JP6056520B2 - Ink jet ink, image forming method, ink cartridge, ink jet recording apparatus, and image formed product - Google Patents

Description

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

Inkjet recording apparatuses are known as image forming apparatuses such as printers, facsimiles, and copying machines. Such an ink jet recording apparatus performs recording by ejecting ink onto a recording medium such as a recording head. Since the image forming process is simple, the apparatus is easy to simplify, and the heating process is not required. Gentle, high-definition images can be recorded at high speed, running costs are low, noise is low, and it is easy to record color images using multi-color inks. ing.
As an ink used for such ink jet recording, water is a main component, and a coloring agent, a wetting agent such as glycerin, a penetrating agent that controls permeability to recording paper, a surfactant, and other additives. A water-based ink containing is generally used for home and office applications.

Inkjet recording using water-based ink is fixed when liquid ink permeates into the recording medium, so an ink jet special paper with improved absorption characteristics, a function of fixing colored components on the paper surface, and a function of protecting colored components has been developed. Has been.
However, inkjet paper is expensive because it undergoes a multi-stage coating process after paper making, and recyclability is inferior to plain paper because it uses many processing chemicals. Therefore, it is desired to obtain sufficient image quality on plain paper.
Plain paper is inferior in ink absorbability to inkjet special paper and does not assist ink performance like special paper, so (1) feathering, (2) bleeding, (3) density reduction, (4) Decrease in color developability, (5) Decrease in water resistance, (6) Decrease in light resistance, (7) Decrease in gas resistance, (8) Decrease in fixability, (9) Occurrence of ink breakthrough In order to solve these problems, it has become an important issue for inkjet recording on plain paper.

In recent years, pigment dispersibility has been improved and particle size has been reduced, and pigments are increasingly used in inkjet inks. To improve the dispersibility of pigments, not only pigment dispersion using surfactants and water-soluble resins as in the past, but also hydrophilicity is imparted by surface modifications such as oxidation treatment, sulfonation treatment, and graft polymerization treatment on the pigment surface. In addition, the self-dispersion stability of the pigment is improved. When such a pigment is used, the above (5) to (7) can be improved. However, the pigment is inferior in density and color developability as compared with the dye, and has a discharge stability, long-term storage stability, It is inferior to dye ink in terms of reliability such as dispersibility.
Therefore, when a pigment is used as a colorant, it is a problem to improve the ink density, color developability, and reliability.
In order to cope with these problems, many inks for inkjet recording using colored polymer particles, particularly emulsions of polyester-based or vinyl-based polymer particles, have been reported. These include ink containing a colorant-encapsulating resin dispersion in which a colorant is insoluble in water and encapsulated in a dispersible resin.

Conventionally, techniques for controlling the permeability of ink to paper have been studied in order to reduce feathering and bleeding, increase print density and color developability, and suppress back-through.
Among inkjet inks on the market, there is a super-penetrating ink in which the surface tension of the ink is adjusted to be lower than 35 mN / m and the permeability to paper is enhanced. Such inks are highly effective in reducing bleeding and have good drying properties on plain paper printing, but have the disadvantages that feathering is likely to occur and the printing density is low and the character quality is likely to deteriorate.
On the other hand, by adjusting the surface tension of the ink to be higher than 35 mN / m and slowing the penetration into the paper, the slow penetration ink that keeps the ink on the surface of the printing surface is on the market, reducing the feathering and improving the printing density Highly effective in improving color developability and reducing back-through. However, as a result of decreasing the permeability to paper, the drying property after printing on plain paper is remarkably deteriorated, resulting in deterioration of fixing property and bleeding between colors when multiple colors are used.

In view of this, a technique has been developed and used that suppresses bleeding between colors and ensures image quality by using an ink set in which a slow penetrating ink and a super penetrating ink are combined. However, when double-sided printing is performed using a slowly penetrating ink, it is necessary to wait for the ink to dry after printing, resulting in poor productivity of double-sided printing.
In order to improve the drying property of the ink, a printing device having a device that heats the paper surface with a heater before and after printing and accelerates drying of the ink has been proposed and put on the market. However, in these proposals, since the part to be heated is added, the apparatus is enlarged and complicated, and energy is wasted for heating, so the advantages of the ink jet recording method are lost. Yes.

In addition to the above, an ink jet ink has been studied in a direction that has both improved reliability and improved image quality. For example, many ink jet inks are designed in such a way as to suppress the increase in viscosity as much as possible in order to prevent nozzle clogging of the head.
For example, Patent Document 1 discloses that the change in viscosity when ink is concentrated twice is within 10 times and the change in particle size is within 3 times, thereby preventing aggregation of pigments from suppressing the spread of ink, It is said that it can prevent omission. However, it is difficult to form high quality on plain paper with this ink.
Patent Document 2 discloses that ink having a viscosity of 5 to 15 mPa · s is necessary to ensure high image quality. In this proposal, the initial evaporation rate is adjusted to ensure reliability, and a specific compound is preferably added as a viscosity modifier for adjusting the viscosity. When the pigment is used, the above (3) and It can be said that it is a solution to (4). However, in this proposal, there is no description about the stability of the particle size of the pigment to be used, and it is said that there is reliability after being left for 24 hours. However, depending on the configuration of the ejected head and the size of the nozzle, If left untreated for a long time, the ink formulation is inferior in reliability.
As described above, in order to ensure high-speed and high-quality printing quality, it is necessary to use ink with high viscosity. However, there is a problem that it is difficult to ensure reliability of ink with high viscosity.

On the other hand, it is known to add a water-insoluble resin to a pigment ink for the purpose of improving image quality.
Further, Patent Document 3 discloses plain paper with an ink in which the ratio of pigment to resin emulsion is in the range of 1: 0.1 to 1: 1 and the average particle size of the coloring component is 0.3 to 1.2 μm. A technique for improving the image quality is disclosed. However, although the ink to which the resin emulsion is added can suppress bleeding and suppress feathering, the image density is insufficient and the reliability as an inkjet ink is not sufficient.
Patent Document 4 discloses an ink having a minimum film-forming temperature of 40 ° C. or more of an ink to which a water-insoluble resin is added, and Patent Document 5 discloses the reliability of an ink in which the particle size of the added emulsion is 50 nm or less. Although measures for improving the image quality have been disclosed, the image quality that can be improved in reliability is not sufficient.
In Patent Document 6, printing unevenness is improved by an ink containing a pigment, a saccharide or a derivative thereof, a polyol having five or more hydroxyl groups, and a resin emulsion. However, this ink has low penetrability with respect to plain paper, and has problems such as occurrence of feathering and bleeding between colors, deterioration of fixing property, and slow drying time.

Further, Patent Document 7 discloses an ink having a solid content of 1.0 to 16% by mass composed of a water-dispersible resin and a self-dispersing pigment, and describes improvement of image quality on plain paper. According to this proposal, the water resistance is improved as compared with the dye, but the image holding performance with respect to the marker pen often used in plain paper is not sufficient.
Further, when the pigment dispersion and the resin emulsion are added to the ink, the solid content is increased and the ink viscosity is increased. For example, Patent Documents 8 and 9 propose ink formulations in which a viscosity increase is small even when the solid content is increased by adding a resin that forms micelle aggregates to the ink. However, these proposals have insufficient permeability on plain paper and have a problem in recording image quality. The permeability to paper is explained by capillary absorption represented by the Lucas-Washburn equation. However, the higher the viscosity, the lower the surface tension and the contact angle between the paper and the ink, the lower the permeability.

Patent Document 10 proposes an improvement in image quality by using an ink having a viscosity of 5 mPa · s or more containing a polymer emulsion in which a water-insoluble or hardly soluble coloring material is contained in a fluorosurfactant and polymer fine particles. However, in this proposal, it is known that the hue changes due to an increase in the solid content of the pigment in the ink. It is difficult to obtain a preferable hue with a high concentration pigment, and water resistance and fixing properties with a self-dispersing pigment. There is a problem that it is difficult to say.
Patent Document 11 discloses a water-based ink for an inkjet containing a pigment and two kinds of resins, and the resin contributing to the dispersion of the pigment does not precipitate at pH 4 to 6, and the other resin is used for the dispersion of the pigment. Although it is described that it is a non-contributing resin and precipitates at pH 4 to 6, it is excellent in image scratch resistance and gloss, but is still unsatisfactory in terms of image density.

  The present invention solves the above-described problems of the prior art, enables recording at a high image density on plain paper, has good ink storage stability, and stores the recording apparatus used for printing after storage. An object of the present invention is to provide an ink jet ink that has good discharge stability from a nozzle and has both high image density and storage stability.

上記式中、Ｒ１は水素原子又はメチル基、Ｒ２は炭素数４〜２２のアルキレン基、Ｘ１はＮＨ基又は酸素原子、Ｍ１は水素原子、１価の無機カチオン又は有機カチオンを表す。 The above problem is solved by the following invention 1).
1) Copolymers containing a pigment, water, a water-soluble organic solvent and the monomer (A) represented by the following general formula (1) as essential components and one or more aliphatic monomers as copolymerization components. An ink-jet ink comprising a polymer, having an initial pH of 9 to 11, and an increase rate of the viscosity with respect to the initial viscosity when the pH is lowered to 8.5 is 50% or more.
General formula (1)

In the above formula, R1 represents a hydrogen atom or a methyl group, R2 represents an alkylene group having 4 to 22 carbon atoms, X1 represents an NH group or an oxygen atom, M1 represents a hydrogen atom, a monovalent inorganic cation or an organic cation.

  According to the present invention, high image density recording is possible on plain paper, ink storage stability is good, and ejection stability from the head nozzle after storing the recording device used for printing is also good. In addition, an inkjet ink having both high image density and storage stability can be provided.

FIG. 3 is a diagram illustrating an example of an ink bag of an ink cartridge according to the present invention. FIG. 4 is a diagram illustrating an ink cartridge in which an ink bag is accommodated in a cartridge case. The perspective view which shows an example of a serial type inkjet recording device. Explanatory drawing of the internal structure of the apparatus of FIG.

上記式中、Ｒ３は水素原子又はメチル基、Ｒ４は炭素数１〜４のアルキレン基、Ｘ２はＮＨ基又は酸素原子、Ｍ２は水素原子、１価の無機カチオン又は有機カチオンを表す。

一般式（３）

上記式中、Ｒ５は水素原子又はメチル基、Ｒ６は炭素数１〜１２のアルキル基、フッ化アルキル基、アミノアルキル基、又はヒドロキシアルキル基、Ｘ３はＮＨ基又は酸素原子を表す。
３） 前記モノマー（Ａ）が、１２−メタクリルアミドドデカン酸、モノマー（Ｂ）が、２−アクリルアミド−２−メチルプロパンスルホン酸、モノマー（Ｃ）がメタクリル酸ラウリルであることを特徴とする２）記載のインクジェット用インク。
４） １）〜３）のいずれかに記載のインクジェット用インクを用いて画像を形成することを特徴とする画像形成方法。
５） １）〜３）のいずれかに記載のインクジェット用記録インクを容器中に収容したインクカートリッジ。
６） ５）記載のインクカートリッジを搭載したインクジェット記録装置。
７） ６）記載のインクジェット記録装置により印字された画像形成物。 Hereinafter, the present invention 1) will be described in detail, but the following 2) to 7) are also included in the embodiments of the present invention, and these will be described together.

2) The aliphatic monomer contains at least one of a monomer (B) represented by the following general formula (2) and a monomer (C) represented by the following general formula (3) 1 ) Inkjet ink as described.
General formula (2)

In the above formula, R3 represents a hydrogen atom or a methyl group, R4 represents an alkylene group having 1 to 4 carbon atoms, X2 represents an NH group or an oxygen atom, M2 represents a hydrogen atom, a monovalent inorganic cation or an organic cation.

General formula (3)

In the above formula, R5 represents a hydrogen atom or a methyl group, R6 represents an alkyl group having 1 to 12 carbon atoms, a fluorinated alkyl group, an aminoalkyl group, or a hydroxyalkyl group, and X3 represents an NH group or an oxygen atom.
3) The monomer (A) is 12-methacrylamide decanoic acid, the monomer (B) is 2-acrylamido-2-methylpropanesulfonic acid, and the monomer (C) is lauryl methacrylate 2) The ink for inkjet described.
4) An image forming method comprising forming an image using the ink jet ink according to any one of 1) to 3).
5) An ink cartridge containing the inkjet recording ink according to any one of 1) to 3) in a container.
6) An ink jet recording apparatus equipped with the ink cartridge described in 5).
7) An image formed product printed by the ink jet recording apparatus described in 6).

The initial pH of the inkjet ink of the present invention (hereinafter sometimes referred to as ink) is adjusted to 9 to 11, preferably 9.5 to 10. By setting the pH within this range, the viscosity (initial viscosity) of the ink can be lowered, and an ink having sufficient fluidity and storage stability can be produced.
The ink of the present invention contains a copolymer having the monomer (A) as an essential component and one or more aliphatic monomers as copolymerization components. When the pH is 8.5 or lower, this copolymer becomes highly hydrophobic and hardly dissolves in water, so that it precipitates and aggregates. As a result, the viscosity of the ink increases. This characteristic is unique to the present invention not found in conventional inks.

  The ink of the present invention is suitable for image formation using plain paper. The pH of plain paper (paper surface) is generally in the range of 6.5 to 7.5. When ink lands on such a paper surface, the ink is affected by the pH of the paper surface. That is, it is affected by the acidic component existing on the paper surface and / or the paper surface. When ink having a pH before discharge (initial pH) of 9 to 11 lands on the surface of plain paper, the pH of the ink drops to a value between the initial pH value and the pH value of the paper surface. To do. The pH of the ink after landing is usually lowered to 8.5 or less. Therefore, when the ink of the present invention lands on the paper surface, it aggregates and thickens, whereby the penetration into the paper is suppressed and a large amount of pigment remains on the paper surface. Therefore, a high image density can be obtained.

The ink of the present invention has a low viscosity by increasing the pH before discharging, ensuring sufficient fluidity and storage stability, discharging and landing on the paper surface, and increasing the viscosity after decreasing the pH of the ink Let It is necessary to increase the viscosity change accompanying the decrease in pH, and when the pH decreases to 8.5, the rate of increase of the viscosity with respect to the initial viscosity is 50% or more, preferably 50 to 300%, more preferably 60 to 210. %.
The viscosity is measured at 25 ° C. using a viscometer MODEL RC-500 l manufactured by Toki Sangyo Co., Ltd. First, the viscosity (initial viscosity) of the ink adjusted to a desired pH (initial pH) in the range of pH 9 to 11 is measured. Next, the viscosity of the ink is measured when the pH is adjusted to 8.5 with an aqueous HCl solution or the like. And a viscosity increase rate is computed by a following formula.
Viscosity increase rate (%) = [(viscosity after pH adjustment−initial viscosity) / initial viscosity] × 100

As the other aliphatic monomer used as a copolymerization component, the monomer (B) and the monomer (C) are preferable.
In the present invention, by using the copolymer as a dispersant, an ink having a high image density and good ejection stability can be obtained.
The copolymer can be obtained by a known polymerization method. For example, water may be used as a medium, and a polymerization initiator, a chain transfer agent or the like may be added to the monomer as necessary, and polymerization may be performed at room temperature to 100 ° C.

The monomer (A) is a compound obtained by reaction of acrylic acid, alkyl-substituted acrylic acid, acrylamide, or alkyl-substituted acrylamide with a fatty acid.
R1 is hydrogen or a methyl group, and the alkyl group may be linear or branched. R2 is an alkylene group having 4 to 22 carbon atoms, and may be linear or branched. Examples of R2 include an octylene group having 8 carbon atoms, an 11 undecylene group, and a 12 dodecylene group. R2 may contain an aromatic ring or a carbon-carbon double bond in the structure, and may be, for example, a vinylene group, a methylphenylene group, a vinylphenylene group, or the like. X1 is an NH group or an oxygen atom, and an NH group is particularly preferable.

M1 is hydrogen, a monovalent inorganic cation or an organic cation. Any monovalent inorganic cation or organic cation may be used as long as it can form a carboxylic acid salt. Examples of the monovalent inorganic cation include sodium ion, potassium ion, lithium ion, and the like. Examples of the organic cation include ammonium ion, monoethanolammonium ion, and triethanolammonium ion.
M1 can be reversibly converted to a carboxylic acid (M1 = hydrogen) or sodium salt (M1 = sodium) form using a suitable amount of dilute hydrochloric acid or dilute sodium hydroxide solution after polymer production. It is.
Specific examples of the monomer (A) include 11-methacrylamidoundecanoic acid, 8-acrylamidooctanoic acid, 12-acrylamidododecanoic acid, 12-methacrylamideamidododecanoic acid, 3- {4-[(methacryloxy) methyl] phenyl} acrylic. An acid etc. are mentioned.

The monomer (B) is a compound obtained by a reaction of acrylic acid, alkyl-substituted acrylic acid, acrylamide, or alkyl-substituted acrylamide and alkylsulfonic acid.
R3 is hydrogen or a methyl group, and the alkyl group may be linear or branched. R4 is an alkylene group having 1 to 4 carbon atoms, and may be linear or branched. Examples of R4 include a methylene group, an ethylene group and a propylene group, with an ethylene group and a propylene group being particularly preferred. X2 represents a -NH- group or an oxygen atom, and a -NH- group is particularly preferable.

M2 is hydrogen or a monovalent inorganic cation or organic cation. The monovalent inorganic cation or the organic cation may be any as long as it can form a sulfonic acid salt. Examples of the monovalent inorganic cation include sodium ion, potassium ion, lithium ion, and the like. Examples of the organic cation include ammonium ion, monoethanolammonium ion, and triethanolammonium ion.
M2 can be reversibly converted into a sulfonic acid (M2 = hydrogen) or sodium salt (M2 = sodium) form using a suitable amount of dilute hydrochloric acid or dilute sodium hydroxide solution after polymer production. It is.
Specific examples of the monomer (B) include 2-acrylamido-2-methylpropanesulfonic acid and potassium 3-methacryloxypropanesulfonate.

The monomer (C) is a compound obtained by a reaction of acrylic acid, alkyl-substituted acrylic acid, acrylamide, or an alkyl-substituted acrylamide with an alkyl-containing compound.
R5 is hydrogen or a methyl group, and the alkyl group may be linear or branched. R6 is an alkyl group having 1 to 12 carbon atoms, a fluorinated alkyl group containing one or more fluorine atoms, an aminoalkyl group containing one or more amino groups, or a hydroxyalkyl group containing one or more hydroxyl groups. is there. These alkyl groups may be linear or branched.

Examples of when R6 is an alkyl group include a methyl group, an ethyl group, a pentyl group, an octyl group, a decyl group, a 2-ethylhexyl group, and the like, and a 2-ethylhexyl group is particularly preferable. Examples of when R6 is a fluorinated alkyl group include a trifluoromethyl group, a trifluoroethyl group, a tetrafluoropropyl group, and the like, and a trifluoroethyl group and a tetrafluoropropyl group are particularly preferable. Examples of when R6 is an aminoalkyl group include an aminoethyl group, an aminopropyl group, an N, N-dimethylaminoethyl group, and the like, and an N, N-dimethylaminoethyl group is particularly preferable. Examples of when R6 is a hydroxyalkyl group include a hydroxyethyl group, a hydroxypropyl group, a dihydroxypropyl group, etc., and a hydroxyethyl group is particularly preferable. X3 is a -NH- group or an oxygen atom.
Specific examples of the monomer (C) include acrylic acid-2-ethylhexyl, acrylic acid-2,2,2-trifluoropropyl, methacrylic acid-2,2,3,3-tetrafluoropropyl group, acrylic acid-2 -(N, N-dimethylamino) ethyl, 2-dimethylaminoethyl methacrylate, lauryl methacrylate, N-hydroxyethyl acrylate, glycerol monomethacrylate and the like.

As the copolymer, in terms of dispersibility and image density, the ratio of the monomer (A) to the monomer (B) is (A) :( B) = 95: 5 to 30:70 in molar ratio. It is preferably 90:10 to 65:35, more preferably 90:10 to 80:20.
Similarly, in terms of dispersibility and image density, the ratio of monomer (A) to monomer (C) is preferably (A) :( C) = 95: 5 to 30:70, more preferably Is 90:10 to 65:35, more preferably 90:10 to 80:20.
Similarly, in terms of dispersibility and image density, the ratio of the monomer (A), the monomer (B), and the monomer (C) is a molar ratio of the monomer (A) :( B) :( C) = 95: 3: 2-30: 40: 30 is preferable, More preferably, it is 90: 6: 4-65: 20: 15, More preferably, it is 90: 6: 4-80: 15: 5.
The weight average molecular weight of the copolymer is preferably 500 to 200,000 (GPC method, pullulan conversion), more preferably 1,000 to 100,000 in terms of ink viscosity and pigment adsorption.

Of the pigments used in the present invention, carbon black is preferred as the black pigment. Examples of carbon black include ketjen black, furnace black, acetylene black, thermal black, and gas black. Further, carbon black whose surface has been oxidized or alkali-treated, or carbon black that has been coated with various surfactants or resins and grafted or encapsulated can be used.
In particular, when acidic carbon obtained by oxidizing the carbon black surface is used, the drying property is improved and the effect of improving the image density is great. Further, carbon black coated with a resin having a sulfonic acid group or a carboxy group and imparted by grafting the functional group can also be used.

Examples of the acidic carbon include MA7, MA8, MA100, MA600, # 45, # 50, # 2200B, # 2350, # 2650, OIL 7B, OIL 11B (manufactured by Mitsubishi Kasei Co., Ltd.), Raven 1035, Raven 1040, Raven 1060. , Raven 1080, RAVEN 1255, Raven 3500, Raven C (Colombia), REGAL400R, MOGUL L (Cabot), Color Black FW1, Color Black FW18, Color Black S150, Color Black S160, Color Black S160, Color Black S160, Color Black SP, , Printex75, Printex 140U, Printex 140V, Special Black4, Sp cial Black 100, Special Black 250, Special Black 350, NIPEX150, NIPEX180IQ (Degussa), and the like.
Among these, carbon black having a pH of 5 or less and a volatile content of 3.5 to 8.0% by weight are preferable, and gas black is preferable in terms of drying property and image density.

Examples of magenta pigments include Pigment Red 5, Pigment Red 7, Pigment Red 12, Pigment Red 48 (Ca), Pigment Red 48 (Mn), Pigment Red 57 (Ca), Pigment Red 57: 1, Pigment Red 112, and Pigment Red. 122, pigment red 123, pigment red 168, pigment red 184, pigment red 202, pigment violet 19, and the like.
Examples of cyan pigments include Pigment Blue 1, Pigment Blue 2, Pigment Blue 3, Pigment Blue 15, Pigment Blue 15: 3, Pigment Blue 15: 4, Pigment Blue 16, Pigment Blue 22, Pigment Blue 60, Bat Blue 4, Bat Blue 60 etc. are mentioned.

  Examples of yellow pigments include Pigment Yellow 1, Pigment Yellow 2, Pigment Yellow 3, Pigment Yellow 12, Pigment Yellow 13, Pigment Yellow 14, Pigment Yellow 16, Pigment Yellow 17, Pigment Yellow 73, Pigment Yellow 74, Pigment Yellow 75, Pigment Yellow 83, Pigment Yellow 93, Pigment Yellow 95, Pigment Yellow 97, Pigment Yellow 98, Pigment Yellow 114, Pigment Yellow 120, Pigment Yellow 128, Pigment Yellow 129, Pigment Yellow 138, Pigment Yellow 150, Pigment Yellow 151, Pigment Yellow 154 Pigment Yellow 155, Pigment Yellow 180, etc. It is.

By using Pigment Yellow 74 as the yellow pigment, Pigment Red 122 and Pigment Violet 19 as the magenta pigment, and Pigment Blue 15 as the cyan pigment, a well-balanced ink having excellent color tone and light resistance can be obtained.
The pigment concentration in the pigment dispersion is preferably 0.1 to 50% by weight, particularly preferably 0.1 to 30% by weight.
Further, as the pigment used in the present invention, a pigment using the copolymer as a dispersant for the pigment dispersion is more preferable. Further, when the copolymer is used for carbon black, the image density effect is most prominent. In addition, you may use together the pigment mentioned above in the range which does not impair an effect.

The content of the copolymer as a dispersant needs to be appropriately selected depending on the type of pigment. Usually, 0.005 to 5 parts by weight is preferable, 0.01 to 2 parts by weight is more preferable, and 0.02 to 0.5 parts by weight is most preferable with respect to 1 part by weight of the pigment. If it is the said range, the dispersibility of a pigment will improve and the aging stability of a pigment dispersion and an ink will improve. In particular, in the range of 0.02 to 0.5 parts by weight, the temporal stability of the pigment dispersion and the ink is most improved.
Further, it can be used in combination with other dispersants as long as the effect of the copolymer as a dispersant is not impaired. Examples of other dispersants include various surfactants such as anionic surfactants, cationic surfactants, amphoteric surfactants, and nonionic surfactants, and polymer type dispersants.

  Examples of the anionic surfactant include alkyl sulfocarboxylates, α-olefin sulfonates, polyoxyethylene alkyl ether acetates, N-acyl amino acids and salts thereof, N-acyl methyl taurate, alkyl sulfate polyoxy Alkyl ether sulfate, alkyl sulfate, polyoxyethylene alkyl ether phosphate, rosin acid soap, castor oil sulfate, lauryl alcohol sulfate, alkylphenol phosphate, naphthalenesulfonate formalin condensate, alkyl phosphate Alkyl allyl sulfone hydrochloride, diethyl sulfosuccinate, diethyl hexyl sulfosuccinate, dioctyl sulfosuccinate and the like.

Examples of the cationic surfactant include 2-vinylpyridine derivatives and poly-4-vinylpyridine derivatives.
Examples of the amphoteric surfactant include lauryldimethylaminoacetic acid betaine, 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine, coconut oil fatty acid amidopropyldimethylaminoacetic acid betaine, polyoctylpolyaminoethylglycine, and others. Examples include imidazoline derivatives.

Nonionic surfactants include the following.
Ethers such as polyoxyethylene nonyl phenyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene dodecyl phenyl ether, polyoxyethylene lauryl ether, polyoxyethylene oleyl ether, polyoxyethylene alkyl ether, polyoxyethylene allyl ether, etc. Polyoxyethylene oleic acid, polyoxyethylene oleate, polyoxyethylene distearate, sorbitan laurate, sorbitan monostearate, sorbitan monooleate, sorbitan sesquioleate, polyoxyethylene monooleate, polyoxyethylene stearate Esters such as 2,4,7,9-tetramethyl-5-decyne-4,7-diol, 3,6-dimethyl-4-oct Down-3,6-diol, 3,5-dimethyl-1-hexyne-3-acetylene glycol such as ol

  Water is used as a dispersion medium for the pigment dispersion, but various organic solvents may be used in combination as required. For example, as water-soluble organic solvents, alcohols such as methanol, ethanol, 1-propanol and 2-propanol, polyhydric alcohols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol and glycerin, N-methylpyrrolidone, 2-pyrrolidone and the like Pyrrolidone derivatives, ketones such as acetone and methyl ethyl ketone, alkanolamines such as monoethanolamine, diethanolamine, and triethanolamine.

For pigment dispersion and ink, resin, wetting agent, surfactant, penetrating agent, pH adjuster, antiseptic / antifungal agent, chelating reagent, rust inhibitor, antioxidant, UV absorber, oxygen as necessary Various additives such as an absorbent and a light stabilizer can be blended.
The wetting agent is not particularly limited and may be appropriately selected depending on the intended purpose. For example, polyhydric alcohols, polyhydric alcohol alkyl ethers, polyhydric alcohol aryl ethers, nitrogen-containing heterocyclic compounds, amides , Amines, sulfur-containing compounds, propylene carbonate, ethylene carbonate, and other wetting agents. These may be used individually by 1 type and may use 2 or more types together.

Examples of polyhydric alcohols include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, 1,3-butanediol, 3-methyl- 1,3-butanediol, 1,5-pentanediol, hexylene glycol, 1,6-hexanediol, glycerin, 1,2,3-butanetriol, 1,2,4-butanetriol, 1,2,6 -Hexanetriol, petriol, trimethylolethane, trimethylolpropane and the like.
Examples of the polyhydric alcohol alkyl ethers include ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, tetraethylene glycol monomethyl ether, propylene glycol monoethyl ether, and the like. It is done.
Examples of polyhydric alcohol aryl ethers include ethylene glycol monophenyl ether and ethylene glycol monobenzyl ether.

Examples of the nitrogen-containing heterocyclic compound include 2-pyrrolidone, N-methyl-2-pyrrolidone, N-hydroxyethyl-2-pyrrolidone, 1,3-dimethylimidazolidinone, ε-caprolactam, γ-butyrolactone, and the like. Is mentioned.
Examples of amides include formamide, N-methylformamide, N, N-dimethylformamide, and the like.
Examples of amines include monoethanolamine, diethanolamine, triethanolamine, monoethylamine, diethylamine, triethylamine, and the like.
Examples of the sulfur-containing compounds include dimethyl sulfoxide, sulfolane, thiodiethanol, and the like.

Other humectants are preferably sugars. Examples of saccharides include monosaccharides, disaccharides, oligosaccharides (including trisaccharides and tetrasaccharides), polysaccharides, and the like. Specific examples include glucose, mannose, fructose, ribose, xylose, arabinose, galactose, maltose, cellobiose, lactose, sucrose, trehalose, maltotriose, and the like. Here, the polysaccharide means a saccharide in a broad sense, and is used to include a substance that exists widely in nature such as α-cyclodextrin and cellulose. Examples of derivatives of these saccharides include reducing sugars of the aforementioned saccharides (for example, sugar alcohols represented by the general formula: HOCH ₂ (CHOH) nCH ₂ OH (n = 2 to 5)), oxidized sugars ( For example, aldonic acid, uronic acid, etc.), amino acids, thioic acid and the like. Among these, sugar alcohols are preferable, and specific examples include maltitol and sorbit.
Among the above wetting agents, glycerin, diethylene glycol, triethylene glycol, 1,3-butanediol, 3-methyl-1,3-butanediol, 2-pyrrolidone, N-methyl from the viewpoint of storage stability and ejection stability. 2-pyrrolidone is particularly preferred.

The blending ratio of the pigment and the wetting agent greatly affects the ink ejection stability from the head. If the blending amount of the wetting agent is small even though the pigment solid content is high, the evaporation of water near the ink meniscus of the nozzle may progress, resulting in ejection failure.
The content of the wetting agent in the ink is preferably about 20 to 35% by weight, and more preferably 22.5 to 32.5% by weight. Within this range, the results of ink drying, storage test, reliability test and the like are very good. If the content is less than 20% by weight, the ink may easily dry on the nozzle surface, resulting in ejection failure. If the content exceeds 35% by weight, the dryness on the paper surface is poor and the character quality on plain paper is poor. May decrease.

As the surfactant, those having a low surface tension and a high leveling property are used, depending on the type of pigment and the combination with the wetting agent. For example, fluorine-based surfactants and silicone-based surfactants can be mentioned, and fluorine-based surfactants are preferable.
As the fluorine-based surfactant, those having 2 to 16 carbon atoms substituted by fluorine are preferable, and those having 4 to 16 carbon atoms are more preferable. When the fluorine-substituted carbon number is less than 2, the effect of fluorine may not be obtained, and when it exceeds 16, problems such as ink storage stability may occur.
Examples of fluorosurfactants include perfluoroalkyl sulfonic acid compounds, perfluoroalkyl carboxylic acid compounds, perfluoroalkyl phosphate ester compounds, perfluoroalkyl ethylene oxide adducts, and perfluoroalkyl ether groups in the side chain. And polyoxyalkylene ether polymer compounds. Among these, a polyoxyalkylene ether polymer compound having a perfluoroalkyl ether group in the side chain is particularly preferable because of its low foaming property.

Examples of the perfluoroalkyl sulfonic acid compound include perfluoroalkyl sulfonic acid, perfluoroalkyl sulfonate, and the like.
Examples of the perfluoroalkyl carboxylic acid compound include perfluoroalkyl carboxylic acid and perfluoroalkyl carboxylate.
Examples of the perfluoroalkyl phosphate compound include perfluoroalkyl phosphate esters, perfluoroalkyl phosphate salts, and the like.
The polyoxyalkylene ether polymer compound having a perfluoroalkyl ether group in the side chain includes a polyoxyalkylene ether polymer having a perfluoroalkyl ether group in the side chain, and a polyoxyalkylene ether polymer having a perfluoroalkyl ether group in the side chain. And a salt of a polyoxyalkylene ether polymer having a perfluoroalkyl ether group in the side chain.
As counter ions of salts in these fluorosurfactants, Li, Na, K, NH ₄ , NH ₃ CH ₂ CH ₂ OH, NH ₂ (CH ₂ CH ₂ OH) ₂ , NH (CH ₂ CH ₂ OH) ₃ etc. are mentioned.

  As a fluorine-type surfactant, what was synthesize | combined suitably may be used, or a commercial item may be used. Examples of commercially available products include DuPont's FS-300, Neos' FT-110, FT-250, FT-251, FT-400S, FT-150, FT-400SW, and OM-nova's PF-151N. Is mentioned.

There is no restriction | limiting in particular as a silicone type surfactant, According to the objective, it can select suitably, The thing which does not decompose | disassemble at high pH is preferable. For example, side chain modified polydimethylsiloxane, both terminal modified polydimethylsiloxane, one terminal modified polydimethylsiloxane, side chain both terminal modified polydimethylsiloxane, etc. are mentioned, and polyoxyethylene group, polyoxyethylene polyoxypropylene as modified groups Those having a group are particularly preferred because they exhibit good properties as an aqueous surfactant.
As the silicone-based surfactant, an appropriately synthesized product or a commercially available product may be used. Commercially available products can be easily obtained from, for example, Big Chemie, Shin-Etsu Silicone, Toray Dow Corning Silicone.

  The content of the surfactant in the ink is preferably 0.01 to 3.0% by weight, and more preferably 0.5 to 2% by weight. If the content is less than 0.01% by weight, the effect of adding the surfactant may be lost. If the content exceeds 3.0% by weight, the permeability to the recording medium becomes higher than necessary, and the image density decreases. And strikethrough may occur.

The penetrant preferably contains at least one polyol compound having a solubility in water at 20 ° C. of 0.2 to 5.0% by weight. Examples of such a polyol compound include 2-ethyl-2-methyl-1,3-propanediol, 3,3-dimethyl-1,2-butanediol, and 2,2-diethyl-1,3-propanediol. 2-methyl-2-propyl-1,3-propanediol, 2,4-dimethyl-2,4-pentanediol, 2,5-dimethyl-2,5-hexanediol, 5-hexene-1,2- Examples thereof include aliphatic diols such as diol and 2-ethyl-1,3-hexanediol.
Among these, 2-ethyl-1,3-hexanediol and 2,2,4-trimethyl-1,3-pentanediol are particularly preferable.

  Other penetrants that can be used in combination are not particularly limited as long as they can be dissolved in the ink and adjusted to desired physical properties, and can be appropriately selected according to the purpose. For example, diethylene glycol monophenyl ether, ethylene glycol Examples thereof include alkyl and aryl ethers of polyhydric alcohols such as monophenyl ether, ethylene glycol monoallyl ether, diethylene glycol monobutyl ether, propylene glycol monobutyl ether and tetraethylene glycol chlorophenyl ether, and lower alcohols such as ethanol.

  The content of the penetrant in the ink is preferably 0.1 to 4.0% by weight. If the content is less than 0.1% by weight, quick-drying may not be obtained and a blurred image may be obtained. If the content exceeds 4.0% by weight, the dispersion stability of the colorant is impaired and the nozzle is clogged. In some cases, the recording medium becomes more permeable and the permeability to the recording medium becomes higher than necessary, resulting in a decrease in image density and through-through.

The pH adjuster is not particularly limited as long as it can adjust the pH to 9 to 11 without adversely affecting the ink to be prepared, and can be appropriately selected according to the purpose. And alkali metal hydroxides, ammonium hydroxides, phosphonium hydroxides, alkali metal carbonates, and the like. When the pH exceeds 11, the amount of the ink jet head and the ink supply unit that melts out increases, and problems such as ink deterioration, leakage, and ejection failure may occur.
Examples of alcohol amines include diethanolamine, triethanolamine, 2-amino-2-ethyl-1,3-propanediol, and the like. Examples of the alkali metal hydroxide include lithium hydroxide, sodium hydroxide, and potassium hydroxide. Examples of the ammonium hydroxide include ammonium hydroxide and quaternary ammonium hydroxide. Examples of the phosphonium hydroxide include quaternary phosphonium hydroxide. Examples of the alkali metal carbonate include lithium carbonate, sodium carbonate, and potassium carbonate.

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

Examples of the antioxidant include phenolic antioxidants (including hindered phenolic antioxidants), amine-based antioxidants, sulfur-based antioxidants, phosphorus-based antioxidants, and the like.
Examples of the ultraviolet absorber include a benzophenone ultraviolet absorber, a benzotriazole ultraviolet absorber, a salicylate ultraviolet absorber, a cyanoacrylate ultraviolet absorber, and a nickel complex ultraviolet absorber.

The ink of the present invention is a known method, for example, a pigment dispersion, water, a water-soluble organic solvent, a surfactant, etc., and agitation and mixing using a sand mill, ball mill, roll mill, bead mill, nanomizer, homogenizer, ultrasonic disperser, etc. Then, coarse particles are filtered with a filter, a centrifugal separator or the like, and deaerated as necessary.
The pigment concentration in the ink is preferably 0.01 to 20% by weight based on the total amount of the ink. If it is 0.01% by weight or more, the image density is low and the printed image does not lack sharpness. If it is 20% by weight or less, the viscosity of the ink becomes too high or nozzle clogging occurs. There is nothing to do.
The content of the water-soluble organic solvent is 50% by weight or less, preferably 5 to 40% by weight, more preferably 10 to 35% by weight, based on the total amount of the ink.
The ink of the present invention can be suitably used for various recording apparatuses using an ink jet recording system, such as an ink jet recording printer, a facsimile apparatus, a copying apparatus, a printer / fax / copier multifunction machine, and the like.

<Image Forming Method, Image Forming Apparatus (Inkjet Recording Apparatus)>
When an image is formed using the ink of the present invention, an ink flying process is provided in which a stimulus (energy) is applied to the ink and the ink is ejected to form an image on a recording medium. In order to improve image quality such as image density, back-through, and bleeding, a step of applying a pretreatment liquid or a posttreatment liquid may be provided at least before and after the ink is attached to the medium.

-Ink flying process and ink flying means-
The ink flying process is a process of recording on a recording medium by applying a stimulus (energy) to the ink so as to fly.
The ink flying means is means for applying a stimulus (energy) to the ink and causing the ink to fly and recording on a recording medium. The ink flying means is not particularly limited, and examples thereof include various nozzles for ejecting ink.
In the ink jet recording apparatus of the present invention, it is preferable that at least a part of the liquid chamber portion, the fluid resistance portion, the diaphragm, and the nozzle member of the ink jet head are formed of a material containing at least one of silicon and nickel. The diameter of the ink jet nozzle is preferably 30 μm or less, and more preferably 1 to 20 μm.

The stimulus (energy) can be generated by, for example, a stimulus generating means, and the stimulus is not particularly limited and can be appropriately selected according to the purpose, such as heat (temperature), pressure, vibration, and light. Can be mentioned. These may be used individually by 1 type and may use 2 or more types together. Of these, heat and pressure are preferred.
Examples of the stimulus generating means include a heating device, a pressurizing device, a piezoelectric element, a vibration generating device, an ultrasonic oscillator, a light, and the like. Specifically, for example, a piezoelectric actuator such as a piezoelectric element, Examples include thermal actuators that use phase change due to liquid film boiling using electrothermal transducers such as heating resistors, shape memory alloy actuators that use metal phase changes due to temperature changes, electrostatic actuators that use electrostatic force, etc. It is done.

  There is no particular limitation on the mode of ink flight, and it varies depending on the type of stimulus, etc.For example, when the stimulus is “heat”, the thermal energy corresponding to the recording signal is applied to the ink in the recording head, For example, there is a method in which a thermal head or the like is applied, bubbles are generated in the ink by the thermal energy, and the ink is ejected and ejected as droplets from the nozzle holes of the recording head by the pressure of the bubbles. In addition, when the stimulus is “pressure”, for example, by applying a voltage to a piezoelectric element bonded to a position called a pressure chamber in the ink flow path in the recording head, the piezoelectric element bends and the volume of the pressure chamber is reduced. And a method of ejecting and ejecting ink as droplets from the nozzle holes of the recording head.

The size of the ink droplets to be ejected is preferably 3 × 10 ⁻¹⁵ to 40 × 10 ⁻¹⁵ m ³ ( ³ to 40 pL), for example, and the ejection jet speed is preferably 5 to 20 m / s. The drive frequency is preferably 1 kHz or higher, and the resolution is preferably 300 dpi or higher.
Each means is controlled by a control means. The control means is not particularly limited as long as the movement of each means can be controlled, and can be appropriately selected according to the purpose. For example, a sequencer And a device such as a computer.

<Ink cartridge>
The ink cartridge of the present invention contains the ink of the present invention in a container, and further includes other members and the like appropriately selected as necessary. The container is not particularly limited, and its shape, structure, size, material and the like can be appropriately selected according to the purpose. For example, a container having an ink bag formed of an aluminum laminate film, a resin film, or the like. Is preferred.
FIG. 1 is a schematic diagram illustrating an example of an ink bag 241 of an ink cartridge according to the present invention. FIG. 2 is a schematic diagram illustrating an ink cartridge 200 in which the ink bag 241 of FIG. 1 is accommodated in a cartridge case 244.
As shown in FIG. 1, after filling ink into the ink bag 241 from the ink inlet 242 and exhausting the air remaining in the ink bag, the ink inlet 242 is closed by fusion. In use, the ink is supplied to the apparatus by inserting a needle of the apparatus main body into the ink discharge port 243 made of a rubber member. The ink bag 241 is formed of a packaging member such as a non-permeable aluminum laminate film. As shown in FIG. 2, the ink bag 241 is usually housed in a plastic cartridge case 244 and used as an ink cartridge 200 detachably attached to various ink jet recording apparatuses. The ink cartridge 201 of the present invention is particularly preferably used by being detachably mounted on the ink jet recording apparatus of the present invention described later.

Next, an example of the ink jet recording apparatus of the present invention equipped with the ink cartridge will be described with reference to the drawings.
The ink jet recording apparatus shown in FIG. 3 has an apparatus main body 101, a paper feed tray 102 for loading paper into the apparatus main body 101, and a sheet for forming (recording) an image formed (recorded) on the apparatus main body 101. A paper discharge tray 103 and an ink cartridge loading unit 104 are provided. On the upper surface of the ink cartridge loading unit 104, an operation unit 105 such as operation keys and a display is arranged. The ink cartridge loading unit 104 has a front cover 115 that can be opened and closed for attaching and detaching the ink cartridge 200. Reference numeral 111 denotes an upper cover, and reference numeral 112 denotes a front surface of the front cover.

In the apparatus main body 101, as shown in FIG. 4, a carriage 133 is slidably held in the main scanning direction by a guide rod 131 and a stay 132, which are guide members horizontally mounted on left and right side plates (not shown). The scanning is moved by a main scanning motor (not shown).
The carriage 133 is provided with a recording head 134 composed of four ink jet recording heads that eject ink droplets of each color of yellow (Y), cyan (C), magenta (M), and black (Bk). Are arranged in a direction crossing the main scanning direction, and the ink droplet ejection direction is directed downward.

As the ink jet recording head constituting the recording head 134, a piezoelectric actuator such as a piezoelectric element, a thermal actuator using phase change due to liquid film boiling using an electrothermal transducer such as a heating resistor, a metal phase due to temperature change, etc. A shape memory alloy actuator using a change, an electrostatic actuator using an electrostatic force, or the like provided as energy generating means for discharging ink can be used.
In addition, the carriage 133 is equipped with a sub tank 135 for each color for supplying ink of each color to the recording head 134. The sub tank 135 is supplied with ink from the ink cartridge 201 loaded in the ink cartridge loading unit 104 via an ink supply tube (not shown) and is replenished.

On the other hand, as a paper feeding unit for feeding the paper 142 stacked on the paper stacking unit (pressure plate) 141 of the paper feeding tray 102, a half-moon roller (feeding) that separates and feeds the paper 142 from the paper stacking unit 141 one by one. A separation pad 144 made of a material having a large coefficient of friction is provided facing the paper roller 143) and the paper feed roller 143, and the separation pad 144 is urged toward the paper feed roller 143 side.
As a transport unit for transporting the paper 142 fed from the paper feed unit below the recording head 134, a transport belt 151 for transporting the paper 142 by electrostatic adsorption and a guide 145 from the paper feed unit. The counter roller 152 for transporting the paper 142 fed via the transport belt 151 with the transport belt 151 and the paper 142 fed substantially vertically upward are changed by approximately 90 ° to follow the transport belt 151. For this purpose, a conveyance guide 153 and a tip pressure roller 155 urged toward the conveyance belt 151 by a pressing member 154 are provided. In addition, a charging roller 156 that is a charging unit for charging the surface of the conveyance belt 151 is provided.

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

A double-sided paper feeding unit 181 is detachably mounted on the back surface of the apparatus main body 101. The double-sided paper feeding unit 181 takes in the paper 142 returned by the reverse rotation of the transport belt 151, reverses it, and feeds it again between the counter roller 152 and the transport belt 151. A manual paper feed unit 182 is provided on the upper surface of the duplex paper feed unit 181.
In this ink jet recording apparatus, the paper 142 is separated and fed one by one from the paper feed unit, and the paper 142 fed substantially vertically upward is guided by the guide 145 and between the transport belt 151 and the counter roller 152. It is sandwiched and conveyed. Further, the leading end is guided by the conveying guide 153 and pressed against the conveying belt 151 by the leading end pressure roller 155, and the conveying direction is changed by approximately 90 °.

At this time, the conveyance belt 157 is charged by the charging roller 156, and the sheet 142 is conveyed by being electrostatically attracted to the conveyance belt 151. Therefore, by driving the recording head 134 according to the image signal while moving the carriage 133, ink droplets are ejected onto the stopped paper 142 to record one line, and after the paper 142 is conveyed by a predetermined amount, Record the next line. Upon receiving a recording end signal or a signal that the trailing edge of the sheet 142 has reached the recording area, the recording operation is terminated and the sheet 142 is discharged onto the discharge tray 103.
When a near end of the remaining amount of ink in the sub tank 135 is detected, a required amount of ink is supplied from the ink cartridge 201 to the sub tank 135.

In this ink jet recording apparatus, when the ink in the ink cartridge 201 is used up, the casing of the ink cartridge 201 can be disassembled and only the ink bag 241 inside can be replaced. Further, the ink cartridge 201 can supply ink stably even when the ink cartridge 201 is placed vertically and has a front loading configuration. Therefore, the ink cartridge 201 can be replaced even when the upper portion of the apparatus main body 101 is closed, for example, when stored in a rack, or when an object is placed on the upper surface of the apparatus main body 101. Can be easily performed.
In addition, although it demonstrated in the example applied to the serial type (shuttle type) inkjet recording device which a carriage scans, it can apply similarly to the line type inkjet recording device provided with the line type head.

<Image formation>
An image formed product can be obtained by printing on a recording medium using an ink jet recording apparatus equipped with the ink cartridge. The printing method includes a continuous jet type and an on-demand type, and examples of the on-demand type include a piezo method, a thermal method, and an electrostatic method.

  EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated further more concretely, this invention is not limited by these Examples. In the examples, “parts” and “%” are based on weight except in the case of viscosity increase rate.

<Synthesis of copolymer>
Synthesis Example 1: 12-methacrylamide decanoic acid (MAD) / 2-acrylamido-2-methylpropanesulfonic acid (AMPS) copolymer (90/10)
12.36 g (68.41 mmol) of 12-methacrylamide decanoic acid (MAD), 1.58 g (7.62 mmol) of 2-acrylamido-2-methylpropanesulfonic acid (AMPS: Sigma-Aldrich Japan), hydroxylation 0.31 g (7.75 mmol) of sodium and 0.31 g (1.89 mmol) of azobisisobutyronitrile (manufactured by Nacalai Tesque) were dissolved in 59.4 g of methanol. Subsequently, nitrogen was bubbled for 60 minutes for deaeration, and the container was covered with a septum and polymerized by heating at 60 ° C. for 20 hours.
After completion of the polymerization reaction, the reaction solution was dropped into a large excess of ethyl acetate, and the precipitate was collected by suction filtration. After drying under reduced pressure, 17.8 g of random MAD / AMPS copolymer (90/10) compound (1) was obtained (yield: 87.9%).

Synthesis Example 2: 12-methacrylamido dodecanoic acid (MAD) / lauryl methacrylate (LMA) copolymer (90/10)
Compound (2) was obtained in the same manner as in Synthesis Example 1 except that (AMPS) in Synthesis Example 1 was changed to 1.93 g of lauryl methacrylate (LMA).

Synthesis Example 3: 12-methacrylamido dodecanoic acid (MAD) / lauryl methacrylate (LMA) copolymer (80/20)
Compound (3) was obtained in the same manner as in Synthesis Example 2 except that (MAD) in Synthesis Example 2 was changed to 17.02 g and (LMA) was changed to 3.86 g.

Synthesis Example 4: 12-methacrylamido dodecanoic acid (MAD) / 2-acrylamido-2-methylpropanesulfonic acid (AMPS) / lauryl methacrylate (LMA) copolymer (90/6/4)
Compound (4) was obtained in the same manner as in Synthesis Example 1 except that 1.58 g of (AMPS) in Synthesis Example 1 was changed to 0.95 g of (AMPS) and 0.77 g of (LMA).

Synthesis Example 5: 12-methacrylamidododecanoic acid (MAD) / 2-acrylamido-2-methylpropanesulfonic acid (AMPS) / lauryl methacrylate (LMA) copolymer (80/15/5)
Compound (5) was obtained in the same manner as in Synthesis Example 3 except that 3.86 g of (LMA) in Synthesis Example 3 was changed to 2.33 g of (AMPS) and 0.95 g of (LMA).

Synthesis Example 6: 12-methacrylamidododecanoic acid (MAD) / 2-acrylamido-2-methylpropanesulfonic acid (AMPS) copolymer (98/2)
Compound (6) was obtained in the same manner as in Synthesis Example 1 except that the ratio of (MAD) / (AMPS) in Synthesis Example 1 was changed from (90/10) to (98/2).

Synthesis Example 7: 12-methacrylamidododecanoic acid (MAD) / 2-acrylamido-2-methylpropanesulfonic acid (AMPS) copolymer (25/75)
Compound (7) was obtained in the same manner as in Synthesis Example 1 except that the ratio of (MAD) / (AMPS) in Synthesis Example 1 was changed from (90/10) to (25/75).

Synthesis Example 8: 12-methacrylamide decanoic acid (MAD) / lauryl methacrylate (LMA) copolymer (98/2)
Compound (8) was obtained in the same manner as in Synthesis Example 2 except that the ratio of (MAD) / (LMA) in Synthesis Example 2 was changed from (90/10) to (98/2).

Synthesis Example 9: 12-methacrylamidododecanoic acid (MAD) / lauryl methacrylate (LMA) copolymer (25/75)
Compound (9) was obtained in the same manner as in Synthesis Example 2 except that the ratio of (MAD) / (LMA) in Synthesis Example 2 was changed from (90/10) to (25/75).

Synthesis Example 10: 12-methacrylamidododecanoic acid (MAD) / 2-acrylamido-2-methylpropanesulfonic acid (AMPS) / lauryl methacrylate (LMA) copolymer (98/1/1)
Compound (10) was prepared in the same manner as in Synthesis Example 4 except that the ratio of (MAD) / (AMPS) / (LMA) in Synthesis Example 4 was changed from (90/6/4) to (98/1/1). )

Synthesis Example 11: 12-methacrylamidododecanoic acid (MAD) / 2-acrylamido-2-methylpropanesulfonic acid (AMPS) / lauryl methacrylate (LMA) copolymer (25/43/32)
Compound (11) was prepared in the same manner as in Synthesis Example 4 except that the ratio of (MAD) / (AMPS) / (LMA) in Synthesis Example 4 was changed from (90/6/4) to (25/43/32). )

Synthesis Examples 12 and 13
Compound similar to Synthesis Example 1 except that the monomer (MAD) / (AMPS) in Synthesis Example 1 was changed to Monomer (A) / Monomer (B) in the columns of Synthesis Examples 12 and 13 in Table 1 below. (12) and (13) were obtained.

Synthesis Examples 14-18
Except that the monomer (MAD) / (LMA) in Synthesis Example 2 was changed to Monomer (A) / Monomer (C) in the columns of Synthesis Examples 14 to 18 in Table 1 below, the same as Synthesis Example 2, Compounds (14) to (18) were obtained.

Synthesis Examples 19-23
Except that the monomer (MAD) / (AMPS) / (LMA) in Synthesis Example 4 is changed to Monomer (A) / Monomer (B) / Monomer (C) in the columns of Synthesis Examples 19 to 23 in Table 1 below. In the same manner as in Synthesis Example 4, compounds (19) to (23) were obtained.

Synthesis Example 24
Compound (24) was prepared in the same manner as in Synthesis Example 1 except that the monomer (MAD) / (AMPS) in Synthesis Example 1 was changed to Monomer (A) / Monomer (B) in the column of Synthesis Example 24 in Table 1 below. )

Synthesis Example 25
Compound (25) was prepared in the same manner as in Synthesis Example 2 except that the monomer (MAD) / (LMA) in Synthesis Example 2 was changed to the monomer (A) / monomer (C) in the column of Synthesis Example 25 in Table 1 below. )

<List of synthesis examples>

<Preparation of aqueous solutions of compounds (1) to (11), (13), (15) to (18), (20) to (25)>
10 g of each of the above compounds (1) to (11), (13), (15) to (18), (20) to (25) was dissolved in 40 g of a 2% aqueous solution of sodium hydroxide to obtain aqueous solutions (1) to (11 ), (13), (15) to (18), and (20) to (25) were obtained.

<Preparation of aqueous solutions of compounds (12), (14), (19)>
10 g of each of the compounds (12), (14) and (19) was dissolved in 40 g of a 2% aqueous solution of dimethylethanolamine (DMEA) to obtain aqueous solutions (12), (14) and (19).

Preparation Example 1
<Preparation of pigment dispersion (1)>
After premixing the materials of the following formulation, using a disk type bead mill (KDL type batch type manufactured by Shinmaru Enterprises Co., Ltd.), 0.05 mm zirconia beads are used, and the peripheral speed is 10 m / s and the liquid temperature is 10 ° C. for 5 minutes. Distributed. Subsequently, coarse particles were separated by a centrifugal separator (Model 3600 manufactured by Kubota Corporation) to obtain a pigment dispersion (1) having a volume average particle diameter of about 122 nm and a standard deviation of 50.2 nm.
[Prescription of Pigment Dispersion (1)]
・ Carbon black (Degussa: Gas black, NIPEX150) 20 parts ・ Aqueous solution (1) 25 parts ・ Distilled water 65 parts

Preparation Examples 2 to 25
<Preparation of pigment dispersions (2) to (25)>
Pigment dispersions (2) to (25) were obtained in the same manner as Preparation Example 1, except that the aqueous solution (1) of Preparation Example 1 was changed to the aqueous solutions (2) to (25).

Preparation Example 26
<Preparation of pigment dispersion (26)>
A pigment dispersion (26) was obtained in the same manner as in Preparation Example 1, except that the aqueous solution (1) of Preparation Example 1 was changed to a 20% aqueous solution of Naphthalenesulfonate formalin condensate / Na.

Preparation Example 27
<Preparation of pigment dispersion (27)>
The same procedure as in Preparation Example 1 except that the aqueous solution (1) of Preparation Example 1 was changed to an α-olefin / maleic anhydride copolymer (manufactured by Starlight PMC, T-YP112, olefin chain: carbon number 20 to 24). Thus, a pigment dispersion (27) was obtained.

Preparation Example 28
<Preparation of pigment dispersion (28)>
The same procedure as in Preparation Example 1 except that the aqueous solution (1) in Preparation Example 1 was changed to an α-olefin-maleic anhydride copolymer (manufactured by Seiko PMC, T-YP115, olefin chain: 16 to 18 carbon atoms). Thus, a pigment dispersion (28) was obtained.

Preparation Example 29
<Preparation of pigment dispersion (29)>
The same procedure as in Preparation Example 1 except that the aqueous solution (1) of Preparation Example 1 was changed to an α-olefin-maleic anhydride copolymer (T-YP114, olefin chain: 12 to 14 carbon atoms, manufactured by Seiko PMC). Thus, a pigment dispersion (29) was obtained.

Example 1
Ink (1) was prepared by mixing and stirring the materials having the following formulation for 30 minutes.
(Ink formulation of Example 1)
Pigment dispersion (1) (pigment concentration 20%) 40.0 parts Glycerol 5.5 parts 1,3-butanediol 16.5 parts 2-ethyl-1,3-hexanediol 2.0 parts Fluorosurfactant (solid content 40%) 2.5 parts (DuPont: Zonyl FS-300)
Fluoroethylene / vinyl ether alternating copolymer (solid content 50%) 6.0 parts (Asahi Glass Co., Ltd .: Lumiflon FE4300, volume average particle diameter 150 nm,
MFT 30 ℃ or less)
-2-amino-2-ethyl-1,3-propanediol aqueous solution (solid content 40%)
1.5 parts ・ 26.0 parts distilled water

Examples 2-25
Inks (2) to (25) of Examples 2 to 25 were the same as Example 1 except that the pigment dispersion (1) of Example 1 was changed to pigment dispersions (2) to (25). Got.

Comparative Examples 1-4
Inks (26) to (29) of Comparative Examples 1 to 4 were the same as Example 1 except that the pigment dispersion (1) of Example 1 was changed to pigment dispersions (26) to (29). Got.

  For the inks of the above Examples and Comparative Examples, the image density, storage stability, ejection stability, and viscosity increase rate were measured and evaluated as follows. Printing was performed using the ink jet recording apparatus shown in FIGS. The results are shown in Table 2.

(1) Image Density A chart with general symbols of 64 points JIS X 0208 (1997), 2223 created using Microsoft Word 2003 using each ink is printed on a PPC paper 4024 (non-smooth paper) manufactured by Xerox Corporation. After printing, the image density of the symbol part was measured by X-Rite 938 (manufactured by X-Rite). The print mode was “plain paper-fast” mode with the driver attached to the printer. Note that JIS X 0208 (1997), 2223 is a symbol whose outer shape is a regular square and the entire symbol surface is filled with ink.

(2) Storage stability The initial viscosity of the ink was measured using a viscometer (RE500 manufactured by Toyo Seiki Co., Ltd.). Next, 50 g of the ink was sealed in a sample bottle SV-50 manufactured by Nidec Rika Co., Ltd., stored in a 70 ° C. environment for 2 weeks, and then the viscosity was measured again. And the increase rate was calculated by the following formula, and the ranking was performed according to the following criteria.
Increase rate (%) = [(viscosity after storage−initial viscosity) / initial viscosity] × 100

[Ranking criteria]
: Increase rate is less than 5% (good)
○: Increase rate is 5% or more and less than 10% (a level that causes no problem in practical use)
○ △: Increase rate is 10% or more and less than 15% (a level that causes no problem in practical use)
Δ: Increase rate is 15% to less than 20% (problem level)
×: Increase rate is 20% or more (problem level)

(3) Ejection stability After printing on a recording medium, the recording apparatus was left to stand in an environment of 50 ° C. for one month with the inkjet head capped. Whether or not the ejection state of the printing apparatus after being left is restored to the initial ejection state was evaluated according to the following criteria based on the number of cleaning operations.
〔Evaluation criteria〕
A: Printing was possible without cleaning.
○: Recovered by one operation.
◯: Recovered by 2 to 3 operations.
Δ: Recovered by 4 to 5 operations.
X: No recovery was observed even after 6 or more operations.

(4) Viscosity increase rate About the ink of the said Example and the comparative example, the viscosity (initial viscosity) was measured at 25 degreeC using the viscometer MODEL RC-500l by the Toki Sangyo company. Next, the pH was adjusted with an aqueous HCl solution, and the viscosity at pH 8.5 was measured. And the viscosity increase rate was computed from the following formula from these viscosities. Table 2 shows the pH of the ink when the initial viscosity was measured. The pH was measured with an MP220 pH meter manufactured by METTLER TOLEDO.

Viscosity increase rate (%) = [(viscosity after pH adjustment−initial viscosity) / initial viscosity] × 100

As can be seen from Table 2, the inks of Examples 1 to 25 were compared with the inks of Comparative Examples 1 to 4 on the image density, storage stability, ejection stability, and viscosity increase rate on non-smooth paper (plain paper). Is clearly superior, and both image density and storage stability can be achieved, and both characteristics are remarkably excellent.
Further, as can be seen from the comparison of Examples 1-3, Examples 4-5, and Examples 6-11, changing the composition ratio of monomer (A), monomer (B), and monomer (C) changes the image density and storage. Effects related to stability, ejection stability, and viscosity increase rate change. Particularly in Examples 4 to 5, the effect of improving the plain paper image density, storage stability, ejection stability, and viscosity increase rate is remarkable. The same can be said for the comparison between Examples 12 to 18 and Examples 19 to 23 in which the monomer is changed.

DESCRIPTION OF SYMBOLS 101 Main body 102 Paper feed tray 103 Paper discharge tray 104 Ink cartridge loading part 105 Operation part 111 Upper cover 112 Front cover front 115 Front cover 131 Guide rod 132 Stay 133 Carriage 134 Recording head 135 Sub tank 141 Paper stacking part 142 Paper 143 Feed Paper roller 144 Separation pad 145 Guide 151 Conveying belt 152 Counter roller 153 Conveying guide 154 Pressing member 155 Pressure roller 156 Charging roller 157 Conveying roller 158 Tension roller 161 Guide member 171 Separating claw 172 Discharging roller 173 Discharging roller 181 Double-sided paper feeding Unit 182 Manual paper feed unit 200 Ink cartridge 241 Ink bag 242 Ink inlet 243 Ink outlet 244 Cartridge case

JP 2002-337449 A JP 2001-262025 A JP-A-4-332774 Japanese Patent No. 2867491 JP-A-4-18462 Japanese Patent No. 3088588 JP 2004-35718 A JP 2004-99800 A Japanese Patent No. 3088588 JP 2003-226827 A JP 2010-90191 A

Claims (7)

Copolymer containing pigment, water, water-soluble organic solvent and monomer (A) represented by the following general formula (1) as essential components and one or more aliphatic monomers as copolymerization components Ink-jet ink, characterized in that the initial pH is 9 to 11 and the rate of increase of the viscosity when the pH is lowered to 8.5 is 50% or more with respect to the initial viscosity.
General formula (1)

In the above formula, R1 represents a hydrogen atom or a methyl group, R2 represents an alkylene group having 4 to 22 carbon atoms, X1 represents an NH group or an oxygen atom, M1 represents a hydrogen atom, a monovalent inorganic cation or an organic cation. The aliphatic monomer contains at least one of a monomer (B) represented by the following general formula (2) and a monomer (C) represented by the following general formula (3). The ink for inkjet according to 1.
General formula (2)

In the above formula, R3 represents a hydrogen atom or a methyl group, R4 represents an alkylene group having 1 to 4 carbon atoms, X2 represents an NH group or an oxygen atom, M2 represents a hydrogen atom, a monovalent inorganic cation or an organic cation.

General formula (3)

In the above formula, R5 represents a hydrogen atom or a methyl group, R6 represents an alkyl group having 1 to 12 carbon atoms, a fluorinated alkyl group, an aminoalkyl group, or a hydroxyalkyl group, and X3 represents an NH group or an oxygen atom.   The monomer (A) is 12-methacrylamide decanoic acid, the monomer (B) is 2-acrylamido-2-methylpropanesulfonic acid, and the monomer (C) is lauryl methacrylate. Inkjet ink.   An image forming method comprising forming an image using the ink jet ink according to claim 1.   An ink cartridge containing the inkjet recording ink according to claim 1 in a container.   An ink jet recording apparatus equipped with the ink cartridge according to claim 5.   An image formed product printed by the ink jet recording apparatus according to claim 6.

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