JP5664893B2 - Ink jet recording ink, ink jet recording ink set, ink jet recording ink media set, ink cartridge, ink jet recording method, and ink jet recording apparatus. - Google Patents

Description

  The present invention relates to an ink for ink jet recording, an ink set for ink jet recording, an ink cartridge, an ink jet recording method, and an ink jet recording apparatus capable of recording a high-quality image at high speed on plain paper by an ink jet method.

Inkjet recording is known as an excellent recording method in which a recording material is not relatively selected, and research and development have been actively conducted on recording apparatuses, recording methods, recording materials, and the like.
However, inks for ink jet recording have so far mainly used water as a main component and water-based dyes. This is because it is easy to obtain color materials with a high extinction coefficient and high color purity, and it is easy to make multiple colors of ink to widen the color specification range. Since it has various advantages such as the ability to make ink that is less susceptible to kogation, it is also mainstream in current inkjet recording.

In recent years, pigment inks for inkjet recording have attracted attention.
Since pigments are insoluble in water, it is common to use fine particles that are dispersed in a solvent. However, pigment inks for inkjet are pigment inks in which pigments are dispersed in water from the viewpoint of safety. Is the mainstream.
In general, water-based pigment inks tend to cause aggregation and precipitation of pigment particles compared to dye inks, and various dispersion conditions and additives are necessary to achieve long-term storage stability comparable to dye inks. In addition to being difficult to use with a thermal head because of the cause of gating, the colorant color range of color materials is inferior to that of dyes. From the viewpoint of storage stability and water resistance, much attention has been paid.
Inkjet printers using this pigment ink do not dry in time for high-speed printing, and because of this poor drying property, images may blur or curl or cockling on plain paper due to water evaporation after ink landing. Due to such a displacement of plain paper, there is a big problem that transportability in high-speed printing is not ensured, which hinders high-speed printing with water-soluble ink.
On the other hand, heat drying after printing has been proposed as an auxiliary means, but the energy saving property, which is a characteristic of the original ink jet, is significantly impaired.

Conventionally, ink-jet inks containing amino acids and the like are already known, but there is no idea of improving the transportability of printed plain paper as in the present invention. As disclosed in Japanese Utility Model Publication No. 2005-015795, as a problem with dye ink, for the purpose of improving water resistance, bleeding, feathering, etc. on plain paper, for example, with respect to black ink, amino acids (including dipeptides) and As an essential combination of amphoteric surfactants, this ink is used to express the function of reducing ink permeability to plain paper, etc., and amino acids are used for the purpose of obtaining good optical density. In addition, as disclosed in Japanese Patent Application Laid-Open No. 2006-117634 of Patent Document 5, protein or peptide is contained in the ink. In the system, the further combined with amino acids and specific surfactant, an object of preventing clogging reliability of a thermal head.
Regarding the reliability to prevent clogging here, when using a thermal head, the protein or peptide added to the ink decomposes from the structure of the protein or peptide, and the decomposition product is deposited on the head heater, so-called It is stated that the reliability to prevent clogging is prevented by adding a combination of an amino acid and a specific surfactant in the ink, and the reliability to prevent clogging is ensured. doing.

Furthermore, in Japanese Patent Application Laid-Open No. 2006-122900 of Patent Document 6, saccharides, reducing sugars, oxidized saccharides, and the like are added to ink for the purpose of improving the reliability of preventing clogging, and water evaporation of the ink around the nozzle is performed. Although it is described that clogging is prevented by suppressing, particularly in the present invention, for example, with water-soluble ink using a pigment, the water content in the ink is reduced, and the ink is contained in the ink. The inclusion of a dipeptide does not give both improvement in clogging prevention reliability, media transportability such as beading and cockling, and image reliability during high-speed printing.
The image reliability described here refers to light resistance, water resistance, and fixing property of a printed image portion of a printed matter on a medium.

Further, it has been found that by containing an anionic fluorosurfactant containing a perfluoro lower hydrocarbon group in the ink of the present invention, the colorant component in the ink is agglomerated and fixed suddenly after landing on the paper surface.
This effect has led to an improvement in image density, fixing property, and ink drying property with a small amount of ink adhesion, and it has been found that there is a significant effect on the problems in the present invention.
Although the detailed reason is not clear, the anionic fluorosurfactant containing the perfluoro lower hydrocarbon group used in the present invention is an aggregating agent, and after the ink has landed on the paper surface, the pigment is immediately aggregated and fixed. Therefore, it seems that this effect comes out.

On the other hand, conventional ink-jet paper, particularly glossy media for ink-jet printing, can be classified into a swelling type and a void type. This gap type is mainly provided with an ink absorbing layer having a gap for taking ink on a substrate, and further provided with a porous glossy layer if necessary. As disclosed in Japanese Patent Application Laid-Open No. 2005-212327 of Patent Document 1 and Japanese Patent Application Laid-Open No. 11-078225 of Patent Document 2, a coating solution in which silica or alumina hydrate is dispersed is formed on a substrate, or It is obtained by applying a plurality of layers and applying a gloss layer containing a large amount of colloidal silica as required.
This type of paper is designed with an emphasis on matching with the mainstream dye inks, and is already widely used as inkjet paper, especially glossy paper. When these papers are used, high-definition output with high gloss can be obtained, but on the other hand, the raw materials are very expensive and the manufacturing process is complicated, so the manufacturing cost is also comparable to that of general glossy coated paper for commercial printing. Then it is very expensive. For this reason, applications tend to be limited to cases where high-quality output is required, such as photo output, and it is difficult to use in commercial printing fields that require large amounts of output at low cost, such as flyers, catalogs, and brochures. It is. In recent years, the number of colors of ink used for printing for further image quality tends to increase, and the required ink absorption capacity tends to increase. In order to increase the ink absorption capacity of the media, it is sufficient to increase the thickness of the ink receiving layer (coat layer). However, as the thickness is increased, an expensive material is used and the unit price of the media is increased.

  As the pigment constituting the ink absorbing layer (receiving layer), a material having a small refractive index and low concealability, that is, a material capable of keeping the transparency of the layer high and having a large oil absorption (specific surface area) is used. There is a need. Therefore, at present, not a cheap white pigment such as calcium carbonate or kaolin, but an expensive low refractive index and high oil absorption pigment such as silica or alumina hydrate must be used in a large amount. This is because if a pigment with low transparency and high concealability is used in the ink absorbing layer, the color material in the ink soaked in the ink absorbing layer is concealed by these highly concealing pigments, and the concentration is expressed. It is because it will not do. In fact, when ink-jet printing with a dye ink on paper using such a highly concealed pigment, the density is low only as a result of the color material existing near the surface layer no matter how much the amount of ink to be applied is increased. The image will not have contrast. If a material having a small oil absorption amount is used, the ink cannot be absorbed in time and beading is likely to occur.

For these reasons, recently, the use of organic fine particles having a small refractive index as disclosed in Japanese Patent Application Laid-Open No. 2003-255717 of Patent Document 3 has also been attempted to achieve both refractive index and whiteness. However, the production cost of organic fine particles is also high, and it is still difficult to obtain an inexpensive receiving paper that matches the dye ink.
In addition, the design concept for long-term preservation of the resulting image is low in resistance to dye molecules themselves, ultraviolet rays and ozone, so the dye is soaked as deeply as possible in the ink receiving layer of the media to block out the effects of air and ultraviolet rays as much as possible. In addition, the mainstream is to protect the dye with an antioxidant or stabilizer added in advance to the image receiving layer of the media. Therefore, the penetration depth is ensured (compensated) by using a large amount of ink having a relatively low color material density, and image storability is maintained. Accordingly, the amount of ink necessary for outputting an image naturally increases, and it is difficult not only to reduce the size of the cartridge but also to increase the printing cost.
In view of the above, in inkjet recording, it is very difficult to provide inexpensive dedicated paper or a printing method capable of high-quality output.

  On the other hand, in recent years, pigment inks for inkjet recording have attracted attention. Since pigments are insoluble in water, it is common to use fine particles that are dispersed in a solvent. However, pigment inks for inkjet are pigment inks in which pigments are dispersed in water from the viewpoint of safety. Is the mainstream. In general, water-based pigment inks tend to cause aggregation and precipitation of pigment particles compared to dye inks, and various dispersion conditions and additives are necessary to achieve long-term storage stability comparable to dye inks. In addition to being difficult to use with a thermal head because of the cause of gating, the colorant color range is inferior to that of dyes, but there are many disadvantages such as high black density, printing quality and storage after recording. From the point of property and water resistance, it has come to attract much attention. Ink jet printers using this pigment ink may have the color material of ink close to that of general commercial printing ink, and the texture of the printed material can be brought close to that of commercial printing. When printing on coated paper for commercial printing with ink, the ink will not be dried in time and the image will bleed, or the pigment will not fix at all after drying. The reality is that it can only handle printing on high media. This is because the design philosophy relating to the formation of inkjet images is not different from the philosophy of using dye inks, and color material pigments are only taken from the viewpoint of dyes with high light resistance. This is because no consideration is given.

The present invention has been made in order to solve the following problems in view of the above circumstances.
That is, the object of the present invention is ideal in combination with the ink-jet pigment ink shown in the present invention, which is excellent in reliability such as improved transportability at high-speed printing, clogging prevention reliability, and high storage stability. An ink jet recording ink, an ink set for ink jet recording, an ink cartridge, an ink jet recording method, and an ink jet recording apparatus are provided.

As a result of intensive studies by the present inventors in order to solve the above problems, the following knowledge has been obtained.
That is, the said subject is achieved by following (1)-( 11 ) of this invention.
(1) “Ink jet recording ink suitable for ink jet recording, comprising water, a water-soluble organic solvent, a colorant, and containing a dipeptide and a perfluoro lower hydrocarbon group. Containing an activator ,
An ink for inkjet recording, wherein the fluorosurfactant is of the following general formula (I) ;

（Ｒ_１、Ｒ_２、Ｒ_３はフッ素含有基、フッ素原子のいずれかを表わし、ＭはＬｉ、Ｎａ、Ｋを表わす）」；
（２）「前記ジペプチドが、アラニルグルタミンあるいはグリシルグルタミン、ビスアラニルシスティン、ビスグリシルシスティンから選ばれる少なくとも１種類であることを特徴とする前記（１）項に記載のインクジェット記録用インク」；

(R ₁ , R ₂ , and R ₃ each represents a fluorine-containing group or a fluorine atom, and M represents Li, Na, or K) ”;
(2) “The dipeptide is at least one selected from alanylglutamine, glycylglutamine, bisalanylcystine, and bisglycylcystine”. ";

( 3 ) "The water-soluble organic solvent is glycerin, trimethylolpropane, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 2-methyl-1,3-propanediol, 1, 3-butanediol, 2,3-butanediol, 1,4-butanediol, 2-methyl-1,3-butanediol, 3-methyl-1,3-butanediol, 1,5-pentanediol, 1, At least one selected from 6-hexanediol, 2-methyl-2,4-hexanediol, 2-pyrrolidone, N-methyl-2-pyrrolidone, N-hydroxyethyl-2-pyrrolidone, tetramethylurea, urea above, wherein the at more than (1) or (2) of Jet recording ink according ";
( 4 ) "Ink for inkjet recording according to any one of items (1) to ( 3 ), wherein the dipeptide is contained in an amount of 2 to 20% by weight as a solid content";
( 5 ) “Inkjet recording ink set comprising black ink and color ink, wherein the black ink and the color ink are the inkjet recording ink according to any one of (1) to ( 4 )” ";
( 6 ) "Ink cartridge characterized by containing the ink according to any one of (1) to ( 4 ) or the ink set according to ( 5 )" in a container;
( 7 ) “Recording using the ink for inkjet recording according to any one of (1) to ( 4 ) or the ink set according to ( 5 ), with an ink adhesion amount of 15 g / m ² or less. An inkjet recording method characterized by:
( 8 ) “Inkjet recording method according to item ( 7 ), including at least an ink flying step of applying a stimulus to the ink and causing the ink to fly to form an image on the recording medium”;
( 9 ) "The inkjet recording method according to ( 8 ), wherein the stimulus is at least one selected from heat, pressure, vibration and light";
( 10 ) "Ink for inkjet recording according to any one of items (1) to ( 4 ) or ink set according to item ( 5 ), and ink for storing ink for inkjet recording or ink set" An ink jet recording apparatus comprising: a cartridge; and an ink ejecting unit that ejects the ink for ink jet recording toward the recording medium and performs printing with an ink adhesion amount of 15 g / m ² or less;
( 11 ) “The ink for ink jet recording according to any one of (1) to ( 4 ) or the ink of the ink set according to ( 5 ) is ejected as droplets from a recording head to form an image on a sheet. Ink jet recording apparatus comprising a unit that can perform double-sided printing by inverting paper.

According to the present invention, various problems in the prior art can be solved, and by using the ink jet recording ink shown in the present invention, an ideal ink jet recording ink having excellent reliability such as high clogging prevention reliability and high storage stability. Ink sets for ink jet recording, ink cartridges, ink jet recording methods, and ink jet recording apparatuses can be provided.
An ink for inkjet recording comprising water, a water-soluble organic solvent, and a colorant as the ink of the present invention, and a dipeptide and a perfluoro lower hydrocarbon group-containing anionic fluorine-based interface as a solid humectant in the ink Ink for ink jet recording characterized by containing an activator, which reduces curling and cockling during high-speed printing, has excellent transportability, and has a high optical density (OD) recorded image. An ink jet recording apparatus that can provide an image with high uniformity without being observed, has excellent reliability for preventing clogging, and ensures long-term reliability is achieved.

It is the schematic which shows an example of the ink cartridge of this invention. FIG. 2 is a schematic view including a case (exterior) of the ink cartridge of FIG. 1. FIG. 4 is a perspective explanatory view showing a state where an ink cartridge loading unit cover of the ink jet recording apparatus is opened. It is a schematic block diagram explaining the whole structure of an inkjet recording device. It is a schematic enlarged view which shows an example of the inkjet head of this invention. It is an element enlarged view showing an example of an ink jet head of the present invention. It is a principal part expanded sectional view which shows an example of the inkjet head of this invention.

Hereinafter, the ink for ink jet recording, the ink set for ink jet recording, the ink cartridge, the ink jet recording method, and the ink jet recording apparatus of the present invention will be described in detail.
The ink condition essential for the present invention must be very penetrable, and the surface tension at 25 ° C. is preferably 20 to 35 mN / m, and if it is less than 20 mN / m, the head wiping operation is performed. Later, all of the ink on the head nozzle surface cannot be wiped off, which may adversely affect the head reliability after being left for a long time, and if it exceeds 35 mN / m, the ink permeability to the medium in the present invention will be increased. As a result, there is a risk that the dot spread of ink droplets will be insufficient and the effect of reducing beading on the media will be diminished.
Further, the viscosity at 25 ° C. is 5 mPa · s or more and 20 mPa · s or less, and if 5 mPa · s, there is a possibility of adversely affecting the transportability such as beading to the media and cockling, and if greater than 20 mPa · s, Viscosity increases greatly at low temperatures such as 10 ° C., which may adversely affect head ejection stability and clogging prevention reliability.
In addition, the dipeptide used in the present invention contains at least one selected from alanyl glutamine, glycylglutamine, bisalanylcystine, and bisglycylcystine as the dipeptide used in the present invention. It has been found that by including a group-containing anionic fluorosurfactant, it is possible to satisfy both clogging prevention reliability, media transportability such as beading and cockling, and image reliability.

In the following, the components of the ink essential to the present invention will be described.
In the ink of the present invention, examples of the colorant include hydrophobic dyes and pigments.
The hydrophobic dye as used herein refers to a dye that is insoluble or hardly soluble in water and soluble in an organic solvent, and examples thereof include oil-soluble dyes and disperse dyes. It can be used as a polymer emulsion. Here, oil-soluble dyes and disperse dyes are preferable from the viewpoint of good adsorption / encapsulation properties, but pigments are particularly preferably used from the light resistance of the obtained image.
The term “containing a hydrophobic dye” as used herein means either or both of a state in which a hydrophobic dye is encapsulated in polymer fine particles and a state in which the surface is adsorbed on the surface of the polymer fine particles. In this case, it is not necessary for all of the colorant blended in the ink of the present invention to be encapsulated or adsorbed in the polymer fine particles, and the colorant is dispersed in the emulsion as long as the effects of the present invention are not impaired. Also good.
The colorant is not particularly limited as long as it is a water-insoluble or poorly water-soluble colorant that can be adsorbed by the polymer.
In the present invention, water-insoluble or poorly water-soluble means that the coloring material does not dissolve 0.1 parts by weight or more with respect to 100 parts by weight of water at 20 ° C. This means that no separation or sedimentation of the material is observed.

The description of the colorant used in the present invention is further shown below.
Examples of the pigment used in the present invention include carbon black as a black pigment, and examples of the color pigment include anthraquinone, phthalocyanine blue, phthalocyanine green, diazo, monoazo, pyranthrone, perylene, heterocyclic yellow, quinacridone, and (thio) indigoid. Including.
Representative examples of phthalocyanine blue include copper phthalocyanine blue and its derivatives (Pigment Blue 15).
Representative examples of quinacridone include Pigment Orange 48, Pigment Orange 49, Pigment Red 122, Pigment Red 192, Pigment Red 202, Pigment Red 206, Pigment Red 207, Pigment Red 209, Pigment Violet 19 and Pigment Violet 42.
Representative examples of anthraquinones include pigment red 43, pigment red 194 (perinone red), pigment red 216 (brominated pyrantrone red) and pigment red 226 (pyrantron red).
Representative examples of pyrerin are Pigment Red 123 (Bell Million), Pigment Red 149 (Scarlet), Pigment Red 179 (Maroon), Pigment Red 190 (Red), Pigment Violet, Pigment Red 189 (Yellow Shade Red) and Pigment Red. 224.
Representative examples of thioindigoid include Pigment Red 86, Pigment Red 87, Pigment Red 88, Pigment Red 181, Pigment Red 198, Pigment Violet 36 and Pigment Violet 38.
Representative examples of heterocyclic yellow include pigment yellow 117 and pigment yellow 138.
Examples of other suitable colored pigments include those described in The Color Index, Third Edition (The Society of Dyers and Colorists, 1982).

In the pigment used in the ink of the present invention, at least one hydrophilic group is bonded to the pigment surface directly or through another atomic group, and the pigment can be stably dispersed without using a dispersant. Can be used.
As the pigment having a hydrophilic group introduced on the surface thereof used in the present invention, those having ionicity are preferable, and those having an anionic charge or those having a cationic charge are suitable.
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 ( where, M in the formula is a hydrogen atom, 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. It is done.
In the present invention, it is particularly preferable to use those in which —COOM and —SO ₃ M are bonded to the pigment surface. Examples of a method for obtaining an anionically charged pigment include a method of oxidizing a pigment with sodium hypochlorite, a method of sulfonation, and a method of reacting a diazonium salt, but the present invention is not limited thereto. I don't mean.
For example, a quaternary ammonium group can be used as the hydrophilic group bonded to the surface of the color pigment charged with a cation. More preferably, a pigment having at least one quaternary ammonium group bonded to the pigment surface is used.

In the pigment used in the ink of the present invention, a pigment dispersion in which a pigment is dispersed in an aqueous medium with a dispersant can also be used.
As a preferable dispersant, a known dispersant used for preparing a pigment dispersion can be used, and examples thereof include the following.
Polyacrylic acid, polymethacrylic acid, acrylic acid-acrylonitrile copolymer, vinyl acetate-acrylic acid ester copolymer, acrylic acid-acrylic acid alkyl ester copolymer, styrene-acrylic acid copolymer, styrene-methacrylic acid copolymer Polymer, styrene-acrylic acid-acrylic acid alkyl ester copolymer, styne-methacrylic acid-acrylic acid alkyl ester copolymer, styrene-α-methylstyrene-acrylic acid copolymer, styrene-α-methylstyrene-acrylic Acid copolymer-alkyl acrylate ester copolymer, styrene-maleic acid copolymer, vinyl naphthalene-maleic acid copolymer, vinyl acetate-ethylene copolymer, vinyl acetate-fatty acid vinyl ethylene copolymer, vinyl acetate -Maleic acid ester copolymer, vinyl acetate Rotonic acid copolymer, vinyl acetate-acrylic acid copolymer, etc.

The nonionic or anionic activator dispersant used to disperse the pigment can be appropriately selected according to the pigment type or the ink formulation. Nonionic surfactants include polyoxyethylene lauryl ether, polyoxyethylene Polyoxyethylene alkyl ethers such as ethylene myristyl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene alkyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, etc. , Polyoxyethylene α-naphthyl ether, polyoxyethylene β-naphthyl ether, polyoxyethylene monostyryl phenyl ether, polyoxyethylene distyryl ether Nyl ether, polyoxyethylene alkyl naphthyl ether, polyoxyethylene monostyryl naphthyl ether, polyoxyethylene distyryl naphthyl ether, polyoxyethylene polyoxypropylene block copolymer and the like.
Also used are surfactants in which a part of polyoxyethylene in the above surfactant is replaced with polyoxypropylene, and surfactants condensed with a compound having an aromatic ring such as polyoxyethylene alkylphenyl ether with formalin. it can.

The HLB of the nonionic surfactant is preferably from 12 to 19.5, more preferably from 13 to 19. If the HLB is less than 12, there is a tendency for the dispersion stability to deteriorate due to poor compatibility of the surfactant with the dispersion medium. If the HLB exceeds 19.5, the surfactant is difficult to adsorb on the pigment, so that the dispersion stability is also maintained. There is a tendency to deteriorate.
Anionic surfactants include polyoxyethylene alkyl ether sulfate, polyoxyethylene alkyl phenyl ether sulfate, polyoxyethylene monostyryl phenyl ether sulfate, polyoxyethylene distyryl phenyl ether sulfate, polyoxyethylene alkyl ether phosphorus Acid salt, polyoxyethylene alkyl phenyl ether phosphate, polyoxyethylene monostyryl phenyl ether phosphate, polyoxyethylene distyryl phenyl ether phosphate, polyoxyethylene alkyl ether carboxylate, polyoxyethylene alkyl phenyl ether Carboxylate, polyoxyethylene monostyryl phenyl ether carboxylate, polyoxyethylene distyryl phenyl ether carboxylate, naphthalene Sulfonate formalin condensate, melanin sulfonate formalin condensate, dialkyl sulfosuccinic acid ester salt, sulfosuccinic acid alkyl disalt, polyoxyethylene alkyl sulfosuccinic acid disalt, alkyl sulfoacetate, α-olefin sulphonate, alkylbenzene sulfone Acid salts, alkylnaphthalene sulfonates, alkyl sulfonates, N-acyl amino acid salts, acylated peptides, soaps, and the like. Among these, polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxy Particularly preferred is the sulfate or phosphate of ethylene distyryl phenyl ether.

  The addition amount of the surfactant-based dispersant is preferably 10% by weight to 50% by weight of the pigment. If the addition amount of the surfactant-based dispersant is less than 10% by weight of the pigment, the storage stability of the pigment dispersion and the ink is reduced or the dispersion takes an extremely long time. Since it becomes too high, the discharge stability tends to decrease.

Further, a resin-coated colorant can also be suitably used as the colorant, which will be described below.
It consists of a polymer emulsion in which polymer fine particles contain a colorant that is insoluble or hardly soluble in water. In the present invention, “containing a color material” means either or both of a state in which a color material is enclosed in 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 enclosed 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.
In the present invention, water-insoluble or poorly water-soluble means that the coloring material does not dissolve 10 parts by weight or more with respect to 100 parts by weight of water at 20 ° C. This means that no separation or sedimentation is observed.
Examples of the coloring material include dyes such as oil-soluble dyes and disperse dyes, pigments, and the like.
Oil-soluble dyes and disperse dyes are preferable from the viewpoint of good adsorption and encapsulation, but pigments are preferably used from the light resistance of the obtained image.

In addition, the colorant used in the present invention is preferably dissolved in an organic solvent, for example, a ketone solvent in an amount of 2 g / liter or more, preferably 20 to 600 g / liter, from the viewpoint of efficiently impregnating the polymer fine particles. Is more preferable.
As the polymer that forms the polymer emulsion, for example, vinyl polymers, polyester polymers, polyurethane polymers, and the like can be used.
Particularly preferred polymers are vinyl polymers and polyester polymers, and specific examples thereof include those disclosed in JP-A Nos. 2000-53897 and 2001-139849.
Moreover, 10-200 mass parts is preferable with respect to 100 mass parts of said polymers, and, as for the compounding quantity of the said coloring agent, 25-150 mass parts is more preferable. The average particle diameter of the polymer fine particles containing the colorant is preferably 0.16 μm or less in the ink.
The content of the polymer fine particles is preferably 8 to 20% by mass, more preferably 8 to 12% by mass in solid content in the recording ink.

An example of the hydrophobic dye of the present invention is shown below.
Examples of the oil-soluble dye include C.I. I. Solvent Black, C.I. I. Solvent Yellow, C.I. I. Solvent Red, C.I. I. Solvent Violet, C.I. I. Solvent Blue, C.I. I. Solvent Green, C.I. I. Examples are products of various product numbers such as Solvent Orange, which are commercially available from Orient Chemical Co., Ltd., BASF Co., etc.
Examples of disperse dyes include C.I. I. Disperse Yellow, C.I. I. Disperse Orange, C.I. I. Disperse Red, C.I. I. Dispers Violet, C.I. I. Disperse Blue, C.I. I. Products of each part number such as Disperse Green are listed. Of these, C.I. I. Solvent Yellow 29 and 30, C.I. I. Solvent Blue 70, C.I. I. Solvent Red 18 and 49, C.I. I. Solvent blacks 3 and 7 and nigrosine-based black dyes are preferred. Examples of the hydrophobic dye include, but are not limited to, these.

In the present invention, wettability and penetrability to recording paper can be remarkably improved by using a surfactant, particularly an anionic fluorosurfactant containing a perfluoro lower hydrocarbon group.
Further, it has been found that the specific fluorine-based surfactant of the present invention agglomerates and fixes the colorant component in the ink abruptly after landing on the paper surface. This effect has led to an improvement in image density, fixing property, and ink drying property with a small amount of ink adhesion, and it has been found that there is a significant effect on the problems in the present invention.
Although the detailed reason is not clear, the specific fluorosurfactant used in the present invention acts as an aggregating agent, and after the ink has landed on the paper surface, the pigment is quickly aggregated and fixed, so this effect is obtained. It seems to be.
In addition to the specific fluorosurfactant of the present invention, it is also possible to use another fluorosurfactant. By using it together with the fluorosurfactant used in the present invention, wetting with paper is possible. And high penetrability, high color developability and color material uniformity on the ink jet recording medium, and very low beading and good image quality.
Although the details are not clear, the specific fluorosurfactant used in the present invention is considered to be able to keep the beading extremely low due to the effect of uniformly dispersing the color material and spreading the pixel diameter uniformly. As a result, ideal ink jet recording ink, ink set for ink jet recording, ink cartridge, and ink jet recording method are excellent in reliability such as anti-clogging reliability and storage stability with reduced curling and cockling after printing. It is estimated that an ink jet recording apparatus can be provided.

  The following structural formula (I) shows the following structure as a particularly suitable surfactant in the present invention.

（Ｒ_１、Ｒ_２、Ｒ_３はフッ素含有基、フッ素原子のいずれかを表わし、ＭはＬｉ、Ｎａ、Ｋを表わす）

(R ₁ , R ₂ , R ₃ represent either a fluorine-containing group or a fluorine atom, and M represents Li, Na, K)

In the present invention, the fluorosurfactant represented by the general formula (I) is preferably added in an amount of 0.5 wt% to 20 wt%, more preferably 1 wt% to 10 wt% in the ink. Added. If the added amount is less than the lower limit, the pigment aggregation after ink landing on the paper, the fixing effect is inferior, the roller is rubbed with a roller at the time of conveyance, and dirt is generated, or the ink is attached to the conveyance belt when reversed for double-sided printing. It may not be compatible with high-speed printing or double-sided printing due to contamination. If the added amount is more than the upper limit, the ink storage stability is lowered.
Moreover, as other fluorine-type surfactant, the surfactant shown by the following general formula (II) can be used conveniently.

（ここで、一般式（II）中、Ｒ１、Ｒ３は水素またはフッ素含有基を表わす。Ｒ２、Ｒ４はフッ素含有基を表わす。ｍ、ｎ、ｐ、ｑ、及びｒは、整数を表わす。）
これらは、既に市販されており、例えば一般式（Ｉ）の界面活性剤は、（株）ネオス社 ＦＴ−１１０等として、また、一般式（II）の界面活性剤は、ＯＭＮＯＶＡ社 ＰＦ−１５１Ｎ等として入手することができる。

(In the general formula (II), R1 and R3 represent hydrogen or a fluorine-containing group. R2 and R4 represent a fluorine-containing group. M, n, p, q, and r represent integers.)
These are already commercially available. For example, the surfactant of general formula (I) is FT-110, etc., manufactured by Neos Co., Ltd. The surfactant of general formula (II) is OMNOVA PF-151N. And so on.

Further, in addition to the fluorine-based surfactants of the above general formulas (I) and (II) used in the present invention, the following fluorine-based surfactants can be used in combination.
That is, perfluoroalkyl sulfonate, perfluoroalkyl carboxylate, perfluoroalkyl phosphate ester, perfluoroalkyl ethylene oxide adduct, perfluoroalkyl betaine, perfluoroalkylamine oxide compound, etc. Examples of commercially available compounds include Surflon S-111, S-112, S-113, S121, S131, S132, S-141, and S-145 (manufactured by Asahi Glass Co., Ltd.), Fullrad FC-93, FC- 95, FC-98, FC-129, FC-135, FC-170C, FC-430, FC-431, FC-4430 (manufactured by Sumitomo 3M), MegaFuck F-470, F-1405, F474 (Dainippon) Ink Chemical Industries, Ltd.), Zonyl FS-300 FSN, (manufactured by Du Pont) FSN-100, FSO, (manufactured by JEMCO Inc.) EFTOP EF-351,352,801,802, etc. can be used to easily obtain can present invention. Among these, Zonyl FS-300, FSN, FSN-100, and FSO (manufactured by DuPont), which are particularly excellent in reliability and color development, can be preferably used.

Further, surfactants that can be used in combination with the above fluorine-based surfactants include interfacial polyoxyethylene alkyl ether acetate, dialkyl sulfosuccinate, polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, polyoxyethylene polyoxypropylene block Examples include copolymers, polyoxyethylene alkyl esters, polyoxyethylene sorbitan fatty acid esters, and acetylene glycol surfactants.
More specifically, as an anionic surfactant, polyoxyethylene alkyl ether acetate and / or dialkylsulfosuccinic acid having a branched alkyl chain of 5 to 7 carbon chains is used to wet the plain paper. Becomes better.
Further, the surfactants mentioned here can exist stably in the ink of the present invention without inhibiting the dispersion state.

Examples of the polyol having 7 to 11 carbon atoms used as a penetrant in the present invention include 2-ethyl-1,3-hexanediol and 2,2,4-trimethyl-1,3-pentanediol.
The addition amount is preferably 0.1% to 20% by weight, more preferably 0.5% to 10% by weight. If the amount added is less than the lower limit, the ink will have poor penetrability to the paper, and will be rubbed with a roller during conveyance, causing smudges, or when reversing for double-sided printing, ink will adhere to the conveyance belt and smear will occur. Or high-speed printing or double-sided printing. If the addition amount is greater than or equal to the upper limit, the printed dot diameter increases, the line width of the characters becomes wider, and the image definition decreases.

Examples of the additive include an antifungal agent, an antirust agent, and a pH adjuster.
By using 1,2-benzisothiazolin-3-one as an antifungal agent, it is possible to provide an ink having an excellent antifungal effect while ensuring reliability such as storage stability and ejection stability.
In particular, in combination with the wetting agent of the present invention, even if the addition amount is conventionally difficult to suppress the generation of bacteria and sputum, the effect can be sufficiently exerted, by suppressing the addition amount In addition, since phenomena such as particle aggregation and ink thickening can be prevented, ink performance can be exhibited over a long period of time.
The amount of 1,2-benzisothiazolin-3-one added is preferably 0.01 to 0.04 parts by weight of the total amount of ink as the active ingredient amount. If it is less than 0.01 part by weight, the anti-mold property is slightly lowered. In the case of 0.04 parts or more, particle aggregation occurs when the ink is stored for a long period of time (for example, 2 years at room temperature, 1 to 3 months at 50 to 60 ° C.), or ink viscosity is initially Long-term storage stability problems such as a 50% to 100% increase in viscosity occur, and the initial printing performance cannot be maintained.

As the pH adjuster, any substance can be used as long as the pH can be adjusted to 7 or more without adversely affecting the ink to be prepared.
Examples thereof include amines such as diethanolamine and triethanolamine, hydroxides of alkali metal elements such as lithium hydroxide, sodium hydroxide and potassium hydroxide, ammonium hydroxide, quaternary ammonium hydroxide, and quaternary phosphonium. Other examples include aminopropanediol derivatives such as hydroxides, alkali metal carbonates such as lithium carbonate, sodium carbonate, and potassium carbonate. Aminopropanediol derivatives are water-soluble organic basic compounds such as 1-amino-2,3-propanediol, 1-methylamino-2,3-propanediol, 2-amino-2-methyl-1, Examples thereof include 3-propanediol and 2-amino-2-ethyl-1,3-propanediol, and particularly preferred examples include 2-amino-2-ethyl-1,3-propanediol.

Examples of the rust inhibitor include acidic sulfite, sodium thiosulfate, ammonium thiodiglycolate, diisopropylammonium nitrite, pentaerythritol tetranitrate, and dicyclohexylammonium nitrite.
Depending on the purpose, a water-soluble ultraviolet absorber, a water-soluble infrared absorber, or the like can be added.
Here, the solid moisturizing agent used in the present invention refers to a water-soluble substance having a water retention function and solid at room temperature of 25 ° C. In the ink vehicle, it dissolves or partially dissolves in the ink. A compound that does not impair the dispersion stability of the pigment (does not cause pigment aggregation).

Among the dipeptides mentioned in the present invention, especially alanylglutamine has extremely high solubility in water at 20 ° C. compared to conventional amino acids and the like, and when added to ink, the dispersion stability of the pigment In addition, it is possible to add 1 to 20 parts by weight, preferably 5 to 10 parts by weight, in the ink as a solid weight content.
Here, if the amount is less than 1 part by weight, the anti-clogging stability of the present invention is not effective, and if the addition amount is more than 20 parts by weight, the viscosity becomes too high, which affects the anti-clogging stability. I know.

In the present invention, the anti-clogging stability of the dipeptide is, for example, that the high water solubility of the dipeptide is increased, and thus it is stably dissolved in the ink. It is presumed that it also has a function as a dispersion stabilizer because it does not adversely affect the properties and has a weak affinity for the pigment.
In addition, as a moisturizing agent, alanine and the like are natural moisturizing ingredients that exist in the human stratum corneum, and glutamine is a substance that is easily taken up by human cells. It is a highly safe moisturizing substance that is widely used as an external preparation for skin, and this high moisturizing property is combined with the part contributing to the pigment dispersibility for the prevention of clogging this time. By maintaining the ink moisture retention in the vicinity of the nozzle, aggregation of the pigment component accompanying drying is prevented, and this remarkably high clogging prevention reliability is expressed.
In addition, for media transportability such as beading and cockling, and image quality reliability, the pigment dispersibility is not adversely affected, the ink permeability is not hindered, and a large amount is added to the ink as a solid content. If possible, it is possible to relatively reduce the amount of water contained in the ink by adding a dipeptide, improving fixability, reducing beading, and relatively reducing the amount of water. In addition, it is considered that this contributes to curling and cockling reduction during printing, and the use of the ink of the present invention has a very remarkable effect on the problems of the present invention. It is thought that it is expressed.
Here, the relative reduction in the amount of water refers to the relative amount of water with respect to the system to which the dipeptide has not been added in the present invention, and by adding the dipeptide, depending on the added solid content, This means that the amount of water is relatively reduced.

The water-dispersible resin that can be used in the present invention can be suitably used by at least one selected from a polyurethane resin emulsion and an acrylic-silicone resin emulsion, or a combination thereof, and can be used as an ink adjustment raw material. Or, it exists as an O / W type emulsion after the ink preparation of the present invention.
When at least one selected from the above is used, these emulsions are present in the ink in a total amount of 1 to 40% by weight, preferably 1 to 20% by weight.
In polyurethane resin emulsions, normal polyurethane resins that are relatively hydrophilic are emulsified using an emulsifier on the outside. There is an emulsion type emulsion.
Among the combinations of pigments and the like that can be used in the ink of the present invention, an anionic self-emulsifying type polyurethane resin emulsion is always excellent in dispersion stability. In this case, the polyurethane resin is preferably an ether type rather than a polyester type or polycarbonate type in terms of pigment fixing property and dispersion stability. The reason is not clear, but many non-ether types have poor solvent resistance, and tend to cause aggregation and increase in viscosity when the ink is stored at high temperature.

The average particle size of the ether polyurethane resin emulsion is 300 nm or less, preferably 100 nm or less, more preferably 80 nm or less. In particular, by setting the average particle size to 100 nm or less, the reliability of the ink jet printer, such as the stability of ink ejection after being left for a long time, is improved.
The glass transition point of the ether polyurethane resin emulsion is preferably in the range of −50 ° C. to 150 ° C. More preferably, it is the range of -10 degreeC-100 degreeC. The reason is not clear, but when the glass transition point exceeds 150 ° C, the film formation property of the ether polyurethane resin emulsion is glassy and hard, but the pigment particles and the ether polyurethane resin emulsion land on the image support at the same time. On the other hand, the scratch resistance of the printed part is surprisingly fragile. On the other hand, at 150 ° C. or lower, the film formation property of the ether polyurethane resin emulsion is rubbery and soft, but it can be excellent in scratch resistance. However, when the temperature is lower than −50 ° C., the film is too soft and the scratch resistance is inferior. From the above points, with the same addition amount, the glass transition point is −50 ° C. to 150 ° C. from the viewpoint of scratch resistance of the printed matter. The range of was found to be preferable.
In addition, the glass transition point of resin as used in the field of this invention can be measured with the measuring method of either DSC (differential scanning calorimeter) or TMA (thermomechanical analysis).

The ether polyurethane resin emulsion preferably has a minimum film-forming temperature of room temperature or lower, more preferably 25 ° C. or lower. When the film formation of the ether polyurethane resin emulsion is carried out at room temperature or lower, particularly 25 ° C. or lower, the binding of paper fibers automatically proceeds without any special treatment such as heating or drying of the image-formed image support. This is preferable.
Here, the “minimum film-forming temperature (MFT)” means that the aqueous emulsion particles obtained by dispersing the ether-based polyurethane resin emulsion particles in water are thinly cast on a metal plate such as aluminum to raise the temperature. Is defined as the lowest temperature at which a transparent continuous film is formed.

Next, the acrylic-silicone resin emulsion that can be used in the present invention will be described.
The acrylic-silicone resin emulsion of the present invention is a silicon-modified acrylic resin emulsion that can be obtained by polymerizing an acrylic monomer and a silane compound in the presence of an emulsifier.
As acrylic monomers, acrylic ester monomers such as methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, acryloyl morpholine, N, N′-dimethylaminoethyl acrylate, Methacrylic acid ester monomers such as methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, 2-hydroxyethyl methacrylate, N, N′-dimethylaminoethyl methacrylate, N-methylolacrylamide, methoxymethylacrylamide, etc. And carboxylic acid-containing monomers such as maleic acid acrylate, maleic acid, fumaric acid, itaconic acid, acrylic acid and methacrylic acid.

  Examples of the emulsifier of the present invention include alkylbenzene sulfonic acid or its salt, dialkyl sulfosuccinic acid ester or its salt, alkyl naphthalene sulfonic acid or its salt, formalin condensate of alkyl naphthalene sulfonate, higher fatty acid salt, higher fatty acid Ester sulfonate, ethylenediamine polyoxypropylene-polyoxyethylene condensate, sorbitan fatty acid ester or salt thereof, aromatic or aliphatic phosphate ester or salt thereof, dodecylbenzene sulfonate, dodecyl sulfate, lauryl sulfate , Dialkylsulfosuccinate, polyoxyethylene alkylphenyl ether sulfate, polyoxyethyne alkylpropenyl phenyl ether sulfate, alkylphenyl ether disulfonate, polyoxyethylene Alkyl phosphate, polyoxyethylene alkyl ether acetate, polyoxyethylene lanolin alcohol ether, polyoxyethylene lanolin fatty acid ester, lauryl alcohol ethoxylate, lauryl ether sulfate ester, lauryl ether phosphate ester, sorbitan fatty acid ester, fatty acid diethanolamine And a formalin condensate of naphthalene sulfonic acid. Here, examples of the salt include sodium and ammonium.

Moreover, the reactive emulsifier which has an unsaturated double bond can also be used as an emulsifier of this invention.
Examples of reactive emulsifiers include Adekari Soap SE, NE, PP (Asahi Denka Kogyo Co., Ltd.), Latemuru S-180 (Kao Co., Ltd.), Eleminol JS-2, Eleminol RS-30 (Sanyo Kasei Kogyo Co., Ltd.) And Aqualon RN-20 (Daiichi Kogyo Seiyaku Co., Ltd.).

  Examples of the silane compound of the present invention include tetramethoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane, tetraethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, and phenyltriethoxysilane. , Diphenyldiethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, decyltrimethoxysilane, decyltrimethoxysilane, trifluoropropyltrimethoxysilane and the like.

  Moreover, the monomer generally known as a silane coupling agent can also be used, and examples thereof include vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, p-styryltrimethoxysilane, 3 -Methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, -methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2 (aminoethyl) ) 3-aminopropylmethyldimethoxysilane, N-2 (aminoethyl) 3-aminopropyltrimethoxysilane, N-2 (aminoethyl) 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-amino Propyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N- (vinylbenzyl) -2-aminoethyl-3 Aminopropyltrimethoxysilane hydrochloride, 3-ureidopropyltriethoxysilane, 3-chloropropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, bis (triethoxysilylpropyl) tetra Examples thereof include sulfide and 3-isocyanatopropyltriethoxysilane.

In the present invention, the hydrolyzable silyl group is a silyl group containing a hydrolyzable group. Examples of the hydrolyzable group include an alkoxy group, a mercapto group, a halogen group, an amide group, an acetoxy group, an amino group, and an isopropenoxy group. Groups and the like.
The silyl group is hydrolyzed to become a silanol group, and the silanol group is dehydrated and condensed to form a siloxane bond.
In the silicon-modified acrylic resin used in the ink of the present invention, it is preferable that the hydrolyzable silyl group disappears by hydrolysis through a polymerization reaction. If the hydrolyzable silyl group remains, the storage stability when used as an ink is deteriorated, which is not preferable.
The average particle diameter of the resin fine particles is preferably 10 nm to 300 nm, more preferably 40 nm to 200 nm. When the average particle size is synthesized so as to be 10 nm or less, the viscosity of the resin emulsion becomes high, and it becomes difficult to obtain an ink viscosity that can be ejected by a printer. When the average particle size is 300 nm or more, particles are clogged in the nozzles of the printer, resulting in ejection failure.

The amount of silicon derived from the silicon-modified acrylic resin contained in the ink of the present invention is preferably 100 ppm or more and 400 ppm or less. When the amount of silicon is less than 100 ppm, a coating film excellent in scratch resistance and marker resistance cannot be obtained, and when the amount of silicon is more than 400 ppm, the tendency to hydrophobicity increases and the stability in aqueous ink decreases.
The minimum film-forming temperature of the silicon-modified acrylic resin used in the ink of the present invention is preferably 20 ° C. or lower. If the minimum film forming temperature is higher than 20 ° C., sufficient fixability cannot be obtained. That is, if the print portion is rubbed or traced with a marker, the pigment is removed and the print medium is soiled.

  Next, in the present invention, the water dispersible resin and the pigment as the colorant are present in the ink in a total amount of 5 to 40% by weight, and the weight ratio of the water dispersible resin and the pigment as the colorant (water dispersibility). (Resin) / (pigment as a colorant) is more preferably 0.5 to 4, and high fixability with respect to an inexpensive medium used in the present invention and printed matter close to commercial printed matter are described in the present invention. This is achieved by a combination of ink and media.

As an important constituent requirement for the ink in the present invention, it is preferable to add 2 to 20 parts by weight, preferably 3 to 10 parts by weight of the dipeptide as a solid humectant in the ink, more preferably 3 to 10 parts by weight. It has been found in the present invention that the total solid content and ratio of the aforementioned water-dispersible resin and pigment as a colorant in the ink are necessary to achieve the object.
That is, regarding the total solid content in the ink, it is necessary that the water-dispersible resin and the pigment as the colorant be present in the ink in an amount of 5 to 40% by weight. It is insufficient for the media to be used, and when it is added in an amount of 40% by weight or more, the viscosity becomes too high, which adversely affects reliability such as ink ejection properties. More preferably, it is 5 to 20% by weight, and depending on the type of color material described later, resin dispersion and resin-coated pigment can also be used, and the resin dispersant and coating resin at that time are also combined with the water-dispersible resin. The resin solid content.

  In addition, when the weight ratio of the water-dispersible resin and the pigment as the colorant (water-dispersible resin) / (pigment as the colorant) is 0.5 to 4, the present invention is less than 0.5. In the media used in the above, the fixing property is insufficient, and if it is larger than 4, the density of the coloring material with respect to the resin is too low, leading to a decrease in image quality such as a decrease in density and a decrease in image uniformity. For this reason, with respect to the media used in the present invention, as an important component of the ink used in the present invention, 1 to 20 parts by weight, preferably 3 to 3 parts by weight of dipeptide as a solid humectant, The addition of 10 parts by weight, more preferably, the total amount of solids and the ratio of the water-dispersible resin and the pigment as the colorant in the ink are 5 to 40% by weight in total in the ink, And the weight ratio (water-dispersible resin) / (pigment as a colorant) of water-dispersible resin and the pigment as a colorant is 0.5-4.

Next, specific examples of the water-soluble organic solvent of the present invention include the following.
Ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, tetraethylene glycol, polyethylene glycol, polypropylene glycol, 1,3-butanediol, 2-methyl-1,3-butanediol, 3- Methyl-1,3-butanediol, 2,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, glycerol, 1,2,6-hexanetriol, 1, Polyhydric alcohols such as 2,4-butanetriol, 1,2,3-butanetriol, 2-methyl-2,4-pentanediol, petriol, 3-methoxy-3-methyl-1-butanediol;
Polyhydric alcohol alkyl ethers 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, propylene glycol monoethyl ether;
Polyhydric alcohol aryl ethers such as ethylene glycol monophenyl ether, ethylene glycol monobenzyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monobutyl ether, diethylene glycol isobutyl ether, triethylene glycol isobutyl ether, diethylene glycol isopropyl ether;
Nitrogen-containing heterocyclic compounds such as 2-pyrrolidone, N-methyl-2-pyrrolidone, N-hydroxyethyl-2-pyrrolidone, 1,3-dimethylimidazolidinone, ε-caprolactam, γ-butyrolactone;
Amides such as formamide, N-methylformamide, N, N-dimethylformamide;
Amines such as monoethanolamine, diethanolamine, triethanolamine, monoethylamine, diethylamine, triethylamine;
Sulfur-containing compounds such as dimethyl sulfoxide, sulfolane, thiodiethanol, thiodiglycol;
Propylene carbonate, ethylene carbonate and the like.

  Among these organic solvents, glycerin, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,3-butanediol, 2-methyl-1,3-butanediol, 3-methyl -1,3-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, 2-pyrrolidone, N-methyl-2-pyrrolidone, N-hydroxyethyl-2-pyrrolidone, 1, 3-dimethyl-2-imidazolidinone is preferred Arbitrariness. These are excellent in solubility and prevention of poor jetting characteristics due to water evaporation.

In the present invention, it is necessary to strictly limit the total amount of ink in order to prevent the color material from penetrating into the ink and efficiently distribute it in the vicinity of the surface of the medium while ensuring the drying property of the ink.
If a large amount of ink is used as in conventional inkjet recording, the colorant pigment in the ink penetrates together with the water-soluble organic solvent contained in the ink, or the penetration of the solvent component of the ink is not in time, This is because it greatly impedes drying properties.
It has been found that the maximum total amount of ink required to solve the problems of the present invention is 15 g / m ² , desirably 12 g / m ² or less. The amount of ink can be easily adjusted.

Also, by reducing the total amount of ink required for printing, the capacity of the ink cartridge can be reduced compared to conventional ink jet printers, and the apparatus can be made compact. Further, if the cartridge size is the same as the conventional one, the replacement frequency of the ink cartridge can be reduced, and printing at a lower cost is possible.
Basically, the smaller the total amount of ink, the better the drying performance after landing on high-speed printing, and curling and cockling can be reduced. However, if the amount is too small, the image dot diameter after printing becomes too small and the solid part Therefore, it is desirable to set the total amount of ink within this range according to the target image.

In the present invention, the total amount of ink was measured using a gravimetric method. Specifically, a rectangle of 5 cm × 20 cm is printed on My Paper (made by Ricoh), which is PPC paper, the weight is measured immediately after printing, the weight before printing is subtracted, and the value is multiplied by 100 to obtain the total amount of ink. .
The ink according to the present invention, as an inkjet head, uses a piezoelectric element as pressure generating means for pressurizing the ink in the ink flow path, and deforms the diaphragm that forms the wall surface of the ink flow path to change the volume in the ink flow path. A so-called piezo type that discharges ink droplets (refer to Japanese Patent Laid-Open No. 2-51734), or a so-called thermal type that generates bubbles by heating ink in an ink flow path using a heating resistor ( JP, 61-59911, A), the diaphragm and the electrode which form the wall surface of an ink channel are arranged facing, and the diaphragm is deformed by the electrostatic force generated between the diaphragm and the electrode, A pre-equipped with any inkjet head such as an electrostatic type (see Japanese Patent Laid-Open No. 6-71882) that changes the volume of the ink flow path to eject ink droplets. It is also good to use in the data.

As described above, the recording medium in the ink media set is used in combination with the ink in the ink media set.
The combination of the recording medium and the ink can be suitably used in various fields, and can be suitably used in an image recording apparatus (printer or the like) using an ink jet recording method. For example, the following ink of the present invention It can be particularly suitably used for a cartridge, an ink record, an ink jet recording apparatus, and an ink jet recording method.

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 and the like 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. For example, at least an ink bag formed of an aluminum laminate film, a resin film, or the like 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 mounted on 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.
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, control means, and the like.
The inkjet recording method of the present invention includes at least an ink flying process, and further includes other processes appropriately selected as necessary, for example, a stimulus generation process, a control process, 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.
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 ink jet 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 preferably 1 to 20 μm.
Further, it is preferable that a sub tank for supplying ink is provided on the inkjet head, and the sub tank is replenished with ink from the ink cartridge through a supply tube.

In the ink jet 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 droplets of ink to be ejected is preferably 1 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 has an apparatus main body (101), a paper feed tray (102) for loading paper mounted on the apparatus main body (101), and an image mounted on the apparatus main body (101). A paper discharge tray (103) for stocking the formed paper and an ink cartridge loading section (104) are provided. On the upper surface of the ink cartridge loading section (104), an operation section (105) such as operation keys and a display is arranged. The ink cartridge loading unit (104) has an openable / closable front cover (115) for attaching and detaching the ink cartridge (201).
As shown in FIGS. 4 and 5, a guide rod (131), which is a guide member horizontally mounted on left and right side plates (not shown), and a stay (132) are provided in the apparatus main body (101). 133) is slidably held in the main scanning direction, and is moved and scanned in the direction of the arrow in FIG. 5 by a main scanning motor (not shown).
The carriage (133) includes a plurality of recording heads (134) including four inkjet 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 an inkjet recording head constituting the recording head (134), a piezoelectric actuator such as a piezoelectric element, a thermal actuator that utilizes a phase change caused by liquid film boiling using an electrothermal transducer such as a heating resistor, and a temperature change A shape memory alloy actuator using a metal phase change, an electrostatic actuator using an electrostatic force, or the like provided as an energy generating means for discharging ink can be used.

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 section (104) via an ink supply tube (not shown). Is done.
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 feed tray (103), 1 sheet (142) is fed from the paper stacking unit (141). A half-moon roller (sheet feeding roller (143)) that separates and feeds one sheet at a time, and a sheet separation roller (144) made of a material having a large coefficient of friction, facing the sheet feeding roller (143), and this separation pad (144) It is biased toward the paper feed roller (143).
A conveying belt (151) for electrostatically adsorbing and conveying the paper (142) as a conveying unit for conveying the paper (142) fed from the paper feeding unit below the recording head (134). A counter roller (152) for conveying the paper (142) sent from the paper supply unit via the guide (145) between the conveying belt (151) and a paper (substantially vertically upward) ( 142) and a leading guide roller 153 urged toward the conveying belt (151) by the holding member (154). (155) and a charging roller (156) which is a charging means for charging the surface of the conveyor belt (151).

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 adsorbing 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), It has the same material as the surface layer and a back layer (medium resistance layer, earth layer) that has been subjected to resistance control by carbon. On the back side of the conveyance belt (151), a guide member (161) is arranged corresponding to the printing area by the recording head (134). 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 transport belt (151), and paper discharge A roller (172) and a paper discharge roller (173) are provided, and a paper discharge tray (103) is arranged below the paper discharge roller (172).
A double-sided paper feeding unit (181) is detachably attached to 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 double-sided paper feed unit (181).

In this ink jet recording apparatus, the sheet (142) is separated and fed one by one from the sheet feeding unit, and the sheet (142) fed substantially vertically upward is guided by the guide (145) and the transport belt (151). ) And the counter roller (152). Further, the leading end is guided by the conveying guide (153) and pressed against the conveying belt (151) by the leading end pressure roller (155), and the conveying direction is changed by about 90 °.
At this time, the conveying roller (157) is charged by the charging roller (156), and the sheet (142) is electrostatically attracted to the conveying belt (151) and conveyed. Therefore, by driving the recording head (134) according to the image signal while moving the carriage (133), ink droplets are ejected onto the stopped sheet (142) to record one line, and the sheet ( 142) is carried a predetermined amount, and then the next line is recorded. Upon receiving a recording end signal or a signal that the rear end of the paper (142) has reached the recording area, the recording operation is finished and the paper (142) is discharged to the paper discharge tray (103).
When the ink remaining amount near end 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 vertically placed and has a front loading configuration. Therefore, even when the upper part of the apparatus main body (101) is closed and installed, for example, even if the apparatus is stored in a rack or an object is placed on the upper surface of the apparatus main body (101), the ink The cartridge (201) can be easily replaced.
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 inkjet 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 to be an ink supply port (not shown) and a common liquid chamber (1b), an engraving and a nozzle to be a fluid resistance portion (2a) and a pressurized liquid chamber (2b). A flow path plate (20) having a communication port (2c) communicating with (3a), a nozzle plate forming a nozzle (3a), a convex portion (6a), a diaphragm portion (6b), and an ink inflow port (6c). ), A laminated piezoelectric element (50) bonded to the diaphragm (60) via an adhesive layer (70), and a base (50) to which the laminated piezoelectric element (50) is fixed. 40).
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 composed of 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. Are stacked alternately. The internal electrode layer is connected to the external electrode at both ends.
The laminated piezoelectric element (50) is divided onto comb teeth by half-cut dicing, and each one is used as a drive part (5f) and a support part (5g) (non-drive part). 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. 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) is an island-shaped convex portion (island) that joins the thin film diaphragm portion (6b) and the laminated piezoelectric element (50) serving as the drive portion (5f) formed at the center portion of the diaphragm portion (6b). Part) (6a), a thick film part including a beam to be joined to the support part, and an opening serving as an ink inflow port (6c) are formed by stacking two Ni plating films by electroforming. 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 drive part (5f) of the laminated piezoelectric element (50), and the coupling of the diaphragm (60) and the frame (10) are bonded layers including a gap material ( 70) is bonded by patterning.
The flow path plate (20) uses a silicon single crystal substrate, is engraved to be a fluid resistance portion (2a), a pressurized liquid chamber (2b), and a through-hole to be a communication port (2c) at a position relative to the nozzle (3a) Was 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 was provided, and this was used as the fluid resistance portion (2a).
The nozzle plate (30) is formed of a metal material, for example, an Ni plating film by an electroforming method, and has a large number of nozzles (3a) which are fine discharge ports for flying ink droplets. . The inner 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 on the ink droplet outlet side. The nozzle pitch of each row was 150 dpi.
The ink ejection surface (nozzle surface side) of the nozzle plate (30) is provided with a water repellent treatment layer 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, etc.), baking after solvent application 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 drive waveform (pulse voltage of 10 to 50 V) is applied to the drive unit (5f) according to the recording signal, thereby causing displacement in the stacking direction in the drive unit (5f). The pressurized liquid chamber (2b) is pressurized through the diaphragm (60) to increase the pressure, and ink droplets are ejected from the nozzle (3a).
Thereafter, the ink pressure in the pressurized liquid chamber (2b) decreases with the end of ink droplet ejection, and negative pressure is generated in the pressurized liquid chamber (2b) due to the inertia of the ink flow and the discharge process of the drive pulse. Then, the process proceeds to the ink filling 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), the fluid resistance portion (2a), and the pressurized liquid chamber ( 2b) is filled.
The fluid resistance portion (2a) is effective in damping the residual pressure vibration after ejection, but becomes resistant to the refilling due to the 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 cycle) until the transition to the next ink droplet ejection operation.

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

<Adjustment Example 1> (Surface-treated carbon black pigment dispersion)
90 g of carbon black with a CTAB specific surface area of 150 m ² / g and DBP oil absorption of 100 ml / 100 g is added to 3000 ml of 2.5N normal sodium sulfate solution, stirred at a temperature of 60 ° C. and a speed of 300 rpm, and reacted for 10 hours for oxidation treatment. Was done. The reaction solution was filtered, and the carbon black separated by filtration was neutralized with a sodium hydroxide solution and subjected to ultrafiltration. The obtained carbon black was washed with water, dried, and dispersed in pure water to 20% by weight.

<Adjustment Example 2> (Surface-treated yellow pigment dispersion)
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 having a pigment concentration of 15%.

<Adjustment Example 3> (Preparation of surface-treated magenta pigment)
According to the procedure of Preparation Example 2, a surface-modified magenta pigment was prepared. I. Instead of Pigment Yellow 128, Pigment Red 122 was used. Similar to the above example, the obtained surface-modified colored pigment is easily dispersed in an aqueous medium upon stirring and desalted and concentrated with an ultrafiltration membrane to obtain a magenta pigment dispersion having a pigment concentration of 15%. .

<Adjustment Example 4> (Adjustment of surface-treated cyan pigment)
According to the procedure of Preparation Example 2, a surface-modified cyan pigment was prepared. I. Instead of CI Pigment Yellow 128, C.I. I. Pigment cyan 15: 3 was used. Similar to the above example, the obtained surface-modified colored pigment was easily dispersed in an aqueous medium upon stirring and desalted and concentrated with an ultrafiltration membrane to obtain a cyan pigment dispersion having a pigment concentration of 15%. .

<Synthesis Example 1> (Preparation of polymer dispersion)
After sufficiently replacing the inside of the 1 L flask equipped with a mechanical stirrer, thermometer, nitrogen gas inlet tube, reflux tube and dropping funnel with nitrogen gas, 11.2 g of styrene, 2.8 g of acrylic acid, 12.0 g of lauryl methacrylate, 4.0 g of polyethylene glycol methacrylate, 4.0 g of styrene macromer (manufactured by Toagosei Co., Ltd., trade name: AS-6) and 0.4 g of mercaptoethanol were charged, and the temperature was raised to 65 ° C.
Next, styrene 100.8 g, acrylic acid 25.2 g, lauryl methacrylate 108.0 g, polyethylene glycol methacrylate 36.0 g, hydroxyethyl methacrylate 60.0 g, styrene macromer (manufactured by Toagosei Co., Ltd., trade name: AS-6) ) A mixed solution of 36.0 g, mercaptoethanol 3.6 g, azobisdimethylvaleronitrile 2.4 g and methyl ethyl ketone 18 g was dropped into the flask over 2.5 hours. After completion of dropping, a mixed solution of 0.8 g of azobisdimethylvaleronitrile and 18 g of methyl ethyl ketone was dropped into the flask over 0.5 hours. After aging at 65 ° C. for 1 hour, 0.8 g of azobisdimethylvaleronitrile was added, and further aging was performed for 1 hour.
After completion of the reaction, 364 g of methyl ethyl ketone was added to the flask to obtain 800 g of a polymer solution having a concentration of 50%.

<Adjustment Example 5> (Preparation of phthalocyanine pigment-containing polymer fine particle dispersion)
After 28 g of the polymer solution prepared in Synthesis Example 1, 26 g of phthalocyanine pigment, 13.6 g of 1 mol / L potassium hydroxide solution, 20 g of methyl ethyl ketone, and 30 g of ion-exchanged water were sufficiently stirred, they were kneaded using a three-roll mill. The obtained paste was put into 200 g of ion-exchanged water and sufficiently stirred, and then methyl ethyl ketone and water were distilled off using an evaporator to obtain a cyan polymer fine particle dispersion.

<Adjustment Example 6> (Adjustment of dimethylquinacridone pigment-containing polymer fine particle dispersion)
A magenta polymer fine particle dispersion was obtained in the same manner as in Synthesis Example 1 except that the phthalocyanine pigment of Synthesis Example 1 was changed to Pigment Red 122.

<Adjustment Example 7> (Adjustment of monoazo yellow pigment-containing polymer fine particle dispersion)
A yellow polymer fine particle dispersion was obtained in the same manner as in Synthesis Example 1 except that the phthalocyanine pigment of Synthesis Example 1 was changed to Pigment Yellow 74.

<Adjustment Example 8> (Adjustment of carbon black pigment-containing polymer fine particle dispersion)
A black polymer fine particle dispersion was obtained in the same manner as in Synthesis Example 1 except that the phthalocyanine pigment in Synthesis Example 1 was changed to carbon black.

（上記構造式中、Ｒは１〜２０のアルキル基、アリル基またはアラルキル基を表わし、
ｍは０〜７の整数を表わし、ｎは２０〜２００の整数を表わす。）

(In the above structural formula, R represents an alkyl group of 1 to 20, an allyl group or an aralkyl group,
m represents an integer of 0 to 7, and n represents an integer of 20 to 200. )

<Adjustment Example 9> (Adjustment of phthalocyanine pigment dispersion)
C. I. Pigment Cyan 15: 3 150 g, R = alkyl group, m = 10, n = 40 pigment dispersant polyethylene ethylene naphthyl ether 110 g represented by the above structural formula, Pionine A-51-B (manufactured by Takemoto Yushi Co., Ltd.) ) 2g and 738g of distilled water were mixed, and this mixture was pre-dispersed and then circulated and dispersed for 20 hours in a disk-type bead mill (Shinmaru Enterprises KDL type, media: 0.3 mmφ zirconia ball used) to obtain a phthalocyanine pigment A dispersion was obtained.

<Adjustment Example 10> (Adjustment of dimethylquinacridone pigment dispersion)
In adjustment example 9, C.I. I. Pigment Cyan 15: 3 as C.I. A dimethylquinacridone pigment dispersion was obtained in the same manner as in Preparation Example 9 except that the pigment was changed to I Pigment Red 122.

<Adjustment Example 11> (Adjustment of monoazo yellow pigment dispersion)
In adjustment example 9, C.I. I. Pigment Cyan 15: 3 as C.I. A monoazo yellow pigment dispersion was obtained in the same manner as in Preparation Example 9 except that the pigment was changed to I Pigment Yellow 74.

  Below, the synthesis example of acrylic-silicone-type resin emulsion is shown among the water-dispersible resin which can be used conveniently by this invention.

<Synthesis Example 2> (Synthesis 1 of silicon-modified acrylic resin fine particles not containing reactive silyl group)
A flask equipped with a mechanical stirrer, thermometer, nitrogen gas inlet tube, reflux tube and dropping funnel was sufficiently replaced with nitrogen gas, and then 10 g of Aqualon RN-20 (Daiichi Kogyo Seiyaku), 1 g of potassium persulfate and pure 286 g of water was charged and the temperature was raised to 65 ° C.
Next, 150 g of methyl methacrylate, 100 g of 2-ethylhexyl acrylate, 20 g of acrylic acid, 20 g of vinyltriethoxysilane, 10 g of Aqualon RN-20, 10 g of potassium persulfate 10 g of Aqualon RN-20, 4 g of potassium persulfate and pure water 398.3 g of the mixed solution was dropped into the flask over 2.5 hours. The mixture was further heated and aged at 80 ° C. for 3 hours and then cooled, and the pH was adjusted to 7 to 8 with potassium hydroxide.
The particle diameter of the resin measured using Microtrac UPA was 130 nm.
The minimum film forming temperature (MTF) was 0 ° C.

<Synthesis Example 3> (Synthesis 2 of silicon-modified acrylic resin fine particles containing no reactive silyl group)
A flask equipped with a mechanical stirrer, thermometer, nitrogen gas inlet tube, reflux tube and dropping funnel was sufficiently replaced with nitrogen gas, and then 10 g of Aqualon RN-20 (Daiichi Kogyo Seiyaku), 1 g of potassium persulfate and pure 286 g of water was charged and the temperature was raised to 65 ° C.
Next, 150 g of methyl methacrylate, 100 g of 2-ethylhexyl acrylate, 20 g of acrylic acid, 40 g of hexyltrimethoxysilane, 10 g of Aqualon RN-20, 10 g of potassium persulfate 10 g of Aqualon RN-20, 4 g of potassium persulfate and pure water 398.3 g of the mixed solution was dropped into the flask over 3 hours. The mixture was further heated and aged at 80 ° C. for 3 hours and then cooled, and the pH was adjusted to 7 to 8 with potassium hydroxide.
The particle diameter of the resin measured using Microtrac UPA was 148 nm.
The minimum film forming temperature (MTF) was 0 ° C.

<Synthesis Example 4> (Synthesis of reactive silyl group-containing silicon-modified acrylic resin fine particles)
The examples described in JP-A-6-157861 were re-examined to synthesize silicon-modified acrylic resin fine particles containing reactive silyl groups.
After fully replacing the inside of the flask equipped with a mechanical stirrer, thermometer, nitrogen gas inlet tube, reflux tube and dropping funnel with nitrogen gas, 100 g of pure water, 3 g of sodium dodecylbenzenesulfonate and 1 g of polyethylene glycol nonylphenyl ether were added. First, 1 g of ammonium persulfate and 0.2 g of sodium hydrogen sulfite were added, and the temperature was raised to 60 ° C.
Next, 30 g of butyl acrylate, 40 g of methyl methacrylate, 19 g of butyl methacrylate, 10 g of vinylsilanetriol potassium salt and 1 g of 3-methacryloxypropylmethyldimethoxysilane were dropped into the flask over 3 hours. At this time, polymerization was carried out by adjusting the polymerization reaction solution to pH 7 with an aqueous ammonia solution. The particle diameter of the resin measured using Microtrac UPA was 160 nm.

Examples and Comparative Examples of the present invention are shown below, but the present invention is not limited to these. In addition, the amount of each component described in the examples is based on weight.
An ink composition having the following formulation was prepared and adjusted with a 10% 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 obtained the ink composition.
Hereinafter, the present invention will be described in more detail with reference to ink production examples, but the present invention is not limited to the following ink production examples. In addition, the amount (%) of each component described below is based on weight.

(Ink Production Example 1) Black ink 1
Carbon black produced in Preparation Example 1 5 wt% (as solid content)
Dipeptide (alanylglutamine) 5wt%
Acrylic-silicone resin emulsion of Synthesis Example 2 4 wt% (as solid content)
Diethylene glycol 10wt%
Glycerin 20wt%
2-pyrrolidone 2wt%
R1, R2, R3 of formula (I): C2F5, M: Na 2t%
R1, R2, R3, R4 of the general formula (II): CF3, p, r: 4, q: 1, m, n: 10
1wt%
2,2,4-Trimethyl-1,3-pentanediol 2wt%
Ion exchange water was added to make 100%.

(Ink Production Example 2) Yellow ink 1
Yellow pigment dispersion prepared in Preparation Example 2 4.5 wt% (as solid content)
Dipeptide (alanylglutamine) 10wt%
Acrylic-silicone resin emulsion of Synthesis Example 1 10 wt% (as solid content)
1,3-butanediol 10wt%
Glycerin 20wt%
2-pyrrolidone 2wt%
R1, R2, R3 of general formula (I): C2F5, M: Na 2 wt%
2,2,4-Trimethyl-1,3-pentanediol 2wt%
Ion exchange water was added to make 100%.

(Ink Production Example 3) Magenta ink 1
Magenta pigment dispersion prepared in Preparation Example 6 6% by weight (as solid content)
Dipeptide (bisalanylcystine) 10wt%
Acrylic-silicone resin emulsion of Synthesis Example 3 12 wt% (as solid content)
Triethylene glycol isobutyl ether 4wt%
Glycerin 25wt%
R1, R2, R3 of general formula (I): C2F5, M: Na 1 wt%
Zonyl FS-300 (DuPont) 1wt%
2-ethyl-1,3-hexanediol 2wt%
Ion exchange water was added to make 100%.

(Ink Production Example 4) Cyan ink 1
Cyan pigment dispersion prepared in Preparation Example 4 4 wt% (as solid content)
Dipeptide (alanylglutamine) 15wt%
Acrylic-silicone resin emulsion of Synthesis Example 4 15 wt% (as solid content)
3-methyl-1,3-butanediol 10wt%
Glycerin 20wt%
R1, R2, R3 of general formula (I): C2F5, M: Na 2 wt%
2-ethyl-1,3-hexanediol 2wt%
Ion exchange water was added to make 100%.

(Ink Production Example 5) Cyan ink 2
Cyan pigment dispersion prepared in Preparation Example 3.5 wt% (as solid content)
Dipeptide (alanylglutamine) 12wt%
W-5025 (Mitsui Takeda Chemicals Urethane Resin Emulsion)
10wt% (as solid content)
1,6-hexanediol 10wt%
Glycerin 20wt%
R1, R2, R3 of formula (I): C2F5, M: Na 4 wt%
FS-300 (DuPont) 0.3wt%
2-ethyl-1,3-hexanediol 2wt%
Ion exchange water was added to make 100%.

(Ink Production Example 6) Magenta ink 2
Magenta pigment dispersion prepared in Preparation Example 4.5 wt% (as solid content)
Dipeptide (alanylglutamine) 10wt%
W-5661 (Mitsui Takeda Chemicals Urethane Resin Emulsion)
10wt% (as solid content)
Dipropylene glycol 15wt%
Glycerin 25wt%
R1, R2, R3 of general formula (I): C2F5, M: Na 2 wt%
2-ethyl-1,3-hexanediol 2wt%
Ion exchange water was added to make 100%.

(Ink Production Example 7) Yellow ink 2
Yellow pigment dispersion prepared in Preparation Example 3.5 wt% (as solid content)
Dipeptide (alanylglutamine) 10wt%
Acrylic-silicone resin emulsion of Synthesis Example 3 15 wt% (as solid content)
2-methyl-2,4-pentanediol 10wt%
Glycerin 25wt%
R1, R2, R3 of general formula (I): C2F5, M: Na 2 wt%
2,2,4-Trimethyl-1,3-pentanediol 3wt%
Ion exchange water was added to make 100%.

(Ink Production Example 8) Black ink 2
Black pigment dispersion prepared in Preparation Example 6.5 wt% (as solid content)
Dipeptide (alanylglutamine) 15wt%
Acrylic-silicone resin emulsion of Synthesis Example 2 12 wt% (as solid content)
1,6-hexanediol 15wt%
Glycerin 20wt%
R1, R2, R3 of general formula (I): C2F5, M: Na 2 wt%
2-ethyl-1,3-hexanediol 2wt%
Ion exchange water was added to make 100%.

(Ink Production Example 9) Cyan ink 3
Cyan pigment dispersion prepared in Preparation Example 4 4 wt% (as solid content)
Dipeptide (bisglycylglutamine) 8wt%
W-5025 (Mitsui Takeda Chemicals Urethane Resin Emulsion)
10wt% (as solid content)
1,3-butanediol 10wt%
Glycerin 20wt%
R1, R2, R3 of general formula (I): C2F5, M: Na 2 wt%
2-ethyl-1,3-hexanediol 2wt%
Ion exchange water was added to make 100%.

(Ink Production Example 10) Magenta ink 3
Magenta pigment dispersion prepared in Preparation Example 6 6% by weight (as solid content)
Dipeptide (alanylglutamine) 15wt%
W-5661 (Mitsui Takeda Chemicals Urethane Resin Emulsion)
10wt% (as solid content)
1,5-pentanediol 15wt%
Glycerin 25wt%
R1, R2, R3 of general formula (I): C2F5, M: Na 1 wt%
2-ethyl-1,3-hexanediol 2wt%
Ion exchange water was added to make 100%.

(Ink Production Example 11) Yellow ink 3
Yellow pigment dispersion prepared in Preparation Example 5 5 wt% (as solid content)
Dipeptide (Glycylglutamine) 8wt%
Acrylic-silicone resin emulsion of Synthesis Example 3 15 wt% (as solid content)
2-methyl-2,4-pentanediol 8wt%
Glycerin 20wt%
R1, R2, R3 of general formula (I): C2F5, M: Na 2 wt%
2,2,4-Trimethyl-1,3-pentanediol 3wt%
Ion exchange water was added to make 100%.

(Comparative Production Examples 1 to 4)-Adjustment of Comparative Pigment Ink-
Comparative Production Example 1 Comparative Pigment Cyan Ink Cyan ink was obtained in the same manner as in Ink Production Example 5 except that dipeptide (alanylglutamine) was not added.
Comparative Production Example 2 Comparative Pigment Magenta Ink Magenta ink was obtained in the same manner as Ink Production Example 6, except that no dipeptide (alanylglutamine) was added.
Comparative production example 3 Comparative pigment yellow ink A yellow ink was obtained in the same manner as in ink production example 7 except that dipeptide (alanylglutamine) was not added.
Comparative production example 4 Comparative pigment black ink A black ink was obtained in the same manner as in ink production example 8 except that dipeptide (alanylglutamine) was not added.

(Comparative Production Examples 5 to 8) -Preparation of dye ink-
The components shown below were mixed, sufficiently stirred and dissolved, and then filtered under pressure using a fluoropore filter (trade name: manufactured by Sumitomo Electric Co., Ltd.) having a pore size of 0.45 μm to prepare a dye ink set. .
Dye ink composition:
Dye Species Comparative Production Example 5 Yellow C.I. I. Direct yellow 86
Comparative Production Example 6 Cyan C.I. I. Direct Blue 199
Comparative Production Example 7 Magenta C.I. I. Acid Red 285
Comparative Production Example 8 Black C.I. I. Direct black 154
Ink prescription above each dye 4wt%
Glycerin 7wt%
Thiodiglycol 7wt%
Urea 7wt%
F470 (Dainippon Ink Co., Ltd.) 1wt%
Ion exchange water was added to make 100%.

Hereinafter, Table 1 shows an ink production example and a comparative production example, and the ink composition will be described.
In addition, the surface tension, viscosity, and weight solid content (% by weight) of the dipeptide in the ink are described in the table.

[Examples 1-5, Comparative Examples 1-2]
Next, Table 2 shows an evaluation ink set. (Examples and comparative examples)

Using the ink composition and ink set described in Tables 1 and 2 on My Paper (made by Ricoh), which is PPC paper, using a drop-on-demand printer prototype having 300 dpi and 384 nozzle resolution, image resolution Printing was performed at 600 dpi.
The maximum droplet size was 18 pl, and the total amount of secondary colors was regulated to 140%, and the amount of adhesion was regulated. During solid printing, solid images and characters were printed so that the total amount of ink in 300 dots square did not exceed 15 g / m ² . The image quality and image reliability of the obtained image were evaluated.
The results are shown in Table 3.
Those marked with x in the evaluation result are inappropriate as an inkjet image.
The evaluation items and evaluation methods of the inventive examples and comparative examples shown in Table 2 below are shown below.

(Evaluation items and measurement methods)
(1) Image quality Back-through density The image density of the back surface of the green solid image portion of the example and the comparative example was measured, and the value obtained by subtracting the density of the background portion was taken as the back-through density.
Considering this concentration and visual judgment, the evaluation was made according to the following criteria.
〔Evaluation criteria〕
A: Print-through density is 0.1 or less, and uniform printing is achieved without occurrence of minute print-through.
A: The print-through density is 0.15 or less, and the print is uniform without occurrence of minute print-through.
(Triangle | delta): Although the back-through density is 0.15 or less, generation | occurrence | production of minute back-through is recognized.
X: Generation | occurrence | production of a serious through-through is recognized.
2. Beading The degree of beading in the green solid image portions of the examples and comparative examples was visually observed, and the rank was evaluated according to the following criteria.
〔Evaluation criteria〕
5: Uniform printing without occurrence of beading.
4: The occurrence of beading is slightly observed, but it is at a level that does not matter at all.
3: The occurrence of beading is recognized, but the image quality is not impaired.
2: The occurrence of beading is clearly observed.
1: Significant beading is observed.
3. Evaluation of curling and cockling The inks of Examples and Comparative Examples were continuously printed on 200 sheets, and poor conveyance was observed.
〔Evaluation criteria〕
◎: There is no rubbing on the transfer route by cockling, and no jam occurs. ○: Some rubbing occurs on the transfer route by cock ring, but no jam occurs.
Δ: After printing and paper discharge, curling occurs, and when paper is partially stacked, paper fall is observed, but no jamming occurs .: Jam generation is 2 or more. (2) Image reliability <Evaluation of scratch resistance>
As an evaluation image, a black, cyan, magenta, yellow, red, green, and blue square (3 cm × 3 cm) was used. After printing for 24 hours, use a clock meter (CM-1 type), and attach white cotton cloth (JISL 0803 cotton 3) to the friction piece with double-sided adhesive foam tape (# 4016 t = 1.6, manufactured by 3M). The density of the color material that rubbed back and forth and adhered to the cotton cloth was measured using a spectrocolorimetric densitometer (Model-938 manufactured by X-Rite Co., Ltd.).
〔Evaluation criteria〕
◎: Color material concentration attached to cotton cloth is less than 0.05 ○: Color material concentration attached to cotton cloth is 0.05 or more and less than 0.1 ×: Color material concentration attached to cotton cloth is 0.1 or more Is shown in Table 3.

(3) Clogging prevention reliability (discharge stability)
<Evaluation 1> Reliability evaluation for prevention of clogging in intermittent printing Using the printer shown in FIG. 3 described in the detailed description in the present invention, printing is performed on My Paper (manufactured by Ricoh). In the chart in which the printing area in the image area is 5% of the total printing area of each color, each of the yellow, magenta, cyan, and black inks of the present invention was printed at 100% duty.
The printing conditions were a recording density of 360 dpi and one-pass printing.
In addition, Evaluation 2 was performed after Evaluation 1 was performed using the ink sets in the above Examples and Comparative Examples.
As intermittent printing, the above chart is printed continuously for 20 sheets, then it is put into a resting state where no discharge is performed for 20 minutes, this is repeated 50 times, 1000 sheets are printed in total, and then the same chart is printed. The presence or absence of streaks, white spots, and jet disturbance in the 5% chart solid portion was visually evaluated.
<Evaluation criteria>
◯: There are no streaks, white spots, and jet turbulence in the solid portion. Δ: Some streaks, white spots, and jet turbulence are observed in the solid portion. Shows the results for the example of evaluation 1.

<Evaluation 2> Clogging Prevention Reliability after Continuous Printing and Leaving Left Tables 5, 6 and 7 show the evaluation results of clogging prevention reliability.
In the present invention, the evaluation is performed in each environment, that is, in environment 1 (temperature 23 ° C., humidity 50%), environment 2 (temperature 10 ° C., humidity 15%), environment 3 (temperature 27 ° C., humidity 80%). Using the printer shown in FIG. 3 described above, printing is performed on My Paper (manufactured by Ricoh). As the printing pattern, the Japan Electronic Industry Promotion Association Standard Test Pattern J6 chart has a recording density of 360 dpi and one-pass printing. Then, after 500 continuous printings, the same printing as before leaving was carried out after leaving for 20 hours, and the presence or absence of streaks in the solid image portion, white spots, and jetting disturbance was visually evaluated.
<Evaluation criteria>
◯: No streaks, white spots, or jet turbulence in the solid part △: Some streaks, white spots, or jet turbulence are observed in the solid part.

1b Common liquid chamber 2a Fluid resistance part 2b Pressurized liquid chamber 2c Communication port 2d Partition 3a Nozzle 5f Drive part 5g Support part (non-drive part)
6a Convex portion 6b Diaphragm portion 6c Ink inlet 10 Frame 20 Flow path plate 30 Nozzle plate 40 Base 50 Multilayer piezoelectric element 60 Vibration plate 70 Adhesive layer 101 Main body 102 Paper feed tray 103 Paper discharge tray 104 Ink cartridge loading portion 105 Operation portion 111 Upper cover 112 Front surface 115 Front cover 131 Guide rod 132 Stay 133 Carriage 134 Recording head 135 Sub tank 141 Paper stacking unit 142 Paper 143 Paper feed roller 144 Separation pad 145 Guide 151 Transport belt 152 Counter roller 153 Transport guide 154 Holding member 155 Addition Pressure roller 156 Charging roller 157 Transport roller 158 Tension roller 161 Guide member 171 Separation claw 172 Paper discharge roller 173 Paper discharge roller 181 Double-sided paper feed unit 182 Manual feed Paper 200 ink cartridge 201 ink cartridge 241 ink bag 242 ink inlet 243 ink discharge port 244 cartridge exterior

JP 2005-212327 A Japanese Patent Application Laid-Open No. 11-078225 JP 2003-025717 A Japanese Patent Laid-Open No. 2005-015795 JP 2006-117634 A JP 2006-122900 A

Claims (11)

An ink for ink jet recording suitable for ink jet recording, which contains water, a water-soluble organic solvent, a colorant, and a dipeptide and an anionic fluorosurfactant containing a perfluoro lower hydrocarbon group Is what
An ink for ink jet recording, wherein the fluorosurfactant is of the following general formula (I):

(R ₁ , R ₂ , R ₃ represent either a fluorine-containing group or a fluorine atom, and M represents Li, Na, K)   The ink for inkjet recording according to claim 1, wherein the dipeptide is at least one selected from alanylglutamine, glycylglutamine, bisalanylcystine, and bisglycylcystine. The water-soluble organic solvent is glycerin, trimethylolpropane, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 2-methyl-1,3-propanediol, 1,3-butanediol. 2,3-butanediol, 1,4-butanediol, 2-methyl-1,3-butanediol, 3-methyl-1,3-butanediol, 1,5-pentanediol, 1,6-hexanediol , 2-methyl-2,4-hexanediol, 2-pyrrolidone, N-methyl-2-pyrrolidone, N-hydroxyethyl-2-pyrrolidone, tetramethylurea, urea. inkjet according to claim 1 or 2, characterized in that Recording ink. The ink for inkjet recording according to any one of claims 1 to 3 , wherein the dipeptide is contained in a solid content of 2 to 20% by weight. An ink set for ink jet recording comprising the black ink and the color ink, wherein the black ink and the color ink are the ink for ink jet recording according to any one of claims 1 to 4 . An ink cartridge comprising the ink according to any one of claims 1 to 4 or the ink set according to claim 5 contained in a container. The ink jet recording method, which comprises recording by the ink jet using the recording ink or ink set according to claim 5, 15g / m ² or less of the ink deposition amount according to any one of claims 1 to 4. The ink jet recording method according to claim 7 , further comprising an ink flying step of applying a stimulus to the ink and causing the ink to fly to form an image on the recording medium. The inkjet recording method according to claim 8 , wherein the stimulus is at least one selected from heat, pressure, vibration, and light. An ink jet recording ink according to any one of claims 1 to 4 or the ink set according to claim 5 , and an ink cartridge that accommodates the ink for ink jet recording or the ink set, and the ink jet recording ink cartridge. An ink jet recording apparatus comprising ink flying means for flying ink toward the recording medium and printing with an ink adhesion amount of 15 g / m ² or less. An apparatus for recording an image on a sheet by ejecting the ink for ink jet recording according to any one of claims 1 to 4 or the ink of the ink set according to claim 5 as droplets from a recording head. An ink jet recording apparatus comprising a unit capable of duplex printing.

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