JP4921753B2 - INK FOR RECORDING, INK CARTRIDGE, INK RECORDED MATERIAL, INKJET RECORDING DEVICE AND INKJET RECORDING METHOD - Google Patents

Description

  The present invention relates to a recording ink, and an ink cartridge, an ink record, an ink jet recording apparatus, and an ink jet recording method using the recording ink.

Conventionally, dyes have been used as colorants for ink jet recording inks, but the dye inks are inferior in water resistance and wrinkle resistance and have a drawback of being easily smeared on plain paper. In order to improve these drawbacks, a pigment ink using a pigment as a colorant has been proposed. Although this pigment ink is excellent in water resistance and weather resistance and can record an image with little bleeding, there is a problem that it is inferior in fixability. Therefore, attempts have been made to improve the fixing property by adding various resins. For example, a method of recording an image with little bleeding by adding a thermoplastic resin emulsion to pigment ink has been proposed (see Patent Document 1). However, in this proposal, since the drying is performed, there is a disadvantage that the apparatus becomes complicated and consumes electric power.
Also, an ink composition using acrylic silicone resin fine particles containing an alkoxysilyl group (see Patent Document 2), a coating agent comprising a reactive resin emulsion having a hydrolyzable silyl group and an amineimide group (see Patent Document 3), Etc. have been proposed. However, these proposals do not take into consideration improvements in fixability and storage stability, and are not suitable for actual use.
Patent Document 4 discloses a vinyl monomer having a specific reactive silyl group present in the form of a salt, a vinyl monomer having a reactive silyl group other than this, and a copolymerizable with these. There has been proposed a method of producing a polymer emulsion by emulsion polymerization of another vinyl monomer while allowing a hydrolyzable silyl group to exist stably. However, this proposal has a drawback that the resin fine particles in which the hydrolyzable silyl group remains reacts in the ink, thereby reducing the long-term storage stability of the ink.

  Patent Document 5 proposes an emulsion resin obtained by radical polymerization of an ethylenically unsaturated monomer in the presence of a radical reactive emulsifier, and a recording liquid in which a pigment is dispersed in an aqueous medium. However, in this proposal, there is no disclosure or suggestion about the presence or absence of alkoxysilyl groups remaining in the emulsion resin, and in this proposal, a standing test is performed on the emulsion resin, glycerin, and water dispersion, Since the composition containing an emulsion resin, glycerin, and water has a high surface tension, the permeability to a recording medium is poor. Furthermore, since the ink containing the resin component tends to stay on the recording medium after printing, the permeability tends to be poor. When high-speed printing or high-speed double-sided printing is performed using ink with poor penetrability, there is a problem that a roller for transporting the recording medium rubs the printed portion immediately after printing and stains occur.

  Patent Document 6 proposes a method in which a polymerizable monomer is subjected to emulsion polymerization, and an organosiloxane compound is absorbed in the obtained polymer particles to perform condensation. In this proposal, the fine particles themselves form a film having excellent resistance, but in the case of ink containing a pigment, it is necessary to add a large amount of resin fine particles in order to fix the pigment and impart excellent scratch resistance and marker resistance. Become. However, such an ink containing a large amount of resin has a problem that the ink is dried in the vicinity of the nozzle that ejects the ink during printing, and the liquid droplet is liable to be bent or non-ejection.

  Therefore, it has excellent ejection stability and storage stability, quickly penetrates into the recording medium, forms a coating, does not cause stains in high-speed printing and double-sided printing, has excellent marker resistance, and has low bleeding. Recording ink that can be recorded has not been provided yet, and the rapid development thereof is desired.

JP-A-9-176533 Japanese Patent No. 3011087 Japanese Patent Laid-Open No. 5-25354 JP-A-6-157861 JP 2002-294105 A JP-A-7-278480

  This invention is made | formed in view of this present condition, and makes it a subject to solve the said various problems in the past and to achieve the following objectives. That is, the present invention is excellent in ejection stability and storage stability, quickly penetrates into a recording medium to form a coating, does not cause stains in high-speed printing or double-sided printing, has excellent marker resistance, and has no bleeding. It is an object of the present invention to provide a recording ink capable of recording a small number of high-quality images, and an ink cartridge, an ink recorded matter, an ink jet recording apparatus, and an ink jet recording method using the recording ink.

As a result of intensive investigations by the present inventors in order to solve the above-mentioned problems, it is possible to improve the scratch resistance and marker resistance in a recording ink containing at least water, a colorant, resin fine particles, and a penetrant. Found that a silicone-modified acrylic resin containing no hydrolyzable silyl group is optimal as resin fine particles capable of forming a tough film and fixing a colorant after landing on a recording medium.
That is, since the siloxane bond in the silicone resin has high binding energy, the coating film containing the siloxane bond is excellent in scratch resistance and solvent resistance. Although it is possible to add the silicone resin to the ink, in order to allow the silicone resin to be more stably present in the film, it is preferable to introduce a siloxane bond by modifying the silicone resin having excellent film forming ability. As such a resin, a silicone-modified acrylic resin that does not contain a hydrolyzable silyl group in which a siloxane bond is introduced into an acrylic resin that does not require a curing agent and has excellent coating film forming performance is particularly suitable in terms of high storage stability. I found out.
Further, in order to quickly dry the ink after printing on the recording medium to form a film, it is preferable that the solvent in the ink composition quickly permeates the recording medium. However, the ink containing the resin component tends to stay on the recording medium after printing. Ink that tends to stay on the recording medium can record images with high density and low bleeding, but if it penetrates slowly, it penetrates through the conveyance part of the recording medium during double-sided printing in devices that do not have high-speed printing or drying means. There is a problem in that no ink component rubs and stains occur. Therefore, in the recording ink of the present invention, by using a diol compound having 7 to 11 carbon atoms as a penetrating agent, the penetrating property to the recording medium is good even when a resin component is contained, and a high image density is maintained. The present inventors have found that it is possible to realize ink that does not cause image bleeding.

The present invention is based on the above findings by the present inventors, and means for solving the above problems are as follows. That is,
<1> At least water, a colorant, resin fine particles, a water-soluble organic solvent, and a penetrant, the penetrant is a diol compound having 7 to 11 carbon atoms, and the resin fine particles are hydrolyzable silyl groups. A recording ink comprising a silicone-modified acrylic resin that does not contain any of the above.
<2> The recording ink according to <1>, wherein the resin fine particles have a volume average particle diameter of 10 to 300 nm.
<3> The recording ink according to any one of <1> to <2>, wherein the amount of silicon (Si) derived from the silicone-modified acrylic resin in the recording ink is 50 to 400 ppm.
<4> The recording ink according to any one of <1> to <3>, wherein a minimum film-forming temperature (MFT) of the resin fine particles is 20 ° C. or less.
<5> The water-soluble organic solvent is glycerin, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,3-butanediol, 2,3-butanediol, 1,4-butane. Diol, 1,5-pentanediol, tetraethylene glycol, 1,6-hexanediol, 2-methyl-2,4-pentanediol, polyethylene glycol, 1,2,4-butanetriol, 1,2,6-hexane The recording according to any one of <1> to <5>, wherein the recording is at least one selected from triol, thiodiglycol, 2-pyrrolidone, N-methyl-2-pyrrolidone, and N-hydroxyethyl-2-pyrrolidone. Ink.
<6> The recording ink according to any one of <1> to <5>, wherein the colorant is at least one of a pigment, a dye, and colored fine particles.
<7> The recording material according to <6>, wherein the pigment has at least one hydrophilic group on a surface thereof and exhibits at least one of water dispersibility and water solubility in the absence of a dispersant. Ink.
<8> For recording according to any one of <1> to <7>, wherein 0.05 to 1.2 parts by mass of silicone-modified acrylic resin fine particles not containing a hydrolyzable silyl group are added to 1 part by mass of the pigment. Ink.
<9> Contains a nonionic surfactant, and the nonionic surfactant is an acetylene glycol surfactant, polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, polyoxyethylene alkyl ester, and polyoxyethylene sorbitan The recording ink according to any one of <1> to <8>, which is at least one selected from fatty acid esters.
<10> From the above <1> to <1> that contains a fluorosurfactant, and the fluorosurfactant is at least one selected from the following structural formulas (1), (2), and (3) The recording ink according to any one of 9>.
However, in said structural formula (1), m represents the integer of 0-10. n represents an integer of 1 to 40.
However, in the structural formula (2), Rf represents CF ₃ or CF ₂ CF ₃ . m represents an integer of 6 to 25, n represents an integer of 1 to 4, and p represents 1 to 4.
However, in the structural formula (3), Rf represents CF ₃ or CF ₂ CF ₃ . q represents the integer of 1-6.
<11> Any of the above <1> to <9>, which contains an anionic surfactant, and the anionic surfactant is at least one selected from polyoxyethylene alkyl ether acetates and dialkylsulfosuccinates The recording ink according to claim 1.
<12> The recording ink according to any one of <1> to <11>, further including an aminopropanediol compound.
<13> The recording ink according to any one of <1> to <12>, wherein the recording ink has a viscosity at 25 ° C. of 7 to 20 mPa · s.
<14> The recording ink according to any one of <1> to <13>, wherein the solid content in the recording ink is 6 to 20% by mass.
<15> The recording ink according to any one of <1> to <14>, which is at least one selected from cyan ink, magenta ink, yellow ink, and black ink.
<16> An ink cartridge comprising the recording ink according to any one of <1> to <15> contained in a container.
<17> An ink jet having at least ink flying means for recording an image by applying a stimulus to the recording ink according to any one of <1> to <15> and causing the recording ink to fly. It is a recording device.
<18> The inkjet recording apparatus according to <17>, wherein the stimulus is at least one selected from heat (temperature), pressure, vibration, and light.
<19> The inkjet recording apparatus according to any one of <17> to <18>, further including a reversing unit that reverses the recording surface of the recording medium and enables duplex printing.
<20> The inkjet recording apparatus according to any one of <17> to <19>, further including an endless transport belt and a transport unit configured to transport the surface of the transport belt while charging and holding the recording medium.
<21> The head according to any one of <17> to <20>, further including a head and a subtank for supplying ink on the head, wherein the subtank is supplemented with ink from an ink cartridge through a supply tube. It is an inkjet recording device of description.
<22> Inkjet comprising at least an ink flying step of recording an image by applying a stimulus to the recording ink according to any one of <1> to <15> and causing the recording ink to fly. It is a recording method.
<23> The inkjet recording method according to <22>, wherein the stimulus is at least one selected from heat (temperature), pressure, vibration, and light.
<24> An ink record comprising an image formed using the recording ink according to any one of <1> to <15> on a recording medium.

  The recording ink of the present invention contains at least water, a colorant, resin fine particles, a water-soluble organic solvent, and a penetrant, the penetrant is a diol compound having 7 to 11 carbon atoms, and the resin fine particles are Made of silicone-modified acrylic resin that does not contain hydrolyzable silyl groups, it excels in ejection stability and storage stability, quickly penetrates the recording medium and forms a film, and causes stains in high-speed printing and double-sided printing. Therefore, high-quality image recording with excellent marker resistance and less bleeding is possible.

  The ink cartridge of the present invention comprises the recording ink of the present invention contained in a container. The ink cartridge is suitably used for a printer using an ink jet recording method. When recording is performed using the ink contained in the ink cartridge, it is excellent in ejection stability and storage stability, and quickly penetrates into the recording medium to form a film, which may cause stains in high-speed printing and double-sided printing. In addition, it has excellent marker resistance and high-quality image recording with little bleeding.

  The ink jet recording apparatus of the present invention comprises at least ink flying means for recording an image by applying energy to the recording ink of the present invention and causing the recording ink to fly. In the ink jet recording apparatus, the ink flying means applies energy to the recording ink of the present invention and causes the recording ink to fly to record an image. As a result, it has excellent ejection stability and storage stability, quickly penetrates into the recording medium, forms a coating, does not cause stains in high-speed printing and double-sided printing, has excellent marker resistance, and has high bleeding. Image recording is possible.

  The ink jet recording method of the present invention includes at least an ink flying step of recording an image by applying energy to the recording ink of the present invention and causing the recording ink to fly. In the ink jet recording method, in the ink flying process, energy is applied to the recording ink of the present invention, and the recording ink is ejected to record an image. As a result, it has excellent ejection stability and storage stability, quickly penetrates into the recording medium, forms a coating, does not cause stains in high-speed printing and double-sided printing, has excellent marker resistance, and has high bleeding. Image recording is possible.

  The ink recorded matter of the present invention has an image formed on the recording medium using the recording ink of the present invention. The ink recorded matter has excellent ejection stability and storage stability, quickly penetrates the recording medium to form a coating, does not cause stains in high-speed printing or double-sided printing, has excellent marker resistance, and bleeding A high-quality image with a small amount is held on the recording medium.

  According to the present invention, the conventional problems can be solved, the ejection stability and the storage stability are excellent, the film is quickly penetrated into the recording medium to form a film, and no stain is generated in high-speed printing or double-sided printing. It is possible to provide a recording ink excellent in marker properties and capable of high-quality image recording with less bleeding, an ink cartridge, an ink recorded matter, an ink jet recording apparatus, and an ink jet recording method using the recording ink.

(Ink for recording)
The recording ink of the present invention contains at least water, a colorant, resin fine particles, a water-soluble organic solvent, and a penetrant, the penetrant is a diol compound having 7 to 11 carbon atoms, and the resin fine particles are It consists of a silicone-modified acrylic resin that does not contain a hydrolyzable silyl group, and contains a surfactant, an aminopropanediol compound, and other components as required.

As the resin fine particles, a silicone-modified acrylic resin containing no hydrolyzable silyl group obtained by polymerizing an acrylic monomer and a silane compound in the presence of an emulsifier is used.
Examples of the polymerization include radical polymerization, emulsion polymerization, dispersion polymerization, seed polymerization, and suspension polymerization.

  The acrylic monomer is not particularly limited and may be appropriately selected depending on the intended purpose. For example, methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, acryloyl Acrylic acid ester monomers such as morpholine and N, N′-dimethylaminoethyl acrylate; methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, 2-hydroxyethyl methacrylate, N, N′-dimethylamino Methacrylic acid ester monomers such as ethyl methacrylate; Amide acrylates such as N-methylolacrylamide and methoxymethylacrylamide; Carbohydrates such as maleic acid, fumaric acid, itaconic acid, acrylic acid and methacrylic acid Acid-containing monomers.

The emulsifier is not particularly limited and may be appropriately selected depending on the intended purpose. For example, alkylbenzenesulfonic acid or a salt thereof, dialkylsulfosuccinic acid ester or a salt thereof, alkylnaphthalenesulfonic acid or a salt thereof, alkylnaphthalenesulfonic acid Formalin condensate of salt, higher fatty acid salt, sulfonate of higher fatty acid ester, polyoxypropylene-polyoxyethylene condensate of ethylenediamine, sorbitan fatty acid ester or salt thereof, aromatic or aliphatic phosphate ester or salt thereof, dodecyl Benzene sulfonate, dodecyl sulfate, lauryl sulfate, dialkyl sulfosuccinate, polyoxyethylene alkyl phenyl ether sulfate, polyoxyethyne alkyl propenyl phenyl ether sulfate, alkyl phenyl 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 diethanolamide, formalin condensate of naphthalenesulfonic acid, and the like. Examples of these salts include sodium and ammonium.
In addition, a reactive emulsifier having an unsaturated double bond can be used as the emulsifier. Examples of the reactive emulsifier include Adeka Soap SE, NE, PP (Asahi Denka Kogyo Co., Ltd.). Company-made), Latemuru S-180 (manufactured by Kao Corporation), Eleminol JS-2, Eleminol RS-30 (Sanyo Chemical Industries), Aqualon RN-20 (Daiichi Kogyo Seiyaku Co., Ltd.), and the like.

The silane compound is not particularly limited and may be appropriately selected depending on the purpose. For example, tetramethoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane, tetraethoxysilane, Examples include methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, diphenyldiethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, decyltrimethoxysilane, decyltrimethoxysilane, and trifluoropropyltrimethoxysilane. .
Moreover, the monomer generally known as a silane coupling agent can also be used, and examples thereof include vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, and p-styryltrimethoxysilane. 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2 (Aminoethyl) 3-aminopropylmethyldimethoxysilane, N-2 (aminoethyl) 3-aminopropyltrimethoxysilane, N-2 (aminoethyl) 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N- (vinylbenzyl) -2-amino Ethyl-3-aminopropyltrimethoxysilane hydrochloride, 3-ureidopropyltriethoxysilane, 3-chloropropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, bis (triethoxysilyl) Propyl) tetrasulfide, 3-isocyanatopropyltriethoxysilane, and the like.

The hydrolyzable silyl group in the silicone-modified acrylic resin containing no hydrolyzable silyl group means 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. Examples of the hydrolyzable silyl group include a halogenosilyl group, an acyloxysilyl group, an amidosilyl group, an aminoxysilyl group, an alkenyloxysilyl group, an aminosilyl group, an oximesilyl group, an alkoxysilyl group, and a thioalkoxysilyl group. It is done.
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 present invention, the hydrolyzable silyl group in the silicone-modified acrylic resin disappears by hydrolysis through a polymerization reaction, and the silicone-modified acrylic resin does not contain a hydrolyzable silyl group. If the hydrolyzable silyl group remains, the storage stability of the recording ink may be deteriorated.
Here, the confirmation that the silicone-modified acrylic resin does not contain a hydrolyzable silyl group is made by comparing the ²⁹ Si-NMR peak of the raw material with the ²⁹ Si-NMR peak of the sample, and by the hydrolyzable silyl group. This can be done by the disappearance of the peak.

  10-300 nm is preferable and, as for the volume average particle diameter of the said resin fine particle, 40-200 nm is more preferable. When the volume average particle size is less than 10 nm, the viscosity of the resin emulsion increases, and it may be difficult to obtain an ink viscosity that can be ejected by an inkjet printer. Particles may be clogged and discharge failure may occur.

The addition amount of the silicone-modified acrylic resin fine particles not containing the hydrolyzable silyl group to the pigment is 0.05 to 1.2 parts by mass of the silicone-modified acrylic resin fine particles not containing the hydrolyzable silyl group with respect to 1 part by mass of the pigment. It is preferable to add, and 0.2 to 1.0 part by mass is more preferable. If the silicone-modified acrylic resin fine particles are less than 0.05 parts by mass, sufficient fixability may not be obtained, and if it exceeds 1.2 parts by mass, sufficient image density may not be obtained.
The amount of silicon (Si) derived from the silicone-modified acrylic resin in the recording ink is preferably 100 to 400 ppm, and more preferably 100 to 300 ppm. When the amount of silicon is less than 100 ppm, a coating film having excellent scratch resistance and marker resistance may not be obtained, and when it exceeds 400 ppm, the tendency to hydrophobicity increases and the stability in aqueous inks decreases. There is.
Here, the amount of silicon (Si) in the recording ink can be measured by, for example, a high frequency induction plasma emission analyzer.

The minimum film-forming temperature (MFT) of the silicone-modified acrylic resin containing no hydrolyzable silyl group is preferably 20 ° C. or less, and more preferably 0 ° C. or less. If the minimum film-forming temperature exceeds 20 ° C., sufficient fixability may not be obtained, and if the printed part is rubbed or traced with a marker, the pigment may be removed and the recording medium may be soiled.
Here, the minimum film-forming temperature (MFT) can be measured by, for example, a film-forming temperature measuring device.

-Penetration agent-
As the penetrant, a diol compound having 7 to 11 carbon atoms is used. If the number of carbon atoms is less than 7, sufficient permeability cannot be obtained, and the recording medium is soiled during double-sided printing, or the ink spread on the recording medium is insufficient and the filling of the pixels becomes worse. A decrease in image density may occur, and if it exceeds 11, storage stability may decrease.
As the diol compound, for example, 2-ethyl-1,3-hexanediol, 2,2,4-trimethyl-1,3-pentanediol and the like are suitable.

  The addition amount of the diol compound is preferably 0.1 to 20% by mass, and more preferably 0.5 to 10% by mass. If the amount added is too small, the permeability of the ink to the paper will be inferior, the roller will be rubbed with a roller during conveyance, and the ink will be applied to the conveyance belt when the recording surface of the recording medium is reversed for double-sided printing. It may cause stains and may not be compatible with high-speed printing or double-sided printing. On the other hand, if the addition amount is too large, the print dot diameter becomes large, the line width of the character becomes wide, and the image sharpness may decrease.

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

The average particle diameter of the polymer fine particles (colored fine particles) containing the coloring material is preferably 0.16 μm or less in the ink.
The content of the colored fine particles is preferably 8 to 20% by mass, more preferably 8 to 12% by mass in solid content in the recording ink.

Examples of the colorant include dyes such as water-soluble dyes, oil-soluble dyes, and disperse dyes, and pigments. Oil-soluble dyes and disperse dyes are preferable from the viewpoint of good adsorptivity and encapsulation, but pigments are preferably used from the light resistance of the obtained image.
In addition, from the viewpoint of efficiently impregnating the polymer fine particles, each of the dyes is preferably dissolved in an organic solvent, for example, a ketone solvent in an amount of 2 g / liter or more, and more preferably 20 to 600 g / liter.
The water-soluble dye is a dye classified into an acid dye, a direct dye, a basic dye, a reactive dye, and a food dye in the color index, and preferably has excellent water resistance and light resistance.
Examples of the acid dyes and food dyes include C.I. I. Acid Yellow 17, 23, 42, 44, 79, 142; C.I. I. Acid Red 1,8,13,14,18,26,27,35,37,42,52,82,87,89,92,97,106,111,114,115,134,186,249,254 289; I. Acid Blue 9, 29, 45, 92, 249; I. Acid Black 1, 2, 7, 24, 26, 94; I. Food Yellow 3, 4; I. Food red 7, 9, 14; I. Food black 1, 2 etc. are mentioned.
Examples of the direct dye include C.I. I. Direct yellow 1,12,24,26,33,44,50,86,120,132,142,144; I. Direct red 1,4,9,13,17,20,28,31,39,80,81,83,89,225,227; I. Direct orange 26, 29, 62, 102; I. Direct Blue 1, 2, 6, 15, 22, 25, 71, 76, 79, 86, 87, 90, 98, 163, 165, 199, 202; I. Direct black 19, 22, 32, 38, 51, 56, 71, 74, 75, 77, 154, 168, 171 and the like.
Examples of the basic dye include C.I. I. Basic yellow 1, 2, 11, 13, 14, 15, 19, 21, 23, 24, 25, 28, 29, 32, 36, 40, 41, 45, 49, 51, 53, 63, 64, 65, 67, 70, 73, 77, 87, 91; C.I. I. Basic Red 2,12,13,14,15,18,22,23,24,27,29,35,36,38,39,46,49,51,52,54,59,68,69,70, 73, 78, 82, 102, 104, 109, 112; I. Basic blue 1,3,5,7,9,21,22,26,35,41,45,47,54,62,65,66,67,69,75,77,78,89,92,93, 105, 117, 120, 122, 124, 129, 137, 141, 147, 155; I. Basic black 2, 8 etc. are mentioned.
Examples of the reactive dye include C.I. I. Reactive Black 3, 4, 7, 11, 12, 17; C.I. I. Reactive Yellow 1,5,11,13,14,20,21,22,25,40,47,51,55,65,67; I. Reactive Red 1,14,17,25,26,32,37,44,46,55,60,66,74,79,96,97; I. Reactive blue 1, 2, 7, 14, 15, 23, 32, 35, 38, 41, 63, 80, 95, and the like.

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

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

There is no restriction | limiting in particular as a color of the said pigment, According to the objective, it can select suitably, For example, the thing for black, the thing for color, etc. are mentioned. These may be used individually by 1 type and may use 2 or more types together.
Examples of the black color include carbon black (CI pigment black 7) such as furnace black, lamp black, acetylene black, channel black, copper, iron (CI pigment black 11), oxidation, and the like. Examples thereof include metals such as titanium, organic pigments such as aniline black (CI pigment black 1), and the like.

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

  As the pigment, a color pigment that can be stably dispersed without using a dispersant in which at least one hydrophilic group is bonded to the surface of the pigment directly or via another atomic group is suitably used. As a result, unlike the conventional ink, a dispersant for dispersing the pigment becomes unnecessary. As the pigment dispersible in water without the dispersant, 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 ( although, M in the formula is hydrogen 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. Etc. Among these, it is preferable to use those in which —COOM and —SO ₃ M are bonded to the surface of the color pigment.

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

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

  As a method for producing carbon black dispersible in water without a cationic dispersant to which the hydrophilic group is bonded, for example, as a method for bonding N-ethylpyridyl group represented by the following structural formula, Is treated with 3-amino-N-ethylpyridinium bromide, but of course the present invention is not limited thereto.

In the present invention, the hydrophilic group may be bonded to the surface of carbon black via another atomic group. Examples of other atomic groups include an alkyl group having 1 to 12 carbon atoms, a phenyl group which may have a substituent, or a naphthyl group which may have a substituent. Specific examples of the case where the above-described hydrophilic group is bonded to the surface of carbon black via another atomic group include, for example, —C ₂ H ₄ COOM (where M represents an alkali metal or quaternary ammonium). , -PhSO ₃ M (where Ph represents a phenyl group, M represents an alkali metal, quaternary ammonium), -C ₅ H ₁₀ NH ₃ ^+, etc. Of course, the present invention is not limited thereto.

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

  The addition amount of the pigment as the colorant in the recording ink is preferably 4 to 15% by mass, and more preferably 5 to 12% by mass. In general, when the pigment concentration is increased, the image density is increased and the image quality is improved. However, the reliability such as fixing property, ejection stability, and clogging is liable to be adversely affected. However, in the present invention, even if the amount of the pigment added is increased, the fixing property can be ensured while maintaining the reliability such as ejection stability and clogging.

-Water-soluble organic solvent-
The water-soluble organic solvent is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include polyhydric alcohols, polyhydric alcohol alkyl ethers, polyhydric alcohol aryl ethers, and nitrogen-containing heterocycles. Examples thereof include compounds, amides, amines, sulfur-containing compounds, propylene carbonate, and ethylene carbonate. These may be used alone or in combination of two or more.
Examples of the polyhydric alcohols include ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, 1,3-propanediol, 1,3-butanediol, 2,3-butanediol, 1,4-butanediol, 3-methyl-1,3-butanediol, 1,5-pentanediol, 1,6-hexanediol, 2-methyl-2,4-pentanediol, Examples include tetraethylene glycol, polyethylene glycol, glycerin, 1,2,6-hexanetriol, 1,2,4-butanetriol, 1,2,3-butanetriol, and petriol.
Examples of the polyhydric alcohol alkyl ethers include ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, tetraethylene glycol monomethyl ether, and propylene glycol monoethyl ether. It is done.
Examples of the polyhydric alcohol aryl ethers include ethylene glycol monophenyl ether and ethylene glycol monobenzyl ether.
Examples of the nitrogen-containing heterocyclic compound include N-methyl-2-pyrrolidone, N-hydroxyethyl-2-pyrrolidone, 2-pyrrolidone, 1,3-dimethylimidazolidinone, and ε-caprolactam.
Examples of the amides include formamide, N-methylformamide, formamide, N, N-dimethylformamide and the like.
Examples of the amines include monoethanolamine, diethanolamine, triethanolamine, monoethylamine, diethylamine, and triethylamine.
Examples of the sulfur-containing compounds include dimethyl sulfoxide, sulfolane, thiodiethanol, thiodiglycol, and the like.
Among these, glycerin, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1 from the viewpoint of obtaining excellent effects on solubility and prevention of poor jetting characteristics due to water evaporation , 3-butanediol, 2,3-butanediol, 1,4-butanediol, 3-methyl-1,3-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-hydroxy Ethyl-2-pyrrolidone is particularly preferred.

  The content of the water-soluble organic solvent in the recording ink is preferably 15 to 40% by mass, and more preferably 20 to 35% by mass. If the content is too small, the nozzle is likely to be dried and defective ejection of droplets may occur. If the content is too large, the ink viscosity is increased, and the proper viscosity range may be exceeded.

-Surfactant-
Examples of the surfactant include an anionic surfactant, a cationic surfactant, a nonionic surfactant, a fluorine surfactant, and an amphoteric surfactant. These surfactants can be used alone or in combination of two or more.

  Examples of the anionic surfactant include alkyl allyl, alkyl naphthalene sulfonate, alkyl phosphate, alkyl sulfate, alkyl sulfonate, alkyl ether sulfate, alkyl sulfosuccinate, alkyl ester sulfate, and alkyl benzene sulfonate. , Alkyl diphenyl ether disulfonate, alkyl aryl ether phosphate, alkyl aryl ether sulfate, alkyl aryl ether ester sulfate, olefin sulfonate, alkane olefin sulfonate, polyoxyethylene alkyl ether phosphate, polyoxyethylene Alkyl ether sulfate, ether carboxylate, sulfosuccinate, α-sulfo fatty acid ester, fatty acid salt, higher fatty acid and amino acid condensate, naphthenate, etc. It is, among these, polyoxyethylene alkyl ether acetate and dialkyl sulfosuccinate salt.

  Examples of the nonionic surfactant include acetylene glycol surfactants, polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyoxyethylene alkyl esters, polyoxyethylene sorbitan fatty acid esters, and the like.

Examples of the cationic surfactant include alkylamine salts, dialkylamine salts, aliphatic amine salts, benzalkonium salts, quaternary ammonium salts, alkylpyridinium salts, imidazolinium salts, sulfonium salts, phosphonium salts, and the like. Can be mentioned.
Examples of the amphoteric surfactant include imidazoline derivatives such as imidazolinium betaine, dimethylalkyl lauryl betaine, alkylglycine, and alkyldi (aminoethyl) glycine.

  Examples of the fluorine-based surfactant include compounds represented by any of the following structural formulas (1) to (3).

However, in said structural formula (1), m represents the integer of 0-10. n represents an integer of 1 to 40.
However, in the structural formula (2), Rf represents CF ₃ or CF ₂ CF ₃ . m represents an integer of 6 to 25, n represents an integer of 1 to 4, and p represents 1 to 4.
However, in the structural formula (3), Rf represents CF ₃ or CF ₂ CF ₃ . q represents the integer of 1-6.

Examples of the compounds represented by the structural formulas (1) to (3) include perfluoroalkyl sulfonate, perfluoroalkyl carboxylate, perfluoroalkyl phosphate, perfluoroalkyl ethylene oxide adduct, perfluoroalkyl sulfonate, Fluoroalkyl betaines, perfluoroalkylamine oxide compounds and the like can be mentioned.
As a concrete commercial item of the said fluorosurfactant, since it is easy to obtain, for example, Surflon S-111, S-112, S-113, S121, S131, S132, S-141, 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 Co., Ltd.), Zonyl FS-300, FSN, FSN-100, FSO (DuPont), Ftop EF-351, 352, 801, 802 (Gemco) is preferred. Among these, Zonyl FS-300, FSN, FSN-100, and FSO (manufactured by DuPont), which are excellent in reliability and color development, can be particularly preferably used.
The addition amount of the surfactant can be appropriately adjusted within a range in which the pigment is stably dispersed and the other effects of the present invention are not lost.

-Aminopropanediol compound-
The aminopropanediol compound is a water-soluble organic basic compound, and for example, an aminopropanediol derivative is suitable.
There is no restriction | limiting in particular as said aminopropanediol derivative, According to the objective, it can select suitably, For example, 1-amino-2,3-propanediol, 1-methylamino-2,3-propanediol, 2 -Amino-2-methyl-1,3-propanediol, 2-amino-2-ethyl-1,3-propanediol, etc., among which 2-amino-2-ethyl-1,3-propane Diols are particularly preferred.

  The addition amount of the aminopropanediol compound in the recording ink is preferably 0.01 to 10% by mass, more preferably 0.1 to 5.0% by mass, and still more preferably 0.1 to 2.0% by mass. . If the amount added is too large, disadvantages such as an increase in pH and an increase in viscosity may occur.

  The other components are not particularly limited and can be appropriately selected as necessary. For example, pH adjusters, antiseptic / antifungal agents, rust preventives, antioxidants, ultraviolet absorbers, oxygen absorbers, And light stabilizers.

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

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

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

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

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

  In the recording ink of the present invention, at least water, a colorant, silicone-modified acrylic resin fine particles not containing a hydrolyzable silyl group, and a penetrating agent, and if necessary, other components are dispersed or dissolved in an aqueous medium, Furthermore, it stirs and mixes as needed. The dispersion can be performed by, for example, a sand mill, a homogenizer, a ball mill, a paint shaker, an ultrasonic disperser, etc., and stirring and mixing are performed by a stirrer using a normal stirring blade, a magnetic stirrer, a high-speed disperser, or the like. be able to.

The physical properties of the recording ink of the present invention are not particularly limited and may be appropriately selected depending on the intended purpose. For example, the solid content, viscosity, surface tension, pH and the like are preferably in the following ranges.
The solid content in the recording ink is preferably 6 to 20% by mass, more preferably 8 to 15% by mass. If the solid content is less than 6% by mass, sufficient image density may not be obtained after printing.
Here, the solid content in the ink in the present invention mainly means a water-insoluble colorant and resin fine particles.

The viscosity at 25 ° C. is preferably 7 to 20 mPa · s, more preferably 5 to 10 mPa · s. If the viscosity exceeds 20 mPa · s, it may be difficult to ensure ejection stability.
The surface tension is preferably 25 to 55 mN / m at 20 ° C. If the surface tension is less than 25 mN / m, bleeding on the recording medium becomes remarkable and stable jetting may not be obtained. If the surface tension exceeds 55 mN / m, ink penetration into the recording medium is sufficient. However, the drying time may be prolonged.
As said pH, 7-10 are preferable, for example.

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

  The recording ink of the present invention uses an piezoelectric head as a pressure generating means for pressurizing ink in an ink flow path as an ink jet head, and deforms a diaphragm that forms the wall surface of the ink flow path to increase the volume in the ink flow path. A so-called piezo type that discharges ink droplets by changing (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. (Refer to Japanese Patent Application Laid-Open No. 61-59911), a diaphragm that forms the wall surface of an ink flow path and an electrode are arranged opposite to each other, and the diaphragm is deformed by an electrostatic force generated between the diaphragm and the electrode. Therefore, a printer equipped with any inkjet head such as an electrostatic type (see Japanese Patent Application Laid-Open No. 6-71882) that discharges ink droplets by changing the volume in the ink flow path. Can also be used well.

  The recording ink of the present invention can be suitably used in various fields, and can be suitably used in an image recording apparatus (printer or the like) based on an ink jet recording method. The recording ink is heated at 50 to 200 ° C. and can be used for a printer or the like having a function of accelerating printing and fixing. The following ink cartridge, ink recorded matter, ink jet recording apparatus, and ink jet recording method It can be particularly preferably used.

(ink cartridge)
The ink cartridge of the present invention contains the recording ink 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 attached to various ink jet recording apparatuses.

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

(Inkjet recording apparatus and inkjet recording method)
The ink jet recording apparatus of the present invention includes at least ink flying means, and further includes other means appropriately selected as necessary, for example, stimulus generation means, 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.

-Ink flying process and ink flying means-
The ink flying step is a step of recording an image by applying a stimulus to the recording ink of the present invention and causing the recording ink to fly.
The ink flying means is means for recording an image by applying a stimulus to the recording ink of the present invention and causing the recording ink to fly. 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.
In addition, it is preferable that a sub tank for supplying ink is provided on the ink jet head, and the sub tank is replenished with ink from an ink cartridge through a supply tube.

  The stimulus can be generated, for example, by the stimulus generating means, and the stimulus is not particularly limited and can be appropriately selected according to the purpose, such as heat (temperature), pressure, vibration, light, etc. Is mentioned. 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 are no particular restrictions on the manner in which the recording ink flies, and it varies depending on the type of the stimulus. For example, when the stimulus is “heat”, a recording signal is output to the recording ink in the recording head. Corresponding thermal energy is applied using, for example, a thermal head, bubbles are generated in the recording ink by the thermal energy, and the recording ink is formed into droplets from the nozzle holes of the recording head by the pressure of the bubbles. And a method of discharging and jetting. 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 the recording ink is ejected and ejected as droplets from the nozzle holes of the recording head.

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

It is preferable to have a reversing unit that can perform double-sided printing by reversing the recording surface of the recording medium. Examples of the reversing means include a conveying belt having electrostatic force, a means for holding a recording medium by air suction, and a combination of a conveying roller and a spur.
It is preferable to have an endless transport belt and transport means for transporting the surface of the transport belt while charging and holding the recording medium. In this case, it is particularly preferable to charge the conveying belt by applying an AC bias of ± 1.2 kV to ± 2.6 kV to the charging roller.

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

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

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

The carriage 133 is provided with a plurality of recording heads 134 including four inkjet recording heads that eject recording ink droplets of each color of yellow (Y), cyan (C), magenta (M), and black (Bk). The ejection ports are arranged in a direction crossing the main scanning direction, and are mounted with the ink droplet ejection direction facing downward.
As the ink jet recording head constituting the recording head 134, a piezoelectric actuator such as a piezoelectric element, a thermal actuator using phase change due to liquid film boiling using an electrothermal transducer such as a heating resistor, a metal phase due to temperature change, etc. A shape memory alloy actuator using a change, an electrostatic actuator using an electrostatic force, or the like as an energy generating means for discharging recording ink can be used.
In addition, the carriage 133 is equipped with a sub tank 135 for each color for supplying ink of each color to the recording head 134. The sub tank 135 is supplied with the recording ink of the present invention from the ink cartridge 1 of the present invention loaded in the ink cartridge loading section 105 via a recording ink supply tube (not shown).

  On the other hand, as a paper feeding unit for feeding the paper 142 stacked on the paper stacking unit (pressure plate) 141 of the paper feed tray 103, the half-moon roller for separating and feeding the paper 142 one by one from the paper stacking unit 141. The sheet feeding roller 143 and the sheet feeding roller 143 are opposed to each other, and a separation pad 144 made of a material having a large friction coefficient is provided. The separation pad 144 is urged toward the sheet feeding roller 143 side.

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

  The conveyance belt 151 is an endless belt, is stretched between the conveyance roller 157 and the tension roller 158, and can circulate in the belt conveyance direction. The transport belt 151 includes, for example, a surface layer serving as a sheet 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), and the surface layer. It has a back layer (medium resistance layer, earth layer) that is made of the same material and has resistance controlled by carbon. On the back side of the conveyance belt 151, a guide member 161 is arranged corresponding to a printing area by the recording head 134. Note that, as a paper discharge unit for discharging the paper 142 recorded by the recording head 134, a separation claw 171 for separating the paper 142 from the conveyance belt 151, a paper discharge roller 172, and a paper discharge roller 173 are provided. The paper discharge tray 103 is disposed below the paper discharge roller 172.

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

In this ink jet recording apparatus, the paper 142 is separated and fed one by one from the paper feed unit, and the paper 142 fed substantially vertically upward is guided by the guide 145 and between the transport belt 151 and the counter roller 152. It is sandwiched and conveyed. Further, the leading end is guided by the conveying guide 153 and pressed against the conveying belt 151 by the leading end pressure roller 155, and the conveying direction is changed by approximately 90 °.
At this time, the conveyance belt 157 is charged by the charging roller 156, and the sheet 142 is conveyed by being electrostatically attracted to the conveyance belt 151. Therefore, by driving the recording head 134 according to the image signal while moving the carriage 133, ink droplets are ejected onto the stopped paper 142 to record one line, and after the paper 142 is conveyed by a predetermined amount, Record the next line. Upon receiving a recording end signal or a signal that the trailing edge of the sheet 142 has reached the recording area, the recording operation is terminated and the sheet 142 is discharged onto the discharge tray 103.
When the recording ink remaining amount near end in the sub tank 135 is detected, a required amount of recording ink is supplied from the ink cartridge 1 to the sub tank 135.

  In this ink jet recording apparatus, when the recording 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 recording ink stably even when the ink cartridge 201 is placed vertically and has a front loading configuration. Therefore, when the upper portion of the apparatus main body 101 is closed and installed, for example, even when the apparatus main body 101 is stored in a rack or an object is placed on the upper surface of the apparatus main body 101, the ink cartridge 201 is replaced. Can be easily performed.

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

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

Hereinafter, an 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 serving as an ink supply port (not shown) and a common liquid chamber 1b, and a communication port 2c communicating with the fluid resistance portion 2a and the engraving serving as the pressurized liquid chamber 2b and the nozzle 3a. The formed flow path plate 20, the nozzle plate forming the nozzle 3 a, the vibration plate 60 having the convex portion 6 a, the diaphragm portion 6 b, and the ink inlet 6 c, and the vibration plate 60 bonded to each other through the adhesive layer 70. A laminated piezoelectric element 50 and a base 40 to which the laminated piezoelectric element 50 is fixed are provided.
The base 40 is made of a barium titanate ceramic, and the laminated piezoelectric elements 50 are arranged in two rows and joined.
The laminated piezoelectric element 50 is 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 alternately. Are stacked. The internal electrode layer is connected to the external electrode at both ends.
The laminated piezoelectric element 50 is divided on comb teeth by half-cut dicing, and is used as a drive unit 5f and a support unit 5g (non-drive unit) one by one. The length of the outside of the external electrode is limited by cutting or the like so as to be divided by half-cut dicing, and these become a plurality of individual electrodes. The other is not divided by dicing but is conductive and becomes a common electrode.
The FPC 8 is soldered to the individual electrodes of the drive unit. 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 joined to a thin film diaphragm portion 6b, an island-shaped convex portion (island portion) 6a that joins the laminated piezoelectric element 50 that is the driving portion 5f formed at the center portion of the diaphragm portion 6b, and a support portion. A thick film portion including a beam and an opening serving as an ink inflow port 6c are formed by stacking two layers of 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 portion 6a of the diaphragm 60 and the movable portion 5f of the laminated piezoelectric element 50, and the coupling of the diaphragm 50 and the frame 10 are bonded by patterning the adhesive layer 70 including a gap material.

As the flow path plate 20, a silicon single crystal substrate was used, and the engraving to be the fluid resistance portion 2a and the pressurized liquid chamber 2b and the through-hole to be the communication port 2c at the position with respect to the nozzle 3a were patterned by an etching method.
The portion left by etching becomes the partition wall 2d of the pressurized liquid chamber 2b. Further, in this head, a portion for narrowing the etching width is provided and this is used as the fluid resistance portion 2a.
The nozzle plate 30 is formed of a metal material, for example, an Ni plating film formed by an electroforming method, and has a large number of nozzles 3a that are fine discharge ports for causing ink droplets to fly. The 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 as the diameter 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 3b that is 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 driving waveform (pulse voltage of 10 to 50 V) is applied to the driving unit 5f in accordance with the recording signal, thereby causing displacement in the stacking direction in the driving unit 5f, and the diaphragm 30. The pressurized liquid chamber 2b is pressurized through the pressure to increase the pressure, and ink droplets are ejected from the nozzle 3a.
Thereafter, the ink pressure in the pressurizing liquid chamber 2b is reduced with the end of ink droplet ejection, and negative pressure is generated in the pressurizing liquid chamber 2b due to the inertia of the ink flow and the discharge process of the drive pulse, and the ink is filled. Move to the process. At this time, the ink supplied from the ink tank flows into the common liquid chamber 1b, passes from the common liquid chamber 1b through the ink inlet 6c, passes through the fluid resistance portion 2a, and is filled into the pressurized liquid chamber 2b.
The fluid resistance portion 2a has an effect on the attenuation of the residual pressure vibration after ejection, but it is resistant to the maximum filling (refill) due to surface tension. By appropriately selecting the fluid resistance portion, it is possible to balance the attenuation of the residual pressure and the refill time, and to shorten the time (drive cycle) until the transition to the next ink droplet ejection operation.

(Ink record)
The ink recorded matter recorded by the ink jet recording apparatus and the ink jet recording method of the present invention is the ink recorded matter of the present invention. The ink recorded matter of the present invention has an image formed on the recording medium using the recording ink of the present invention.
There is no restriction | limiting in particular as said recording medium, According to the objective, it can select suitably, For example, a plain paper, glossy paper, special paper, cloth, a film, an OHP sheet etc. are mentioned. These may be used individually by 1 type and may use 2 or more types together.
The ink recorded matter has high image quality, no bleeding, excellent temporal stability, and can be suitably used for various purposes as a material on which various prints or images are recorded.

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

(Preparation Example 1)
-Preparation of 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 allowed to react for 10 hours. The oxidation treatment was performed. 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 so that the pigment concentration was 20% by mass. Thus, a surface-treated carbon black pigment dispersion was prepared.

(Preparation Example 2)
-Preparation of surface-treated yellow pigment dispersion-
As a yellow pigment, C.I. I. Pigment Yellow 128 was subjected to low-temperature plasma treatment to produce a yellow pigment into which a carboxyl group was introduced. A dispersion of this in ion-exchanged water was desalted and concentrated with an ultrafiltration membrane to prepare a yellow pigment dispersion having a pigment concentration of 15% by mass.

(Preparation Example 3)
-Preparation of surface-treated magenta pigment-
In Preparation Example 2, C.I. I. Pigment Yellow 128 instead of C.I. I. A magenta pigment into which a carboxyl group was introduced was prepared in the same manner as in Preparation Example 2, except that CI Pigment Red 122 was used.
The resulting surface treated magenta pigment was readily dispersed in an aqueous medium upon stirring.

(Preparation Example 4)
-Preparation of surface-treated cyan pigment-
In Preparation Example 2, C.I. I. Pigment Yellow 128 instead of C.I. I. A cyan pigment into which a carboxyl group was introduced was prepared in the same manner as in Preparation Example 2, except that CI Pigment Cyan 15: 3 was used.
The resulting surface treated cyan pigment was easily dispersed in an aqueous medium upon stirring.

(Synthesis Example 1)
-Synthesis of polymer dispersion-
After sufficiently replacing the inside of the 1 L flask equipped with a mechanical stirrer, thermometer, nitrogen gas introduction 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 Then, 4.0 g of polyethylene glycol methacrylate, 4.0 g of styrene macromer (manufactured by Toa Gosei Co., Ltd., trade name: AS-6) and 0.4 g of mercaptoethanol were charged and heated to 65 ° C. Next, 100.8 g of styrene, 25.2 g of acrylic acid, 108.0 g of lauryl methacrylate, 36.0 g of polyethylene glycol methacrylate, 60.0 g of hydroxyethyl methacrylate, styrene macromer (trade name: AS-6, manufactured by Toagosei Co., Ltd.) 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 50% by mass polymer solution.

(Preparation Example 5)
-Preparation of phthalocyanine pigment-containing polymer fine particle dispersion-
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, and then 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 prepare a cyan polymer fine particle dispersion.

(Preparation Example 6)
-Preparation of dimethylquinacridone pigment-containing polymer fine particle dispersion-
In Preparation Example 5, the phthalocyanine pigment was changed to C.I. I. A magenta polymer fine particle dispersion was prepared in the same manner as in Preparation Example 5, except that the pigment red 122 was used.

(Preparation Example 7)
-Preparation of monoazo yellow pigment-containing polymer fine particle dispersion-
In Preparation Example 5, the phthalocyanine pigment was changed to C.I. I. A yellow polymer fine particle dispersion was prepared in the same manner as in Preparation Example 5, except that the pigment yellow 74 was used.

(Preparation Example 8)
-Preparation of carbon black pigment-containing polymer fine particle dispersion-
A black polymer fine particle dispersion was prepared in the same manner as in Preparation Example 5 except that the phthalocyanine pigment was changed to carbon black in Preparation Example 5.

(Synthesis Example 2)
-Synthesis of silicone-modified acrylic resin fine particles containing no reactive silyl groups-
After sufficiently replacing the inside of the flask equipped with a mechanical stirrer, thermometer, nitrogen gas introduction tube, reflux tube, and dropping funnel with nitrogen gas, 10 g of Aqualon RN-20 (Daiichi Kogyo Seiyaku Co., Ltd.), persulfuric acid 1 g of potassium and 286 g of pure water were 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 (Daiichi Kogyo Seiyaku Co., Ltd.), 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 peak of ^{29 Si-NMR} of the obtained silicone-modified acrylic resin fine particles as compared to the peak of ^{29 Si-NMR} in the raw material, be free of reactive silyl groups since the peaks due hydrolyzable silyl group is lost Was confirmed.
<Measurement conditions for ²⁹ Si-NMR>
Equipment used: NMR (solid state measurement)
SR-MAS (Sweet Resin-Magic Angle)
^Spinning) - it was 29 Si-NMR measurement.
Sample tube: manufactured by zirconia Cap: manufactured by Daiflon Volume average particle diameter (D50%) measured with a particle size distribution measuring device (Microtrac UPA, manufactured by Nikkiso Co., Ltd.) of the silicone-modified acrylic resin fine particles containing no reactive silyl group Was 130 nm. Moreover, the minimum film-forming temperature (MFT) measured with the film-forming temperature measuring apparatus was 0 degreeC.

(Synthesis Example 3)
-Synthesis of silicone-modified acrylic resin fine particles containing no reactive silyl groups-
After sufficiently replacing the inside of the flask equipped with a mechanical stirrer, thermometer, nitrogen gas inlet tube, reflux tube, and dropping funnel with nitrogen gas, 10 g of Aqualon RN-20 (Daiichi Kogyo Seiyaku Co., Ltd.) 1 g of potassium sulfate and 286 g of pure water were 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 (Daiichi Kogyo Seiyaku Co., Ltd.), 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 resulting silicone-modified acrylic resin fine particles, in the same manner as in Synthesis Example 2, a peak of ^{29 Si-NMR} and compared with the peak of ^{29 Si-NMR} in the raw materials, the peak due to hydrolyzable silyl group is lost From this, it was confirmed that no reactive silyl group was contained.
The volume average particle diameter (D50%) measured with a particle size distribution measuring device (Microtrac UPA, manufactured by Nikkiso Co., Ltd.) of the silicone-modified acrylic resin fine particles containing no reactive silyl group was 148 nm. Moreover, the minimum film-forming temperature (MFT) measured with the film-forming temperature measuring apparatus was 0 degreeC.

(Synthesis Example 4)
-Synthesis of reactive silyl group-containing silicone-modified acrylic resin fine particles-
The examples described in Japanese Patent Application Laid-Open No. 6-157861 were additionally tested, and silicone-modified acrylic resin fine particles containing reactive silyl groups were synthesized.
A flask equipped with a mechanical stirrer, thermometer, nitrogen gas introduction tube, reflux tube, and dropping funnel was sufficiently replaced with nitrogen gas, and then 100 g of pure water, 3 g of sodium dodecylbenzenesulfonate, 1 g of polyethylene glycol nonylphenyl ether Were added, 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 resulting silicone-modified acrylic resin fine particles, in the same manner as in Synthesis Example 2, a peak of ^{29 Si-NMR} and compared with the peak of ^{29 Si-NMR} in the raw materials, the peak due to hydrolyzable silyl group is present From the results, it was confirmed that a reactive silyl group was contained.
The volume average particle diameter (D50%) measured with a particle size distribution measuring device (Microtrac UPA, Nikkiso Co., Ltd.) of the silicone-modified acrylic resin fine particles containing reactive silyl groups was 160 nm. Moreover, the minimum film-forming temperature (MFT) measured with the film-forming temperature measuring apparatus was 0 degreeC.

(Synthesis Example 5)
-Synthesis of silicone-modified acrylic resin fine particles containing no reactive silyl groups-
After sufficiently replacing the inside of the flask equipped with a mechanical stirrer, thermometer, nitrogen gas inlet tube, reflux tube, and dropping funnel with nitrogen gas, 10 g of Aqualon RN-20 (Daiichi Kogyo Seiyaku Co., Ltd.) 1 g of potassium sulfate and 286 g of pure water were 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 (Daiichi Kogyo Seiyaku Co., Ltd.), 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 resulting silicone-modified acrylic resin fine particles, in the same manner as in Synthesis Example 2, a peak of ^{29 Si-NMR} and compared with the peak of ^{29 Si-NMR} in the raw materials, the peak due to hydrolyzable silyl group is lost From this, it was confirmed that no reactive silyl group was contained. The volume average particle diameter (D50%) measured by a particle size distribution measuring device (Microtrac UPA, manufactured by Nikkiso Co., Ltd.) of the silicone-modified acrylic resin fine particles containing no reactive silyl group was 310 nm. Moreover, the minimum film-forming temperature (MFT) measured with the film-forming temperature measuring apparatus was 0 degreeC.

(Synthesis Example 6)
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, 30 g of Aqualon RN-20 (Daiichi Kogyo Seiyaku Co., Ltd.), potassium persulfate 1 g and 286 g of pure water were 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, 30 g of Aqualon RN-20 (Daiichi Kogyo Seiyaku Co., Ltd.), 4 g of potassium persulfate, and 400 g of pure water The 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 resulting silicone-modified acrylic resin fine particles, in the same manner as in Synthesis Example 2, a peak of ^{29 Si-NMR} and compared with the peak of ^{29 Si-NMR} in the raw materials, the peak due to hydrolyzable silyl group is lost From this, it was confirmed that no reactive silyl group was contained. The volume average particle diameter (D50%) measured by a particle size distribution measuring device (Microtrac UPA, manufactured by Nikkiso Co., Ltd.) of the silicone-modified acrylic resin fine particles not containing the reactive silyl group was 48 nm. Moreover, the minimum film-forming temperature (MTF) measured with the film-forming temperature measuring apparatus was 0 degreeC.

(Synthesis Example 7)
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, 130 g of Aqualon RN-20 (Daiichi Kogyo Seiyaku Co., Ltd.), potassium persulfate 1 g and 286 g of pure water were 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, 30 g of Aqualon RN-20 (Daiichi Kogyo Seiyaku Co., Ltd.), 4 g of potassium persulfate, and 400 g of pure water The 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 resulting silicone-modified acrylic resin fine particles, in the same manner as in Synthesis Example 2, a peak of ^{29 Si-NMR} and compared with the peak of ^{29 Si-NMR} in the raw materials, the peak due to hydrolyzable silyl group is lost From this, it was confirmed that no reactive silyl group was contained. The volume average particle diameter (D50%) measured by a particle size distribution measuring device (Microtrac UPA, manufactured by Nikkiso Co., Ltd.) of the silicone-modified acrylic resin fine particles containing no reactive silyl group was 10 nm. Moreover, the minimum film-forming temperature (MTF) measured with the film-forming temperature measuring apparatus was 0 degreeC.

Example 1
-Production of black pigment ink-
An ink composition having the following formulation was prepared and adjusted with a 10% by weight aqueous solution of lithium hydroxide so that the pH was 9. Then, it filtered with the membrane filter with an average hole diameter of 0.8 micrometer, and produced the ink.
<Ink composition>
-Carbon black pigment dispersion of Preparation Example 1 ... 10.0% by mass (solid content)
-Silicone-modified acrylic resin fine particles of Synthesis Example 2 ... 5.0% by mass (solid content)
・ Diethylene glycol: 18.0% by mass
・ Glycerin: 6.0% by mass
・ 2-Pyrrolidone: 2.0% by mass
・ Surfactant (Softanol EP7025, manufactured by Nippon Shokubai Co., Ltd.) ... 1.0% by mass
・ 2,2,4-Trimethyl-1,3-pentanediol: 2.0% by mass
・ Ion exchange water: 56.0% by mass

(Example 2)
-Manufacture of yellow pigment ink-
An ink composition having the following formulation was prepared and adjusted with a 10% by weight aqueous solution of lithium hydroxide so that the pH was 9. Then, it filtered with the membrane filter with an average hole diameter of 0.8 micrometer, and produced the ink.
<Ink composition>
-Yellow pigment dispersion of Preparation Example 2 6.0 mass% (solid content)
-Silicone-modified acrylic resin fine particles of Synthesis Example 2 ... 5.0% by mass (solid content)
・ 1,5-pentanediol ... 20.0 mass%
・ Glycerin: 5.0% by mass
・ Surfactant (Softanol EP7025, manufactured by Nippon Shokubai Co., Ltd.) ... 1.0% by mass
・ 2-ethyl-1,3-hexanediol: 2.0% by mass
・ Ion exchange water: 61.0% by mass

(Example 3)
-Manufacture of magenta pigment ink-
An ink composition having the following formulation was prepared and adjusted with a 10% by weight aqueous solution of lithium hydroxide so that the pH was 9. Then, it filtered with the membrane filter with an average hole diameter of 0.8 micrometer, and produced the ink.
<Ink composition>
-Magenta pigment dispersion of Preparation Example 3 7.0 mass% (solid content)
-Silicone-modified acrylic resin fine particles of Synthesis Example 2 ... 3.0% by mass (solid content)
・ 1,3-butanediol: 18.0% by mass
・ Glycerin: 6.0% by mass
・ N-methyl-2-pyrrolidone: 3.0% by mass
・ Surfactant (Softanol EP7025, manufactured by Nippon Shokubai Co., Ltd.) ... 1.0% by mass
・ 2,2,4-Trimethyl-1,3-pentanediol: 2.0% by mass
・ Ion exchange water: 60.0% by mass

Example 4
-Manufacture of cyan pigment ink-
An ink composition having the following formulation was prepared and adjusted with a 10% by weight aqueous solution of lithium hydroxide so that the pH was 9. Then, it filtered with the membrane filter with an average hole diameter of 0.8 micrometer, and produced the ink.
<Ink composition>
-Cyan pigment dispersion of Preparation Example 4. 6.0% by mass (solid content)
-Silicone-modified acrylic resin fine particles of Synthesis Example 2 ... 5.0% by mass (solid content)
・ 1,5-pentanediol ... 20.0 mass%
・ Glycerin: 5.0% by mass
・ Surfactant (Softanol EP7025, manufactured by Nippon Shokubai Co., Ltd.) ... 1.0% by mass
・ 2-ethyl-1,3-hexanediol: 2.0% by mass
・ Ion exchange water: 61.0% by mass

(Example 5)
-Production of black pigment ink-
An ink composition having the following formulation was prepared and adjusted with a 10% by weight aqueous solution of lithium hydroxide so that the pH was 9. Then, it filtered with the membrane filter with an average hole diameter of 0.8 micrometer, and produced the ink.
<Ink composition>
-Carbon black pigment polymer dispersion of Preparation Example ... 10.0 mass% (solid content)
-Silicone-modified acrylic resin fine particles of Synthesis Example 2 ... 2.0% by mass (solid content)
・ 1,6-hexanediol: 15.0% by mass
・ Glycerin: 7.0% by mass
・ 2-Pyrrolidone: 2.0% by mass
・ Surfactant (Softanol EP7025, manufactured by Nippon Shokubai Co., Ltd.) ... 1.0% by mass
・ 2,2,4-Trimethyl-1,3-pentanediol: 2.0% by mass
・ Ion exchange water: 61.0% by mass

(Example 6)
-Manufacture of cyan pigment ink-
An ink composition having the following formulation was prepared and adjusted with a 10% by weight aqueous solution of lithium hydroxide so that the pH was 9. Then, it filtered with the membrane filter with an average hole diameter of 0.8 micrometer, and produced the ink.
<Ink composition>
-Cyan pigment polymer dispersion of Preparation Example 5 7.0 mass% (solid content)
-Silicone-modified acrylic resin fine particles of Synthesis Example 2 ... 3.0% by mass (solid content)
・ 1,5-pentanediol: 16.0% by mass
・ Glycerin: 6.0% by mass
・ N-methyl-2-pyrrolidone: 5.0% by mass
・ Surfactant (Softanol EP7025, manufactured by Nippon Shokubai Co., Ltd.) ... 2.0% by mass
・ 2,2,4-Trimethyl-1,3-pentanediol: 2.0% by mass
・ Ion exchange water: 59.0% by mass

(Example 7)
-Manufacture of magenta pigment ink-
An ink composition having the following formulation was prepared and adjusted with a 10% by weight aqueous solution of lithium hydroxide so that the pH was 9. Then, it filtered with the membrane filter with an average hole diameter of 0.8 micrometer, and produced the ink.
<Ink composition>
-Magenta pigment polymer dispersion of Preparation Example 6 6.0 mass% (solid content)
-Silicone-modified acrylic resin fine particles of Synthesis Example 2 ... 3.0% by mass (solid content)
・ 1,3-butanediol ... 20.0 mass%
・ Glycerin: 5.0% by mass
・ Surfactant (Softanol EP7025, manufactured by Nippon Shokubai Co., Ltd.) ... 2.0% by mass
・ 2-ethyl-1,3-hexanediol: 3.0% by mass
・ Ion exchange water: 61.0% by mass

(Example 8)
-Manufacture of yellow pigment ink-
An ink composition having the following formulation was prepared and adjusted with a 10% by weight aqueous solution of lithium hydroxide so that the pH was 9. Then, it filtered with the membrane filter with an average hole diameter of 0.8 micrometer, and produced the ink.
<Ink composition>
-Yellow pigment polymer dispersion of Preparation Example ... 5.0% by mass (solid content)
-Silicone-modified acrylic resin fine particles of Synthesis Example 2 ... 2.0% by mass (solid content)
・ 1,5-pentanediol ... 20.0 mass%
・ Glycerin: 6.0% by mass
・ N-methyl-2-pyrrolidone: 3.0% by mass
・ Surfactant (Softanol EP7025, manufactured by Nippon Shokubai Co., Ltd.) ... 2.0% by mass
・ 2,2,4-Trimethyl 1-1,3-pentanediol: 2.0% by mass
・ Ion exchange water: 60.0% by mass

Example 9
-Production of black pigment ink-
An ink composition having the following formulation was prepared and adjusted with a 10% by weight aqueous solution of lithium hydroxide so that the pH was 9. Then, it filtered with the membrane filter with an average hole diameter of 0.8 micrometer, and produced the ink.
<Ink composition>
-Carbon black pigment dispersion of Preparation Example 1 ... 10.0% by mass (solid content)
-Silicone modified acrylic resin fine particles of Synthesis Example 2 10.0 mass% (solid content)
・ Diethylene glycol: 16.0% by mass
・ Glycerin: 8.0% by mass
・ 2-Pyrrolidone: 2.0% by mass
・ Surfactant (Softanol EP7025, manufactured by Nippon Shokubai Co., Ltd.) ... 2.0% by mass
・ 2,2,4-Trimethyl-1,3-pentanediol ... 1.0% by mass
・ Ion exchange water: 51.0% by mass

(Example 10)
-Production of black pigment ink-
An ink composition having the following formulation was prepared and adjusted with a 10% by weight aqueous solution of lithium hydroxide so that the pH was 9. Then, it filtered with the membrane filter with an average hole diameter of 0.8 micrometer, and produced the ink.
<Ink composition>
-Carbon black pigment dispersion of Preparation Example 1 8.0% by mass (solid content)
-Silicone-modified acrylic resin fine particles of Synthesis Example 2 ... 4.0% by mass (solid content)
・ 3-methyl-1,3-butanediol ... 16.0% by mass
・ Glycerin: 8.0% by mass
・ Surfactant (Softanol EP7025, manufactured by Nippon Shokubai Co., Ltd.) ... 2.0% by mass
・ 2-ethyl-1,3-hexanediol: 1.0% by mass
・ 1-Amino-2,3-propanediol: 0.5% by mass
・ Ion exchange water: 60.5% by mass

( Reference Example 11)
-Manufacture of yellow pigment ink-
An ink composition having the following formulation was prepared and adjusted with a 10% by weight aqueous solution of lithium hydroxide so that the pH was 9. Then, it filtered with the membrane filter with an average hole diameter of 0.8 micrometer, and produced the ink.
<Ink composition>
-Yellow pigment dispersion of Preparation Example 2 6.0 mass% (solid content)
-Silicone-modified acrylic resin fine particles of Synthesis Example 2 ... 1.0 mass%
・ 1,6-hexanediol ... 21.0% by mass
・ 2-Pyrrolidone: 2.0% by mass
・ Glycerin: 7.0% by mass
・ Surfactant (Softanol EP7025, manufactured by Nippon Shokubai Co., Ltd.) ... 1.0% by mass
・ 2-ethyl-1,3-hexanediol: 2.0% by mass
・ Ion exchange water: 60.0% by mass

(Example 12)
-Production of black pigment ink-
An ink composition having the following formulation was prepared and adjusted with a 10% by weight aqueous solution of lithium hydroxide so that the pH was 9. Then, it filtered with the membrane filter with an average hole diameter of 0.8 micrometer, and produced the ink.
<Ink composition>
-Carbon black pigment dispersion of Preparation Example 1 ... 13.0% by mass (solid content)
・ Silicone-modified acrylic resin fine particles of Synthesis Example 2 8.0 mass% (solid content)
・ Diethylene glycol: 14.0% by mass
・ Glycerin: 7.0% by mass
・ Surfactant (Softanol EP7025, manufactured by Nippon Shokubai Co., Ltd.) ... 1.0% by mass
・ 2-ethyl-1,3-hexanediol: 2.0% by mass
・ Ion exchange water: 55.0% by mass

( Reference Example 13)
-Production of black pigment ink-
An ink composition having the following formulation was prepared and adjusted with a 10% by weight aqueous solution of lithium hydroxide so that the pH was 9. Then, it filtered with the membrane filter with an average hole diameter of 0.8 micrometer, and produced the ink.
<Ink composition>
-Carbon black pigment dispersion of Preparation Example 1 ... 10.0% by mass (solid content)
-Silicone modified acrylic resin fine particles of Synthesis Example 2 0.5 mass% (solid content)
・ 3-methyl-1,3-butanediol ... 16.0% by mass
・ Glycerin: 5.0% by mass
・ Surfactant (Softanol EP7025, manufactured by Nippon Shokubai Co., Ltd.) ... 1.0% by mass
・ 2-ethyl-1,3-hexanediol: 2.0% by mass
・ Ion exchange water: 65.5% by mass

(Example 14)
-Production of black pigment ink-
An ink composition having the following formulation was prepared and adjusted with a 10% by weight aqueous solution of lithium hydroxide so that the pH was 9. Then, it filtered with the membrane filter with an average hole diameter of 0.8 micrometer, and produced the ink.
<Ink composition>
-Carbon black pigment dispersion of Preparation Example 1 ... 10.0% by mass (solid content)
-Silicone modified acrylic resin fine particles of Synthesis Example 3 8.0 mass%
・ 1,3-butanediol: 18.0% by mass
・ Glycerin: 6.0% by mass
・ Surfactant (Softanol EP7025, manufactured by Nippon Shokubai Co., Ltd.) ... 1.0% by mass
・ 2,2,4-Trimethyl-1,3-pentanediol: 2.0% by mass
・ Ion exchange water: 55.0% by mass

(Example 15)
-Production of black pigment ink-
An ink composition having the following formulation was prepared and adjusted with a 10% by weight aqueous solution of lithium hydroxide so that the pH was 9. Then, it filtered with the membrane filter with an average hole diameter of 0.8 micrometer, and produced the ink.
<Ink composition>
-Carbon black pigment dispersion of Preparation Example 1 ... 10.0% by mass (solid content)
-Silicone-modified acrylic resin fine particles in Synthesis Example 5: 8.0% by mass
・ 1,3-butanediol: 18.0% by mass
・ Glycerin: 6.0% by mass
・ Surfactant (Softanol EP7025, manufactured by Nippon Shokubai Co., Ltd.) ... 1.0% by mass
・ 2,2,4-Trimethyl-1,3-pentanediol: 2.0% by mass
・ Ion exchange water: 55.0% by mass

(Example 16)
-Production of black pigment ink-
An ink composition having the following formulation was prepared and adjusted with a 10% by weight aqueous solution of lithium hydroxide so that the pH was 9. Then, it filtered with the membrane filter with an average hole diameter of 0.8 micrometer, and produced the ink.
<Ink composition>
-Carbon black pigment dispersion of Preparation Example 1 ... 10.0% by mass (solid content)
-Silicone-modified acrylic resin of Synthesis Example 6: 5.0% by mass (solid content)
・ 1,6-hexanediol: 18.0% by mass
・ Glycerin: 6.0% by mass
・ 2-Pyrrolidone: 2.0% by mass
・ Surfactant (Softanol EP7025, manufactured by Nippon Shokubai Co., Ltd.) ... 1.0% by mass
・ 2,2,4-Trimethyl-1,3-pentanediol: 2.0% by mass
・ Ion exchange water: 56.0% by mass

(Example 17)
-Production of black pigment ink-
An ink composition having the following formulation was prepared and adjusted with a 10% by weight aqueous solution of lithium hydroxide so that the pH was 9. Then, it filtered with the membrane filter with an average hole diameter of 0.8 micrometer, and produced the ink.
<Ink composition>
-Carbon black pigment dispersion of Preparation Example 1 ... 10.0% by mass (solid content)
-Silicone-modified acrylic resin of Synthesis Example 7: 5.0% by mass (solid content)
・ 1,6-hexanediol: 18.0% by mass
・ Glycerin: 6.0% by mass
・ 2-Pyrrolidone: 2.0% by mass
・ Surfactant (Softanol EP7025, manufactured by Nippon Shokubai Co., Ltd.) ... 1.0% by mass
・ 2,2,4-Trimethyl-1,3-pentanediol: 2.0% by mass
・ Ion exchange water: 56.0% by mass

(Example 18)
-Manufacture of cyan pigment ink-
An ink composition having the following formulation was prepared and adjusted with a 10% by weight aqueous solution of lithium hydroxide so that the pH was 9. Then, it filtered with the membrane filter with an average hole diameter of 0.8 micrometer, and produced the ink.
<Ink composition>
-Cyan pigment polymer dispersion of Preparation Example 4 6.0 mass% (solid content)
Aqua Aqua Asi 91 (Daicel Chemical Industries, Ltd., silicone-modified acrylic resin: MFT = 25 ° C.) 4.0% by mass (solid content)
・ 1,6-hexanediol ... 20.0 mass%
・ Glycerin: 5.0% by mass
・ Surfactant (Softanol EP7025, manufactured by Nippon Shokubai Co., Ltd.) ... 1.0% by mass
・ 2-ethyl-1,3-hexanediol: 2.0% by mass
・ Ion exchange water: 62.0% by mass

(Example 19)
-Manufacture of cyan pigment ink-
An ink composition having the following formulation was prepared and adjusted with a 10% by weight aqueous solution of lithium hydroxide so that the pH was 9. Then, it filtered with the membrane filter with an average hole diameter of 0.8 micrometer, and produced the ink.
<Ink composition>
-Cyan pigment polymer dispersion of Preparation Example 4 6.0 mass% (solid content)
-Silicone-modified acrylic resin fine particles of Synthesis Example 2 ... 4.0% by mass (solid content)
・ 1,3-butanediol: 19.5% by mass
・ Glycerin: 6.5% by mass
・ Fluorosurfactant (Structural Formula 1 below): 1.0% by mass
・ 2-ethyl-1,3-hexanediol: 2.0% by mass
・ Ion exchange water: 61.0% by mass

However, in said structural formula (1), m represents 2 and n represents 10.

(Example 20)
-Production of black pigment ink-
An ink composition having the following formulation was prepared and adjusted with a 10% by weight aqueous solution of lithium hydroxide so that the pH was 9. Then, it filtered with the membrane filter with an average hole diameter of 0.8 micrometer, and produced the ink.
<Ink composition>
-Carbon black pigment dispersion of Preparation Example 1 8.0% by mass (solid content)
-Silicone-modified acrylic resin fine particles of Synthesis Example 2 6.0 mass% (solid content)
・ 1,3-butanediol ... 18.0 mass%
・ Glycerin: 6.0% by mass
・ Fluorosurfactant (Structural Formula 2 below): 1.0% by mass
・ 2-ethyl-1,3-hexanediol: 2.0% by mass
・ Ion exchange water: 59.0% by mass

In the structural formula (2), Rf represents CF ₂ CF ₃ . Note that m represents 21, n represents 4, and p represents 4.

(Example 21)
An ink composition having the following formulation was prepared and adjusted with a 10% by weight aqueous solution of lithium hydroxide so that the pH was 9. Then, it filtered with the membrane filter with an average hole diameter of 0.8 micrometer, and produced the ink.
<Ink composition>
-Carbon black pigment dispersion of Preparation Example ... 9.0% by mass (solid content)
-Silicone-modified acrylic resin fine particles of Synthesis Example 2 ... 2.0% by mass (solid content)
・ 1,6-pentanediol: 16.0% by mass
・ 2-Pyrrolidone: 2.0% by mass
・ Glycerin: 7.0% by mass
・ Fluorosurfactant (Structural Formula 3 below): 1.0% by mass
・ 2,2,4-Trimethyl-1,3-pentanediol ... 2.0% by mass
・ Ion exchange water: 61.0% by mass

In the structural formula (3), Rf represents CF ₂ CF ₃ . Note that q represents 6.

(Comparative Example 1)
-Manufacture of magenta pigment ink-
An ink composition having the following formulation was prepared and adjusted with a 10% by weight aqueous solution of lithium hydroxide so that the pH was 9. Then, it filtered with the membrane filter with an average hole diameter of 0.8 micrometer, and produced the ink.
<Ink composition>
-Magenta pigment dispersion of Preparation Example 3 6.0 mass% (solid content)
・ 1,6-hexanediol ... 20.0 mass%
・ Glycerin: 5.0% by mass
・ Surfactant (Softanol EP7025, manufactured by Nippon Shokubai Co., Ltd.) ... 1.0% by mass
・ 2-ethyl-1,3-hexanediol: 2.0% by mass
・ Ion-exchanged water: 66.0% by mass

(Comparative Example 2)
-Manufacture of cyan pigment ink-
An ink composition having the following formulation was prepared and adjusted with a 10% by weight aqueous solution of lithium hydroxide so that the pH was 9. Then, it filtered with the membrane filter with an average hole diameter of 0.8 micrometer, and produced the ink.
<Ink composition>
-Cyan pigment dispersion of Preparation Example 4. 6.0% by mass (solid content)
-Silicone-modified acrylic resin fine particles of Synthesis Example 4 ... 3.0% by mass (solid content)
・ 1,5-pentanediol ... 20.0 mass%
・ Glycerin: 6.0% by mass
・ Surfactant (Softanol EP7025, manufactured by Nippon Shokubai Co., Ltd.) ... 1.0% by mass
・ 2,2,4-Trimethyl-1,3-pentanediol: 2.0% by mass
・ Ion exchange water: 62.0% by mass

(Comparative Example 3)
-Production of black pigment ink-
An ink composition having the following formulation was prepared and adjusted with a 10% by weight aqueous solution of lithium hydroxide so that the pH was 9. Then, it filtered with the membrane filter with an average hole diameter of 0.8 micrometer, and produced the ink.
<Ink composition>
-Carbon black pigment dispersion of Preparation Example 1 ... 10.0% by mass (solid content)
Aquabrid 4720 (manufactured by Daicel Chemical Industries, Ltd., acrylic resin, MFT = 50 ° C.) 4.0% by mass (solid content)
・ 1,3-butanediol: 18.0% by mass
・ Glycerin: 6.0% by mass
・ Surfactant (Softanol EP7025, manufactured by Nippon Shokubai Co., Ltd.) ... 1.0% by mass
・ 2,2,4-Trimethyl-1,3-pentanediol: 2.0% by mass
・ Ion exchange water: 59.0% by mass

(Comparative Example 4)
-Production of black pigment ink-
An ink composition having the following formulation was prepared and adjusted with a 10% by weight aqueous solution of lithium hydroxide so that the pH was 9. Then, it filtered with the membrane filter with an average hole diameter of 0.8 micrometer, and produced the ink.
<Ink composition>
-Carbon black pigment dispersion of Preparation Example 1 ... 10.0% by mass (solid content)
・ Pesresin A210 (manufactured by Takamatsu Yushi Co., Ltd., polyester resin, MFT = 20 ° C. or less): 4.0% by mass (solid content)
・ 1,3-butanediol: 18.0% by mass
・ Glycerin: 6.0% by mass
・ Surfactant (Softanol EP7025, manufactured by Nippon Shokubai Co., Ltd.) ... 1.0% by mass
・ 2,2,4-Trimethyl-1,3-pentanediol: 2.0% by mass
・ Ion exchange water: 59.0% by mass

(Comparative Example 5)
-Manufacture of cyan pigment ink-
An ink composition having the following formulation was prepared and adjusted with a 10% by weight aqueous solution of lithium hydroxide so that the pH was 9. Then, it filtered with the membrane filter with an average hole diameter of 0.8 micrometer, and produced the ink.
<Ink composition>
-Cyan pigment dispersion of Preparation Example 4. 6.0% by mass (solid content)
-Silicone-modified acrylic resin fine particles of Synthesis Example 2 ... 3.0% by mass (solid content)
・ 1,5-pentanediol ... 20.0 mass%
・ Glycerin: 6.0% by mass
・ Surfactant (Softanol EP7025, manufactured by Nippon Shokubai Co., Ltd.) ... 1.0% by mass
・ Ion-exchanged water: 64.0% by mass

(Comparative Example 6)
-Production of black pigment ink-
An ink composition having the following formulation was prepared and adjusted with a 10% by weight aqueous solution of lithium hydroxide so that the pH was 9. Then, it filtered with the membrane filter with an average hole diameter of 0.8 micrometer, and produced the ink.
<Ink composition>
-Carbon black pigment dispersion of Preparation Example 1 8.0% by mass (solid content)
-Silicone-modified acrylic resin of Synthesis Example 2 ... 5.0% by mass (solid content)
・ 1,3-butanediol: 18.0% by mass
・ Glycerin: 6.0% by mass
・ Surfactant (Softanol EP7025, manufactured by Nippon Shokubai Co., Ltd.) ... 1.0% by mass
・ 3,3-dimethyl-1,2-butanediol ... 2.0% by mass
・ Ion exchange water: 60.0% by mass

Next, various properties of the recording inks of Examples 1 to 10 , 12 , 14 to 21 , Reference Examples 11 and 13 and Comparative Examples 1 to 6 obtained were evaluated as follows. The results are shown in Tables 1 to 3.

<Ink viscosity>
The ink viscosity in each recording ink was measured at 25 ° C. using an R-type viscometer (manufactured by Toki Sangyo Co., Ltd.).

<Amount of silicon (Si) in recording ink>
The amount of silicon (Si) in each recording ink was measured by a high frequency induction plasma emission analyzer.

<Volume average particle diameter of ink>
The volume average particle diameter (D50%) was measured using a particle size distribution measuring device (Microtrac UPA, manufactured by Nikkiso Co., Ltd.) for each recording ink.

<Image clarity>
The ink jet printer shown in FIGS. 3 to 5 is filled with inks of Examples 1 to 10 , 12 , 14 to 21 , Reference Examples 11 and 13, and Comparative Examples 1 to 6 , and Type 6200 paper (manufactured by NBS Ricoh Co., Ltd.). In addition, printing was performed at a resolution of 600 dpi. After the printing was dried, two colors were overlapped to visually observe boundary bleeding (bleeding) and image bleeding (feathering), and evaluated according to the following criteria. Further, the image density was measured using a reflection type color spectrophotometric densitometer (manufactured by X-Rite).
〔Evaluation criteria〕
○: A clear image with no blurring.
(Triangle | delta): Beard-like bleeding has generate | occur | produced in part.
X: The blur has occurred so that the outline of the character is not clear.

<Fixability>
The ink jet printer shown in FIGS. 3 to 5 is filled with inks of Examples 1 to 10 , 12 , 14 to 21 , Reference Examples 11 and 13, and Comparative Examples 1 to 6 , and Type 6200 paper (manufactured by NBS Ricoh Co., Ltd.). In addition, printing was performed at a resolution of 600 dpi. After the printing was dried, the printed portion was rubbed 10 times with a cotton cloth, and the transfer of the pigment onto the cotton cloth was visually observed and evaluated according to the following criteria.
〔Evaluation criteria〕
◎: Pigment transfer to cotton cloth is not seen at all ○: Pigment transfer to cotton cloth is hardly seen △: Some pigment transfer is seen ×: Clearly pigment is transferred

<Marker resistance>
The ink jet printer shown in FIGS. 3 to 5 is filled with inks of Examples 1 to 10 , 12 , 14 to 21 , Reference Examples 11 and 13, and Comparative Examples 1 to 6 , and Type 6200 paper (manufactured by NBS Ricoh Co., Ltd.). In addition, printing was performed at a resolution of 600 dpi. After the printing was dried, the printed portion was traced with a fluorescent marker (Made by Mitsubishi Pencil Co., Ltd., PROPUS2), and the degree of contamination generated by removing the pigment was visually observed and evaluated according to the following criteria.
〔Evaluation criteria〕
(Double-circle): The stain | pollution | contamination by discoloration is not seen at all.
◯: Almost no stain due to discoloration is observed.
Δ: Some dirt is seen.
X: Dirt spreads along the marker.

<Ink ejection properties>
The ink jet printer shown in FIGS. 3 to 5 is filled with inks of Examples 1 to 10 , 12 , 14 to 21 , Reference Examples 11 and 13, and Comparative Examples 1 to 6 , and Type 6200 paper (manufactured by NBS Ricoh Co., Ltd.). In addition, continuous 200 sheets were printed at a resolution of 600 dpi, and ejection disorder and ejection failure were evaluated according to the following criteria.
〔Evaluation criteria〕
A: Discharge turbulence or non-discharge is not observed at all.
○: Discharge turbulence or non-discharge is hardly observed.
Δ: Non-ejection and ejection disturbance of 3 nozzles or less.
X: There are non-ejection and ejection disturbance of 4 nozzles or more.

<Ink storage stability>
The inks of Examples 1 to 10 , 12 , 14 to 21 , Reference Examples 11 and 13 and Comparative Examples 1 to 6 were filled in a cartridge and stored at 50 ° C. for 3 weeks. Evaluation was made according to the criteria.
〔Evaluation criteria〕
A: No thickening or aggregation is observed.
○: Viscosity and aggregation are hardly observed.
Δ: Some thickening is observed.
X: Thickening and aggregation are remarkable.

<Double-sided printability>
The ink jet printer shown in FIGS. 3 to 5 is filled with each ink of Examples 1 to 10 , 12 , 14 to 21 , Reference Examples 11 and 13, and Comparative Examples 1 to 6 to Type 6200 (manufactured by NBS Ricoh Co., Ltd.). Printing was performed at a resolution of 600 dpi. Immediately after printing on one side, the paper was turned over through a dedicated unit and printed on the back side. This was carried out continuously for 100 sheets, and the paper stain generated by rubbing the ink not permeating when reversing and the transportability after reversal were evaluated according to the following criteria.
〔Evaluation criteria〕
○: Ink stains generated by rubbing during reversal are not observed.
Δ: No more than 10 sheets are rubbed during reversal to which ink adheres.
X: There are 11 or more sheets to which the ink adheres by rubbing during reversal.

In Example 10, since 1-amino-2,3-propanediol was added, it was recognized that the ink storage stability and the ink dischargeability were superior to those of other examples.

In Example 17, the volume-average particle size is 10 nm, and the silicone-modified acrylic resin fine particles of Synthesis Example 7 that do not contain a reactive silyl group are added. As a result of the large amount of surfactant contained in the ink coating film, sufficient film strength cannot be obtained, and the fixability and marker resistance are somewhat inferior to those of other examples.

The recording ink of the present invention is excellent in ejection stability and storage stability, quickly penetrates the recording medium to form a film, does not generate stains in high-speed printing or double-sided printing, and has excellent marker resistance, High-quality image recording with little bleeding is possible, and it can be suitably used for an ink cartridge, an ink recorded matter, an ink jet recording apparatus, and an ink jet recording method.
The ink jet recording apparatus and the ink jet recording method of the present invention can be applied to various types of recording by the ink jet recording method, and are particularly suitable for, for example, an ink jet recording printer, a facsimile apparatus, a copying apparatus, a printer / fax / copier multifunction machine, and the like. Can be applied to.

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

Explanation of symbols

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

Claims (23)

It contains at least water, a colorant, resin fine particles, a water-soluble organic solvent, and a penetrant, the penetrant is a diol compound having 7 to 11 carbon atoms, and the resin fine particles do not contain a hydrolyzable silyl group. Made of silicone-modified acrylic resin,
The content of the silicone-modified acrylic resin not containing the hydrolyzable silyl group, Ri 0.2-1.0 parts by der respect to the colorant, 1 part by mass the colorant is a pigment or colored fine particles A recording ink characterized by the above.   The recording ink according to claim 1, wherein the resin fine particles have a volume average particle diameter of 10 to 300 nm. The recording ink according to claim 1, wherein the minimum film-forming temperature (MFT) of the resin fine particles is 20 ° C. or less.   The recording ink according to claim 3, wherein the minimum film-forming temperature (MFT) of the resin fine particles is 0 ° C. or less. Water-soluble organic solvents are glycerin, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,3-butanediol, 2,3-butanediol, 1,4-butanediol, 3 -Methyl-1,3-butanediol, 1,5-pentanediol, tetraethylene glycol, 1,6-hexanediol, 2-methyl-2,4-pentanediol, polyethylene glycol, 1,2,4-butanetriol 1,2,6-hexanetriol,
The recording ink according to claim 1, which is at least one selected from thiodiglycol, 2-pyrrolidone, N-methyl-2-pyrrolidone, and N-hydroxyethyl-2-pyrrolidone. The pigment has at least one hydrophilic group on its surface and is water dispersible in the absence of a dispersant and
The recording ink according to claim 1, which is a pigment exhibiting at least one of water solubility. The diol compound having 7 to 11 carbon atoms is 2-ethyl-1,3-hexanediol and 2,
7. Any of 2,4-trimethyl-1,3-pentanediol
This is a recording ink. Containing a nonionic surfactant, the nonionic surfactant is an acetylene glycol type
Surfactant, polyoxyethylene alkyl ether, polyoxyethylene alkyl pheny
Ether, polyoxyethylene alkyl ester and polyoxyethylene sorbitan fat
The description according to any one of claims 1 to 7, which is at least one selected from fatty acid esters.
Ink for recording. The fluorine-containing surfactant is contained, and the fluorine-containing surfactant is at least one selected from the following structural formulas (1), (2), and (3). Description
Ink for recording.
However, in said structural formula (1), m represents the integer of 0-10. n is an integer from 1 to 40
To express.
However, in the structural formula (2), Rf is CF ₃ Or CF ₂ CF ₃ Represents. n = 4, m =
21, p = 4.
However, in the structural formula (3), Rf is CF ₃ Or CF ₂ CF ₃ Represents. q = 6 is represented. Containing an anionic surfactant, the anionic surfactant comprising polyoxyethylene alcohol
At least one selected from kill ether acetate and dialkylsulfosuccinate
The recording ink according to claim 1. The description according to any one of claims 1 to 10, further comprising an aminopropanediol compound.
Ink for recording. The viscosity of the recording ink at 25 ° C is 7 to 20 mPa · s.
The recording ink according to any one of the above. The solid content in the recording ink is 6 to 20% by mass.
The recording ink described. Small ink selected from cyan ink, magenta ink, yellow ink and black ink
The recording ink according to claim 1, wherein the recording ink is at least one kind. The recording ink according to claim 1 is contained in a container.
Ink cartridge. A stimulus is applied to the recording ink according to any one of claims 1 to 14, and the recording ink is used.
An ink jet comprising at least ink jetting means for flying to record an image
Jet recording device. 2. The stimulus is at least one selected from heat (temperature), pressure, vibration, and light.
6. An ink jet recording apparatus according to item 6. 17. A reversing means for reversing the recording surface of the recording medium to enable double-sided printing.
8. The ink jet recording apparatus according to any one of 7 above. An endless transport belt and the transport belt surface are charged and transported while holding the recording medium.
The ink jet recording apparatus according to claim 16, further comprising a conveying unit. A head and a sub-tank for supplying ink onto the head.
The ink is replenished from an ink cartridge through a supply tube.
An ink jet recording apparatus according to any one of the above. A stimulus is applied to the recording ink according to any one of claims 1 to 14, and the recording ink is used.
An ink jet comprising at least an ink flying step of flying to record an image
Recording method. 3. The stimulus is at least one selected from heat (temperature), pressure, vibration, and light.
2. The ink jet recording method according to 1. An image formed on the recording medium using the recording ink according to any one of claims 1 to 14.
An ink recorded matter comprising an image.