JP2010076395A - Inkjet recording method, ink cartridge, recording unit, inkjet recording apparatus - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an inkjet recording method by which high image density and good printing grade can be given and which is excellent in scratch resistance in various recording media. <P>SOLUTION: In the inkjet recording method, a pigment ink composition and a reaction solution are stuck to the recording medium to perform printing. The reaction solution comprises a compound expressed by general formula (1) by 0.3 to 10% and a metal salt by 1 to 15%. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to an ink jet recording method, an ink cartridge, a recording unit, and an ink jet recording apparatus, and more specifically, an ink jet recording method, an ink cartridge, a recording unit, and an ink jet for performing printing by attaching a reaction liquid and a pigment ink composition to a recording medium. The present invention relates to a recording apparatus.

  Inkjet recording, which has the feature that high-resolution and high-quality images can be printed at high speed with an inexpensive device, is a printing method in which droplets of an ink composition are ejected and attached to a recording medium such as paper. Is the method. The ink used in the ink jet recording apparatus is mainly composed of a solvent, a color material, and an additive. For such inks, a uniform image with high resolution and high density without blurring on paper can be obtained, that the ink can be quickly dried on paper, and that the image has good fastness (abrasion resistance), There are required characteristics such as good long-term storage stability. In addition, office inkjet printers that have been launched in recent years are required not only to have high image quality but also to be capable of high-speed printing.

  In order to obtain a high-resolution, high-density, blur-free image, a technique using ink that suppresses penetration into the paper and spread on the paper is effective. However, on the other hand, when used with an inkjet printer that performs high-speed printing due to the slow drying speed, it is likely to cause a problem that offsets the paper with the undried ink when the paper overlaps on the tray after printing. . In addition, when performing double-sided printing, undried ink may contaminate the inside of the printer such as a transport roller.

  As a technique for achieving both high image quality and quick drying, so-called 2 using a liquid (hereinafter sometimes referred to as “reaction liquid”) that does not contain a colorant mainly for the purpose of further improving the image quality is used in addition to ink. A liquid printing method is mentioned.

  In general, a component that promotes aggregation of a coloring material in ink is added to the reaction liquid used in such a two-liquid printing system.

  For example, a two-liquid printing method using an agglutination reaction by contact of an ink containing an anionic substance and a reaction liquid containing a cationic polymer (see Patent Document 1), a cationic water-soluble resin comprising polyallylamine / polyvinylamine A method of agglomerating ink with a liquid composition (reaction liquid) containing a liquid (see Patent Document 2, Patent Document 3, etc.), and a colorant is agglomerated by applying a treatment liquid containing a polyvalent metal salt and / or polyallylamine. Examples thereof include methods (see Patent Document 4 and Patent Document 5).

  Such a two-liquid printing method generally provides an image with high resolution, high image density and little bleeding, as compared to a printing method using only conventional ink, and is also quick to dry after printing. Has characteristics.

In addition, a method for obtaining excellent image quality using a dicyandiamide resin has been proposed. For example, a method for obtaining a high-quality image using an ink composition comprising a colorant and an amidine compound (see Patent Document 6), and a high-quality image via an intermediate transfer member using a dicyandiamide resin reaction solution. And a method of obtaining (see Patent Document 7).
JP 2004-130799 A JP 2000-263922 A JP 2000-281948 A JP-A-9-207424 JP 2000-37942 A JP 2003-138184 A JP 2003-246135 A

  The present inventors have studied a two-liquid ink jet recording method using a reaction liquid containing a cationic polymer and a pigment ink.

  However, in the conventional method, there are problems such as high image density and scratch resistance, and excellent ink jet discharge characteristics in a head in which at least the area around the discharge port on the discharge port forming surface of the print head is formed as a water-repellent region. It was found that they cannot be solved at the same time.

  For example, when polyethyleneimine or polyallylamine is used, although high image density is obtained, scratch resistance cannot be obtained.

  Then, as a result of examining various cationic polymers, it was found that high image density and abrasion resistance can be expressed by using a dicyandiamide / diethylenetriamine polymer represented by the following general formula (1).

しかし、顔料インク中に上記ポリマーを添加すると、顔料分散体と凝集を起こしてしまい、インク化できなかった。

However, when the above polymer was added to the pigment ink, it aggregated with the pigment dispersion and could not be made into an ink.

  In addition, when a two-liquid ink jet recording method using a reaction liquid containing the above polymer is studied, at least the area around the discharge port forming surface of the print head is formed as a water-repellent region. When a printing durability test was carried out using the reaction solution, the reaction solution pooled around the discharge port and the flight direction of the reaction solution shifted.

  That is, the object of the present invention is to provide high image density and good print quality on various recording media, excellent scratch resistance, and at least the area around the discharge port on the discharge port forming surface of the print head. An object of the present invention is to provide an ink jet recording method using a reaction liquid having excellent ink jet discharge characteristics in a head formed as an aqueous region.

  An ink jet recording method according to an embodiment of the present invention that can achieve the above object is an ink jet recording method in which a pigment ink composition and a reaction liquid are attached to a recording medium and printing is performed. An ink jet recording method, wherein the reaction solution is a reaction solution containing 0.3% to 10% of the compound of the general formula (1) and 1% to 15% of a metal salt. is there.

  Further, in the ink jet recording method in which the effects of the present invention are more remarkably exhibited, the print head for printing the reaction liquid is characterized in that at least a region around the discharge port is formed as a water-repellent region on the discharge port forming surface. This is an ink jet recording method using a print head.

  Furthermore, an ink jet recording method in which the effect of the present invention is more remarkably exhibited is an ink jet recording method characterized in that the metal salt is a polyvalent metal salt. Furthermore, there is an ink jet recording method in which the pigment contained in the pigment ink is dispersed by an anionic substance or has an anionic group on the surface.

  An ink jet recording method according to an embodiment of the present invention is an ink jet recording method including at least a step of applying any of the reaction liquids described above to a recording medium prior to the ink described above.

  An ink cartridge according to another embodiment of the present invention is an ink cartridge characterized by containing any of the ink sets described above.

  Further, a recording unit according to another embodiment of the present invention includes an ink storage portion that stores any one of the ink sets described above, and an ink jet head that discharges ink that constitutes the ink set. The recording unit is provided with a recording unit.

  An ink jet recording apparatus according to another embodiment of the present invention includes an ink containing portion that contains any one of the ink sets described above, and an ink jet head that discharges the ink constituting the ink set. An ink jet recording apparatus comprising:

  According to the present invention, high image density and good print quality can be provided on various recording media, and excellent scratch resistance can be realized.

  In addition, it is possible to provide a reaction liquid having excellent inkjet discharge characteristics in a head in which at least the area around the discharge port on the discharge port forming surface of the print head is formed as a water-repellent region.

  Next, details of the present invention will be described in accordance with the description of the embodiments.

  In the above configuration, the reason why high image density and good print quality can be provided and excellent scratch resistance is not known in detail, but is presumed as follows.

  When the reaction liquid and the pigment ink composition come into contact, the dicyandiamide diethylenetriamine polymer represented by the general formula (1) in the reaction liquid is dissolved and / or dispersed in the pigment dispersion and other components in the pigment ink composition. Is considered to break down and agglomerate it. These aggregates are considered to suppress the penetration of the pigment, which is a coloring material, into the recording medium. As a result, it is considered that high image density and good print quality are realized. In addition, a color image has an advantage that non-uniform color mixing, that is, color bleeding, can be effectively prevented in a boundary area of different colors.

  Further, the dicyandiamide / diethylenetriamine polymer is stably dissolved in the reaction liquid, but when this reaction liquid is deposited on the recording medium together with the pigment ink composition, the dicyandiamide / diethylenetriamine polymer is included in the pigment ink composition. The polymer interacts electrostatically with the pigment dispersion, while the polymer also interacts with the recording medium and can be stably immobilized on the recording medium. As the polymer is fixed to the recording medium, the pigment is also fixed to the recording medium together with the polymer, and it is considered that excellent scratch resistance is expressed. Further, it is considered that an image with less bleeding and color bleeding can be realized as a result of the pigment being fixed to the recording medium satisfactorily.

  Further, the reason why the ink jet discharge characteristics are excellent in a head in which at least the area around the discharge port on the discharge port forming surface of the print head is formed as a water-repellent region is presumed as follows.

  It is considered that the dicyandiamide / diethylenetriamine polymer in the reaction solution is shrunk (a state in which it is weakly aggregated) by the metal salt contained in the reaction solution. This is also expected from the fact that the viscosity of the reaction solution is reduced by adding a metal salt. If such a state is taken, since the polymer is contracted compared to the state where no metal salt is added, when the reaction liquid contacts the discharge port forming surface, there are few contact opportunities, It is considered that the ability of the polymer to wet and spread on the discharge port forming surface can be suppressed.

  Next, the present invention will be described in more detail with reference to preferred embodiments.

(Reaction solution)
The reaction liquid used in the present invention basically comprises a dicyandiamide-diethylenetriamine polymer represented by the general formula (1) that generates an aggregate when it comes into contact with the ink composition, and a metal salt.

  According to a preferred embodiment of the present invention, the weight average molecular weight of the dicyandiamide diethylenetriamine polymer is preferably in the range of about 10,000 to 1,000,000. According to the preferable form of this invention, it is preferable that said polymer is the range of 0.3 to 10 weight% with respect to the reaction liquid whole quantity. When the content of the polymer is 0.3% by weight or less, the scratch resistance that is the effect of the present invention is not exhibited. On the other hand, if the content is 10% by weight or more, the viscosity of the reaction solution increases, and ink jet suitability cannot be maintained. Furthermore, in the present invention, a resin different from the above polymer may be added to the reaction liquid in consideration of the scratch resistance of the printed matter.

  The metal salt that can be used in the reaction solution is composed of monovalent metal ions, divalent or higher polyvalent metal ions, and anions that bind to these polyvalent metal ions, and is soluble in water. is there. Specific examples of the polyvalent metal ions include divalent metal ions such as Ca2 +, Cu2 +, Ni2 +, Mg2 +, Zn2 +, and Ba2 +, and trivalent metal ions such as Al3 +, Fe3 +, Cr3 +, and Y3 +. However, it is not limited to this. In addition, the content of the salt in the reaction solution is preferably 1 to 15% by mass in view of the effect of the present invention. Further, the reaction solution does not necessarily have to show no absorption in the visible range. Even if absorption is shown in the visible range, absorption in the visible range may be used as long as it does not substantially affect the image.

(Aqueous medium)
Examples of the aqueous medium used in the reaction liquid according to the present invention include water or a mixed solvent of water and a water-soluble organic solvent. As the water-soluble organic solvent, those having an effect of preventing the reaction solution from drying are particularly preferable. Specifically, for example, alkyl alcohols having 1 to 4 carbon atoms such as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol; dimethylformamide, Amides such as dimethylacetamide; Ketones or ketoalcohols such as acetone and diacetone alcohol; Ethers such as tetrahydrofuran and dioxane; Polyalkylene glycols such as polyethylene glycol and polypropylene glycol; Ethylene glycol, propylene glycol, butylene glycol, tri 2 to 6 alkylene groups such as ethylene glycol, 1,2,6-hexanetriol, thiodiglycol, hexylene glycol, diethylene glycol Alkylene glycols containing carbon atoms; lower alkyl ether acetates such as polyethylene glycol monomethyl ether acetate; glycerin; ethylene glycol monomethyl (or ethyl) ether, diethylene glycol methyl (or ethyl) ether, triethylene glycol monomethyl (or ethyl) ether, etc. Lower alkyl ethers of polyhydric alcohols; polyhydric alcohols such as trimethylolpropane and trimethylolethane; N-methyl-2-pyrrolidone, 2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone and the like. The above water-soluble organic solvents can be used alone or as a mixture. It is desirable to use deionized water as the water.

  Although content of the water-soluble organic solvent contained in the reaction liquid concerning this invention is not specifically limited, Preferably the range of 3-50 mass% is suitable with respect to the reaction liquid total mass. The content of water contained in the reaction solution is preferably in the range of 50 to 95% by mass with respect to the total mass of the reaction solution. In addition to the above components, surfactants, antifoaming agents, antiseptics, antifungal agents, and the like can be added to obtain a reaction solution having desired physical properties as required.

(Pigment ink)
The reaction solution described above is used for recording in combination with a pigment ink composition in which a pigment is dispersed or dissolved in an aqueous medium by an ionic group, or further by an anionic group, so that a high-quality image is formed. A favorable effect such as Hereinafter, these pigments will be described in detail.

(Pigment)
Examples of the pigment that can be used include carbon black and organic pigments.

(Carbon black)
Examples of the carbon black include carbon black pigments such as furnace black, lamp black, acetylene black, and channel black. For example, Raven (Raven (RAVEN is a registered trademark)) 7000, Rayvan 5750, Rayvan 5250, Rayvan 5000, Rayvan 3500. , Ray-Van 2000, Ray-Van 1500, Ray-Van 1250, Ray-Van 1200, Ray-Van 1190 ULTRA-II, Ray-Van 1170, Ray-Van 1255 (manufactured by Columbia), Black Pearls (BLACK PEARLS is a registered trademark) L, Legal (REGAL Is a registered trademark)) 400R, Legal 330R, Legal 660R, Mogulu (MOGU Are registered trademarks)), L, Monarch 700, Monak 800, Monak 880, Monak 900, Monak 1000, Monak 1100, Monak 1300, Monak 1400, Vulcan (Valcan (VULCAN is a registered trademark)) XC-72R (above Cabot) Color Black FW1, Color Black FW2, Color Black FW2V, Color Black FW18, Color Black FW200, Color Black S150, Color Black S160, Color Black S170, Printex (Printex / Printex is Registered trademark)) 35, Printex U, Printex V, Printex 140U, Printex 140V, Special Black k) 6, Special Black 5, manufactured by Special Black 4A, Special Black 4 (more than Degussa), No. 25, no. 33, no. 40, no. 47, no. 52, no. 900, no. 2300, MCF-88, MA600, MA7, MA8, MA100 (manufactured by Mitsubishi Chemical Co., Ltd.) can be used, but is not limited thereto, and conventionally known carbon black can be used. is there. Further, magnetic fine particles such as magnetite and ferrite, titanium black and the like may be used as the black pigment.

(Organic pigment)
Specific examples of organic pigments include insoluble azo pigments such as Toluidine Red, Toluidine Maroon, Hansa Yellow, Benzidine Yellow, and Pyrazolone Red, soluble azo pigments such as Ritol Red, Helio Bordeaux, Pigment Scarlet, and Permanent Red 2B, Alizarin, Indantron , Derivatives from vat dyes such as thioindigo maroon, phthalocyanine pigments such as phthalocyanine blue and phthalocyanine green, quinacridone pigments such as quinacridone red and quinacridone magenta, perylene pigments such as perylene red and perylene scarlet, isoindolinone yellow Isoindolinone pigments such as isoindolinone orange, imidazolone face such as benzimidazolone yellow, benzimidazolone orange, and benzimidazolone red Pyranthrone pigments such as pyranthrone red, pyranthrone orange, thioindigo pigments, condensed azo pigments, thioindigo pigments, flavanthrone yellow, acylamide yellow, quinophthalone yellow, nickel azo yellow, copper azomethine yellow, perinone orange, Other pigments such as anthrone orange, dianthraquinonyl red, dioxazine violet can be exemplified.

  Further, when the organic pigment is represented by a color index (CI) number, C.I. I. Pigment Yellow 12, 13, 14, 17, 20, 24, 74, 83, 86, 93, 109, 110, 117, 120, 125, 128, 137, 138, 147, 148, 151, 153, 154, 166, 168, C.I. I. Pigment orange 16, 36, 43, 51, 55, 59, 61, C.I. I. Pigment Red 9, 48, 49, 52, 53, 57, 97, 122, 123, 149, 168, 175, 176, 177, 180, 192, 215, 216, 217, 220, 223, 224, 226, 227, 228, 238, 240, C.I. I. Pigment violet 19, 23, 29, 30, 37, 40, 50, C.I. I. Pigment blue 15, 15: 3, 15: 1, 15: 4, 15: 6, 22, 60, 64, C.I. I. Pigment green 7, 36, C.I. I. Examples thereof include CI Pigment Brown 23, 25, 26, and the like. Of course, conventionally known organic pigments can be used in addition to the above.

(Dispersant)
When using the above-described carbon black or organic pigment, it is preferable to use a dispersant in combination. As the dispersant, those capable of stably dispersing the above pigment in an aqueous medium by the action of an anionic group are suitably used. Specific examples of the dispersant include, for example, a styrene-acrylic acid copolymer, a styrene-acrylic acid-alkyl acrylate copolymer, a styrene-maleic acid copolymer, and a styrene-maleic acid-alkyl acrylate copolymer. Styrene-methacrylic acid copolymer, styrene-methacrylic acid-acrylic acid alkyl ester copolymer, styrene-maleic acid half ester copolymer, vinyl naphthalene-acrylic acid copolymer, vinyl naphthalene-maleic acid copolymer, A styrene-maleic anhydride-maleic acid half ester copolymer or a salt thereof is included. These dispersants preferably have a weight average molecular weight in the range of 1,000 to 30,000, and particularly preferably in the range of 3,000 to 15,000.

(Self-dispersing pigment)
As the coloring material, a pigment that can be dispersed in an aqueous medium without a dispersant by bonding an ionic group (anionic group) to the pigment surface, a so-called self-dispersing pigment can also be used. For example, self-dispersing carbon black can be mentioned. Examples of the self-dispersing carbon black include those in which an anionic group is bonded to the surface of the carbon black.

(Anionic carbon black)
As the anionic carbon black, for example, at least one anionic group selected from —COO (M2), —SO3 (M2), —PO3H (M2), and —PO3 (M2) 2 is bonded to the surface of the carbon black. Can be mentioned. In the above formula, M2 represents a hydrogen atom, an alkali metal, ammonium or organic ammonium.

  Among these, carbon black obtained by bonding —COO (M2) or —SO3 (M2) to the surface of carbon black to be anionic is particularly suitable for use in the present invention because of its excellent dispersibility in ink. To get. By the way, among those expressed as “M2” in the hydrophilic group, specific examples of the alkali metal include, for example, Li, Na, K, Rb and Cs, and specific examples of the organic ammonium include, for example, Methyl ammonium, dimethyl ammonium, trimethyl ammonium, ethyl ammonium, diethyl ammonium, triethyl ammonium, methanol ammonium, dimethanol ammonium, trimethanol ammonium and the like.

  The ink of the present invention containing self-dispersing carbon black in which M2 is ammonium or organic ammonium can further improve the water resistance of a recorded image, and can be particularly preferably used in this respect. This is considered to be due to the fact that when the ink is applied onto the recording medium, ammonium is decomposed and ammonia is evaporated. Here, the self-dispersing carbon black in which M2 is ammonium includes, for example, a method of substituting M2 with ammonium using an ion exchange method for self-dispersing carbon black in which M2 is an alkali metal, Then, ammonium hydroxide is added to make M2 ammonium.

  An example of a method for producing an anionically charged self-dispersing carbon black is a method of oxidizing carbon black with sodium hypochlorite. By this method, a -COONa group is chemically bonded to the carbon black surface. Can be made.

  By the way, various hydrophilic groups as described above may be directly bonded to the surface of carbon black. Alternatively, another atomic group may be interposed between the carbon black surface and the hydrophilic group, and the hydrophilic group may be indirectly bonded to the carbon black surface. Here, specific examples of the other atomic group include, for example, a linear or branched alkylene group having 1 to 12 carbon atoms, a substituted or unsubstituted phenylene group, and a substituted or unsubstituted naphthylene group. . Here, as a substituent of a phenylene group and a naphthylene group, a C1-C6 linear or branched alkyl group is mentioned, for example. Specific examples of combinations of other atomic groups and hydrophilic groups include, for example, -C2H4COO (M2), -Ph-SO3 (M2), -Ph-COO (M2), etc. (where Ph is a phenyl group) For example).

  By the way, in the present invention, two or more kinds of self-dispersing carbon blacks described above may be used as the ink coloring material appropriately selected. Further, the addition amount of the self-dispersing carbon black in the ink is preferably in the range of 0.1 to 15% by mass, particularly 1 to 10% by mass with respect to the total mass of the ink. By setting this range, the self-dispersing carbon black can maintain a sufficiently dispersed state in the ink. Further, for the purpose of adjusting the color tone of the ink, a dye may be added as a coloring material in addition to the self-dispersing carbon black.

(Colored fine particles / microencapsulated pigment)
In addition to the color materials described above, pigments microencapsulated with a polymer or the like, or colored fine particles in which resin particles are coated with a color material can be used. The microcapsule inherently has dispersibility in an aqueous medium, but a dispersant as described above may be further coexisted in the ink in order to improve dispersion stability. In addition, when the colored fine particles are used as a coloring material, it is preferable to use the anionic dispersant described above.

(Aqueous medium)
The aqueous medium in which the pigment as described above is dispersed is not particularly limited, and the same aqueous medium as described above can be used as the aqueous medium used in the reaction liquid. Further, when the color ink is attached to a recording medium by an ink jet method (for example, bubble jet (registered trademark) method), the ink has a desired viscosity and surface tension so as to have excellent ink jet discharge characteristics as described above. It is preferable to prepare so that it has.

  Examples of the aqueous medium used in the pigment ink composition according to the present invention include water or a mixed solvent of water and a water-soluble organic solvent. As the water-soluble organic solvent, those having an effect of preventing the reaction solution from drying are particularly preferable. Specifically, for example, alkyl alcohols having 1 to 4 carbon atoms such as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol; dimethylformamide, Amides such as dimethylacetamide; Ketones or ketoalcohols such as acetone and diacetone alcohol; Ethers such as tetrahydrofuran and dioxane; Polyalkylene glycols such as polyethylene glycol and polypropylene glycol; Ethylene glycol, propylene glycol, butylene glycol, tri 2 to 6 alkylene groups such as ethylene glycol, 1,2,6-hexanetriol, thiodiglycol, hexylene glycol, diethylene glycol Alkylene glycols containing carbon atoms; lower alkyl ether acetates such as polyethylene glycol monomethyl ether acetate; glycerin; ethylene glycol monomethyl (or ethyl) ether, diethylene glycol methyl (or ethyl) ether, triethylene glycol monomethyl (or ethyl) ether, etc. Lower alkyl ethers of polyhydric alcohols; polyhydric alcohols such as trimethylolpropane and trimethylolethane; N-methyl-2-pyrrolidone, 2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone and the like. The above water-soluble organic solvents can be used alone or as a mixture. Moreover, it is desirable to use deionized water as water.

  The content of the water-soluble organic solvent contained in the ink composition according to the present invention is not particularly limited, but is preferably in the range of 3 to 50% by mass with respect to the total mass of the ink composition. Further, the content of water contained in the ink composition is preferably in the range of 50 to 95% by mass with respect to the total mass of the reaction solution. In addition to the above components, a moisturizing agent may be added as necessary, and a surfactant, an antifoaming agent, an antiseptic, an antifungal agent, etc. may be added to obtain an ink having a desired physical property value. It doesn't matter.

(Ink set)
The color tone of the ink that constitutes the ink set in combination with the reaction liquid is not particularly limited. For example, the ink may have at least one color tone selected from yellow, magenta, cyan, red, green, blue, and black. Specifically, it can be used by appropriately selecting from the above-described color materials so as to obtain ink having a desired color tone.

  Further, the ink to be combined with the reaction liquid is not limited to one type, and it is more preferable to combine two or more inks having different color tones to make an ink set suitable for forming a multicolor image. In this case, at least one of the two or more inks may react with the reaction liquid.

  As long as the color material is dispersed in the aqueous medium by the action of ionic groups, the other ink may be an ink containing a dye as a color material. The ink may be dispersed by the action of ionic groups. According to such an ink set, it is possible to suppress bleeding when inks of different color tones are applied adjacently on a recording medium, which is a problem when a multicolor image is formed by an ink jet apparatus.

  More specifically, bleeding that is a problem in an inkjet multicolor image is at least one selected from black ink and other color inks (for example, yellow ink, magenta ink, cyan ink, red ink, green ink, and blue ink). In particular, in the present invention, black ink is used as an ink in which a color material is dispersed in an aqueous medium by the action of an ionic group so as to interact with the reaction liquid. Are preferably combined. Other color inks may be inks in which a dye is dissolved in an aqueous medium, or of course, inks in which a color material is dispersed in an aqueous medium by the action of ionic groups, as in black inks.

(Recording device)
The present invention is used for an ink jet discharge type head, and is also effective as an ink storage container in which the ink is stored or as a filling ink. In particular, the present invention provides an excellent effect in a bubble jet (registered trademark) type recording head and recording apparatus among ink jet recording methods.

  As its typical configuration and principle, for example, those performed using the basic principle disclosed in US Pat. Nos. 4,723,129 and 4,740,796 are preferable. This method can be applied to both the so-called on-demand type and the continuous type. In particular, in the case of the on-demand type, the electric circuit arranged corresponding to the sheet or liquid path holding the ink is used. By applying at least one drive signal corresponding to the recording information and giving a rapid temperature rise exceeding nucleate boiling to the heat conversion body, heat energy is generated in the electrothermal conversion body, and the heat acting surface of the recording head This is effective because the film can be boiled, and as a result, the drive signals can be made to correspond one-to-one and bubbles in the ink can be formed. By the growth and contraction of the bubbles, ink is ejected through the ejection opening to form at least one droplet. It is more preferable that the drive signal has a pulse shape, because the bubble growth and contraction is performed immediately and appropriately, and thus ink discharge with particularly excellent responsiveness can be achieved. As this pulse-shaped drive signal, those described in US Pat. Nos. 4,463,359 and 4,345,262 are suitable. Further excellent recording can be performed by employing the conditions described in US Pat. No. 4,313,124 of the invention relating to the temperature rise rate of the heat acting surface.

  As the configuration of the recording head, in addition to the combination configuration (linear liquid channel or right-angle liquid channel) of the discharge port, the liquid channel, and the electrothermal transducer as disclosed in each of the above-mentioned specifications, the heat acting part The present invention is also effective for configurations using US Pat. No. 4,558,333 and US Pat. No. 4,459,600, which disclose a configuration in which is disposed in a bending region. In addition, the present invention is also effective for a configuration (Japanese Patent Laid-Open No. 59-123670, etc.) in which a discharge hole is used as a discharge portion of the electrothermal converter when common to a plurality of electrothermal converters. . Furthermore, as a full-line type recording head having a length corresponding to the width of the maximum recording medium that can be recorded by the recording apparatus, the length is set by combining a plurality of recording heads as disclosed in the above specification. Either a satisfying configuration or a single integrated recording head configuration may be used, but the present invention can exhibit the above-described effects more effectively.

  In addition, it is mounted on the main body of the device so that it can be electrically connected to the main body of the device and supplied with ink from the main body of the device. The present invention is also effective when a cartridge type recording head is used.

  In the present invention, it is preferable to add recovery means for the recording head, preliminary auxiliary means, etc. provided as the configuration of the recording apparatus to be applied, because the effects of the present invention can be further stabilized. . Specific examples thereof include a capping unit for the recording head, a cleaning unit, a pressure or suction unit, an electrothermal converter, a heating element different from this, or a preheating unit using a combination thereof, This is a preliminary ejection mode in which ejection different from recording is performed.

  Hereinafter, although it demonstrates more concretely using an Example, this invention is not limited by the following Example, unless the summary is exceeded.

  In the following description, “parts” or “%” are based on mass unless otherwise specified.

(Pigment dispersion Bk1)
To a solution of 5 g of concentrated hydrochloric acid dissolved in 5.3 g of distilled water, 1.58 g of anthranilic acid was added at 5 ° C. By stirring using an ice bath, a solution in which 1.78 g of sodium nitrite is dissolved in 8.7 g of distilled water at 5 ° C. is added to the above solution so that the temperature is always kept at 10 ° C. or lower. It was. After stirring for 15 minutes, 7 g of carbon black having a specific surface area of 220 m2 / g and a DBP oil absorption of 105 mL / 100 g was added to the solution while stirring the solution. Thereafter, the mixture was further stirred for 15 minutes. The obtained slurry was Toyo Filter Paper No. 2 (manufactured by Advantech), the pigment particles were sufficiently washed with water, dried in an oven at 110 ° C., and further distilled water was added to the pigment to prepare a pigment dispersion having a pigment concentration of 10% by mass.

  The hydrophilic group density of the self-dispersing carbon black produced as described above was measured as follows and found to be 2.6 μmol / m 2. As a measuring method, an ion meter (manufactured by DKK) was used to measure the sodium ion concentration, and the hydrophilic group density was converted from the value. Then, by substituting ammonium ions with ammonium ions using an ion exchange method, the self-dispersing carbon black in which a hydrophilic group -Ph-COONH4 group was introduced was dispersed on the surface of the carbon black. A pigment dispersion Bk1 was obtained. The pigment dispersion Bk1 obtained had a solid content of 10%.

(Preparation of ink)
The components shown below were mixed and sufficiently stirred to dissolve, and then pressure filtered through a Fuji film microfilter (Fuji Film (registered trademark)) having a pore size of 1.0 μm to prepare ink used in this example. did.

（反応液の調製）
以下に示す成分を混合し、十分に攪拌して溶解した後、ポアサイズ１．０ｕｍのミクロフィルター（富士フィルム製）にて加圧ろ過し、本実施例に用いる反応液を調整した。

(Preparation of reaction solution)
The components shown below were mixed and sufficiently stirred to dissolve, and then pressure filtered with a micro filter (manufactured by Fuji Film) having a pore size of 1.0 μm to prepare a reaction solution used in this example.

１（商品名：アセチレノールＥ１００（アセチレノールは登録商標）；川研ファインケミカル（株）社製）
２（商品名：ユニセンスＫＨＰ−１０Ｌ；センカ（株）社製）
３（商品名：ＰＡＡ−ＨＣｌ−３Ｌ；日東紡社製）
４（商品名：ポリエチレンイミン７００００；純正化学（株）社製）
５Ａｌｄｒｉｃｈ社製
６Ａｌｄｒｉｃｈ社製
上記に示したように調製したインク１、２及び反応液１〜６，Ａ〜Ｊを用いて、実施例１、２及び参考例１、比較例１〜とした。（下記表）

1 (Product name: Acetylenol E100 (Acetylenol is a registered trademark); Kawaken Fine Chemicals Co., Ltd.)
2 (Product name: UNISENSE KHP-10L; manufactured by Senka Co., Ltd.)
3 (trade name: PAA-HCl-3L; manufactured by Nittobo)
4 (trade name: Polyethyleneimine 70000; manufactured by Junsei Chemical Co., Ltd.)
5 Aldrich Co. 6 Aldrich Co. Using Examples 1 and 2 and Reference Examples 1 and Comparative Examples 1 and 2 using the inks 1 and 2 and the reaction liquids 1 to 6 and A to J prepared as described above. (Table below)

＜評価＞
表５及び表６で示した実施例及び参考例、比較例のインクセットを用いてそれぞれの評価を行った。評価は、記録信号に応じて熱エネルギーをインクに付与することによりインクを吐出させるオンデマンド型マルチ記録ヘッドを有するインクジェット記録装置ＢＪＦ−９００（キヤノン製）を用いて、被記録媒体上に画像形成することによって行った。

<Evaluation>
Each evaluation was performed using the ink sets of Examples, Reference Examples, and Comparative Examples shown in Table 5 and Table 6. Evaluation is performed by forming an image on a recording medium using an inkjet recording apparatus BJF-900 (manufactured by Canon) having an on-demand multi-recording head that discharges ink by applying thermal energy to the ink in accordance with a recording signal. Went by.

  The reaction solution was applied so that the applied amount around 600 * 600 dpi was 5 ng.

The recording medium used at this time was an office planner (manufactured by Canon Marketing Japan Inc.). (Office planner is a registered trademark)
<Image density>
The image density (OD value) of a solid image one day after recording was measured using a reflection densitometer (trade name: Macbeth RD-918; manufactured by Macbeth). The evaluation criteria are as follows.

O; O. D. 1.4 or more Δ; D. 1.35 or more and 1.4 or less ×; D. 1.35 or less <Abrasion resistance>
A scratch resistance test was performed using a weight with a load of 40 g / cm 2 and evaluated according to the following criteria.

  ○: Almost no tail is seen from a distance of 1 m.

  Δ: If you look closely, you can see the tail.

  X: The tail is clearly seen.

<Reaction repellency>
BJF-900 recording head cut out from the discharge port chip was immersed in each reaction solution for 2 weeks, and one drop of pure water with a dropper was added to the surface soaked, and the contact angle was determined. Comparison was made with the contact angle of an unimmersed wafer.

  The evaluation criteria are as follows.

  (Double-circle); It is an equivalent contact angle compared with the wafer which is not immersed.

  ○: The contact angle is almost the same as that of a wafer not immersed.

  (Triangle | delta); A contact angle is low compared with the wafer which is not immersed.

  X: The contact angle is clearly low.

<Adhesive recovery>
The recording head for BJF-900 equipped with an ink tank filled with the reaction liquid was removed from the main body and left in a constant temperature bath at 35 ° C. and 10% relative humidity for 1 week. Specifically, after confirming that all the nozzles were able to print on the main body, the recording head was removed from the printer main body while the ink tank was mounted, and left under the above conditions. The recording head was again attached to the printer, and printing was performed on a dedicated OHP sheet (manufactured by Seiko Epson Corporation).

  ○: All nozzles were printable.

  Δ: There were about 10 nozzles that could not be printed.

  X: There were 10 or more nozzles that could not be printed.

＊７反応液Ｄが吐出しなかった。

* 7 Reaction liquid D was not discharged.

Claims (8)

An ink jet recording method for performing printing by attaching a pigment ink composition and a reaction liquid to a recording medium, wherein the reaction liquid contains 0.3% or more and 10% or less of a compound of the following general formula (1) An ink jet recording method comprising: a reaction solution containing 1% to 15% of a metal salt.

  2. The print head according to claim 1, wherein the print head for printing the reaction liquid uses a print head in which at least a region around a discharge port on a discharge port forming surface is formed as a water-repellent region. Inkjet recording method.   The inkjet recording method according to claim 1, wherein the metal salt is a polyvalent metal salt.   The inkjet recording method according to any one of claims 1 to 3, wherein the pigment contained in the pigment ink is dispersed by an anionic substance or has an anionic group on the surface.   The ink jet recording method according to claim 1, further comprising at least a step of applying the reaction liquid to a recording medium prior to the ink.   An ink cartridge containing the ink set according to any one of claims 1 to 4.   An ink storage unit that stores the ink set according to any one of claims 1 to 4 and an ink jet head for discharging the ink that constitutes the ink set. To record unit.   An ink storage unit that stores the ink set according to any one of claims 1 to 4, and an ink jet head for discharging the ink that constitutes the ink set. An inkjet recording apparatus.