JP2006089694A - Ink composition and inkjet recording method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an ink composition capable of improving charge density per unit volume of ink particles, having sufficiently rapid electrophoresis rate of ink particles in a discharge part in an inkjet recording apparatus and capable of attaining sufficient concentration of ink particles and capable of obtaining good-quality image free from blot thereby and to provide an inkjet recording method. <P>SOLUTION: In ink composition containing a dispersion medium and charge particles containing at least coloring material, the charge particles contain at least one kind of polymer having a nitrogen atom-containing heterocyclic group. The inkjet recording method comprises flying ink drops by an inkjet recording system utilizing an electrostatic field by using the ink composition. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to an ink composition and an ink jet recording method. More specifically, the charge density per unit volume of ink particles can be improved, and the electrophoretic speed of ink particles at a discharge portion in an ink jet recording apparatus is sufficiently high. The present invention relates to an ink composition and an ink jet recording method in which a sufficient quality of an image without blurring is obtained because the particles are sufficiently concentrated.

  As an image recording method for forming an image on a recording medium such as paper based on an image data signal, an electrophotographic method, a sublimation type and a melt type thermal transfer method, an ink jet method and the like are known. Among these, the electrophotographic system requires a process of forming an electrostatic latent image on a photosensitive drum by charging and exposure, and therefore the system is complicated and the apparatus is expensive. The thermal transfer method is less expensive than the electrophotographic method, but has problems such as high running costs and waste materials due to the use of an ink ribbon. On the other hand, the ink jet method is an inexpensive apparatus and ejects ink only to a required image portion to form an image directly on a recording medium. Therefore, the ink can be used efficiently and the running cost is low. Furthermore, there is little noise and it is excellent as an image recording method.

  Inkjet recording methods include, for example, a method in which ink droplets are ejected by the pressure of steam generated by the heat of a heating element, a method in which ink droplets are ejected by mechanical pressure pulses generated by a piezoelectric element, and an electrostatic field. There is a system (see Patent Documents 1 and 2) that causes ink droplets containing charged particles to fly. Here, the method of flying ink droplets with steam or mechanical pressure cannot control the flying direction of the ink droplets, and the ink droplets are accurately delivered to the desired position on the printing medium due to distortion of the ink nozzles or air convection. May be difficult to land on.

  On the other hand, the method using an electrostatic field controls the flying direction of the ink droplets by the electrostatic field, so that the ink droplets can be landed accurately at a desired position, and a high-quality image formation (printed material) is created. Can be better.

As an ink composition used for inkjet recording using an electrostatic field, an ink composition containing a dispersion medium and charged particles including at least a coloring material is used (see Patent Documents 3 and 4). By changing the color material, the ink composition containing the color material can create four color inks of yellow, magenta, cyan, and black, and can also create special color inks of gold and silver . Therefore, it is useful because a color image formed product (printed product) can be produced. However, in order to maintain high speed and high image quality and to stably output a color image formed product (printed product), the electrophoretic speed of the ink particles at the ejection part in the ink jet recording apparatus is sufficiently high, and the ink particles are concentrated. It has been confirmed that this needs to occur sufficiently, and for that purpose it is necessary to impart sufficient charge to the ink particles. However, a liquid developer composed of toner particles of 0.5 μm or less generally used in an electrophotographic system is not suitable for this ink jet system. In addition, if the particle size is increased, it is possible to increase the charge amount of the ink particles. However, the charge amount of the ink particles is not satisfactory at present, and the charge amount of the ink particles changes with time. difficult.
Japanese Patent No. 3315334 US Pat. No. 6,158,844 JP-A-8-291267 US Pat. No. 5,952,2048

  The present invention has been made in view of the above-described problems in the prior art, and can improve the charge density per unit volume of ink particles, and the electrophoretic velocity of ink particles at a discharge portion in an ink jet recording apparatus can be sufficiently high. An object of the present invention is to provide an ink composition and an ink jet recording method which can obtain an image of good quality without bleeding because the particles are sufficiently concentrated.

  The present invention is as follows.

  1. An ink composition comprising a dispersion medium and charged particles containing at least a coloring material, wherein the charged particles contain at least one polymer having a nitrogen atom-containing heterocyclic group.

  2. In the ink composition containing a dispersion medium, a charged particle containing at least a coloring material, and a charge generator, the charged particle contains at least one polymer having a nitrogen atom-containing heterocyclic group, and the polymer is An ink composition comprising a repeating unit represented by the following general formula (1), wherein the charge generator contains a proton-donating charge generator.

(In the general formula (1), L ₁ is a linking group to the polymer main chain, and has a total number of 50 atoms consisting of a single bond or two or more atoms selected from C, H, N, O, S and P. The following divalent linking groups are represented, and a ₁ and a ₂ may be the same or different from each other, and are each via a hydrogen atom, a halogen atom, a cyano group, a hydrocarbon group, —COO—Z ₁ or a hydrocarbon. —COO—Z ₁ (Z ₁ represents a hydrogen atom or a hydrocarbon group). R ₁ represents an aliphatic group having 6 or more carbon atoms.)
3. In the ink jet recording method in which an ink composition is ejected as ink droplets by an ink jet recording method using an electrostatic field, Or 2. An ink jet recording method using the ink composition described above.

  According to the present invention, since the charged particles (ink particles) contain at least one polymer having a nitrogen atom-containing heterocyclic group, the charge density per unit volume of the ink particles can be improved, and the ejection unit in the ink jet recording apparatus Ink composition and ink-jet recording method are provided, in which the electrophoretic speed of the ink particles is sufficiently high and the ink particles are sufficiently concentrated, so that an image of good quality can be obtained without bleeding.

The ink composition of the present invention contains charged particles including at least a dispersion medium and a coloring material, and the charged particles contain at least one polymer having a nitrogen atom-containing heterocyclic group. The polymer having a nitrogen atom-containing heterocyclic group is preferably contained in a coloring material coating agent described below.

Hereinafter, each component of the ink composition of the present invention will be described.
[Dispersion medium]
The dispersion medium used in the ink composition of the present invention is preferably a dielectric liquid having a high electrical resistivity, specifically, 10 ¹⁰ Ωcm or more. If a dispersion medium having a low electrical resistivity is used, electrical continuity is generated between adjacent recording electrodes, which is not suitable for this embodiment. Further, the dielectric constant of the dielectric liquid is preferably 5 or less, more preferably 4 or less, and still more preferably 3.5 or less. By setting the relative dielectric constant in such a range, an electric field is effectively applied to charged particles in the dielectric liquid, which is preferable.

Examples of the dispersion medium used in the present invention include linear or branched aliphatic hydrocarbons, alicyclic hydrocarbons, or aromatic hydrocarbons, halogen substitution products of these hydrocarbons, and silicone oil. For example, hexane, heptane, octane, isooctane, decane, isodecane, decalin, nonane, dodecane, isododecane, cyclohexane, cyclooctane, cyclodecane, toluene, xylene, mesitylene, Isopar C, Isopar E, Isopar G, Isopar H, Isopar L, Isopar M (Isopar: trade name of Exxon), Shellsol 70, Shellsol 71 (Shellsol: trade name of Shell Oil), Amsco OMS, Amsco 460 solvent (Amsco: Trade name of Spirits), KF-96L ( A trade name of Shin-Etsu Silicone Co., Ltd.) or the like can be used alone or in combination. The content of the dispersion medium with respect to the entire ink composition is preferably in the range of 20 to 99% by mass. In 20 mass% or more, the particle | grains containing a coloring material can be disperse | distributed to a dispersion medium favorably, and in 99 mass% or less, content of a coloring material can be satisfied.
[Color material]
As the coloring material used in the ink composition of the present invention, known dyes and pigments can be used, and can be selected according to applications and purposes. For example, it is preferable to use a pigment from the viewpoint of the color tone of the recorded image recorded matter (printed matter) (for example, “Dispersion Stabilization and Surface Treatment Technology / Evaluation” issued by the Technical Information Association, December 2001, 2.5). (Refer to the first edition of Japan, hereinafter referred to as “Non-Patent Document 1”). By changing the color material, four color inks of yellow, magenta, cyan, and black can be created. In particular, the use of offset printing inks or pigments used for proofing is preferable because the same color tone as that of offset printed matter can be obtained.

  Examples of pigments for yellow ink include C.I. I. Pigment yellow 1, C.I. I. Monoazo pigments such as CI Pigment Yellow 74; I. Pigment yellow 12, C.I. I. Disazo pigments such as CI Pigment Yellow 17; I. Non-benzidine azo pigments such as CI Pigment Yellow 180; I. Azo lake pigments such as CI Pigment Yellow 100; I. Condensed azo pigments such as CI Pigment Yellow 95; I. Pigment Yellow 115, etc., acidic dye lake pigments, C.I. I. Pigment Yellow 18 and other basic dye lake pigments, anthraquinone pigments such as Flavantrone Yellow, isoindolinone pigments such as isoindolinone yellow 3RLT, quinophthalone pigments such as quinophthalone yellow, isoindoline pigments such as isoindoline yellow, C.I. I. Nitroso pigments such as CI Pigment Yellow 153, C.I. I. Metal complex azomethine pigments such as CI Pigment Yellow 117; I. And isoindolinone pigments such as CI Pigment Yellow 139.

Examples of pigments for magenta ink include C.I. I. Monoazo pigments such as CI Pigment Red 3; I. Disazo pigments such as CI Pigment Red 38; I. Pigment red 53: 1 etc. and C.I. I. Azo lake pigments such as CI Pigment Red 57: 1; I. Condensed azo pigments such as CI Pigment Red 144; I. Acidic dye lake pigments such as C.I. Pigment Red 174; I. Basic dye lake pigments such as CI Pigment Red 81; I. Anthraquinone pigments such as CI Pigment Red 177; I. Thioindigo pigments such as CI Pigment Red 88; I. Perinone pigments such as CI Pigment Red 194; I. Perylene pigments such as CI Pigment Red 149; I. Quinacridone pigments such as CI Pigment Red 122; I. Isoindolinone pigments such as CI Pigment Red 180; I. And alizarin lake pigments such as CI Pigment Red 83.

  Examples of the pigment for cyan ink include C.I. Disazo pigments such as I. Pigment Blue 2.5; I. Phthalocyanine pigments such as CI Pigment Blue 15; I. Pigment Blue 24, etc., acidic dye lake pigments, C.I. I. Basic dye lake pigments such as CI Pigment Blue 1; I. Anthraquinone pigments such as CI Pigment Blue 60; I. And alkaline blue pigments such as CI Pigment Blue 18.

  Examples of the pigment for black ink include organic pigments such as aniline black pigments, iron oxide pigments, and carbon black pigments such as furnace black, lamp black, acetylene black, and channel black.

  Furthermore, processed pigments typified by microlith pigments such as Microlith-A, -K, and -T can also be suitably used. Specific examples thereof include Microlith Yellow 4G-A, Micro Resled BP-K, Microlith Blue 4G-T, and Microlith Black CT.

  Various pigments can be used as necessary, such as calcium carbonate and titanium oxide pigments for white ink, aluminum powder for silver ink, and copper alloy for gold ink.

  Basically, it is preferable to use one kind of pigment for each color, from the viewpoint of simplicity of ink production. However, as a hue adjustment, for example, for black ink, phthalocyanine is mixed with carbon black. Are preferably used in combination of two or more. Alternatively, the pigment may be surface-treated by a known method such as rosin treatment (Non-Patent Document 1).

The content of the color material (pigment) with respect to the entire ink composition is preferably in the range of 0.1 to 50% by mass. When the amount is 0.1% by mass or more, the pigment amount is sufficient, and a sufficiently good color is obtained in the printed matter. When the amount is 50% by mass or less, the particles containing the coloring material can be favorably dispersed in the dispersion medium. More preferably, it is 1-30 mass%.
[Coating agent]
In the ink composition of the present invention, the coloring material such as a pigment is preferably dispersed (particulated) in a state of being coated with a coating agent, rather than directly dispersed (particulated) in a dispersion medium. By covering with a coating agent, it is possible to shield the charge of the color material and to impart desirable charge characteristics. In the present invention, after ink jet recording on a recording medium, the image is fixed by a heating means such as a heat roller. At this time, the coating material is melted by heat and can be fixed efficiently. According to the present invention, the polymer having a nitrogen atom-containing heterocyclic group is desirably contained in the coating agent.

Examples of the nitrogen-containing heterocyclic ring include 5-membered or more aromatic rings or non-aromatic rings containing one nitrogen atom, and specific examples include a pyrrole ring, a pyridine ring, a pyrrolidine ring, and a piperidine ring. Further, it may be a nitrogen-containing heteroaromatic ring further containing one or more heteroatoms selected from the group consisting of an oxygen atom, a nitrogen atom and a sulfur atom. Examples of such nitrogen-containing heteroaromatic rings include pyrazole ring, imidazole ring, triazole ring, tetrazole ring, oxazole ring, isoxazol ring, thiazole ring, thiadiazole ring, thiatetrazole ring,
Examples include a pyridazine ring, a pyrimidine ring, a pyrazine ring, and a triazine ring. Among these, in terms of performance, those in which the lone pair of nitrogen atom in the nitrogen-containing heteroaromatic ring is not conjugated are preferable. A pyrazine ring is particularly preferred.
In addition, one or more of such nitrogen atom-containing heterocycles may be substituted with an arbitrary substituent, and examples of the substituent include an alkyl group, an alkynyl group, an aryl group, and a halogen atom (—F, —Br, — Cl, -I), hydroxyl group, alkoxy group, aryloxy group, mercapto group, alkylthio group, arylthio group, alkyldithio group, aryldithio group, amino group, N-alkylamino group, N, N-dialkylamino group, N -Arylamino group, N, N-diarylamino group, N-alkyl-N-arylamino group, acyloxy group, carbamoyloxy group, N-alkylcarbamoyloxy group, N-arylcarbamoyloxy group, N, N-dialkylcarbamoyl Oxy group, N, N-diarylcarbamoyloxy group, N-alkyl-N-ali Rucarbamoyloxy group, alkylsulfoxy group, arylsulfoxy group, acylthio group, acylamino group, N-alkylacylamino group, N-arylacylamino group, ureido group, N′-alkylureido group, N ′, N′- Dialkylureido group, N′-arylureido group, N ′, N′-diarylureido group, N′-alkyl-N′-arylureido group, N-alkylureido group, N-arylureido group, N′-alkyl- N-alkylureido group, N′-alkyl-N-arylureido group, N ′, N′-dialkyl-N-alkylureido group, N ′, N′-dialkyl-N-arylureido group, N′-aryl- N-alkylureido group, N′-aryl-N-arylureido group, N ′, N′-diaryl-N-alkylureido group, N ′, N′- Diaryl-N-arylureido group, N′-alkyl-N′-aryl-N-alkylureido group, N′-alkyl-N′-aryl-N-arylureido group, alkoxycarbonylamino group, aryloxycarbonylamino group N-alkyl-N-alkoxycarbonylamino group, N-alkyl-N-aryloxycarbonylamino group, N-aryl-N-alkoxycarbonylamino group, N-aryl-N-aryloxycarbonylamino group, formyl group, acyl Group, carboxyl group and its conjugate base (hereinafter referred to as carboxylate, including metal salts), alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, N-alkylcarbamoyl group, N, N-dialkylcarbamoyl group, N- Arylcarbamoyl group, N, N- A diarylcarbamoyl group, an N-alkyl-N-arylcarbamoyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, a sulfo group (—SO ₃ H) and a conjugate base group thereof (referred to as a sulfonate group). (Including metal salts), alkoxysulfonyl groups, aryloxysulfonyl groups, sulfinamoyl groups, N-alkylsulfinamoyl groups, N, N-dialkylsulfinamoyl groups, N-arylsulfinamoyl groups, N, N-diaryls Sulfinamoyl group, N-alkyl-N-arylsulfinamoyl group, sulfamoyl group, N-alkylsulfamoyl group, N, N-dialkylsulfamoyl group, N-arylsulfamoyl group, N, N- Diarylsulfamoyl group, N-alkyl-N-arylsulfamoyl group, N-acylsulfamoyl group and its conjugate base group, N-alkylsulfonylsulfamoyl group (—SO ₂ NHSO ₂ (alkyl): alkyl = Alkyl group, the same shall apply hereinafter) and its conjugate base group, N-allylsulfonylsulfamoyl group _{-SO 2 NHSO 2 (allyl):} allyl = allyl, hereinafter the same) and its conjugated base group, N- alkylsulfonylcarbamoyl group (-CONHSO ₂ (alkyl)) and its conjugated base group, N- allyl sulfonyl carbamoyl group ( -CONHSO ₂ (allyl)) and its conjugated base group, an alkylsulfonylamino group, an arylsulfonylamino group, an alkoxysilyl group (-Si (Oalkyl) _3), allyloxy silyl group (-Si (Oallyl) _3), hydroxysilyl Group (—Si (OH) ₃ ) and its conjugate base group, phosphono group (—PO ₃ H ₂ ) and its conjugate base group (referred to as phosphonate group, including metal salts), dialkylphosphono group (—PO ₃ ( alkyl) ₂ ), diarylphosphono group (—PO ₃ (aryl) ₂ : aryl = aryl group, the same shall apply hereinafter), alkylarylphosphono group (—PO ₃ (alky l) (aryl)), monoalkylphosphono group (—PO ₃ (alkyl)) and its conjugate base group (referred to as alkylphosphonate group, including metal salts), monoarylphosphono group (—PO ₃ H ( aryl)) and its conjugated base groups (referred to as arylphosphonate groups, including metal salts), phosphonooxy groups (—OPO ₃ H ₂ ) and their conjugated base groups (referred to as phosphonatoxy groups, including metal salts), dialkylphosphones Nooxy group (—OPO ₃ H (alkyl) ₂ ), diarylphosphonooxy group (—OPO ₃ (aryl) ₂ ), alkylarylphosphonooxy group (—OPO ₃ (alkyl) (aryl)), monoalkylphospho A nooxy group (—OPO ₃ H (alkyl)) and its conjugate base group (referred to as an alkylphosphonatoxy group). Metal salt), monoarylphosphonooxy group (—OPO ₃ H (aryl)) and its conjugate base group (referred to as arylphosphonatoxy group, including metal salt), alkylazo group, arylazo group, cyano group, A nitro group, a heterocyclic group, etc. are mentioned.

  The above substituents may be further substituted if possible. Further, adjacent substituents may be bonded to form a ring, and such a ring may be an aromatic ring, a non-aromatic ring, or a carbocycle, Furthermore, a heterocycle may be formed by containing one or more heteroatoms selected from the group consisting of a nitrogen atom, an oxygen atom, and a sulfur atom. The nitrogen atom-containing heterocycle may be a ring assembly.

  The synthesis of the polymer having a nitrogen atom-containing heterocyclic group is preferably obtained by polymerizing a compound having a nitrogen atom-containing heterocyclic group and a polymerizable unsaturated group. From the viewpoint of synthesis and performance, the polymerizable group is preferably a (meth) acryloyl group or a (meth) acrylamide group. These polymerizable groups are particularly preferably bonded to the nitrogen atom-containing heterocycle via a substituent on the nitrogen atom-containing heterocycle.

  Specific examples of the monomer having a nitrogen-containing heterocyclic group are shown below, but the present invention is not limited thereto.

  The content of the nitrogen-containing heterocyclic group in the polymer having a nitrogen atom-containing heterocyclic group is preferably 1% by mass to 99% by mass, more preferably 2% by mass to 80% by mass, and still more preferably from the viewpoint of charge development. It is 3 mass%-70 mass%.

  Furthermore, the polymer having a nitrogen atom-containing heterocyclic group in the present invention preferably further has a repeating unit represented by the following general formula (1). By containing this repeating unit, the particle forming property is excellent.

In general formula (1), L ₁ is a linking group to the polymer main chain, and has a total number of atoms of 50 or less consisting of a single bond or two or more atoms selected from C, H, N, O, S and P. A ₁ and a ₂ may be the same as or different from each other, and each represents a hydrogen atom, a halogen atom, a cyano group, a hydrocarbon group, —COO—Z ₁ or — COO-Z ₁ (Z ₁ represents a hydrogen atom or a hydrocarbon group). R ₁ represents an aliphatic group having 6 or more carbon atoms.

In the general formula (1), L ₁ preferably represents a linking group of —COO—, —OCO—, — (CH ₂ ) _k —OCO—, — (CH ₂ ) _k —COO— or —O—. . However, the linking groups may be used in combination. More preferred examples of L ₁ include —COO— and —OCO—. Here, k represents an integer of 1 to 4.

More preferred structures of a ₁ and a ₂ include a hydrogen atom and a methyl group.

R ₁ represents an aliphatic group having 6 or more carbon atoms, for example, a linear or branched alkyl group or alkenyl group. Specifically, hexyl group, 2-ethylhexyl group, octyl group, dodecyl group, tridecyl group, tetradecyl group, hexadecyl group, octadecyl group, eicosanyl group, hexenyl group, octenyl group, decenyl group, dodecenyl group, hexadecenyl group, octadecenyl group Group, linolel group and the like.

  The content of the repeating unit represented by the general formula (1) in the polymer is preferably 1% by mass to 50% by mass, more preferably 1% by mass to 30% by mass from the viewpoint of ease of particle formation.

  In the present invention, the polymer containing at least the repeating unit represented by the general formula (1) is preferably copolymerized with another copolymerizable monomer.

As other copolymerizable monomers, known polymerizable monomers can be used. Specifically, methyl (meth) acrylate, ethyl (meth) acrylate, (n- or i-) propyl (meth) acrylate , (N-, i-, sec- or t-) butyl (meth) acrylate, amyl (meth) acrylate, adamantyl (meth) acrylate, chloroethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2- Hydroxypropyl (meth) acrylate, 2-hydroxypentyl (meth) acrylate, cyclohexyl (meth) acrylate, allyl (meth) acrylate, trimethylolpropane mono (meth) acrylate, pentaerythritol mono (meth) acrylate, benzyl (meth) acrylate , Meto Cibenzyl (meth) acrylate, chlorobenzyl (meth) acrylate, hydroxybenzyl (meth) acrylate, hydroxyphenethyl (meth) acrylate, dihydroxyphenethyl (meth) acrylate, furfuryl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, phenyl ( Such as meth) acrylate, hydroxyphenyl (meth) acrylate, chlorophenyl (meth) acrylate, sulfamoylphenyl (meth) acrylate, 2-phenoxyethyl (meth) acrylate, 2- (hydroxyphenylcarbonyloxy) ethyl (meth) acrylate, etc. (Meth) acrylic acid esters, acrylamide, N-methylacrylamide, N-ethylacrylamide, N-propylacrylamide, N- Chill acrylamide, N-
Benzylacrylamide, N-hydroxyethylacrylamide, N-phenylacrylamide, N-tolylacrylamide, N- (hydroxyphenyl) acrylamide, N- (sulfamoylphenyl) acrylamide, N- (phenylsulfonyl) acrylamide, N- (tolylsulfonyl) ) Acrylamides such as acrylamide, N, N-dimethylacrylamide, N-methyl-N-phenylacrylamide, N-hydroxyethyl-N-methylacrylamide, methacrylamide, N-methylmethacrylamide, N-ethylmethacrylamide, N- Propyl methacrylamide, N-butyl methacrylamide, N-benzyl methacrylamide, N-hydroxyethyl methacrylamide, N-phenyl methacrylamide, N-tolylme Kurylamide, N- (hydroxyphenyl) methacrylamide, N- (sulfamoylphenyl) methacrylamide, N- (phenylsulfonyl) methacrylamide, N- (tolylsulfonyl) methacrylamide, N, N-dimethylmethacrylamide, N- Examples thereof include methacrylamides such as methyl-N-phenylmethacrylamide and N-hydroxyethyl-N-methylmethacrylamide, vinyl esters such as vinyl acetate, vinyl butyrate and vinyl benzoate. In addition, as a polymer in this invention, it is preferable not to copolymerize a styrene-type monomer on a synthetic | combination and a viewpoint of performance.

  The polymer having a nitrogen atom-containing heterocyclic group of the present invention preferably has a mass average molecular weight (Mw) in the range of 2,000 to 1,000,000, more preferably from the viewpoint of ease of particle formation. It is in the range of 3,000 to 500,000, more preferably 5000 to 200,000. The polydispersity (mass average molecular weight / number average molecular weight; Mw / Mn) is preferably 1.0 to 7.0, more preferably 1.0 to 5.0, and still more preferably 1.0 to 4.0. Range. Further, from the viewpoint of ease of fixing, a polymer having a glass transition point or a melting point in the range of 40 to 120 ° C. is preferable.

As physical properties of the polymer having a nitrogen atom-containing heterocyclic group of the present invention, the dynamic elastic modulus at 50 ° C. is 10 ⁶ Pa or more and the dynamic elastic modulus at 100 ° C. is 10 ³ Pa or more and 10 ⁵ Pa or less. It is particularly preferred.

  Here, the dynamic elastic modulus as the polymer physical property indicates the ease of deformation and fluidity of the polymer, and its behavior belongs to a scientific system called rheology. The dynamic elastic modulus is the thermal fluidity of the ink particles, that is, the flow property, the difficulty of seeing off the image onto the recording paper superimposed thereon, that is, the blocking resistance, and the thermal fixing of the ink image. This is considered to be closely related to an offset or the like at which a part of the image is transferred to the heat roller.

  The measurement of the dynamic elastic modulus is well known in the art and can be measured with good reproducibility. For example, using a measuring device called a rheometer, the polymer melted by heating is rotated by a rotor (gap 1 mm). ), The vibration is given at a certain frequency, and the deviation of the frequency can be obtained.

  More specifically, for example, 3 g of finely pulverized sample is set in a sample chamber of a rheometer “Rheosol-G1000” manufactured by UBM, and melted at 200 ° C. according to a predetermined measurement method. After that, the rotor is vibrated at a frequency of 1 Hz while the temperature is lowered, and a “temperature-dynamic elastic modulus curve” is automatically recorded, and the dynamic elastic modulus can be measured. As a preferable behavior of this dynamic elastic modulus curve, it is preferable to have two inflection points in the range of 40 ° C to 100 ° C.

  In addition to the polymer having a nitrogen atom-containing heterocyclic group of the present invention, the coating agent component may contain other components. The content of the component other than the polymer having a nitrogen atom-containing heterocyclic group in the coating agent component is preferably in the range of 0 to 99% by mass, more preferably 0 to 70% by mass with respect to the total amount of the coating agent. is there.

The other components are not particularly limited, but the melting point of (meth) acrylic polymer, styrene / (meth) acrylic polymer, high molecular compound having a melting point such as crystalline polyester, crystalline polyethylene, etc. The low molecular component is particularly preferable. The melting point (Tm) is preferably in the range of 30 to 120 ° C, more preferably in the range of 30 to 110 ° C, and still more preferably in the range of 40 to 100 ° C. In this temperature range of the melting point (Tm), the fixability of the image is further enhanced. Here, in the present invention, the melting point (Tm) means the peak temperature of the endothermic peak in the DSC measurement.

The content of the coating agent with respect to the entire ink composition is preferably in the range of 0.1 to 40% by mass. When the amount is 0.1% by mass or more, the amount of the coating agent is sufficient, and sufficient fixability is obtained. When the amount is 40% by mass or less, particles containing the coloring material and the coating agent can be favorably formed.
[Dispersant]
In the present invention, the mixture of the colorant and the coating agent is dispersed (particulated) in the dispersion medium, but it is more preferable to use a dispersant in order to control the particle diameter and suppress the sedimentation of the particles.

  Suitable dispersants include surfactants typified by sorbitan fatty acid esters such as sorbitan monooleate and polyethylene glycol fatty acid esters such as polyoxyethylene distearate. Further, for example, a copolymer of styrene and maleic acid, and an amine-modified product thereof, a copolymer of styrene and a (meth) acrylic compound, a (meth) acrylic polymer, a copolymer of polyethylene and a (meth) acrylic compound, rosin, BYK-160, 162, 164, 182 (polyurethane polymer manufactured by Big Chemie), EFKA-401, 402 (acrylic polymer manufactured by EFKA), Solsperse 17000, 24000 (polyester polymer manufactured by Geneca), and the like. In the present invention, from the viewpoint of long-term storage stability of the ink composition, the mass average molecular weight is in the range of 1,000 to 1,000,000 and the polydispersity (mass average molecular weight / number average molecular weight). Is preferred to be in the range of 1.0 to 7.0. Furthermore, it is most preferable to use a graft polymer or a block polymer.

  The polymer that is particularly preferably used as a dispersant in the present invention is represented by a polymer component composed of at least one of the structural units represented by the following general formulas (5) and (6), and the following general formula (7). It is a graft polymer containing at least a polymer component containing at least a structural unit as a graft chain.

In the formula, X ₅₁ represents an oxygen atom or —N (R ₅₃ ) —. R ₅₁ represents a hydrogen atom or a methyl group, R ₅₂ represents a hydrocarbon group having 1 to 10 carbon atoms, and R ₅₃ represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms. R ₆₁ represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogen atom, a hydroxyl group, or an alkoxy group having 1 to 20 carbon atoms. X ₇₁ represents an oxygen atom or —N (R ₇₃ ) —. R ₇₁ represents a hydrogen atom or a methyl group, R ₇₂ represents a hydrocarbon group having 4 to 30 carbon atoms, and R ₇₃ represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms. The hydrocarbon group of R ₅₂ and R ₇₂ may contain an ether bond, an amino group, a hydroxy group, or a halogen substituent.

  The graft polymer is obtained by polymerizing a radical polymerizable monomer corresponding to the general formula (7), preferably in the presence of a chain transfer agent, introducing a polymerizable functional group at the terminal of the obtained polymer, It can be obtained by copolymerizing with a radically polymerizable monomer corresponding to 5) or (6).

  Examples of the radical polymerizable monomer corresponding to the general formula (5) include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, and (meth) acrylic acid. Hexyl (meth) acrylate cyclohexyl, phenyl (meth) acrylate, benzyl (meth) acrylate, etc., (meth) acrylate esters of 2-hydroxyethyl (meth) acrylate, and N-methyl (meth) acrylamide And (meth) acrylamides such as N-propyl (meth) acrylamide, N-phenyl (meth) acrylamide, and N, N-dimethyl (meth) acrylamide.

  Examples of the radical polymerizable monomer corresponding to the general formula (6) include styrene, 4-methylstyrene, chlorostyrene, methoxystyrene, and the like.

  Examples of the radical polymerizable monomer corresponding to the general formula (7) include hexyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, dodecyl (meth) acrylate, ( (Meth) stearyl acrylate, and the like.

Specific examples of these graft polymers include polymers represented by the following structural formulas.

Contains a polymer component containing at least one of the structural units represented by general formulas (5) and (6) and a polymerization component containing at least the structural unit represented by general formula (7) as a graft chain. The graft polymer to be processed may have only the structural unit represented by the general formula (5) and / or (6) and the general formula (7), or may contain other components. A preferred composition ratio between the polymer component containing the graft chain and the other polymer components is 10:90 to 90:10. Within this range, good particle formability is obtained, and a desired particle diameter is easily obtained, which is preferable. These polymers may be used alone as a dispersant, or may be used in combination of two or more.

The content of the dispersant with respect to the entire ink composition is preferably in the range of 0.01 to 30% by mass. Within this range, good particle formability can be obtained, and a desired particle diameter can be obtained.
[Charge generator]
In the present invention, a mixture of a colorant and a coating agent is dispersed (particulated) in a dispersion medium using a dispersant, and a charge generating agent is used in combination to control the charge amount of the particles.

  As the charge generating agent used in the present invention, known ones can be used. For example, metal salts of fatty acids such as naphthenic acid, octenoic acid, oleic acid, stearic acid, metal salts of sulfosuccinic acid esters, Japanese Patent Publication No. 45-556, Japanese Patent Publication No. 52-37435, Japanese Patent Publication No. 52-37049 Oil-soluble sulfonic acid metal salts disclosed in Japanese Patent Publication No. 45-9594, phosphate ester metal salts disclosed in Japanese Patent Publication No. 45-9594, abietic acid or hydrogen disclosed in Japanese Patent Publication No. 48-2.5666 Metal salt of added abietic acid, alkylbenzenesulfonic acid Ca salt disclosed in JP-B-55-2620, JP-A-52-107837, JP-A-52-38937, JP-A-57-90643, JP-A-57-139753 Nonionics such as metal salts of aromatic carboxylic acids or sulfonic acids and polyoxyethylated alkylamines described in Surfactants, fats and oils such as lecithin and linseed oil, polyvinyl pyrrolidone, organic acid esters of polyhydric alcohols, phosphate ester surfactants disclosed in JP-A-57-210345, JP-B 56-24944 The sulfonic acid resin etc. which are shown by gazette gazette can be used. In addition, amino acid derivatives described in JP-A-60-21056 and 61-50951 can also be used. Moreover, the copolymer etc. which contain the maleic acid half amide component described in each gazette of Unexamined-Japanese-Patent No. 60-173558 and 60-179750 are mentioned. Further, quaternized amine polymers described in JP-A Nos. 54-31739 and 56-24944 can be given.

In the present invention, it is more preferable to use a charge generating agent having a proton donating group (proton donating charge generating agent). Examples of the proton donating group include a carboxyl group, a hydroxyl group, a phosphono group, a sulfo group, a thiol group, an imide group, and a sulfonamide group. In the present invention, it is more preferable to use a compound having an acid group as a charge generating agent. Specific examples include a carboxylic acid group, a sulfonic acid group, a phosphonic acid group, an imide group, a sulfonamide group, and a phenolic hydroxyl group. Particularly preferred acid groups include —COOH, —SO ₃ H, —OSO ₃ H, —PO ₃ H ₂ , —OPO ₃ H ₂ , —CONHSO ₂ , —SO ₂ NHSO _{2, and the} like.

  The charge generator may be a low molecular compound or a high molecular compound as long as it is soluble in the dispersion medium. As a method for introducing an acid group into a polymer compound, from the viewpoint of ease of synthesis, a monomer having an acid group is selected from known (meth) acrylic acid esters, (meth) acrylamides, vinyl esters, styrenes, etc. Although it is preferable to copolymerize with other polymerizable monomers, it is not limited to this.

Specific examples of the monomer having an acid group include acrylic acid, methacrylic acid, vinyl benzoic acid, maleic anhydride, maleic imide, 3-sulfopropyl acrylate, 3-sulfopropyl methacrylate, 4-styrene sulfonic acid, acid phosphoxy Examples include, but are not limited to, ethyl methacrylate, 3-chloro-2-acid phosphoxypropyl methacrylate, and acid phosphooxypolyoxyethylene glycol monomethacrylate. In the present invention, two or more of the above charge generating agents may be used in combination as appropriate. In this case, the amount of the charge generating agent having an acid group is preferably 50% by mass or more, more preferably 70% by mass, and further preferably 80% by mass with respect to the total amount of the charge generating agent.

Further, the charge applied to the ink particles may be positively charged or negatively charged. The content of the charge generating agent with respect to the entire ink composition is preferably in the range of 0.0001 to 10% by mass. The electrical conductivity of the ink composition of the present invention is preferably 10 nS / m to 300 nS / m, and the electrical conductivity of the charged particles is preferably 50% or more of the electrical conductivity of the ink composition. These conditions can be easily adjusted by increasing or decreasing the content of the charge generating agent.
[Other ingredients]
In the present invention, a preservative for preventing corruption, a surfactant for controlling surface tension, and the like can be further contained depending on the purpose.
[Create charged particles]
As described above, an ink composition containing charged particles including at least a coloring material is prepared by dispersing (particulating) the coloring material and the coating agent in a dispersion medium using a dispersing agent and a charge generating agent. can do. Examples of the dispersion (particulate) method include the following.

  1) A colorant and a coating agent are mixed in advance, and then dispersed (particulated) using a dispersant and a dispersion medium, and a charge generating agent is added.

  2) Disperse (particulate) using a coloring material, a coating agent, a dispersant and a dispersion medium at the same time, and add a charge generating agent.

  3) Disperse (particulate) using a coloring material, a coating agent, a dispersant, a charge generating agent and a dispersion medium at the same time.

  Examples of the apparatus used for mixing and dispersing include a kneader, a dissolver, a mixer, a high-speed disperser, a sand mill, a roll mill, a ball mill, an attritor, and a bead mill (the aforementioned Non-Patent Document 1).

  The ink particles (charged particles) in the present invention should have a diameter of 0.5 to 4 μm, preferably 0.7 to 3.5 μm, more preferably 0.8 to 3 μm. This size is larger than normal electrophotographic liquid developer toner (0.1 to 0.4 μm) and smaller than normal electrophotographic dry developer toner (5 to 15 μm).

The viscosity (20 ° C.) of the ink composition of the present invention is preferably in the range of 0.5 to 5 mPa · s. Preferably, it exists in the range of 0.8-4 mPa * s. The surface tension of the ink composition is preferably in the range of 10 to 70 mN / m. More preferably, it exists in the range of 15-50 mN / m.
[Inkjet recording apparatus]
In the present invention, the ink composition described above is recorded on a recording medium by an ink jet recording method. In the present invention, it is preferable to use an ink jet recording system using an electrostatic field. Ink jet recording methods that use an electrostatic field concentrate the charged particles of the ink composition at the discharge position by electrostatic force by applying a voltage between the control electrode and the back electrode on the back of the recording medium, and record from the discharge position. This is a method of flying to a medium. For example, when the charged particles are positive, the voltage applied between the control electrode and the back electrode is such that the control electrode is a positive electrode and the back electrode is a negative electrode. The same effect can be obtained by charging the recording medium instead of applying a voltage to the back electrode.

As a method of flying ink, for example, there is a method of flying ink from a needle-like tip such as an injection needle, and recording can be performed using the ink composition of the present invention. However, it is difficult to replenish charged particles after the charged particles are concentrated and discharged, and it is difficult to perform stable long-term recording. When the ink is circulated in order to forcibly supply charged particles, the ink overflows from the tip of the injection needle, so the meniscus shape at the tip of the injection needle, which is the discharge position, is not stable, and stable recording is performed. It is difficult to do and is suitable for short-term recording.

  On the other hand, a method of circulating the ink composition without overflowing the ink composition from the ejection opening is preferably used. For example, ink is circulated in an ink chamber having an ejection opening, and a voltage is applied to a control electrode formed at the periphery of the ejection opening, so that it exists in the ejection opening and the leading end faces the recording medium side. In the method in which the concentrated ink droplets fly from the tip of the ink guide, the replenishment of charged particles by the circulation of the ink and the meniscus stability at the ejection position can be compatible, so that stable recording can be performed for a long time. it can. Further, in this method, since the portion where the ink is in contact with the outside air is very small with only the discharge opening, the evaporation of the solvent is suppressed and the ink physical properties are stabilized, so that it can be suitably used in the present invention.

  A configuration example of an ink jet recording apparatus suitable for applying the ink composition of the present invention is shown below.

  First, an outline of an apparatus that performs single-sided four-color printing on a recording medium shown in FIG. 1 will be described.

  An ink jet recording apparatus 1 shown in FIG. 1 supplies ink to an ejection head 2 composed of ejection heads 2C, 2M, 2Y and 2K for four colors for forming a full-color image, and further the ink from the ejection head 2 A head driver 4 for driving the ejection head 2 by an output from an external device such as a computer (not shown), a RIP (raster image processor), and a position control means 5. Further, the ink jet recording apparatus 1 includes a transport belt 7 stretched around three rollers 6A, 6B, and 6C, a transport belt position detection unit 8 including an optical sensor that can detect the position of the transport belt 7 in the width direction, An electrostatic attraction unit 9 for holding the recording medium P on the conveyance belt, a static elimination unit 10 and a mechanical unit 11 for peeling the recording medium P from the conveyance belt 7 after completion of image formation are provided. Upstream and downstream of the conveyance belt 7, the feed roller 12 and the guide 13 that supply the recording medium P from the stocker (not shown) to the conveyance belt 7, the ink is fixed to the recording medium P after peeling, and the paper discharge stocker (not shown). A fixing means 14 and a guide 15 for conveying the toner are disposed. In addition, the inkjet printing apparatus 1 has a recording medium position detecting means 16 at a position facing the ejection head 2 with the conveyance belt 7 interposed therebetween, and further collects the solvent vapor generated from the ink composition. A solvent recovery unit composed of the exhaust fan 17 and the solvent vapor adsorbent 18 is disposed, and the vapor inside the apparatus is discharged outside the apparatus through the recovery unit.

A known roller can be used as the feed roller 12, and the feed roller 12 is arranged so as to increase the feeding ability to the recording medium. Further, since dirt, paper powder, or the like may adhere on the recording medium P, it is desirable to remove them. The recording medium P supplied by the feed roller is transported to the transport belt 7 through the guide 13. The back surface (preferably metal back surface) of the conveyor belt 7 is installed via a roller 6A. The recording medium transported is electrostatically attracted onto the transport belt by the electrostatic attracting means 9. In FIG. 1, electrostatic adsorption is performed by a scorotron charger connected to a negative high voltage power source. The recording medium P is electrostatically adsorbed without floating on the transport belt 7 by the electrostatic adsorption means 9 and the surface of the recording medium is uniformly charged. Here, the electrostatic attraction means is also used as a charging means for the recording medium, but may be provided separately. The charged recording medium P is transported to the ejection head portion by the transport belt 7, and electrostatic ink jet image formation is performed by superimposing the recording signal voltage with the charging potential as a bias. The recording medium P on which the image is formed is neutralized by the neutralizing unit 10, peeled off by the conveying unit 7 by the mechanical unit 11, and conveyed to the fixing unit. The peeled recording medium P is sent to the image fixing means 14 and fixed. The fixed recording medium P is discharged through a guide 15 to a discharge stocker (not shown). The apparatus also has a means for recovering the solvent vapor generated from the ink composition. The recovery means is composed of the solvent vapor absorbing material 18, and a gas containing solvent vapor in the apparatus is introduced into the adsorbent by the exhaust fan 17, and after the vapor is adsorbed and recovered, it is exhausted outside the apparatus. The apparatus is not limited to the above example, and the number, shape, relative arrangement, charging polarity, and the like of constituent devices such as rollers and chargers can be arbitrarily selected. In the above system, four-color drawing is described. However, a multicolor system may be combined with light color ink or special color ink.

  The ink jet recording apparatus used in the above ink jet printing method includes an ejection head 2 and an ink circulation system 3. The ink circulation system 3 further includes an ink tank, an ink circulation device, an ink concentration control device, an ink temperature management device, and the like. In addition, the ink tank may include a stirring device.

  As the ejection head 2, a single channel head, a multi-channel head, or a full line head can be used, and main scanning is performed by the rotation of the transport belt 7.

  An ink jet head suitably used in the present invention is an ink jet method in which charged particles in an ink flow path are electrophoresed to increase the ink concentration in the vicinity of an opening and discharge is performed. Ink droplets are ejected by electrostatic attraction caused by the counter electrode disposed on the back surface of the medium. Therefore, if the recording medium or the counter electrode does not face the head, or if no voltage is applied to the recording medium or the counter electrode even at the position facing the head, the voltage is accidentally applied to the ejection electrode. Ink droplets are not ejected even when a pressure is applied or vibration is applied, and the inside of the apparatus is not soiled.

  An ejection head preferably used in the ink jet apparatus is shown in FIGS. As shown in FIGS. 2 and 3, the inkjet head 70 includes an electrically insulating substrate 74 that constitutes the upper wall of the ink flow path 72 where the ink flow Q in one direction is formed, and the ink to the recording medium P. And a plurality of discharge portions 76 that discharge toward the surface. Each of the ejection portions 76 is provided with an ink guide portion 78 that guides the ink droplet G flying from the ink flow path 72 toward the recording medium P, and the substrate 74 has an opening through which the ink guide portion 78 is inserted. 75 is formed, and the ink meniscus 42 is formed between the ink guide portion 78 and the inner wall surface of the opening 75. The gap d between the ink guide portion 78 and the recording medium P is preferably about 200 μm to 1000 μm. Further, the ink guide part 78 is fixed to the support bar part 40 on the lower end side.

  The substrate 74 includes an insulating layer 44 that electrically isolates two discharge electrodes at a predetermined interval, a first discharge electrode 46 formed above the insulating layer 44, and an insulation that covers the first discharge electrode 46. It has a layer 48, a guard electrode 50 formed on the insulating layer 48, and an insulating layer 52 that covers the guard electrode 50. The substrate 74 includes a second ejection electrode 56 formed below the insulating layer 44 and an insulating layer 58 that covers the second ejection electrode 56. The guard electrode 50 is provided in order to prevent an electric field from being affected by the voltage applied to the first ejection electrode 46 and the second ejection electrode 56 in the adjacent ejection section.

Further, the ink jet head 70 constitutes the bottom surface of the ink flow path 72, and the ink flow is generated by the induced voltage that is constantly generated by the pulsed discharge voltage applied to the first discharge electrode 46 and the second discharge electrode 56. A floating conductive plate 62 that moves positively charged ink particles (charged particles) R in the path 72 upward (that is, toward the recording medium side) is provided in an electrically floating state. In addition, a coating film 64 that is electrically insulating is formed on the surface of the floating conductive plate 62 to prevent the physical properties and components of the ink from becoming unstable due to charge injection into the ink. The electric resistance of the insulating coating film is preferably 10 ¹² Ω · cm or more, and more preferably 10 ¹³ Ω · cm or more. In addition, the insulating coating film is desirably resistant to corrosion with respect to ink, and this prevents the floating conductive plate 62 from being corroded by ink. Further, the floating conductive plate 62 is covered with the insulating member 66 from below, and the floating conductive plate 62 is completely electrically insulated by such a configuration.

There are one or more floating conductive plates 62 per head unit (for example, when there are four heads C, M, Y, and K, the number of floating conductive plates is at least one each, and C and M The floating conductive plate is not shared between the head units.

  As shown in FIG. 3, in order to cause ink to fly from the inkjet head 70 and record on the recording medium P, the ink in the ink flow path 72 is circulated to generate an ink flow Q, and the guard electrode A predetermined voltage (for example, +100 V) is applied to 50. Furthermore, a flying electric field that attracts the positive charged particles R in the ink droplet G that has been guided by the ink guide portion 78 and flew from the opening 75 to the recording medium P is generated by the first ejection electrode 46 and the second ejection electrode. A positive voltage is applied to the first ejection electrode 46, the second ejection electrode 56, and the recording medium P so as to be formed between the recording medium P and the recording medium P (1 kV when the gap d is 500 μm). A potential difference of about ~ 3.0 kV is taken as a guide).

  In this state, when a pulse voltage is applied to the first ejection electrode 46 and the second ejection electrode 56 in accordance with the image signal, the ink droplet G having an increased charged particle concentration is ejected from the opening 75 (for example, initial charged particles). When the concentration is 3 to 15%, the charged particle concentration of the ink droplet G is 30% or more).

  At that time, the ink droplet G is applied to the first ejection electrode 46 and the second ejection electrode 56 so that the ink droplet G is ejected only when the pulse voltage is applied to both the first ejection electrode 46 and the second ejection electrode 56. Adjust the voltage value.

  In this way, when a pulsed positive voltage is applied, the ink droplet G is guided by the ink guide portion 78 from the opening 75 and flies to adhere to the recording medium P, and the first ejection is applied to the floating conductive plate 62. A positive induced voltage is generated by the positive voltage applied to the electrode 46 and the second ejection electrode 56. Even if the voltage applied to the first ejection electrode 46 and the second ejection electrode 56 is pulsed, this induced voltage is a substantially steady voltage. Accordingly, the charged particles R that are positively charged in the ink flow path 72 are subjected to the upward movement force by the electric field formed between the floating conductive plate 62 and the guard electrode 50 and the recording medium P, and The concentration of charged particles R increases near the substrate 74. As shown in FIG. 3, when the number of ejection units (that is, channels for ejecting ink droplets) to be used is large, the number of charged particles necessary for ejection increases, but the first ejection electrode 46 and the second ejection electrode to be used are used. Since the number of 56 increases, the induced voltage induced in the floating conductive plate 62 increases, and the number of charged particles R moving to the recording medium side also increases.

  In the above, an example in which the colored particles are positively charged has been described. However, the colored particles may be negatively charged. In that case, all the above-mentioned charging polarities are reversed.

In the present invention, it is preferable to fix the ink by an appropriate heating means after discharging the ink onto the recording medium. As the heating means to be used, a contact-type heating device such as a heat roller, a heat block, or a belt heating, and a non-contact type heating device such as a dryer, an infrared lamp, a visible light lamp, an ultraviolet lamp, or a hot air oven may be used. it can. These heating devices are preferably continuous with and integrated with the ink jet recording apparatus. The temperature of the recording medium at the time of fixing is preferably in the range of 40 ° C. to 200 ° C. for ease of fixing. The fixing time is preferably in the range of 1 microsecond to 20 seconds.
[Replenishment of ink composition]
In the ink jet recording method using an electrostatic field, charged particles in the ink composition are concentrated and discharged. Accordingly, when the ink composition is discharged for a long time, the charged particles in the ink composition are reduced, and the electrical conductivity of the ink composition is lowered. Further, the ratio between the electric conductivity of the charged particles and the electric conductivity of the ink composition changes. Further, when discharging, charged particles having a larger diameter tend to be discharged preferentially than charged particles having a smaller diameter, so that the average diameter of the charged particles is reduced. Further, since the solid content in the ink composition changes, the viscosity also changes.

Due to these changes in physical property values, as a result, ejection failure occurs, the optical density of recorded images decreases, and ink bleeding occurs. For this reason, by reducing the amount of charged particles by replenishing the ink composition having a higher concentration (higher solid content concentration) than the ink composition initially charged in the ink tank, the electrical conductivity of the ink composition The ratio between the electric conductivity of the charged particles and the electric conductivity of the ink composition can be kept within a certain range. Further, the average particle diameter and viscosity can be maintained. Further, by maintaining the physical property value of the ink composition within a certain range, the ink discharge is stably and uniformly performed for a long time. The replenishment at this time is preferably performed mechanically or manually, for example, by detecting a physical property value such as the electrical conductivity or optical density of the ink liquid used and calculating the shortage. Further, the amount of the ink composition to be used may be calculated based on the image data, and may be formed mechanically or manually.
[Recording medium]
In the present invention, various recording media can be used depending on the application. For example, if paper, plastic film, metal, and paper on which plastic or metal is laminated or vapor-deposited, plastic film on which metal is laminated or vapor-deposited, etc., printed matter can be obtained directly by ink jet recording. Moreover, an offset printing plate can be obtained if the support body etc. which roughened metals, such as aluminum, are used. Furthermore, if a plastic support is used, a flexographic printing plate or a color filter for a liquid crystal screen can be obtained. The shape of the recording medium may be planar such as a sheet shape or three-dimensional such as a cylindrical shape. Further, if a silicon wafer or a wiring board is used as a recording medium, it can be applied to manufacture of a semiconductor or a printed wiring board.
[Fixing]
In the present invention, it is preferable to fix the ink by an appropriate heating means after the ink is discharged onto the recording medium. As the heating means to be used, a contact-type heating device such as a heat roller, a heat block, or a belt heating and a non-contact type heating device such as a dryer, an infrared lamp, a visible light lamp, an ultraviolet lamp, or a hot air oven may be used. it can. These heating devices are preferably integrated with an inkjet recording apparatus.

  By combining the ink composition, the ink jet recording apparatus, and the replenishment of the ink composition described above, it is possible to stably obtain a high-quality image recorded matter with no ink bleeding and high image density over a long period of time. Can do.

  Hereinafter, although an example and a comparative example explain the present invention in detail, the present invention is not limited to these.

[Coating polymer (AP-1)]
In a 500 ml three-necked flask containing 46.6 g of 1-methoxy-2-propanol (MFG), methyl methacrylate 40 g (0.399 mol), butyl methacrylate 45 g (0.316 mol), stearyl methacrylate 5 g (0.0148 mol), monomer (M -3) A mixed solvent of 10 g (0.039 mol), dimethyl 2,2′-azobis (2-methylpropionate) (V-601) 3.45 g (15.37 mmol) and MFG 186.4 g under a nitrogen atmosphere, The mixture was added dropwise at 80 ° C. over 2.5 hours, reacted for another 2.5 hours, then heated to 90 ° C. and reacted for 2 hours. This reaction solution was reprecipitated with water and vacuum dried to obtain 92 g of polymer (AP-1). The weight average molecular weight was 19000, and the polydispersity (mass average molecular weight / number average molecular weight) was 2.4.
[Coating polymer (AP-2)]
In a 500 ml three-necked flask containing 46.6 g of 1-methoxy-2-propanol (MFG), methyl methacrylate 40 g (0.399 mol), butyl methacrylate 45 g (0.316 mol), stearyl methacrylate 5 g (0.0148 mol), monomer (M −
8) A mixed solvent of 10 g (0.055 mol), 3.61 g (15.7 mmol) of dimethyl 2,2′-azobis (2-methylpropionate) (V-601) and 186.4 g of MFG under a nitrogen atmosphere, 80 The mixture was added dropwise at 2.5 ° C. over 2.5 hours, and further reacted for 2.5 hours, and then heated to 90 ° C. and reacted for 2 hours. This reaction solution was reprecipitated with water and vacuum dried to obtain 90 g of polymer (AP-2). The weight average molecular weight was 21,000, and the polydispersity (mass average molecular weight / number average molecular weight) was 1.9.
[Coating polymer (AP-3)]
In a 500 ml three-necked flask containing 46.6 g of 1-methoxy-2-propanol (MFG), 35 g (0.350 mol) of methyl methacrylate, 50 g (0.352 mol) of butyl methacrylate, 5 g (0.0148 mol) of stearyl methacrylate, monomer (M -10) A mixed solvent of 10 g (0.095 mol), dimethyl 2,2′-azobis (2-methylpropionate) (V-601) 3.74 g (16.24 mmol) and MFG 186.4 g under a nitrogen atmosphere, The mixture was added dropwise at 80 ° C. over 2.5 hours, and after further reaction for 2.5 hours, the temperature was raised to 90 ° C. and reacted for 2 hours. This reaction solution was reprecipitated with water and vacuum dried to obtain 89 g of polymer (AP-3). The weight average molecular weight was 18000, and the polydispersity (mass average molecular weight / number average molecular weight) was 2.0.
[Coating polymer (AP-4)]
In a 500 ml three-necked flask containing 46.6 g of 1-methoxy-2-propanol (MFG), 30 g (0.300 mol) of methyl methacrylate, 60 g (0.526 mol) of ethyl methacrylate, 5 g (0.0148 mol) of stearyl methacrylate, monomer (M -19) A mixed solvent of 5 g (0.028 mol), dimethyl 2,2′-azobis (2-methylpropionate) (V-601) 4.0 g (17.38 mmol) and MFG 186.4 g under a nitrogen atmosphere, The mixture was added dropwise at 80 ° C. over 2.5 hours, and after further reaction for 2.5 hours, the temperature was raised to 90 ° C. and reacted for 2 hours. This reaction solution was reprecipitated with water and vacuum dried to obtain 94 g of polymer (AP-4). The mass average molecular weight was 20000, and the polydispersity (mass average molecular weight / number average molecular weight) was 2.4.
[Coating polymer (AP-5)]
In a 500 ml three-necked flask containing 46.6 g of 1-methoxy-2-propanol (MFG), 90 g (0.510 mol) of benzyl methacrylate, 5 g (0.0148 mol) of stearyl methacrylate, 5 g (0.022 mol) of monomer (M-21) , A mixed solvent of dimethyl 2,2′-azobis (2-methylpropionate) (V-601) 2.52 g (10.94 mmol) and MFG 186.4 g in a nitrogen atmosphere at 80 ° C. over 2.5 hours. After dropwise addition and reaction for 2.5 hours, the temperature was raised to 90 ° C. and reacted for 2 hours. This reaction solution was reprecipitated with water and vacuum dried to obtain 93 g of polymer (AP-5). The weight average molecular weight was 19000, and the polydispersity (mass average molecular weight / number average molecular weight) was 2.1.
[Coating polymer (AP-6)]
In a 500 ml three-necked flask containing 46.6 g of 1-methoxy-2-propanol (MFG), 50 g (0.499 mol) of methyl methacrylate, 35 g (0.407 mol) of methyl acrylate, 5 g (0.0148 mol) of stearyl methacrylate, monomer (M -24) A mixed solvent of 10 g (0.033 mol), dimethyl 2,2′-azobis (2-methylpropionate) (V-601) 4.39 g (19.08 mmol), and MFG 186.4 g under a nitrogen atmosphere, The mixture was added dropwise at 80 ° C. over 2.5 hours, reacted for another 2.5 hours, then heated to 90 ° C. and reacted for 2 hours. This reaction solution was reprecipitated with water and vacuum dried to obtain 91 g of a polymer (AP-6). The weight average molecular weight was 21,000, and the polydispersity (mass average molecular weight / number average molecular weight) was 2.2.
[Coating polymer (AP-7)]
In a 500 ml three-necked flask containing 46.6 g of 1-methoxy-2-propanol (MFG), methyl methacrylate 45 g (0.450 mol), butyl methacrylate 35 g (0.246 mol), dodecyl methacrylate 10 g (0.039 mol), monomer (M -30) 10 g (0.037 mol), a mixed solvent of dimethyl 2,2′-azobis (2-methylpropionate) (V-601) 3.56 g (15.44 mmol), MFG 186.4 g under a nitrogen atmosphere, The mixture was added dropwise at 80 ° C. over 2.5 hours, and after further reaction for 2.5 hours, the temperature was raised to 90 ° C. and reacted for 2 hours. This reaction solution was reprecipitated with water and vacuum dried to obtain 90 g of polymer (AP-7). The weight average molecular weight was 19000, and the polydispersity (mass average molecular weight / number average molecular weight) was 2.4.
[Coating polymer (AP-8)]
In a 500 ml three-necked flask containing 46.6 g of 1-methoxy-2-propanol (MFG), methyl methacrylate 45 g (0.450 mol), butyl methacrylate 40 g (0.281 mol), stearyl methacrylate 5 g (0.0148 mol), monomer (M -3) 5 g (0.020 mol), N, N-dimethylaminoethyl methacrylate 5 g (0.032 mol), dimethyl 2,2′-azobis (2-methylpropionate) (V-601) 3.67 g (15. 96 mmol), and 186.4 g of a mixed solvent of MFG was added dropwise at 80 ° C. over 2.5 hours under a nitrogen atmosphere. After further reaction for 2.5 hours, the temperature was raised to 90 ° C. and reacted for 2 hours. This reaction solution was reprecipitated with water and vacuum dried to obtain 92 g of polymer (AP-8). The mass average molecular weight was 25000, and the polydispersity (mass average molecular weight / number average molecular weight) was 2.2.
[Coating polymer (AP-9)]
In a 500 ml three-necked flask containing 46.6 g of 1-methoxy-2-propanol (MFG), methyl methacrylate 40 g (0.399 mol), butyl methacrylate 45 g (0.316 mol), dodecyl methacrylate 5 g (0.020 mol), monomer (M -8) 5 g (0.027 mol), N, N-dimethylaminoethyl methacrylate 5 g (0.032 mol), dimethyl 2,2′-azobis (2-methylpropionate) (V-601) 3.66 g (15 .88 mmol) and 186.4 g of a mixed solvent of MFG were added dropwise at 80 ° C. over 2.5 hours under a nitrogen atmosphere, and after further reaction for 2.5 hours, the temperature was raised to 90 ° C. and reacted for 2 hours. This reaction solution was reprecipitated with water and vacuum dried to obtain 93 g of polymer (AP-9). The weight average molecular weight was 24,000, and the polydispersity (mass average molecular weight / number average molecular weight) was 2.3.
[Example 1]
<Preparation of ink composition [EC-1]>
10 g of a cyan pigment and 20 g of a coating polymer [AP-1] were placed in a table type kneader PBV-0.1 manufactured by Irie Shokai Co., Ltd., and the heater temperature was set to 100 ° C. and heated and mixed for 2 hours. 30 g of the obtained mixture was coarsely pulverized with a trio-brender manufactured by Trio Science Co., Ltd., and further finely pulverized with a SK-M10 type sample mill manufactured by Kyoritsu Riko Co., Ltd. 30 g of the obtained finely pulverized product was predispersed in a paint shaker manufactured by Toyo Seiki Seisakusho together with 7.5 g of the dispersant [BZ-1], 75 g of Isopar G, and glass beads having a diameter of about 3.0 mm. After removing the glass beads, together with zirconia ceramic beads having a diameter of about 0.6 mm, Shinmaru Enterprises Co., Ltd. Type KDL Dynomill, maintaining the internal temperature at 2.5 ° C. for 5 hours, followed by 45 ° C. for 5 hours, Dispersion (particle formation) was performed at a rotational speed of 2,000 rpm. Zirconia ceramic beads were removed from the obtained dispersion, and 316 g of Isopar G and 0.6 g of the charge generating agent [CT-1] were added to obtain an ink composition [EC-1].

The charge generating agents used in this example and the following examples or comparative examples are shown below.
[Charge generating agent (CT-1)]
It was obtained by reacting 1-octadecene and maleic anhydride copolymer with 1-hexadecylamine. The weight average molecular weight was 17,000.
[Charge generating agent (CT-2)]
Metal soap Zirconyl naphthenate.

Further, the dispersant [BZ-1] is a polymer of stearyl methacrylate having a methacryloyl group at its terminal by mass polymerization of stearyl methacrylate in the presence of 2-mercaptoethanol and further reacting with methacrylic anhydride (mass average). The molecular weight was 7,600), and was obtained by radical polymerization with styrene. The mass average molecular weight was 110,000.
[Examples 2 to 9]
The same material except that the coating material [AP-1] was changed to [AP-2] to [AP-9] and the charge generating agent was changed as shown in Table 1 below. Ink compositions [EC-2 to 9] were prepared by various methods.
[Comparative Example 1]
The ink composition [RC-] was obtained in the same manner as in Example 1 except that the coating agent [AP-1] in Example 1 was changed to polymethyl methacrylate (Mw15000) manufactured by Aldrich [BP-1] as a comparative polymer. 1] was created.
[Comparative Example 2]
Example 1 is the same as Example 1 except that the coating agent [AP-1] in Example 1 is replaced with a comparative polymer, methyl methacrylate / butyl methacrylate / stearyl methacrylate (45/45/10 wt%) copolymer [BP-2]. Thus, an ink composition [RC-2] was prepared.
<Inkjet recording / image evaluation>
The ink composition [EC-1] of Example 1 was filled in the ink tank in the ink jet recording apparatus shown in FIGS. Here, a 150 dpi (three-row staggered arrangement with a channel density of 50 dpi) and 833 channel head of the type shown in FIG. 2 was used as the ejection head, and a silicon rubber heat roller incorporating a 1 kW heater was used as the fixing means. As the ink temperature control means, a throw-in heater and a stirring blade were provided in the ink tank, the ink temperature was set to 30 ° C., and the temperature was controlled with a thermostat while rotating the stirring blade at 30 rpm. Here, the stirring blade was also used as a stirring means for preventing precipitation and aggregation. In addition, the ink flow path is partially transparent, and the LED light emitting element and the light detecting element are arranged between them, and the ink dilution liquid (Isopar G) or concentrated ink (the solid content concentration of the ink composition is determined by the output signal). The concentration was controlled by charging. A fine coated paper for offset printing was used as a recording medium. After removing dust on the surface of the recording medium by air pump suction, the ejection head is brought close to the recording medium to the image forming position, image data to be recorded is transmitted to the image data calculation control unit, and the recording belt is rotated by rotation of the conveying belt. The ink composition was discharged while sequentially moving the discharge head while transporting the recording medium, and an image was formed with a drawing resolution of 2400 dpi. As the conveyor belt, a metal belt and polyimide film bonded together are used, and a line-shaped marker is placed in the vicinity of one end of the belt along the conveyor direction, and this is optically read by the conveyor belt position detection means. An image was formed by driving the control means. At this time, the distance between the ejection head and the recording medium was kept at 0.5 mm by the output from the optical gap detector. Further, the surface potential of the recording medium was set to −1.5 kV at the time of ejection, and a pulse voltage of +500 V was applied (pulse width 50 μsec) at the time of ejection, and image formation was performed at a driving frequency of 15 kHz.

The resulting gray scale image recorded matter (printed matter) was evaluated for the degree of stripe unevenness and ink bleeding. Specifically, the degree of bleeding of the drawn image is visually evaluated, ○ is regarded as bleeding, and Δ is
Slight bleeding was observed, and x was defined as bleeding.
<Charge evaluation>
The charge amount of the ink composition is obtained from the specific conductivity measured using the LCR meter and the liquid electrode (LP-05 type manufactured by Kawaguchi Electric Manufacturing Co., Ltd.) under the conditions of an applied voltage of 5 V and a frequency of 1 kHz. The conductivity of the ink particles was determined by subtracting the specific conductivity of the supernatant obtained by applying the ink composition to the centrifuge from the specific conductivity of the entire ink composition. Centrifugation was performed for 30 minutes using a small high-speed cooling centrifuge (Tomy Seiko Co., Ltd. SRX-201) under conditions of a rotational speed of 14500 rpm and a temperature of 23 ° C.

  The charge generation efficiency of the ink particles was obtained from the following equation.

Ink particle charge generation efficiency (%) = (ink particle charge amount Q1 / ink composition charge amount Q2) × 100
The ink compositions were evaluated in the same manner for Examples 2-9 and Comparative Examples 1-2. The results are shown in Table 1.

  As is apparent from Table 1, by using the ink composition of the present invention, it is possible to obtain good charge generation efficiency, particle charge amount, and drawn image quality. Furthermore, the charge amount and charge generation efficiency can be further increased by the combination of the coating polymer of the present invention and the charge generator having an acid group.

It is a whole lineblock diagram showing typically an example of an ink jet printer used for the present invention. It is a perspective view which shows the structure of the inkjet head of the inkjet recording device of this invention (In order to make it intelligible, the edge of the guard electrode in each discharge part is not drawn). FIG. 3 is a side sectional view showing a distribution state of charged particles when the number of ejection units of the inkjet head shown in FIG. 2 is large (corresponding to an arrow XX in FIG. 2).

Explanation of symbols

G Injected ink droplet P Recording medium Q Ink flow R Charged particle 1 Inkjet recording device 2, 2Y, 2M, 2C, 2K Discharge head 3 Ink circulation system 4 Head driver 5 Position control means 6A, 6B, 6C Conveying belt stretch Roller 7 Conveying belt 8 Conveying belt position detecting means 9 Electrostatic adsorbing means 10 Static eliminating means 11 Mechanical means 12 Feed roller 13 Guide 14 Image fixing means 15 Guide 16 Recording medium position detecting means 17 Discharge fan 18 Solvent vapor adsorbing material 38 Ink Guide 40 Support bar 42 Ink meniscus 44 Insulating layer 46 First ejection electrode 48 Insulating layer 50 Guard electrode 52 Insulating layer 56 Second ejection electrode 58 Insulating layer 62 Floating conductive plate 64 Coating film 66 Insulating member 70 Inkjet head 72 Ink flow Path 74 Substrate 75, 75A, 75B Opening 76, 76A, 76B Discharge Delivery part 78 Discharge part

Claims (3)

  An ink composition comprising a dispersion medium and charged particles containing at least a coloring material, wherein the charged particles contain at least one polymer having a nitrogen atom-containing heterocyclic group. In the ink composition containing a dispersion medium, a charged particle containing at least a coloring material, and a charge generator, the charged particle contains at least one polymer having a nitrogen atom-containing heterocyclic group, and the polymer is An ink composition comprising a repeating unit represented by the following general formula (1), wherein the charge generator contains a proton-donating charge generator.

(In the general formula (1), L ₁ is a linking group to the polymer main chain, and has a total number of 50 atoms consisting of a single bond or two or more atoms selected from C, H, N, O, S and P. The following divalent linking groups are represented, and a ₁ and a ₂ may be the same or different from each other, and are each via a hydrogen atom, a halogen atom, a cyano group, a hydrocarbon group, —COO—Z ₁ or a hydrocarbon. —COO—Z ₁ (Z ₁ represents a hydrogen atom or a hydrocarbon group). R ₁ represents an aliphatic group having 6 or more carbon atoms.)   An ink jet recording method in which an ink composition is ejected as ink droplets by an ink jet recording method using an electrostatic field, wherein the ink composition according to claim 1 or 2 is used as the ink composition. .

Images