JP3486434B2 - Aqueous pigment ink and ink jet recording method using the same - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an ink jet recording liquid, and more specifically, it uses a water-based pigment dispersion as an ink to produce high-quality paper, copy paper, letter paper, thermal transfer paper,
Business Forms paper for wire dot printer,, etc. relates to an ink for recording on so-called plain paper.

[0002]

2. Description of the Related Art Recently, attempts have been made to use an aqueous pigment ink for on-demand ink jet recording. The purpose is to provide a recorded material excellent in fastness such as water resistance and light resistance by using an aqueous pigment ink even in the ink jet system. Ink jet printer inks are generally required to have the following performances. (1) To give an image of sufficient density (2) Good dryness on the recording material (3) No bleeding on the recorded image (4) Image quality of the recorded image even when contacted with water, alcohol, etc. No flow (5) Recorded characters and images have excellent scratching properties (6) No nozzle clogs at the tip of the nozzle (7) When printing continuously or when starting recording after leaving for a long time , Inconvenience such as blurring of recorded image does not occur (8) Ink is stable during storage (9) There is no problem in user safety (10) When used, as a member constituting recording means It does not cause a problem even if they come into contact with each other. Further, in the ink jet recording method utilizing heat energy, in addition to the above-mentioned required items, (11) it has excellent heat resistance and does not adversely affect the heat energy generating element.

By the way, it has been pointed out that the conventional technique of the aqueous pigment ink for inkjet, which is obtained by adding water and a water-soluble organic solvent to the aqueous pigment dispersion, has a problem that the printed matter has poor scratching property. And has poor abrasion resistance, difficult to read and rubbing the coloring material when I Tsu mystery of the printed matter with a marker, the marker is dirty, dirty hands and clothes, refer to it, such as easy tampering easy to erase with eraser or the like. It uses plain paper,
This is particularly noticeable when the coloring material is fixed on the surface of the paper so that the printing density becomes high.

The abrasion resistance of the water-based pigment ink is poor because the so-called binding resin (binder resin) used in existing printing inks is little added or the binder resin is not contained in practice and the dispersant is not contained. It is thought that this is because only the resin as described above exists in the ink.

[0005] The reason for sufficient binder to the aqueous pigment ink for inkjet can not be added, inkjet inks there is a requirement that must be two Yuton low viscosity fluid. If the viscosity of the ink is increased or the resin is dissolved, the response frequency is lowered and the start-up characteristics at the time of re-driving after the ejection is stopped are deteriorated. Further, in the case of an ink jet system that uses thermal energy for foaming ink, foaming is less likely to occur, and adverse effects such as a decrease in droplet volume are also seen. Therefore, it has been difficult to add an effective amount of resin to scratch resistance, especially in a dispersed ink.

[0006]

SUMMARY OF THE INVENTION The present invention has been made in view of the current state of the art as described above, and realizes recording having excellent fixability and excellent print quality, and particularly excellent scratch resistance of printed matter. The present invention provides an aqueous pigment ink for inkjet and an inkjet recording method using this ink.

[0007]

That is, the present invention is
Aqueous solution consisting of water, water-soluble organic solvent and pigment dispersion
In the pigment ink, in the inkfollowing ( Isocyanar
To ) The polyisocyanate exemplified in the item ( A
Mino alcohol and alcohol amine ) Item
A reaction product of an amino alcohol represented by the general formula
( 1 ) , ( Two ) Or ( Three ) Indicated byPolyisocyanate
Characterized by containing a mino alcohol addition compound
It is a water-based pigment ink that
A method of recording a jet is provided.

Polyisocyanate used in the present invention
Amino alcohol adduct ( hereinafter abbreviated as polyurea compound)
To), the aqueous pigment Lee in order to improve the abrasion resistance of printed matter
Other than water-soluble polymer compounds
Of the novel composition found from the study of the binding substances of
Including. A water-based pigment ink containing this is suitable as an inkjet ink.

The polyurea compound, pigment, dispersant, organic solvent and other components used in the aqueous pigment ink of the present invention will be described in detail below. (Polyurea Compound) The polyurea compound of the present invention is obtained by reacting an amino alcohol with a polyisocyanate. The polyurea compound is a polyol having a hydroxy group at the end, which has two or more urea bonds as a linking group. The polyurea compound is a novel substance having a molecular weight of 1000 or less and solid at room temperature and having water miscibility and moisture retention. In the absence of water, the polyurea compound has a strong hydrogen bonding force of the urea bond and the hydrophobicity of the alkyl group such as hexamethylene group and isophorone group, which are the skeletal atomic groups of the polyisocyanate compound. It is considered that the function as a binder appears. It is considered that the strong cohesive force of the urea bond also acts to strongly bond the solidified dispersion particles. These may be the cause of improving the abrasion resistance. The polyurea compound is
It is almost neutral in itself and very slowly hydrolyzes to form the starting non-volatile amine. Therefore, the stability of the pigment dispersion using the dispersant having a carboxyl group, a sulfone group or the like as a hydrophilic group is not adversely affected.

The general structure of the polyurea compound used in the aqueous pigment ink of the present invention and the substances used in the synthesis are shown below.

HO-R ₁ -NHCONH-R-NHCONH-R ₂ -OH R = residue of polyisocyanate

[0012]

[Chemical 2]

[0013]

[Chemical formula 3] (Isocyanate) As the isocyanate compound used in the synthesis of the polyurea compound of the present invention, hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, bis (isocyanate) Natomethyl) cyclohexane, dicyclohexylmethane diisocyanate,
Lysine diisocyanate, trimethylhexamethylene diisocyanate, and tolylene diisocyanate, hexamethylene diisocyanate, adduct, urethane modified product, allophanate modified product, biuret modified product,
A modified isocyanurate is used. In order to synthesize the polyurea compound of the present invention, basically a bifunctional isocyanate is used, but it is of course possible to use a polyfunctional isocyanate having a functionality of 3 or more in combination. (Amino alcohol and alcohol amine) Examples of amino alcohol and alcohol amine to be reacted with polyisocyanate include ethanolamine, N-methylethanolamine, 2- (2-aminoethyl) ethanolamine, diethanolamine, N-ethyldiethanolamine and triethanol. The amines are 2-amino-2-methylpropanol, 2-ethyl-2-amino-1,3-propanediol, 2-aminoethoxyethylene glycol, tris (hydroxymethyl) aminomethane, and tris (hydroxymethyl) aminoethane.

Since polyisocyanate and amino alcohol each have extremely high reactivity in a dry nitrogen atmosphere, they can be easily and equivalently reacted at room temperature. By gradually dropping the amine into the polyisocyanate as usual, the reaction of the isocyanate with the hydroxyl group is suppressed, and the selective reaction with the amine proceeds.

Typical compounds synthesized in this way are the following substances. Compound Example 1 Reaction product of hexamethylene diisocyanate and monoethanolamine HOCH ₂ CH ₂ -NHCONH- (CH ₂ ) ₆ -NHCONH-CH ₂ CH ₂ OH Compound Example 2 Hexamethylene diisocyanate and monoethanolamine and reaction products of diethanolamine _{(HOCH 2 CH 2) 2 -NCONH-} (CH 2) 6 -NHCONH-CH 2 CH 2 OH compound example 3 reaction product of hexamethylene diisocyanate and diethanolamine (HOCH ₂ CH _{2) 2 -NCONH- (CH 2) 6 -NHCONH-} (CH 2 CH 2 OH) 2 compound example 4 the reaction product of hexamethylene diisocyanate and 2-aminoethoxy ethylene glycol _{HO-CH 2 CH 2 OCH 2} CH 2 -NCONH- (CH ₂ ) ₆ -NHCONH-CH ₂ CH ₂ OCH ₂ CH ₂
-OH Compound Example 5 Reaction product of hexamethylene diisocyanate and 2-amino-2-methylpropanol

[0016]

[Chemical 4] Compound Example 6 Reaction product of hexamethylene diisocyanate and triethanolamine

[0017]

[Chemical 5] Compound Example 7 Reaction product of hexamethylene diisocyanate and 2-ethyl-2-amino-1,3-propanediol

[0018]

[Chemical 6] Compound Example 8 Reaction product of isophorone diisocyanate and monoethanolamine

[0019]

[Chemical 7] Compound Example 9 Reaction product of Coronate L and monoethanolamine

[0020]

[Chemical 8] The compounds as described above are typical substances of the polyurea compound used in the present invention. The compound used in the present invention is not limited to these, and the reaction product of the above-mentioned polyvalent isocyanate and amine is also preferably used.

The content of the polyurea compound in the ink is
It is 0.5-15% by weight, preferably 3-10% by weight. (Pigment) The amount of the pigment contained in the ink used in the present invention is preferably 1 to 20% by weight, and more preferably 2 to 12%. As the carbon black used for the black ink, a furnace method, a channel method, or
High specific surface area carbon produced by activating petroleum coke with a large amount of alkali, and fluorine treatment from the gas phase to the above carbon black materials, plasma treatment of polymerizable monomers having hydrophilicity, hydrophilicity It may be carbon black that has been subjected to a treatment such as graft polymerization of a monomer having a property from a liquid phase.

The carbon black as described above has a primary particle size of 15 to 40 mμ and a specific surface area by the BET method of 50.
To 3000 square meters / g, DBP oil absorption is 40 to 1
50ml / 100g, volatile content is 0.5 to 10%, p
The H value has 2 to 9.

Those carbon black pigments (CIPigm
ent Black 7) No.2300, No.900, MCF-88, No.3
3, No.40, No.45, No.52, MA7, MA8, MA100, No.2200B
(Made by Mitsubishi Kasei); Raven 700, Raven 5750, Raven
5250, Raven 5000, Raven 3500, Raven 1255 (Made in Colombia); Regal 400R, Regal 330R, Regal 660R,
Mogul L, Monarch 700, Monarch 800, Monarch 880,
Monarch 900, Monarch 1000, Monarch 1100, Mona
rch 1300, Monarch 1400, (above Cabot); Col
orBlack FW1, ColorBlack FW2, ColorBlack FW2V, Col
orBlack FW18, ColorBlack FW200, ColorBlack S150,
ColorBlack S160, ColorBlack S170, Printex 35,
Printex U, Printex V, Printex 140U, Printex140
V, SpecialBlack 6, Special Black 5, Special Bla
ck 4A, Special Black 4, (manufactured by Degussa); Maxsorb G-40, Maxsorb G-15, Maxsorb G-08, (manufactured by Kansai Thermochemical Co., Ltd.) and the like can be used.

Pigments used for yellow ink include CIPigment Yellow 1, CIPigment Yellow 2, CI
Pigment Yellow 3, CIPigment Yellow 12, CIPigment
Yellow 13, CIPigment Yellow 14, CIPigment Yello
w 16, CIPigment Yellow 17, CIPigment Yellow 73,
CIPigment Yellow 74, CIPigment Yellow 75, CIPi
gment Yellow 83, CIPigment Yellow 93, CIPigment
Yellow 95, CIPigment Yellow 97, CIPigment Yellow
98, CIPigment Yellow 114, CIPigment Yellow 128,
CIPigment Yellow 129, CIPigment Yellow 151, CI
Pigment Yellow 154, CIPigment Red 5, CIPigment Red 7,
CIPigment Red 12, CIPigment Red 48 (Ca), CIPigm
ent Red 48 (Mn), CIPigment Red 57 (Ca), CIPigment
Red 57: 1, CIPigment Red 112, CIPigment Red 123,
CIPigment Red 168, CIPigment Red 184, CIPigmen
t Red 202, CIPigment Blue 1, CIPigment Blue 2, CIPigm as pigments used as cyan ink
ent Blue 3, CIPigment Blue 15: 3, CIPigment Blue
15: 34, CIPigment Blue 16, CIPigment Blue 22, CI
Pigment Blue 60, CIVat Blue 4, CIVat Blue 60, and the like, but are not limited thereto. In addition, those newly manufactured for the present invention can also be used. (Dispersant) The dispersant used in the ink of the present invention is an alkali-soluble water-soluble resin and has a weight average molecular weight of 10
00 to 30,000, preferably 3000 to 1
It is in the range of 5000. Specifically, hydrophobic monomers such as styrene, styrene derivatives, vinylnaphthalene, vinylnaphthalene derivatives, alkyl esters of allyl acid, alkyl esters of methacrylic acid, and α, β-ethylenically unsaturated carboxylic acids and their aliphatic alcohols. Copolymers composed of hydrophilic monomers such as esters, acrylic acid, methacrylic acid, maleic acid, itaconic acid, fumaric acid, and their derivatives, and salts thereof. The copolymer may have any structure such as random, block or graft, and the acid value is in the range of 100 to 430, preferably 130 to 360. As the dispersant used in the present invention, it is also possible to use water-soluble polymers such as polyvinyl alcohol and carboxymethyl cellulose, water-soluble resins such as naphthalene sulfonic acid formaldehyde condensate and polystyrene sulfonic acid.
However, the alkali-soluble water-soluble resin has an advantage that the viscosity of the dispersion liquid can be lowered and the dispersion is easy.
The amount of these dispersants used is in the range of pigment weight; dispersant weight = 10: 3 to 10: 0.5. The suitable ratio is experimentally determined by using the selected pigment and dispersant, but the amount of the resin which is not adsorbed to the pigment and is dissolved is preferably 2% by weight or less in the ink. (Base) A base is required to use the dispersant used in the ink of the present invention in an aqueous system. Suitable bases therefor include ethanolamine, diethanolamine, triethanolamine, N-methylethanolamine, N-
Ethyldiethanolamine, 2-amino-2-methylpropanol, 2-ethyl-2-amino-1,3-propanediol, 2- (2-aminoethyl) ethanolamine, tris (hydroxymethyl) aminomethane, ammonia, piperidine, Organic bases such as morpholine and β-dihydroxyethylurea; inorganic bases such as sodium hydroxide, potassium hydroxide and lithium hydroxide are used.
The optimum base species varies depending on the type of pigment and dispersant selected, but is preferably non-volatile, stable and highly water-retentive. The amount of the base used is basically the amount calculated from the acid value of the dispersant, and is used as the amount of the base necessary for neutralizing it. In some cases, more than the equivalent amount of acid may be used. It ’s improved dispersibility,
The purpose is to adjust the pH of the ink, adjust the recording performance, improve the moisturizing property, and the like.

The pigment and dispersant as described above are dispersed in an aqueous medium. (Solvent) The recording liquid of the present invention is mainly composed of water, and a water-soluble solvent is mixed and used. The total amount of the water-soluble solvent is approximately 5 to 40% by weight with respect to the entire ink. In preparing the aqueous pigment inks of the present invention, the choice of solvent system is important in order to control storage stability and moisture retention and fixability on plain paper. It is convenient to classify water-soluble organic solvents into the following three groups.

The first group of solvents is suitable for moisturizing properties and dispersion stability, and has good print quality because of its suppressed wettability to plain paper. The content is 5% by weight or more, preferably 10% by weight or more in the recording liquid. Even if a relatively large amount of the first group of solvents is used, the penetrability does not become too high and the printing quality does not deteriorate.

Since the second group of solvents has very good wettability with respect to plain paper, the addition of a small amount of solvent improves the initial wettability of the recording liquid onto the paper and improves the fixability. It is used within the range of 5% by weight or less in the recording liquid.

The solvents of the third group are different from those of the first group and the second group in terms of wettability.
It is located in the middle size of the group, and even if it is added more than the solvent of the second group, the deterioration of the quality is small, and it is added mainly for imparting ejection stability. Here, the ejection stability means, for example, variations in volume and flight speed of droplets in a inkjet head of a valve jet system, frequency response, and the like.

As the solvent belonging to the first group, ethylene glycol, diethylene glycol, triethylene glycol, tripropylene glycol, glycerin, 1,
2,4-butanetriol, 1,2,6-hexanetriol, 1,2,5-pentanetriol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, dimethylsulfoxide, diamine Acetone alcohol, glycerin monoallyl ether, propylene glycol, butylene glycol, polyethylene glycol 300, thiodiglycol, N-methyl-2-pyrrolidone, 2-pyrrolidone, γ-butyrolactone, 1,3-dimethyl-2-imidazolidinone, Sulforane, trimethylolpropane, trimethylolethane, neopentyl glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monoallyl ether Le, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, beta-dihydroxyethyl urea,
Urea, acetonylacetone, pentaerythritol,
1,4-cyclohexanediol and the like.

Solvents belonging to the second group include hexylene glycol, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monoisobutyl ether, ethylene glycol monophenyl ether, diethylene glycol diethyl ether, diethylene glycol monobutyl ether, diethylene glycol monoisobutyl. Ether, triethylene glycol monobutyl ether, triethylene glycol dimethyl ether, triethylene glycol didiethyl ether, tetraethylene glycol dimethyl ether, tetraethylene glycol diethyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monopropyi Ether, dipropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, glycerol monoacetate, glyceryl Sen syringe acetate, glycidyl Sen phosphorus triacetate, ethylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether acetate, cyclohexanol, 1,2-cyclohexanediol, 1
-Butanol, 3-methyl-1,5-pentanediol, 3-hexene-2,5-diol, 2,3-butanediol, 1,5-pentanediol, 2,4-pentanediol, 2,5-hexane Examples include diols.

Solvents belonging to the third group include ethanol, n-propanol, 2-propanol, 1-methoxy-2-propanol, furfuryl alcohol, tetrahydrofurfuryl alcohol and the like. (Surfactant) In addition to the above-mentioned materials, a surfactant, a preservative, an antioxidant, and other auxiliary materials for controlling physical properties can be added to the aqueous pigment ink of the present invention.
As the surfactant, polyoxyethylene alkyl ethers, polyoxyethylene alkylphenol ethers, polyoxyethylene alkyl esters, sorbitan esters, sorbitan ester ethers, oxyethylene oxypropylene block polymers, oxyethylene alkyl amines, Nonionic surfactants such as alcoholic amides of fatty acids, fatty acid esters of polyhydric alcohols, ethylene oxide adducts of acetylene glycol, etc .; dimethylalkyl (coconut) betaine, dimethylalkyllauryl betaine, alkylglycine,
Amidobetaine type, imidazoline type and other amphoteric surfactants; octadecylamine acetate, tetradecylamine acetate, tallow alkyl propylene diamine acetate, octadecyl trimethyl ammonium chloride, alkyl (tallow) trimethyl ammonium chloride, dodecyl trimethyl ammonium chloride, alkyl (Palm)
Trimethylammonium chloride, hexadecyltrimethylammonium chloride, behenyltrimethylammonium chloride, alkyl (beef tallow) imidazolinone quaternary salt, alkyldimethylbenzylammonium chloride, octadecyldimethylbenzylammonium chloride, dioleyldimethylammonium chloride, polyoxyethylenedodecylmethylammonium chloride And other cationic surfactants.

These surfactants have various purposes of addition, such as improvement in penetrability into paper, wettability with ejection device member, flow characteristics, and auxiliary agent for dispersion stability. (Preparation of Ink) As a method of preparing the ink of the present invention,
First, a pigment is added to an aqueous solution of a dispersant, stirred, and then dispersed using a dispersing means described below, followed by centrifugation to remove coarse particles, pressure filtration using a membrane, and the like. A dispersion is obtained. Next, the above-mentioned solvent is added to this dispersion, and other additives (surfactant,
A pH adjusting agent, an antiseptic agent, etc.) is added and stirred to prepare a recording liquid.

The disperser used in the present invention may be any disperser which is generally used, as long as the average particle diameter is efficiently obtained in the desired range. Examples include ball mills, sand mills, roll mills, and the like. Among them, a high speed type sand mill is preferable, and examples thereof include a super mill, a sand grinder, a bead mill, an agitator mill, a grain mill, a dyno mill, a pearl mill, a cobol mill, and the like (all are trade names). Further, it is also possible to apply a dispersion device of a system in which the dispersion liquid is jetted from a jet nozzle under high pressure without using beads, for example. In the present invention, as a method for obtaining a dispersion having a desired particle size distribution, there are used methods such as reducing the size of the pulverizing media of the disperser, applying pressure filtration after pulverization, and classifying by centrifugation. Well, there is a combination of them. (Recording device) As a recording device suitable for recording using the ink of the present invention, there are a Continuus type inkjet recording device, an on-demand type inkjet recording device using a piezoelectric element, and recording in the ink inside the recording head. A valve jet type ink jet recording apparatus that applies thermal energy corresponding to a signal and generates droplets by the energy is exemplified. The ink jet recording apparatus used in the present invention has a frequency of 1 to 8 KHz and a droplet volume of 10 to 150.
The recording head has a pl and a nozzle density of about 180 to 600 dpi.

Next, the recording apparatus of the present invention will be described. In the present invention, it is preferable to apply a recording signal to the recording ink of the recording head and eject the droplets by the generated thermal energy. A recording head using an electromechanical conversion element can also be used. The structure of the recording head, which is the main part of the apparatus using thermal energy, is shown in FIGS. The head 13 includes a heating head 15 having a heating resistor used for thermal recording, such as glass, ceramic, or plastic in which an ink flow path is formed (thin film head is shown in the figure, but the present invention is not limited to this. It is not a thing) and is obtained by adhering. The heating head 15 includes a protective film 16 made of silicon oxide, aluminum electrodes 17-1 and 17-2, a heating resistor layer 18 made of nichrome, a heat storage layer 19, and a substrate having good heat dissipation such as alumina. Made up of 20.

The recording ink 21 reaches the ejection orifice 22 and forms a meniscus 23 by the pressure P. Here, when an electric signal is applied to the electrodes 17-1 and 17-2, the area indicated by n of the heating head 15 rapidly generates heat, bubbles are generated in the ink 21 in contact with the area, and the meniscus 23 is generated by the pressure. Are projected, become recording liquid droplets 24 from the orifice 22, and fly toward the recording medium 25.
FIG. 3 shows a schematic view of a recording head in which a large number of the heads shown in FIG. 1 are arranged. The recording head is made by closely adhering a glass plate 27 having a large number of flow paths to a heating head 28 similar to that described in FIG.

Incidentally, FIG. 1 shows the head 1 along the ink flow path.
3 is a sectional view of FIG. 3, and FIG. 2 is a sectional view taken along line AB of FIG. 1. FIG. 4 shows an example of an ink jet recording apparatus incorporating the head.

In FIG. 4, reference numeral 61 denotes a blade as a wiping member, one end of which is held by a blade holding member to become a fixed end, which is in the form of a cantilever. The blade 61 is arranged at a position adjacent to the recording area of the recording head, and in the case of this example, is held in a protruding form in the moving path of the recording head. Reference numeral 62 denotes a cap, which is arranged at a home position adjacent to the blade 61, and has a configuration in which it moves in a direction perpendicular to the moving direction of the recording head and comes into contact with the ejection surface to perform capping. Further, 63 is an ink absorber provided adjacent to the blade 61, and like the blade 61, is held in a form protruding in the moving path of the recording head. The blade 61, the cap 62, and the absorber 63 constitute an ejection recovery unit 64, and the blade 61 and the absorber 63 remove water, dust, and dust on the ink ejection port surface. Reference numeral 65 denotes a recording head having ejection energy generating means, which ejects ink to a recording material facing the ejection port surface where the ejection ports are arranged to perform recording, and 66 denotes a recording head 65 in which the recording head 65 is mounted.
It is a carriage for moving the. Carriage 66
Are slidably engaged with the guide shaft 67, and the carriage 66
Is connected to a belt 69 driven by a motor 68 (not shown). This allows the carriage 66 to move along the guide shaft 67, and the recording head 6
It is possible to move the recording area and the area adjacent to the recording area by 5.

Reference numeral 51 is a paper feed section for inserting a recording material, and 52 is a paper feed roller driven by a motor (not shown). With these configurations, the recording material is fed to the position facing the ejection opening surface of the recording head, and is ejected to the ejection portion provided with the ejection roller 53 as the recording progresses.

In the above configuration, when the recording head 65 returns to the home position after recording is completed, the head recovery unit 64
The carriage 62 is retracted from the movement path of the recording head 65, but the blade 61 is projected in the movement path. As a result, the ejection port surface of the recording head 65 is wiped. When the cap 62 comes into contact with the ejection port surface of the recording head 65 to perform capping, the cap 62 moves so as to project into the moving path of the recording head. When the recording head 65 moves from the home position to the recording start position, the cap 62 and the blade 61 are in the same position as the above-mentioned position during wiping. As a result, even during this movement, the ejection port surface of the recording head 65 is wiped.

The above-described movement of the recording head to the home position is performed not only at the end of recording and at the time of ejection recovery, but also at the home adjacent to the recording area at a predetermined interval while the recording head moves in the recording area for recording. The wiper is moved to the position, and the wiping is performed along with the move.

FIG. 5 shows an ink cartridge 4 containing ink to be supplied to the head through an ink supply tube.
It is a figure which shows an example of 5. Here, 40 is an ink bag containing the supply ink, and a rubber stopper 42 is provided at the tip thereof.
Is provided. By inserting a needle (not shown) into this stopper 42, the ink in the ink bag 40 can be supplied to the head. An ink absorber 44 receives the waste ink. The ink jet recording apparatus used in the present invention is not limited to the above-described head and ink cartridge which are separate bodies, and those in which they are integrated as shown in FIG. 6 are also preferably used. In FIG.
Reference numeral 70 is an ink jet cartridge in which an ink absorber impregnated with ink is stored.
The ink in the ink absorber is ejected as ink droplets from the head portion 71 having a plurality of orifices. Reference numeral 72 is an atmosphere communication port for communicating the inside of the cartridge with the atmosphere. The inkjet cartridge 70 is used in place of the recording head 65 shown in FIG. 4, and is detachable from the carriage 66.

[0042]

EXAMPLES The effects of the production and use of the water-based pigment ink of the present invention will be described in detail below with reference to examples. [Example 1] (Preparation of pigment dispersion liquid) Styrene / methacrylic acid / ethyl acrylate copolymer (glass transition temperature 74 ° C, acid value 4
00, weight average molecular weight 6000) potassium hydroxide solution (neutralization rate 110%, resin solid content 2 parts) 80 parts, ethylene glycol 5 parts, carbon black (Mo
15 parts of gul L cablack) was used to prepare an aqueous dispersion. A vertical sand mill was used for dispersion. The solid content of this dispersion was about 16%, and the average particle size was 95 mμ. (Preparation of ink) 40 parts of the above-mentioned dispersion substance of compound example 1 10 parts ethylene glycol monomethyl ether 15 parts glycerin 5 parts diethylene glycol monobutyl ether 0.5 part isopropyl alcohol 3 parts ion-exchanged water 26.5 parts Book prepared in this way The aqueous pigment ink of the invention has a viscosity of 3.5 cps, a surface tension of 48 dyn / cm, a pH of 9.
5, the average particle size was 100 mμ. Example 2 (Preparation of Pigment Dispersion) Styrene / acrylic acid / methyl methacrylate copolymer (glass transition temperature 87 ° C., acid value 280, weight average molecular weight 11,000) in diethanolamine (neutralization ratio 110%, resin Solid content 2.5 parts) 8
An aqueous pigment dispersion was prepared using 0 part, 5 parts of ethylene glycol and 15 parts of carbon black (made by Regal 400 Cablack). A vertical sand mill was used for dispersion. The solid content of this dispersion is about 17% and the average particle size is 103.
It was mμ. (Preparation of Ink) 40 parts of the above-mentioned dispersion substance of compound example 3 5 parts triethylene glycol / diethylene glycol (40:60 weight ratio) 15 parts ethylene glycol monobutyl ether 1.0 part 1-methoxy-2-propanol 5 parts ion-exchanged water 34.0 parts The water-based pigment ink of the present invention thus prepared has a viscosity of 2
3.2 cps, surface tension 44 dyn / cm, pH 9.
5, the average particle size was 103 mμ. Example 3 (Preparation of Pigment Dispersion) Morpholine solution of styrene / acrylic acid / n-butyl acrylate copolymer (glass transition temperature 65 ° C., acid value 360, weight average molecular weight 9000) (neutralization rate 110%) , 80 parts of resin solid content, 5 parts of ethylene glycol, and 15 parts of carbon black (manufactured by Color Black S-170 Degussa) were used to prepare an aqueous pigment dispersion. A vertical sand mill was used for dispersion. The solid content of this dispersion is 16.5% and the average particle size is 11
It was 0 mμ. (Preparation of Ink) 40 parts of the above-mentioned dispersion substance 7 of compound example 4 7 parts glycerin / ethylene glycol (50:50 weight ratio) 25 parts hexylene glycol 0.5 part tetrahydrofurfuryl alcohol 3 parts ion-exchanged water 24.5 The water-based pigment ink of the present invention thus prepared has a viscosity of 2.8 cps, a surface tension of 46 dyn / cm and a pH of 9.
7. The average particle size was 110 mμ. [Example 4] The following ink was prepared using the dispersion of Example 1. (Preparation of Ink) Dispersion of Example 1 40 parts Compound of Example 6 3 parts Glycerin 15 parts Diethylene glycol monobutyl ether 0.5 parts Isopropyl alcohol 3 parts Ion-exchanged water 38.5 parts Aqueous solution of the present invention prepared in this manner The pigment ink has a viscosity of 3.1 cps, a surface tension of 45 dyn / cm, and a pH of 9.
2. The average particle size was 105 mμ. [Example 5] The following ink was prepared using the dispersion of Example 2. (Preparation of Ink) Dispersion of Example 2 40 parts Compound of Example 7 5 parts Glycerin / Ethylene glycol (15: 5) 25 parts Diethylene glycol monobutyl ether 0.2 parts Isopropyl alcohol 2 parts Acetylenol EH 0.1 parts Ion exchange Water 27.7 parts The thus prepared water-based pigment ink of the present invention has a viscosity of 3.5 cps, a surface tension of 40.0 dyn / cm, and a pH.
The average particle diameter was 9.4 and 105 mμ. Example 6 (Preparation of Pigment Dispersion) Monoethanolamine solution of styrene / acrylic acid / ethyl methacrylate copolymer (glass transition temperature 74 ° C., acid value 140, weight average molecular weight 9500) (neutralization rate 105% , Resin solids 2 parts) 80
Parts, 5 parts ethylene glycol, carbon black (MC
An aqueous pigment dispersion was prepared using 15 parts of F-88 Mitsubishi Kasei).

The solid content of this dispersion was 16%, and the average particle size was 103 mμ. (Preparation of ink) 40 parts of the above-mentioned dispersion liquid 10 parts of the compound of Example 8 10 parts triethylene glycol monomethyl ether 20 parts 1,5-pentanediol 2.0 parts n-propanol 4.0 parts ion-exchanged water 24.0 parts The water-based pigment ink of the present invention adjusted to have a viscosity of 2.8 cps, a surface tension of 38 dyn / cm, and a pH of 9.
3, the average particle size was 103 mμ. Example 7 (Preparation of Pigment Dispersion Liquid) Styrene / acrylic acid / methyl methacrylate copolymer (glass transition temperature 87 ° C., acid value 280, weight average molecular weight 11000) in diethanolamine (neutralization ratio 110%, resin Solid content 1.5 parts) 8
0 parts, 5 parts ethylene glycol, 1 part Permanent Pink F-6B (made by Pigment Red 57-1 Hoechst)
An aqueous pigment dispersion was prepared using 5 parts. The solid content of this dispersion was 16%, and the average particle size was 125 mμ. (Preparation of ink) 40 parts of the above dispersion liquid 5 parts of the compound of Example 9 5 parts 1,2,5-butanetriol / triethylene glycol monoethyl ether (65:35 weight ratio) 30 parts ethylene glycol monobutyl ether 0.3 parts ethanol 4 parts Ion-exchanged water 20.7 parts The aqueous pigment ink of the present invention thus prepared has a viscosity of 2.5 cps, a surface tension of 43 dyn / cm, a pH of 9.
3, the average particle size was 103 mμ. [Example 8] (Preparation of pigment dispersion liquid) Styrene / acrylic acid / ethyl acrylate copolymer (glass transition temperature 68 ° C, acid value 25
0, weight average molecular weight 13000) of aminomethyl propanol solution (neutralization rate 110%, resin solid content 2.5 parts) 80 parts, ethylene glycol 5 parts, permanent yellow GR (Pigment Yellow 13 Hoechst) 1
An aqueous pigment dispersion was prepared using 5 parts. The solid content of this dispersion was 17%, and the average particle size was 115 mμ. (Preparation of Ink) Dispersion 40 parts The substance of Compound Example 6 8 parts Diethylene glycol 20 parts Ethylene glycol monobutyl ether 1.0 part 1-Methoxy-2-propanol 5.0 parts Ion-exchanged water 26.0 parts The aqueous pigment ink of the present invention has a viscosity of 3.0 cps, a surface tension of 47 dyn / cm, a pH of 9.
6, the average particle size was 115 mμ. Example 9 (Preparation of Pigment Dispersion Liquid) Styrene / methacrylic acid / dimethylaminoethyl acrylate copolymer (glass transition temperature 87 ° C., acid value 210, weight average molecular weight 7000) in triethanolamine (neutralization ratio 110 %, Resin solid content 2.0 parts), ethylene glycol 5 parts, and Fastgen Blue FGF (Pigment Blue 15: 3 manufactured by Dainippon Ink) 15 parts to prepare an aqueous pigment dispersion.
The solid content of this dispersion was 16%, and the average particle size was 95 mμ. (Preparation of Ink) 40 parts of the above-mentioned dispersion liquid 5 parts of the compound of Example 8 5 parts ethylene glycol / glycerin (40:60 weight ratio) 25 parts triethylene glycol monobutyl ether 1.0 part 2-propanol 1.0 part deionized water 28 0.0 parts The thus-prepared aqueous pigment ink of the present invention has a viscosity of 2.7 cps, a surface tension of 51 dyn / cm, and a pH of 9.
2. The average particle size was 95 mμ. [Comparative Example 1] In the recording liquid of Example 1, the polyurea compound of Compound Example 1 was not used, but water was added instead, and Comparative Example 1
Recording liquid. [Comparative Example 2] The recording liquid of Comparative Example 2 was obtained by adding the styrene-maleic acid resin (molecular weight 1500, acid value 300) instead of the polyurea compound of Compound Example 3 in the recording liquid of Example 2. did. Comparative Example 3 The recording liquid of Comparative Example 3 was prepared by adding the glycerin ester resin of rosin instead of the polyurea compound of Compound Example 4 in the recording liquid of Example 3. Comparative Example 4 The recording liquid of Comparative Example 4 was prepared by adding urea instead of the polyurea compound of Compound Example 6 in the recording liquid of Example 4.

The following evaluations were carried out using the recording liquids of the above Examples and Comparative Examples. (Example of use of recording liquid) Each of the prepared recording liquids was filled in a BC-01 cartridge (bubble jet type inkjet recording device: recording head used for BJ-10V; manufactured by Canon), and the following four performance evaluations were performed. went. 1) Print density 2) Rubbing property 3) Recovery property after printing pause, and 4) Frequency response was evaluated by a discharge tester. Evaluation Method: (Print Density) A commercially available electrophotographic copy paper was driven simultaneously with all nozzles to prepare a 1.3 cm × 2.0 cm solid print patch, which was dried for 24 hours, and then the optical density of the patch was measured. . (Scratchability) Print 12-point Chinese characters on a commercially available electrophotographic copy paper (NP-Dry Canon), and print 2 in the room.
After naturally drying for 4 hours, the characters were strongly rubbed with a commercially available water-based color marker (yellow, pH = 9), and the quality of scratchability was judged from the blurring of the characters and the stains on the markers.

Rank A: No bleeding of characters, and the marker is not dirty.

Rank B: Character bleeding has occurred.
The characters can be read.

Rank C: Bleeding around the character part is remarkable and the character is difficult to read. The marker itself becomes dirty. (Recoverability after printing pause) After stopping printing, the printer is kept in an environment of 50 ° C. for 3 hours, then returned to room temperature, printed again, and the start-up state is judged from the printing of characters.

Rank A: Clearly printable from the beginning Rank B: 5-10 characters are faint but normal soon.

Rank C: Fading is more noticeable on one page.
It will be normal from the second page. (Frequency response) Printing is performed at drive frequencies of 2 KHz, 4 KHz, and 6 KHz, and the response is judged from the solid pattern state.

Rank A: Responsiveness of 6 KHz.

Rank B: Responsiveness of 4 KHz.

Rank C: Responsiveness of 2 KHz.

The evaluation results are summarized in Table 1.

[0054]

[Table 1] [Results] As shown in Table 1, it can be seen that the recording liquid of the present invention is excellent in print density and scratching property, and at the same time, is good in recoverability after printing is stopped. It is also found that the ink material has a frequency response required for practical use.

[0055]

The aqueous pigment ink of the present invention provides storage stability, ejection reliability, print density in plain paper recording, and sharp quality. In particular, the rubbing property of a recorded character and an image is improved, a recording excellent in mechanical fastness under various conditions is provided, and it contributes to the spread of the inkjet recording system.

[Brief description of drawings]

FIG. 1 is a cross-sectional view illustrating a configuration example of a head that ejects ink by thermal energy.

FIG. 2 is a cross-sectional view illustrating a cross section taken along the line AB of FIG.

FIG. 3 is an external view illustrating a multi-head in which a large number of heads in FIG. 1 are arranged.

FIG. 4 is a perspective view illustrating an example of an apparatus for performing the inkjet recording method of the present invention.

FIG. 5 is a cross-sectional view illustrating an example of an ink cartridge.

FIG. 6 is a perspective view illustrating a recording apparatus in which a head and an ink cartridge are integrated.

[Explanation of symbols]

13 heads 14 groove 15 heating head 16 Protective film 17-1, 17-2 Aluminum electrode 18 Heating resistor layer 19 Heat storage layer 20 substrates 21 ink 22 Discharge orifice 23 Meniscus 24 recording droplets 25 Recorded material 26 multi groove 27 glass plate 28 heating head 40 ink bags 42 Stopper 44 ink absorber 45 ink cartridge 51 paper feeder 52 Paper feed roller 53 Paper ejection roller 61 blade 62 cap 63 ink absorber 64 Discharge recovery unit 65 recording head 66 carriage 67 Guide shaft 68 motor 69 belt 70 inkjet cartridge 71 Head 72 Air communication port

Front Page Continuation (72) Inventor Yuko Suga 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc. (56) Reference JP-A-53-77704 (JP, A) (58) Fields investigated ( Int.Cl. ⁷ , DB name) C09D 11/00-11/20 B41J 2/01-2/01 B41M 5/00

Claims (2)

(57) [Claims] 1. A least water, a water-soluble organic solvent, and the aqueous pigment ink comprising a face <br/> fee dispersion, in the ink, hexamethylene diisocyanate, Isoforonji
Isocyanate, xylylene diisocyanate, Tolyre
Diisocyanate, diphenylmethane diisocyanate
Bis ( isocyanatomethyl ) cyclohexane, disi
Chlohexyl methane diisocyanate, lysine diisocyanate
Anate and trimethylhexamethylene diisocyanate
G, these adducts, modified urethane, allophane
Modified products, biuret modified products and isocyanurate modified products
A polyisocyanate selected from the group consisting of
Ethanolamine, N - methylethanolamine, 2 - (2 -
Aminoethyl) ethanolamine, diethanolamine
N, N - ethyldiethanolamine, triethanolamine
Min, 2 - amino - 2 - methyl propanol, 2 - ethyl -
2 - amino - 1, 3 - propanediol, 2 - Aminoetoki
Ciethylene glycol, tris ( hydroxymethyl ) ami
Nomethane and tris ( hydroxymethyl ) aminoethane?
A reaction product of an amino alcohol selected from the group consisting of
There are, in general formula (1), (2) or (3) aqueous pigment ink characterized by containing an amino alcohol adduct polyisocyanate represented by. [Chemical 1] 2. An inkjet recording method using the water-based pigment ink according to claim 1.