JP2005298608A - Ink for inkjet recording - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an excellent color balance after long-term storage of a printed image by combining an optimum combination of dyes in an ink using two or more dyes and aligning the weather resistance (ΔE) of each dye, and brightness, To provide ink with excellent saturation.
An ink for inkjet recording, comprising at least a triphenylmethane cyan color material, a copper phthalocyanine cyan color material, and a yellow color material.
[Selection figure] None

Description

  The present invention relates to an inkjet recording ink.

The ink used in an ink jet recording apparatus such as an ink jet printer is prepared by selecting an optimum material from among many materials. For example, even if attention is focused only on dyes, there are direct dyes, acid dyes, etc., each having different characteristics. For example, printing ink with a direct dye has a relatively excellent weather resistance, and printing with ink with an acid dye gives a printed matter with high brightness and saturation. There is a feature that is.
In such a background, for example, Patent Document 1 discloses an azopyridone type dye having a specific structure as a coloring material that is effective for widening the color reproduction range of the yellow region and has high color development and excellent weather resistance. Ink is used.
JP-T-2002-504613

  However, while the applications of the ink jet recording apparatus are being expanded, the ink is required to have high brightness, high saturation, and excellent weather resistance. There is a problem that a dye satisfying all of the above has not yet been found.

For example, a direct dye is relatively excellent in weather resistance, but has low brightness and saturation. In contrast, acid dyes provide high brightness and saturation, but poor weather resistance. Also, in ink using two or more dyes, if there is a large difference in the weather resistance of each dye, the color balance in the long-term storage of the image after printing tends to be lost, and the image quality tends to deteriorate more greatly. . Long-term storage means discoloration due to sunlight or various illumination light (light resistance) and discoloration due to oxidizing gas (ozone, NO _x , SO _x, etc.) contained in trace amounts in the atmosphere (gas resistance) ) Image robustness. For example, when the green ink is stored for a long time after printing, if the cyan dye or the cyan part of the green dye alone is large, an image with a strong yellowishness is produced as compared with the image immediately after printing.

  Accordingly, an object of the present invention is to provide an ink jet recording ink that uses two or more dyes, by combining the dyes optimally, and by aligning the weather resistance (ΔE) of the respective dyes, An object of the present invention is to provide an ink for ink jet recording excellent in color balance, lightness and chroma.

  As a result of intensive studies in view of the above object, the present inventors have achieved excellent brightness and saturation, and color balance by using an ink containing at least a triphenylmethane-based cyan color material, a copper phthalocyanine-based cyan color material, and a yellow color material. The present invention has been completed by finding that deterioration of image quality after long-term storage can be prevented without breaking the image.

  That is, the present invention provides an ink for ink jet recording (hereinafter simply referred to as “ink”) comprising at least a triphenylmethane cyan color material, a copper phthalocyanine cyan color material, and a yellow color material.

  In the ink of the present invention, when the total mass of the triphenylmethane cyan color material and the copper phthalocyanine cyan color material is A and the mass of the yellow color material is B, A / B is 1/20. The above A / B is preferably 1/10 or more and 1/4 or less, and the A / B is 1/10 or more and 5 or less. More preferably, the A / B is most preferably 1/5 or more and 3 or less.

  The triphenylmethane cyan colorant in the ink of the present invention is C.I. I. Acid blue 9 is preferred.

  In addition, the ink of the present invention has a hue angle difference Δh in the CIELAB color space display system in a light fastness test in a light resistance test under a condition that causes a fading corresponding to sunlight fading through a pseudo indoor window of three years or more. The difference in hue angle Δh in the CIELAB color space display system after exposure for 2 hours under the conditions of an ink tank temperature of 40 ° C., a relative humidity of 55%, and a 3 ppm ozone atmosphere. It is preferably within 6 °.

（式中、Ｒ₁及びＲ₂は各々独立に置換もしくは未置換のアルキル基、アリール基、アリールアルキル基、又は水素の何れかを表す。Ｒ₃及びＲ₅はそれぞれ独立に、カルボキシル基、スルホン酸基、リン酸基、又はそれらの塩の基、又はこれらの基で置換されたアルキル基を表す。Ｒ₄及びＲ₆はそれぞれ独立に、Ｒ₃及びＲ₅に対して定義した以外の基を表す。ｐ及びｒは、それぞれ独立に１乃至５の整数を表し、ｑ及びｓは、それぞれ独立に０乃至４の整数を表す。又、ｐ＋ｑが５以下の値を有し、ｒ＋ｓが５以下の値を有す。） In addition, the ink of the present invention preferably includes a color material represented by the following chemical formula as a yellow color material by the ink.

(Wherein R ₁ and R ₂ each independently represents a substituted or unsubstituted alkyl group, aryl group, arylalkyl group, or hydrogen. R ₃ and R ₅ each independently represent a carboxyl group, a sulfone group, or a sulfone group. An acid group, a phosphoric acid group, or a salt group thereof, or an alkyl group substituted with these groups, R ₄ and R ₆ are each independently a group other than those defined for R ₃ and R ₅ . P and r each independently represent an integer of 1 to 5, q and s each independently represent an integer of 0 to 4. Further, p + q has a value of 5 or less, and r + s is 5 It has the following values.)

  According to the present invention, it is possible to provide an ink excellent in lightness and saturation and excellent in color balance by long-term storage of a printed image.

Hereinafter, the present invention will be described in more detail with reference to preferred embodiments.
(ink)
The color material of the ink used in the present invention may be a commonly used color material such as a dye or a pigment that is generally used, or a newly synthesized color material, within the scope of the present invention. It can be appropriately selected and used. In addition, the three color materials are essential for the color material to be contained in the ink, but another color material can also be contained.
In particular, in the present invention, it is preferable to use an acid dye or a direct dye as a color material for yellow and cyan. Acid dyes and direct dyes can obtain good color on various recording media such as plain paper, glossy paper, coated paper, and special media with a coated layer or ink receiving layer on the surface. Therefore, it can be suitably used in the present invention.

  Specific examples of acid dyes and direct dyes are shown below as examples of yellow and cyan coloring materials that can be used in the present invention, but the present invention is not limited thereto.

(Yellow color material)
C. I. Direct yellow: 8, 11, 12, 27, 28, 33, 39, 44, 50, 58, 85, 86, 87, 88, 89, 98, 100, 110, 132, 173; I. Acid Yellow: 1, 3, 7, 11, 17, 23, 25, 29, 36, 38, 40, 42, 44, 76, 98, 99.

又、本発明には国際公開番号：ＷＯ ０２／０８１５８０ Ａ１に挙げられている例示化合物２も好適に用いることができる。

The following exemplary compound 1

In the present invention, the exemplified compound 2 listed in International Publication No. WO 02/081580 A1 can also be suitably used.

  In addition, two or more color materials among the color materials listed above may be mixed and used. Furthermore, as a criterion for selecting a yellow color material, considering the light resistance and ozone resistance of the cyan color material of the other party, sunlight faded through a pseudo indoor window of 3 years or more of an image obtained by yellow ink obtained from the yellow color material. The value of the color difference ΔE in the CIELAB color space display system in the light fastness test under conditions that produce a discoloration equivalent to 5 is less than or equal to 5 and less than 20, and the in-tank temperature of the image by the yellow ink obtained from the yellow color material is 40 ° C. More preferably, the value of the color difference ΔE in the CIELAB color space display system after exposure for 2 hours under the condition of an ozone atmosphere of 55% relative humidity and 3 ppm is 5 or more and less than 40.

上記一般式Ｉ中、ＣｕＰｃは、銅フタロシアニン残基を表している。又、Ｑはアルカリ金属（例えば、Ｌｉ、Ｎａ、Ｋ、Ｒｂ、Ｃｓ、Ｆｒ等）又はアンモニウムである。又、ｘは１、２、３又は４であり、ｙは１、２又は３である。そしてｘ＋ｙ＝２のものを含まないか、或いは実質的に含まない。即ち、本発明に係るインクが含んでいるフタロシアニン系色材として、具体的には下記の構造を有する色材の何れか、若しくはそれらの混合物を含み、ｘ＋ｙ＝２の構造のものは含んでいないか、或いは実質的に含んでいない。 (Copper phthalocyanine cyan color material)

In the above general formula I, CuPc represents a copper phthalocyanine residue. Q is an alkali metal (for example, Li, Na, K, Rb, Cs, Fr, etc.) or ammonium. X is 1, 2, 3 or 4, and y is 1, 2 or 3. And x + y = 2 is not included or substantially not included. That is, the phthalocyanine color material contained in the ink according to the present invention specifically includes any of the color materials having the following structures, or a mixture thereof, and does not include those having the structure of x + y = 2. Or substantially free.

(Triphenylmethane cyan color material)
C. I. Acid Blue: 1, 3, 5, 7, 9, 11, 13, 15, 17, 22, 24, 26, 34, 48, 75, 83, 84, 86, 88, 90, 91, 93, 99, 100 103, 104, 108, 109, 110, 119, 147, 269.

  Among the dyes described above, not only good color reproducibility is obtained, but also the reliability of the ink jet recording apparatus, such as clogging of the recording head, solubility in the ink liquid medium, and ink storage stability. In particular, AY (CI Acid Yellow) 17, AY23, DY (CI Direct Yellow) 86, DY132, DY173, Exemplary Compounds 1, 2, Further, ABL (CI Acid Blue) 9, DBL (CI Direct Blue) 199, DBL 307, and Exemplified Compounds 3 to 9 can be suitably used as cyan color materials.

  Further, when considered as an ink set with other inks, considering the color gamut expansion effect, particularly the color gamut expansion effect for the sRGB color space, in order to obtain a more preferable hue, the triphenylmethane cyan A / B is 1/20 or more and 1/2 or less, more preferably A / B is 1 when the total mass of the material and the copper phthalocyanine cyan color material is A and the mass of the yellow color material is B. More preferably, it is / 10 or more and ¼ or less. Moreover, in order to make the difference Δh in hue angle within 6 ° in the light resistance and ozone resistance tests while giving high saturation and lightness, A / B is 1/10 or more, 5 or less, Preferably, A / B is 1/5 or more and 3 or less.

  The total content of the three color materials contained in the ink is preferably 0.1 to 15% by mass with respect to the total mass of the ink. Further, the ratio of use of the triphenylmethane cyan color material (color material a) and the copper phthalocyanine cyan color material (color material b) is color material a / color material b = 1/2 to 1/1. Is preferred.

  The above-described color material is used in an image forming method and an image forming apparatus suitable for the present invention, such as powder, aqueous solution, etc., and a method generally used in these various image forming methods and image forming apparatuses. Can be used after processing. As an example, the ink of the present invention used in an ink jet recording apparatus will be described. The ink of the present invention is generally used by dissolving or dispersing the colorant in an aqueous medium mainly composed of water.

  As the aqueous medium, water alone or one containing water and a water-soluble organic solvent can be used. The water-soluble organic solvent is not particularly limited as long as it shows water solubility, and alcohol, polyhydric alcohol, polyglycol, glycol ether, nitrogen-containing polar solvent, sulfur-containing polar solvent, ureas, saccharides, etc. Any solvent that is used as a solvent for inkjet ink can be used without any problem. These solvents are used for maintaining the moisture retention of the ink, improving the solubility and dispersibility of the coloring material, and penetrating the ink into the recording paper. These solvents can be used alone or in combination.

  In general, the content of the water-soluble organic solvent is preferably in the range of 1 to 50% by mass, more preferably in the range of 3 to 40% by mass with respect to the entire ink. The water content in the ink is preferably in the range of 30 to 95% by mass in order to maintain good dye solubility and ink ejection stability.

  Furthermore, in addition to the above components, the ink of the present invention contains a surfactant, a pH adjuster, a rust inhibitor, a preservative, a fungicide, an antioxidant, a reduction inhibitor, an evaporation accelerator, a chelating agent as necessary. Various additives such as a water-soluble polymer may be contained.

  For example, surfactants include anionic surfactants such as fatty acid salts, higher alcohol sulfates, liquid fatty oil sulfates, alkylallyl sulfonates, polyoxyethylene alkyl ethers, polyoxyethylene alkyl esters There are nonionic surfactants such as polyoxyethylene sorbitan alkyl esters, acetylene alcohol, and acetylene glycol, and one or more of these can be appropriately selected and used. Among the above-mentioned, acetylene alcohols and acetylene glycols can be preferably used in order to exhibit an effect excellent in permeability to plain paper. The amount used varies depending on the amount of dispersant added, but is preferably 0.01 to 5% by mass relative to the total amount of ink. At this time, the surface tension of the ink at 25 ° C. is preferably 10 mN / m (dyn / cm) or more, more preferably 20 mN / m or more, and the activator so that the surface tension is 60 mN / m or less. It is preferable to determine the amount to be added. This is because, in the ink jet recording system used in the present invention, it is possible to effectively suppress the occurrence of printing misalignment (deviation of the landing point of ink droplets) due to wetting of the nozzle tip. The ink is preferably adjusted to have a desired viscosity and pH in order to obtain good ejection characteristics in the ink jet recording apparatus.

(Recording medium)
The recording medium that can be used in the present invention is generally used as a special medium having a coating layer or an ink receiving layer on its surface, such as plain paper, glossy paper, coated paper, or glossy film. Recording media that are present can be used. Among these, a special medium having a hydrophilic porous particle layer, a porous polymer layer, etc. on a substrate is an example of a recording medium that can provide an image with higher vividness, contrast, and transparency. it can.

  An example of a special medium as a recording medium used in the present invention will be described in more detail. A coloring material such as a dye or a pigment is adsorbed on fine particles forming a hydrophilic porous structure in the ink receiving layer, and at least this It is a recording medium on which an image is formed by the adsorbed color material, and is particularly suitable when using an ink jet method. Such a recording medium is preferably a so-called absorption type in which ink is absorbed by a gap formed in an ink receiving layer on a support.

  The absorption type ink receiving layer is constituted as a hydrophilic porous layer mainly composed of fine particles and containing a binder and other additives as required. Examples of fine particles include inorganic pigments such as silica, clay, talc, calcium carbonate, kaolin, alumina or alumina hydrate, diatomaceous earth, titanium oxide, hydrotalcite, zinc oxide, urea formalin resin, ethylene resin And organic pigments such as styrene resins, and one or more of these are used.

  Examples of suitable binders include water-soluble polymers and latex. For example, polyvinyl alcohol or a modified product thereof, starch or a modified product thereof, gelatin or a modified product thereof, gum arabic, carboxymethylcellulose, hydroxyethylcellulose, hydroxypropylmethylcellulose and other cellulose derivatives, SBR latex, NBR latex, methyl methacrylate-butadiene copolymer Polymer latex, functional group-modified polymer latex, vinyl copolymer latex such as ethylene vinyl acetate copolymer, polyvinyl pyrrolidone, maleic anhydride or copolymer thereof, acrylate copolymer, etc. Accordingly, two or more kinds can be used in combination. In addition, additives can also be used. For example, a dispersant, a thickener, a pH adjuster, a lubricant, a fluidity modifier, a surfactant, an antifoaming agent, a release agent, and a fluorescence enhancer as necessary. Whitening agents, ultraviolet absorbers, antioxidants and the like are used.

Next, an image recording method using an image recording apparatus suitable for recording an image on a recording medium using the ink described above will be described.
(Recording device)
As a method and apparatus suitable for recording using the ink according to the present invention described above, for example, thermal energy corresponding to the recording signal is applied to the ink in the chamber of the recording head, and droplets are generated by the thermal energy. And a method and an apparatus.

(Device body)
1 and 2 show an example of a schematic configuration of a printer using an ink jet recording method. In FIG. 1, the printer main body M1000 in this embodiment includes an exterior member including a lower case M1001, an upper case M1002, an access cover M1003, and a discharge tray M1004, and a chassis M3019 (see FIG. 1) housed in the exterior member. 2).

  The chassis M3019 is composed of a plurality of plate-shaped metal members having a predetermined rigidity, forms a skeleton of the recording apparatus, and holds each recording operation mechanism described later. The lower case M1001 forms a substantially lower half of the exterior of the apparatus main body M1000, and the upper case M1002 forms a substantially upper half of the exterior of the apparatus main body M1000. A hollow body structure having a storage space for storing the mechanism is formed. An opening is formed in each of the upper surface portion and the front surface portion of the apparatus main body M1000.

  Further, one end of the discharge tray M1004 is rotatably held by the lower case M1001, and the opening formed on the front surface of the lower case M1001 can be opened and closed by the rotation. For this reason, when executing the recording operation, the discharge tray M1004 is rotated to the front side to open the opening so that the recording sheets can be discharged and the discharged recording sheets P are sequentially stacked. It has come to be able to do. In addition, the discharge tray M1004 contains two auxiliary trays M1004a and M1004b. By pulling out each tray as needed, the paper support area can be expanded or reduced in three stages. It has become.

  One end of the access cover M1003 is rotatably held by the upper case M1002, and can open and close an opening formed on the upper surface. By opening the access cover M1003, the access cover M1003 is housed inside the main body. It is possible to replace the print head cartridge H1000 or the ink tank H1900. Although not particularly shown here, when the access cover M1003 is opened and closed, the protrusion formed on the back surface rotates the cover opening and closing lever, and the rotation position of the lever is detected by a micro switch or the like. Thus, the open / closed state of the access cover can be detected.

  On the upper surface of the rear portion of the upper case M1002, a power key E0018 and a resume key E0019 are provided so that they can be pressed, and an LED E0020 is provided. When the power key E0018 is pressed, the LED E0020 is lit and recording is possible. This is to inform the operator. Further, the LED E0020 has various display functions such as blinking method and color change, and informing the operator of printer troubles. When the trouble is solved, the recording is resumed by pressing the resume key E0019.

(Recording mechanism)
Next, the recording operation mechanism in the present embodiment that is housed and held in the printer apparatus main body M1000 will be described.
As a recording operation mechanism in the present embodiment, an automatic feeding unit M3022 that automatically feeds the recording sheet P into the apparatus main body, and a recording sheet P that is sent one by one from the automatic feeding unit are recorded in a predetermined manner. A conveyance unit M3029 for guiding the recording sheet P from the recording position to the discharge unit M3030, a recording unit for performing desired recording on the recording sheet P conveyed to the recording position, and a recovery process for the recording unit And a recovery unit (M5000).

(Recording part)
Here, the recording unit will be described. The recording unit includes a carriage M4001 that is movably supported by a carriage shaft M4021, and a recording head cartridge H1000 that is detachably mounted on the carriage M4001.

(Recording head cartridge)
Next, the recording head cartridge used in the recording unit will be described with reference to FIGS.
As can be seen from the perspective views of FIGS. 3A and 3B, the recording head H1001 of the present invention is one constituent element of the recording head cartridge H1000. The recording head cartridge H1000 includes the recording head H1001. It is composed of an ink tank H1900 (H1901, H1902, H1903, H1904) that is detachably provided on the recording head H1001. The recording head cartridge H1000 is fixedly supported by positioning means and electrical contacts of a carriage M4001 mounted on the ink jet recording apparatus main body, and is detachable from the carriage M4001. The ink tank H1901 is for black ink, the ink tank H1902 is for cyan ink, the ink tank H1903 is for magenta ink, and the ink tank H1904 is for yellow ink. In this way, each of the ink tanks H1901, H1902, H1903, and H1904 is detachable from the recording head H1001, and each ink tank can be replaced, thereby reducing the running cost of printing in the ink jet recording apparatus. The

  Next, the recording head H1001 will be described in detail for each component constituting the recording head. 4 to 10 are explanatory diagrams for explaining each of the suitable head cartridge, the recording head, and the ink tank and the relationship between them according to the present invention. Hereinafter, each component will be described with reference to these drawings.

(1) Recording Head The recording head H1001 is a bubble jet (registered trademark) side that performs recording using an electrothermal transducer that generates thermal energy for causing film boiling in ink according to an electrical signal. This is a recording head that is of a shooter type.
As shown in the exploded perspective view of FIG. 4, the recording head H1001 includes a recording element unit H1002, an ink supply unit H1003, and a tank holder H2000.

  Further, as shown in the exploded perspective view of FIG. 5, the recording element unit H1002 includes a first recording element substrate H1100, a second recording element substrate H1101, a first plate H1200, an electrical wiring tape H1300, and an electrical contact substrate H2200. The ink supply unit H1003 includes an ink supply member H1500, a flow path forming member H1600, a joint rubber H2300, a filter H1700, and a seal rubber H1800.

(1-1) Recording Element Unit FIG. 6 is a partially exploded perspective view for explaining the configuration of the first recording element substrate H1100. In the first recording element substrate H1100, for example, an anisotropic etching is performed in which an ink supply port H1102 including a long groove-like through-hole as an ink channel is formed on a Si substrate H1110 having a thickness of 0.5 to 1 mm using a crystal orientation of Si. The electrothermal conversion elements H1103 are formed in a zigzag pattern on each side of the ink supply port H1102 between the ink supply ports H1102, and electric power is supplied to the electrothermal conversion elements H1103 and the electrothermal conversion elements H1103. The electrical wiring such as Al for supplying is formed by a film forming technique. Furthermore, electrode portions H1104 for supplying electric power to the electric wiring are arranged on both outer sides of the electrothermal transducer H1103, and bumps H1105 such as Au are formed on the electrode portion H1104. On the Si substrate, an ink channel wall H1106 and an ejection port H1107 for forming an ink channel corresponding to the electrothermal conversion element H1103 are formed of a resin material by a photolithography technique, and the ejection port group H1108 is formed. Forming. Accordingly, since the ejection port is provided to face the electrothermal conversion element H1103, the ink supplied from the ink flow path H1102 is ejected by bubbles generated by the electrothermal conversion element H1103.

  FIG. 7 is a partially exploded perspective view for explaining the configuration of the second recording element substrate H1101. The second recording element substrate H1101 is a recording element substrate for ejecting ink of three colors, and has three ink supply ports H1102 formed in parallel, and electric is provided on both sides of each ink supply port. A heat conversion element and an ink discharge port are formed. Of course, like the first recording element substrate H1100, an ink supply port, an electrothermal conversion element, an electric wiring, an electrode portion, and the like are formed on the Si substrate, and an ink flow path and an ink discharge are made of a resin material on the Si substrate by a photolithography technique. An exit is formed. Similarly to the first recording element substrate, a bump H1105 such as Au is formed on the electrode portion H1104 for supplying electric power to the electric wiring.

Next, the first plate H1200 is made of, for example, an alumina (Al ₂ O ₃ ) material having a thickness of 0.5 to 10 mm. The material of the first plate is not limited to alumina, and has a linear expansion coefficient equivalent to that of the material of the recording element substrate H1100, and is equivalent to the thermal conductivity of the material of the recording element substrate H1100. Alternatively, it may be made of a material having an equivalent or higher thermal conductivity. Examples of the material of the first plate H1200 include silicon (Si), aluminum nitride (AlN), zirconia, silicon nitride (Si ₃ N ₄ ), silicon carbide (SiC), molybdenum (Mo), and tungsten (W). Either may be sufficient.

  The first plate H1200 has ink supply ports H1201 for supplying black ink to the first recording element substrate H1100 and inks for supplying cyan, magenta, and yellow ink to the second recording element substrate H1101. A supply port H1201 is formed, the ink supply port 1102 of the printing element substrate corresponds to the ink supply port H1201 of the first plate H1200, and the first printing element substrate H1100 and the second printing element substrate H1101. Are bonded and fixed to the first plate H1200 with high positional accuracy. The first adhesive H1202 used for bonding is desirably a low viscosity, low curing temperature, cured in a short time, has a relatively high hardness after curing, and has ink resistance. The first adhesive H1202 is, for example, a thermosetting adhesive mainly composed of an epoxy resin, and the thickness of the adhesive layer is desirably 50 μm or less.

  The electrical wiring tape H1300 applies an electrical signal for ejecting ink to the first recording element substrate H1100 and the second recording element substrate H1101, and includes a plurality of recording element substrates. It has an opening, an electrode terminal H1302 (not shown) corresponding to the electrode portion H1104 of each recording element substrate, and an external signal input terminal H1301 for receiving an electrical signal from the main body device located at the end of the wiring tape. The electrode terminal portion H1303 (not shown) for electrical connection with the electrical contact substrate H2200 is connected, and the electrode terminal H1302 and the electrode terminal 1303 are connected by a continuous copper foil wiring pattern.

  The electrical wiring tape H1300, the first recording element substrate 1100, and the second recording element substrate H1101 are electrically connected to each other, and the connection method is, for example, the electrode portion 1104 of the recording element substrate and the electrical wiring tape H1300. The electrode terminal H1302 is electrically bonded by a thermal ultrasonic pressure bonding method.

The second plate H1400 is, for example, a single plate-like member having a thickness of 0.5 to 1 mm, and is formed of a ceramic material such as alumina (Al ₂ O ₃ ) or a metal material such as Al or SUS. Yes. The first recording element substrate H1100 and the second recording element substrate H1101 that are bonded and fixed to the first plate H1200 have openings that are larger than the outer dimensions thereof. Further, the first recording element substrate H1100 and the second recording element substrate H1101 and the electric wiring tape H1300 are bonded to the first plate H1200 with a second adhesive H1203 so that the electric wiring tape H1300 can be electrically connected in a plane. The back surface of the wiring tape H1300 is bonded and fixed with a third adhesive H1306.

  Electrical connection portions of the first recording element substrate H1100 and the second recording element substrate H1101 and the electric wiring tape H1300 are sealed with a first sealant H1307 (not shown) and a second sealant H1308. Protects electrical connections from ink corrosion and external impacts. The first sealing agent mainly seals the back surface side of the connection portion between the electrode terminal H1302 of the electric wiring tape and the electrode portion H1105 of the recording element substrate and the outer peripheral portion of the recording element substrate, and the second sealing agent. Seals the front side of the connecting part.

Further, an electrical contact substrate H2200 having an external signal input terminal H1301 for receiving an electrical signal from the main unit is connected to the end portion of the electrical wiring tape by thermocompression bonding using an anisotropic conductive film or the like.
The electric wiring tape H1300 is bent at one side surface of the first plate H1200, and is bonded to the side surface of the first plate H1200 with a third adhesive H1306 (not shown). As the third adhesive H1306, for example, a thermosetting adhesive having a thickness of 10 to 100 μm mainly composed of an epoxy resin is used.

(1-2) Ink Supply Unit The ink supply member H1500 is formed by resin molding, for example. As the resin material, it is desirable to use a resin material mixed with 5 to 40% of glass filler in order to improve the shape rigidity. As shown in FIGS. 5 and 8, the ink supply member H1500 is one component of the ink supply unit H1003 for guiding ink from the ink tank H1900 to the recording element unit H1002, and the flow path forming member H1600 is ultrasonically welded. As a result, an ink flow path H1501 is formed. Further, a filter H1700 for preventing dust from entering from the outside is joined to the joint H1517 engaged with the ink tank H1900 by welding. Further, in order to prevent ink from evaporating from the joint H1517, A seal rubber H1800 is attached. The ink supply member H1500 also has a part of the function of holding the removable ink tank H1900, and has a first hole H1503 for engaging the second claw H1910 of the ink tank H1900.

  Also, a mounting guide H1601 for guiding the recording head cartridge H1000 to the mounting position on the carriage M4001 of the main body of the ink jet recording apparatus, an engaging portion H1508 for mounting and fixing the recording head cartridge to the carriage M4001 with a head set lever, and a carriage M4001. Abutting portion H1509 in the X direction (carriage scanning direction), abutting portion H1510 in the Y direction (recording medium conveyance direction), and abutting portion H1511 in the Z direction (ink ejection direction) for positioning at a predetermined mounting position. I have. In addition, a terminal fixing portion H1512 for positioning and fixing the electrical contact substrate H2200 of the recording element unit H1002 is provided, and a plurality of ribs are provided around the terminal fixing portion H1512 to increase the rigidity of the surface having the terminal fixing portion H1512. ing.

(1-3) Coupling of recording head unit and ink supply unit As shown in FIG. 4 described above, the recording head H1001 is completed by coupling the recording element unit H1002 to the ink supply unit H1003 and further to the tank holder H2000. To do. The coupling is performed as follows. The ink supply port of the recording element unit H1002 (ink supply port H1201 of the first plate H1200) and the ink supply port of the ink supply unit H1003 (ink supply port H1601 of the flow path forming member H1600) are communicated so that ink does not leak. Therefore, each member is fixed with the screw H2400 so as to be pressure-bonded via the joint rubber H2300. At the same time, the recording element unit H1002 is accurately positioned and fixed with respect to the reference positions in the X, Y, and Z directions of the ink supply unit.

  The electrical contact substrate H1301 of the recording element unit H1002 is positioned and fixed to one side surface of the ink supply member H1500 by terminal positioning pins H1515 (2 places) and terminal positioning holes H1309 (2 places). The fixing method is, for example, fixing by crimping a terminal coupling pin H1515 provided on the ink supply member H1500, but may be fixed using other fixing means. The completed drawing is shown in FIG. Further, the recording head H1001 is completed by fitting the coupling hole and coupling portion of the ink supply member H1500 with the tank holder into the tank holder H2000 and coupling them. A completed drawing is shown in FIG.

(2) Description of Print Head Cartridge FIGS. 3A and 3B described above are diagrams for explaining mounting of the print head H1001 and the ink tanks H1901, H1902, H1903, and H1904 constituting the printhead cartridge H1000. The ink tanks H1901, H1902, H1903, and H1904 contain corresponding color inks. Further, as shown in FIG. 8, each ink tank is formed with an ink supply port H1907 for supplying ink in the ink tank to the recording head H1001. For example, when the ink tank H1901 is attached to the recording head H1001, the ink supply port H1907 of the ink tank H1901 is brought into pressure contact with the filter H1700 provided in the joint portion H1520 of the recording head H1001, and the black ink in the ink tank H1901 is supplied with ink. The ink is supplied from the port H1907 to the first recording element substrate through the first plate H1200 through the ink flow path H1501 of the recording head H1001. Then, ink is supplied to the foaming chamber H1109 having the electrothermal conversion element H1103 and the discharge port H1107, and is ejected toward a recording sheet as a recording medium by the thermal energy given to the electrothermal conversion element H1103.

EXAMPLES Next, although an Example and a comparative example are given and this invention is demonstrated further more concretely, this invention is not limited by the following Example, unless the summary is exceeded. In the following description, “%” is based on mass unless otherwise specified.
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 0.2 μm to prepare inks of the present invention and comparative examples.

(Example 1)
・ Glycerin 10%
・ Diethylene glycol 10%
・ Acetylene glycol ethylene oxide adduct (trade name: acetylenol EH; manufactured by Kawaken Fine Chemical Co., Ltd.) 1%
-Colorant of general formula I [(x + y = 4) / (x + y = 3) = 2.3,
Trade name: Projet Cyan 1 (Avecia) 0.4%
・ Acid Blue 9 0.4%
-Exemplary compound 2 2.13%
-Mixture of Li salt and Na salt of Exemplified Compound 1 (molar ratio Li salt: Na salt = 2: 1)
1.07%
・ Water 75%

(Example 2)
・ Glycerin 10%
・ Diethylene glycol 10%
・ Acetylene glycol ethylene oxide adduct (trade name: acetylenol EH; manufactured by Kawaken Fine Chemical Co., Ltd.) 1%
-Colorant of general formula I [(x + y = 4) / (x + y = 3) = 2.3,
Trade name: Projet Cyan 1 (Avecia) 0.55%
・ Acid Blue 9 0.25%
-Exemplary compound 2 2.13%
-Mixture of Li salt and Na salt of Exemplified Compound 1 (molar ratio Li salt: Na salt = 2: 1)
1.07%
・ Water 75%

(Comparative Example 1)
・ Glycerin 10%
・ Diethylene glycol 10%
・ Acetylene glycol ethylene oxide adduct (trade name: acetylenol EH; manufactured by Kawaken Fine Chemical Co., Ltd.) 1%
-Colorant of general formula I [(x + y = 4) / (x + y = 3) = 2.3,
Trade name: Projet Cyan 1 (Avecia) 0.8%
・ Direct Yellow 132 3.2%
・ Water 75%

(Comparative Example 2)
・ Glycerin 10%
・ Diethylene glycol 10%
・ Acetylene glycol ethylene oxide adduct (trade name: acetylenol EH; manufactured by Kawaken Fine Chemical Co., Ltd.) 1%
・ Acid Blue 9 0.8%
・ Direct Yellow 132 3.2%
・ Water 75%

(Comparative Example 3)
・ Glycerin 10%
・ Diethylene glycol 10%
・ Acetylene glycol ethylene oxide adduct (trade name: acetylenol EH; manufactured by Kawaken Fine Chemical Co., Ltd.) 1%
-Colorant of general formula I [(x + y = 4) / (x + y = 3) = 2.3,
Trade name: Projet Cyan 1 (Avecia) 0.4%
・ Acid Blue 9 0.4%
・ Direct Yellow 132 3.2%
・ Water 75%

(Comparative Example 4)
・ Glycerin 10%
・ Diethylene glycol 10%
・ Acetylene glycol ethylene oxide adduct (trade name: acetylenol EH; manufactured by Kawaken Fine Chemical Co., Ltd.) 1%
-Colorant of general formula I [(x + y = 4) / (x + y = 3) = 2.3,
Trade name: Projet Cyan 1 (Avecia) 0.4%
・ Acid Blue 9 0.4%
-Mixture of Li salt and Na salt of Exemplified Compound 1 (molar ratio Li salt: Na salt = 2: 1)
3.2%
・ Water 75%

<Evaluation>
The recording ink prepared as described above is packed in an ink cartridge for BJF-900 manufactured by Canon Inc., and a solid image is formed at a resolution of 1200 × 1200 dpi and a discharge amount of 4.5 pl per nozzle using BJF900. Color development, light resistance and gas resistance were evaluated. As a recording medium, Canon Inc. Inkjet Glossy Media PR-101 was used. The evaluation method is described below. In each case, the evaluation was performed after printing and after 24 hours of natural drying.

(1) Color development evaluation apparatus; Gretag Spectrolino (trade name: manufactured by Gretag)
Evaluation method: CIE L ^* a ^* b ^* of the test sample was measured, and brightness L ^* and chroma C ^* were calculated from the following formulas.
C ^* = (a ^{* 2} + b ^{* 2} ) ^1/2
h = 180 ° + tan ⁻¹ (b ^* / a ^* ) a ^* ≦ 0, b ^* ≧ 0

(2) Light resistance evaluation device: Xenon Fade Meter Ci3000 manufactured by Atlas
Exposure condition: In-tank temperature 25 ° C., relative humidity 55%, illuminance xenon lamp 0.39 W / m ² , 30 hours Evaluation method: CIE L ^* a ^* b ^* of test sample after exposure as in (1) above Was measured. The hue difference ΔE was calculated from the following formula, and the hue angle difference Δh was calculated from the formula (1).
ΔE = (ΔL ^{* 2} + Δa ^{* 2} + Δb ^{* 2} ) ^1/2

(3) Gas resistance Evaluation apparatus; Ozone fade meter Exposure conditions: 2 hours under conditions of 40 ° C in the tank, 55% relative humidity and 3 ppm in an ozone atmosphere Evaluation method: After exposure as in (1) above CIE L ^* a ^* b ^* of the test sample was measured. Further, the color difference ΔE and the hue angle difference Δh were calculated in the same manner as in (2) above.

  As described above, according to the present invention, it is possible to provide an ink that is excellent in lightness and saturation and excellent in color balance due to long-term storage of a printed image.

1 is a perspective view illustrating an external configuration of an inkjet printer according to an embodiment of the present invention. It is a perspective view which shows the state which removed the exterior member of what is shown in FIG. FIG. 3A is a perspective view of a suitable recording head cartridge on which the ink jet recording head of the present invention can be mounted, and FIG. 3B is an exploded perspective view thereof. FIG. 4 is an exploded perspective view illustrating a configuration of the recording head illustrated in FIG. 3. FIG. 4 is an exploded perspective view in which the recording head shown in FIG. 3 is further finely disassembled. FIG. 4 is a partially cutaway explanatory perspective view showing a configuration of a recording element substrate of the recording head cartridge in FIG. 3. FIG. 4 is a partially cut-out explanatory perspective view illustrating a configuration of another recording element substrate of the recording head cartridge in FIG. 3. FIG. 4 is a cross-sectional view of a main part of the recording head cartridge of FIG. FIG. 4 is a perspective view showing an assembly of a recording element unit and an ink supply unit of the recording head cartridge of FIG. 3. FIG. 4 is a perspective view illustrating a bottom surface side of the recording head cartridge in FIG. 3.

Explanation of symbols

M1000: apparatus main body M1001: lower case M1002: upper case M1003: access cover M1004: discharge tray M2015: paper gap adjusting lever M3001: LF roller M3006: paper discharge roller M3019: chassis M3022: automatic feeding unit M3029: transport unit M3030: Discharge unit M4001: Carriage M4002: Carriage cover M4007: Head set lever M4021: Carriage shaft M5000: Recovery system unit E0001: Carriage motor E0002: LF motor E0018: Power key E0019: Resume key E0020: LED
H1000: Printhead cartridge H1001: Printhead (inkjet printhead)
H1002: Recording element unit H1003: Ink supply unit H1100: First recording element substrate H1101: Second recording element substrate H1102: Ink supply port (supply port)
H1103: Electrothermal conversion element (recording element)
H1104: Electrode H1105: Bump H1106: Ink channel wall H1107: Ejection port H1108: Ejection port group H1110: Si substrate H1200: First plate (first support member)
H1201: Ink communication port H1202: First adhesive H1203: Second adhesive H1300: Electrical wiring tape (flexible wiring board)
H1301: External signal input terminal H1302: Electrode lead H1306: Third adhesive H1307: First sealant H1308: Second sealant H1309: Terminal positioning hole H1310: Terminal fixing portion H1400: Second plate H1500 : Ink supply member H1501: ink flow path H1503: first hole H1509: X abutting portion H1510: Y abutting portion H1511: Z abutting portion H1512: terminal fixing portion H1516: terminal positioning pin H1520: joint portion H1600: flow Path forming member H1601: Installation guide H1602: Ink communication port H1700: Filter H1800: Seal rubber H1900: Ink tank H1901: Black ink tank H1902: Cyan ink tank H1903: Magenta ink tank H1904: Yellow in Tank H1907: ink feed port H1910: second pawl H2000: the tank holder H2200: electric contact substrate H2300: joint seal member H2400: Bis

Claims (9)

  An ink for ink jet recording, comprising at least a triphenylmethane cyan color material, a copper phthalocyanine cyan color material, and a yellow color material.   When the total mass of the triphenylmethane cyan color material and the copper phthalocyanine cyan color material is A and the mass of the yellow color material is B, A / B is 1/20 or more and 1/2 or less. The ink for inkjet recording according to claim 1.   The ink for inkjet recording according to claim 2, wherein the A / B is 1/10 or more and 1/4 or less.   The ink for inkjet recording according to claim 2, wherein the A / B is 1/10 or more and 5 or less.   The ink for inkjet recording according to claim 2, wherein the A / B is 1/5 or more and 3 or less.   The triphenylmethane cyan colorant is C.I. I. The ink for inkjet recording according to any one of claims 1 to 5, which is Acid Blue 9.   The hue angle difference Δh in the CIELAB color space display system in a light fastness test under a condition that causes a fading corresponding to sunlight fading through a pseudo indoor window of 3 years or more of the image by the ink is within 6 °. The ink for inkjet recording of any one of 6.   2. A hue angle difference Δh in a CIELAB color space display system in a two-hour exposure under an ozone atmosphere of 40 ° C., 55% relative humidity and 3 ppm in an ink image of the ink is within 6 °. The ink for inkjet recording of any one of -7. The ink for inkjet recording according to any one of claims 1 to 8, wherein the yellow color material contains at least a color material represented by the following chemical formula.

(Wherein R ₁ and R ₂ each independently represents a substituted or unsubstituted alkyl group, aryl group, arylalkyl group, or hydrogen. R ₃ and R ₅ each independently represent a carboxyl group, a sulfone group, or a sulfone group. An acid group, a phosphoric acid group, or a salt group thereof, or an alkyl group substituted with these groups, R ₄ and R ₆ are each independently a group other than those defined for R ₃ and R ₅ . P and r each independently represent an integer of 1 to 5, q and s each independently represent an integer of 0 to 4. Further, p + q has a value of 5 or less, and r + s is 5 It has the following values.)

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