JP2007106109A - Ink media set, ink cartridge, ink recorded material, ink jet recording apparatus and ink jet recording method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an ink media set comprising an ink and a recording medium which can record a high quality image being free from a white dot and density irregularity by an ink jet recording system, an ink cartridge, an ink recorded material, an ink jet recording apparatus and an ink jet recording method. <P>SOLUTION: For the ink media set comprising an ink containing at least a coloring agent, water, a wetting agent, a penetrant and the content of the coloring agent being 4-15 mass%, and recording media comprising surface size processing a backing by a surface size liquid containing a water soluble polymer, an area processing rate of a water soluble polymer concentration abnormal part having under 0.5X (however, X represents an average value of the water soluble polymer in the recording media) is 10% or under to feature the ink media set. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to an ink media set composed of ink and a recording medium capable of recording a high-quality image free from white spots and density unevenness by an ink jet recording method, an ink cartridge using the ink media set, and ink recording The present invention relates to an inkjet recording apparatus and an inkjet recording method.

Conventionally, inkjet recording is known as an excellent recording method that does not select a recording medium, and research and development have been actively conducted on recording apparatuses, recording methods, recording materials, and the like.
However, an inkjet recording apparatus that has been developed and commercialized so far must be (i) good without using a dedicated recording medium developed for inkjet, such as inkjet paper and inkjet transparency film. Fixability, (ii) so-called “cut”, characters, recorded image without blurring or blurring (hereinafter sometimes referred to as “feathering”), (iii) optical density (Optical) It is difficult to obtain a recorded image with high Density (OD). That is, plain paper copier paper (PPC paper), letter paper, bond paper, postcard, stationery, envelope, report paper, etc., paper that is commonly used in offices, homes, etc., and is generally commercially available When such a recording medium such as a transparency film (OHP film) is used, it is difficult to satisfy the characteristics (i) to (iii) at the same time.

  The ink jet paper is generally expensive, and the ink jet paper is a single-side coated paper. Therefore, when recording is performed on an uncoated surface, the fixing property and the print quality are remarkably lowered. There is a drawback. This is one of the reasons why ink jet recording apparatuses are not widely used.

Therefore, using plain paper copier paper (PPC paper), (i) good fixability, (ii) so-called “cut” good, print quality that does not cause blurring or feathering in the periphery of characters and images Various attempts have been made to obtain excellent recorded images, (iii) recorded images with high optical density (OD).
For example, (1) a strongly alkaline ink having a pH of about 13 (see, for example, Patent Documents 1 to 3), and (2) a method of recording by heating a solid wax-like ink at room temperature and discharging it in a molten state (patent References 4 and 5), (3) a method of recording using oil-based ink using a water-insoluble organic solvent as a liquid medium, and the like have been proposed.
Further, as to only the purpose of obtaining good fixability of the above characteristic (i), (4) ink containing a large amount of surfactant (see Patent Document 6), (5) glycerin and N-methyl-2-pyrrolidone And an ink combining a direct dye and a surfactant having a low surface tension in an amount of CMC (critical micelle concentration) or less (see Patent Document 7), (6) making the pH of the ink highly alkaline, and further providing a fluorine-based surface activity Ink added with an agent (see Patent Documents 1 and 3) has been proposed.

However, the method of using the ink of the above (1) is a printing method in which the ink is strongly alkaline and dangerous in handling, and acid paper using rosin or the like as a sizing agent has good fixability and good print quality However, in recent years, neutral paper using alkyl ketene dimer, stearic anhydride, etc., whose production volume has been increasing in Japan, has a tendency to significantly decrease the fixability, and further, the printing quality tends to decrease slightly. . In addition, since the strongly alkaline ink has a large penetrating power inside the paper, it has a drawback that it is easy to pass through and double-sided recording is extremely difficult.
The method (2) is an excellent method capable of satisfying the above characteristics (i) to (iii). However, the printed portion is raised and the printed matter is transferred when a plurality of printed matter is left to stand. Or the papers are stuck together. Another problem is that the device becomes complicated because a means for heating the ink is required.
The method (3) is particularly excellent in fixability, but it is necessary to consider the odor and safety of organic solvents contained in the ink. It is used only for industrial purposes such as printing lot numbers, and is not used in offices and general homes.
The method of using the ink (4) is not an excellent method because there is a problem in print quality as disclosed in Patent Documents 7 and 8 and the like.
In the method of using the ink of (5), the drying speed of the ink after printing (hereinafter sometimes referred to as “fixability”) is about 8 to 15 seconds, as clearly shown in the examples. Although it can be said that the fixing property is excellent compared to the conventional ink, the time of 8 to 15 seconds seems to be long from the standpoint of using the recording apparatus, and it comes from the recording apparatus depending on the paper. If the printed matter is picked up immediately, the hand may be soiled with ink, and depending on the paper, feathering may become prominent, so further improvement is desired.
The method using the ink of (6) can reduce the fixing time to 5 seconds or less. However, as clarified about the method of using the ink of (1), it is safe and fixing on neutral paper. There is a problem in the printability, print quality, and see-through property, which is not preferable.

On the other hand, various types of starch have been used for plain paper in order to improve the characteristics of plain paper that does not have an ink-jet coating layer, particularly the inkjet image characteristics. Conventionally, starch has been externally added to paper as an internal binder or a surface sizing solution as a binder to enhance paper strength, improve surface strength, improve dimensional stability, or improve the yield of additives. In order to improve the suitability of plain paper for inkjet images, for example, in (7) Patent Document 9, a surface sizing solution containing a water-soluble polymer that defines the mass ratio of polyvinyl alcohol (PVA) and starch is applied. It is disclosed. (8) Patent Document 10 discloses the application of phosphorylated starch or cationized starch. (9) Patent Document 11 discloses that starch is applied as a permeation retarder that retards permeation of ink. (10) Patent Document 12 discloses that a surface sizing agent in which starch, an AKD sizing agent, and a styrene resin are mixed is applied. (11) Patent Document 13 discloses applying a surface sizing agent containing starch and an acrylic resin. (12) Patent Document 14 discloses that paper is made from a pulp slurry containing cationized starch in order to improve the yield of the internally added sizing agent, enhance paper strength, and further improve the water resistance of the image. (13) Patent Document 15 discloses that paper containing a specific cationic polymer and cationized starch suppresses ink repelling and improves water resistance. (14) Patent Document 16 and Patent Document 17 disclose that the application of a size press solution containing starch or a starch derivative improves the suppression of feathering and improves the toner fixing property of an electrophotographic system. .
According to these proposals, a certain degree of effect can be obtained, but it is difficult to obtain image characteristics equal to or higher than those of the dedicated inkjet paper having a coat layer. In particular, solid images printed on plain paper with an inkjet printer, white spots and density unevenness seen in dark color image areas with relatively large amounts of ink adhesion, have reached a level that is as uniform as inkjet paper. Not in.

On the other hand, it is desirable to use a water-based ink as an ink-jet ink in consideration of odor, safety, ink handling property, etc. in consideration of applications for office and general household use. When the water-based ink is used, generally, if a recording medium is soiled with a fingerprint or the like, feathering tends to occur only in that portion. In addition, depending on the paper, the print quality may change remarkably between the front and back of the paper, so it is necessary to pay close attention to the handling of the recording medium when the recording medium is set in the ink jet recording apparatus.
Furthermore, for example, a multi-layer using a water-based ink containing 1 to 5% by mass of a water-soluble dye, 20 to 50% by mass of a water-soluble organic solvent such as glycols, and having a surface tension of about 40 to 55 dyne / cm. In an ink jet recording apparatus using nozzles, nozzles that do not print (not used for printing) may clog in the middle of printing due to evaporation of water from the nozzles. After printing, “1” is printed and the nozzle used to print “−” normally discharges, but the other nozzles fail to discharge and “1” cannot be printed correctly. is there.

  Further, if the ink jet recording apparatus is left for a while after printing (for example, about two days and nights assuming weekends and holidays), a non-ejection phenomenon that may occur due to an increase in ink viscosity due to evaporation of moisture from the nozzles may occur. It is often observed, and every time the recording apparatus is used, an operation for solving the non-ejection phenomenon is required. This type of trouble is relatively common when using an inkjet recording device that uses relatively small energy to fly ink, and is a foam jet type that has lower ejection energy than an inkjet recording device that uses piezo elements. It is often found in recording devices, and various improvements have been proposed.

  Therefore, in order to prevent the above trouble, it is necessary to incorporate various recovery devices such as a cap and a pump into the ink jet recording apparatus. As a result, the ink jet recording apparatus becomes larger, complicated, and expensive. It has become one. In addition, other conventional technologies have not yet been provided that sufficiently satisfy all the characteristics such as ink fixability, image sharpness, image density, and recording media transportability, and are further improved and developed. This is the current situation.

JP 56-57862 A JP-A-57-102970 JP-A-57-102971 JP-A 61-159470 JP 62-48774 A JP 55-29546 A JP 56-49771 A Japanese Patent Laid-Open No. 55-80477 Japanese Patent Laid-Open No. 5-177921 Japanese Patent Laid-Open No. 6-1152240 Japanese Patent No. 3155656 Japanese Patent No. 2648983 JP-A-7-276788 JP-A-8-282094 Japanese Patent Laid-Open No. 10-119425 JP 2000-71606 A JP 2004-58395 A

An object of the present invention is to solve various problems in the prior art and achieve the following objects. That is, the present invention uses (i) a recording medium equivalent to plain paper, (ii) high optical density (OD), good color development, (iii) little feathering, and fine line recording is possible. Yes, (iv) Good fixability, (v) Less uneven white spots and density unevenness in the image area, and (vi) Smooth and natural reproduction recording of complicated Chinese characters, diagonal lines and curved parts It is an object of the present invention to provide an ink media set, an ink cartridge using the ink in the ink media set, and an ink recorded matter.
The present invention also provides an ink jet recording apparatus and an ink jet recording method using the ink media set of the present invention that are highly reliable and can always perform normal printing at any time without using a complicated recovery device. Objective.

Means for solving the above problems are as follows. That is,
<1> an ink containing at least a colorant, water, a wetting agent, and a penetrating agent, wherein the content of the colorant is 4 to 15% by mass;
A recording medium obtained by sizing the surface of a support with a surface sizing solution containing at least a water-soluble polymer, and an ink media set comprising:
The area of the water-soluble polymer concentration abnormal portion where the amount of water-soluble polymer attached to the recording medium is less than 0.5X (where X represents the average value of the amount of water-soluble polymer attached to the recording medium). The ink media set is characterized in that the occupation ratio is 10% or less.
<2> The recording medium is a cut medium, and the amount of water-soluble polymer attached to the abnormal portion of the water-soluble polymer concentration is less than 0.5X and 0.1X or more (where X is the water-soluble polymer in the recording medium The ink media set according to <1>, which represents an average value of the adhesion amount.
<3> The ink media set according to any one of <1> to <2>, wherein the average value X of the adhesion amount of the water-soluble polymer in the recording medium is 0.5 to 7.0% by mass.
<4> The ink media set according to any one of <1> to <3>, wherein the portion having the maximum area in the water-soluble polymer concentration abnormal portion satisfies the following formula (1).
E <645 × (Dx × Dy) ^−1/2 formula (1)
In the formula (1), E represents the area (mm ² ) of the water-soluble polymer concentration abnormal portion, Dx represents the resolution in the main scanning direction (dpi), and Dy represents the resolution in the sub-scanning direction (dpi). ).
<5> The ink media set according to <4>, wherein the resolution in the main scanning direction is 300 dpi or more.
<6> The above <1> to <5>, wherein the water-soluble polymer is at least one selected from starches, polyvinyl alcohol, carboxy-modified polyvinyl alcohol, carboxymethyl cellulose, hydroxyethyl cellulose, cellulose sulfate, polyethylene oxide, and gelatin. The ink media set according to any one of the above.
<7> The ink medium according to any one of <1> to <6>, wherein the water-soluble polymer is starch, and the adhesion amount of the starch on a recording medium is determined by a color density of iodine-starch reaction. Is a set.
<8> The ink media set according to any one of <1> to <7>, wherein the ink has a viscosity at 25 ° C. of 5 to 20 cps.
<9> The ink media set according to any one of <1> to <8>, wherein the colorant is a water-dispersible colorant including a pigment.
<10> The <9>, wherein the water dispersible colorant is a pigment having at least one hydrophilic group on the surface and exhibiting at least one of water dispersibility and water solubility in the absence of the dispersant. Ink media set.
<11> The ink media set according to <10>, wherein the hydrophilic group is any one of a carboxyl group, a sulfone group, a carbonyl group, and a hydroxyl group.
<12> The ink media set according to any one of <9> to <11>, wherein the water-dispersible colorant is a pigment having a volume average particle diameter of 0.01 to 0.16 μm.
<13> The ink media set according to any one of <9> to <12>, wherein the water-dispersible colorant is a polymer emulsion in which polymer fine particles contain a colorant that is insoluble or hardly soluble in water.
<14> The ink media set according to <13>, wherein the polymer fine particles have a volume average particle diameter of 0.01 to 0.16 μm.
<15> The penetrant contains any of a polyol compound having 8 or more carbon atoms and a glycol ether compound, and the polyol compound having 8 or more carbon atoms is 2-ethyl-1,3-hexanediol, and 2,2 , 4-trimethyl-1,3-pentanediol, the ink media set according to any one of <1> to <14>.
<16> The ink media set according to any one of <1> to <15>, wherein the wetting agent is at least one selected from a polyol compound, a lactam compound, a urea compound, and a saccharide.
<17> The polyol compound is glycerin, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,3-butanediol, 2,3-butanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 2-methyl-2,4-pentanediol, 1,2,4-butanetriol, 1, The ink media set according to <16>, which is at least one selected from 2,6-hexanetriol, thiodiglycol, pentaerythritol, trimethylolethane, and trimethylolpropane.
<18> Any of <16> to <17>, wherein the lactam compound is at least one selected from 2-pyrrolidone, N-methyl-2-pyrrolidone, N-hydroxyethyl-2-pyrrolidone, and ε-caprolactam An ink media set according to claim 1.
<19> The ink according to any one of <16> to <18>, wherein the urea compound is at least one selected from urea, thiourea, ethyleneurea, and 1,3-dimethyl-2-imidazolidinone. Media set.
<20> The ink media set according to any one of <16> to <19>, wherein the saccharide is at least one selected from maltose, sorbitol, gluconolactone, and maltose.
<21> The ink media set according to any one of <1> to <20>, wherein the content of the wetting agent in the ink is 10 to 50% by mass.
<22> The ink contains a surfactant, and the surfactant is selected from the following general formulas (I), (II), (III), (IV), (V), and (VI) The ink media set according to any one of <1> to <21>, which is at least one kind.
R ¹ —O— (CH ₂ CH ₂ O) _h CH ₂ COOM —General Formula (I)
In the general formula (I), R ¹ represents an alkyl group, h represents an integer of 3 to 12, M represents an alkali metal ion, a quaternary ammonium, a quaternary phosphonium, and an alkanolamine. Represents one selected from
In the general formula (II), R ² represents an alkyl group, M represents an alkali metal ion, quaternary ammonium, any one selected from the quaternary phosphonium, and alkanolamine.
In the general formula (III), ^{R 3} is represents a hydrocarbon group, k is an integer of 5-20.
_{^{R 4 - (OCH 2 CH 2}} ) j OH ··· formula (IV)
In the general formula (IV), ^{R 4} represents a hydrocarbon group, j is an integer of 5-20.
In the general formula (V), ^{R 6} represents a hydrocarbon group, L and p are each an integer of 1-20.
However, in said general formula (VI), q and r represent the integer of 0-40, respectively.
<23> An ink cartridge characterized in that the ink in the ink media set according to any one of <1> to <22> is contained in a container.
<24> Ink flight for forming an image on the recording medium of the ink media set by applying a stimulus to the ink in the ink media set according to any one of <1> to <22> and causing the ink to fly. An ink jet recording apparatus comprising at least means.
<25> The inkjet recording apparatus according to <24>, wherein the stimulus is at least one selected from heat, pressure, vibration, and light.
<26> Ink flying step of applying a stimulus to the ink in the ink media set according to any one of <1> to <22> and causing the ink to fly to form an image on a recording medium in the ink media set An ink jet recording method comprising:
<27> The inkjet recording method according to <26>, wherein the stimulus is at least one selected from heat, pressure, vibration, and light.
<28> The inkjet recording method according to any one of <26> to <27>, wherein the maximum ink adhesion amount is 8 to 20 g / m ² at a resolution of 300 dpi or more.
<29> An ink comprising an image formed using the ink in the ink media set on the recording medium in the ink media set according to any one of <1> to <22>. It is a record.

The ink media set of the present invention includes at least a colorant, water, a wetting agent, and a penetrating agent, and the content of the colorant is 4 to 15% by mass;
A recording medium formed by subjecting the support to a surface size treatment with a surface size liquid containing at least a water-soluble polymer,
The area of the water-soluble polymer concentration abnormal portion where the amount of water-soluble polymer attached to the recording medium is less than 0.5X (where X represents the average value of the amount of water-soluble polymer attached to the recording medium). The occupation ratio is 10% or less.
In the ink media set of the present invention, (i) using a recording medium equivalent to plain paper, (ii) high optical density (OD) and good color development, (iii) less feathering, Recordable, (iv) good fixability, (v) less uneven white spots and density unevenness in the image area, (vi) smooth and natural in complex Chinese characters, shaded areas and curved areas Reproduction recording is possible.

  The ink cartridge of the present invention is formed by containing ink in the ink media set of the present invention in a container. The ink cartridge is suitably used for a printer using an ink jet recording method. When recording is performed using ink contained in the ink cartridge, (i) using a recording medium equivalent to plain paper, (ii) high optical density (OD) and good color development, (iii) feather There are few rings, fine lines can be recorded, (iv) good fixability, (v) non-uniform white spots and density unevenness in the image area, and (vi) complex Chinese characters, diagonal lines and curves Smooth and natural reproduction recording of the part is possible.

  The ink jet recording apparatus of the present invention has at least ink flying means for applying a stimulus to the ink in the ink media set of the present invention and causing the ink to fly to form an image on the recording medium of the ink media set. It becomes. In the ink jet recording apparatus, the ink flying means applies energy to the ink in the ink media set of the present invention and causes the ink to fly to record an image. As a result, using a recording medium equivalent to plain paper and predetermined ink, it is possible to perform normal image recording immediately at any time with high reliability without using a complicated recovery device.

  The ink jet recording method of the present invention includes at least an ink flying step of applying a stimulus to the ink in the ink media set of the present invention and causing the ink to fly to form an image on a recording medium in the ink media set. . In the ink jet recording method, in the ink flying process, energy is applied to the ink in the ink media set of the present invention, and the ink is ejected to record an image. As a result, using a recording medium equivalent to plain paper and predetermined ink, it is possible to perform normal image recording immediately at any time with high reliability without using a complicated recovery device.

  The ink recorded matter of the present invention has an image formed using the ink in the ink media set on the recording medium in the ink media set. In the ink recorded matter, using a recording medium equivalent to plain paper and a predetermined ink, (ii) high optical density (OD) and good color developability, (iii) less feathering and fine line recording Yes, (iv) good fixability, (v) less uneven white spots and density unevenness in the image area, and (vi) smooth and natural reproduction recording of complicated Chinese characters, diagonal lines and curved areas. An image is held on the recording medium.

  According to the present invention, a conventional problem can be solved, and a recording medium containing a water-soluble polymer with a uniform concentration with little bias is combined with a predetermined ink, and the image has white spots and density unevenness. There can be provided an ink media set capable of obtaining a low color development and high light fast image at low cost, and an ink cartridge, an ink record, an ink jet recording apparatus and an ink jet recording method using the ink media set.

(Ink media set)
The ink media set of the present invention includes ink and a recording medium, and further includes other elements as necessary.

<Ink>
The ink contains at least water, a colorant, a penetrating agent, and a wetting agent, and further contains a surfactant and, if necessary, other components.

-Colorant-
As the colorant, it is preferable to use at least one of a pigment, a dye, and colored fine particles.
As the colored fine particles, an aqueous dispersion of fine polymer particles containing at least one coloring material of pigment and dye is preferable. Among these, an aqueous dispersion containing a pigment is more preferable.
Here, the term “containing a color material” means either or both of a state in which the color material is enclosed in the polymer fine particles and a state in which the color material is adsorbed on the surface of the polymer fine particles. In this case, it is not necessary for all of the color material blended in the ink of the present invention to be encapsulated or adsorbed in the polymer fine particles, and the color material is dispersed in the emulsion as long as the effects of the present invention are not impaired. Also good. The color material is not particularly limited as long as it is water-insoluble or hardly water-soluble and can be adsorbed by the polymer, and can be appropriately selected according to the purpose.
Here, the “water-insoluble or hardly water-soluble” means that the coloring material does not dissolve 10 parts by mass or more with respect to 100 parts by mass of water at 20 ° C. Further, “dissolve” means that separation or sedimentation of the coloring material is not observed on the surface layer or the lower layer of the aqueous solution visually.

The volume average particle diameter of the polymer fine particles (colored fine particles) containing the colorant is preferably 0.01 to 0.16 μm in the ink.
When the volume average particle size of the polymer fine particles is less than 0.01 μm, dispersion may become unstable and agglomerate, and when it exceeds 0.16 μm, it may cause clogging in a filter or a discharge part. In addition, when the volume average particle diameter is outside the range of 0.01 to 0.16 μm, storage stability and ejection reliability may be impaired.

Examples of the colorant include water-soluble dyes, oil-soluble dyes, dyes such as disperse dyes, pigments, and the like. Oil-soluble dyes and disperse dyes are preferable from the viewpoint of good adsorptivity and encapsulation, but pigments are preferably used from the light resistance of the obtained image.
From the viewpoint of efficiently impregnating the polymer fine particles, each of the dyes is preferably dissolved in an organic solvent, for example, a ketone solvent in an amount of 2 g / liter or more, and more preferably 20 to 600 g / liter.
The water-soluble dye is a dye classified into an acid dye, a direct dye, a basic dye, a reactive dye, and a food dye in the color index, and preferably has excellent water resistance and light resistance. .

  Examples of the acid dyes and food dyes include C.I. I. Acid Yellow 17, 23, 42, 44, 79, 142; C.I. I. Acid Red 1,8,13,14,18,26,27,35,37,42,52,82,87,89,92,97,106,111,114,115,134,186,249,254 289; I. Acid Blue 9, 29, 45, 92, 249; I. Acid Black 1, 2, 7, 24, 26, 94; I. Food Yellow 3, 4; I. Food red 7, 9, 14; I. Food black 1, 2 etc. are mentioned.

  Examples of the direct dye include C.I. I. Direct yellow 1,12,24,26,33,44,50,86,120,132,142,144; I. Direct red 1,4,9,13,17,20,28,31,39,80,81,83,89,225,227; I. Direct orange 26, 29, 62, 102; I. Direct Blue 1, 2, 6, 15, 22, 25, 71, 76, 79, 86, 87, 90, 98, 163, 165, 199, 202; I. Direct black 19, 22, 32, 38, 51, 56, 71, 74, 75, 77, 154, 168, 171 and the like.

  Examples of the basic dye include C.I. I. Basic yellow 1, 2, 11, 13, 14, 15, 19, 21, 23, 24, 25, 28, 29, 32, 36, 40, 41, 45, 49, 51, 53, 63, 64, 65, 67, 70, 73, 77, 87, 91; I. Basic Red 2,12,13,14,15,18,22,23,24,27,29,35,36,38,39,46,49,51,52,54,59,68,69,70, 73, 78, 82, 102, 104, 109, 112; I. Basic Blue 1,3,5,7,9,21,22,26,35,41,45,47,54,62,65,66,67,69,75,77,78,89,92,93, 105, 117, 120, 122, 124, 129, 137, 141, 147, 155; I. Basic black 2, 8 etc. are mentioned.

  Examples of the reactive dye include C.I. I. Reactive Black 3, 4, 7, 11, 12, 17; C.I. I. Reactive Yellow 1,5,11,13,14,20,21,22,25,40,47,51,55,65,67; I. Reactive Red 1,14,17,25,26,32,37,44,46,55,60,66,74,79,96,97; I. Reactive blue 1, 2, 7, 14, 15, 23, 32, 35, 38, 41, 63, 80, 95, and the like.

There is no restriction | limiting in particular as said pigment, According to the objective, it can select suitably, For example, any of an inorganic pigment and an organic pigment may be sufficient.
Examples of the inorganic pigment include titanium oxide, iron oxide, calcium carbonate, barium sulfate, aluminum hydroxide, barium yellow, cadmium red, chrome yellow, and carbon black. Among these, carbon black is preferable. In addition, as said carbon black, what was manufactured by well-known methods, such as a contact method, a furnace method, and a thermal method, is mentioned, for example.

  Examples of the organic pigment include azo pigments, polycyclic pigments, dye chelates, nitro pigments, nitroso pigments, and aniline black. Among these, azo pigments and polycyclic pigments are more preferable. Examples of the azo pigment include azo lakes, insoluble azo pigments, condensed azo pigments, and chelate azo pigments. Examples of the polycyclic pigment include phthalocyanine pigments, perylene pigments, perinone pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, indigo pigments, thioindigo pigments, isoindolinone pigments, and quinofullerone pigments. Examples of the dye chelates include basic dye chelates and acidic dye chelates.

There is no restriction | limiting in particular as a color of the said pigment, According to the objective, it can select suitably, For example, black, a color, etc. are mentioned. These may be used alone or in combination of two or more.
Examples of the black pigment include carbon black (CI pigment black 7) such as furnace black, lamp black, acetylene black, and channel black, copper, iron (CI pigment black 11), and titanium oxide. And organic pigments such as aniline black (CI Pigment Black 1).

As the color pigment, for yellow ink, for example, C.I. I. Pigment Yellow 1 (Fast Yellow G), 3, 12 (Disazo Yellow AAA), 13, 14, 17, 23, 24, 34, 35, 37, 42 (Yellow Iron Oxide), 53, 55, 74, 81, 83 (Disazo Yellow HR), 95, 97, 98, 100, 101, 104, 108, 109, 110, 117, 120, 128, 138, 150, 153, and the like.
For magenta, for example, C.I. I. Pigment Red 1, 2, 3, 5, 17, 22 (Brilliant First Scarlet), 23, 31, 38, 48: 2 (Permanent Red 2B (Ba)), 48: 2 (Permanent Red 2B (Ca)), 48 : 3 (Permanent Red 2B (Sr)), 48: 4 (Permanent Red 2B (Mn)), 49: 1, 52: 2, 53: 1, 57: 1 (Brilliant Carmine 6B), 60: 1, 63: 1, 63: 2, 64: 1, 81 (Rhodamine 6G Lake), 83, 88, 92, 101 (Bengara), 104, 105, 106, 108 (Cadmium Red), 112, 114, 122 (Dimethylquinacridone), 123, 146, 149, 166, 168, 170, 172, 177, 178, 179, 185, 190, 193, 209, 2 9, and the like.
For cyan, for example, C.I. I. Pigment Blue 1, 2, 15 (copper phthalocyanine blue R), 15: 1, 15: 2, 15: 3 (phthalocyanine blue G), 15: 4, 15: 6 (phthalocyanine blue E), 16, 17: 1, 56, 60, 63 and the like.
In addition, as the intermediate colors for red, green and blue, C.I. I. Pigment red 177, 194, 224, C.I. I. Pigment orange 43, C.I. I. Pigment violet 3, 19, 23, 37, C.I. I. Pigment green 7, 36, and the like.

Examples of the pigment include self-dispersing pigments that have at least one hydrophilic group directly on the surface of the pigment and can be stably dispersed or dissolved without using a dispersant bonded through another atomic group. Preferably used. As a result, unlike the conventional ink, a dispersant for dispersing the pigment becomes unnecessary. As the self-dispersing pigment, those having ionicity are preferable, and those having an anionic charge or those having a cationic charge are suitable.
The volume average particle diameter of the self-dispersing pigment is preferably 0.01 to 0.16 μm in the ink.
When the volume average particle size of the self-dispersing pigment is less than 0.01 μm, dispersion may become unstable and agglomerate, and when it exceeds 0.16 μm, it may cause clogging in a filter or a discharge part. When the volume average particle size is outside the range of 0.01 to 0.16 μm, storage stability and ejection reliability may be impaired.

Examples of the anionic hydrophilic group, for _{example, -COOM, -SO 3 M, -PO} 3 HM, -PO 3 M 2, -SO 2 NH 2, -SO 2 NHCOR, -COM, -OM ( where in the formula M represents a hydrogen atom, an alkali metal, ammonium or organic ammonium, and R represents an alkyl group having 1 to 12 carbon atoms, a phenyl group which may have a substituent, or a naphthyl group which may have a substituent. And the like. Among these, it is preferable to use those in which —COOM, —SO ₃ M, —COM, and —OM are bonded to the color pigment surface.

  Further, “M” in the hydrophilic group includes, for example, lithium, sodium, potassium and the like as an alkali metal. Examples of the organic ammonium include mono to trimethyl ammonium, mono to triethyl ammonium, and mono to trimethanol ammonium. As a method of obtaining the anionically charged color pigment, as a method of introducing —COONa to the color pigment surface, for example, a method of oxidizing the color pigment with sodium hypochlorite, a method of sulfonation, a diazonium salt The method of making it react is mentioned.

  As the cationic hydrophilic group, for example, a quaternary ammonium group is preferable, a quaternary ammonium group listed below is more preferable, and any of these bonded to the pigment surface is suitable as a coloring material.

  As a method for producing the cationic self-dispersing carbon black to which the hydrophilic group is bonded, for example, as a method for bonding an N-ethylpyridyl group represented by the following structural formula, carbon black is converted to 3-amino-N -Although the method of processing with an ethyl pyridium bromide is mentioned, of course, this invention is not limited to these.

In the present invention, the hydrophilic group may be bonded to the surface of carbon black through another atomic group. Examples of other atomic groups include an alkyl group having 1 to 12 carbon atoms, a phenyl group which may have a substituent, or a naphthyl group which may have a substituent. Specific examples of the case where the above hydrophilic group is bonded to the surface of carbon black through another atomic group include, for example, —C ₂ H ₄ COOM (where M represents an alkali metal or quaternary ammonium). ), - PhSO ₃ M (however, Ph represents a phenyl group, M represents an alkali metal or quaternary _{ammonium), - C 5 H 10 NH} 3 + , and the like.

In the present invention, a pigment dispersion using a pigment dispersant can also be used.
As the pigment dispersant, as the hydrophilic polymer compound, in the natural system, plant polymers such as gum arabic, tragan gum, guar gum, karaya gum, locust bean gum, arabinogalactone, pectin, quince seed starch, alginic acid, Examples include seaweed polymers such as carrageenan and agar, animal polymers such as gelatin, casein, albumin and collagen, and microbial polymers such as xanthene gum and dextran. For semi-synthetic systems, cellulose polymers such as methylcellulose, ethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, carboxymethylcellulose, starch polymers such as sodium starch glycolate and sodium starch phosphate, sodium alginate, propylene glycol alginate And seaweed polymers such as Pure synthetic systems include polyvinyl polymers such as polyvinyl alcohol, polyvinyl pyrrolidone, and polyvinyl methyl ether, non-crosslinked polyacrylamide, polyacrylic acid or alkali metal salts thereof, acrylic resins such as water-soluble styrene acrylic resins, and water-soluble styrene malees. Acid resin, water-soluble vinyl naphthalene acrylic resin, water-soluble vinyl naphthalene maleic resin, polyvinyl pyrrolidone, polyvinyl alcohol, alkali metal salts of β-naphthalene sulfonic acid formalin condensate, cationic functional groups such as quaternary ammonium and amino groups Examples thereof include a polymer compound having a salt in the side chain and a natural polymer compound such as shellac. Among these, those having a carboxyl group introduced from a homopolymer of acrylic acid, methacrylic acid or styrene acrylic acid or a copolymer of a monomer having another hydrophilic group are particularly preferred as the polymer dispersant.
The weight average molecular weight of the copolymer is preferably 3,000 to 50,000, more preferably 5,000 to 30,000, and still more preferably 7,000 to 15,000.
The mixing mass ratio of the pigment and the dispersant is preferably in the range of 1: 0.06 to 1: 3, and more preferably in the range of 1: 0.125 to 1: 3.

  The content of the colorant in the ink is 4 to 15% by mass, preferably 6 to 15% by mass, and more preferably 8 to 12% by mass. If the content is less than 4% by mass, the image density may decrease due to a decrease in coloring power, or feathering or bleeding may deteriorate due to a decrease in viscosity. If left unattended, the nozzles will easily dry, causing non-ejection phenomenon, the viscosity becomes too high, penetrability will decrease, and the dots will not spread, so the image density will decrease. , The image may become blurred.

-Penetration agent-
There is no restriction | limiting in particular as said penetrant, According to the objective, it can select suitably, For example, it is preferable to contain either a C8 or more polyol compound and a glycol ether compound.
If the polyol compound has less than 8 carbon atoms, sufficient penetrability cannot be obtained, and the recording medium is soiled during double-sided printing, or ink spreading on the recording medium is insufficient, resulting in poor pixel filling. Therefore, character quality and image density may be reduced.
Examples of the polyol compound having 8 or more carbon atoms include 2-ethyl-1,3-hexanediol (solubility: 4.2% (25 ° C.)), 2,2,4-trimethyl-1,3-pentanediol. (Solubility: 2.0% (25 ° C.)) is preferable.
Examples of the glycol ether compound include polyhydric alcohol alkyls such as ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, tetraethylene glycol monomethyl ether, and propylene glycol monoethyl ether. Examples of ethers include polyhydric alcohol aryl ethers such as ethylene glycol monophenyl ether and ethylene glycol monobenzyl ether.

  There is no restriction | limiting in particular in the addition amount of the said penetrant, According to the objective, it can select suitably, 0.1-20 mass% is preferable, and 0.5-10 mass% is more preferable.

-Wetting agent-
There is no restriction | limiting in particular as said wetting agent, According to the objective, it can select suitably, For example, at least 1 sort (s) selected from a polyol compound, a lactam compound, a urea compound, and saccharides is suitable.

Examples of the polyol compound include ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, polypropylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4 butanediol, 1,5 pentanediol, Polyhydric alcohols such as 1,6 hexanediol, glycerol, 1,2,6-hexanetriol, 1,2,4-butanetriol, 1,2,3-butanetriol, petriol; ethylene glycol monoethyl ether, ethylene Glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, tetraethylene glycol monomethyl ether, propylene group Polyhydric alcohol alkyl ethers such as coal monoethyl ether; polyhydric alcohol aryl ethers such as ethylene glycol monophenyl ether and ethylene glycol monobenzyl ether; diethanolamine, triethanolamine, thiodiethanol, pentaerythritol, trimethylolethane, And methylolpropane. These may be used alone or in combination of two or more.
Among these, glycerin, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1 from the viewpoint of obtaining excellent effects on solubility and prevention of poor jetting characteristics due to water evaporation , 3-butanediol, 2,3-butanediol, 1,4-butanediol, 1,5-pentanediol, tetraethylene glycol, 1,6-hexanediol, 2-methyl-2,4-pentanediol, polyethylene Glycol, 1,2,4-butanetriol, 1,2,6-hexanetriol, thiodiglycol, pentaerythritol, trimethylolethane, and trimethylolpropane are preferred.

Examples of the lactam compound include at least one selected from 2-pyrrolidone, N-methyl-2-pyrrolidone, N-hydroxyethyl-2-pyrrolidone, and ε-caprolactam.
Examples of the urea compound include at least one selected from urea, thiourea, ethylene urea, and 1,3-dimethyl-2-imidazolidinone. In general, the amount of urea added to the ink is preferably 0.5 to 50% by mass, and more preferably 1 to 20% by mass.

Examples of the saccharide include monosaccharides, disaccharides, oligosaccharides (including trisaccharides and tetrasaccharides), polysaccharides, and derivatives thereof. Among these, glucose, mannose, fructose, ribose, xylose, arabinose, galactose, maltose, cellobiose, lactose, sucrose, trehalose, and maltotriose are preferable, and maltose, sorbitol, gluconolactone, and maltose are particularly preferable.
The polysaccharide means a saccharide in a broad sense and can be used to include substances widely existing in nature such as α-cyclodextrin and cellulose.
The saccharide derivative is represented by a reducing sugar of the saccharide (for example, sugar alcohol [wherein general formula: HOCH ₂ (CHOH) _n CH ₂ OH (where n represents an integer of 2 to 5)). ], Oxidized sugars (for example, aldonic acid, uronic acid, etc.), amino acids, thioic acids, etc. Among them, sugar alcohols are particularly preferable, and examples of the sugar alcohols include maltitol, sorbit, and the like. It is done.

  The content of the wetting agent in the ink is preferably 10 to 50% by mass, and more preferably 20 to 35% by mass. If the content is too small, the nozzle is likely to be dried and defective ejection of droplets may occur. If the content is too large, the ink viscosity is increased and the proper viscosity range may be exceeded.

-Surfactant-
The surfactant is not particularly limited and may be appropriately selected depending on the intended purpose. For example, an anionic surfactant, a nonionic surfactant, an amphoteric surfactant, a nonionic surfactant, an acetylene glycol type Surfactant etc. are mentioned, Especially at least 1 sort (s) selected from the following general formula (I), (II), (III), (IV), (V), and (VI) is preferable.

R ¹ —O— (CH ₂ CH ₂ O) _h CH ₂ COOM —General Formula (I)
In the general formula (I), R ¹ represents an alkyl group, h represents an integer of 3 to 12, M represents an alkali metal ion, a quaternary ammonium, a quaternary phosphonium, and an alkanolamine. Represents one selected from

In the general formula (II), R ² represents an alkyl group, M represents an alkali metal ion, quaternary ammonium, any one selected from the quaternary phosphonium, and alkanolamine.

In the general formula (III), ^{R 3} is represents a hydrocarbon group, k is an integer of 5-20.
_{^{R 4 - (OCH 2 CH 2}} ) j OH ··· formula (IV)
In the general formula (IV), ^{R 4} represents a hydrocarbon group, j is an integer of 5-20.

In the general formula (V), ^{R 6} represents a hydrocarbon group, L and p are each an integer of 1-20.

However, in said general formula (VI), q and r represent the integer of 0-40, respectively.

Hereinafter, the surfactants of the structural formulas (I) and (II) are specifically shown in free acid form.
(I-1): CH ₃ (CH ₂ ) ₁₂ O (CH ₂ CH ₂ O) ₃ CH ₂ COOH
_{(I-2): CH 3} (CH 2) 12 O (CH 2 CH 2 O) 4 CH 2 COOH
(I-3): CH ₃ (CH ₂ ) ₁₂ O (CH ₂ CH ₂ O) ₅ CH ₂ COOH
(I-4): CH ₃ (CH ₂ ) ₁₂ O (CH ₂ CH ₂ O) ₆ CH ₂ COOH

  Examples of the anionic surfactant include polyoxyethylene alkyl ether acetate, dodecyl benzene sulfonate, laurate, polyoxyethylene alkyl ether sulfate salt, and the like.

Examples of the nonionic surfactant include acetylene glycol surfactants, polyoxyethylene alkyl ethers, polyoxypropylene polyoxyethylene alkyl ethers, polyoxyethylene alkyl esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene alkyls. Examples include phenyl ether, polyoxyethylene alkylamine, polyoxyethylene alkylamide, and the like.
Examples of the acetylene glycol surfactant include 2,4,7,9-tetramethyl-5-decyne-4,7-diol, 3,6-dimethyl-4-octyne-3,6-diol, , 5-dimethyl-1-hexyn-3-ol and the like. Commercially available products can be used as the acetylene glycol surfactant, and examples thereof include Surfinol 104, 82, 465, 485 manufactured by Air Products, Inc. and TG. Among these, Surfynol 465, 104 and TG are particularly preferable because they exhibit good print quality.

  Examples of the amphoteric surfactant include lauryl aminopropionate, lauryl dimethyl betaine, stearyl dimethyl betaine, lauryl dihydroxyethyl betaine, lauryl dimethylamine oxide, myristyl dimethylamine oxide, stearyl dimethylamine oxide, dihydroxyethyl lauryl amine oxide, Polyoxyethylene coconut oil alkyldimethylamine oxide, dimethylalkyl (coconut) betaine, dimethyllauryl betaine, and the like.

  The content of the surfactant in the ink is preferably 0.05 to 10% by mass, and more preferably 0.1 to 5% by mass.

-Other ingredients-
The other components are not particularly limited and may be appropriately selected as necessary. For example, resin emulsion, pH adjuster, antiseptic / antifungal agent, rust preventive, antioxidant, ultraviolet absorber, oxygen An absorber, a light stabilizer, etc. are mentioned.

-Resin emulsion-
The resin emulsion is obtained by dispersing resin fine particles in water as a continuous phase, and may further contain a dispersant such as a surfactant, if necessary.
The content of resin fine particles as the dispersed phase component (content of resin fine particles in the resin emulsion) is preferably 10 to 70% by mass. Further, the volume average particle diameter of the resin fine particles is preferably 10 to 1,000 nm, more preferably 20 to 300 nm in consideration of use in an ink jet recording apparatus.

The resin particles in the dispersed phase are not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include acrylic resin particles, vinyl acetate resin particles, styrene resin particles, butadiene resin particles, and styrene. -Butadiene copolymer resin fine particles, vinyl chloride copolymer resin fine particles, acrylic-styrene copolymer resin fine particles, acrylic silicone resin fine particles, and the like are mentioned. Among these, acrylic silicone resin fine particles are particularly preferable.
As said resin emulsion, what was synthesize | combined suitably may be used and a commercial item may be used.
Examples of the commercially available resin emulsion include Microgel E-1002, E-5002 (styrene-acrylic resin emulsion, manufactured by Nippon Paint Co., Ltd.), and Boncoat 4001 (acrylic resin emulsion, manufactured by Dainippon Ink & Chemicals, Inc.). ), Boncoat 5454 (styrene-acrylic resin emulsion, manufactured by Dainippon Ink & Chemicals, Inc.), SAE-1014 (styrene-acrylic resin emulsion, manufactured by Nippon Zeon Co., Ltd.), Cybinol SK-200 (acrylic resin emulsion, Seiden Chemical Co., Ltd.), Primal AC-22, AC-61 (acrylic resin emulsion, manufactured by Rohm and Haas), Nanoacryl SBCX-2821, 3689 (acrylic silicone resin emulsion, Toyo Ink Co., Ltd.) Company Ltd.), # 3070 (methyl methacrylate polymer resin emulsion, manufactured by Mikuni Color Ltd.).

  The content of the resin fine particles in the recording ink is preferably 0.1 to 50% by mass, more preferably 0.5 to 20% by mass, and still more preferably 1 to 10% by mass. When the content is less than 0.1% by mass, clogging resistance and ejection stability may not be sufficiently improved. When the content exceeds 50% by mass, the storage stability of the ink may be reduced. .

  Examples of the antiseptic / antifungal agent include 1,2-benzisothiazolin-3-one, sodium dehydroacetate, sodium sorbate, sodium 2-pyridinethiol-1-oxide, sodium benzoate, and sodium pentachlorophenol. Can be mentioned.

  The pH adjuster is not particularly limited as long as it can adjust the pH to 7 or more without adversely affecting the ink to be prepared, and any substance can be used according to the purpose. Examples of the pH adjuster include amines such as diethanolamine and triethanolamine, hydroxides of alkali metal elements such as lithium hydroxide, sodium hydroxide and potassium hydroxide; ammonium hydroxide and quaternary ammonium hydroxide. Quaternary phosphonium hydroxide, alkali metal carbonates such as lithium carbonate, sodium carbonate, potassium carbonate, and the like.

  Examples of the rust inhibitor include acidic sulfite, sodium thiosulfate, ammonium thiodiglycolate, diisopropylammonium nitrite, pentaerythritol tetranitrate, and dicyclohexylammonium nitrite.

Examples of the antioxidant include phenol-based antioxidants (including hindered phenol-based antioxidants), amine-based antioxidants, sulfur-based antioxidants, phosphorus-based antioxidants, and the like.
Examples of the phenolic antioxidants (including hindered phenolic antioxidants) include butylated hydroxyanisole, 2,6-di-tert-butyl-4-ethylphenol, stearyl-β- (3,5 -Di-tert-butyl-4-hydroxyphenyl) propionate, 2,2'-methylenebis (4-methyl-6-tert-butylphenol), 2,2'-methylenebis (4-ethyl-6-tert-butylphenol), 4,4′-Butylidenebis (3-methyl-6-tert-butylphenol), 3,9-bis [1,1-dimethyl-2- [β- (3-tert-butyl-4-hydroxy-5-methylphenyl) ) Propionyloxy] ethyl] 2,4,8,10-tetrixaspiro [5,5] undecane, 1,1,3-tris (2-methyl-4- Hydroxy-5-tert-butylphenyl) butane, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, tetrakis [methylene-3- (3 ′, 5′-di-tert-butyl-4′-hydroxyphenyl) propionate] methane, and the like.
Examples of the amine-based antioxidant include phenyl-β-naphthylamine, α-naphthylamine, N, N′-di-sec-butyl-p-phenylenediamine, phenothiazine, N, N′-diphenyl-p-phenylenediamine. 2,6-di-tert-butyl-p-cresol, 2,6-di-tert-butylphenol, 2,4-dimethyl-6-tert-butyl-phenol, butylhydroxyanisole, 2,2′-methylenebis ( 4-methyl-6-tert-butylphenol), 4,4′-butylidenebis (3-methyl-6-tert-butylphenol), 4,4′-thiobis (3-methyl-6-tert-butylphenol), tetrakis [methylene -3 (3,5-di-tert-butyl-4-dihydroxyphenyl) propionate] methane, 1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, and the like.
Examples of the sulfur-based antioxidant include dilauryl 3,3′-thiodipropionate, distearyl thiodipropionate, lauryl stearyl thiodipropionate, dimyristyl 3,3′-thiodipropionate, distearyl β. , β′-thiodipropionate, 2-mercaptobenzimidazole, dilauryl sulfide and the like.
Examples of the phosphorus antioxidant include triphenyl phosphite, octadecyl phosphite, triisodecyl phosphite, trilauryl trithiophosphite, trinonylphenyl phosphite, and the like.

Examples of the ultraviolet absorber include benzophenone ultraviolet absorbers, benzotriazole ultraviolet absorbers, salicylate ultraviolet absorbers, cyanoacrylate ultraviolet absorbers, and nickel complex salt ultraviolet absorbers.
Examples of the benzophenone-based ultraviolet absorber include 2-hydroxy-4-n-octoxybenzophenone, 2-hydroxy-4-n-dodecyloxybenzophenone, 2,4-dihydroxybenzophenone, and 2-hydroxy-4-methoxybenzophenone. 2,2 ′, 4,4′-tetrahydroxybenzophenone, and the like.
Examples of the benzotriazole ultraviolet absorber include 2- (2′-hydroxy-5′-tert-octylphenyl) benzotriazole, 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-4′-octoxyphenyl) benzotriazole, 2- (2′-hydroxy-3′-tert-butyl-5′-methylphenyl) -5-chlorobenzotriazole, and the like.
Examples of the salicylate-based ultraviolet absorber include phenyl salicylate, p-tert-butylphenyl salicylate, p-octylphenyl salicylate, and the like.
Examples of the cyanoacrylate ultraviolet absorber include ethyl-2-cyano-3,3′-diphenyl acrylate, methyl-2-cyano-3-methyl-3- (p-methoxyphenyl) acrylate, and butyl-2- And cyano-3-methyl-3- (p-methoxyphenyl) acrylate.
Examples of the nickel complex ultraviolet absorber include nickel bis (octylphenyl) sulfide, 2,2′-thiobis (4-tert-octylferrate) -n-butylamine nickel (II), 2,2′-thiobis. (4-tert-octyl ferrate) -2-ethylhexylamine nickel (II), 2,2′-thiobis (4-tert-octyl ferrate) triethanolamine nickel (II), and the like.

  The ink in the ink media set of the present invention is produced by dispersing or dissolving at least a colorant, a penetrating agent, a wetting agent, and, if necessary, other components in water, and further stirring and mixing as necessary. The dispersion can be performed by, for example, a sand mill, a homogenizer, a ball mill, a paint shaker, an ultrasonic disperser, etc., and stirring and mixing are performed by a stirrer using a normal stirring blade, a magnetic stirrer, a high-speed disperser, or the like. be able to.

As physical properties of the ink, for example, the viscosity, surface tension, pH, and the like are preferably in the following ranges.
The viscosity is preferably 5 to 20 cps and more preferably 8 to 20 cps at 25 ° C. If the viscosity exceeds 20 cps, it may be difficult to ensure ejection stability.
The surface tension is preferably 40 dyne / cm or less, and more preferably 17 to 40 dyne / cm at 25 ° C. When the surface tension is 40 dyne / cm or less, quick fixing can be performed on almost all recording media.
As said pH, 7-10 are preferable, for example.

  There is no restriction | limiting in particular as coloring of the said ink, According to the objective, it can select suitably, Yellow, magenta, cyan, black etc. are mentioned. When recording is performed using an ink set in which two or more of these colorings are used in combination, a multicolor image can be formed. When recording is performed using an ink set in which all colors are combined, a full color image is formed. be able to.

  The ink in the ink media set of the present invention is an ink jet head that uses a piezoelectric element as pressure generating means for pressurizing ink in the ink flow path, and deforms the diaphragm that forms the wall surface of the ink flow path. A so-called piezo-type device that discharges ink droplets by changing the product (see Japanese Patent Laid-Open No. 2-51734), or a so-called thermal device that generates bubbles by heating ink in an ink flow path using a heating resistor. Type (see Japanese Patent Application Laid-Open No. 61-59911), the diaphragm and the electrode forming the wall surface of the ink flow path are arranged opposite to each other, and the diaphragm is deformed by the electrostatic force generated between the diaphragm and the electrode Thus, any ink jet such as an electrostatic type that discharges ink droplets by changing the volume of the ink flow path (see JP-A-6-71882) can be used. It can be satisfactorily used in the printer for mounting a head.

<Recording media>
The recording medium has a support and, if necessary, other configurations.
The support is characterized by being subjected to surface sizing treatment with a surface sizing solution containing at least a water-soluble polymer.

The recording medium is characterized in that the area occupation ratio of the water-soluble polymer concentration abnormal portion is 10% or less. The water-soluble polymer concentration abnormal portion is a portion where the water-soluble polymer adhesion amount is less than 0.5X (where X represents the average value of the water-soluble polymer adhesion amount on the recording medium). Show.
The area occupancy of the water-soluble polymer concentration abnormal portion indicates the area occupancy with respect to the entire printing surface of the recording medium, and when there are a plurality of water-soluble polymer concentration abnormal portions, the water-soluble polymer concentration abnormal portion It shows the total area of all parts. The entire printing surface of the recording medium is a printable range of the recording medium, and usually indicates the total front and back area of the recording medium because the surface size processing is performed on both sides of the support. However, this does not apply to recording media intended only for single-sided printing.
The average value X of the adhesion amount of the water-soluble polymer is preferably 0.5 to 7.0% by mass.
Due to the size treatment with the surface sizing liquid, the amount of the water-soluble polymer adhering to the surface of the recording medium is less than 0.5X (where X represents the average value of the amount of water-soluble polymer adhering to the recording medium). If the (water-soluble polymer concentration abnormal portion) is present in the recording medium, it may cause white spots or density unevenness in the normal portion. In other words, since the ink tends to wet and spread in the portion where the water-soluble polymer adhesion amount is small, the dot area may be easily increased, and in the portion where the water-soluble polymer adhesion amount is large, the dot area tends to be small or the ink May be easily repelled.

The area of the water-soluble polymer concentration abnormal portion where the amount of water-soluble polymer adhering to the recording medium is less than 0.5X (where X represents the average value of the amount of water-soluble polymer adhering to the recording medium). The occupation ratio is characterized by being 10% or less, preferably 5% or less, and more preferably 3% or less.
If the area occupancy ratio of the water-soluble polymer concentration abnormal portion exceeds 10%, abnormal images such as white spots and density unevenness are conspicuous, and a high-quality image cannot be obtained.

  When the recording medium is cut media, the amount of the water-soluble polymer attached to the abnormal portion of the water-soluble polymer concentration is less than 0.5X and 0.1X or more (where X is the amount of water-soluble polymer attached to the recording medium) It represents the average value of the amount.) When the recording medium is cut media, if the amount of water-soluble polymer attached to the water-soluble polymer concentration abnormal portion is less than 0.1X, extreme density unevenness may occur.

Moreover, it is preferable that the area occupation rate of the location which has the largest area in the said water-soluble polymer density | concentration abnormal part satisfy | fills following formula (1).
E <645 × (Dx × Dy) ^−1/2 formula (1)
In the formula (1), E represents the area (mm ² ) of the water-soluble polymer concentration abnormal portion, Dx represents the resolution in the main scanning direction (dpi), and Dy represents the resolution in the sub-scanning direction (dpi). ).
This is because the relationship between the size of the polymer concentration abnormal portion, the resolution in the main scanning direction, and the resolution in the sub-scanning direction satisfies the formula (1), so that abnormal images such as white spots and density unevenness are not easily noticeable. Thus, it is possible to form a high-quality image such as an inkjet dedicated paper having a coating layer. In particular, when the resolution in the main scanning direction of ink jet recording is 300 dpi or more, the polymer concentration abnormal portion severely affects the image quality. Therefore, it is preferable that the area of the polymer concentration abnormal portion satisfies the formula (1).

As the water-soluble polymer, various polymers can be used as described later. For example, when starches are used, the average starch concentration in the recording medium is high selectivity of the enzyme that is a biological substance. Can be measured by a biosensor employing a “flow injection analysis method (FIA method)”. Specific examples of the biosensor include BF-5 series manufactured by Oji Scientific Instruments.
The measurement flow can be exemplified as follows, but is not limited thereto.
(1) Accurately weigh 0.1 to 0.2 g of a recording media sample in a test tube.
(2) After adding 2 g of a glucoamylase (starch degrading enzyme, activity 60 IU / ml ± 20%) solution, leave the test tube in a 50 ° C. water bath for 2 hours (contained in the sample in this pretreatment step) Starch is hydrolyzed and extracted into solution as glucose).
(3) After leaving for 2 hours, only the solution is taken out, and the glucose concentration is measured with the biosensor BF-5 (the hydrogen peroxide produced by the reaction with glucose is measured by glucose osidase (GOD) on the surface of the enzyme electrode). The glucose concentration is measured from the change in current value that occurs when oxidized by the platinum anode).
(4) The average starch concentration of the recording medium is calculated from the sample amount and the glucose concentration.

  The abnormal starch concentration part can determine the recording medium based on the degree of coloration of the iodine-starch reaction by sampling inspection or the like. It becomes darker). The determination can be made by performing binarization processing according to the degree of coloration of the captured image by visual inspection or using a device such as a scanner or a CCD. Specific examples of the apparatus include, but are not limited to, a dot analyzer manufactured by Oji Scientific Instruments, a digital microscope manufactured by Keyence Corporation, and the like.

Further, using the ink media set, the maximum ink deposition amount is controlled to 8 to ²⁰ g / m ² at a resolution of 300 dpi or more. When the average starch concentration is low, the ink tends to wet and spread on average, so the dot area is large, and an image can be formed with a small amount of ink attached. Therefore, a large amount of ink is required.

-Support-
The support is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include paper based on wood fibers, and sheet-like materials such as non-woven fabrics mainly composed of wood fibers and synthetic fibers. .

  There is no restriction | limiting in particular as said paper, According to the objective, it can select suitably according to the objective, For example, wood pulp, waste paper pulp, etc. are used. Examples of the wood pulp include NBKP, LBKP, NBSP, LBSP, GP, and TMP.

  As the raw material of the used paper pulp, the white paper, ruled white, cream white, card, special white, medium white, imitation, fair white, Kent, white, as shown in the used paper standard quality standard table of the used paper recycling promotion center Art, special upper limit, another upper limit, newspaper, magazine, etc. are mentioned. Specifically, printer paper such as non-coating computer paper, thermal paper, and pressure-sensitive paper as information-related paper; OA waste paper such as PPC paper; coating of art paper, coated paper, finely coated paper, matte paper, etc. Paper: High quality paper, color quality, notebook, notepaper, wrapping paper, fancy paper, medium quality paper, newsprint, reprint paper, super paper, imitation paper, pure white roll paper, uncoated paper such as milk carton, etc. Examples of used paper and paperboard include chemical pulp paper and high-yield pulp-containing paper. These may be used individually by 1 type and may use 2 or more types together.

The waste paper pulp is generally produced from a combination of the following four steps.
(1) For disaggregation, waste paper is treated with mechanical force and chemicals with a pulper to loosen it into a fibrous form, and the printing ink is peeled off from the fiber.
(2) Dust removal is to remove foreign matter (plastic etc.) and dust contained in waste paper with a screen, cleaner or the like.
(3) In the deinking, the printing ink peeled off from the fiber using a surfactant is removed from the system by a flotation method or a cleaning method.
(4) Bleaching increases the whiteness of the fiber using an oxidizing action or a reducing action.
When mixing the used paper pulp, the mixing ratio of the used paper pulp in the total pulp is preferably 40% or less from the viewpoint of curling after recording.

  As the internal filler used for the support, for example, a conventionally known pigment is used as a white pigment. Examples of the white pigment include light calcium carbonate, heavy calcium carbonate, kaolin, clay, talc, calcium sulfate, barium sulfate, titanium dioxide, zinc oxide, zinc sulfide, zinc carbonate, satin white, aluminum silicate, diatomaceous earth, White inorganic pigments such as calcium silicate, magnesium silicate, synthetic silica, aluminum hydroxide, alumina, lithopone, zeolite, magnesium carbonate, magnesium hydroxide; styrene plastic pigment, acrylic plastic pigment, polyethylene, microcapsule, urea resin And organic pigments such as melamine resin. These may be used individually by 1 type and may use 2 or more types together.

  Examples of the internally added sizing agent used for making the support include neutral rosin sizing agents used for neutral papermaking, alkenyl succinic anhydride (ASA), alkyl ketene dimer (AKD), and petroleum resins. System sizing agents and the like. Among these, a neutral rosin sizing agent or alkenyl succinic anhydride is particularly preferable. The alkyl ketene dimer has a large size effect, so the addition amount may be small, but the friction coefficient of the recording paper (medium) surface is lowered and slippery, which is not preferable from the viewpoint of transportability during ink jet recording. There is.

-Surface size liquid-
The surface sizing solution used for the surface sizing treatment contains at least a water-soluble polymer, a cationic compound, and further contains other components as required.

There is no restriction | limiting in particular as said water-soluble polymer, According to the objective, it can select suitably, For example, starches (for example, starch, oxidized starch, phosphate esterified starch, self-modified starch, cationized starch, or various Modified starch), polyvinyl alcohol resin, anion modified polyvinyl alcohol resin, cation modified polyvinyl alcohol resin, modified product of polyvinyl alcohol resin such as acetal modified polyvinyl alcohol resin, carboxy modified polyvinyl alcohol resin; polyurethane resin; polyvinyl pyrrolidone and polyvinyl pyrrolidone and acetic acid Copolymer of vinyl, copolymer of vinylpyrrolidone, dimethylaminoethyl and methacrylic acid, copolymer of quaternized vinylpyrrolidone, dimethylaminoethyl and methacrylic acid, vinylpyrrolidone and methacrylamido Modified products of polyvinylpyrrolidone such as propyltrimethylammonium chloride copolymer; celluloses such as carboxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, cellulose sulfate; modified products of cellulose such as cationized hydroxyethylcellulose; polyester resin, polyacrylic acid ( Esters), melamine resins, or modified products thereof, synthetic resins such as polyester and polyurethane copolymers; poly (meth) acrylic acid, poly (meth) acrylamide, polyethylene oxide, sodium polyacrylate, sodium alginate, gelatin, etc. Is mentioned. These may be used alone or in combination of two or more. Among these, starches (for example, starch, oxidized starch, phosphate esterified starch, self-modified starch, cationized starch, or various modified starches), polyvinyl alcohol, carboxy-modified polyvinyl alcohol, carboxymethyl cellulose, hydroxyethyl cellulose, cellulose sulfate, Polyethylene oxide and gelatin are particularly preferred.
Content in the said surface size liquid of the said water-soluble polymer is 0.1-30 mass% in solid content, and 1-20 mass% is more preferable.

  The cationic compound is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include dimethylamine-epichlorohydrin polycondensate, dimethylamine-ammonia-epichlorohydrin condensate, poly (trimethylaminoethyl methacrylate). -Methyl sulfate), diallylamine hydrochloride-acrylamide copolymer, poly (diallylamine hydrochloride-sulfur dioxide), polyallylamine hydrochloride, poly (allylamine hydrochloride-diallylamine hydrochloride), acrylamide-diallylamine copolymer, polyvinylamine Copolymer, dicyandiamide, dicyandiamide-ammonium chloride-urea-formaldehyde condensate, polyalkylene polyamine-dicyandiamide ammonium salt condensate, dimethyl diallylammonium chloride Polydiallylmethylamine hydrochloride, poly (diallyldimethylammonium chloride), poly (diallyldimethylammonium chloride-sulfur dioxide), poly (diallyldimethylammonium chloride-diallylamine hydrochloride derivative), acrylamide-diallyldimethylammonium chloride copolymer, acrylic Examples thereof include acid salt-acrylamide-diallylamine hydrochloride copolymer, polyethyleneimine, ethyleneimine derivatives such as acrylicamine polymer, and polyethyleneimine alkylene oxide modified products. These may be used individually by 1 type and may use 2 or more types together.

The cation equivalent of the cationic compound by colloid titration method (using polyvinyl potassium sulfate and toluidine blue) is preferably 3 to 8 meq / g. If the cation equivalent is within this range, good results can be obtained within the dry adhesion range.
Here, in the measurement of the cation equivalent by the colloid titration method, the cationic compound is diluted with distilled water so as to have a solid content of 0.1% by mass, and pH adjustment is not performed.

The dry adhesion amount of the cationic compound to the support is preferably 0.3 to 2.0 g / m ² . If the dry adhesion amount of the cationic compound is lower than 0.3 g / m ² , sufficient image density improvement and feathering reduction effects may not be obtained.

Examples of the other components include a fluorescent brightener, a water resistant substance, and a pigment.
Examples of the fluorescent brightener include stilbene compounds, coumarin compounds, biphenyl compounds, benzoxazoline compounds, naphthalimide compounds, pyrazoline compounds, carbostyril compounds, diaminostilbene disulfonic acid derivatives, imidazole derivatives, Examples include coumarin derivatives, triazole derivatives, carbazole derivatives, pyridine derivatives, naphthalic acid derivatives, imidazolone derivatives, and the like. Among these, stilbene compounds are preferable.
The content of the fluorescent brightener in the base paper is not particularly limited, but is preferably 0.01 to 0.5% by mass, and more preferably 0.02 to 0.2% by mass.
Examples of the water-resistant substance include latex / emulsions such as styrene-butadiene copolymer, ethylene-vinyl acetate copolymer, polyethylene resin, vinylidene chloride copolymer; polyamide polyamine epichlorohydrin, and the like.
Examples of the pigment include calcium carbonate, clay, kaolin, talc, barium sulfate, and titanium oxide.

  The method for attaching the surface sizing liquid to the support is not particularly limited and may be appropriately selected depending on the intended purpose. For example, the size by a method such as a two-roll, metering blade, gate roll, or bill blade is used. Examples thereof include a press, a short dwell coater, a roll coater, an air knife coater, a blade coater, and a spray.

The surface resistivity of the recording medium is preferably 1.0 × 10 ^{9 to} 9.9 × 10 ¹³ Ω, and more preferably 1.0 × 10 ^{10 to} 9.9 × 10 ¹² Ω. Thereby, even if it uses for the said inkjet recording system of the conveyance system by electrostatic attraction, image degradation and a conveyance defect do not arise.

  Here, the surface resistivity (unit: Ω) is calculated by a calculation formula based on JIS K6911, specifically, a 4329A type insulation resistance meter (HIGH REISTANCE METER) manufactured by Yokogawa Hewlett-Packard Company. And a 16008A type electrode (RESITIVITY CELL), measured according to the instruction manual at an applied voltage of 100 V and a charge time of 60 seconds under an environmental condition of 23 ° C. and 50% RH, and can be obtained by calculation.

  As described above, the recording medium in the ink media set is used in combination with the ink in the ink media set. The ink media set in which the recording medium and the ink are combined can be suitably used in various fields, and can be suitably used in an image recording apparatus (printer or the like) using an inkjet recording method. The ink cartridge, ink recording material, ink jet recording apparatus, and ink jet recording method of the present invention can be used particularly preferably.

(ink cartridge)
The ink cartridge of the present invention contains the ink in the ink media set of the present invention in a container, and further includes other members appropriately selected as necessary.
The container is not particularly limited, and its shape, structure, size, material and the like can be appropriately selected according to the purpose. Preferred examples include those possessed.

Next, the ink cartridge will be described with reference to FIGS. Here, FIG. 1 is a view showing an example of the ink cartridge of the present invention, and FIG. 2 is a view including a case (exterior) of the ink cartridge of FIG.
As shown in FIG. 1, the ink cartridge 200 is filled into the ink bag 241 from the ink inlet 242 and exhausted, and then the ink inlet 242 is closed by fusion. In use, the needle of the apparatus main body is pierced into the ink discharge port 243 made of a rubber member and supplied to the apparatus.
The ink bag 241 is formed of a packaging member such as a non-permeable aluminum laminate film. As shown in FIG. 2, the ink bag 241 is usually housed in a plastic cartridge case 244 and is detachably attached to various ink jet recording apparatuses.

  The ink cartridge of the present invention contains ink in the ink media set of the present invention and can be used by being detachably attached to various ink jet recording apparatuses, and can be detachably attached to the ink jet recording apparatus of the present invention described later. It is particularly preferable to install and use.

(Inkjet recording apparatus and inkjet recording method)
The ink jet recording apparatus of the present invention includes at least ink flying means, and further includes other means appropriately selected as necessary, for example, stimulus generation means and control means.
The ink jet recording method of the present invention includes at least an ink flying step, and further includes other steps appropriately selected as necessary, for example, a stimulus generation step, a control step, and the like.
The ink jet recording method of the present invention can be preferably carried out by the ink jet recording apparatus of the present invention, and the ink flying step can be suitably carried out by the ink flying means. Moreover, the said other process can be suitably performed by the said other means.

-Ink flying process and ink flying means-
The ink flying step is a step of recording an image on a recording medium in the ink media set by applying a stimulus to the ink in the ink media set of the present invention and causing the ink to fly.
The ink flying means is means for applying a stimulus to the ink in the ink media set of the present invention and causing the ink to fly to record an image on a recording medium in the ink media set. The ink flying means is not particularly limited, and examples thereof include various nozzles for ejecting ink.
In the present invention, it is preferable that at least a part of the liquid chamber portion, the fluid resistance portion, the vibration plate, and the nozzle member of the inkjet head is formed of a material containing at least one of silicon and nickel.
The nozzle diameter of the inkjet nozzle is preferably 30 μm or less, and more preferably 1 to 20 μm.
In addition, it is preferable that a sub tank for supplying ink is provided on the ink jet head, and the sub tank is replenished with ink from an ink cartridge through a supply tube.
In the inkjet recording method of the present invention, the maximum ink adhesion amount is preferably 8 to ²⁰ g / m ² at a resolution of 300 dpi or more.

  The stimulus can be generated by, for example, the stimulus generating means, and the stimulus is not particularly limited and can be appropriately selected according to the purpose, and includes heat, pressure, vibration, light, and the like. . These may be used individually by 1 type and may use 2 or more types together. Among these, heat and pressure are preferable.

  Examples of the stimulus generating means include a heating device, a pressurizing device, a piezoelectric element, a vibration generating device, an ultrasonic oscillator, a light, and the like. Specifically, for example, a piezoelectric actuator such as a piezoelectric element, Examples include thermal actuators that use phase change due to liquid film boiling using electrothermal transducers such as heating resistors, shape memory alloy actuators that use metal phase changes due to temperature changes, electrostatic actuators that use electrostatic force, etc. It is done.

  There is no particular limitation on the mode of ink flying in the ink media set, and it varies depending on the type of the stimulus. For example, when the stimulus is “heat”, a recording signal is output to the ink in the recording head. A method of applying corresponding thermal energy using, for example, a thermal head, generating bubbles in the ink by the thermal energy, and discharging and ejecting the ink as droplets from the nozzle holes of the recording head by the pressure of the bubbles , Etc. Further, when the stimulus is “pressure”, for example, by applying a voltage to a piezoelectric element bonded to a position called a pressure chamber in an ink flow path in the recording head, the piezoelectric element bends and the volume of the pressure chamber is increased. And a method of ejecting and ejecting the ink as droplets from the nozzle holes of the recording head.

  The size of the ink droplets to be ejected is preferably 3 to 40 pl, the speed of ejection and ejection is preferably 5 to 20 m / s, and the driving frequency is 1 kHz or more. The resolution is preferably 300 dpi or more.

  The control means is not particularly limited as long as the movement of each means can be controlled, and can be appropriately selected according to the purpose. Examples thereof include devices such as sequencers and computers.

  One mode for carrying out the ink jet recording method of the present invention by the ink jet recording apparatus of the present invention will be described with reference to the drawings. The ink jet recording apparatus shown in FIG. 3 stocks an apparatus main body 101, a paper feed tray 102 for loading paper mounted on the apparatus main body 101, and paper on which an image is recorded (formed) mounted on the apparatus main body 101. A paper discharge tray 103 and an ink cartridge loading unit 104. On the upper surface of the ink cartridge loading unit 104, an operation unit 105 such as operation keys and a display is arranged. The ink cartridge loading unit 104 has a front cover 115 that can be opened and closed for attaching and detaching the ink cartridge 201.

  In the apparatus main body 101, as shown in FIGS. 4 and 5, the carriage 133 is slid in the main scanning direction by guide rods 131 and stays 132 which are horizontally mounted on left and right side plates (not shown). It is held movably and moved and scanned in the direction of the arrow in FIG. 5 by a main scanning motor (not shown).

The carriage 133 is provided with a recording head 134 composed of four ink jet recording heads that eject ink droplets of each color of yellow (Y), cyan (C), magenta (M), and black (Bk). Are arranged in a direction crossing the main scanning direction, and the ink droplet ejection direction is directed downward.
As the ink jet recording head constituting the recording head 134, a piezoelectric actuator such as a piezoelectric element, a thermal actuator using phase change due to liquid film boiling using an electrothermal transducer such as a heating resistor, a metal phase due to temperature change, etc. A shape memory alloy actuator using a change, an electrostatic actuator using an electrostatic force, or the like provided as energy generating means for discharging ink can be used.
In addition, the carriage 133 is equipped with a sub tank 135 for each color for supplying ink of each color to the recording head 134. The sub tank 135 is supplied with ink in the ink media set of the present invention from the ink cartridge 201 of the present invention loaded in the ink cartridge loading unit 105 via an ink supply tube (not shown).

  On the other hand, as a paper feeding unit for feeding the paper 142 stacked on the paper stacking unit (pressure plate) 141 of the paper feeding tray 102, a half-moon roller (feeding) that separates and feeds the paper 142 from the paper stacking unit 141 one by one. A separation pad 144 made of a material having a large coefficient of friction is provided facing the paper roller 143) and the paper feed roller 143, and the separation pad 144 is urged toward the paper feed roller 143 side.

  As a transport unit for transporting the paper 142 fed from the paper feed unit below the recording head 134, a transport belt 151 for transporting the paper 142 by electrostatic adsorption and a guide 145 from the paper feed unit. The counter roller 152 for transporting the paper 142 fed via the transport belt 151 with the transport belt 151 and the paper 142 fed substantially vertically upward are changed by approximately 90 ° so as to follow the transport belt 151. A conveying guide 153 and a tip pressure roller 155 urged toward the conveying belt 151 by a pressing member 154, and a charging roller 156 as a charging means for charging the surface of the conveying belt 151. It has been.

  The conveyance belt 151 is an endless belt, is stretched between the conveyance roller 157 and the tension roller 158, and can circulate in the belt conveyance direction. The transport belt 151 includes, for example, a surface layer serving as a sheet adsorption surface formed of a resin material having a thickness of about 40 μm that is not subjected to resistance control, for example, a copolymer of tetrafluoroethylene and ethylene (ETFE), and the same surface layer. It has a back layer (medium resistance layer, earth layer) that has been subjected to resistance control with carbon as a material. On the back side of the conveyance belt 151, a guide member 161 is arranged corresponding to a printing area by the recording head 134. Note that, as a paper discharge unit for discharging the paper 142 recorded by the recording head 134, a separation claw 171 for separating the paper 142 from the conveyance belt 151, a paper discharge roller 172, and a paper discharge roller 173 are provided. The paper discharge tray 103 is disposed below the paper discharge roller 172.

  A double-sided paper feeding unit 181 is detachably mounted on the back surface of the apparatus main body 101. The double-sided paper feeding unit 181 takes in the paper 142 returned by the reverse rotation of the transport belt 151, reverses it, and feeds it again between the counter roller 152 and the transport belt 151. A manual paper feed unit 182 is provided on the upper surface of the duplex paper feed unit 181.

In this ink jet recording apparatus, the paper 142 is separated and fed one by one from the paper feed unit, and the paper 142 fed substantially vertically upward is guided by the guide 145 and between the transport belt 151 and the counter roller 152. It is sandwiched and conveyed. Further, the leading end is guided by the conveyance guide 153 and pressed against the conveyance belt 151 by the pressure roller 155, and the conveyance direction is changed by approximately 90 °.
At this time, the conveyance belt 157 is charged by the charging roller 156, and the sheet 142 is conveyed by being electrostatically attracted to the conveyance belt 151. Therefore, by driving the recording head 134 according to the image signal while moving the carriage 133, ink droplets are ejected onto the stopped paper 142 to record one line, and after the paper 142 is conveyed by a predetermined amount, Record the next line. Upon receiving a recording end signal or a signal that the trailing edge of the sheet 142 has reached the recording area, the recording operation is terminated and the sheet 142 is discharged onto the discharge tray 103.
When a near-end remaining amount of ink in the sub tank 135 is detected, a required amount of ink is supplied from the ink cartridge 201 to the sub tank 135.

  In this ink jet recording apparatus, when the ink in the ink cartridge 201 of the present invention is used up, the casing of the ink cartridge 201 can be disassembled and only the ink bag inside can be replaced. Further, the ink cartridge 201 can supply ink stably even when the ink cartridge 201 is placed vertically and has a front loading configuration. Therefore, when the upper portion of the apparatus main body 101 is closed and installed, for example, even when the apparatus main body 101 is stored in a rack or an object is placed on the upper surface of the apparatus main body 101, the ink cartridge 201 is replaced. Can be easily performed.

  Here, an example is described in which the present invention is applied to a serial (shuttle type) ink jet recording apparatus that is scanned by a carriage, but the present invention can be similarly applied to a line type ink jet recording apparatus having a line type head.

  Further, the ink jet recording apparatus and the ink jet recording method of the present invention can be applied to various types of recording by the ink jet recording method. For example, the ink jet recording apparatus, the facsimile apparatus, the copying apparatus, the printer / fax / copier multifunction machine, etc. It can be particularly preferably applied.

Hereinafter, an ink jet head to which the present invention is applied will be described.
FIG. 6 is an enlarged view of elements of an ink jet head according to an embodiment of the present invention, and FIG. 7 is an enlarged cross-sectional view of the main part in the channel-to-channel direction of the head.
This ink jet head includes a frame 10 formed with an engraving serving as an ink supply port (not shown) and a common liquid chamber 1b, and a communication port 2c communicating with the fluid resistance portion 2a and the engraving serving as the pressurized liquid chamber 2b and the nozzle 3a. The formed flow path plate 20, the nozzle plate forming the nozzle 3 a, the vibration plate 60 having the convex portion 6 a, the diaphragm portion 6 b, and the ink inlet 6 c, and the vibration plate 60 bonded to each other through the adhesive layer 70. A laminated piezoelectric element 50 and a base 40 to which the laminated piezoelectric element 50 is fixed are provided.
The base 40 is made of a barium titanate ceramic, and the laminated piezoelectric elements 50 are arranged in two rows and joined.
The laminated piezoelectric element 50 is formed by alternately laminating a lead zirconate titanate (PZT) piezoelectric layer having a thickness of 10 to 50 μm / layer and an internal electrode layer made of silver-palladium (AgPd) having a thickness of several μm / layer. is doing. The internal electrode layer is connected to the external electrode at both ends.
The laminated piezoelectric element 50 is divided on comb teeth by half-cut dicing, and is used as a drive unit 5f and a support unit 5g (non-drive unit) one by one. The length of the outside of the external electrode is limited by cutting or the like so as to be divided by half-cut dicing, and these become a plurality of individual electrodes. The other is not divided by dicing but is conductive and becomes a common electrode.
The FPC 8 is soldered to the individual electrodes of the drive unit 5f. In addition, the common electrode is provided with an electrode layer at the end of the laminated piezoelectric element, and is wound around and joined to the Gnd electrode of the FPC 8. A driver IC (not shown) is mounted on the FPC 8 to control application of a driving voltage to the driving unit 5f.

The diaphragm 60 includes a thin-film diaphragm portion 6b, an island-shaped convex portion (island portion) 6a that joins a laminated piezoelectric element 50 including a drive portion 5f and a support portion 5g formed at the center of the diaphragm portion 6b. A thick film part including a beam joined to the support part and an opening serving as the ink inlet 6c are formed by stacking two Ni plating films by an electroforming method. The diaphragm portion has a thickness of 3 μm and a width of 35 μm (one side).
The island-shaped convex part 6a of the diaphragm 60 and the driving part 5f of the laminated piezoelectric element 50, and the coupling of the diaphragm 50 and the frame 10 are bonded by patterning the adhesive layer 70 including a gap material.

As the flow path plate 20, a silicon single crystal substrate was used, and the engraving to be the fluid resistance portion 2a and the pressurized liquid chamber 2b and the through-hole to be the communication port 2c at the position relative to the nozzle 3a were patterned by an etching method.
The portion left by etching becomes the partition wall 2d of the pressurized liquid chamber 2b. Further, in this head, a portion for narrowing the etching width is provided, and this is used as the fluid resistance portion 2a.
The nozzle plate 30 is formed of a metal material, for example, an Ni plating film formed by an electroforming method, and has a large number of nozzles 3a that are fine discharge ports for causing ink droplets to fly. The internal shape (inner shape) of the nozzle 3a is formed in a horn shape (may be a substantially cylindrical shape or a substantially frustum shape). The diameter of the nozzle 3a is approximately 20 to 35 μm as the diameter on the ink droplet outlet side. The nozzle pitch of each row was 150 dpi.
The ink discharge surface (nozzle surface side) of the nozzle plate 30 is provided with a water-repellent treatment layer 3b that has been subjected to a water-repellent surface treatment (not shown). Ink, such as PTFE-Ni eutectoid plating, electrodeposition coating of fluororesin, vapor-deposited fluororesin (for example, fluorinated pitch), baking after solvent coating of silicone resin and fluororesin A water-repellent film selected according to the physical properties is provided to stabilize the ink droplet shape and flight characteristics so as to obtain high-quality image quality. Among these, for example, various materials are known as the fluororesin, but a modified perfluoropolyoxetane (manufactured by Daikin Industries, Ltd., trade name: OPTOOL DSX) has a thickness of 30 to 100 mm. Thus, good water repellency can be obtained by vapor deposition.

The frame 10 that forms the engraving that becomes the ink supply port and the common liquid chamber 1b is made by resin molding.
In the ink jet head configured as described above, a driving waveform (pulse voltage of 10 to 50 V) is applied to the driving unit 5f in accordance with the recording signal, thereby causing displacement in the stacking direction in the driving unit 5f, and the diaphragm 30. The pressurized liquid chamber 2b is pressurized through the pressure to increase the pressure, and ink droplets are ejected from the nozzle 3a.
Thereafter, the ink pressure in the pressurizing liquid chamber 2b is reduced with the completion of ink droplet ejection, and negative pressure is generated in the pressurizing liquid chamber 2b due to the inertia of the ink flow and the discharge process of the driving pulse, and the ink is filled. Move to the process. At this time, the ink supplied from the ink tank flows into the common liquid chamber 1b, passes from the common liquid chamber 1b through the ink inlet 6c, passes through the fluid resistance portion 2a, and is filled into the pressurized liquid chamber 2b.
The fluid resistance portion 2a is effective in damping the residual pressure vibration after ejection, but becomes resistant to the maximum filling (refill) due to surface tension. By appropriately selecting the fluid resistance portion, it is possible to balance the attenuation of the residual pressure and the refill time, and to shorten the time (drive period) until the transition to the next ink droplet ejection operation.

(Ink record)
The ink recorded matter recorded by the ink jet recording apparatus and the ink jet recording method of the present invention is the ink recorded matter of the present invention. The ink recorded matter of the present invention has an image formed by using ink in the ink media set on a recording medium in the ink media set.
There is no restriction | limiting in particular as said recording medium, According to the objective, it can select suitably, For example, a plain paper, glossy paper, special paper, cloth, a film, an OHP sheet etc. are mentioned. These may be used alone or in combination of two or more.
The ink recorded matter has high image quality, no bleeding, excellent temporal stability, and can be suitably used for various purposes as a material on which various prints or images are recorded.

  Examples of the present invention will be described below, but the present invention is not limited to these examples.

(Production Example 1)
-Carbon black dispersion treated with hypochlorous acid 1-
After mixing 300 g of commercially available pH 2.5 acidic carbon black (trade name Monarch 1300, manufactured by Cabot Corporation) in 1000 ml of water, 450 g of sodium hypochlorite (effective chlorine concentration 12%) was added dropwise, Stir at 105 ° C. for 8 hours. To this solution, 100 g of sodium hypochlorite (effective chlorine concentration: 12%) was added and dispersed for 3 hours by a horizontal disperser.
The obtained slurry was diluted 10 times with water, pH was adjusted with lithium hydroxide, desalted and concentrated with an ultrafiltration membrane to an electric conductivity of 0.2 mS / cm, and carbon black having a pigment concentration of 16% by mass. Dispersion 1 was prepared.
Next, coarse particles were removed by centrifugation, and filtered through a nylon filter having an average pore diameter of 1 μm to obtain a carbon black dispersion 1.
The volume average particle size (D50%) of the obtained carbon black dispersion 1 measured by a particle size distribution measuring device (Microtrac UPA, manufactured by Nikkiso Co., Ltd.) was 95 nm.

(Production Example 2)
-Color pigment dispersion subjected to surface chemical treatment (yellow pigment dispersion 1, magenta pigment dispersion 1, cyan pigment dispersion 1)-
As a yellow pigment, C.I. I. Pigment Yellow 128 was subjected to low-temperature plasma treatment to prepare a pigment into which a carboxylic acid group was introduced. A dispersion of this in ion-exchanged water was desalted and concentrated with an ultrafiltration membrane to obtain a yellow pigment dispersion 1 having a pigment concentration of 20% by mass. The obtained yellow pigment dispersion 1 had a volume average particle size of 70 nm as measured with a particle size distribution analyzer (Microtrac UPA, manufactured by Nikkiso Co., Ltd.).
Similarly, C.I. I. A magenta pigment dispersion 1 having a pigment concentration of 24% by mass was prepared using Pigment Magenta 122. The obtained magenta pigment dispersion 1 had a volume average particle size of 60 nm as measured with a particle size distribution analyzer (Microtrac UPA, manufactured by Nikkiso Co., Ltd.).
Similarly, C.I. I. A cyan pigment dispersion 1 having a pigment concentration of 20% by mass was prepared using CI Pigment Cyan 15: 3. The obtained cyan pigment dispersion 1 had a volume average particle size of 80 nm as measured with a particle size distribution analyzer (Microtrac UPA, manufactured by Nikkiso Co., Ltd.).

(Production Example 3)
-Production of support 1-
A 0.3 mass% slurry having the following composition was made with a long paper machine to prepare a support having a basis weight of 79 g / m ² .
LBKP (freeness 450 mlcsf) ... 100 parts Light calcium carbonate (trade name: TP-121, manufactured by Okutama Kogyo Co., Ltd.) 10 parts by weight Aluminum sulfate 1.0 parts by weight Amphoteric starch (Product name: Cato 3210, manufactured by NSC Japan) 1.0 parts by weight Neutral rosin sizing agent (trade name: NeuSize M-10, manufactured by Harima Kasei Co., Ltd.) 0.3 parts by weight Improved yield Agent (trade name: NR-11LS, manufactured by Hymo Co., Ltd.) 0.02 parts by mass

(Production Example 4)
−Preparation of recording paper 1−
The produced support 1 was dried with an oxidized starch of 1.2 g / m ² and a cationic compound (trade name: Himax SC-700, manufactured by Hymo Co., Ltd., cation equivalent 5.0 meq / g). A4 size recording paper 1 was prepared by attaching using a size press device so as to be 0.5 g / m ² , performing machine calendar processing, and cutting. The average starch concentration of the obtained recording paper 1 was 2% by mass. The total printing area of the recording paper 1 was 124.740 mm ² , and the area of the concentration abnormal portion of the water-soluble polymer was 9.980 mm ² .

(Production Example 5)
−Preparation of recording paper 2−
A recording paper 2 was produced in the same manner as the recording paper 1 except that the dry adhesion amount of oxidized starch on the recording paper 1 was 2.5 g / m ² . The average starch concentration of the obtained recording paper 2 was 4.3% by mass. The total printing area of the recording paper 2 was 124.740 mm ² , and the area of the water-soluble polymer concentration abnormal portion was 5.600 mm ² .

(Production Example 6)
−Preparation of recording paper 3−
A recording paper 3 was prepared in the same manner as the recording paper 1 except that the dry adhesion amount of oxidized starch on the recording paper 1 was 4.5 g / m ² . The resulting recording paper 3 had an average starch concentration of 6% by mass. The total printing area of the recording paper 3 was 124.740 mm ² , and the area of the concentration abnormal portion of the water-soluble polymer was 3.300 mm ² .

(Production Example 7)
−Preparation of recording paper 4−
A recording paper 4 was produced in the same manner as the recording paper 2 except that a portion of the recording paper 2 where the surface size liquid was partially uncoated was locally provided. The average starch concentration of the obtained recording paper 4 was 2.1% by mass. The total printing area of the recording paper 4 was 124.740 mm ² , and the area of the concentration abnormal portion of the water-soluble polymer was 59.000 mm ² .

(Production Example 8)
−Preparation of recording paper 5−
A recording paper 5 was produced in the same manner as the recording paper 1 except that the oxidized starch of the recording paper 1 was not added. The average starch concentration of the resulting recording paper 5 was 0.0% by mass.

(Production Example 9)
-Production of recording paper 6-
A recording paper 6 was prepared in the same manner as the recording paper 1 except that the dry adhesion amount of oxidized starch on the recording paper 1 was 7.0 g / m ² . The average starch concentration of the obtained recording paper 6 was 10.0% by mass. The total printing area of the recording paper 6 was 124.740 mm ² , and the area of the water-soluble polymer concentration abnormal portion was not detected.

  Next, with respect to the obtained recording sheets 1 to 6, the average starch concentration, the starch adhesion amount distribution, and the area occupancy ratio of the starch concentration abnormal portion were measured as follows. The results are shown in Table 1.

<Measurement of average starch concentration>
The average starch concentration of each recording paper was measured as follows.
(1) Accurately weigh 0.1 to 0.2 g of the recording medium in a test tube.
(2) After adding 2 g of a glucoamylase (starch degrading enzyme, activity 60 IU / ml ± 20%) solution, leave the test tube in a 50 ° C. water bath for 2 hours (contained in the sample in this pretreatment step) Starch is hydrolyzed and extracted into solution as glucose).
(3) After leaving for 2 hours, only the solution is taken out, and the glucose concentration is measured with the biosensor BF-5 (the hydrogen peroxide produced by the reaction with glucose is measured by glucose osidase (GOD) on the surface of the enzyme electrode). The glucose concentration is measured from the change in current value that occurs when oxidized by the platinum anode).
(4) The average starch concentration of the recording medium is calculated from the sample amount and the glucose concentration.

<Coloring by iodine-starch reaction>
In the recording sheets 1 to 3, depending on the average starch concentration, the purple color was darkened visually, but in some places, lightly colored portions were observed.
In the recording paper 4, about half of the uncoated portion is not colored, and the coated portion has the same purple color as the coated portion of the recording paper 2, and can be judged visually. Contrast occurred.
In the recording paper 5, there was no coloration due to iodine-starch reaction uniformly over the entire surface.
The recording paper 6 showed a uniform coloration, and when judged visually, the purple color was darkest.

<Measurement of area occupancy of water-soluble polymer concentration abnormal part>
After coloring the recording paper 1 to 4 by iodine-starch reaction, a flatbed scanner Nexscan F4200 (manufactured by Heidelberg) is used as an image input device, and the color image is taken in at a resolution of 1200 dpi, and water is obtained by image binarization processing. Area of the water-soluble polymer concentration abnormal portion (location where the amount of the water-soluble polymer attached is less than 0.5X) was determined.

(Production Example 10)
-Preparation of black ink composition-
An ink composition having the following formulation was prepared and adjusted with a 10% by weight aqueous solution of lithium hydroxide so that the pH was 9. Then, it filtered with the membrane filter with an average hole diameter of 0.8 micrometer, and the black ink composition 1 was prepared.
Carbon dispersion 1 ... 50.0% by mass (pigment solid content: 8.0% by mass)
・ Triethylene glycol: 22.5% by mass
・ Glycerol: 7.5% by mass
・ 2-pyrrolidone: 5.0% by mass
-Surfactant represented by the following structural formula: 2.0% by mass
_{CH 3 (CH 2) 12 O} (CH 2 CH 2 O) 3 CH 2 COOH
・ 2-ethyl-1,3-hexanediol: 2.0% by mass
・ Emulsion: 3.0% by mass
・ Proxel LV (preservative) ... 0.2% by mass
・ Ion exchange water

(Production Example 11)
-Preparation of magenta ink composition-
An ink composition was prepared by adjusting the pH to 9 with lithium hydroxide in the same manner as in Production Example 1 except that the following composition was used.
-Magenta dispersion 1 ... 50.0% by mass (pigment solid content: 12.0% by mass)
・ 1,3-Dimethylimidazolidinone: 15.0% by mass
・ Glycerol: 15.0% by mass
・ 2-pyrrolidone: 5.0% by mass
-ECTD-6NEX (manufactured by Nikko Chemicals, anionic surfactant) ... 2.0 mass%
・ 2,2,4-Trimethyl-1,3-pentanediol ... 2.0% by mass
・ Emulsion: 3.0% by mass
・ Proxel LV (preservative) ... 0.2% by mass
・ Ion exchange water

(Production Example 12)
-Preparation of yellow ink composition-
An ink composition was prepared by adjusting the pH to 9 with sodium hydroxide in the same manner as in Production Example 1 except that the following composition was used.
-Yellow dispersion 1 ... 40.0 mass% (pigment solid content: 8.0 mass%)
・ Multitose: 25.0% by mass
・ Glycerol: 15.0% by mass
・ N-methyl-2-pyrrolidone: 5.0% by mass
・ Dispanol TOC (Non-Oxide Surfactant, manufactured by NOF Corporation) ... 2.0% by mass
・ 2-ethyl-1,3-hexanediol: 2.0% by mass
・ Emulsion: 3.0% by mass
・ Proxel LV (preservative) ・ ・ ・ ・ 0.2% by mass
・ Ion exchange water

(Production Example 13)
-Preparation of cyan ink composition-
An ink composition was prepared by adjusting the pH to 9 with lithium hydroxide in the same manner as in Production Example 1 except that the following composition was used.
Cyan dispersion 1 ... 50.0% by mass (pigment solid content: 10.0% by mass)
・ 1,3-Dimethylimidazolidinone: 15.0% by mass
・ Glycerol: 15.0% by mass
・ 2-pyrrolidone: 5.0% by mass
-ECTD-6NEX (manufactured by Nikko Chemicals, anionic surfactant) ... 2.0 mass%
・ 2,2,4-Trimethyl-1,3-pentanediol ... 2.0% by mass
・ Emulsion: 3.0% by mass
・ Proxel LV (preservative) ... 0.2% by mass
・ Ion exchange water

  Next, about each obtained ink composition, the ink viscosity was measured at 25 degreeC using the viscometer (RL-500, the Toki Sangyo Co., Ltd. make).

Example 1
-Preparation of ink media set and image recording-
First, an ink set 1 comprising a black ink composition, a yellow ink composition, a magenta ink composition, and a cyan ink composition was prepared by a conventional method.
Using the obtained ink set 1 and recording paper 1 as a recording medium, using a drop-on-demand printer prototype having nozzles of 300 dpi and nozzle resolution 384, with an image resolution of 600 dpi and a maximum ink droplet of 18 pl. Printing was performed. Subsequently, the total amount of secondary colors was regulated to 140%, and the amount of adhesion was regulated, and solid images and characters were printed.

(Example 2)
-Preparation of ink media set and image recording-
In Example 1, printing and printing were performed in the same manner as in Example 1 except that the recording paper 1 was changed to the recording paper 2.

(Example 3)
-Preparation of ink media set and image recording-
In Example 1, printing and printing were performed in the same manner as in Example 1 except that the recording paper 1 was changed to the recording paper 3.

Example 4
-Preparation of ink media set and image recording-
In Example 1, printing and printing were performed in the same manner as in Example 1 except that the recording paper 1 was changed to the recording paper 6.

(Comparative Example 1)
-Preparation of ink media set and image recording-
In Example 1, printing and printing were performed in the same manner as in Example 1 except that the recording paper 1 was changed to the recording paper 4.
Moreover, the uncoated part of Comparative Example 1 was about half of the A4 size, and the area E of the portion where the penetration inhibitor concentration was abnormal was 59.000 mm ² . On the other hand, since the recording resolution of Comparative Example 1 is 600 dpi × 600 dpi, the right side of the following formula 1 is 645 × (Dx × Dy) ^−1/2 = 1.08 mm ² , and the following formula 1 is not satisfied.
E <645 × (Dx × Dy) ^−1/2 formula (1)
In the formula (1), E represents the area (mm ² ) of the water-soluble polymer concentration abnormal portion, Dx represents the resolution in the main scanning direction (dpi), and Dy represents the resolution in the sub-scanning direction (dpi). ).

(Comparative Example 2)
-Preparation of ink media set and image recording-
In Example 1, printing and printing were performed in the same manner as in Example 1 except that the recording paper 1 was changed to the recording paper 5.

  Next, for each of the obtained image recording prints of Examples 1 to 4 and Comparative Examples 1 to 2, the maximum ink adhesion amount, image quality, image density, feathering, and occurrence of white spots are as follows. evaluated. The results are shown in Table 2.

<Maximum ink adhesion>
The maximum amount of ink adhering so that the solid was well filled and the ink overflowed and did not bleed was measured.

<Image density>
About each solid image of an Example and a comparative example, it measured using the D50 light source using X-Rite938 (made by X-Rite).

<Evaluation of feathering>
The degree of feathering in each character image of the examples and comparative examples was visually observed and evaluated according to the following criteria.
〔Evaluation criteria〕
A: Clear printing with no feathering.
○: Feathering slightly occurred.
Δ: Beard feathering occurs.
X: The blur has occurred so that the outline of the character is not clear.

<Evaluation of white spot>
The degree of white spots in the solid image portion of cyan in each character image of the example and the comparative example was visually observed and evaluated according to the following criteria.
〔Evaluation criteria〕
A: Less than 3 white spots occur in 1 cm ² or no white spots are observed.
○: 3 to 9 white spots occur in 1 cm ² .
Δ: 10 to 19 white spots occur in 1 cm ² .
X: ²⁰ to 29 white spots are generated in 1 cm ² .
XX: 30 or more white spots are generated in 1 cm ² .

The ink media set of the present invention can record high-quality images without white spots and density unevenness, and can form high-quality images with high color saturation and good color tone even on plain paper. It can be suitably used for an ink record, an ink jet recording apparatus, and an ink jet recording method.
The ink jet recording apparatus and the ink jet recording method of the present invention can be applied to various types of recording by the ink jet recording method, and are particularly suitable for, for example, an ink jet recording printer, a facsimile apparatus, a copying apparatus, and a printer / fax / copier multifunction machine. Can be applied to.

FIG. 1 is a schematic view showing an example of the ink cartridge of the present invention. FIG. 2 is a schematic view including a case (exterior) of the ink cartridge of FIG. FIG. 3 is a perspective explanatory view showing a state where the cover of the ink cartridge loading unit of the ink jet recording apparatus is opened. FIG. 4 is a schematic configuration diagram illustrating the overall configuration of the inkjet recording apparatus. FIG. 5 is a schematic enlarged view showing an example of the inkjet head of the present invention. FIG. 6 is an element enlarged view showing another example of the ink jet head of the present invention. FIG. 7 is an enlarged cross-sectional view of a main part of the ink jet head of FIG.

Explanation of symbols

DESCRIPTION OF SYMBOLS 10 Frame 20 Flow path plate 30 Nozzle plate 40 Base 50 Laminated piezoelectric element 60 Vibrating plate 70 Adhesive layer 101 Apparatus main body 102 Paper feed tray 103 Paper discharge tray 104 Ink cartridge loading part 111 Upper cover 112 Front surface 115 Front cover 131 Guide rod 132 Stay 133 Carriage 134 Recording Head 135 Subtank 141 Paper Placement Unit 142 Paper 144 Separation Pad 151 Conveying Belt 152 Again Counter Roller 156 Charging Roller 157 Conveyance Roller 158 Densation Roller 171 Separation Claw 172 Paper Discharge Roller 173 Paper Discharge Roller 181 Double-sided Paper Feed Unit 201 Ink cartridge 241 Ink bag 242 Ink inlet 243 Ink outlet 244 Cartridge exterior

Claims (29)

An ink containing at least a colorant, water, a wetting agent, and a penetrating agent, wherein the content of the colorant is 4 to 15% by mass;
A recording medium obtained by sizing the surface of a support with a surface sizing solution containing at least a water-soluble polymer, and an ink media set comprising:
The area of the water-soluble polymer concentration abnormal portion where the amount of water-soluble polymer attached to the recording medium is less than 0.5X (where X represents the average value of the amount of water-soluble polymer attached to the recording medium). An ink media set having an occupation ratio of 10% or less.   The recording medium is a cut medium, and the amount of water-soluble polymer attached to the abnormal portion of the water-soluble polymer concentration is less than 0.5X and 0.1X or more (where X is the amount of water-soluble polymer attached to the recording medium) The ink media set according to claim 1, which represents an average value.   3. The ink media set according to claim 1, wherein the average value X of the amount of the water-soluble polymer adhering to the recording medium is 0.5 to 7.0 mass%. The ink media set according to any one of claims 1 to 3, wherein a portion having the maximum area in the water-soluble polymer concentration abnormal portion satisfies the following formula (1).
E <645 × (Dx × Dy) ^−1/2 formula (1)
In the formula (1), E represents the area (mm ² ) of the water-soluble polymer concentration abnormal portion, Dx represents the resolution in the main scanning direction (dpi), and Dy represents the resolution in the sub-scanning direction (dpi). ).   The ink media set according to claim 4, wherein the resolution in the main scanning direction is 300 dpi or more.   The ink according to any one of claims 1 to 5, wherein the water-soluble polymer is at least one selected from starches, polyvinyl alcohol, carboxy-modified polyvinyl alcohol, carboxymethyl cellulose, hydroxyethyl cellulose, cellulose sulfate, polyethylene oxide, and gelatin. Media set.   The ink media set according to any one of claims 1 to 6, wherein the water-soluble polymer is starch, and the amount of the starch attached to the recording medium is determined by the color density of the iodine-starch reaction.   The ink media set according to any one of claims 1 to 7, wherein the ink has a viscosity at 25 ° C of 5 to 20 cps.   The ink media set according to any one of claims 1 to 8, wherein the colorant is a water-dispersible colorant containing a pigment.   The ink media set according to claim 9, wherein the water-dispersible colorant is a pigment having at least one hydrophilic group on the surface and exhibiting at least one of water-dispersibility and water-solubility in the absence of the dispersant. .   The ink media set according to claim 10, wherein the hydrophilic group is any one of a carboxyl group, a sulfone group, a carbonyl group, and a hydroxyl group.   The ink media set according to any one of claims 9 to 11, wherein the water-dispersible colorant is a pigment having a volume average particle diameter of 0.01 to 0.16 µm.   The ink media set according to any one of claims 9 to 12, wherein the water dispersible colorant is a polymer emulsion in which polymer fine particles contain a colorant that is insoluble or hardly soluble in water.   The ink media set according to claim 13, wherein the polymer fine particles have a volume average particle diameter of 0.01 to 0.16 μm.   The penetrant contains either a polyol compound having 8 or more carbon atoms or a glycol ether compound, and the polyol compound having 8 or more carbon atoms is 2-ethyl-1,3-hexanediol, and 2,2,4- The ink media set according to claim 1, which is any one of trimethyl-1,3-pentanediol.   The ink media set according to any one of claims 1 to 15, wherein the wetting agent is at least one selected from a polyol compound, a lactam compound, a urea compound, and a saccharide.   The polyol compound is glycerin, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,3-butanediol, 2,3-butanediol, 1,3. -Propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 2-methyl-2,4-pentanediol, 1,2,4-butanetriol, 1,2,6 The ink media set according to claim 16, which is at least one selected from hexanetriol, thiodiglycol, pentaerythritol, trimethylolethane, and trimethylolpropane.   The ink medium according to claim 16, wherein the lactam compound is at least one selected from 2-pyrrolidone, N-methyl-2-pyrrolidone, N-hydroxyethyl-2-pyrrolidone, and ε-caprolactam. set.   The ink media set according to any one of claims 16 to 18, wherein the urea compound is at least one selected from urea, thiourea, ethylene urea, and 1,3-dimethyl-2-imidazolidinone.   The ink media set according to any one of claims 16 to 19, wherein the saccharide is at least one selected from maltose, sorbitol, gluconolactone, and maltose.   21. The ink media set according to claim 1, wherein the content of the wetting agent in the ink is 10 to 50% by mass. The ink contains a surfactant, and the surfactant is at least one selected from the following general formulas (I), (II), (III), (IV), (V), and (VI) The ink media set according to any one of claims 1 to 21.
R ¹ —O— (CH ₂ CH ₂ O) _h CH ₂ COOM —General Formula (I)
In the general formula (I), R ¹ represents an alkyl group, h represents an integer of 3 to 12, M represents an alkali metal ion, a quaternary ammonium, a quaternary phosphonium, and an alkanolamine. Represents one selected from
In the general formula (II), R ² represents an alkyl group, M represents an alkali metal ion, quaternary ammonium, any one selected from the quaternary phosphonium, and alkanolamine.
In the general formula (III), ^{R 3} is represents a hydrocarbon group, k is an integer of 5-20.
_{^{R 4 - (OCH 2 CH 2}} ) j OH ··· formula (IV)
In the general formula (IV), ^{R 4} represents a hydrocarbon group, j is an integer of 5-20.
In the general formula (V), ^{R 6} represents a hydrocarbon group, L and p are each an integer of 1-20.
However, in said general formula (VI), q and r represent the integer of 0-40, respectively.   23. An ink cartridge comprising the ink in the ink media set according to claim 1 contained in a container.   23. At least ink ejecting means for applying a stimulus to the ink in the ink media set according to claim 1 and causing the ink to eject to form an image on a recording medium of the ink media set. An ink jet recording apparatus.   The inkjet recording apparatus according to claim 24, wherein the stimulus is at least one selected from heat, pressure, vibration, and light.   23. At least an ink flying step of applying a stimulus to the ink in the ink media set according to claim 1 and causing the ink to fly to form an image on a recording medium in the ink media set. An inkjet recording method.   27. The ink jet recording method according to claim 26, wherein the stimulus is at least one selected from heat, pressure, vibration and light. The inkjet recording method according to any one of claims 26 to 27, wherein the maximum ink adhesion amount is 8 to 20 g / m ² at a resolution of 300 dpi or more. An ink recorded matter comprising an image formed using the ink in the ink media set on the recording medium in the ink media set according to any one of claims 1 to 22.