel standard polystyrene F-550"
（酸価の測定方法）
　ＪＩＳ試験方法Ｋ　００７０－１９９２に準拠して測定した。テトラヒドロフランに試料０．５ｇを溶解させ、フェノールフタレインを指示薬として、０．１Ｍ水酸化カリウムアルコール溶液で滴定することにより求めた。 (Method of measuring acid number)
It measured based on JIS test method K 0070-1992. A sample of 0.5 g was dissolved in tetrahydrofuran and determined by titration with a 0.1 M potassium hydroxide alcohol solution using phenolphthalein as an indicator.
（水への溶解度の測定方法）
　目開き２５０μｍおよび９０μｍの篩を用い２５０μｍ～９０μｍの範囲に粒子径を整えたポリマー０．５ｇを、４００メッシュの金網を加工して得た袋に封入したものを試験片（Ｍ）とした。次に、前記試験片（Ｍ）を水５０ｍｌに浸漬し、２５℃の温度下で２４時間緩やかに攪拌しながら放置した。２４時間後、前記試験片（Ｍ）を１１０℃に設定した乾燥機で２時間乾燥させた。前記試験片（Ｍ）を水に浸漬する前後の質量の変化を測定し、次式により溶解度を算出した。 (Method of measuring solubility in water)
A test piece (M) was obtained by sealing 0.5 g of a polymer whose particle diameter was adjusted in the range of 250 μm to 90 μm using sieves with openings of 250 μm and 90 μm, and sealing it in a bag obtained by processing a 400 mesh wire mesh. Next, 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.
　溶解度（ｇ／１００ｍｌ）＝［（水に浸漬する前の試験片（Ｍ）の質量（ｇ））－（水に浸漬した後の試験片（Ｍ）の質量（ｇ））］×２ 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
（水中での微粒子形成の判断方法および平均粒子径（ｎｍ）の測定方法））
（１）前記酸価の測定方法に従い、ポリマーの酸価を求めた。
（２）水５０ｍｌに対して、ポリマーを１ｇ添加後、上記（１）で得たポリマーの酸価を１００％中和するだけの０．１ｍｏｌ／Ｌ水酸化カリウム水溶液を加え、１００％中和とした。
（３）１００％中和させた液を、２５℃の温度下で、２時間超音波洗浄機（株式会社エスエヌディ超音波洗浄器ＵＳ－１０２、３８ｋＨｚ自励発信）中で超音波を照射し分散させた後、２４時間室温で放置した。 (Method for judging formation of fine particles in water and measuring method for average particle size (nm))
(1) The acid value of the polymer was determined according to the method for measuring the acid value.
(2) To 50 ml of water, after adding 1 g of a polymer, add a 0.1 mol / L aqueous potassium hydroxide solution that only neutralizes 100% of the acid value of the polymer obtained in (1) above, and neutralize 100%. And
(3) 100% neutralized solution is dispersed at a temperature of 25 ° C. for 2 hours in an ultrasonic cleaner (SSN Corporation ultrasonic cleaner US-102, 38 kHz self-excited transmission) for dispersion The mixture was allowed to stand at room temperature for 24 hours.
　前記放置して得た液の、液面から２センチメートルの深さにある液をサンプル液として、動的光散乱式粒子径分布測定装置（日機装株式会社製、動的光散乱式粒子径測定装置「マイクロトラック粒度分布計ＵＰＡ－ＳＴ１５０」）を用い、粒子の光散乱情報から微粒子形成の有無を確認し、微粒子が存在する場合はその体積平均粒子径を測定した。 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.
（表面張力の測定方法）
　前記水中での微粒子形成の判断方法で得たサンプル液と同様のサンプル液を、ウィルヘルミ表面張力計を用い測定した値とした。 (Method of measuring surface tension)
The same sample solution as the sample solution obtained by the method for determining the formation of fine particles in water was taken as a value measured using a Wilhelmy surface tension meter.
　前記合成例で得られたポリマーの原料、反応条件、物性値を表１に示す。 Table 1 shows the raw materials, reaction conditions, and physical properties of the polymer obtained in the synthesis example.
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
　表１中、ＢｕＬｉはノルマルブチルリチウムを表し、Ｓｔはスチレンを表し、ＤＰＥは１，１－ジフェニルエチレンを表し、α－ＭｅＳｔはαメチルスチレンを表し、
ｔＢＭＡはメタクリル酸ｔｅｒｔ－ブチルを表す。 In Table 1, BuLi represents normal butyl lithium, St represents styrene, DPE represents 1,1-diphenylethylene, and α-MeSt represents α-methylstyrene.
tBMA represents tert-butyl methacrylate.
（製造例１　水性顔料分散体（Ｙ）の調製）
　顔料としてフタロシアニン系顔料ファストゲンブルーＰｉｇｍｅｎｔ（ＤＩＣ（株）製：Ｃ．Ｉ．ピグメント１５：３）を１５０質量部、ポリマー（Ｐ－１）を４５質量部、トリエチレングリコールを１５０質量部、３４質量％水酸化カリウム水溶液２０質量部を、１．０Ｌのインテンシブミキサー（日本アイリッヒ株式会社）に仕込み、ローター周速２．９４ｍ／ｓ、パン周速１ｍ／ｓで、２５分間混練した。　次に、前記インテンシブミキサー容器内の混練物に、撹拌を継続しながら、分散媒（ｉ）としてイオン交換水４５０質量部を徐々に加えた後、分散媒（ｉｉ）としてイオン交換水１８５質量部をさらに加え混合することによって、顔料濃度１５質量％の水性顔料分散体（Ｙ）を得た。 Production Example 1 Preparation of Aqueous Pigment Dispersion (Y)
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. Next, 450 parts by mass of ion exchange water is gradually added as a dispersion medium (i) to the kneaded material in the intensive mixer container while continuing stirring, and then 185 parts by mass of ion exchange water as a dispersion medium (ii) Were further added and mixed to obtain an aqueous pigment dispersion (Y) having a pigment concentration of 15% by mass.
（バインダー樹脂の調製）
　攪拌機、温度計、冷却管、窒素導入管を装備した４つ口のフラスコに、「ニューコール７０７ＳＦ」（日本乳化剤(株)製アニオン性乳化剤）１６ｇ、「ノイゲンＴＤＳ－２００Ｄ」（第一工業製薬(株)製ノニオン性乳化剤）６．５ｇおよび脱イオン水２２０ｇを仕込み、窒素気流下に８０℃に昇温した後、過硫酸アンモニウム０．８ｇを脱イオン水１６ｇに溶解させた水溶液を添加した。さらに２－エチルヘキシルアクリレート６０ｇ、スチレン１００ｇ、メタクリル酸メチル２７ｇ、アクリルアミド３ｇ、メタクリル酸６ｇの混合液を、３時間かけて滴下した。滴下終了後、２時間反応せしめた後、２５℃まで冷却し、２８質量％アンモニア水１．５ｇで中和せしめ、脱イオン水を加えることによって、ガラス転移温度（Ｔｇ）３５℃、平均粒子径５０ｎｍのアクリル系樹脂水分散液（Ｘ－１）を得た。アクリル系樹脂分散液（Ｘ－１）の最終固形分濃度は３９質量％であった。 (Preparation of binder resin)
A four-necked flask equipped with a stirrer, thermometer, cooling pipe, and nitrogen introduction pipe, 16 g of "Nyukol 707SF" (Nippon Emulsifier Co., Ltd. anionic surfactant), "Nuygen TDS-200D" After charging 6.5 g of nonionic emulsifier (manufactured by KK Co., Ltd.) and 220 g of deionized water and raising the temperature to 80 ° C. under a nitrogen stream, an aqueous solution in which 0.8 g of ammonium persulfate was dissolved in 16 g of deionized water was added. Further, a mixed solution of 60 g of 2-ethylhexyl acrylate, 100 g of styrene, 27 g of methyl methacrylate, 3 g of acrylamide and 6 g of methacrylic acid was dropped over 3 hours. After completion of the addition, the mixture is reacted for 2 hours, cooled to 25 ° C., neutralized with 1.5 g of 28 mass% ammonia water, and added with deionized water to have a glass transition temperature (Tg) of 35 ° C., average particle size An acrylic resin aqueous dispersion (X-1) of 50 nm was obtained. The final solid content concentration of the acrylic resin dispersion liquid (X-1) was 39% by mass.
（水性インクの調製）
　水性顔料分散体（Ｙ）を３７．９ｇに、ＭＢ（（株）ダイセル製３－メトキシ－１－ブタノール）６．０ｇ、プロピレングリコール８．０ｇ、グリセリン９．０ｇ、トリエチレングリコール０．４７ｇ、ＳＣ－Ｐ１０００（阪本薬品工業（株）製ポリオキシプロピレン（１４）ポリグリセルエーテル）２．０ｇ、エチレン尿素５．６２ｇ、トリエタノールアミン０．２ｇ、ＳＵＲＦＹＮＯＬ　１０４ＰＧ５０（エアープロダクツ社製アセチレンジアルコール系界面活性剤）１．６ｇ、ＴＥＧＯ　Ｗｅｔ　ＫＬ２４５（巴工業（株）製、ポリエーテル変性シロキサンコポリマー）０．０１２ｇ、ＡＣＴＩＣＩＤＥ　Ｂ－２０（ソー・ジャパン（株）製、防腐剤）、ボンコートＣＭ－８４３０（ＤＩＣ（株）製、アクリル系樹脂）水溶液１３．６１ｇ、イオン交換水１５．４９ｇを加えて攪拌し、水性インク（Ｙ１）を得た。 (Preparation of water-based ink)
37.9 g of an aqueous pigment dispersion (Y), 6.0 g of MB (3-methoxy-1-butanol manufactured by Daicel Corporation), 8.0 g of propylene glycol, 9.0 g of glycerin, 0.47 g of triethylene glycol, SC-P1000 (Sakamoto Yakuhin Kogyo Co., Ltd. product polyoxypropylene (14) polyglycer ether) 2.0 g, ethylene urea 5.62 g, triethanolamine 0.2 g, SURFYNOL 104 PG 50 (air products, acetylene dialcohol system interface Activator: 1.6 g, TEGO Wet KL 245 (manufactured by Sakai Industry Co., Ltd., polyether-modified siloxane copolymer) 0.012 g, ACTICIDE B-20 (manufactured by So Japan Co., Ltd., preservative), Bon coat CM-8430 ( 13.61 g of an aqueous solution of an acrylic resin manufactured by DIC Corporation, 15.49 g of ion exchanged water was added and stirred to obtain an aqueous ink (Y1).
（実施例１）
　京セラ株式会社製インクジェットヘッドＫＪ４Ｂ－ＹＨに、水性インク（Ｙ１）を充填し、ヘッドノズルプレート面からのインクサブタンクの水頭差を＋３５ｃｍ、負圧－５．０ｋＰａに設定することで供給圧を調整した。また、インクジェットヘッドのインク吐出口を有する面（ｘ）から、前記面（ｘ）に対して仮定した垂線と、段ボールとが交わる位置（ｙ）までの距離（ギャップ）は２ｍｍに設定した。 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. . In addition, 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.
　段ボールとしては、吸水量５ｇ／ｍ２の層を備えたライナーを片面に有する全厚３ｍｍのＢフルートタイプを使用した。 As the cardboard, 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.
　前記インクジェットヘッドの駆動条件を、インクジェットヘッドの標準電圧及び標準温度とし、水性インクの液滴サイズを１８ｐＬに設定した。 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.
　前記した条件のもと、前記インクジェットヘッドを備えたプリンターを用いて、前記段ボールの層に相当する面に、６００×６００ｄｐｉでベタ印刷を行った。 Under the conditions described above, 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.
　上記印刷直後の段ボールの印刷面に、段ボールの搬送方向に対して９０°、印刷面に対しては垂直から６０°の角度で、送風の温度が４０℃及び送風速度が５ｍ／ｓとなるように送風した。送風時間は１秒とした。また、前記送風と同時に、赤外線（ヘレウス社製ＺＫＢ１２００/３４０Ｇ、カーボンヒーター１０００Ｗ×７本、出力１００％）を用い、前記印刷面の垂直方向の距離１００ｍｍの位置から加熱した。加熱、乾燥時間は１秒間、乾燥時の印刷面の温度は６０℃であった。 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. At the same time as the air blowing, infrared rays (ZKB1200 / 340G manufactured by Heraeus, carbon heaters 1000W × 7, output 100%) were used to heat from a position at a distance of 100 mm in the vertical direction of the printing surface. The heating and drying time was 1 second, and the temperature of the printing surface at the time of drying was 60.degree.
（実施例２）
　実施例１で行った送風の温度を常温とした以外は、実施例１と同様の方法で、印刷物を得た。乾燥時の印刷面の温度は６０℃であった。 (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.
（実施例３）
　実施例１で行った送風の温度を常温とし、かつ、送風時間を３０秒とし、かつ、赤外線を用いた加熱を行わなかったこと以外は、実施例１と同様の方法で印刷物を得た。 (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.
（実施例４）
　段ボールとして、吸水量１０ｇ／ｍ２の層を備えたライナーを片面に有する全厚５ｍｍのＡフルートタイプを使用した以外は、実施例１と同様にして、印刷・乾燥を行った。 (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.
（実施例５）
　段ボールとして、吸水量１０ｇ／ｍ２の層を備えたライナーを片面に有する全厚５ｍｍのＡフルートタイプを使用した以外は、実施例２と同様にして、印刷・乾燥を行った。 (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.
（実施例６）
段ボールとして、吸水量１０ｇ／ｍ２の層を備えたライナーを片面に有する全厚５ｍｍのＡフルートタイプを使用した以外は、実施例３と同様にして、印刷・乾燥を行った。 (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.
（比較例１）
　乾燥手段を赤外線のみとして送風を行わなかったこと以外は、実施例１と同様の方法で印刷物を得た。 (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.
（比較例２）
　送風工程を行わず、無風の環境下で自然乾燥を３０秒間行ったこと以外は、実施例１と同様の方法で印刷物を得た。 (Comparative 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.
（比較例３）
　乾燥手段を赤外線のみとして送風を行わなかったこと以外は、実施例４と同様の方法で印刷物を得た。 (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.
（比較例４）
　送風工程を行わず、無風の環境下で自然乾燥を３０秒間行ったこと以外は、実施例４と同様の方法で印刷物を得た。 (Comparative 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.
　印刷物の（１）段ボールのフルートに起因した色ムラ、（２）モットリング（まだら模様の色ムラ）の有無を目視で評価した。また、（３）乾燥のしやすさや印刷物の生産効率の指標となるタック性は、前記乾燥直後の印刷物、及び、乾燥後３０秒間放置した後の印刷物の表面を、それぞれ不織布で１０回擦った際に、不織布にインクが付着したか否かを目視で評価した。 The presence or absence of (1) color unevenness due to the flute of the corrugated paper and (2) mottling (color unevenness of mottled pattern) was visually evaluated. In addition, (3) the ease of drying and tackiness, which is an index of the production efficiency of printed matter, were 10 times each of the printed matter immediately after the drying and the surface of the printed matter after leaving for 30 seconds after drying rubbed with nonwoven fabric. At that time, it was visually evaluated whether the ink adhered to the non-woven fabric.
　（１）色ムラ
　○；フルートに起因した色ムラを確認できなかった。
　△；フルートに起因した色ムラをわずかに確認できたが、実用上許容されるレベルのものであった。
　×；フルートに起因した色ムラを確認することができた。
　（２）モットリング
　○；モットリングを確認できなかった。
　△；モットリングをわずかに確認できたが、実用上許容されるレベルのものであった。　×；モットリングを確認することができた。 (1) Uneven color 色; Uneven color due to the flute could not be confirmed.
Δ: Slight unevenness in color caused by the flute was confirmed, but at a practically acceptable level.
×: Uneven color due to the flute could be confirmed.
(2) Mottling ○: Mottling could not be confirmed.
Δ: Mottling was slightly confirmed, but at a practically acceptable level. X: Mottling could be confirmed.
（３）タック性
　○；不織布にインクが付着していなかった
　△；不織布に僅かにインクが付着していたものの、実用上許容されるレベルのものであった。 (3) Tackability ;; no ink adhered to non-woven fabric △; ink slightly adhered to non-woven fabric, but at a practically acceptable level.
　×；不織布にインクが付着していた。 ×: Ink adhered to the non-woven fabric.
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000005
　実施例１、２及び３で示すとおり、印刷物の色ムラの発生防止には、印刷面に送風することが効果的であった。また、実施例１で示すとおり、前記送風温度は、４０℃とした方が、タック性が軽減し、乾燥時間を短縮することができた。また、実施例１及び２で示すとおり、前記送風工程とともに赤外線による加熱乾燥工程を採用することで、印刷物のモットリングを軽減することができた。一方、比較例１で示すとおり、送風工程を採用せず、赤外線による加熱乾燥のみでは、印刷物に色ムラが発生し、乾燥直後にはタック性が残った。また、比較例２で示すとおり、送風工程を採用せず自然乾燥のみの場合には、モットリング発生、タック性悪化により乾燥時間が長くなる傾向となるため、印刷物の生産性を低下させた。 As shown in Examples 1, 2 and 3, in order to prevent the occurrence of color unevenness in the printed matter, it was effective to blow air on the printing surface. In addition, as shown in Example 1, when the air blowing temperature was 40 ° C., the tackiness was reduced and the drying time could be shortened. In addition, as shown in Examples 1 and 2, 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. On the other hand, as shown in 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. Further, as shown in 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.
　また比較例３及び４で示すとおり、送風工程を採用しない場合には、吸水量の比較的大きい段ボールにおいて色ムラやモットリングが発生し、タック性が残った。実施例４，５，６に示すように、印刷面に送風することで色ムラの発生が抑制され、モットリングの発生が抑制され、タック性が軽減された。 In addition, as shown in Comparative Examples 3 and 4, when the air blowing step was not employed, color unevenness and mottling occurred in a cardboard having a relatively large amount of water absorption, and tackiness remained. As shown in Examples 4, 5 and 6, by blowing air to the printing surface, the occurrence of color unevenness was suppressed, the occurrence of mottling was suppressed, and the tackiness was reduced.
　したがって、波型に形成された中芯の少なくとも片面にライナーが形成され、かつライナーの上に吸水量が１５ｇ／ｍ２以下である層を有する段ボールに対して水性インクでインクジェット印刷を施した後に乾燥させる場合に、スジ状のムラの無い意匠性に優れた印刷面を得るためには、印刷面に送風する工程が必須であり、さらには良好な乾燥性及び印刷物の良好な生産性を得るうえで赤外線乾燥の併用が有効であることがわかった。なお、前記乾燥性が良好であることは、前記乾燥時間をより短縮できることを指し、前記生産性が良好であることは、前記乾燥時間を短縮できることによって印刷物の生産効率を向上できることを指す。 Therefore, after 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 In the case of drying, in order to obtain a printing surface excellent in design without streaky unevenness, 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. In addition, 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.
１：Ｔ字型マイクロミキサーＭ１
２：Ｔ字型マイクロミキサーＭ２
３：Ｔ字型マイクロミキサーＭ３
４：チューブリアクターＲ１
５：チューブリアクターＲ２
６：チューブリアクターＲ３
７：プレクーリングの為のチューブリアクターＰ１
８：プレクーリングの為のチューブリアクターＰ２
９：プレクーリングの為のチューブリアクターＰ３
１０：プレクーリングの為のチューブリアクターＰ４
１１：吸水量１５ｇ／ｍ２以下の層（ａ）とライナーとの積層
１２：フルート
１３：印刷物
１４：印刷面
１５：スジ状の色ムラ 1: 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

Claims (10)

  1. 吸水量１５ｇ／ｍ２以下の層（ａ）を有する段ボール（Ａ）に、水性インクで印刷を施した後、印刷面に送風する工程［１－１］を含む工程［１］を経ることによって前記水性インクを乾燥させることを特徴とする印刷物の製造方法。 After performing printing with a water-based ink on a cardboard (A) having a layer (a) having a water absorption of 15 g / m 2 or less, by passing through the step [1-1] including blowing the printing surface A method of producing a printed matter, comprising drying the aqueous ink.
  2. 前記段ボール（Ａ）が、フルートの少なくとも一方の面にライナーを有し前記ライナーの表面に前記層（ａ）を有するもの、または、前記フルートの少なくとも一方の面にライナーとして前記層（ａ）を有するものである請求項１に記載の印刷物の製造方法。 The corrugated cardboard (A) has a liner on at least one surface of a flute and the layer (a) on the surface of the liner, or the layer (a) as a liner on at least one surface of the flute The manufacturing method of the printed matter of Claim 1 which has.
  3. 前記層（ａ）が炭酸カルシウムを含有する層である請求項１または２に記載の印刷物の製造方法。 The method for producing a printed matter according to claim 1 or 2, wherein the layer (a) is a layer containing calcium carbonate.
  4. 前記工程［１－１］における送風温度が２０℃～１４０℃の範囲であり、送風速度が０．１ｍ／ｓ～２０ｍ／ｓの範囲である請求項１～３のいずれか１項に記載の印刷物の製造方法。 The blowing temperature in the step [1-1] is in the range of 20 ° C. to 140 ° C., and the blowing speed is in the range of 0.1 m / s to 20 m / s. Production method of printed matter.
  5. 前記工程［１］が、前記工程［１－１］とは別の加熱工程［１－２］を含む工程である請求項１～４のいずれか１項に記載の印刷物の製造方法。 5. The method for producing a printed matter according to any one of claims 1 to 4, wherein the step [1] includes a heating step [1-2] different from the step [1-1].
  6. 前記加熱工程［１－２］が、輻射熱を用いた加熱工程である請求項５に記載の印刷物の製造方法。 The method for producing a printed matter according to claim 5, wherein the heating step [1-2] is a heating step using radiant heat.
  7. 前記輻射熱を用いた加熱工程が、波長０．７μｍ～１０００μｍの範囲の赤外線を用いた加熱工程である請求項６に記載の印刷物の製造方法。 7. The method for producing a printed matter according to claim 6, wherein the heating step using the radiant heat is a heating step using an infrared ray having a wavelength of 0.7 μm to 1000 μm.
  8. 前記段ボール（Ａ）が有する前記層（ａ）に前記水性インクを印刷する方法が、インクジェット記録装置を用いた印刷方法である請求項１～７のいずれか１項に記載の印刷物の製造方法。 The method for producing a printed matter according to any one of claims 1 to 7, wherein the method of printing the aqueous ink on the layer (a) of the corrugated cardboard (A) is a printing method using an inkjet recording device.
  9. 前記インクジェット記録装置を用いた印刷方法が、インクジェットヘッドのインク吐出口を有する面（ｘ）から、前記面（ｘ）の垂線と前記段ボール（Ａ）とが交わる位置（ｙ）までの距離が１ｍｍ以上である構成を備えたインクジェット記録装置を用いた印刷方法である請求項８に記載の印刷物の製造方法。 The printing method using the ink jet recording apparatus has a distance of 1 mm from the surface (x) of the ink jet head having the ink discharge port to the position (y) where the perpendicular line of the surface (x) intersects with the cardboard (A). The method for producing a printed matter according to claim 8, which is a printing method using an inkjet recording apparatus having the above-described configuration.
  10. 前記水性インクが、粘度２ｍＰａ・ｓ～２０ｍＰａ・ｓの範囲で、かつ、表面張力２０ｍＮ／ｍ～４０ｍＮ／ｍの範囲である請求項１～９のいずれか１項に記載の印刷物の製造方法。 The method for producing a printed matter according to any one of claims 1 to 9, wherein the aqueous ink has a viscosity of 2 mPa · s to 20 mPa · s and a surface tension of 20 mN / m to 40 mN / m.
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