JP2015134890A - Ink, ink cartridge using the same and inkjet image formation apparatus - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an ink jet recording ink that enables a highly glossy and clear white image.SOLUTION: An ink jet recording ink contains: an aqueous medium; dispersant; a hollow resin particle; and an organic white pigment having a chemical structure expressed by a formula (I). [X is an identical or different H, a methyl group, an ethyl group, a methoxy group, an ethoxy group, a chlorine atom or a sulfone group; Ris an alkyl group, an alkenyl group, an aralkyl group, an aryl group or a cycloalkyl group; R-Rare each independently H or R. With regard to R-R, these two or three substituent groups may act with a nitrogen atom to form a heterocyclic group.]

Description

  The present invention relates to ink, an ink cartridge using the ink, and an inkjet image forming apparatus.

Demand for white ink is increasing as ink for inkjet recording. As a typical example, an ink using titanium oxide as a white color material has been developed (see, for example, Patent Document 1). However, when titanium oxide is used as the color material, the specific gravity of the color material particles of titanium oxide is very large compared to water or solvent used in the aqueous medium, so that the ink tends to settle. There were problems such as clogging at the discharge nozzles of the recording head provided as a flying means.
In order to improve the clogging problem at the discharge nozzle due to the sedimentation of the color material in the ink, it has been studied to reduce the difference in specific gravity between the color material and the solvent.
For example, Patent Document 2 proposes a white pigment composition in which a color material is an organic substance (a compound having a specific structure).
In addition, as another method of using a coloring material as an organic material, use of an organic resin having a hollow structure has been studied. For example, Patent Document 3 proposes that a hollow body in which the surface of a hollow base particle made of a highly crosslinked polymer is coated with a copolymer of an unsaturated carboxylic acid monomer and another monomer is used as a coloring material for white ink. Yes.

According to the white pigment composition of Patent Document 2, the film quality (gloss) of the coating film is good, but sufficient concealability cannot be obtained, and there is a problem in practicality. On the other hand, according to the organic resin having a hollow structure of Patent Document 3, the concealability is sufficient, but since the gloss of the image is low, improvement has been demanded.
The present invention has been made in view of the above prior art, and an object of the present invention is to provide an ink that has a high concealment ratio of a printed image and can obtain a clear white image with high gloss.

As a result of intensive studies by the present inventors, the above-mentioned problem can be obtained by using hollow resin particles and an organic white pigment in combination as a color material (white color material) contained as an ink component, so-called ink composition. And the present invention has been completed.
That is, the above-mentioned problem is an ink comprising an aqueous medium, a dispersant, and a color material as components, and the white material has hollow resin particles and an organic white pigment having a chemical structure represented by the following general formula (I) It is solved by the ink characterized by containing.

[In the formula (I), X represents the same or different hydrogen atom, methyl group, ethyl group, methoxy group, ethoxy group, chlorine atom, sulfone group, and R ₁ represents an alkyl group, alkenyl group, aralkyl group, aryl group. Or a cycloalkyl group, R ₂ , R ₃ and R ₄ independently of each other represent a hydrogen atom or R ₁ , and R ₂ , R ₃ and R ₄ are combined with these two or three substituents. A heterocyclic group may be formed together with the nitrogen atom. ]

  According to the present invention, there is provided an ink that has a high concealment ratio of a printed image and can obtain a clear white image with high gloss.

1 is an explanatory perspective view of an inkjet image forming apparatus according to the present invention. It is a schematic sectional drawing explaining the whole structure of the mechanism part of the inkjet image forming apparatus shown in FIG. FIG. 3 is a schematic plan view of a main part of the mechanism part of FIG. 2. It is the plane schematic which shows the detail of the mechanism part of an inkjet image forming apparatus separately.

  As described above, the ink in the present invention is an ink comprising an aqueous medium, a dispersant, and a color material as components, and the color material has hollow resin particles and a chemical structure represented by the following general formula (I). It contains the organic white pigment which has.

[In the formula (I), X represents the same or different hydrogen atom, methyl group, ethyl group, methoxy group, ethoxy group, chlorine atom, sulfone group, and R ₁ represents an alkyl group, alkenyl group, aralkyl group, aryl group. Or a cycloalkyl group, R ₂ , R ₃ and R ₄ independently of each other represent a hydrogen atom or R ₁ , and R ₂ , R ₃ and R ₄ are combined with these two or three substituents. A heterocyclic group may be formed together with the nitrogen atom. ]

Below, the form for implementing this invention is demonstrated.
Note that it is easy for a person skilled in the art to make other embodiments by changing or correcting the present invention within the scope of the claims, and these changes and modifications are included in the scope of the claims. The following description exemplifies an embodiment of the present invention, and does not limit the scope of the claims.

The application of the ink of the present invention is not particularly limited, but it can be preferably used as an ink for ink jet recording. Hereinafter, “ink” may be referred to as “ink-jet recording ink”.
The composition of the ink of the present invention (inkjet recording ink) includes an aqueous medium, a dispersant, and a coloring material. As the coloring material (hereinafter sometimes referred to as “white coloring material”), hollow resin particles are used. And an organic white pigment having a chemical structure represented by the general formula (I).
Thus, by using together the hollow resin particles and the organic white pigment having the chemical structure represented by the general formula (I) as the white color material, the concealability and gloss of the printed image are compatible. That is, the color material (white color material) composed of the hollow resin particles and the organic white pigment has high dispersion stability in the ink, the color material does not settle during the storage period of the ink, and the printed image is The concealment rate of the color material is improved, and a clear white image with high glossiness can be obtained.

As the components constituting the ink of the present invention, so-called components, aqueous media (water and water-soluble organic solvents), dispersants (water-soluble resins and water-soluble surfactants), and coloring materials (hollow resin particles and the above general formula (I) ) Organic white pigments having a chemical structure represented by)), but if necessary, a film-forming resin, a penetrating agent, an image preservability improving agent (such as a hindered amine, an ultraviolet absorber, an antioxidant), Other components (pH adjuster, antiseptic / antifungal agent, chelating reagent, rust preventive agent, oxygen absorber, light stabilizer, etc.) can be contained.
Hereinafter, components constituting the ink of the present invention will be described. The “organic white pigment having the chemical structure represented by the general formula (I)” may be abbreviated as “pigment”.

[Hollow resin particles]
Since it is desired that the hollow resin particles used in the ink of the present invention do not precipitate in the ink, those having a specific gravity substantially equal to the specific gravity of the ink are preferable.
When using resin fine particles that do not have a hollow structure, in order to avoid sedimentation, it is necessary to match the specific gravity of the resin fine particles to the ink. In this case, the resin composition is examined, the polymerization (crosslinking) reaction is controlled, Since it is necessary to comprehensively control the particle size, the technical barrier becomes high.
On the other hand, if hollow resin particles are used, the portion of the ink that was hollow at the time of drying is filled with the ink, that is, the vehicle. Therefore, the density of the hollow resin particles can be regarded as almost the same as that of the ink, and the sedimentation occurs. More suppressed.

Examples of the resin composition of the hollow resin particles used in the present invention include acrylic resins such as acrylic resins, styrene-acrylic resins, and cross-linked styrene-acrylic resins, urethane resins, maleic resins, and the like. These hollow resin particles may be used alone or in combination.
The volume average particle diameter of the hollow resin particles is 0.2 μm to 1.0 μm in consideration of the concealment property of the printed image and the clogging of the ink flow path and the nozzle of the recording head in the inkjet image forming apparatus. Is more preferable, and 0.3 μm to 0.8 μm is more preferable.
In addition, the measurement of a volume average particle diameter can be performed by Microtrac UPA-EX150 (made by Nikkiso Co., Ltd.), for example.

  It does not specifically limit as a hollow resin particle used by this invention, A well-known thing can be used and what is marketed can also be used. As the commercially available hollow resin particles, for example, those composed of styrene-acrylic resin, MH5055 [manufactured by Nippon Zeon Co., Ltd.], Ropaque OP-62, OP-84J, OP-91, HP -1055, HP-91, ULTRA (above, manufactured by Rohm and Haas Co., Ltd.) and SX-863 (A), SX-864 (B), SX -866 (A), SX-866 (B), SX-868 [above, manufactured by JSR Corporation], Ropaque ULTRA E, ULTRA DUAL (above, manufactured by Rohm and Haas) and the like.

[Organic white pigment]
As the organic white pigment used in the present invention, a bis-stilbene pigment having a chemical structure represented by the following structural formula (I) is preferably used.

[In the formula (I), X represents the same or different hydrogen atom, methyl group, ethyl group, methoxy group, ethoxy group, chlorine atom, sulfone group, and R ₁ represents an alkyl group, alkenyl group, aralkyl group, aryl group. Or a cycloalkyl group, R ₂ , R ₃ and R ₄ independently of each other represent a hydrogen atom or R ₁ , and R ₂ , R ₃ and R ₄ are combined with these two or three substituents. A heterocyclic group may be formed together with the nitrogen atom. ]

  In the above general formula (I), specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a dodecyl group, an octadecyl group, and the like, and examples of the alkenyl group include an ethylene group and a propylene group. Examples of the aralkyl group include a benzyl group. Examples of the aryl group include a phenyl group, a biphenyl group, and a naphthyl group. Examples of the cycloalkyl group include a cyclohexyl group. Includes a pyridyl group, a pyrrolidyl group, a piperidino group, a morpholino group, and the like.

The organic white pigment having the chemical structure represented by the general formula (I) is not limited, but can be obtained by, for example, the following production method.
First, the sodium salt of the anion component of the general formula (I) (compound having a bisstyryl biphenyl structure) is added to water and dissolved under heating (about 60 ° C.). Next, a quaternary ammonium compound [used as a cation component in the general formula (I)] dissolved in water is injected into the heated melt. In this case, the addition amount of the quaternary ammonium compound is equivalent or excessive to the sodium salt of the compound having a bisstyryl biphenyl structure. After the injection of the quaternary ammonium compound, the reaction is completed by heating and stirring (about 60 ° C.) for about 1 hour. A white precipitate is deposited. Subsequently, the deposited precipitate is filtered off, sufficiently washed with water and dried to obtain the target composite salt.
In addition, as a quaternary ammonium compound used as the cation component of the general formula (I), R ₁ is an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a dodecyl group, an octadecyl group, an ethylene group, 5-membered formed with alkenyl group such as propylene group, aralkyl group such as benzyl group, aryl group such as phenyl group or cycloalkyl group such as cyclohexyl group, or N atom such as pyrrolidine, piperidine, morpholine or pyridine Or a 6-membered heterocyclic group, R ₂ , R ₃ and R ₄ are each independently a hydrogen atom or a group listed for R ₁ , or R ₂ , R ₃ and R ₄ Those in which two or three substituents are heterocyclic groups formed together with a nitrogen atom are used. The quaternary ammonium compound comprises a halogen atom, preferably a chlorine atom, which forms a salt.

The volume average particle diameter of the organic white pigment is preferably 0.01 μm to 0.7 μm, more preferably 0.01 μm to 0.6 μm, and particularly preferably 0.1 μm to 0.5 μm. When the average particle size is 0.1 μm or more, more concealment can be ensured, and light resistance and feathering do not deteriorate. Further, when the thickness is 0.5 μm or less, the discharge port is not clogged and the filter in the printer is not further clogged, and the discharge stability can be obtained.
In addition, the measurement of a volume average particle diameter can be performed by Microtrac UPA-EX150 (made by Nikkiso Co., Ltd.), for example.

The blending ratio [organic white pigment] / [hollow resin particles] (mass ratio) of the organic white pigment and the hollow resin particles is preferably 0.5 / 1 to 3/1.
When the blending ratio of the organic white pigment and the hollow resin particles is in the above range, the concealment property and glossiness of the printed image can be maintained in a good balance.
Moreover, it is preferable that the total compounding quantity of the said organic white pigment and hollow resin particle is 5.0-12.0 mass parts in 100 mass parts of the total ink composition.
When the total blending amount of the organic white pigment and the hollow resin particles is within the above range, a clear white image with high gloss and high gloss can be obtained.

[Dispersant]
The organic white pigments (abbreviations, pigments) listed above can be made into inks by dispersing them in an aqueous medium (water and a water-soluble organic solvent) using a dispersant. As a dispersant for dispersing the powder made of such an organic pigment, a normal water-soluble resin or a surfactant (water-soluble surfactant) can be used.
Specific examples of water-soluble resins include styrene, styrene derivatives, vinyl naphthalene derivatives, aliphatic alcohol esters of α, β-ethylenically unsaturated carboxylic acids, acrylic acid, acrylic acid derivatives, maleic acid, maleic acid derivatives, itacon. Polymeric dispersants such as block copolymers composed of at least two monomers selected from acids, itaconic acid derivatives, fumaric acid, fumaric acid derivatives, etc., random copolymers, or salts thereof It is done.
These water-soluble resins are alkali-soluble resins that are soluble in an aqueous solution in which a base is dissolved. Among these, those having a weight average molecular weight of 3000 to 20000 are used as inks for inkjet recording. It is particularly preferred because of the advantages that it can be reduced in viscosity and can be easily dispersed.

The simultaneous use of the polymer dispersant and the self-dispersing pigment is a preferable combination because an appropriate dot diameter can be obtained. The reason is not clear, but it is thought as follows.
By containing the polymer dispersant, the penetration into the recording medium (recording paper) is suppressed. On the other hand, since the aggregation of the self-dispersing pigment is suppressed by containing the polymer dispersant, the self-dispersing pigment can smoothly spread in the lateral direction. Therefore, it is considered that the dots spread widely and thinly and ideal dots can be formed.

  As the surfactant used in the ink of the present invention, an anionic surfactant or a nonionic surfactant (nonionic surfactant), an amphoteric surfactant, an acetylene glycol surfactant, a fluorine interface An activator, a silicone surfactant, or the like is used. A surfactant that does not impair the dispersion stability is selected depending on the combination of the color material, the wetting agent and the water-soluble organic solvent.

  Examples of the anionic surfactant include polyoxyethylene alkyl ether acetate, dodecylbenzene sulfonate, oxalate sulfonate, laurate, and polyoxyethylene alkyl ether sulfate salt.

  Examples of the nonionic surfactant include polyoxyethylene alkyl ether, polyoxyethylene polyoxypropylene alkyl ether, polyoxyethylene alkyl ester, polyoxyethylene polyoxypropylene alkyl ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene Examples thereof include ethylene alkyl phenyl ether, polyoxyethylene alkyl amine, and polyoxyethylene alkyl amide.

  Examples of amphoteric surfactants include lauryl aminopropionate, lauryl dimethyl betaine, stearyl dimethyl betaine, and lauryl dihydroxyethyl betaine. Specific examples below are preferably used, but are not limited thereto. Examples include lauryl dimethylamine oxide, myristyl dimethylamine oxide, stearyl dimethylamine oxide, dihydroxyethyl lauryl amine oxide, polyoxyethylene coconut oil alkyl dimethyl amine oxide, dimethyl alkyl (coconut) betaine, and dimethyl lauryl betaine.

  Examples of acetylene glycol surfactants include 2,4,7,9-tetramethyl-5-decyne-4,7-diol, 3,6-dimethyl-4-octyne-3,6-diol, 3,5- An acetylene glycol type such as dimethyl-1-hexyn-3-ol (for example, Surfynol 104, 82, 465, 485 or TG from Air Products (USA)) can be used.

  Fluorosurfactants include perfluoroalkyl sulfonate, perfluoroalkyl carboxylate, perfluoroalkyl phosphate ester, perfluoroalkyl ethylene oxide adduct, perfluoroalkyl betaine, perfluoroalkylamine oxide compounds, Examples thereof include polyoxyalkylene ether polymers having a fluoroalkyl ether group in the side chain, sulfate salts thereof, and fluorine-based aliphatic polymer esters.

  Examples of such commercially available fluorosurfactants include Surflon S-111, S-112, S-113, S121, S131, S132, S-141, S-145 (manufactured by Asahi Glass Co., Ltd.), and fullrad. FC-93, FC-95, FC-98, FC-129, FC-135, FC-170C, FC-430, FC-431, FC-4430 (manufactured by Sumitomo 3M), FT-110, 250, 251, 400S (manufactured by Neos), Zonyl FS-62, FSA, FSE, FSJ, FSP, TBS, UR, FSO, FSO-100, FSN N, FSN-100, FS-300, FSK (manufactured by Dupont), Polyfox Examples thereof include PF-136A, PF-156A, and PF-151N (manufactured by OMNOVA).

  The silicone surfactant is not particularly limited and may be appropriately selected depending on the intended purpose. However, those which do not decompose even at a high pH are preferable. For example, side chain modified polydimethylsiloxane, both end modified polydimethyl Examples include siloxane, one-end-modified polydimethylsiloxane, and side-chain both-end-modified polydimethylsiloxane, and polyether-modified silicone surfactants having a polyoxyethylene group or a polyoxyethylene polyoxypropylene group as a modifying group are water-based interfaces. It is particularly preferred because it exhibits good properties as an activator.

  The polyether-modified silicone surfactant is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a polyalkylene oxide structure represented by the following structural formula (II) is converted to Si of dimethylpolysiloxane. And compounds introduced into the partial side chain.

  [In the structural formula (II), m, n, a, and b represent integers. R and R ′ each represent an alkylene group and an alkyl group. ]

  A commercial item can be used as said polyether modified silicone type surfactant, For example, KF-618, KF-642, KF-643 (all are the Shin-Etsu Chemical Co., Ltd. product) etc. are mentioned.

  The above-mentioned various surfactants are not limited to these, and may be used alone or in combination. Even when the surfactant alone is not easily dissolved in the ink, it can be solubilized by mixing to exist stably.

  The total content of the surfactant in the ink is desirably 0.01 to 5% by mass in order to exert a penetrating effect. When the total content of the surfactant is 0.01% by mass or more, the effect of addition is obtained, and when the total content is 5% by mass or less, the permeability to the recording medium is not increased more than necessary, and the image density is increased. There will be no problems such as lowering of image quality or occurrence of strikethrough. In order to cope with many commercially available papers, 0.5 to 2% by mass is more preferable.

The composition constituting the ink of the present invention includes water and an aqueous medium such as a water-soluble organic solvent.
〔water〕
As water, ion-exchanged water is preferably used and used together with the following water-soluble organic solvent.
(Water-soluble organic solvent)
Examples of the water-soluble organic solvent include polyhydric alcohols, polyhydric alcohol alkyl ethers, polyhydric alcohol aryl ethers, nitrogen-containing heterocyclic compounds, amides, amines, sulfur-containing compounds, propylene carbonate, and ethylene carbonate. Is mentioned.
Preferable water-soluble organic solvents include polyhydric alcohols having an equilibrium water content in an environment of 23 ° C. and 80% of 30% by mass or more.

  Specific examples thereof include 1,2,3-butanetriol (38% by mass), 1,2,4-butanetriol (41% by mass), glycerin (49% by mass), diglycerin (38% by mass), tri Examples include ethylene glycol (39% by mass), tetraethylene glycol (37% by mass), diethylene glycol (43% by mass), and 1,3-butanediol (35% by mass). Among these, glycerin and 1,3-butanediol are particularly preferably used because they can reduce the viscosity when containing water.

  When such a water-soluble organic solvent is used in an amount of 10% by mass or more of the whole ink, the waste ink in the maintaining device provided in the ink ejection device and the ejection stability ensuring of the ink ejected from the recording head of the inkjet image forming apparatus This is preferable because it is excellent in preventing sticking. The content of the water-soluble organic solvent in the ink is preferably about 10 to 50% by mass with respect to the total amount of the ink. If it is the said range, it will become possible to ensure solubility and it can prevent the discharge failure of the ink resulting from precipitation of solid content, such as a pigment.

  Further, if necessary, a water-soluble solvent having an equilibrium water content of less than 30% by mass can be used. Examples include polyhydric alcohols, polyhydric alcohol alkyl ethers, polyhydric alcohol aryl ethers, cyclic ethers, amines, amides, sulfur-containing compounds, propylene carbonate, ethylene carbonate, and other water-soluble organic solvents. Can be mentioned.

  Examples of the polyhydric alcohols include ethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, 3-methyl-1,3-butanediol, 1,5-pentanediol, 2- Methyl-2,4-pentanediol, hexylene glycol, 1,6-hexanediol, 1,2,6-hexanetriol, trimethylolethane, trimethylolpropane, 3-methyl-1,3-hexanediol, propylpropylene Diglycol etc. are mentioned.

  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, ethylene glycol mono-2-ethylhexyl ether, propylene glycol monoethyl ether. And triethylene glycol dimethyl ether.

Examples of the polyhydric alcohol aryl ethers include ethylene glycol monophenyl ether and ethylene glycol monobenzyl ether.
Examples of the cyclic ethers include epoxies, oxetanes, tetrahydrofurans, tetrahydropyrans, and crown ethers. Oxetanes and tetrahydrofurans are preferred in the present invention, and oxetanes are desirable from the viewpoint of water solubility.
Examples of the amines include monoethanolamine, diethanolamine, triethanolamine, N, N-dimethylmonoethanolamine, N-methyldiethanolamine, N-methylethanolamine, N-phenylethanolamine, and 3-aminopropyldiethylamine. Is mentioned.

Examples of the amide compounds include 2-pyrrolidone, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, ε-caprolactam, γ-butyrolactone, β-methoxy-N, N-dimethylpropionamide. , Β-butoxy-N, N-dimethylpropionamide and the like.
Formamide, N-methylformamide, N, N-dimethylformamide, and N, N-diethylformamide also exist as amide compounds, but they are highly harmful and are not preferred for use.
The amide compound has the effect of solubilizing the dye and has the effect of suppressing crystal precipitation when the ink is dried.
Examples of the sulfur-containing compounds include dimethyl sulfoxide, sulfolane, thiodiglycol, and the like.
Such a water-soluble organic solvent is preferably added in an amount of 0 to 30% by mass with respect to the ink.

  10-50 mass% is preferable and, as for the total content in the ink of the water-soluble organic solvent, 15-40 mass% is more preferable. When the content is 10% by mass or more, the ejection stability of the ink ejected from the recording head does not decrease, and the non-volatile component is deposited and fixed by the maintenance device in the inkjet image forming apparatus. There is nothing to do. In addition, when the content is 50% by mass or less, the deposition of non-volatile components is not caused by a slight drying, and the drying property on the recording medium is improved, and the glossy paper-like color is improved. It does not take time to stabilize.

[Film-forming resin]
The ink of the present invention preferably contains a film-forming resin. The film-forming resin is preferably present as a resin emulsion dispersed in water as a continuous phase.
The type of film-forming resin is not particularly limited and can be appropriately selected according to the purpose. For example, urethane resin, polyester resin, acrylic resin, vinyl acetate resin, styrene resin, butadiene resin, Examples thereof include styrene-butadiene resin, vinyl chloride resin, acrylic styrene resin, acrylic silicone resin, and the like.

  As said film forming resin, what was synthesize | combined suitably may be used and a commercial item may be used. Examples of commercially available film-forming resins include Microgel E-1002, E-5002 (styrene-acrylic resin fine particles: manufactured by Nippon Paint Co., Ltd.), and Boncoat 4001 (acrylic resin fine particles: Dainippon Ink & Chemicals, Inc.). Manufactured), Boncoat 5454 (styrene-acrylic resin fine particles: manufactured by Dainippon Ink and Chemicals, Inc.), SAE-1014 (styrene-acrylic resin fine particles: manufactured by Nippon Zeon Co., Ltd.), Cybinol SK-200 (acrylic resin fine particles) : Seiden Chemical Co., Ltd.), Primal AC-22, AC-61 (acrylic resin fine particles: manufactured by Rohm and Haas), Nanoacryl SBCX-2821, 3689 (acrylic silicone resin fine particles: manufactured by Toyo Ink Manufacturing Co., Ltd.) , # 3070 (methyl methacrylate polymer tree Particles: manufactured by Mikuni Color Co., Ltd.), and the like.

Among these film-forming resins, acrylic resins and urethane resins that are particularly excellent in fixability and ink stability are more preferable. In addition, the film-forming resin may contain a dispersant such as a surfactant as necessary, but from the viewpoint of easily obtaining an ink having a better coating film performance, a so-called self-emulsifying type may be used. Emulsions are preferred.
In that case, it is preferable from the viewpoint of water dispersibility that an anionic group is contained in the range of 5 to 100 mgKOH / g, and 5 to 50 mgKOH / mg gives excellent scratch resistance and chemical resistance. This is particularly preferable.
In addition, when the anionic group is, for example, a carboxyl group or a sulfonic acid group, good water dispersion stability can be obtained. In order to introduce these anionic groups into the resin, monomers having these anionic groups may be used.

Further, the particle diameter of the film-forming resin is preferably 10 to 1,000 nm, more preferably 10 to 200 nm, and further preferably 10 to 50 nm, particularly considering use in an ink jet recording apparatus. By using resin fine particles having a volume average particle size of 10 to 50 nm, the film forming property of the resin is enhanced, and a continuous film of tough resin is formed, so that a printed matter with high strength can be obtained.
Here, the volume average particle diameter can be measured using, for example, a particle size analyzer (Microtrac Model UPA9340, manufactured by Nikkiso Co., Ltd.).

  The content of the film-forming resin is preferably in the range of 1 to 10% by mass with respect to the total amount of ink in terms of fixability and ink stability, and the range of 5 to 10% by mass improves the smoothness of the ink layer and is high. It is more preferable because glossiness can be obtained and fixability to a substrate is improved.

(Penetration agent)
The penetrant used in the ink desirably contains at least one polyol having a solubility in water at 20 ° C. of 0.2% by mass or more and less than 5.0% by mass.
Among such polyols, aliphatic diols include 2-ethyl-2-methyl-1,3-propanediol, 3,3-dimethyl-1,2-butanediol, and 2,2-diethyl-1,3. -Propanediol, 2-methyl-2-propyl-1,3-propanediol, 2,4-dimethyl-2,4-pentanediol, 2,5-dimethyl-2,5-hexanediol, 5-hexene-1 , 2-diol, 2-ethyl-1,3-hexanediol and the like. Of these, the most desirable are 2-ethyl-1,3-hexanediol and / or 2,2,4-trimethyl-1,3-pentanediol.

Other penetrants that can be used in combination include polyethylene alcohols such as diethylene glycol monophenyl ether, ethylene glycol monophenyl ether, ethylene glycol monoallyl ether, diethylene glycol monophenyl ether, diethylene glycol monobutyl ether, propylene glycol monobutyl ether, and tetraethylene glycol chlorophenyl ether. Examples thereof include alkyl and aryl ethers, lower alcohols such as ethanol, and the like, but are not limited thereto as long as they can be dissolved in ink and adjusted to desired physical properties.
The amount of penetrant added is preferably in the range of 0.1 to 4.0% by mass with respect to the total amount of ink. When the addition amount is 0.1% by mass or more, quick drying is obtained, so that a blurred image does not occur. Further, when the addition amount is 4.0% or less, the dispersion stability of the colorant is improved, the nozzle of the recording head is not clogged, and the permeability to the recording medium is unnecessarily high. There is no problem such as a decrease in image density and occurrence of show-through.

<Image preservability improver>
Examples of the image preservability improver used in the ink of the present invention include hindered amines, ultraviolet absorbers, and antioxidants. Since an inkjet recording image is greatly affected by light and gas, it is preferable to add a hindered amine or an ultraviolet absorber.

[Hindert amine]
As the hindered amine used in the present invention, any of N—CH ₃ type, N—H type, and N—OR type can be used, but N—CH ₃ type and N—OR type are preferable. Some of these hindered amines are miscible with water by mixing with butyl carbitol or butyl cellosolve, but are preferably water-insoluble liquids or powders dispersed therein.
Examples of such hindered amines dispersed in water include TINUVIN 123DW manufactured by BASF, Adecanol UC-5225 and Adecanol UC-606 manufactured by ADEKA.
The amount of hindered amine added to the ink depends on the concentration of the dye to be protected, and the amount of the active ingredient is preferably 1% by mass to 10% by mass with respect to the solid content of the color material, and 2% by mass to 7%. The mass% is more preferable.

[Ultraviolet absorber]
Examples of the ultraviolet absorber include benzophenone ultraviolet absorbers, benzotriazole ultraviolet absorbers, salicylate ultraviolet absorbers, hydroxyphenyltriazine ultraviolet absorbers, cyanoacrylate ultraviolet absorbers, nickel complex ultraviolet absorbers, Etc.

  Examples of the benzophenone-based ultraviolet absorber include 2-hydroxy-4-n-octoxybenzophenone, 2-hydroxy-4-n-dodecyloxybenzophenone, 2,4-dihydroxybenzophenone, and 2-hydroxy-4-methoxybenzophenone. 2,2 ′, 4,4′-tetrahydroxybenzophenone, and the like.

  Examples of the benzotriazole ultraviolet absorber include 2- (2′-hydroxy-5′-tert-octylphenyl) benzotriazole, 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-4′-octoxyphenyl) benzotriazole, 2- (2′-hydroxy-3′-tert-butyl-5′-methylphenyl) -5-chlorobenzotriazole, and the like.

  Examples of the salicylate-based ultraviolet absorber include phenyl salicylate, p-tert-butylphenyl salicylate, p-octylphenyl salicylate, and the like.

  Examples of the cyanoacrylate ultraviolet absorber include ethyl-2-cyano-3,3′-diphenyl acrylate, methyl-2-cyano-3-methyl-3- (p-methoxyphenyl) acrylate, and butyl-2- And cyano-3-methyl-3- (p-methoxyphenyl) acrylate.

  Examples of the nickel complex ultraviolet absorber include nickel bis (octylphenyl) sulfide, 2,2′-thiobis (4-tert-octylferrate) -n-butylamine nickel (II), 2,2′-thiobis. (4-tert-octylferrate) -2-ethylhexylamine nickel (II), 2,2′-thiobis (4-tert-octylferrate) triethanolamine nickel (II), and the like.

Of these, hydroxyphenyltriazine and benzotriazole are preferred, and these aqueous dispersions are preferred for addition to water-based inks.
Examples of such water-dispersed products include TINUVIN 1130, TINUVIN 99DW, TINUVIN 400DW, TINUVIN 477DW, and UC-3140 from ADEKA, among which TINUVIN 477DW is particularly preferable.

  The amount of the ultraviolet absorber added to the ink depends on the color material concentration to be protected, and the amount of the active ingredient is desirably 1% by mass to 10% by mass with respect to the solid content of the color material, and 2% by mass to 7 mass% is more preferable.

〔Antioxidant〕
Examples of the antioxidant include phenolic antioxidants (including hindered phenolic antioxidants), amine-based antioxidants, sulfur-based antioxidants, phosphorus-based antioxidants, and the like.
Examples of the phenolic antioxidant (including hindered phenolic antioxidant) 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-tri (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) propio Nate] methane, 1,1,3-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, and 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.
Since both are poorly water-soluble, it is preferable to add to the ink using a water dispersion. ADEKA SDX-2855 is such an aqueous dispersion.
The addition amount of the antioxidant to the ink is desirably 0 to 10% by mass with respect to the total amount of the ink, and can be added as necessary.

<Other ingredients>
Other components are not particularly limited and may be appropriately selected as necessary. Examples thereof include pH adjusters, antiseptic / antifungal agents, chelating reagents, rust preventive agents, oxygen absorbers, and light stabilizers. It is done.

[PH adjuster]
The pH adjuster is not particularly limited as long as the pH can be adjusted to 7 to 11, and can be appropriately selected according to the purpose. For example, alcohol amines, alkali metal hydroxides, ammonium Hydroxides, phosphonium hydroxides, alkali metal carbonates, and the like.
When the pH is less than 7 or more than 11, the amount of the recording head and the ink supply unit of the inkjet image forming apparatus that melts out is large, and problems such as ink deterioration, leakage, and ejection failure may occur. Examples of the alcohol amines include diethanolamine, triethanolamine, 2-amino-2-ethyl-1,3-propanediol, and the like.
Examples of the alkali metal hydroxide include lithium hydroxide, sodium hydroxide, and potassium hydroxide.
Examples of the ammonium hydroxide include ammonium hydroxide and quaternary ammonium hydroxide.
Examples of the phosphonium hydroxide include quaternary phosphonium hydroxide.
Examples of the alkali metal carbonate include lithium carbonate, sodium carbonate, and potassium carbonate.

[Antiseptic and antifungal agent]
Examples of antiseptic and antifungal agents include sodium dehydroacetate, sodium sorbate, 2-pyridinethiol-1-oxide sodium, sodium benzoate, sodium pentachlorophenol, and the like.
[Chelating reagent]
Examples of the chelating reagent include sodium ethylenediaminetetraacetate, sodium nitrilotriacetate, sodium hydroxyethylethylenediaminetriacetate, sodium diethylenetriaminepentaacetate, sodium uramil diacetate, and the like.
[Rust preventive]
Examples of the rust inhibitor include acidic sulfite, sodium thiosulfate, ammonium thiodiglycolate, diisopropylammonium nitrite, pentaerythritol tetranitrate, and dicyclohexylammonium nitrite.

[Ink manufacturing method]
The ink of the present invention comprises a dispersant and a coloring material (hollow resin particles and an organic white pigment having a chemical structure represented by the general formula (I)) and other components selected as necessary in an aqueous medium. Manufactured by dispersing or dissolving.
That is, first, an organic white pigment having a chemical structure represented by the general formula (I), a surfactant, and water (ion-exchanged water) were mixed to form a primary pigment dispersion, and this primary pigment dispersion was prepared in advance. A polymer dispersion stabilizer solution is added and stirred sufficiently to obtain a pigment dispersion. Next, the obtained pigment dispersion, hollow resin particles, film-forming resin (emulsion), penetrant, and other components as necessary are dispersed or dissolved in an aqueous medium (water and water-soluble organic solvent). Then, the mixture is appropriately mixed with stirring.
The stirring and mixing can be performed, for example, with a sand mill, a homogenizer, a ball mill, a paint shaker, an ultrasonic disperser, or the like, and can be performed with a stirrer using a normal stirring blade, a magnetic stirrer, a high-speed disperser, or the like.

[Ink properties]
The physical properties of the ink are not particularly limited and may be appropriately selected depending on the intended purpose. For example, the viscosity and surface tension are preferably in the following ranges.
The viscosity of the ink at 25 ° C. is preferably 2 to 20 mPa · s. By setting the ink viscosity to 3 mPa · s or more when ejected from the recording head, there is an effect that residual vibration during ink ejection is less likely to occur, and it is easy to suppress vibration after ejection by the drive waveform, and in a short time. The next discharge can be performed. This makes it suitable for high-speed printing. On the other hand, by suppressing the ink viscosity to 15 mPa · s or less, the ink ejection property is easily stabilized. Since the viscosity changes depending on the use environment, it is preferable that the ink viscosity satisfies the above range within the assumed use range, and the viscosity at 25 ° C. is more preferably 5 to 10 mPa · s.
The viscosity can be measured, for example, by adjusting the temperature to each temperature using a viscometer (RE-550L, manufactured by Toki Sangyo Co., Ltd.).

The static surface tension of the ink is preferably 20 to 40 mN / m at 25 ° C., more preferably 20 to 35 mN / m. If the static surface tension is within this range, the permeability is high and effective in reducing bleeding, and the drying property on plain paper printing is good. Further, since dot enlargement occurs on the surface of glossy paper, color development on glossy paper is improved.
Since the surface tension is 40 mN / m or less, the spread of dots is not suppressed due to the size of the glossy paper surface layer, and the amount of ink attached is not increased to improve the concealment. There is no increase in cost or longer drying time. On the other hand, when it is 20 mN / m or more, the nozzle plate of the recording head is not excessively wetted, and wiping spots due to maintenance cause ink permeation around the nozzle holes and non-uniform wettability, or ejection of ink droplets. It does not cause bending or non-ejection.

As described above, the color of the ink of the present invention is white, which has a high concealment ratio of a printed image and has a high gloss and a clear white image. The white ink of the present invention is accommodated in the ink accommodating portion of the inkjet image forming apparatus, and the ink droplets are ejected from the nozzles of the recording head by applying energy, whereby a predetermined image can be formed on the recording medium.
The ink (white ink) of the present invention can be used by being stored in an ink cartridge provided with an ink storage portion. At that time, it is also possible to use an ink cartridge provided with a plurality of ink storage portions and to be mounted together with ink of other colors.
There is no restriction | limiting in particular in the color of the ink used with the white ink of this invention, According to the objective, it can select suitably, Yellow, magenta, cyan, black etc. are used. When recording is performed using an ink set including two or more of these colors including the white ink of the present invention, a multicolor image can be formed, and recording is performed using an ink set combining all colors. A full-color image can be formed.
In addition, by using red, green, blue, gray, light cyan, light magenta, and dark yellow inks other than process colors including the white ink of the present invention, the color gamut of a full color image can be expanded and the graininess of the image can be reduced. it can. In addition, since the total amount of secondary color adhesion can be reduced, poor absorption of the recording medium is unlikely to occur, beading and bleeding can be reduced, and hue bending and hue change during drying can be reduced.

  The white ink of the present invention and the inks of the other colors can be obtained by deforming the diaphragm that forms the wall surface of the ink flow path by using a piezoelectric element as pressure generating means for pressurizing the ink in the ink flow path. A so-called piezo-type device that discharges ink droplets by changing the product (for example, see Japanese Patent Publication No. 2-51734), or a heating resistor is used to heat the ink in the ink flow path to generate bubbles. A so-called thermal type (see, for example, Japanese Patent Publication No. 61-59911), a diaphragm that forms the wall surface of an ink flow path and an electrode are arranged to face each other, and vibration is generated by an electrostatic force generated between the diaphragm and the electrode. Any ink jet such as an electrostatic type (for example, see Japanese Patent Application Laid-Open No. 6-71882) in which ink drops are ejected by changing the volume of the ink flow path by deforming the plate Head can be satisfactorily used in the printer for mounting (recording head). The ink can be used, for example, in a printer having a function of accelerating print fixing by heating the recording medium and the ink at 50 to 200 ° C. before or after printing.

<Image forming method>
In the image forming method using the ink of the present invention, a step of forming an image by applying a stimulus (energy) to the ink accommodated in the ink accommodating portion and ejecting (flying) ink droplets from the recording head onto the recording medium ( Image forming step).
Any known ink jet recording method can be applied as a method of forming an image on a recording medium by flying ink. Examples of such a method include an ink jet recording method of scanning a recording head and an ink jet recording method of recording an image on a certain sheet of recording medium by using a lined head.

    In the ink flying process, there is no particular limitation on the driving method of the recording head, which is an ink flying means, an on-demand type using a piezoelectric element actuator using PZT, a method of applying thermal energy, an actuator using electrostatic force, etc. The recording head can be used, or recording can be performed with a continuous ejection type charge control type head. In the method of applying thermal energy, it is difficult to freely control the ejection of droplets, and the dispersion of images tends to increase due to the type of recording medium, etc., but the treatment liquid is applied to the recording medium. By doing so, these problems can be solved, and stable high image quality can be obtained regardless of the type of recording medium.

<Inkjet image forming apparatus>
The ink jet image forming apparatus of the present invention has at least ink ejecting means for forming an image on a recording medium by applying energy to the ink of the present invention accommodated in an ink accommodating portion and ejecting the ink droplets from a recording head. It is characterized by this.
The ink jet image forming apparatus is provided with a recording head. As such a recording head, a vibration plate that forms a wall surface of the ink flow path using a piezoelectric element as pressure generating means for pressurizing ink in the ink flow path. A so-called piezo-type device that deforms and changes the volume of the ink flow path to eject ink droplets (see, for example, Japanese Patent Publication No. 2-51734), or heat energy in the ink flow path using a heating resistor. A so-called thermal type that generates air bubbles by heating ink (see, for example, Japanese Patent Publication No. 61-59911), and a diaphragm and an electrode that form a wall surface of the ink flow path are arranged to face each other. The electrostatic type of discharging the ink droplets by changing the volume of the ink flow path by deforming the diaphragm by the electrostatic force generated between Cases such as see Japanese Patent 71882) are also included.
In particular, a piezoelectric type that deforms the diaphragm and a thermal type that discharges with thermal energy are effective.

Here, the inkjet image forming apparatus of the present invention will be described with reference to the drawings. FIG. 1 is an explanatory perspective view (viewed from the front side) of an inkjet image forming apparatus according to the present invention. The ink jet image forming apparatus shown in FIG. 1 stocks an apparatus main body 101, a paper feed tray 102 for loading paper mounted on the apparatus main body 101, and paper on which an image is recorded (formed) mounted on the apparatus main body 101. And a paper discharge tray 103. The upper surface of the upper cover 111 of the apparatus main body 101 is a substantially flat surface, and the front surface of the front cover 112 of the apparatus main body 101 is inclined obliquely rearward with respect to the upper surface. On the lower side of the front surface of the inclined front cover 112, a paper discharge tray 103 and a paper feed tray 102 protruding forward (front side) are provided. Further, the front end portion of the front cover 112 has an ink cartridge loading portion 104 that protrudes forward from the front surface and loads the ink cartridge 200 at a position lower than the upper cover 111. An operation unit 105 such as operation keys and a display is arranged on the upper surface of the unit 104. The ink cartridge loading unit 104 has an openable / closable ink cartridge loading unit cover 115 for attaching and detaching the ink cartridge. As shown in FIGS. 2 and 3, in the apparatus main body 101, a carriage 133 is slidably held in the main scanning direction by guide rods 131 and stays 132 that are horizontally mounted on left and right side plates (not shown). The main scanning motor (not shown) moves and scans in the carriage scanning direction of FIG.
Here, the ink cartridge accommodates at least the ink of the present invention in a container (ink accommodating portion), and other members appropriately selected as necessary can also be configured. The shape, structure, size, and material of the container are not particularly limited and can be appropriately selected according to the purpose. Preferred examples include those having at least an ink bag formed of an aluminum laminate film, a resin film, or the like.
For example, the ink cartridge is filled in an ink bag from an ink injection port (not shown) and exhausted, and then the ink injection port is closed by fusion. In use, the needle of the apparatus main body is pierced into an ink discharge port made of a rubber member and supplied to the apparatus. The ink bag is formed of a packaging member such as a non-permeable aluminum laminate film. The ink bag is usually housed in a plastic cartridge case and is detachably mounted on various ink jet image forming apparatuses.
2 is a schematic cross-sectional view illustrating the entire configuration of the mechanism unit of the inkjet image forming apparatus shown in FIG. 1, and FIG. 3 is a schematic plan view of the main part of the mechanism unit of FIG.

2 and 3, the carriage 133 has a recording head 134 that ejects ink droplets of different colors (for example, yellow, cyan, magenta, black, etc.) in addition to the ink (white ink) of the present invention. A plurality of ink ejection openings are arranged in a direction crossing the main scanning direction, and are mounted with the ink droplet ejection direction facing downward. 1 to 3 show an example in which the number of recording heads is four. However, the present invention is not limited to this, and in addition to the ink of the present invention (white ink), depending on the number of inks of other colors to be used. The required number of recording heads is deployed.
As a head constituting the recording head 134, a piezoelectric actuator such as a piezoelectric element, a thermal actuator that uses a phase change caused by film boiling of a liquid using an electrothermal transducer such as a heating resistor, and a metal phase change caused by a temperature change are used. A shape memory alloy actuator, an electrostatic actuator using an electrostatic force, or the like provided as energy generating means for discharging ink can be used.

In order to improve ejection stability and wiping properties, a layer formed of Ni / PTFE eutectoid, silicone resin, and fluorine-based water repellency imparting agent is provided on the nozzle surface, which is an ink ejection portion of the recording head. In the present invention, the surface energy of the inner wall of the nozzle hole is defined by the ejected liquid (ink), but the surface energy of the nozzle surface is more effective when combined with that of the inner wall of the nozzle hole. Accordingly, the inner wall of the nozzle hole is subjected to the same treatment as the nozzle surface as necessary.
This is also very effective when the inner wall surface of the nozzle hole is covered with a layer formed of a silicone resin or a fluorine-based water repellent agent.

The silicone resin is an organopolysiloxane having a siloxane bond made of Si and O as a basic skeleton and having an organic group in a side chain. Examples of the method for forming the silicone layer include application by pouring a liquid silicone solution or dispersion into the nozzle holes, but are not particularly limited. When forming the silicone layer, mask the parts that do not form the silicone layer, such as the back of the nozzle plate, except for the electrodeposition method, with photoresist, water-soluble resin, etc. A silicone layer can be formed. The thickness of the silicone layer is preferably about 0.1 to 5.0 μm, and particularly preferably 0.5 to 2.0 μm in consideration of nozzle diameter accuracy and the like.
The fluorine-based water repellency-imparting agent is not particularly limited as a low-molecular substance, a resin, or the like. For example, JP-A-2002-145645, JP-A-9-286639, JP-A-2000-94567 And the like.

  The carriage 133 shown in FIGS. 2 and 3 supplies each color for supplying the recording head 134 with ink of another color (for example, yellow, cyan, magenta, black, etc.) in addition to the ink of the present invention (white ink). The sub tank 135 is mounted. Ink is replenished and supplied to the sub tank 135 from the ink cartridge loaded in the ink cartridge loading unit 104 via an ink supply tube (not shown).

  On the other hand, as a paper feeding unit for feeding the paper 142 stacked on the paper stacking unit (pressure plate) 141 of the paper feed tray 103, half a month to separate and feed the paper 142 one by one from the paper stacking unit (pressure plate) 141. A separation pad 144 made of a material having a large coefficient of friction is provided opposite to the roller (sheet feeding roller) 143 and the sheet feeding roller 143, and 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 on the lower side of the recording head 134, a transport belt 151 for electrostatically attracting and transporting the paper 142, and a paper feed unit A counter roller 152 for transporting the paper 142 fed through the guide 145 while sandwiching it between the transport belt 151 and the paper 142 fed substantially vertically upward are changed by approximately 90 ° and copied onto the transport belt 151. A conveyance guide 153 for adjusting the pressure and a tip pressure roller 155 urged toward the conveyance belt 151 by a pressing member 154.

  In addition, a charging roller 156 that is a charging unit for charging the surface of the conveyance belt 151 is provided. Here, the conveyance belt 151 is an endless belt, and is configured to be looped around the conveyance roller 157 and the tension roller 158 in the belt conveyance direction. The transport belt 151 includes, for example, a surface layer which is a sheet adsorbing surface formed of a pure resin material having a thickness of about 40 μm which is not subjected to resistance control, for example, ETFE pure material, and resistance control by carbon using the same material as the surface layer. And a back layer (medium resistance layer, earth layer). In addition, a guide member 161 is disposed on the back side of the conveyance belt 151 so as to correspond to a printing area by the recording head 134. Further, as a paper discharge unit for discharging the paper 142 recorded by the recording head 134, a separation claw 171 for separating the paper 142 from the transport belt 151, a paper discharge roller 172, and a paper discharge roller 173 are provided. A paper discharge tray 103 is provided 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. Further, a manual paper feed unit 182 is provided on the upper surface of the double-sided paper feed unit 181.

  In the inkjet image forming apparatus configured as described above, the sheets 142 are separated and fed one by one from the sheet feeding unit, and the sheet 142 fed substantially vertically upward is guided by the guide 145, and includes the transport belt 151 and the counter roller. The front end is guided by a transport guide 153 and pressed against the transport belt 151 by a front end pressure roller 155, and the transport direction is changed by approximately 90 °.

At this time, the conveyance belt 151 is charged by the charging roller 156, and the sheet 142 is electrostatically attracted to the conveyance belt 151 and conveyed. Therefore, by driving the recording head 134 according to the image signal while moving the carriage 133, ink droplets are ejected onto the stopped 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 paper 142 has reached the recording area, the recording operation is finished and the paper 142 is discharged onto the paper discharge tray 103.
When a near-end remaining amount of ink in the sub tank 135 is detected, a required amount of ink is supplied to the sub tank 135 from the ink cartridge.

Further, the details of the mechanism part of the inkjet image forming apparatus are separately shown in FIG. As shown in FIG. 4, in the non-printing area on one side of the carriage 33 in the scanning direction, a maintenance device 91 according to the present invention for maintaining and recovering the nozzle state of the recording head 34 is arranged. The maintenance device 91 (hereinafter also referred to as “subsystem”) includes caps 92 for capping each nozzle surface of the recording head 34, a wiper blade 93 for wiping the nozzle surface, and an increaser. An empty discharge receiver 94 that receives droplets when performing empty discharge for discharging droplets that do not contribute to recording in order to discharge viscous ink, and an ink that is integrally formed with the empty discharge receiver and that adheres to the wiper blade 93 is removed. A wiper cleaner 94 as a cleaning member for cleaning, and a cleaner roller 96 constituting a cleaner means for pressing the wiper blade 93 against the wiper cleaner side when the wiper blade 93 is cleaned. In the above configuration, when the recording head 34 passes through the position of the wiper blade 93 and protrudes into the movement path, the ejection port of the recording head 34 is wiped.
Although FIG. 4 shows an example of filling general color ink, in the present invention, at least one of the ink cartridge loading portions of the present invention (white ink) is filled.
In FIG. 4, names corresponding to other reference numerals whose detailed descriptions are omitted are shown below.
6: ink cartridge loading unit, 10 (10k, 10c, 10m, 10y): ink cartridge, 21: frame, 21A: side plate, 21B: side plate, 21C: rear plate, 22: flexible cable, 23: supply pump unit, 25 : Body side holder, 26: fixing rib, 31: guide rod, 33: carriage, 34 (34k, 34c, 34m, 34y): recording head, 35 (35k, 35c, 35m, 35y): sub tank, 37: ink supply Tube: 42: Paper 51: Conveying belt 57: Conveying roller 58: Tension roller 91: Subsystem including maintenance and recovery device 92: Cap member 93: Wiper blade 94: Empty discharge receiver / wiper cleaner 96: Cleaner roller, 98: Empty discharge receptacle, 99: Opening

The present invention will be described below in more detail based on examples, but the technical scope of the present invention is not limited to the following examples.
Further, in the following description, unless otherwise specified, parts indicate parts by mass and% indicates mass%.

Preparation Example 1 Preparation of Polymer Dispersion Stabilizer Solution Each component of the following formulation was stirred and mixed using a stirrer to prepare a polymer dispersion stabilizer solution.
[Formulation of polymer dispersion stabilizer solution]
Styrene-maleic acid copolymer ... 10 parts [Polymarlon 351, manufactured by Arakawa Chemical Industries, Ltd.]
1N-KOH aqueous solution ... 68.6 parts Ion-exchanged water ... 21.4 parts

(Preparation Example 2) Preparation of pigment dispersion A <Preparation of primary pigment dispersion A>
First, a surfactant having the following formulation is dissolved in ion-exchanged water, and after the following pigment is mixed and sufficiently wetted, a wet disperser DYNOMILL KDL A type (manufactured by WAB) is filled with zirconia beads having a diameter of 0.5 mm. Then, dispersion was performed at 2000 rpm for 3 hours to obtain a primary pigment dispersion A.
[Formulation of primary pigment dispersion A]
Surfactant [DKS NL-450, Daiichi Kogyo Seiyaku Co., Ltd.] 8 parts Ion-exchanged water ... 72 parts Organic white in the following general formula (I), X is H, R ₁ is C ₁₂ H ₂₅ , R ₂ and R ₃ are CH ₃ , and R ₄ is CH ₂ Φ (benzyl group) 20 parts of pigment

<Preparation of pigment dispersion A>
20 parts of the polymer dispersion stabilizer solution prepared in Preparation Example 1 was added to the primary pigment dispersion A obtained above, and the mixture was sufficiently stirred to obtain pigment dispersion A.
When the volume average particle diameter of the dispersed organic white pigment was measured with Microtrac UPA-EX150 (manufactured by Nikkiso Co., Ltd.), the average particle diameter (d ₅₀ ) was 412 nm.

(Preparation Example 3) Preparation of pigment dispersion B <Preparation of primary pigment dispersion B>
First, a surfactant having the following formulation is dissolved in ion-exchanged water, and when the above pigment is mixed and sufficiently wetted, a wet disperser Dino mill KDL A type (manufactured by WAB) is filled with zirconia beads having a diameter of 0.5 mm. Then, dispersion was performed at 2000 rpm for 6 hours to obtain a primary pigment dispersion B.
[Formulation of primary pigment dispersion B]
Surfactant [DKS NL-450, Daiichi Kogyo Seiyaku Co., Ltd.] ... 8 parts Ion-exchanged water ... 72 parts in the following general formula (I), X is OCH ₃ , R ₁ is CH ₂ Φ (benzyl group),
Organic white pigment in which R ₂ and R ₃ are CH ₃ and R ₄ is C ₁₂ H ₂₅ ... 20 parts

To the obtained primary pigment dispersion B, 20 parts of the polymer dispersion stabilizer solution prepared in Preparation Example 1 was added and stirred sufficiently to obtain pigment dispersion B.
When the volume average particle diameter of the dispersed organic white pigment was measured with Microtrac UPA-EX150, the average particle diameter (d ₅₀ ) was 267 nm.

[Preparation of ink]
Example 1
The ink of Example 1 was prepared according to the following formulation. In addition, when the volume average particle diameter of the hollow resin particles (SX866 (A)) was measured with Microtrack UPA-EX150 (manufactured by Nikkiso Co., Ltd.) before producing the ink, the average particle diameter (d ₅₀ ) was It was 620 nm.
As an ink preparation method, first, Acryte WEM-321U, glycerin, 1,3-butanediol, 2-ethyl-1,3-hexanediol, Polyfox PF-156A, Proxel LV, 2-amino-2-ethyl A vehicle is prepared by dissolving -1,3-propanediol in ion-exchanged water, and after adding pigment dispersion A and hollow resin particles, mixing and stirring, pressure filtration is performed with a cellulose acetate membrane filter having a pore size of 0.8 μm. Ink was obtained.
[Ink formulation of Example 1]
Pigment dispersion liquid A ... 18 parts Hollow resin particles [SX866 (A): manufactured by JSR Corporation]・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 3 parts Acrylic urethane water-based emulsion ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 7.9 parts [ACRITT WEM-321U: Taisei Kako Co., Ltd.]
Glycerin ... 7.5 parts 1,3-butanediol ... 22.5 parts 2-ethyl-1,3-hexanediol ... 4 parts Surfactant (Polyfox PF -156A: manufactured by OMONOVA) 3.3 parts antiseptic / antifungal agent (Proxel LV: manufactured by Avicia) 0.2 parts 2-amino-2-ethyl-1 , 3-propanediol ... 0.1 parts Ion-exchanged water ... 33.5 Part

(Example 2)
An ink of Example 2 was prepared according to the following formulation. In addition, when the volume average particle diameter of the hollow resin particles (Ropeke ULTRA) was measured with Microtrac UPA-EX150 (manufactured by Nikkiso Co., Ltd.) before producing the ink, the average particle diameter (d ₅₀ ) was 374 nm. there were.
As a method for preparing the ink, first, Boncoat 4001, glycerin, triethylene glycol, 2,2,4-trimethyl-1,3-pentanediol, Polyfox PF-151N, Proxel LV, and triethanolamine are used as ion-exchanged water. A vehicle was prepared by dissolving, pigment dispersion A and hollow resin particles were added, mixed and stirred, and then pressure filtered through a cellulose acetate membrane filter having a pore size of 0.8 μm to obtain an ink.
[Ink formulation of Example 2]
Pigment dispersion A ... 18 parts Hollow resin particles (Rohpaque ULTRA: manufactured by Rohm and Haas) ... 3 .5 parts Acrylic water-based emulsion [Boncoat 4001: manufactured by DIC Corporation] ... 6 parts Glycerin ... 10 parts triethylene glycol ... 25 parts 2,2,4-trimethyl-1,3-pentanediol ...・ ・ ・ ・ 4 parts Surfactant [Polyfox PF-151N: manufactured by OMONOVA] ・ ・ ・ ・ 2 parts Antiseptic / antifungal agent (Proxel LV: manufactured by Avicia) ・ ・ ・ ・ ・ ・ ・ ・ ・... 0.2 parts Triethanolamine ... Parts of ion-exchanged water ........................... 31.2 parts

(Example 3)
An ink of Example 3 was prepared according to the following formulation. In addition, when the volume average particle diameter of the hollow resin particles (Ropeque ULTRA E) was measured with Microtrac UPA-EX150 (manufactured by Nikkiso Co., Ltd.) before producing the ink, the average particle diameter (d ₅₀ ) was 436 nm. Met.
As a method for preparing the ink, first, Hydran HW-940, glycerin, 3-methyl-1,3-butanediol, 2-ethyl-1,3-hexanediol, zonyl FS-300, Proxel LV, 2-amino- Dissolve 2-ethyl-1,3-propanediol in ion-exchanged water to prepare a vehicle, add pigment dispersion A and hollow resin particles, mix and stir, then press with a cellulose acetate membrane filter with a pore size of 0.8 μm Filtration gave an ink.
[Ink Formulation of Example 3]
Pigment dispersion A ... 28 parts Hollow resin particles (Rohpaque ULTRA E: manufactured by Rohm and Haas) · 4 .5 parts Polyester-based urethane water-based ionomer 7 parts [Hydran HW-940: manufactured by DIC Corporation]
Glycerin ... 6 parts 3-Methyl-1,3-butanediol ... ... 19 parts 2-Ethyl-1,3-hexanediol ... 2 parts Surfactant (Zonyl FS-300: DuPont) ······· 2.5 parts Antiseptic / antifungal agent (Proxel LV: Avicia) ········ 0.2 parts 2-Amino-2 -Ethyl-1,3-propanediol ... 0.1 parts Ion-exchanged water ...・ 30.7 parts

Example 4
An ink of Example 4 was prepared according to the following formulation. In addition, when the volume average particle diameter of the hollow resin particles (ROPEQUE ULTRA DUAL) was measured with Microtrac UPA-EX150 (manufactured by Nikkiso Co., Ltd.) before the ink was prepared, the average particle diameter (d ₅₀ ) was 425 nm. Met.
As an ink preparation method, first, Acryte WEM-321U, glycerin, 1,3-butanediol, 2-ethyl-1,3-hexanediol, Polyfox PF-156A, Proxel LV, 2-amino-2-ethyl A vehicle is prepared by dissolving -1,3-propanediol in ion-exchanged water, and after adding pigment dispersion A and hollow resin particles, mixing and stirring, pressure filtration is performed with a cellulose acetate membrane filter having a pore size of 0.8 μm. Ink was obtained.
[Ink formulation of Example 4]
Pigment dispersion A ... 25 parts Hollow resin particles (Rohpaque ULTRA DUAL: manufactured by Rohm and Haas)・ ・ 2 parts Acrylic urethane water-based emulsion ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 7.9 parts [ACRITT WEM-321U: Taisei Kako Co., Ltd.]
Glycerin ... 7.5 parts 1,3-butanediol ... 22.5 parts 2-Ethyl-1,3-hexanediol 4 parts Surfactant [ Polyfox PF-156A: manufactured by OMONOVA] 3.3 parts Antiseptic / antifungal agent (Proxel LV: manufactured by Avicia) 0.2 parts 2-amino- 2-Ethyl-1,3-propanediol ... 0.1 parts Ion-exchanged water ... .... 27.5 parts

(Example 5)
An ink of Example 5 was prepared according to the following formulation. Before the ink was prepared, the volume average particle diameter of the hollow resin particles (Ropeke OP-62) was measured with a Microtrac UPA-EX150 (manufactured by Nikkiso Co., Ltd.). The average particle diameter (d ₅₀ ) was It was 466 nm.
As a method for preparing the ink, first, Boncoat 4001, glycerin, triethylene glycol, 2,2,4-trimethyl-1,3-pentanediol, Polyfox PF-151N, Proxel LV, and triethanolamine are used as ion-exchanged water. A vehicle was prepared by dissolving, pigment dispersion A and hollow resin particles were added, mixed and stirred, and then pressure filtered through a cellulose acetate membrane filter having a pore size of 0.8 μm to obtain an ink.
[Ink formulation of Example 5]
Pigment dispersion A ················································· 14 parts Hollow resin particles 4 parts Acrylic water-based emulsion [Boncoat 4001: DIC Corporation] 6 parts Glycerin ... 10 parts triethylene glycol ... 25 parts 2,2,4-trimethyl-1,3 -Pentanediol: 4 parts Surfactant (Polyfox PF-151N: manufactured by OMONOVA) 2 parts Antiseptic / antifungal agent (Proxel LV: manufactured by Avicia) ... 0.2 parts Triethanolamine ... ...... 0.1 parts of ion exchange water, ........................... 34.7 parts

(Example 6)
An ink of Example 6 was prepared according to the following formulation. In addition, when the volume average particle diameter of the hollow resin particles (Ropeke OP-84J) was measured with Microtrac UPA-EX150 (manufactured by Nikkiso Co., Ltd.) before the ink was prepared, the average particle diameter (d ₅₀ ) was It was 548 nm.
As a method for preparing the ink, first, Hydran HW-940, glycerin, 3-methyl-1,3-butanediol, 2-ethyl-1,3-hexanediol, zonyl FS-300, Proxel LV, 2-amino- Dissolve 2-ethyl-1,3-propanediol in ion-exchanged water to prepare a vehicle, add pigment dispersion A and hollow resin particles, mix and stir, then press with a cellulose acetate membrane filter with a pore size of 0.8 μm Filtration gave an ink.
[Ink formulation of Example 6]
Pigment dispersion A ... 30 parts Hollow resin particles (Ropeke OP-84J: manufactured by Rohm and Haas)・ ・ 2.5 parts Polyester urethane water ionomer ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 7 parts [Hydran HW-940: manufactured by DIC Corporation]
Glycerin ... 6 parts 3-Methyl-1,3-butanediol ... ..... 19 parts 2-Ethyl-1,3-hexanediol ... 2 parts Surfactant (Zonyl FS -300: manufactured by DuPont) ... 2.5 parts Antiseptic / antifungal agent (Proxel LV: manufactured by Avicia) ... 0.2 parts 2-Amino-2-ethyl-1,3-propanediol ... 0.1 parts Ion-exchanged water ... ... 31.7 parts

(Example 7)
Ink of Example 7 was prepared in the same manner as in Example 1 except that Pigment Dispersion B was used instead of Pigment Dispersion A in Example 1.

(Example 8)
Ink of Example 8 was prepared in the same manner as in Example 2 except that Pigment Dispersion B was used instead of Pigment Dispersion A in Example 2.

Example 9
Ink of Example 9 was prepared in the same manner as in Example 3 except that Pigment Dispersion B was used instead of Pigment Dispersion A in Example 3.

(Example 10)
Ink was prepared in the same manner as in Example 4 except that Pigment Dispersion B was used instead of Pigment Dispersion A in Example 4 to prepare Ink of Example 10.

(Example 11)
Ink of Example 11 was prepared in the same manner as in Example 5 except that Pigment Dispersion B was used instead of Pigment Dispersion A in Example 5.

(Example 12)
Ink was prepared in the same manner as in Example 6 except that Pigment Dispersion B was used instead of Pigment Dispersion A in Example 6 to prepare Ink of Example 12.

(Comparative Example 1)
In Example 1, except for the organic white pigment contained in Pigment Dispersion A, except that the amount of hollow resin particles SX866 (A) added and ion-exchanged water were adjusted so that the colorant content would be equal. Ink was prepared in the same manner as in Example 1 to prepare the ink of Comparative Example 1.

(Comparative Example 2)
In Example 5, except for the organic white pigment contained in Pigment Dispersion A, Example 5 was carried out except that the addition amount of hollow resin particles OP-62 and ion-exchanged water were adjusted so that the colorant content was equivalent. Ink was prepared in the same manner as described above to prepare the ink of Comparative Example 2.

(Comparative Example 3)
In Example 7, except for the organic white pigment contained in Pigment Dispersion B, the amount of the hollow resin particles SX866 (A) and the amount of ion-exchanged water were adjusted so that the colorant content would be the same. Ink was prepared in the same manner as in Example 7 to prepare the ink of Comparative Example 3.

(Comparative Example 4)
In Example 10, except for the organic white pigment contained in Pigment Dispersion B, Example 10 was carried out except that the addition amount of hollow resin particle ULTRA DUAL and ion-exchanged water were adjusted so that the colorant content would be equal. Ink was prepared in the same manner as described above to prepare the ink of Comparative Example 4.

(Comparative Example 5)
In Example 1, except for the hollow resin particles SX866 (A), except that the addition amount of the pigment dispersion A containing an organic white pigment and the ion-exchanged water were adjusted so that the colorant content was equal, Example 1 Ink was prepared in the same manner as described above to prepare the ink of Comparative Example 5.

(Evaluation of concealment of printed images)
Each ink prepared in Examples 1 to 12 and Comparative Examples 1 to 5 is filled into an ink cartridge, and an ink jet printer (IPSiO GX3000 manufactured by Ricoh) is used to fill all the nozzles with no abnormal image. After confirming this, a solid image of 50 mm × 50 mm was printed on the OHP sheet. The black density of the printed portion was measured using a spectrocolorimetric densitometer X-Rite 938 with a commercially available black paper laid under the printed OHP sheet. The measurement results are shown in Table 1. As a reference, the lowermost row of Table 1 shows the black density measurement result of only black paper.
(Evaluation of glossiness)
Moreover, the glossiness of the printed image output above was evaluated according to the following criteria. The evaluation results are shown in Table 1.
A: An unprinted OHP sheet with a uniform gloss that is comparable to that of an unprinted OHP sheet B: A glossy feeling that does not meet the above-mentioned A judgment C: An overall matte tone without glossiness thing

As shown in Table 1, the inks of Comparative Examples 1 to 4 using only hollow resin particles as a white color material are not matte and glossy as a whole. On the other hand, only an organic white pigment is used as the white color material. The ink of Comparative Example 5 was inferior in print image concealment.
On the other hand, in the inks of Examples 1 to 12 of the present invention in which the organic white pigment having the chemical structure represented by the general formula (I) and the hollow resin particles are used in combination, the black density is lowered, and the printed image A clear white image with high concealment ratio and high gloss is obtained.
When the ink of the present invention is filled in an ink cartridge and used in an ink jet image forming apparatus, the coloring material does not settle during the ink storage period, there is no clogging at the discharge nozzle, and printing is performed. The resulting image has an improved concealment ratio of the color material, and a clear white image with high gloss is obtained.

6 Ink cartridge loading section 10 (10k, 10c, 10m, 10y) Ink cartridge 21 Frame 21A Side plate 21B Side plate 21C Rear plate 22 Flexible cable 23 Supply pump unit 25 Body side holder 26 Fixing rib 31 Guide rod 33 Carriage 34 (34k, 34c) , 34m, 34y) Recording head 35 (35k, 35c, 35m, 35y) Sub tank 37 Ink supply tube 42 Paper 51 Conveying belt 57 Conveying roller 58 Tension roller 91 Subsystem 92 including maintenance / recovery device Cap member 93 Wiper blade 94 Air discharge Receptacle / wiper cleaner 96 Cleaner roller 98 Empty discharge receptacle 99 Opening 101 Apparatus main body 102 Paper feed tray 103 Paper discharge tray 104 Ink cartridge loading section 105 Operation section 111 Upper cover Over 112 front cover 115 ink cartridge loading section cover 131 guide rod 132 stay 133 carriage 134 recording head 135 sub tank 141 paper stacking unit (pressure plate)
142 paper
143 Half Moon Roll (Feed Roll)
144 Separation pad 145 Guide 151 Conveying belt 152 Counter roller 153 Conveying guide 154 Pressing member 155 Tip pressure roller 156 Charging roller 157 Conveying roller 158 Tension roller 161 Guide member 171 Separating claw 172 Discharging roller 173 Discharging roller 181 Double-sided paper feeding unit 182 Manual paper feed unit 200 Ink cartridge

JP 2011-231202 A JP-A-11-130975 JP 2009-35672 A

Claims (8)

An ink comprising an aqueous medium, a dispersant, and a coloring material as components, the hollow coloring material containing an organic white pigment having a chemical structure represented by the following general formula (I) as the coloring material Characteristic ink.

[In the formula (I), X represents the same or different hydrogen atom, methyl group, ethyl group, methoxy group, ethoxy group, chlorine atom, sulfone group, and R ₁ represents an alkyl group, alkenyl group, aralkyl group, aryl group. Or a cycloalkyl group, R ₂ , R ₃ and R ₄ independently of each other represent a hydrogen atom or R ₁ , and R ₂ , R ₃ and R ₄ are combined with these two or three substituents. A heterocyclic group may be formed together with the nitrogen atom. ]   2. The ink according to claim 1, wherein a volume average particle diameter of the hollow resin particles is 0.2 μm to 1.0 μm.   3. The ink according to claim 1, wherein the organic white pigment has a volume average particle diameter of 0.1 μm to 0.5 μm.   The blending ratio [organic white pigment] / [hollow resin particles] (mass ratio) of the organic white pigment and the hollow resin particles is 0.5 / 1 to 3/1. The ink according to any one of the above.   5. The total amount of the organic white pigment and the hollow resin particles is 5.0 to 12.0 parts by mass in 100 parts by mass of the total ink composition. 5. Ink.   An ink cartridge comprising an ink container, wherein the ink stored in the ink container is the ink according to any one of claims 1 to 5.   An ink jet image forming apparatus having at least ink flying means for applying energy to ink contained in an ink containing portion and ejecting the ink droplets from a recording head to form an image on a recording medium, wherein the ink is used as the ink. An ink jet image forming apparatus using the ink according to any one of 1 to 5.   An ink jet image forming apparatus comprising the ink cartridge according to claim 6.

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