JP2011132536A - Ink composition and method for forming image - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an ink composition providing stable ejection properties and to provide an image formation method which achieves stable ejection properties and provides an image having excellent rubbing resistance. <P>SOLUTION: The ink composition comprises at least a water-soluble organic solvent (a), a pigment (b), water (c) and a nonionic polymer compound (d) as a thickner, wherein the content of the water-soluble organic solvent (a) is 5-30 mass% relative to the total amount of the ink composition, and viscosity measured by changing the shear rate of the ink composition satisfies the following expression: 0.70≤V<SB>high</SB>/V<SB>low</SB>≤0.95, wherein V<SB>high</SB>is viscosity at 25°C measured at a shear rate of 1.5×10<SP>5</SP>(s<SP>-1</SP>) and V<SB>low</SB>is viscosity at 25°C measured at a shear rate of 3.0×10<SP>3</SP>(s<SP>-1</SP>). <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to an ink composition and an image forming method using the same.

  The ink jet recording method performs recording by ejecting ink droplets from a large number of nozzles formed on an ink jet head, and the noise during the recording operation is low, the running cost is low, and various recording media are used. On the other hand, it is widely used because it can record high-quality images.

  Various recording media such as plain paper, coated paper, glossy paper, OHP sheet, and back print film are commercially available for recording by the ink jet recording method. However, they are inexpensive for business use in general offices. Often plain paper is used. In addition to satisfying the required characteristics, the required characteristics at this time include curling (paper curling and curling) that occurs when a large amount of ink is applied to the paper. It is also important to suppress deterioration in image resolution caused by variations in the flying direction of the ejected ink droplets.

In relation to the above, ink jet recording inks having a specific dispersant and a specific compound are disclosed as inks for ink jet recording that are excellent in ejection stability (see, for example, Patent Documents 1 to 4). ).
JP 2008-231336 A JP 2008-231337 A JP 2008-231338 A JP 2008-231339 A

However, the inks described in Patent Documents 1 to 4 cannot obtain stable ejection properties.
An object of the present invention is to provide an ink composition capable of obtaining stable ejection properties, and an image forming method capable of stable ejection properties and excellent in image abrasion resistance.

<1>
(A) a water-soluble organic solvent, (b) a pigment, (c) water, and (d) a nonionic polymer compound as a thickener, and the content of the water-soluble organic solvent (a) An ink composition having an ink composition of 5 to 30% by mass, wherein the viscosity measured by changing the shear rate of the ink composition satisfies the following formula.

0.70 ≦ V _high / V _low ≦ 0.95

[Where V _high represents a 25 ° C. viscosity (mPa · s) measured at a shear rate of 1.5 × 10 ⁵ (s ⁻¹ ), and V _low represents a shear rate of 3.0 × 10 ³ (s ⁻¹ ). This represents the 25 ° C. viscosity (mPa · s) measured by ]
<2>
2. The ink composition according to claim 1, wherein the (d) thickener is a nonionic polymer compound having a weight average molecular weight of 5,000 to 100,000.
<3>
<1>, wherein the nonionic polymer compound is at least one selected from the group consisting of polyvinyl alcohol, polyvinyl pyrrolidone, polyoxyethylene glycol, and polyoxyethylene polyoxypropylene copolymer. Or the ink composition as described in <2>.
<4>
The ink composition according to any one of <1> or <3>, wherein the pigment (b) is dispersed with a water-insoluble dispersant.
<5>
The ink composition according to any one of <1> to <4>, wherein the pigment (b) is a pigment dispersed by a phase inversion emulsification method.
<6>
The ink composition according to any one of <1> to <5>, further comprising (e) polymer particles.
<7>
(E) The ink composition according to <6>, wherein the polymer particles are self-dispersing polymer particles.
<8>
(B) The total amount of the pigment, the water-insoluble dispersant, and the (e) polymer particles is 7% by mass or more based on the total amount of the ink composition. The ink composition according to any one of the above.
<9>
A plurality of droplet discharge elements, a common flow path communicating with each of the plurality of droplet discharge elements via a supply path, and a common circulation path communicating with the plurality of droplet discharge elements via a reflux path. An image forming apparatus comprising: an ink circulation device that supplies an ink composition from the common flow path to the plurality of droplet discharge elements and circulates the ink composition in the common circulation path. An image forming method comprising forming an image on a recording medium by discharging the ink composition according to any one of 1> to <7>.
<10>
The ink composition is supplied from the common flow path to the plurality of droplet discharge elements having nozzles through the supply path, and the ink composition that has not been discharged from the nozzles is supplied to the common flow path through the reflux path. The image forming method according to <9>, wherein the image forming method circulates in a circulation path.
<11>
The image forming apparatus adjusts a supply amount of the ink composition that can be supplied from the common flow path by changing a pressure difference between the ink compositions in the common flow path and the common circulation path. The image forming method according to <9> or <10> above.
<12>
The droplet discharge element includes a nozzle that discharges the ink composition, a nozzle channel that communicates with the nozzle, a nozzle that communicates with the nozzle via the nozzle channel, and the common channel that passes through the supply channel. <9> to <11>, wherein the common circulation path communicates with the nozzle flow path via the reflux path. The image forming method according to any one of the above.

  According to the present invention, it is possible to provide an ink composition capable of obtaining stable ejection properties, and an image forming method capable of stable ejection properties and excellent in image abrasion resistance.

≪Ink composition≫
The ink composition of the present invention includes (a) a water-soluble organic solvent, (b) a pigment, (c) water, and (d) at least a nonionic polymer compound as a thickener. Is an ink composition having a content of 5 to 30% by mass with respect to the total amount of the ink, and the viscosity measured by changing the shear rate of the ink composition satisfies the following formula.
The ink composition of the present invention has excellent ejection stability by adopting the above-described configuration.

<High shear viscosity>
The ink composition of the present invention requires that the viscosity (high shear viscosity) measured by changing the shear rate satisfies the following formula.
0.70 ≦ V _high / V _low ≦ 0.95
In the formula, V _high represents a 25 ° C. viscosity (mPa · s) measured at a shear rate of 1.5 × 10 ⁵ (s ⁻¹ ), and V _low is a shear rate of 3.0 × 10 ³ (s ⁻¹ ). The measured 25 degreeC viscosity (mPa * s) is represented.
Ink jet recording ejects ink from fine nozzles, so that a high shear rate is applied to the ink at the nozzles. If the viscosity is significantly reduced when the shear rate is changed, ink ejection from the nozzle becomes unstable.
In the present invention, the change when the shear rate is changed is small, and a stable discharge property can be obtained by adjusting to the above range.

Due to the interaction between the pigment particles and the nonionic polymer compound, the viscosity tends to decrease at a high shear rate (V _high / V _low decreases), which tends to cause ejection instability. By adopting the combination of the configurations, stable ejection properties are obtained.
As a method for adjusting the decrease in the viscosity at the shear rate, a method of adding a nonionic polymer compound as a thickener is adopted, but the molecular weight of the nonionic polymer compound to be used, its addition amount, water insolubility Examples thereof include a method of adjusting the amount of the components (pigments, water-insoluble pigment dispersant and polymer particles) and the ratio of the amount of the water-insoluble component and the thickener added.
Moreover, there is no limitation in the method of measuring the viscosity by changing the shear rate, and a publicly known method can be used. For example, a trace sample viscometer VROC manufactured by RheoSense can be used.
In the present invention, the values measured under the following conditions are used as the methods for measuring the viscosity V _high and V _low by changing the shear rate.
A microchip type micro sample viscometer VROC (manufactured by RheoSense) and a measurement chip were C-Type (depth = 100 μm). All the measurement units of the viscometer were stored in an incubator, and the temperature was adjusted to 25 ° C.

<Nonionic polymer compound>
In the ink composition of the present invention, at least one nonionic polymer compound (hereinafter also referred to as polymer thickener) is used as a thickener (d) in a system in which a water-insoluble pigment is dispersed in an aqueous medium. contains.
The nonionic polymer compound is preferably water-soluble. The nonionic polymer compound in the present invention is not particularly limited as long as it is a compound in which the viscosity of the aqueous solution is larger than that of water in the aqueous solution in which the compound is dissolved.
When an ionic (cationic or anionic) polymer compound is added as a polymer thickener, it causes aggregation due to interaction with the dispersed material, resulting in deterioration of ink storage stability and ejection stability. Causes significant deterioration.

The nonionic polymer compound in the present invention preferably has a solubility in 100 g of water (25 ° C.) of 1 g or more.
The high shear viscosity is preferably adjusted by adjusting the molecular weight of a nonionic polymer compound used as a thickener, and a nonionic polymer compound having a weight average molecular weight of 5,000 to 100,000 is used. preferable.
When the weight average molecular weight is 5000 or more, a thickening effect is easily obtained, and it is preferable in that it does not cause deterioration in ejection properties and deterioration in abrasion resistance due to an increase in the addition amount. On the other hand, when the molecular weight is 100,000 or less, a thickening effect can be obtained with a small amount, a decrease in viscosity at high shear can be suppressed, and dischargeability is not deteriorated.
It is more preferably 8000 to 50000 from the viewpoint of compatibility between ejection reliability from the ink nozzle and abrasion resistance.
Examples of the nonionic polymer compound include any of vinyl polymers, polyether polymers, polysaccharide polymers, polyacrylic polymers, pyrrolidone polymers, and cellulose polymers.

  Specific examples of the nonionic polymer compound include gelatins, polyvinyl alcohols, various modified polyvinyl alcohols, polyvinylpyrrolidones, vinyl formals and derivatives thereof, polyoxyalkylene glycols, polyacrylamide, and polydimethylacrylamide. , Polydimethylaminoacrylate, polyacrylic acid soda, acrylic acid methacrylic acid copolymer salt, polymethacrylic acid soda, polymer containing acrylic group of vinyl alcohol acrylate copolymer salt, starch, oxidized starch, carboxyl starch, dialdehyde Starch, dextrin, sodium alginate, gum arabic, casein, pullulan, dextran, cellulose or derivatives thereof (eg, methylcellulose, ethylcellulose, carboxymethylcellulose, Natural polymers such as droxypropyl cellulose or derivatives thereof, polyethylene glycol, polypropylene glycol, polyvinyl ether, polyglycerol, alkyl vinyl ether maleate copolymer, N-vinyl pyrrole maleate copolymer, styrene maleic anhydride copolymer Examples thereof include synthetic polymers such as coalescence.

Among them, from the viewpoint of abrasion resistance and ejection stability, polyvinyl alcohol, polyvinyl pyrrolidone, polyoxyalkylene glycols, gelatins, vinyl formals and derivatives thereof, polymers containing an acrylic group of vinyl acrylate copolymer salt, Natural polymers such as starch, dextrin, gum arabic, casein, pullulan, dextran, cellulose or derivatives thereof (for example, methylcellulose, ethylcellulose, carboxymethylcellulose, hydroxypropylcellulose, etc.) or derivatives thereof are preferred.
Furthermore, polyvinyl alcohol, polyvinyl pyrrolidone, and polyoxyalkylene glycols are more preferable.

The polyoxyalkylene glycols may contain a single oxyalkylene group or may contain two or more oxyalkylene groups. Moreover, when polyoxyalkylene glycol contains 2 or more types of oxyalkylene groups, it may be a random polymer or a block polymer.
In the present invention, the polyoxyalkylene glycol is preferably at least one of polyoxyethylene glycol and polyoxyethylene polyoxypropylene block polymer from the viewpoint of ejection stability.

  The average degree of polymerization of the polyvinyl alcohol is preferably 100 to 3500, more preferably 120 to 2000, from the viewpoint of ejection stability. The degree of saponification is preferably 50 mol% or more, more preferably 70 mol% or more, from the viewpoint of ink dispersion stability.

  The nonionic polymer compound preferably has a weight average molecular weight of 5,000 to 100,000, and is at least one selected from polyvinyl alcohol, polyvinyl pyrrolidone, polyoxyethylene glycol, and polyoxyethylene polyoxypropylene block polymer. The weight average molecular weight is 8000 to 50000, and more preferably at least one selected from polyvinyl alcohol, polyvinyl pyrrolidone, polyoxyethylene glycol, and polyoxyethylene polyoxypropylene block polymer.

In this invention, a nonionic high molecular compound may be used individually by 1 type, and may use 2 or more types together.
The content of the nonionic polymer compound in the ink composition can be appropriately selected according to the type of the nonionic polymer compound. For example, it can be 0.01-20 mass%. Among these, from the viewpoint of ejection stability, 0.01 to 5% by mass is preferable, and 0.1 to 3.0% by mass is more preferable.

<Water-soluble organic solvent>
The ink composition of the present invention contains (a) at least one water-soluble organic solvent, and the water-soluble organic solvent is not particularly limited, but the content of the water-soluble organic solvent is based on the total amount of the ink composition. It is 5-30 mass%, It is characterized by the above-mentioned.
By setting the content of the water-soluble organic solvent in the above range, the abrasion resistance of an image formed using the ink composition of the present invention is improved.
If the content of the water-soluble organic solvent is less than 5% by mass, the ink composition cannot be ejected, and if it exceeds 30% by mass, the abrasion resistance deteriorates.
The content of the water-soluble organic solvent is preferably 8 to 25% by mass and more preferably 10 to 20% by mass with respect to the total amount of the ink composition from the viewpoint of image abrasion resistance.

Moreover, it is preferable that 70 mass% or more is a water-soluble organic solvent of SP value 27.5 or less with respect to the total amount of the said water-soluble organic solvent.
In the present invention, the water-soluble organic solvent means an organic solvent that dissolves 5 g or more in 100 g of water.

The SP value in the present invention means a solubility parameter (SP value) of a solvent, and is a value represented by the square root of the molecular cohesive energy. The SP value is described in Polymer Handbook (Second Edition), Chapter IV, Solubility Parameter Values, and this value is used as the SP value in the present invention. Moreover, a unit is (MPa) ^1/2 and points out the value in 25 degreeC.
In addition, R.D. F. The value calculated by the method described in Fedors, Polymer Engineering Science, 14, p147 (1967) is used as the SP value in the present invention.

  In the present invention, from the viewpoint of image abrasion resistance, the content of the water-soluble organic solvent having an SP value of 27.5 or less is preferably 70% by mass or more based on the total water-soluble organic solvent. It is preferably 80% by mass or more, more preferably 90% by mass or more with respect to the organic solvent. When the content is less than 70% by mass, the abrasion resistance of the image may be lowered.

In the present invention, the water-soluble organic solvent having an SP value of 27.5 or less (hereinafter sometimes referred to as “first water-soluble organic solvent”) is further SP value from the viewpoint of image abrasion resistance. Is preferably 16 to 27.5, and more preferably 18 to 26.5.

Although the specific example of the water-soluble organic solvent whose SP value is 27.5 or less is shown below with SP value, this invention is not limited to these.
Diethylene glycol monoethyl ether (DEGmEE) (SP value 22.4)
・ Diethylene glycol monobutyl ether (DEGmBE) (SP value 21.5)
Triethylene glycol monobutyl ether (TEGmBE) (SP value 21.1)
Propylene glycol monoethyl ether (PGmEE) (SP value 22.3)
Dipropylene glycol (DPG) (SP value 27.1)
Dipropylene glycol monomethyl ether (DPGmME) (SP value 21.3)
Triethylene glycol monoethyl ether (TEGmEE) (SP value 21.7)
Tripropylene glycol monomethyl ether (TPGmME) (SP value 20.4)
Triethylene glycol monomethyl ether (TEGmME) (SP value 22.1)
Tripropylene glycol (TPG) (SP value 24.7, for example, PP-200 (manufactured by Sanyo Chemical Industries))
-Heptaoxypropylene glycol (SP value 21.2, for example, PP-400 (manufactured by Sanyo Chemical Industries)),
1,2-hexanediol (SP value 24.1)
POP (3) glyceryl ether (SP value 26.4, for example, GP-250 (manufactured by Sanyo Chemical Industries))
POP (4) glyceryl ether (SP value 24.9)
POP (5) glyceryl ether (SP value 23.9)
POP (6) glyceryl ether (SP value 23.2, for example GP-400 (manufactured by Sanyo Chemical Industries))
POP (7) glyceryl ether (SP value 22.6)
POP (8) glyceryl ether (SP value 22.1)
POP (9) glyceryl ether (SP value 21.7, for example, GP-600 (manufactured by Sanyo Chemical Industries))
POP (10) glyceryl ether (SP value 21.4)
POP (16) glyceryl ether (SP value 20.2, for example GP-1000 (manufactured by Sanyo Chemical Industries, Ltd.))
POP (4) diglyceryl ether (SP value 26.1, for example, SC-P400 (manufactured by Sakamoto Pharmaceutical Co., Ltd.)),
POP (9) diglyceryl ether (SP value 22.7, for example, SC-P750 (manufactured by Sakamoto Pharmaceutical Co., Ltd.)),
POE (20) diglyceryl ether (SP value 22.4, for example, SC-E1000 (manufactured by Sakamoto Pharmaceutical Co., Ltd.)),
POE (40) diglyceryl ether (SP value 21.0, for example, SC-E2000 (manufactured by Sakamoto Pharmaceutical Co., Ltd.)).
Dioxyethylene dioxypropylene butyl ether (SP value 20.1, for example, 50HB-55 (manufactured by Sanyo Chemical Industries, Ltd.))
Pentaoxyethylene pentaoxypropylene butyl ether (SP value 18.8, for example, 50HB-100 (manufactured by Sanyo Chemical Industries)),
Decaoxyethylene heptaoxypropylene butyl ether (SP value 18.8, for example, 50HB-260 (manufactured by Sanyo Chemical Industries)),
Dodecaoxyethylene dodecaoxypropylene butyl ether (SP value 18.8, for example, 50HB-400 (manufactured by Sanyo Chemical Industries, Ltd.)),
Decaoxyethylene triacontoxypropylene butyl ether (SP value 18.7, for example, PE-62 (manufactured by Sanyo Chemical Industries)),
Pentacosaoxyethylene tricontoxypropylene butyl ether (SP value 18.8, for example, PE-64 (manufactured by Sanyo Chemical Industries, Ltd.)).

  The water-soluble organic solvent having an SP value of 27.5 or less in the present invention is also preferably a compound represented by the following structural formula.

In the structural formula, l, m, and n each independently represent an integer of 1 or more and represent 1 + m + n = 3-15. When l + m + n is 3 or more, a sufficient curl suppressing effect can be obtained. Further, when it is 15 or less, the discharge property is improved. Among them, l + m + n is preferably 3 to 12, and more preferably 3 to 10.
In the above structural formula, AO represents at least one of an oxyethylene group (EO) and an oxypropylene group (PO), and among them, an oxypropylene group is preferable. In addition, each AO of (AO) l, (AO) m, and (AO) n may be the same or different.

  In the present invention, the water-soluble organic solvent having an SP value of 27.5 or less may be used alone or in combination of two or more.

  In the ink composition of the present invention, in addition to the water-soluble organic solvent having an SP value of 27.5 or less, the water-soluble organic solvent having an SP value of more than 27.5 is less than 30% by mass with respect to the total water-soluble organic solvent. It may contain with the content rate of. By including a water-soluble organic solvent having an SP value of more than 27.5 (hereinafter sometimes referred to as “second water-soluble organic solvent”), the effect of preventing drying, the wetting effect or the penetration promoting effect can be more effectively achieved. Obtainable.

Here, the drying prevention effect and the wetting effect mean an effect of preventing clogging due to drying of the ink composition at the ink ejection port of the nozzle. As the drying inhibitor and wetting agent, a water-soluble organic solvent having a vapor pressure lower than that of water is preferable.
Further, the penetration promoting effect means an effect of allowing the ink to penetrate into paper better, and a water-soluble organic solvent is preferably used.

  Examples of the second water-soluble organic solvent in the present invention include glycerin, 1,2,6-hexanetriol, trimethylolpropane, ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, pentaethylene glycol, 2-butene-1,4-diol, 2-ethyl-1,3-hexanediol, 2-methyl-2,4-pentanediol, 1,2-octanediol, 1,2-pentanediol, 4-methyl- Alkanediols (polyhydric alcohols) such as 1,2-pentanediol; glucose, mannose, fructose, ribose, xylose, arabinose, galactose, aldonic acid, glucitol, maltose, cellobiose, lactose, sucrose, trehalo Sugars such as maltotriose; sugar alcohols; hyaluronic acids; so-called solid wetting agents such as ureas; alkyl alcohols having 1 to 4 carbon atoms such as ethanol, methanol, butanol, propanol, isopropanol; ethylene glycol monomethyl ether; Ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol mono-n-propyl ether, ethylene glycol mono-iso-propyl ether, diethylene glycol mono-iso-propyl ether, ethylene glycol mono- n-butyl ether, ethylene glycol mono-t-butyl ether, 1-methyl-1-methoxybut Nord, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-t-butyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-iso-propyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono -Glycol ethers such as n-propyl ether and dipropylene glycol mono-iso-propyl ether; 2-pyrrolidone, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, formamide, acetamide, dimethyl Examples include sulfoxide, sorbit, sorbitan, acetin, diacetin, triacetin, sulfolane, etc., and one or more of these can be used. The

  Among them, polyhydric alcohols are useful for the purpose of drying inhibitors and wetting agents. For example, glycerin, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene 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-pentane Examples include diol, polyethylene glycol, 1,2,4-butanetriol, 1,2,6-hexanetriol, and the like. These may be used individually by 1 type and may use 2 or more types together.

  For the purpose of the penetration enhancer, a polyol compound is preferable. Examples of the aliphatic diol include 2-ethyl-2-methyl-1,3-propanediol, 3,3-dimethyl-1,2-butanediol, 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. Among these, preferred examples include 2-ethyl-1,3-hexanediol and 2,2,4-trimethyl-1,3-pentanediol.

  The second water-soluble organic solvent used in the present invention may be used alone or in combination of two or more.

<(B) Pigment>
The ink composition of the present invention contains at least one pigment. As the pigment, a water dispersible pigment is preferable.

Specific examples of the water-dispersible pigment include the following pigments (1) to (4).
(1) An encapsulated pigment, that is, a polymer emulsion in which a pigment is contained in polymer fine particles. More specifically, the pigment is coated with a hydrophilic water-insoluble resin and is made hydrophilic by a resin layer on the pigment surface. A pigment is dispersed in water.
(2) Self-dispersing pigments, that is, pigments having at least one hydrophilic group on the surface and exhibiting at least one of water dispersibility and water solubility in the absence of a dispersant, more specifically, mainly carbon black Etc. are hydrophilized by surface oxidation treatment so that the pigment alone is dispersed in water.
(3) A resin-dispersed pigment, that is, a pigment dispersed with a water-soluble polymer compound having a weight average molecular weight of 50,000 or less.
(4) A surfactant-dispersed pigment, that is, a pigment dispersed by a surfactant.
It is effective to reduce the free polymer component from the viewpoint of suppressing the decrease in viscosity at high shear. Preferred examples of the water-dispersible pigment include (1) encapsulated pigment and (2) self-dispersed pigment. Particularly preferred examples include (1) encapsulated pigments.

  The encapsulated pigment will be described in detail. The encapsulated pigment resin is not limited, but a polymer compound having self-dispersing ability or solubility ability in a mixed solvent of water and a water-soluble organic solvent and having an anionic group (acidic) is used. preferable. This resin usually has a number average molecular weight of about 1,000 to 100,000, and particularly preferably about 3,000 to 50,000. Further, it is preferable that this resin is dissolved in an organic solvent to form a solution. When the number average molecular weight of the resin is within this range, the function as a coating film in the pigment or as a coating film in the ink composition can be sufficiently exhibited. The resin is preferably used in the form of an alkali metal or organic amine salt.

Specific examples of encapsulated pigment resins include thermoplastic, thermosetting or modified acrylic, epoxy, polyurethane, polyether, polyamide, unsaturated polyester, phenol, silicone, and fluorine-based resins. Molecular compounds, polyvinyl chloride, vinyl acetate, polyvinyl alcohol, polyvinyl butyral, etc., polyesters such as alkyd resins, phthalic resins, melamine resins, melamine formaldehyde resins, aminoalkyd cocondensation resins, urea resins, urea resins, etc. Examples thereof include amino materials, or materials having an anionic group such as copolymers or mixtures thereof.
Among the above resins, anionic acrylic resins include, for example, acrylic monomers having an anionic group (hereinafter referred to as anionic group-containing acrylic monomers), and other monomers that can be copolymerized with these monomers as necessary. Is obtained by polymerization in a solvent. Examples of the anionic group-containing acrylic monomer include an acrylic monomer having one or more anionic groups selected from the group consisting of a carboxyl group, a sulfonic acid group, and a phosphonic group. Among these, an acrylic monomer having a carboxyl group Is particularly preferred.

Specific examples of the acrylic monomer having a carboxyl group include acrylic acid, methacrylic acid, crotonic acid, ethacrylic acid, propylacrylic acid, isopropylacrylic acid, itaconic acid, fumaric acid and the like. Among these, acrylic acid or methacrylic acid is preferable.
The encapsulated pigment can be produced by conventional physical and chemical methods using the above-described components. According to a preferred embodiment of the present invention, JP-A-9-151342, JP-A-10-140065, JP-A-11-209672, JP-A-11-172180, JP-A-10-25440, or JP-A-11-43636 It can be produced by the method disclosed in the issue.

In the present invention, the colorant is preferably a pigment (encapsulated pigment) dispersed by a phase inversion emulsification method (hereinafter also simply referred to as “phase inversion method”).
The phase inversion method refers to, for example, a self-dispersing (phase inversion emulsification) method in which a mixed melt of a resin having self-dispersing ability or solubility and a pigment is dispersed in water. Here, the mixed melt means a mixed state without dissolving, a mixed state with dissolved, or a state including both of these states. A more specific production method of the “phase inversion method” may be the same as that disclosed in JP-A-10-140065.

In the present invention, self-dispersing pigments can also be mentioned as preferred examples. The self-dispersing pigment refers to a large number of hydrophilic functional groups and / or salts thereof (hereinafter referred to as dispersibility-imparting groups) on the pigment surface, either directly or indirectly via an alkyl group, an alkyl ether group, an aryl group, or the like. A pigment that is bonded and dispersible in an aqueous medium without a dispersant. Here, “dispersed in an aqueous medium without a dispersant” refers to a state in which the pigment can be dispersed in an aqueous medium without using a dispersant for dispersing the pigment.
Inks containing a self-dispersing pigment as a colorant do not need to contain a dispersant as described above that is contained in order to disperse a normal pigment. It is easy to prepare ink that is excellent in ejection stability.
Examples of dispersibility-imparting groups to be bonded to the surface of the self-dispersion _{pigment, -COOH, -CO, -OH, -SO} 3 H, -PO 3 H 2 and can quaternary ammonium and exemplary salts thereof, these Is produced by subjecting a pigment as a raw material to physical treatment or chemical treatment to bond (graft) an active species having a dispersibility-imparting group or a dispersibility-imparting group to the surface of the pigment. Examples of the physical treatment include vacuum plasma treatment. Examples of the chemical treatment include a wet oxidation method in which the pigment surface is oxidized with an oxidizing agent in water, and a method in which a carboxyl group is bonded via a phenyl group by bonding p-aminobenzoic acid to the pigment surface. It can be illustrated.
In the present invention, preferred examples include self-dispersing pigments that are surface-treated by oxidation treatment with hypohalous acid and / or hypohalite, or oxidation treatment with ozone. Commercially available products can also be used as the self-dispersing pigment, such as Microjet CW-1 (trade name; manufactured by Orient Chemical Co., Ltd.), CAB-O-JET200, CAB-O-JET300 (above trade names). ; Manufactured by Cabot Corporation).

There is no restriction | limiting in particular as a pigment used in this invention, According to the objective, it can select suitably, For example, any of an organic pigment and an inorganic pigment may be sufficient.
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 pigments 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 quinophthalone pigments. Examples of the dye chelates include basic dye chelates and acidic dye chelates.
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 particularly 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.

  Specific examples of carbon black include Raven7000, Raven5750, Raven5250, Raven5000 ULTRAII, Raven3500, Raven2000, Raven1500, Raven1250, Raven1200, Raven1170, Raven1170, Raven1170, Raven1170, Raven1170, Raven1170, Raven1170, Raven1170, Raven1170 (Manufactured by Carbon), Regal 400R, Regal 330R, Regal 660R, Mogu L, Black Pearls L, Monarch 700, Monarch 800, Monarch 880, Monarch 900, Monarch 1000, Monarch 1100, Mo arc 1300, Monarch 1400 (manufactured by Cabot), Color Black FW1, Color Black FW2, Color Black FW2V, Color Black 18, Color Black FW200, Color Black S150, Color Black S150, Color Black S150, Color Black FW200, Color Black FW200, Color Black FW2 V, Printex 140U, Printex 140V, Special Black 6, Special Black 5, Special Black 4A, Special Black 4 (manufactured by Degussa), No. 25, no. 33, no. 40, no. 45, no. 47, no. 52, no. 900, no. 2200B, no. 2300, MCF-88, MA600, MA7, MA8, MA100 (manufactured by Mitsubishi Chemical Corporation) and the like can be mentioned, but the invention is not limited thereto.

  Examples of the organic pigment that can be used in the present invention include C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 7, 10, 11, 12, 13, 14, 14C, 16, 17, 24, 34, 35, 37, 42, 53, 55, 65, 73, 74, 75, 81, 83, 93, 95, 97, 98, 100, 101, 104, 108, 109, 110, 114, 117, 120, 128, 129, 138, 150, 151, 153, 154, 155, 180 etc. are mentioned.

  Examples of magenta ink pigments include C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 39, 40, 48 (Ca), 48 (Mn), 48: 2, 48: 3, 48: 4, 49, 49: 1, 50, 51, 52, 52: 2, 53: 1, 53, 55, 57 (Ca), 57: 1, 60, 60: 1, 63: 1, 63: 2, 64, 64: 1, 81, 83, 87, 88, 89, 90, 101 (Bengara) ), 104, 105, 106, 108 (cadmium red), 112, 114, 122 (quinacridone magenta), 123, 146, 149, 163, 166, 168, 170, 172, 177, 178, 179, 184, 185, 190, 193, 202, 209, 2 9,269, etc., and C. I. Pigment violet 19, especially C.I. I. Pigment Red 122 is preferable.

Further, as pigments for cyan ink, C.I. I. Pigment Blue 1, 2, 3, 15, 15: 1, 15: 2, 15: 3, 15:34, 16, 17: 1, 22, 25, 56, 60, C.I. I. Bat blue 4, 60, 63 and the like. I. Pigment Blue 15: 3 is preferable.
The above pigments may be used alone or in combination of a plurality selected from the above-mentioned groups or between the groups.

(Dispersant)
In the present invention, a nonionic compound, an anionic compound, a cationic compound, an amphoteric compound, and the like can be used as the dispersant used in the encapsulated pigment or the resin dispersion pigment.
Examples thereof include a copolymer of monomers having an α, β-ethylenically unsaturated group. Examples of monomers having an α, β-ethylenically unsaturated group include ethylene, propylene, butene, pentene, hexene, vinyl acetate, allyl acetate, acrylic acid, methacrylic acid, crotonic acid, crotonic acid ester, itaconic acid, itacone Acid monoester, maleic acid, maleic acid monoester, maleic acid diester, fumaric acid, fumaric acid monoester, vinyl sulfonic acid, styrene sulfonic acid, sulfonated vinyl naphthalene, vinyl alcohol, acrylamide, methacryloxyethyl phosphate, bismethacryloxy Styrene derivatives such as ethyl phosphate, methacryloxyethyl phenyl acid phosphate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, styrene, α-methylstyrene, vinyltoluene , Vinylcyclohexane, vinylnaphthalene, vinylnaphthalene derivatives, alkyl acrylates that may be substituted with aromatic groups, phenyl esters of acrylate, alkyl methacrylates that may be substituted with aromatic groups, phenyl esters of methacrylic acid, methacryl Acid cycloalkyl ester, crotonic acid alkyl ester, itaconic acid dialkyl ester, maleic acid dialkyl ester, vinyl alcohol, and derivatives of the above compounds.

A copolymer obtained by copolymerizing a single monomer or a plurality of monomers having the α, β-ethylenically unsaturated group is used as a polymer dispersant. Specifically, acrylic acid alkyl ester-acrylic acid copolymer, methacrylic acid alkyl ester-methacrylic acid copolymer, styrene-alkyl acrylic acid ester-acrylic acid copolymer, styrene-methacrylic acid phenyl ester-methacrylic acid, Styrene-methacrylic acid cyclohexyl ester-methacrylic acid copolymer, styrene-styrenesulfonic acid copolymer, styrene-maleic acid copolymer, styrene-methacrylic acid copolymer, styrene-acrylic acid copolymer, vinylnaphthalene-maleic Examples include acid copolymers, vinyl naphthalene-methacrylic acid copolymers, vinyl naphthalene-acrylic acid copolymers, polystyrene, polyester, and polyvinyl alcohol.
The dispersant in the present invention is preferably 2,000-60,000 in terms of weight average molecular weight. The dispersant in the present invention preferably has a ratio of addition amount to pigment of 10% or more and 100% or less by mass ratio. The added amount of the dispersant is more preferably 20% or more and 70% or less, and further preferably 40% or more and 50% or less.

  The pigment content in the ink composition of the present invention is preferably from 0.1 to 15% by mass, more preferably from 1 to 10% by mass, from the viewpoint of image density and image storage stability.

<Polymer particles>
The ink composition of the present invention preferably contains at least one polymer particle.
By containing the polymer particles, it is preferable because the abrasion resistance of the image tends to be improved while maintaining the ejection stability and the pigment dispersion stability in the ink composition.
Examples of the polymer particles in the present invention include thermoplastic, thermosetting or modified acrylic, epoxy, polyurethane, polyether, polyamide, unsaturated polyester, phenol, silicone, or fluorine. Resins, polyvinyl resins such as vinyl chloride, vinyl acetate, polyvinyl alcohol or polyvinyl butyral, polyester resins such as alkyd resins and phthalic resins, melamine resins, melamine formaldehyde resins, aminoalkyd cocondensation resins, urea resins, urea resins And the like, or particles of a resin having an anionic group such as a copolymer or a mixture thereof. Among these, anionic acrylic resins include, for example, an acrylic monomer having an anionic group (anionic group-containing acrylic monomer) and, if necessary, other monomers copolymerizable with the anionic group-containing acrylic monomer. Obtained by polymerization in a solvent. Examples of the anionic group-containing acrylic monomer include an acrylic monomer having one or more selected from the group consisting of a carboxyl group, a sulfonic acid group, and a phosphonic group. Among them, an acrylic monomer having a carboxyl group (for example, acrylic acid) Methacrylic acid, crotonic acid, ethacrylic acid, propylacrylic acid, isopropylacrylic acid, itaconic acid, fumaric acid and the like), and acrylic acid or methacrylic acid is particularly preferred.

  The polymer particles in the present invention are preferably self-dispersing polymer particles from the viewpoint of ejection stability and liquid stability (particularly dispersion stability) when a pigment is used, and self-dispersing polymer particles having a carboxyl group are preferred. More preferred. Self-dispersing polymer particles are water-insoluble polymers that can be dispersed in an aqueous medium by the functional groups (particularly acidic groups or salts thereof) of the polymer itself in the absence of other surfactants, By means of water-insoluble polymer particles containing no free emulsifier.

Here, the dispersed state means both an emulsified state (emulsion) in which a water-insoluble polymer is dispersed in an aqueous medium and a dispersed state (suspension) in which a water-insoluble polymer is dispersed in an aqueous medium. It includes the state of.
The water-insoluble polymer in the present invention is preferably a water-insoluble polymer that can be in a dispersed state in which the water-insoluble polymer is dispersed in a solid state from the viewpoint of aggregation rate and fixing property when a liquid composition is used.

  The dispersion state of the self-dispersing polymer particles in the present invention refers to a solution obtained by dissolving 30 g of a water-insoluble polymer in 70 g of an organic solvent (for example, methyl ethyl ketone), and a neutralizing agent capable of neutralizing 100% of the salt-forming group of the water-insoluble polymer. After mixing and stirring (apparatus: stirring apparatus with stirring blade, rotation speed 200 rpm, 30 minutes, 25 ° C.) (sodium hydroxide if the salt-forming group is anionic, acetic acid if cationic) and 200 g of water The state in which even after removing the organic solvent from the mixed solution, it can be visually confirmed that the dispersed state exists stably at 25 ° C. for at least one week.

  The water-insoluble polymer means a polymer having a dissolution amount of 10 g or less when the polymer is dried at 105 ° C. for 2 hours and then dissolved in 100 g of water at 25 ° C., and the dissolution amount is preferable. Is 5 g or less, more preferably 1 g or less. The dissolution amount is the dissolution amount when neutralized with sodium hydroxide or acetic acid according to the kind of the salt-forming group of the water-insoluble polymer.

  The aqueous medium is configured to contain water, and may contain a hydrophilic organic solvent as necessary. In the present invention, it is preferably composed of water and 0.2% by mass or less of a hydrophilic organic solvent with respect to water, and more preferably composed of water.

  The main chain skeleton of the water-insoluble polymer is not particularly limited. For example, a vinyl polymer or a condensation polymer (epoxy resin, polyester, polyurethane, polyamide, cellulose, polyether, polyurea, polyimide, polycarbonate, etc.) is used. it can. Of these, vinyl polymers are particularly preferred.

Preferable examples of the vinyl polymer and the monomer constituting the vinyl polymer include those described in JP-A Nos. 2001-181549 and 2002-88294. In addition, radical transfer of vinyl monomers using dissociable groups (or substituents that can be induced to dissociable groups), polymerization initiators, and iniferters, or dissociable groups on either initiators or terminators A vinyl polymer in which a dissociable group is introduced at the end of a polymer chain by ionic polymerization using a compound having (or a substituent that can be derived from a dissociable group) can also be used.
Moreover, as a suitable example of the monomer which comprises a condensation system polymer and a condensation system polymer, what is described in Unexamined-Japanese-Patent No. 2001-247787 can be mentioned.

  The self-dispersing polymer in the present invention preferably includes a water-insoluble polymer containing a hydrophilic structural unit and a structural unit derived from an aromatic group-containing monomer from the viewpoint of self-dispersibility.

The hydrophilic structural unit is not particularly limited as long as it is derived from a hydrophilic group-containing monomer, and even if it is derived from one kind of hydrophilic group-containing monomer, it contains two or more hydrophilic groups. It may be derived from a monomer. The hydrophilic group is not particularly limited, and may be a dissociable group or a nonionic hydrophilic group.
In the present invention, the hydrophilic group is preferably a dissociable group and more preferably an anionic dissociable group from the viewpoint of promoting self-dispersion and the stability of the formed emulsified or dispersed state. Examples of the dissociable group include a carboxyl group, a phosphoric acid group, and a sulfonic acid group. Among them, a carboxyl group is preferable from the viewpoint of fixability when an ink composition is configured.

The hydrophilic group-containing monomer in the present invention is preferably a dissociable group-containing monomer from the viewpoints of self-dispersibility and aggregation, and is a dissociable group-containing monomer having a dissociable group and an ethylenically unsaturated bond. It is preferable.
Examples of the dissociable group-containing monomer include an unsaturated carboxylic acid monomer, an unsaturated sulfonic acid monomer, and an unsaturated phosphoric acid monomer.

Specific examples of the unsaturated carboxylic acid monomer include acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, citraconic acid, and 2-methacryloyloxymethyl succinic acid. Specific examples of the unsaturated sulfonic acid monomer include styrene sulfonic acid, 2-acrylamido-2-methylpropane sulfonic acid, 3-sulfopropyl (meth) acrylate, and bis- (3-sulfopropyl) -itaconate. It is done. Specific examples of unsaturated phosphoric acid monomers include vinylphosphonic acid, vinyl phosphate, bis (methacryloxyethyl) phosphate, diphenyl-2-acryloyloxyethyl phosphate, diphenyl-2-methacryloyloxyethyl phosphate, dibutyl-2- Examples include acryloyloxyethyl phosphate.
Among the dissociable group-containing monomers, unsaturated carboxylic acid monomers are preferable, and acrylic acid and methacrylic acid are more preferable from the viewpoints of dispersion stability and ejection stability.

The self-dispersing polymer in the present invention preferably contains a polymer having a carboxyl group from the viewpoint of self-dispersibility and the aggregation rate when contacting with the treatment liquid, and has a carboxyl group and has an acid value (mgKOH / g). More preferably, the polymer contains 25 to 100. Furthermore, the acid value is more preferably from 25 to 80, and particularly preferably from 30 to 65, from the viewpoints of self-dispersibility and the aggregation rate when contacted with the treatment liquid.
In particular, when the acid value is 25 or more, the stability of self-dispersibility is good, and when it is 100 or less, the cohesiveness is improved.

The aromatic group-containing monomer is not particularly limited as long as it is a compound containing an aromatic group and a polymerizable group. The aromatic group may be a group derived from an aromatic hydrocarbon or a group derived from an aromatic heterocycle. In the present invention, an aromatic group derived from an aromatic hydrocarbon is preferable from the viewpoint of particle shape stability in an aqueous medium.
The polymerizable group may be a condensation polymerizable polymerizable group or an addition polymerizable polymerizable group. In the present invention, from the viewpoint of particle shape stability in an aqueous medium, an addition polymerizable polymerizable group is preferable, and a group containing an ethylenically unsaturated bond is more preferable.

  The aromatic group-containing monomer in the present invention is preferably a monomer having an aromatic group derived from an aromatic hydrocarbon and an ethylenically unsaturated bond. The aromatic group-containing monomer may be used alone or in combination of two or more.

Examples of the aromatic group-containing monomer include phenoxyethyl (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, and a styrene monomer. Of these, aromatic group-containing (meth) acrylate monomers are preferred from the viewpoint of the balance between the hydrophilicity and hydrophobicity of the polymer chain and the ink fixing property, and phenoxyethyl (meth) acrylate, benzyl (meth) acrylate, and phenyl (meth) are preferred. At least one selected from acrylates is more preferable, and phenoxyethyl (meth) acrylate and benzyl (meth) acrylate are more preferable.
“(Meth) acrylate” means acrylate or methacrylate.

The self-dispersing polymer in the present invention includes a structural unit derived from an aromatic group-containing (meth) acrylate monomer, and the content is preferably 10% by mass to 95% by mass. When the content of the aromatic group-containing (meth) acrylate monomer is 10% by mass to 95% by mass, the stability of the self-emulsification or dispersion state can be improved, and further the increase in ink viscosity can be suppressed.
In the present invention, from the viewpoints of stability in a self-dispersing state, stabilization of particle shape in an aqueous medium due to hydrophobic interaction between aromatic rings, and reduction in the amount of water-soluble components due to appropriate hydrophobicization of particles. More preferably, the content is from mass% to 90 mass%, more preferably from 15 mass% to 80 mass%, and particularly preferably from 25 mass% to 70 mass%.

  The self-dispersing polymer in the present invention can be constituted using, for example, a structural unit derived from an aromatic group-containing monomer and a structural unit derived from a dissociable group-containing monomer. Furthermore, other structural units may be further included as necessary.

The monomer that forms the other structural unit is not particularly limited as long as it is a monomer copolymerizable with the aromatic group-containing monomer and the dissociable group-containing monomer. Among these, an alkyl group-containing monomer is preferable from the viewpoint of flexibility of the polymer skeleton and ease of control of the glass transition temperature (Tg).
Examples of the alkyl group-containing monomer include methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, alkyl (meth) acrylates such as t-butyl (meth) acrylate, hexyl (meth) acrylate, ethylhexyl (meth) acrylate; hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) Ethylenically unsaturated monomers having a hydroxyl group such as acrylate, 4-hydroxybutyl (meth) acrylate, hydroxypentyl (meth) acrylate, hydroxyhexyl (meth) acrylate; Dialkylaminoalkyl (meth) acrylates such as ru (meth) acrylate; N-hydroxyalkyl (meth) such as N-hydroxymethyl (meth) acrylamide, N-hydroxyethyl (meth) acrylamide, N-hydroxybutyl (meth) acrylamide Acrylamide; N-methoxymethyl (meth) acrylamide, N-ethoxymethyl (meth) acrylamide, N- (n-, iso) butoxymethyl (meth) acrylamide, N-methoxyethyl (meth) acrylamide, N-ethoxyethyl (meta And (meth) acrylamides such as N-alkoxyalkyl (meth) acrylamides such as acrylamide and N- (n-, iso) butoxyethyl (meth) acrylamide.

  The molecular weight range of the water-insoluble polymer constituting the self-dispersing polymer particles in the present invention is preferably 3000 to 200,000, more preferably 5000 to 150,000, and more preferably 10,000 to 100,000 in terms of weight average molecular weight. More preferably it is. By setting the weight average molecular weight to 3000 or more, the amount of water-soluble components can be effectively suppressed. Moreover, self-dispersion stability can be improved by making a weight average molecular weight into 200,000 or less.

  The weight average molecular weight is measured by gel permeation chromatography (GPC). GPC uses HLC-8020GPC (manufactured by Tosoh Corporation), TSKgel, Super Multipore HZ-H (manufactured by Tosoh Corporation, 4.6 mm ID × 15 cm) as columns, and THF (tetrahydrofuran) as an eluent. ) Is used. As conditions, the sample concentration is 0.45% by mass, the flow rate is 0.35 ml / min, the sample injection amount is 10 μl, the measurement temperature is 40 ° C., and an IR detector is used. In addition, the calibration curve is “standard sample TSK standard, polystyrene” manufactured by Tosoh Corporation: “F-40”, “F-20”, “F-4”, “F-1”, “A-5000”, It is prepared from 8 samples of “A-2500”, “A-1000”, “n-propylbenzene”.

The water-insoluble polymer constituting the self-dispersing polymer particle in the present invention is a structural unit derived from an aromatic group-containing (meth) acrylate monomer (preferably phenoxyethyl (meth) acrylate) from the viewpoint of controlling the hydrophilicity / hydrophobicity of the polymer. It is preferable that 15-80 mass% of the total mass of a self-dispersing polymer particle is included as a copolymerization ratio for the structural unit derived from and / or the structural unit derived from benzyl (meth) acrylate.
In addition, the water-insoluble polymer has a constitution derived from a carboxyl group-containing monomer having a copolymerization ratio of 15 to 80% by mass of a constitutional unit derived from an aromatic group-containing (meth) acrylate monomer from the viewpoint of controlling the hydrophilicity / hydrophobicity of the polymer. And a structural unit derived from an alkyl group-containing monomer (preferably a structural unit derived from an alkyl ester of (meth) acrylic acid), and a structural unit derived from phenoxyethyl (meth) acrylate and / or Alternatively, a structural unit derived from benzyl (meth) acrylate as a copolymerization ratio of 15 to 80% by mass, a structural unit derived from a carboxyl group-containing monomer, and a structural unit derived from an alkyl group-containing monomer (preferably (meth) A structural unit derived from an alkyl ester having 1 to 4 carbon atoms of acrylic acid) More preferably, the acid value is 25 to 100 and the weight average molecular weight is preferably 3000 to 200,000, the acid value is 25 to 95, and the weight average molecular weight is 5000 to 150,000. It is more preferable that

  Specific examples of the water-insoluble polymer constituting the self-dispersing polymer particles are listed below as exemplary compounds B-01 to B-19, but the present invention is not limited thereto. In addition, the parenthesis represents the mass ratio of the copolymerization component.

B-01: Phenoxyethyl acrylate / methyl methacrylate / acrylic acid copolymer (50/45/5)
B-02: Phenoxyethyl acrylate / benzyl methacrylate / isobutyl methacrylate / methacrylic acid copolymer (30/35/29/6)
B-03: Phenoxyethyl methacrylate / isobutyl methacrylate / methacrylic acid copolymer (50/44/6)
B-04: Phenoxyethyl acrylate / methyl methacrylate / ethyl acrylate / acrylic acid copolymer (30/55/10/5)
B-05: benzyl methacrylate / isobutyl methacrylate / methacrylic acid copolymer (35/59/6)
B-06: Styrene / phenoxyethyl acrylate / methyl methacrylate / acrylic acid copolymer (10/50/35/5)
B-07: benzyl acrylate / methyl methacrylate / acrylic acid copolymer (55/40/5)
B-08: Phenoxyethyl methacrylate / benzyl acrylate / methacrylic acid copolymer (45/47/8)
B-09: Styrene / phenoxyethyl acrylate / butyl methacrylate / acrylic acid copolymer (5/48/40/7)
B-10: benzyl methacrylate / isobutyl methacrylate / cyclohexyl methacrylate / methacrylic acid copolymer (35/30/30/5)
B-11: Phenoxyethyl acrylate / methyl methacrylate / butyl acrylate / methacrylic acid copolymer (12/50/30/8)
B-12: benzyl acrylate / isobutyl methacrylate / acrylic acid copolymer (93/2/5)
B-13: Styrene / phenoxyethyl methacrylate / butyl acrylate / acrylic acid copolymer (50/5/20/25)
B-14: Styrene / butyl acrylate / acrylic acid copolymer (62/35/3)
B-15: Methyl methacrylate / phenoxyethyl acrylate / acrylic acid copolymer (45/51/4)
B-16: Methyl methacrylate / phenoxyethyl acrylate / acrylic acid copolymer (45/49/6)
B-17: Methyl methacrylate / phenoxyethyl acrylate / acrylic acid copolymer (45/48/7)
B-18: Methyl methacrylate / phenoxyethyl acrylate / acrylic acid copolymer (45/47/8)
B-19: Methyl methacrylate / phenoxyethyl acrylate / acrylic acid copolymer (45/45/10)

  The method for producing the water-insoluble polymer constituting the self-dispersing polymer particles in the present invention is not particularly limited. For example, emulsion polymerization is carried out in the presence of a polymerizable surfactant to obtain a surfactant and a water-insoluble polymer. Examples include a method of covalent bonding, and a method of copolymerizing a monomer mixture containing the hydrophilic group-containing monomer and the aromatic group-containing monomer by a known polymerization method such as a solution polymerization method or a bulk polymerization method. Among the polymerization methods, a solution polymerization method is preferable and a solution polymerization method using an organic solvent is more preferable from the viewpoint of aggregation rate and droplet ejection stability when an ink composition is used.

  The self-dispersing polymer particles in the present invention include a polymer synthesized in an organic solvent from the viewpoint of aggregation rate, and the polymer has a carboxyl group (preferably having an acid value of 20 to 100). Part or all of the carboxyl groups of the polymer are preferably neutralized and prepared as a polymer dispersion having water as a continuous phase. That is, the production of the self-dispersing polymer particles in the present invention includes a step of synthesizing a polymer in an organic solvent and a dispersion step of making an aqueous dispersion in which at least a part of the carboxyl groups of the polymer is neutralized. It is preferable to do so.

The dispersion step preferably includes the following step (1) and step (2).
Step (1): Step of stirring a mixture containing a polymer (water-insoluble polymer), an organic solvent, a neutralizing agent, and an aqueous medium Step (2): Step of removing the organic solvent from the mixture

The step (1) is preferably a treatment in which a polymer (water-insoluble polymer) is first dissolved in an organic solvent, then a neutralizing agent and an aqueous medium are gradually added, mixed and stirred to obtain a dispersion. In this way, by adding a neutralizing agent and an aqueous medium to a water-insoluble polymer solution dissolved in an organic solvent, a self-dispersing polymer having a particle size with higher storage stability without requiring strong shearing force. Particles can be obtained.
There is no restriction | limiting in particular in the stirring method of this mixture, Dispersers, such as a generally used mixing stirring apparatus and an ultrasonic disperser, a high-pressure homogenizer, can be used as needed.

Preferred examples of the organic solvent include alcohol solvents, ketone solvents, and ether solvents.
Examples of the alcohol solvent include isopropyl alcohol, n-butanol, t-butanol, ethanol and the like. Examples of the ketone solvent include acetone, methyl ethyl ketone, diethyl ketone, and methyl isobutyl ketone. Examples of ether solvents include dibutyl ether and dioxane. Among these solvents, ketone solvents such as methyl ethyl ketone and alcohol solvents such as isopropyl alcohol are preferable. It is also preferable to use isopropyl alcohol and methyl ethyl ketone in combination for the purpose of moderating the polarity change during the phase inversion from oil to water. By using this solvent in combination, it is possible to obtain self-dispersing polymer particles having a fine particle size with high dispersion stability without aggregation and sedimentation and fusion between particles.
As the aqueous medium, water or a mixed solvent of water and a water-miscible organic solvent (for example, a small amount) is included, and an additive or the like added to the water or the mixed solvent as necessary is also used. be able to.

  The neutralizing agent is used so that a part or all of the dissociable group is neutralized and the self-dispersing polymer forms a stable emulsified or dispersed state in water. When the self-dispersing polymer of the present invention has an anionic dissociative group (for example, a carboxyl group) as a dissociable group, the neutralizing agent used is basic such as an organic amine compound, ammonia, or an alkali metal hydroxide. Compounds. Examples of organic amine compounds include monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monopropylamine, dipropylamine, monoethanolamine, diethanolamine, triethanolamine, N, N-dimethyl-ethanolamine, N, N-diethyl-ethanolamine, 2-dimethylamino-2-methyl-1-propanol, 2-amino-2-methyl-1-propanol, N-methyldiethanolamine, N-ethyldiethanolanine, monoisopropanolamine, di Examples include isopropanolamine and triisopropanolamine. Examples of the alkali metal hydroxide include lithium hydroxide, sodium hydroxide, and potassium hydroxide. Among these, sodium hydroxide, potassium hydroxide, triethylamine, and triethanolamine are preferable from the viewpoint of stabilizing the dispersion of the self-dispersing polymer particles of the present invention in water.

  These basic compounds are preferably used in an amount of 5 to 120 mol%, more preferably 10 to 110 mol%, still more preferably 15 to 100 mol%, based on 100 mol% of the dissociable group. . By setting it as 15 mol% or more, the effect which stabilizes dispersion | distribution of the particle | grains in water expresses, and there exists an effect which reduces a water-soluble component by setting it as 100 mol% or less.

  In the step (2), the aqueous dispersion of the self-dispersing polymer particles is obtained by distilling off the organic solvent from the dispersion obtained in the step (1) by a conventional method such as distillation under reduced pressure and phase-inversion into an aqueous system. A dispersion can be obtained. The organic solvent in the obtained aqueous dispersion has been substantially removed, and the amount of the organic solvent is preferably 0.2% by mass or less, more preferably 0.1% by mass or less.

The average particle size of the polymer particles (particularly self-dispersing polymer particles) is preferably in the range of 10 to 400 nm, more preferably in the range of 10 to 200 nm, still more preferably in the range of 10 to 100 nm, and particularly preferably in terms of volume average particle size. It is the range of 10-50 nm. Manufacturability is improved by having an average particle diameter of 10 nm or more. Moreover, storage stability improves by setting it as an average particle diameter of 400 nm or less. Moreover, there is no restriction | limiting in particular regarding the particle size distribution of a polymer particle, Any of what has a wide particle size distribution or a monodispersed particle size distribution may be sufficient. Further, two or more water-insoluble particles may be mixed and used.
The average particle size and particle size distribution of the polymer particles are determined by measuring the volume average particle size by a dynamic light scattering method using a nanotrack particle size distribution measuring device UPA-EX150 (manufactured by Nikkiso Co., Ltd.). It is what

The content of the polymer particles (particularly self-dispersing polymer particles) in the liquid composition is preferably 1 to 30% by mass with respect to the liquid composition from the viewpoint of glossiness of the image, More preferably, it is 15 mass%.
The polymer particles (particularly self-dispersing polymer particles) can be used singly or in combination of two or more.

In the ink composition of the present invention, the total amount of pigment, water-insoluble dispersant (pigment dispersant), and polymer particles (hereinafter also referred to as water-insoluble components) is 7% by mass or more from the viewpoint of abrasion resistance. It is preferable to adjust so that.
The total amount of the water-insoluble component is preferably in the range of 7 to 20% by mass, and more preferably in the range of 8 to 15% by mass, from the viewpoint of achieving both rubbing resistance and fixability. Moreover, it is preferable that the ratio of the polymer particle in a water-insoluble component is 30-90 mass% from a viewpoint of abrasion resistance, and it is more preferable that it is 40-75 mass%.
In addition, from the viewpoint of suppressing a decrease in viscosity at high shear and improving dischargeability, the ratio of the amount of the polymer thickener to the amount of the water-insoluble component is preferably less than 0.3. It is more preferable to make it smaller.

<Surfactant>
The ink composition of the present invention can contain at least one surfactant. The surface tension of the ink composition can be adjusted by adding a surfactant. As the surfactant, any of nonionic, cationic, anionic, and betaine surfactants may be used. The addition amount of the surfactant is preferably an amount for adjusting the surface tension of the ink of the present invention to 20 to 60 mN / m, more preferably 20 to 45 mN / m, and still more preferably, in order to eject droplets well by inkjet. The amount can be adjusted to 25 to 40 mN / m.
As the surfactant in the present invention, a compound having a structure having both a hydrophilic part and a hydrophobic part in the molecule can be used effectively. Anionic surfactants, cationic surfactants, amphoteric surfactants can be used. Any of the nonionic surfactants can be used. Furthermore, the above-mentioned polymer substance (polymer dispersant) can also be used as a surfactant.

Specific examples of anionic surfactants include, for example, sodium dodecylbenzenesulfonate, sodium lauryl sulfate, sodium alkyldiphenyl ether disulfonate, sodium alkylnaphthalenesulfonate, sodium dialkylsulfosuccinate, sodium stearate, potassium oleate, sodium dioctyl Sulfosuccinate, sodium polyoxyethylene alkyl ether sulfate, sodium polyoxyethylene alkyl ether sulfate, sodium polyoxyethylene alkyl phenyl ether sulfate, sodium dialkylsulfosuccinate, sodium stearate, sodium oleate, t-octylphenoxyethoxypolyethoxyethyl Examples include sodium sulfate, etc., and select one or more of these Rukoto can.
Specific examples of the nonionic surfactant include, for example, polyoxyethylene lauryl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene oleyl phenyl ether, polyoxyethylene nonyl phenyl ether, oxyethylene / oxypropylene block copolymer, t- Examples include octylphenoxyethyl polyethoxyethanol, nonylphenoxyethyl polyethoxyethanol, and the like, and one or more of these can be selected.
Examples of the cationic surfactant include tetraalkylammonium salts, alkylamine salts, benzalkonium salts, alkylpyridium salts, imidazolium salts, and the like. Specific examples thereof include dihydroxyethyl stearylamine and 2-heptadecenyl. -Hydroxyethyl imidazoline, lauryl dimethyl benzyl ammonium chloride, cetyl pyridinium chloride, stearamide methyl pyridium chloride and the like.
The amount of the surfactant added to the ink composition in the invention is not particularly limited, but is preferably 1% by mass or more, more preferably 1 to 10% by mass, and still more preferably 1 to 3%. % By mass.

<Other ingredients>
The ink composition of the present invention may contain other additives. Other additives include, for example, ultraviolet absorbers, anti-fading agents, anti-mold agents, pH adjusters, rust inhibitors, antioxidants, emulsion stabilizers, preservatives, antifoaming agents, viscosity modifiers, and dispersion stabilizers. Known additives such as agents and chelating agents are included.

  Examples of the UV absorber include benzophenone UV absorbers, benzotriazole UV absorbers, salicylate UV absorbers, cyanoacrylate UV absorbers, nickel complex salt UV absorbers, and the like.

  As the antifading agent, various organic and metal complex antifading agents can be used. Organic anti-fading agents include hydroquinones, alkoxyphenols, dialkoxyphenols, phenols, anilines, amines, indanes, chromans, alkoxyanilines, heterocycles, etc. Complex, zinc complex and the like.

  Antifungal agents include sodium dehydroacetate, sodium benzoate, sodium pyridinethione-1-oxide, p-hydroxybenzoic acid ethyl ester, 1,2-benzisothiazolin-3-one, sodium sorbate, sodium pentachlorophenol, etc. Can be mentioned. These are preferably used in the ink in an amount of 0.02 to 1.00% by mass.

  The pH adjuster is not particularly limited as long as it can adjust the pH to a desired value without adversely affecting the ink composition to be prepared, and can be appropriately selected according to the purpose. Amines (eg, diethanolamine, triethanolamine, 2-amino-2-ethyl-1,3-propanediol), alkali metal hydroxides (eg, lithium hydroxide, sodium hydroxide, potassium hydroxide), ammonium Examples thereof include hydroxides (for example, ammonium hydroxide and quaternary ammonium hydroxides), phosphonium hydroxides, alkali metal carbonates, and the like.

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

  Examples of the antioxidant include phenol antioxidants (including hindered phenol antioxidants), amine antioxidants, sulfur antioxidants, phosphorus antioxidants, and the like.

  Examples of the chelating agent include sodium ethylenediaminetetraacetate, sodium nitrilotriacetate, sodium hydroxyethylethylenediaminetriacetate, sodium diethylenetriaminepentaacetate, sodium uramil diacetate and the like.

(Physical properties of ink composition)
The surface tension of the ink composition of the present invention is preferably 20 mN / m or more and 60 mN / m or less. More preferably, it is 20 mN or more and 45 mN / m or less, More preferably, it is 25 mN / m or more and 40 mN / m or less. The surface tension can be adjusted to a desired range by containing a surfactant, for example.

  In addition, the viscosity at 20 ° C. of the ink composition of the present invention is preferably 5 mPa · s or more and 20 mPa · s or less, more preferably 5.5 mPa · s or more and less than 18 mPa · s, from the viewpoint of ejectability. Preferably, it is 6 mPa · s or more and less than 16 mPa · s. Furthermore, the viscosity at 40 ° C. of the ink composition of the present invention is preferably 3 mPa · s or more and 15 mPa · s or less, more preferably 3.5 mPa · s or more and less than 12 mPa · s, and further preferably 4 mPa · s or more. It is less than 10 mPa · s. The viscosity can be adjusted to a desired range, for example, by changing the molecular weight or content of the water-soluble organic solvent. In this invention, it can adjust to a desired range more easily by including the said 1st water-soluble organic solvent.

[Reaction solution]
In the present invention, a reaction liquid (hereinafter also referred to as “treatment liquid”) capable of forming an aggregate by contact with the ink composition can be used together with the ink composition. In particular, in the image forming method of the present invention, by applying the ink composition in advance to the ink jet recording medium before applying the ink composition, the reaction liquid and the ink composition are brought into contact with each other to form an ink aggregate at a high speed. Can do.
The reaction liquid can be applied to the ink jet recording medium either before or after application of the ink composition.
In the present invention, the pH of the reaction liquid is preferably 1 to 6, more preferably 2 to 5, and further preferably 3 to 5, from the viewpoint of the aggregation rate of the ink composition. The treatment liquid in the present invention can be configured to contain at least one acidic compound. As the acidic compound, a compound having a phosphoric acid group, a phosphonic acid group, a phosphinic acid group, a sulfuric acid group, a sulfonic acid group, a sulfinic acid group or a carboxyl group, or a salt thereof can be used. Among these, from the viewpoint of the aggregation rate of the aqueous ink composition, a compound having a phosphate group or a carboxyl group is more preferable, and a compound having a carboxyl group is more preferable.

  As the compound having a carboxyl group in the present invention, polyacrylic acid, acetic acid, glycolic acid, malonic acid, malic acid, maleic acid, ascorbic acid, succinic acid, glutaric acid, fumaric acid, citric acid, tartaric acid, lactic acid, sulfonic acid , Orthophosphoric acid, pyrrolidone carboxylic acid, pyrone carboxylic acid, pyrrole carboxylic acid, furan carboxylic acid, pyridine carboxylic acid, coumaric acid, thiophene carboxylic acid, nicotinic acid, derivatives of these compounds, or salts thereof It is preferable that These compounds may be used alone or in combination of two or more.

The treatment liquid in the present invention can be configured to further contain an aqueous solvent (for example, water) in addition to the acidic compound.
As content of the acidic compound of a processing liquid, it is preferable that it is 5-95 mass% with respect to the total mass of a processing liquid from a viewpoint of the aggregation effect, and it is more preferable that it is 10-80 mass%.

  Moreover, as a preferable example of the reaction liquid that can be used in the present invention to improve high-speed aggregation, a reaction liquid to which a polyvalent metal salt or polyallylamine is added can be mentioned. As a component of the liquid composition, as a polyvalent metal salt, an alkaline earth metal of Group 2A of the periodic table (for example, magnesium and calcium); a transition metal of Group 3B of the periodic table (for example, lanthanum); from Group 3A of the periodic table Cations (for example, aluminum); lanthanides (for example, neodymium); and polyallylamine and polyallylamine derivatives. Preferred examples include calcium and magnesium. Anions that are preferably employed as a counter salt of calcium or magnesium include carboxylate (formic acid, acetic acid, benzoate, etc.), nitrate, chloride, and thiocyanate. As an addition amount to the treatment liquid, the salt is contained in the treatment liquid in an amount ranging from about 1 to about 10% by weight, preferably from about 1.5 to about 7% by weight, more preferably from about 2 to about 6% by weight. Can exist.

  Further, the treatment liquid may contain other additives within a range that does not impair the effects of the present invention. Other additives include, for example, anti-drying agents (wetting agents), anti-fading agents, emulsion stabilizers, penetration enhancers, ultraviolet absorbers, preservatives, anti-fungal agents, pH adjusters, surface tension adjusters, Known additives such as foaming agents, viscosity modifiers, dispersants, dispersion stabilizers, rust preventives, chelating agents can be mentioned, and are shown as specific examples of other additives contained in the above-mentioned aqueous ink composition. Can be applied.

The viscosity of the treatment liquid in the present invention is preferably in the range of 1 to 30 mPa · s, more preferably in the range of 1 to 20 mPa · s, and further in the range of 2 to 15 mPa · s from the viewpoint of the aggregation rate of the ink composition. A range of 2 to 10 mPa · s is particularly preferable.
The surface tension of the treatment liquid is preferably 20 to 60 mN / m, more preferably 20 to 45 mN / m, and more preferably 25 to 40 mN / m from the viewpoint of the aggregation rate of the ink composition. More preferably.

≪Image formation method≫
The image forming method of the present invention includes a plurality of droplet ejection elements, a common channel communicating with each of the plurality of droplet ejection elements via a supply path, and a plurality of droplet ejection elements via a reflux path. An image including an ink circulation device that has a common circulation path that communicates, supplies an ink composition from the common flow path to the plurality of droplet discharge elements, and circulates the ink composition in the common circulation path An image is formed on a recording medium by ejecting the above-described ink composition using a forming apparatus.
That is, the present invention provides an image forming method excellent in stable ejection performance (particularly intermittent ejection performance) and image resolution by using the ink composition and the specific image forming apparatus in the present invention. Is.

(Image forming device)
The image forming apparatus according to the present invention includes a plurality of droplet discharge elements, a common flow path communicating with the plurality of droplet discharge elements via a supply path, and a plurality of droplet discharge elements via a reflux path. An ink circulation device having a common circulation path in communication, supplying an ink composition from the common flow path to the plurality of droplet discharge elements, and circulating the ink composition in the common circulation path; And
Except for the above configuration, the image forming apparatus is not particularly limited and may include other known devices.
In the present invention, since the ink composition to be used is always circulated by adopting the configuration of the image forming method of the present invention, the viscosity of the ink composition in the vicinity of the nozzle is high even in a nozzle that is not in use and is waiting. Therefore, the ejection failure can be prevented. In particular, using the above-described ink composition, it is possible to remarkably prevent defects during intermittent ejection.

[Configuration of ink circulation system]
An ink circulation system of an ink jet recording apparatus which is an embodiment of an image forming apparatus according to the present invention will be described.

FIG. 1 is a schematic diagram showing an ink circulation system of an ink jet recording apparatus.
As shown in FIG. 1, the ink circulation system of the inkjet recording apparatus 10 mainly includes a recording head 50 (50A), an ink tank 100, a sub tank 102, a solvent concentration detector 104, a solvent addition apparatus 106, and a deaeration apparatus 108. Ink is supplied from the ink tank 100 to the recording head 50 via the sub tank 102, and ink droplets are discharged from the plurality of nozzles 64 formed in the recording head 50 and supplied to the recording head 50. Part of the ink circulates inside the head and is returned to the sub tank 102.
Hereinafter, the configuration of each unit will be described.

  A pump 112 is provided in a flow path 110 connecting the ink tank 100 and the sub tank 102. The ink in the ink tank 100 is supplied to the sub tank 102 by the pump 112. The pump 112 is controlled so that the amount of ink in the sub tank 102 is constant. The sub tank 102 has a built-in ink temperature adjusting heating / cooling device 114, and the ink temperature is adjusted by the ink temperature adjusting heating / cooling device 114 so that the ink in the sub tank 102 has a predetermined temperature, thereby reducing the ink viscosity. . For example, a temperature sensor (not shown) for detecting the ink temperature inside the recording head 50 is provided so that the ink temperature inside the recording head 50 becomes a predetermined temperature (for example, 55 ° C.) (that is, a desired ink viscosity is obtained). Thus, there is a mode in which the heating / cooling device 114 for adjusting the ink temperature is controlled.

  The sub tank 102 and the recording head 50 are connected by first and second flow paths 116 and 118. A first flow path 116 is connected via a first supply port 54 formed at one end of a common flow path 52 formed in the recording head 50, and a first flow path formed at the other end of the common flow path 52. The second flow path 118 is connected through the two supply ports 56. The first flow path 116 is a supply flow path for supplying ink from the sub tank 102 to the recording head 50, and is provided with a pump 120 and a filter 122. On the other hand, the second flow path 118 is a circulation flow path for returning a part of the ink supplied to the recording head 50 to the sub tank 102 and is provided with a pump 124.

  The ink in the sub tank 102 is supplied from the first flow path 116 to the recording head 50 through the filter 122 by the pump 120. The fineness (mesh size) of the filter 122 is preferably smaller than the nozzle diameter, and foreign matter mixed into the recording head 50 from the sub tank 102 can be prevented from clogging the nozzle. For example, a filter having a mesh size that is about 10% smaller than the nozzle diameter is used.

  A part of the ink supplied to the recording head 50 is returned from the second flow path 118 to the sub tank 102 by the pump 124 via the common flow path 52. Although not shown, there is also an aspect in which a vacuum deaeration device is installed in the second flow path 118 on the upstream side (the recording head 50 side) from the pump 124.

  Each pressure chamber 58 that communicates with the common flow path 52 is provided with a nozzle flow path 62 that is a communication path with the nozzle 64. The nozzle flow path 72 is provided with a reflux path 72 and communicates with the common circulation path 70 via the reflux path 72. The common circulation path 70 communicates with a recovery port 74 via a connection channel (noted as 71 in FIG. 3), and a flow channel 130 connected to the pump 132 is connected to the recovery port 74.

  FIG. 2 is a schematic diagram illustrating an example of the internal structure of the recording head 50. As shown in FIG. 2, the recording head 50 includes a nozzle 64 that serves as an ink droplet ejection port, a pressure chamber 58, a supply path 60, and a piezoelectric element 68 that deforms a diaphragm 66 that forms the wall surface of the pressure chamber 58. A plurality of droplet discharge elements 80 are provided. Although the detailed configuration of the recording head 50 will be described later, the recording head 50 is configured by arranging a plurality of head units. A large number of droplet discharge elements 80 are arranged in a matrix (two-dimensional) in each head unit. Sequence).

  Each pressure chamber 58 communicates with the common flow path 52 via the supply path 60, and ink is supplied from the common flow path 52 to each pressure chamber 58 via the corresponding supply path 60. The supply path 60 also functions as a supply throttle that suppresses the back flow from the pressure chamber 58 to the common flow path 52. A nozzle 64 communicates with each pressure chamber 58 via a nozzle channel 62.

  A piezoelectric element 68 is provided on the vibration plate 66 constituting the wall surface of each pressure chamber 58. When a driving voltage is applied to the piezoelectric element 68, the volume of the pressure chamber 58 changes according to the deformation of the diaphragm 66. When the diaphragm 66 is deformed in the direction in which the volume of the pressure chamber 58 increases, the meniscus formed in the nozzle 64 is drawn to the ink inflow side (pressure chamber 58 side), and the ink in the common channel 52 is supplied to the supply channel 60. Then, it is sucked into the pressure chamber 58 through and the refill is performed. On the other hand, when the diaphragm 66 is deformed in the direction in which the volume of the pressure chamber 58 decreases, the meniscus of the nozzle 64 is pushed out to the ink discharge side (the side opposite to the pressure chamber 58), and ink droplets are discharged from the nozzle 64. In particular, the interval between the pulling and pushing is preferably ¼ of the fluid resonance period between the pressure chamber 58 and the ink. The pulling and pushing vibrations are superposed to obtain a large displacement, and the ink is easily ejected. It becomes possible.

  When ink is ejected, the ink in the pressure chamber 58 not only flows through the nozzle flow path 62 on the ink ejection side, but also partially flows through the supply path 60 on the ink supply side. The ink flow rate from the pressure chamber 58 toward the nozzle flow path 62 and the ink flow rate toward the supply path 60 are determined by the ratio of the flow path resistance and inertance. In a general ink jet head, the dimensions of each part are determined so as to be approximately 1: 1.

  FIG. 3 is a plan view showing the detailed structure of the recording head 50. 4 is a cross-sectional view (a cross-sectional view taken along line 7-7 in FIG. 3) showing a part of the recording head 50. As shown in FIG. In FIG. 3, the diaphragm 66 and the piezoelectric element 68 are not shown in order to facilitate understanding of the arrangement of the pressure chambers 58. The recording head 50 of this embodiment is configured by arranging a plurality of head units 51 shown in FIGS. 3 and 4. Of course, the head may be composed of one head unit 51.

  As shown in FIG. 3, in the head unit 51, droplet discharge elements 80 including nozzles 64 and pressure chambers 58 are arranged in a matrix (two-dimensional). The common flow path 52 is formed over the entire region where each pressure chamber 58 is formed, and three first and second supply ports 54 and 56 that open to the common flow path 52 are provided. .

  The head unit 51 is provided with a plurality of common circulation paths 70 for each pressure chamber row 59. Each common circulation path 70 communicates with each pressure chamber 58 of the corresponding pressure chamber row 59. Specifically, as shown in FIG. 2, the pressure chambers 58 communicate with each other via corresponding nozzle channels 62 and reflux channels 72. The plurality of common circulation paths 70 are connected to one through a communication flow path 71, and three recovery ports 74 are formed in the communication flow path 71.

As shown in FIG. 4, a piezoelectric element 68 having an individual electrode 69 is provided on a vibration plate 66 constituting the wall surface of the pressure chamber 58. The diaphragm 66 uses a conductive substrate having an electrode layer (conductive layer) formed at least on its surface, and also serves as a common electrode of the piezoelectric element 68. A piezoelectric material such as lead zirconate titanate (piezo) is preferably used for the piezoelectric element 68.
A protective cover 67 is provided so as to cover the piezoelectric element 68 on the vibration plate 66, and insulation protection of the piezoelectric element 68 and other wiring members (not shown) with respect to the ink in the common flow path 52 is achieved. .

In the recording head 50 configured as described above, as shown in FIG. 3, the pressure of the ink in the first supply port 54 formed on the upstream side of the common flow path 52 is P1, and the first pressure formed on the downstream side thereof. When the pressure of the ink at the second supply port 56 is P2, and the pressure of the ink at the recovery port 74 formed at one end of the common circulation path 70 (more specifically, the communication flow path 71) is P3,
When the pressures P1, P2, and P3 are set or controlled so that the relationship of P1>P2> P3 is established, an ink flow from the upstream side to the downstream side of the common flow path 52 is formed and is common. An ink flow is formed from the flow path 52 toward the common circulation path 70 via the supply path 60, the pressure chamber 58, the nozzle flow path 62, and the reflux path 72. In general, since the common channel 52 has a large channel cross-sectional area and a small fluid resistance, the pressure difference ΔP between the first and second supply ports 54 and 56 is about several hundred to several kPa. .

  The flow rate per unit time of the ink flowing in the common flow path 52 is determined from the ink pressure difference (P1-P2) between the first and second supply ports 54 and 56 and the fluid resistance of the common flow path 52. Can do. The flow rate of the common flow path 52 is an amount that can control the temperature change due to heat generation of the recording head 50, and is preferably set to a flow rate that allows air bubbles to flow when they enter the common flow path 52. Both conditions can be met by increasing the flow rate. However, although it is necessary to set a range in which no turbulent flow is generated in the common flow path 52, it is considered that there is no solution at first with respect to the heat generation amount and dimensions of a general inkjet head.

  For example, a realistic flow rate is about 10 to 20 times the ink consumption per unit time in the full ejection state of the head (ejection when ejection is continued at the maximum frequency and maximum ejection volume for drawing). If a head that discharges 2 [pl] at 40 [kHz] has a nozzle density of 1200 [dpi] and has a length of 2 inches per unit, 2 × 2 × 1200 × 40000 [pl / sec] = 0 Since 192 [ml / sec] is the ink consumption, the amount of ink flowing through the common flow path 52 is set to about 2 to 4 [ml / sec].

Further, the pressures P1 and P2 applied to the supply ports 54 and 56 by the pumps 120 and 124 are weak negative pressures so as to slightly draw the meniscus formed in the openings of the nozzles 64 of the recording head 50. And -20 to -60 [mmH ₂ O] with respect to atmospheric pressure.

In general, in an ink jet head, the ink in the nozzle portion is generally made slightly negative with respect to the atmospheric pressure so that the ink does not leak from the non-ejection nozzle. If the negative pressure is too strong, the surface tension of the meniscus loses the pressure and sucks air from the nozzle. For example, when ink having a surface tension of 35 [mN / m] is used for a nozzle having a diameter of 18 [μm], the maximum value of the surface tension is 1.98 × 10 ⁻⁶ [N]. [KN / m ² ]. Since this is 81 [gf / cm ² ] in terms of conversion, the negative pressure is balanced with the meniscus in a state of −810 [mmH ₂ O], and when it exceeds this, the meniscus is broken. However, since there are many nozzles in an actual head, the meniscus with a back pressure lower than this calculated value is caused by the machining accuracy of the nozzle part, surface roughness, defects in the water repellency treatment of the nozzle part, and vibration. Often breaks. Actually, in the experiment, a stable result cannot always be obtained due to the instability factors as described above, but there are many cases where it is broken at −100 to −400 [mmH ₂ O]. Therefore, from the experiment, the upper limit of the back pressure is set to −60 [mmH ₂ O] by looking at the margin. On the other hand, the lower limit is set to −20 [mmH ₂ O] so that ink does not leak due to environmental changes such as atmospheric pressure and temperature, and vibration, even though back pressure is applied. Each value is not a theoretically obtained value but a range in which stable performance based on experiments can be obtained.

  Returning to FIG. 1, the flow path 130 is connected to the recovery port 74 of the recording head 50. The flow path 130 is provided with a pump 132, and the end opposite to the recovery port 74 is connected to the reservoir tank 134. The ink circulated from the common flow path 52 through the supply path 60, the pressure chamber 58, the nozzle flow path 62, the reflux path 72, and the common circulation path 70 from the recovery port 74 through the flow path 130 to the reservoir tank 134 by the pump 132. Collected.

  In the flow path 136 connecting the reservoir tank 134 and the sub tank 102, the solvent concentration detector 104, the solvent addition device 106, and the deaeration device 108 from the upstream side (reservoir tank 134 side) to the downstream side (sub tank 102 side). The pump 138 and the filter 140 are provided in this order.

  When returning the ink collected in the reservoir tank 134 to the sub tank 102 via the flow path 136, first, the solvent concentration detector 104 detects the solvent concentration from the ink density, viscosity, flow rate change, electrical conductivity, and the like. Done. Subsequently, the solvent addition device 106 adds the solvent in the solvent tank 144 to the ink in the flow path 136 according to the detection result by the solvent concentration detector 104. As a result, the circulating ink that has passed through the pressure chamber 58 and the nozzle channel 62, particularly the ink that has increased in viscosity near the nozzle, can be recovered to an appropriate viscosity. As will be described later, the solvent concentration detected by the solvent concentration detector 104 is sent to a solvent concentration control unit (not shown), and the solvent addition device 106 is driven by the solvent concentration control unit.

  Further, the deaeration device 108 connected to the vacuum pump 146 performs a process (deaeration process) for reducing the amount of dissolved air in the ink. Note that the deaeration device 108 is omitted when a vacuum deaeration device is provided on the upstream side (recording head 50 side) of the pump 124 of the second flow path 118 that connects the sub tank 102 and the recording head 50.

  The ink that has been deaerated by the deaerator 108 is returned to the sub tank 102 by the pump 138 via the filter 140. Thereafter, the ink is supplied again to the recording head 50 together with the ink supplied from the ink tank 100.

  According to the configuration of the ink circulation system shown in FIG. 1, since the reservoir tank 134 is disposed between the pump 132 and the solvent addition device 106 or the deaeration device 108, the reservoir 132 is given to the recovery port 74 by the pump 132. It is possible to prevent the pressure P3 from being affected by regeneration treatment such as solvent addition and deaeration.

(Function)
The operation of the ink circulation system of the ink jet recording apparatus which is an embodiment of the image forming apparatus according to the present invention will be described with reference to FIG.

  FIG. 5 is an explanatory diagram of the ink flow for explaining the flow of ink flowing from the common flow path 52 to the common circulation path 70 via the supply path 60.

In FIG. 5, ink supplied from an ink tank (not shown) first flows to a common flow path (supply side) 52. Next, ink is supplied from the common flow path (supply side) 52 to the individual pressure chambers 58 through the supply path 60. The supply path 60 is designed to increase the inertance, and prevents ink from flowing back to the common flow path (supply side) 52 during ejection. The ink introduced into the pressure chamber 58 is ejected from the nozzle as the pressure element (actuator) 68 is driven. In addition to the operation of the pressure element (actuator) 68, the circulation path from the pressure chamber 58 to the common circulation path (circulation side) 70 due to the pressure difference between the common flow path (supply side) 52 and the common circulation path (circulation side) 70. Ink flows through 72. This circulation path is designed so that the inertance becomes large in order to prevent ink during ejection from flowing to the common circulation path (circulation side) 70. The ink that has flowed to the common circulation path (circulation side) 70 returns to the ink tank.
The ink flow is as shown in Table 1 below.
The flow in the circulation is caused by the pressure difference between the liquids in the common flow path (supply side) and the common circulation path (circulation side). Further, the discharge flow is generated by the pressure generated by the pressure element (actuator). This abrupt flow hardly generates any flow in the supply path and circulation path with a large inertance.

  As described above, since the ink is constantly circulated, a change in physical properties due to drying of the ink is suppressed, and the image forming method of the present invention having the ink circulation system is an image forming method excellent in intermittent ink discharge performance. be able to.

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. Unless otherwise specified, “part” and “%” are based on mass.

<Example 1>
~ Preparation of ink composition ~
[Preparation of pigment (coloring material) dispersion]
(Preparation of polymer dispersant PD-1)
In a reaction vessel, 6 parts of styrene, 11 parts of stearyl methacrylate, 4 parts of styrene macromer AS-6 (manufactured by Toa Gosei), 5 parts of Blenmer PP-500 (manufactured by NOF Corporation), 5 parts of methacrylic acid, 0.05 of 2-mercaptoethanol A mixed solution of 24 parts of methyl ethyl ketone was prepared.
Meanwhile, in a dropping funnel, 14 parts of styrene, 24 parts of stearyl methacrylate, 9 parts of styrene macromer AS-6 (manufactured by Toa Gosei), 9 parts of Blemmer PP-500 (manufactured by NOF Corporation), 10 parts of methacrylic acid, 2-mercaptoethanol 0 .13 parts, 56 parts of methyl ethyl ketone and 1.2 parts of 2,2′-azobis (2,4-dimethylvaleronitrile) were added to prepare a mixed solution.
And under nitrogen atmosphere, it heated up to 75 degreeC, stirring the mixed solution in reaction container, and the mixed solution in a dropping funnel was dripped gradually over 1 hour. After 2 hours from the end of dropping, a solution prepared by dissolving 1.2 parts of 2,2′-azobis (2,4-dimethylvaleronitrile) in 12 parts of methyl ethyl ketone was added dropwise over 3 hours, and further at 75 ° C. for 2 hours, The solution was aged at 80 ° C. for 2 hours to obtain a polymer dispersant (PD-1) solution.

  A part of the obtained polymer dispersant solution was isolated by removing the solvent, and the obtained solid content was diluted to 0.1% with tetrahydrofuran to obtain a high-speed GPC (gel permeation chromatography) HLC-8220GPC. Then, three TSKgeL SuperHZM-H, TSKgeL SuperHZ4000, and TSKgeL SuperHZ2000 (manufactured by Tosoh Corporation) were connected in series, and the weight average molecular weight was measured. As a result, the isolated solid had a weight average molecular weight of 25,000 in terms of polystyrene. The calculated acid value was 100 mgKOH / g.

(Preparation of cyan dispersion)
Next, 5.0 g in terms of solid content of the obtained polymer dispersant solution, 10.0 g of cyan pigment Pigment Blue 15: 3 (manufactured by Dainichi Seika), 40.0 g of methyl ethyl ketone, 8.0 g of 1 mol / L sodium hydroxide Then, 82.0 g of ion-exchanged water and 300 g of 0.1 mm zirconia beads were supplied to the vessel and dispersed with a ready mill disperser (manufactured by Imex) at 1000 rpm for 6 hours. The obtained pigment dispersion was concentrated with an evaporator under reduced pressure until methyl ethyl ketone was sufficiently distilled off, and concentrated until the pigment concentration was about 12%.
Thereafter, the pigment dispersion was centrifuged at 8000 rpm for 30 minutes to remove coarse particles remaining as precipitates. The absorbance of the supernatant was measured to determine the pigment concentration.
As described above, a cyan dispersion C1 as a color material was prepared. The average particle diameter of the obtained cyan dispersion liquid C1 was 81 nm.

[Preparation of self-dispersing polymer particles]
-Synthesis Example 1
360.0 g of methyl ethyl ketone was charged into a 2-liter three-necked flask equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen gas inlet tube, and the temperature was raised to 75 ° C. While maintaining the temperature in the reaction vessel at 75 ° C., 180.0 g of phenoxyethyl acrylate, 162.0 g of methyl methacrylate, 18.0 g of acrylic acid, 72 g of methyl ethyl ketone, and “V-601” (manufactured by Wako Pure Chemical Industries, Ltd.) A mixed solution consisting of 44 g was added dropwise at a constant speed so that the addition was completed in 2 hours. After completion of the dropwise addition, a solution consisting of 0.72 g of “V-601” and 36.0 g of methyl ethyl ketone was added, stirred for 2 hours at 75 ° C., and then a solution consisting of 0.72 g of “V-601” and 36.0 g of isopropanol was added. After stirring at 75 ° C. for 2 hours, the temperature was raised to 85 ° C., and stirring was further continued for 2 hours. The weight average molecular weight (Mw) of the obtained copolymer was 64000 (calculated in terms of polystyrene by gel permeation chromatography (GPC), columns used were TSKgel SuperHZM-H, TSKgel SuperHZ4000, TSKgel SuperHZ200 (manufactured by Tosoh Corporation)), The acid value was 38.9 (mgKOH / g).
Next, 668.3 g of the polymerization solution was weighed, and 388.3 g of isopropanol, 1 mol / L.
145.7 ml of NaOH aqueous solution was added, and the temperature inside the reaction vessel was raised to 80 ° C. Next, 720.1 g of distilled water was added dropwise at a rate of 20 ml / min to disperse in water. Thereafter, the temperature in the reaction vessel was maintained at 80 ° C. for 2 hours, 85 ° C. for 2 hours, and 90 ° C. for 2 hours under atmospheric pressure, and then the reaction vessel was depressurized, and isopropanol, methyl ethyl ketone, and distilled water totaled 913. 7 g was distilled off to obtain an aqueous dispersion (emulsion) of self-dispersing polymer particles (B-01) having a solid content concentration of 28.0%. In addition, the number of each structural unit of the compound example (B-01) shown below represents a mass ratio. Hereinafter, the same applies to each structural formula.

-Synthesis Example 2-
In the synthesis of Compound Example (B-01) of Synthesis Example 1, each structural unit of the following compound example is represented by the structural formula instead of 180.0 g of phenoxyethyl acrylate, 162.0 g of methyl methacrylate, and 18.0 g of acrylic acid. The following self-dispersing polymer particles (B-02) to (B-05) and (BH) were prepared in the same manner as in Synthesis Example 1 except that the types of monomers used and the mixing amount thereof were changed so as to achieve a mass ratio of A dispersion liquid of -1) was obtained.
Table 2 shows the physical properties of the obtained (B-02) to (B-05) and (BH-1). In all cases, the amount of 1 mol / L NaOH aqueous solution was adjusted so that the degree of neutralization of the self-emulsifying polymer was 0.75 mol equivalent to 1 mol of the dissociable group.

  In addition, when polymer fine particles having the following structural formula in which the amount of acrylic acid was changed to 3% (acid value: 23) or 15% (acid value: 117) were produced, the polymer fine particles could not be self-dispersed. .

[Preparation of polymer particles by emulsion polymerization]
In a 1 liter three-necked flask equipped with a stirrer and a reflux condenser, 8.1 g of Piionin A-43s (manufactured by Takemoto Yushi Co., Ltd., emulsifier) and 236.0 g of distilled water were added and heated and stirred at 70 ° C. in a nitrogen stream. 6.2 g of styrene, 3.5 g of n-butyl acrylate, 0.3 g of acrylic acid, 1.0 g of ammonium persulfate and 40 g of distilled water were added and stirred for 30 minutes, and then 117.8 g of styrene and 66.5 g of n-butyl acrylate. Then, a monomer solution consisting of 5.7 g of acrylic acid was added dropwise at a constant speed so that the addition was completed in 2 hours. After completion of the dropwise addition, an aqueous solution consisting of 0.5 g of ammonium persulfate and 20 g of distilled water was added and stirred at 70 ° C. for 4 hours, then heated to 85 ° C. and stirred for another 2 hours. The reaction liquid was cooled and filtered to obtain a dispersion of polymer particles represented by the following compound example (BH-1). The physical properties of the polymer particles obtained are shown in Table 2.

[Preparation of ink composition]
Using the colorant dispersion liquid (cyan dispersion liquid C1) and self-dispersing polymer particles (B-01) obtained above, each component was mixed so as to have the following ink composition to prepare an ink composition. did. The prepared ink composition was packed in a plastic disposable syringe and filtered with a PVDF 5μ filter (Millex-SV, Millipore, diameter 25 mm) to obtain ink C1.
(Composition of ink C1)
・ Cyan pigment (Pigment Blue 15: 3) 3%
・ Polymer dispersant (water-insoluble dispersant) PD-1 1.5%
・ Self-dispersing polymer particles B-01 6%
・ Sanix GP250 (manufactured by Sanyo Chemical Industries, hydrophilic organic solvent) 10%
・ Diethylene glycol monoethyl ether (Wako Pure Chemical Industries, hydrophilic organic solvent) 6%
・ New Pole PE108 (Sanyo Chemical Industries, nonionic polymer compound) 0.6%
・ Orphine E1010 (Nisshin Chemical, surfactant) 1%
・ Ultra pure water 69.5%

  Inks C2 to 16 were obtained in the same manner as ink C1, except that the ink composition was changed so that the ink composition shown in Table 3 below was obtained in the preparation of ink C1.

(Preparation of treatment solution)
Each component was mixed so as to have the composition shown in the following table to prepare a treatment solution.

(Measurement of viscosity ratio V _high / V _low at high shear rate)
In the present invention, V _high represents a 25 ° C. viscosity (mPa · s) measured at a shear rate of 1.5 × 10 ⁵ (s ⁻¹ ), and V _low is a shear rate of 3.0 × 10 ³ (s ⁻¹ ). The viscosity at 25 ° C. (mPa · s) measured in the above was expressed and measured as follows to obtain V _high / V _low .
A microchip type micro sample viscometer VROC (manufactured by RheoSense) and a measurement chip were C-Type (depth = 100 μm). All the measurement units of the viscometer were stored in an incubator, and the temperature was adjusted to 25 ° C.

<Evaluation>
(Inkjet recording device)
As the ink jet recording apparatus, the ink jet recording apparatus shown in FIG. 1 set to the following setting conditions was used. However, the apparatus does not use the solvent concentration detector 104, the solvent addition device 106, and the filter 140.
<Setting conditions>
-Ink temperature in the sub tank 102: 25 ° C
Filter 122: mesh size 5 μm
Head unit 51: Nozzle diameter 18 μm, 1200 dpi, length of 1 unit 2 cm Piezoelectric element 68: lead zirconate titanate (piezo)
-Amount of ink flowing through the common flow path 52: 2 to 4 ml / sec

(Image formation)
A recording medium (Tokuhishi Art N basis weight 104.7 g / m ² manufactured by Mitsubishi Paper Industries Co., Ltd.) is fixed on a stage that can move linearly in a predetermined direction at 500 mm / second, and the treatment liquid obtained above is fixed to this. Was applied with a wire bar coater so as to give an application amount of about 5 g / m ² , and dried at 50 ° C. for 2 seconds immediately after the application.
After that, the ink jet recording apparatus is fixedly arranged, and cyan ink is lined under discharge conditions of ink droplet amount 2.4 pL, discharge frequency 24 kHz, resolution 1200 dpi × 600 dpi while moving the recording medium at a constant speed in the sub-scanning direction. The ink was discharged by this method, and a cyan image was printed.
Immediately after the image is printed, the sample is dried at 50 ° C. for 3 seconds, passed between a pair of fixing rollers heated to 60 ° C., and subjected to a fixing process with a nip pressure of 0.20 MPa and a nip width of 4 mm to obtain an evaluation sample. It was.
The fixing roller is composed of a heating roll in which the surface of the core of a SUS cylindrical body with a halogen lamp inside is coated with a silicone resin, and an opposing roll that is in pressure contact with the heating roller. is there.

  Under the conditions without ink circulation, the flow path 130 in FIG. 1 was physically blocked, and the ink flow toward the common circulation path 70 via the reflux path 72 was eliminated to form an image.

(Discharge variation evaluation)
Using “Image Painting Pro” (manufactured by FUJIFILM Corporation) as the recording medium, applying and drying the processing liquid and drying after image printing, without passing through the fixing roller, the discharge frequency is 12 kHz. A line image of 75 × 24000 dpi was drawn.
The center value of the line was measured with a dot analyzer DA-6000 manufactured by Oji Scientific Instruments Co., Ltd., and the standard deviation σ of the deviation amount of each line was calculated, and judged according to the following criteria.
A: σ is smaller than 2 μm A: σ is smaller than 4 μm B: σ is smaller than 6 μm C: σ is 6 μm or more D: stable printing is impossible and measurement is impossible

(Image resolution evaluation)
A thin line image parallel to the moving direction of the stage was formed by the image forming method using the ink composition and the ink jet recording apparatus. The line width was set to 2 dots, the interval between adjacent lines was set to 2 dots, observed with an optical microscope, and evaluated according to the following criteria.
-Evaluation criteria-
A: Good with no non-uniformity in line width and no connection between adjacent lines.
B: Ink droplets coalesce on the recording medium and the line width becomes non-uniform, but adjacent lines are not connected.
C: Adjacent lines are connected.

(Intermittent discharge evaluation)
Using the ink composition obtained above, the intermittent ejection property of the ink was evaluated as follows. The evaluation environment was 25 ° C. and 50% RH.
Using the ink jet recording apparatus, the ink composition prepared above was continuously ejected for 1 minute to form an image by the image forming method, and then the ejection was stopped for 60 minutes. Thereafter, an image was formed again.
Evaluation was made according to the following evaluation criteria based on the pass / fail of the following evaluation items. The image unevenness was visually observed using an optical microscope. The discharge rate was “(number of nozzles allowed to discharge / number of all nozzles) × 100 (%)”.
-Evaluation items-
(1) The discharge rate is 90% or more of all nozzles.
(2) The number of nozzles in which discharge bending is recognized is less than 10% of all nozzles.
(3) No image unevenness is observed in the solid image.

-Evaluation criteria-
A: When all three items are acceptable B: When two items are acceptable C: When two or more items are unacceptable

(Fixability evaluation)
A 50% solid image was printed using the ink composition, and then left in a room adjusted to 25 ° C. and 60% RH for 24 hours. About the obtained sample, the following tape peeling resistance and abrasion resistance were evaluated.
<Tape peel resistance>
A mending tape (width: 18 mm) manufactured by Sumitomo 3M Co., Ltd. was attached to the print section. Subsequently, the tape was peeled off at a speed of 1 cm / second, and the adhesion state of the ink to the tape was evaluated according to the following evaluation criteria.
-Evaluation criteria-
A: Adhesion of ink to the tape was not recognized.
B: Slight adhesion of ink to the tape was observed, but there was no practical problem.
C: Adhesion of ink to the tape is noticeable.

<Abrasion resistance>
Immediately after printing a 50% solid image of 2 cm square, an unrecorded recording medium (the same recording medium used for recording) was overlaid and rubbed 10 times with a load of 150 kg / m ² , and scratches on the recorded image The degree of ink transfer onto the white background of the recording medium (unused sample) that was not recorded was visually observed and evaluated according to the following evaluation criteria.
-Evaluation criteria-
A: There was no transfer of ink.
B: Slight scratches were observed on the recorded image, but the ink transfer was hardly noticeable.
C: The scratch of the recorded image is remarkable and / or the transfer of ink is remarkable.

  As is apparent from Table 5, the examples using the ink of the present invention and the examples using the image forming apparatus provided with the ink and the ink circulation device are images having excellent intermittent ejection properties and excellent resolution. was gotten. On the other hand, it was found that one or more evaluation items were inferior in the comparative example.

It is the schematic which showed the ink circulation system of the inkjet recording device. 2 is a schematic diagram illustrating an example of an internal structure of a recording head 50. FIG. 2 is a plan view showing a detailed structure of a recording head 50. FIG. FIG. 7 is a cross-sectional view (a cross-sectional view taken along line 7-7 in FIG. 3) showing a part of the recording head 50. FIG. 5 is an explanatory diagram of ink flow for explaining the flow of ink flowing from a common flow path 52 to a common circulation path 70 via a supply path 60.

DESCRIPTION OF SYMBOLS 10 Inkjet recording device, 50 (50A) recording head, 51 head unit, 52 common flow path, 54 1st supply port, 56 2nd supply port, 58 pressure chamber, 59 pressure chamber row, 60 supply channel, 62 nozzle Flow path, 64 nozzles, 66 diaphragm, 68 piezoelectric element, 69 individual electrode, 70 common circulation path, 71 connection flow path, 71 communication flow path, 72 reflux path, 74 recovery port, 80 droplet discharge element, 100 ink tank , 102 sub tank, 104 solvent concentration detector, 106 solvent addition device, 108 deaeration device, 110, 130, 136 flow path, 112, 120, 124, 132, 138 pump, 114 heating / cooling device for adjusting ink temperature, 116, 118 1st and 2nd flow path, 122, 140 filter, 134 Zabatanku, 144 solvent tank, 146 a vacuum pump, P1 pressure of the ink in the first supply port 54, the pressure of the ink in the P2 second supply port 56, the pressure of the ink at P3 recovery port 74

Claims (12)

(A) a water-soluble organic solvent, (b) a pigment, (c) water, and (d) at least a nonionic polymer compound as a thickener, wherein the content of (a) the water-soluble organic solvent is based on the total amount of ink. An ink composition having a viscosity of 5 to 30% by mass, wherein the viscosity measured by changing the shear rate of the ink composition satisfies the following formula.

0.70 ≦ V _high / V _low ≦ 0.95

[Where V _high represents a 25 ° C. viscosity (mPa · s) measured at a shear rate of 1.5 × 10 ⁵ (s ⁻¹ ), and V _low represents a shear rate of 3.0 × 10 ³ (s ⁻¹ ). This represents the 25 ° C. viscosity (mPa · s) measured by ] 2. The ink composition according to claim 1, wherein the (d) thickener is a nonionic polymer compound having a weight average molecular weight of 5,000 to 100,000. The nonionic polymer compound is at least one selected from the group consisting of polyvinyl alcohol, polyvinyl pyrrolidone, polyoxyethylene glycol, and a polyoxyethylene polyoxypropylene copolymer. The ink composition according to claim 2. The ink composition according to claim 1, wherein the pigment (b) is dispersed with a water-insoluble dispersant. The ink composition according to claim 1, wherein the pigment (b) is a pigment dispersed by a phase inversion emulsification method. The ink composition according to any one of claims 1 to 5, further comprising (e) polymer particles. The ink composition according to claim 6, wherein the polymer particles (e) are self-dispersing polymer particles. 8. The total amount of the (b) pigment, the water-insoluble dispersant, and the (e) polymer particles is 7% by mass or more based on the total amount of the ink composition. The ink composition according to any one of the above. A plurality of droplet discharge elements, a common flow path communicating with each of the plurality of droplet discharge elements via a supply path, and a common circulation path communicating with the plurality of droplet discharge elements via a reflux path. An image forming apparatus comprising: an ink circulation device that supplies an ink composition from the common flow path to the plurality of droplet discharge elements and circulates the ink composition in the common circulation path. An image forming method comprising forming an image on a recording medium by discharging the ink composition according to claim 1.   The ink composition is supplied from the common flow path to the plurality of droplet discharge elements having nozzles through the supply path, and the ink composition that has not been discharged from the nozzles is supplied to the common flow path through the reflux path. The image forming method according to claim 9, wherein the image forming method circulates in a circulation path. The image forming apparatus adjusts a supply amount of the ink composition that can be supplied from the common flow path by changing a pressure difference between the ink compositions in the common flow path and the common circulation path. The image forming method according to claim 9. The droplet discharge element includes a nozzle that discharges the ink composition, a nozzle channel that communicates with the nozzle, a nozzle that communicates with the nozzle via the nozzle channel, and the common channel that passes through the supply channel. And a pressure chamber to which the ink composition is supplied, and the common circulation path is communicated with the nozzle flow path via the reflux path. The image forming method according to claim 1.