JP2007038673A - Ink cartridge - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an ink cartridge whereby a stable image less in change of a color balance in comparison with an initial state before preserved can be obtained even when the ink cartridge in which stored ink is easy to evaporate is preserved for a long period of time at the physical distribution time, or when the ink cartridge is kept for a long period of time under a condition that it is set in a recorder, etc. <P>SOLUTION: The ink cartridge comprises an inkjet head and a plurality of liquid chambers which store ink different from each other. A minimum value A1 (g/ml) of an ink density of ink stored in each of a plurality of the liquid chambers, and a maximum value B1 (g/ml) of the ink density of ink when the ink stored in each of a plurality of the liquid chambers is evaporated by 10 mass% satisfy (B1-A1)/A1≤0.100. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to an ink cartridge including an ink jet head and a plurality of liquid chambers that store different inks.

  The ink jet recording method is a recording method in which ink droplets are ejected onto plain paper or a dedicated glossy medium to form an image, and is rapidly spreading with the progress of low cost and the improvement of recording speed. Further, in recent years, further improvement in image quality has been promoted, such as the miniaturization of ink droplets to be ejected and the expansion of the color gamut accompanying the introduction of multicolor inks. For this reason, it is desired to suppress the change in physical properties of ink over time, which can affect image characteristics.

  One of the changes in physical properties of the ink over time is a change in physical properties due to evaporation. As a technique related to this problem, an aqueous ink composition capable of reducing the evaporation rate is disclosed (see Patent Document 1). Further, a means for suppressing the evaporation amount by the shape of the ink cartridge is disclosed (see Patent Document 2). Furthermore, a technique for suppressing evaporation of ink by using a specific material as a packaging material for an ink cartridge is disclosed (see Patent Document 3). On the other hand, an ink having a density within a certain range is disclosed (see Patent Document 4). Further, an ink jet recording method using two ink cartridges that can store a plurality of inks is disclosed (see Patent Document 5).

JP-A-5-214282 JP-A-10-278290 JP 2002-331688 A JP 2003-073598 A JP-A-5-202328

  However, the present inventors say that when an ink cartridge having an inkjet head and a plurality of liquid chambers containing different inks is used, the image is likely to change as the physical distribution period or use period becomes longer. I found a new technical problem.

  Accordingly, an object of the present invention is to provide an ink cartridge capable of obtaining an excellent image in which a change in color balance is suppressed even after long-term storage in a physical distribution or a state where it is mounted on a recording apparatus. There is.

The present invention solves the above-described new problem, and is specifically achieved by the following configuration.
That is, the present invention is an ink cartridge including an ink jet head and a plurality of liquid chambers for storing different inks, and the minimum density A1 (g / g) of each ink stored in each of the plurality of liquid chambers. ml), and the maximum ink density B1 (g / ml) of the ink obtained by evaporating 10% by mass of each ink contained in each of the plurality of liquid chambers satisfies (B1-A1) /A1≦0.100. The ink cartridge is characterized by being satisfied.

  In the present invention, the relationship between the ink density in the initial state and the ink density after the ink is evaporated by 10% by mass is defined. However, a 10% by mass reduction can occur under normal use conditions. It is the maximum possible evaporation rate. In addition, when assuming the maximum evaporation rate that can occur under more severe use conditions, it is possible to define the relationship between the ink density in the initial state and the ink density after ink is evaporated by 15% by mass. preferable.

  The initial state is the state of the ink before evaporation, and for example, it is not necessary to consider the elapsed time since the preparation of the ink and the elapsed time since the ink was injected into the ink cartridge. Even if the initial state is defined in this way, the ink jet cartridge satisfying the configuration of the present invention can obtain the above-described remarkable effects. The reason is considered as follows. That is, if it is a normally usable ink cartridge, it is possible to evaporate at least 15% by mass or more, and if it is within this range, the change in density with respect to the evaporation rate is almost linear. There seems to be no.

  According to the present invention, even when an ink cartridge in which the stored ink is likely to evaporate is stored for a long time during distribution, or when it is held for a long time while attached to the recording apparatus, the initial state before storage An ink cartridge that provides a stable image with little change in color balance is provided.

Hereinafter, the present invention will be described in more detail with reference to preferred embodiments. First, the reason why the above remarkable effect can be obtained by the present invention is as follows according to the study by the present inventors.
Inkjet ink usually contains a volatile component. A phenomenon may occur in which the volatile component evaporates from the liquid chamber in which the ink is stored into the atmosphere during distribution or in a state where the volatile component is attached to the main body. On the other hand, liquid chambers that contain ink for ink jet are required to have various performances such as moldability, weldability, ink resistance, mechanical strength, and low thermal expansion coefficient. Therefore, a material having a certain degree of gas permeability may be used as the constituent material of the liquid chamber. In particular, in an ink cartridge having an inkjet head and a plurality of liquid chambers that contain different inks, emphasis is placed on moldability, weldability, and thermal stability, so the liquid chambers are made of a material with relatively high gas permeability. May be configured. If the ink is stored for a long time in such a state of being contained in the liquid chamber, the ink component is likely to evaporate and the physical properties of the ink are likely to change. This change is also influenced by the composition of the ink, the shape of the liquid chamber, and the like, and therefore does not always occur uniformly among the inks. Specifically, when ink such as physical distribution is not used, the ink evaporation rate is greatly affected by the water content in the ink and the area of the surface on which the ink can be evaporated. However, even if the water content is the same and the area of the evaporable surface is the same, the ink density can be greatly affected by the type and amount of the color material and solvent contained in the ink. Further, when the ink cartridge is held in the recording apparatus main body, the remaining amount of ink is usually different for each color depending on the use state of the ink. For this reason, the difference in the evaporation rate of each ink becomes more remarkable, and the difference in the amount of change in the density of the color material and the density of the ink also becomes larger.

  When the density of the color material and the density of the ink are greatly changed as the ink is concentrated, the amount of the color material contained in the ejected ink droplet is also greatly changed. As a result, the amount of color material applied to the recording medium differs between the case where ink before evaporation (initial state) is used and the case where ink after evaporation is used. In particular, if there is a difference in the color material density and the ink density change rate between the inks, the influence on the image becomes very large. This is because the color balance changes after the initial state and after evaporation. This is the above-mentioned new technical problem found by the present inventors, and the present invention can solve this new technical problem.

  FIG. 1 schematically shows how the ink densities of two different inks change as the volatile components evaporate. As shown in the figure, the density of both inks increases due to evaporation of volatile components. In an actual use environment, two or more inks are not substantially used in equal amounts. For this reason, depending on the use status of the ink, only a specific ink is stored in an extremely small state, and it is predicted that the evaporation proceeds more rapidly than other inks.

  For example, the ink 1 and the ink 2 shown in FIG. 1 are inks constituting an ink set, and the ink set is used by being accommodated in an ink cartridge. Further, the ink 1 is extremely used and the ink 2 is almost used. Think about the case that is not. In this case, since the remaining amount of the ink 1 is extremely reduced, the evaporation rate of the ink 1 is increased. On the other hand, since the remaining amount of the ink 2 is large, the evaporation rate is smaller than that of the ink 1 even when the ink 2 is left for the same period as the ink 1. Here, when the evaporation rate of ink 1 (that is, the rate of decrease due to ink evaporation) is 10% by mass, which is the maximum level in a general ink tank usage state, the evaporation rate of ink 1 and ink 2 The difference is up to 10% by mass. Similarly, if the evaporation rate of ink 1 is 15% by mass, which is the maximum when used in a harsh environment, the difference in evaporation rate between ink 1 and ink 2 is as follows. Up to 15% by mass.

  In such a case, the most evaporated ink 1 has the highest ink density after evaporation in the ink set, and the ink 2 having the lowest evaporation rate has the lowest ink density. If the density difference between the two inks after evaporation is too large, in addition to the increase in the color material concentration concentrated by evaporation, the increase in the discharge amount due to the density difference between each ink is added. The difference in the amount of color material in the ejected ink droplets is further widened between the two inks. As a result, the color material density balance between the inks applied to the recording medium with the ink in the initial state and the color material density balance between the inks applied after evaporation are greatly different, so the color balance of the obtained image is remarkably different. It will make it worse.

  In this way, it is necessary to minimize deterioration of color balance in consideration of ink evaporation in consideration of various ink usage conditions. For this purpose, the inventors have found that the difference between the minimum value of the ink density in the initial state and the maximum value of the ink density after evaporation may be controlled within a certain range. More specifically, the minimum value A1 (g / ml) of the ink density before evaporation of the plurality of inks contained in the ink cartridge and the ink density of each ink after evaporation of 10% by mass A plurality of inks are combined so that the maximum value B1 (g / ml) satisfies (B1-A1) /A1≦0.100.

  In addition, the higher the ink evaporation rate, the more easily the color balance is deteriorated. For this reason, it is preferable that the control of the ink density described above is made more strict under a severe use environment such as a high temperature and low humidity environment. Specifically, it is preferable that the maximum value B2 (g / ml) of A1 and the ink density of each ink evaporated by 15% by mass satisfies (B2−A1) /A1≦0.070. .

  In the present invention, it is more preferable that A1 and B1 satisfy (B1-A1) /A1≦0.060. When the plurality of inks are yellow ink, magenta ink, and cyan ink, this range is preferable. Furthermore, in the present invention, it is preferable that A1 and B2 satisfy (B2-A1) /A1≦0.050. By adopting such a configuration, the variation in the ejection amount among the inks is further reduced, and an image having a good secondary color balance as well as a single color balance can be obtained. Furthermore, in the present invention, it is preferable that A1 and B2 satisfy (B2-A1) /A1≦0.040. When the plurality of inks are yellow ink, magenta ink, and cyan ink, this range is preferable.

  Furthermore, in the present invention, it is more preferable that A1 and B1 satisfy (B1-A1) /A1≦0.040. When the plurality of inks are yellow ink, light magenta ink, and light cyan ink, this range is preferable. The definition of the light ink in the present invention will be described later. Furthermore, in the present invention, it is more preferable that A1 and B2 satisfy (B2-A1) /A1≦0.030. By adopting such a configuration, variations in the ejection amount among the inks can be further reduced, and an image excellent in color balance in a halftone region of a single color or a secondary color can be obtained. A low-density gray image is particularly susceptible to variations in ejection amount among gray images, but within this range, a low-density gray image with good color balance can be obtained. When the plurality of inks are yellow ink, light magenta ink, and light cyan ink, these ranges are preferable. The definition of the light ink in the present invention will be described later.

  In the present invention, the difference between the ink density before evaporation and the ink density after evaporation of the ink is 0.030 g / ml or less when the ink evaporation rate is 10% by mass. Is preferred. When the evaporation rate is 15% by mass, it is preferably 0.020 g / ml or less. By adopting such a form, the variation in the ejection amount between the inks is further reduced, and an image having a good color balance in a halftone region of a single color or a secondary color can be stably obtained. In particular, when the evaporation rate of the ink is 10% by mass, it is preferably 0.020 g / ml or less, and when the evaporation rate is 15% by mass, it is preferably 0.018 g / ml or less. Within this range, a gray image with better color balance can be obtained. When the plurality of inks are yellow ink, magenta ink, and cyan ink, this range is preferable.

  As described above, in the present invention, it is preferable that the evaporation rates of a plurality of different inks accommodated in a plurality of liquid chambers be as uniform as possible.

  Equal evaporation is likely to occur when the ink cartridge is stored for a long time during distribution, or in a storage state where the ink cartridge is mounted on the recording apparatus main body and left unused for a long period of time. In particular, a difference in output result depending on the physical distribution period even though it is a new cartridge is not preferable in terms of product quality, and it is necessary to manage printing characteristics more severely. For this purpose, it is preferable to make the area of the surface where the ink can be evaporated equal to or less than a certain level. Furthermore, in order to suppress the evaporation amount and suppress the evaporation from the cartridge housing as much as possible, the shape of the atmosphere communication means provided in the ink cartridge is a so-called maze structure in which the communication path has a bent portion. Is preferred. These specific configurations will be described later in the section of the ink cartridge.

  In the present invention, the minimum value C1 (g / ml) and the maximum value D1 (g / ml) of the ink density of each ink after evaporation of 10% by mass are (D1-C1) / C1. It is preferable that ≦ 0.090 is satisfied. By controlling in this way, the evaporation rates of the respective inks can be made uniform, and the ink density relationship during evaporation can be suppressed within a more preferable range.

  In the present invention, the minimum value C2 (g / ml) and the maximum value D2 (g / ml) of the ink density of each ink after evaporation of 15% by mass are (D2-C2) / C2. More preferably, ≦ 0.060 is satisfied.

  Furthermore, in the present invention, it is preferable that the above C1 and D1 satisfy (D1-C1) /C1≦0.055. Further, it is more preferable that C2 and D2 satisfy (D2−C2) /C2≦0.035. By adopting such a configuration, the variation in the ejection amount among the inks is further reduced, and an image having a good secondary color balance as well as a single color balance can be obtained. When the plurality of inks are yellow ink, magenta ink, and cyan ink, these ranges are preferable.

  Furthermore, in the present invention, it is more preferable that the above C1 and D1 satisfy (D1-C1) /C1≦0.035. Further, it is more preferable that C2 and D2 satisfy (D2-C2) /C2≦0.030. By adopting such a form, the variation in the ejection amount between the inks is further reduced, and an image having a good color balance in a halftone region of a single color or a secondary color can be stably obtained. When the plurality of inks are yellow ink, light magenta ink, and light cyan ink, these ranges are preferable. The definition of the light ink in the present invention will be described later.

[ink]
The physical properties of the ink as described above are affected by various factors such as the amount of water, the type and amount of the solvent, the type and amount of the coloring material, and the type and amount of other additives, so all combinations are described. It is impossible. Furthermore, in the present invention, as is apparent from the technical idea of the present invention described above, it is essential that the physical properties of a plurality of inks satisfy a specific relationship. The specific means for satisfying is not limited. The preferred configurations of the ink used in the present invention are shown below, but the present invention can be carried out by appropriately combining these configurations.

  The ink cartridge according to the present invention is configured to store a plurality of different inks in each of the plurality of liquid chambers, but there is no particular limitation on the combination of ink colors (ink sets) to be stored. As a specific example, there are ink sets of three basic colors of cyan, magenta, and yellow. Further, an ink set suitable for photographic image output having black, light cyan color cyan, and light magenta magenta (so-called light cyan ink or light magenta ink) can be mentioned. In addition, an ink set having red, green, and blue special color inks may be used, but the present invention is not particularly limited thereto. However, as described above, the preferred range of the relationship between the initial state and the ink density of the ink after evaporation may vary depending on what kind of ink is used in combination. The light cyan ink in the present invention is a cyan ink having a low color material density when two types of cyan inks having different densities are present. The light magenta ink is a magenta ink having a low color material density when two types of magenta inks having different color material density exist. The light magenta ink is a magenta ink having a lower color material density when two kinds of magenta inks having different color material densities exist. In the present invention, the color material concentration of the dark ink is preferably 2% by mass or more and 10% by mass or less, and particularly preferably 6% by mass or less, with respect to the total mass of the ink. The color material concentration of the light ink is preferably 0.3% by mass or more and 3% by mass or less, and particularly preferably 2% by mass or less. Hereinafter, the components of the ink will be described.

(Color material)
Each ink constituting the ink set used in the present invention may be a plurality of different inks, and the color materials contained in the ink are not particularly limited, and the color materials listed below can be appropriately contained. it can. Examples of coloring materials that can be contained are listed below, but are not limited thereto.

C. I. Direct yellow: 8, 11, 12, 27, 28, 33, 39, 44, 50, 58, 85, 86, 87, 88, 89, 98, 100, 110, 132, 173, etc .;
C. I. Acid Yellow: 1, 3, 7, 11, 17, 23, 25, 29, 36, 38, 40, 42, 44, 76, 98, 99, etc .;
C. I. Food yellow: 3 etc .;
C. I. Pigment Yellow: 1, 2, 3, 12, 13, 14, 15, 16, 17, 73, 74, 75, 83, 93, 95, 97, 98, 114, 128, 138, 180, etc .;

C. I. Direct Red: 2, 4, 9, 11, 20, 23, 24, 31, 39, 46, 62, 75, 79, 80, 83, 89, 95, 197, 201, 218, 220, 224, 225, 226 227, 228, 229, 230, etc .;
C. I. Acid Red: 6, 8, 9, 13, 14, 18, 26, 27, 32, 35, 42, 51, 52, 80, 83, 87, 89, 92, 106, 114, 115, 133, 134, 145 158, 198, 249, 265, 289 etc .;
C. I. Food Red: 87, 92, 94, etc .;
C. I. Direct violet: 107 etc .;
C. I. Pigment Red: 2, 5, 7, 12, 48: 2, 48: 4, 57: 1, 112, 122, 123, 168, 184, 202, etc .;

C. I. Direct Blue: 1, 15, 22, 25, 41, 76, 77, 80, 86, 90, 98, 106, 108, 120, 158, 163, 168, 199, 226, 307, etc .;
C. I. Acid Blue: 1, 7, 9, 15, 22, 23, 25, 29, 40, 43, 59, 62, 74, 78, 80, 90, 100, 102, 104, 112, 117, 127, 138, 158 161, 203, 204, 221, 244, etc .;
C. I. Pigment Blue: 1, 2, 3, 15, 15: 2, 15: 3, 15: 4, 16, 22, 60, etc .;

C. I. Acid Orange: 7, 8, 10, 12, 24, 33, 56, 67, 74, 88, 94, 116, 142, etc .;
C. I. Acid Red: 111, 114, 266, 374, etc .;
C. I. Direct orange: 26, 29, 34, 39, 57, 102, 118 etc .;
C. I. Food orange: 3 etc .;
C. I. Reactive orange: 1, 4, 5, 7, 12, 13, 14, 15, 16, 20, 29, 30, 84, 107, etc .;
C. I. Disperse Orange: 1, 3, 11, 13, 20, 25, 29, 30, 31, 32, 47, 55, 56, etc .;
C. I. Pigment orange: 43 mag;
C. I. Pigment Red: 122, 170, 177, 194, 209, 224, etc .;

C. I. Acid Green: 1, 3, 5, 6, 9, 12, 15, 16, 19, 21, 25, 28, 81, 84, etc .;
C. I. Direct green: 26, 59, 67, etc .;
C. I. Food Green: 3 etc .;
C. I. Reactive green: 5, 6, 12, 19, 21 etc .;
C. I. Disperse Green: 6, 9 etc .;
C. I. Pigment Green: 7, 36, etc .;

C. I. Acid Blue: 62, 80, 83, 90, 104, 112, 113, 142, 203, 204, 221, 244, etc .;
C. I. Reactive blue: 49 mag;
C. I. Acid Violet: 17, 19, 48, 49, 54, 129, etc .;
C. I. Direct violet: 9, 35, 47, 51, 66, 93, 95, 99 etc .;
C. I. Reactive violet: 1, 2, 4, 5, 6, 8, 9, 22, 34, 36, etc .;
C. I. Disperse violet: 1, 4, 8, 23, 26, 28, 31, 33, 35, 38, 48, 56, etc .;
C. I. Pigment Blue: 15: 6 etc .;
C. I. Pigment violet: 19, 23, 37, etc .;

C. I. Direct black: 17, 19, 22, 31, 32, 51, 62, 71, 74, 112, 113, 154, 168, 195, etc .;
C. I. Acid Black: 2, 48, 51, 52, 110, 115, 156 etc .;
C. I. Food black: 1, 2, etc .;
Carbon black.

  Further, other color materials that can be preferably used in the present invention include color materials represented by the following general formulas (1) to (7). These coloring materials will be described.

（上記一般式（１）中、ｍは、それぞれ独立に１又は２を示す。Ｍ₁は、それぞれ独立に水素原子、アルカリ金属、アルカリ土類金属、有機アミンのカチオン又はアンモニウムイオンを示す。） [Coloring material represented by general formula (1)]

(In the above general formula (1), m independently represents 1 or 2. M ₁ independently represents a hydrogen atom, an alkali metal, an alkaline earth metal, a cation or an ammonium ion of an organic amine.)

  A suitable example of the coloring material represented by the general formula (1) is not particularly limited, and specific examples thereof include structures shown in Table 1 below. For convenience, the ring structures at both ends of the above general formula (1) were designated as A ring and B ring, and the substitution positions were defined as in the following general formula (2). The numbers shown in Table 1 below indicate positions where the sulfonic acid groups in the exemplary compounds Y1 to Y5 are substituted.

（上記一般式（２）中、ｍは、それぞれ独立に１又は２を示す。Ｍ₁は、それぞれ独立に水素原子、アルカリ金属、アルカリ土類金属、有機アミンのカチオン又はアンモニウムイオンを示す。）

(In the general formula (2), m each independently represents 1 or 2. M ₁ each independently represents a hydrogen atom, an alkali metal, an alkaline earth metal, a cation or an ammonium ion of an organic amine.)

Although it does not specifically limit as a suitable example of the coloring material shown by the said General formula (2), Illustrative compound Y1 shown by the following Formula is mentioned as a specific thing.

  Examples of other yellow color materials include compounds having structures described in WO99 / 43754 pamphlet and WO02 / 081580 pamphlet.

（上記一般式（３）中、Ｒ₁は、水素原子、アルキル基、ヒドロキシ低級アルキル基、シクロヘキシル基、モノ又はジアルキルアミノアルキル基、及び、シアノ低級アルキル基のいずれかを示し、Ｙは、塩素原子、ヒドロキシル基、アミノ基、モノ又はジアルキルアミノ基（該アルキル基の部分に、スルホン酸基、カルボキシル基、及び、ヒドロキシル基からなる群から選択される置換基を有していてもよい）のいずれかを示し、Ｒ₂、Ｒ₃、Ｒ₄、Ｒ₅及びＲ₆は、それぞれ独立して、水素原子、炭素数１〜８のアルキル基、及び、カルボキシル基（但し、Ｒ₂、Ｒ₃、Ｒ₄、Ｒ₅及びＲ₆のすべてが水素原子である場合を除く。）のいずれかを示す。） [Coloring material represented by general formula (3)]

(In the general formula (3), R ₁ represents any _one of a hydrogen atom, an alkyl group, a hydroxy lower alkyl group, a cyclohexyl group, a mono- or dialkylaminoalkyl group, and a cyano lower alkyl group, and Y represents chlorine. An atom, a hydroxyl group, an amino group, a mono- or dialkylamino group (the alkyl group may have a substituent selected from the group consisting of a sulfonic acid group, a carboxyl group, and a hydroxyl group) R ₂ , R ₃ , R ₄ , R ₅ and R ₆ are each independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a carboxyl group (provided that R ₂ , R ₃ , R ₄ , R ₅ and R ₆ are all hydrogen atoms.)

  Preferable specific examples of the coloring material represented by the general formula (3) include exemplified compounds M1 to M7 having the following structure in the form of a free acid. In the present invention, among these, exemplary compound M7 is particularly preferably used.

[Coloring material represented by general formula (4)]

(In the above general formula (4), l (el) = 0-2, m = 1-3 and n = 1-3, provided that l + m + n = 3-4, and the substitution position of the substituent is 4 or 4 M is an alkali metal or ammonium, and R ₁ and R ₂ each independently represent a hydrogen atom, a sulfonic acid group or a carboxyl group (provided that R ₁ and R ₂ And Y represents a chlorine atom, a hydroxyl group, an amino group, and a mono- or dialkylamino group.)

It has been found that it is preferable to use a phthalocyanine compound obtained as follows among the color materials represented by the above general formula (4). After converting sulfonic acid group to chlorosulfone group using 4-sulfophthalic acid derivative or phthalocyanine compound obtained by reacting 4-sulfophthalic acid derivative and (anhydrous) phthalic acid derivative in the presence of metal compound as raw material A phthalocyanine compound obtained by reacting an aminating agent in the presence of an organic amine may be used. That is, a phthalocyanine compound into which an unsubstituted sulfamoyl group (—SO ₂ NH ₂ ) and a substituted sulfamoyl group [the following general formula (5)] are introduced is limited to positions 4 and 4 ′ in the above formula (4). The ink used as the color material has extremely excellent environmental gas resistance.

（上記一般式（５）中、Ｒ₁及びＲ₂は、それぞれ独立に、水素原子、スルホン酸基、及び、カルボキシル基のいずれかを示し（但し、Ｒ₁及びＲ₂が同時に水素原子となる場合を除く。）、Ｙは、塩素原子、ヒドロキシル基、アミノ基、及び、モノ又はジアルキルアミノ基のいずれかを示す。）

(In the above general formula (5), R ₁ and R ₂ each independently represent one of a hydrogen atom, a sulfonic acid group, and a carboxyl group (provided that R ₁ and R ₂ simultaneously become hydrogen atoms) And Y represents a chlorine atom, a hydroxyl group, an amino group, and a mono- or dialkylamino group.)

  Preferable specific examples of the group represented by the general formula (5) include groups having the following structure in the form of a free acid. Among these, Exemplified Compound C1 is particularly preferably used.

（上記一般式（６）中、Ｒ₁及びＲ₂は、独立に、水素原子、ヒドロキシル基、アミノ基、カルボキシル基、スルホン酸基、炭素数１〜４のアルキル基、及び、炭素数１〜４のアルコキシ基のいずれかを示し、Ｒ₃及びＲ₄は、独立に、水素原子、炭素数１〜４のアルキル基、炭素数１〜４のアルコキシ基、ヒドロキシル基、ヒドロキシル基若しくは炭素数１〜４のアルコキシ基で置換されてもよい炭素数１〜４のアルキル基、ヒドロキシル基・炭素数１〜４のアルコキシ基・スルホン酸基若しくはカルボキシル基で置換されてもよい炭素数１〜４のアルコキシ基、及び、アルキル基若しくはアシル基によって置換されているアミノ基のいずれかを示し、ｎは０又は１を示す。） [Coloring material represented by general formula (6)]

(In the general formula (6), R ₁ and R ₂ are independently a hydrogen atom, a hydroxyl group, an amino group, a carboxyl group, a sulfonic acid group, an alkyl group having 1 to 4 carbon atoms, and 1 to 1 carbon atoms. 4 shows one of the alkoxy group, R ₃ and R ₄ are independently hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, hydroxyl group, a hydroxyl group or a C 1 -C 1 to 4 carbon atoms which may be substituted with 1 to 4 alkoxy groups, 1 to 4 carbon atoms which may be substituted with hydroxyl groups, alkoxy groups with 1 to 4 carbon atoms, sulfonic acid groups or carboxyl groups An alkoxy group and an amino group substituted by an alkyl group or an acyl group are shown, and n is 0 or 1.)

（上記式（７）中、Ｒ₅、Ｒ₆、Ｒ₇及びＲ₈は、独立に、水素原子、ヒドロキシル基、アミノ基、カルボキシル基、スルホン酸基、炭素数１〜４のアルキル基、炭素数１〜４のアルコキシ基、ヒドロキシル基・炭素数１〜４のアルコキシ基・スルホン酸基若しくはカルボキシル基で置換されているアルコキシ基、カルボキシル基又はスルホン酸基で更に置換されてもよい炭素数１〜４のアルコキシ基、及び、フェニル基・アルキル基・若しくはアシル基によって置換されているアミノ基のいずれかを示し、ｎは０又は１を示す。） [Coloring material represented by general formula (7)]

(In the above formula (7), R ₅ , R ₆ , R ₇ and R ₈ are independently hydrogen atom, hydroxyl group, amino group, carboxyl group, sulfonic acid group, alkyl group having 1 to 4 carbon atoms, carbon An alkoxy group having 1 to 4 carbon atoms, a hydroxyl group, an alkoxy group having 1 to 4 carbon atoms, an alkoxy group substituted with a sulfonic acid group or a carboxyl group, a carbon atom which may be further substituted with a carboxyl group or a sulfonic acid group Or an alkoxy group substituted with a phenyl group, an alkyl group, or an acyl group, and n represents 0 or 1.

  Hereinafter, exemplary compounds Bk1 to Bk3 are exemplified as preferred specific examples of the color material represented by the above formula (6), and exemplary compounds Bk4 to Bk6 are represented as preferred specific examples of the color material represented by the above formula (7). In the form of However, the color material used in the present invention is not limited to these. Further, two or more kinds of color materials as listed below may be used at the same time. Among the above, those using the exemplified compound Bk3 and the exemplified compound Bk4 at the same time are particularly preferable.

<Water-soluble organic solvents and additives>
The ink used in the present invention can be prepared by dissolving or dispersing the color material as described above in an aqueous medium. As the aqueous medium used in this case, it is preferable to use a mixed medium of water and a water-soluble organic solvent. Moreover, it does not specifically limit about what kind of water-soluble organic solvent is contained, Various water-soluble organic solvents can be used arbitrarily. The water-soluble organic solvent is not particularly limited as long as it is water-soluble, and examples thereof include alcohols, polyhydric alcohols, polyglycols, glycol ethers, nitrogen-containing polar solvents, and sulfur-containing polar solvents. Although the water-soluble organic solvent which can be used for the ink used by this invention below is illustrated, it is not limited to these water-soluble organic solvents.

Specifically, the following can be used. 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;
Amides such as dimethylformamide and 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;
Alkylene glycols in which the alkylene group contains 2 to 6 carbon atoms, such as ethylene glycol, propylene glycol, butylene glycol, triethylene glycol, 1,2,6-hexanetriol, thiodiglycol, hexylene glycol, diethylene glycol and the like ;
Lower alkyl ether acetates such as polyethylene glycol monomethyl ether acetate;
Lower alkyl ethers of polyhydric alcohols such as ethylene glycol monomethyl (or ethyl) ether, diethylene glycol methyl (or ethyl) ether, triethylene glycol monomethyl (or ethyl) ether;
Polyhydric alcohols such as trimethylolpropane and trimethylolethane;
Examples include glycerin, N-methyl-2-pyrrolidone, 2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone. The water-soluble organic solvents as described above can be used alone or as a mixture.

  In addition, for the ink, a surfactant, a pH adjuster, a rust inhibitor, an antiseptic, an antifungal agent, an antioxidant, an anti-reduction agent, an evaporation accelerator, a chelating agent, and a water-soluble agent are added as necessary. Various additives such as a polymer may be contained.

[ink cartridge]
Next, the ink cartridge of the present invention will be described with reference to the drawings. The ink cartridge of the present invention includes an inkjet head and a plurality of liquid chambers that store different inks. The ink cartridge of the present invention only needs to have such a configuration, and any other configuration may be used. That is, the technical feature of the present invention is that a new technical problem in an ink cartridge having a plurality of liquid chambers is configured such that the physical properties of a plurality of inks stored in each liquid chamber satisfy a specific relationship. It is in. For example, an ink cartridge having a configuration described in the accompanying drawings can be given, but the present invention is not limited to this. 2 to 7 are explanatory views for explaining a suitable recording head in which the present invention is implemented or applied. Hereinafter, each component will be described with reference to these drawings.

  The recording head (ink cartridge) of the present invention has a configuration in which the head and the ink tank are integrated as shown in FIGS. The recording head (ink cartridge) H1001 in FIGS. 2 and 3 is mounted with three color inks of cyan ink, magenta ink, and yellow ink, respectively. The recording head H1001 is fixedly supported by positioning means and electrical contacts of a carriage mounted on the ink jet recording apparatus main body, and is detachable from the carriage. When the mounted ink is consumed, Exchanged.

Next, the recording head (ink cartridge) will be described in detail step by step for each component constituting the recording head.
[Recording head (ink cartridge)]
The illustrated recording head (ink cartridge) H1001 is a bubble jet (registered trademark) recording head that uses an electrothermal transducer that generates thermal energy for causing film boiling in ink in accordance with an electrical signal. This recording head is a so-called side shooter type recording head arranged such that the electrothermal transducer and the ink discharge port face each other. In the present invention, from the viewpoint of high-quality output on plain paper and high-speed printing, the head has a nozzle row in which 150 or more nozzles are arranged at a pitch interval of 300 dpi or more and the discharge amount of each nozzle is 30 pl or less. It is preferable. Furthermore, from the viewpoint of achieving both photo image quality and high-speed printing, it is preferable that the head has a nozzle row in which 100 or more nozzles with a discharge amount of 6 pl or less are arranged at a pitch interval of 600 dpi or more.

(1-1) Recording head (ink cartridge)
A recording head (ink cartridge) H1001 is for ejecting ink of three colors, cyan, magenta, and yellow. As shown in the exploded perspective view of FIG. 3, the recording element substrate H1101, the electric wiring tape H1301, and the ink A supply holding member H1501 is provided. Further, filters H1701, H1702, and H1703, ink absorbers H1601, H1602, and H1603, a cover member H1901, and a seal member H1801 are provided.

(1-1-1) Recording Element Substrate FIG. 4 is a partially broken perspective view for explaining the configuration of the recording element substrate H1101, and includes three ink supply ports H1102 for cyan, magenta, and yellow. Are formed in parallel. Electrothermal conversion elements H1103 and discharge ports H1107 are arranged in a row in a staggered manner on both sides of each ink supply port H1102. On the silicon substrate H1110, electrical wiring, fuses, electrode portions H1104, and the like are formed. An ink flow path wall H1106 and an ejection port H1107 are formed thereon by a photolithography technique using a resin material, and a bump H1105 such as Au is formed on the electrode portion H1104 for supplying power to the electrical wiring. Yes.

(1-1-2) Nozzle Structure FIG. 5 is a diagram schematically showing a nozzle portion provided in an inkjet head to which the ink according to the present invention is applied. FIG. 5A is a diagram showing the nozzle shape when viewed from the discharge port side of the nozzle. FIG. 5B is a view showing a cross section taken along the broken line XY in FIG. In FIG.5 (b), H2101 shows a silicon substrate and H2102 shows the thermal storage layer which consists of a thermal oxidation layer. H2103 is an interlayer made of a silicon oxide layer or nitride layer that also serves as a heat storage, H2104 is a heating resistance layer, and H2105 is a wiring made of a metal material such as Al, Al-Si, and Al-Cu. This is a metal wiring layer. H2106 represents a protective layer that also functions as an insulating layer including a silicon oxide layer, a nitride layer, a carbide layer, and the like. In particular, since the protective layer H2106 is in direct contact with the ink, it is chemically stable against alkali and the like, and is required to have sufficient resistance against physical impact, and also has electrical insulation. There is a high need to combine them. Therefore, in particular, a silicon nitride layer or a carbide layer can be suitably used as the forming material. H2107 is a heat generating portion, and heat generated by the heat generating resistor of the heat generating resistance layer H2104 acts on the ink.

  The heat generating portion H2107 in the ink jet head is a portion that is exposed to high temperature due to heat generation by the heat generating resistor, and that is mainly subjected to cavitation impact and chemical action due to ink as the ink foams and the foam shrinks after foaming. . For this reason, the heat generating portion H2107 is provided with a protective layer H2106 in order to protect the electrothermal conversion element from this cavitation impact and chemical action by ink. The thickness of the protective layer H2106 is from the viewpoint of the thermal conversion efficiency important for efficiently converting the electric pulse applied to the heating resistor, the physical impact of the ink accompanying the foaming phenomenon, and the protection against chemical corrosion. 50 nm to 500 nm is a preferred range.

  That is, if the layer thickness is less than 50 nm, the discharge durability of the heat generating part is insufficient, or the influence of fluctuations in the input energy becomes sensitive to the layer thickness change due to the dissolution of the protective layer due to storage. Sometimes. On the other hand, when the layer thickness exceeds 500 nm, a large amount of energy is required for foaming, and when the nozzles are arranged at a high density and the discharge frequency is increased, the temperature of the nozzle tends to increase. Furthermore, in the present invention, the thickness of the protective layer is particularly preferably 100 nm or more and 450 nm or less in order to further increase the number of nozzles, increase the density, and provide high durability. On the protective layer H2106, a discharge element including a discharge port H2109 for discharging ink is formed using a flow path forming member H2108.

  The hatched portion H2110 in FIGS. 5A and 5B is a liquid chamber portion of the nozzle portion that is filled with ink. Ink is supplied from a common liquid chamber of H2111 arranged on the right side of the nozzle portion, and after foaming and forming bubbles in the heat generating portion H2107, the ink is pushed out from the discharge port H2109 and discharged as ink droplets.

(1-1-3) Electric Wiring Tape The electric wiring tape H1301 forms an electric signal path for applying an electric signal for ejecting ink to the recording element substrate H1101, and incorporates the recording element substrate. The opening is formed. Near the edge of the opening, an electrode terminal H1304 connected to the electrode portion H1104 of the recording element substrate is formed. The electrical wiring tape H1301 is formed with an external signal input terminal H1302 for receiving an electrical signal from the main unit, and the electrode terminal H1304 and the external signal input terminal H1302 are connected by a continuous copper foil wiring pattern. Yes.

  The electrical connection between the electric wiring tape H1301 and the second recording element substrate 1101 is made by electrically bonding the bump H1105 and the electrode terminal H1304 by a thermal ultrasonic pressure bonding method. The bump H1105 is formed on the electrode portion H1104 of the second recording element substrate H1101, and the electrode terminal H1304 is formed on the electric wiring tape H1301 corresponding to the electrode portion H1104 of the second recording element substrate H1101.

(1-1-4) Ink Supply Holding Member The ink supply holding member H1501 is formed by resin molding, and as a constituent material, for example, thermoplasticity that can be molded by injection molding, compression molding, thermoforming, or the like is possible. A resin material can be suitably used. Suitable thermoplastic resins include, but are not limited to, polyesters, polycarbonates, polypropylenes, polyethylenes, polystyrenes, polyphenylene ethers, and mixtures and modifications thereof. Of these, polyphenylene ether is preferable, and an alloy of polyphenylene ether and a styrene material is particularly preferable. Alloys of polyphenylene ether and polyphenylene ether and styrene-based materials are excellent in moldability and heat resistance, and are therefore very preferably used in the ink cartridge as in the present invention. In addition, since these materials have relatively high gas permeability, the present invention works extremely effectively. As the resin material, it is preferable to use a thermoplastic resin material in which a filler is mixed in an amount of 5 to 40% by mass from the viewpoint of improving the shape rigidity and suppressing gas permeability. Preferred fillers are not limited to inorganic materials, but include glass, silica or graphite (graphite). In the case where the recording head is directly mounted on the ink supply holding member as in this embodiment, the ink resistance and the welding property, and the adhesive expansion with the adhesive and the thermal expansion due to heat are high. As required. From the viewpoint of the balance of these required performances, a resin material obtained by mixing a filler as described above into an alloy of polyphenylene ether and styrene-based material is particularly preferable.

  As shown in FIG. 3, the ink supply holding member H1501 holds the absorbers H1601, H1602, and H1603 for generating negative pressure for holding cyan, magenta, and yellow inks therein independently. It has a space. The ink supply holding member H1501 further includes an ink supply function for forming an independent ink flow path for introducing ink to each ink supply port H1102 of the recording element substrate H1100. Ink absorbers H1601, H1602, and H1603 are preferably compressed PP (polypropylene) fibers, but may be compressed urethane fibers. Filters H1701, H1702, and H1703 for preventing dust from entering the inside of the recording element substrate H1101 are joined to the boundary portions with the ink absorbers H1601, H1602, and H1603 in the upstream portion of each ink flow path by welding. . Each filter H1701, H1702, and H1703 may be a SUS metal mesh type, but a SUS metal fiber sintered type is preferred.

In the present invention, it is preferable that the shape of the ink supply holding member is such that the area of the surface where the ink can be evaporated is substantially the same for each liquid chamber, as shown in FIG. This is because the amount of ink evaporation in each liquid chamber can be made uniform to some extent, and the evaporation tends to be uniform for each ink. Specifically, when designing a plurality of liquid chambers, the ratio β / α of the area βcm ² of the surface in which the ink in each liquid chamber can evaporate with respect to the volume αcm ³ of each liquid chamber constituting the ink cartridge. Of these, it is preferable that the difference between the maximum value and the minimum value be 0.5 or less. The surface on which the ink can evaporate means a surface on which the ink can evaporate through a member existing between the ink and the atmosphere. For example, the outer wall surface of the ink jet cartridge shown in FIG. 3 is a surface on which ink can be evaporated, but the surface between the ink liquid chamber and the ink liquid chamber prevents ink from being evaporated by the adjacent ink, so that the ink can be evaporated. It ’s not like that. As a specifically preferable liquid chamber, according to the study by the present inventors, for example, in the case of an ink cartridge containing three colors of ink, the liquid chamber divided into T-shapes as shown in FIG. Structure is mentioned. Such a structure is preferable because it is easy to arrange so that the balance between the volume α of each liquid chamber and the area β of the evaporable surface is uniform between the liquid chambers.

  An ink supply port H1201 for supplying cyan, magenta, and yellow ink to the recording element substrate H1101 is formed in the downstream portion of the ink flow path. The recording element substrate H1101 is bonded and fixed to the ink supply holding member H1501 with high positional accuracy so that each ink supply port 1102 of the recording element substrate H1101 communicates with each ink supply port H1201 of the ink supply holding member H1501. The first adhesive used for the bonding is preferably a low viscosity, low curing temperature, cured in a short time, has a relatively high hardness after curing, and has ink resistance. For example, a thermosetting adhesive mainly composed of an epoxy resin is used as the first adhesive, and the thickness of the adhesive layer at that time is preferably about 50 μm.

  Further, a part of the back surface of the electric wiring tape H1301 is bonded and fixed to the plane around the ink supply port H1201 by the second adhesive. The electrical connection portion between the second recording element substrate H1101 and the electrical wiring tape H1301 is sealed with a first sealant H1307 and a second sealant H1308 (see FIG. 7), and the electrical connection portion is made of ink. Protected against corrosion and external impacts. The first sealing agent H1307 mainly seals the back surface side of the connection portion between the electrode terminal H1302 of the electric wiring tape H1300 and the bump H1105 of the recording element substrate and the outer peripheral portion of the recording element substrate, and the second sealing agent. The agent H1308 seals the front side of the connection portion described above. The unbonded portion of the electric wiring tape H1301 is bent and fixed to the side surface of the ink supply holding member H1501 that is substantially orthogonal to the surface having the ink supply port H1201 by heat caulking or bonding.

(1-1-5) Lid Member The lid member H1901 is welded to the upper opening of the ink supply holding member H1501, thereby closing the independent spaces inside the ink supply holding member H1501. However, the lid member H1901 has narrow ports H1911, H1912, and H1913 for releasing pressure fluctuations in the respective chambers inside the ink supply holding member H1501, and fine grooves H1921, H1922, and H1923 that communicate with the narrow ports. The other ends of the fine grooves H1921 and H1922 join in the middle of the fine groove H1923. Further, most of the narrow holes H1911, H1912, and H1913, the fine grooves H1921, H1922, and the fine grooves H1923 are covered with a seal member H1801, and the other end of the fine groove H1923 is opened to form an air communication port. It is preferable to form an air communication port having such a maze structure because evaporation of ink volatile components from the air communication port can be effectively suppressed. The lid member H1901 has an engaging portion H1930 for fixing the recording head to the ink jet recording apparatus.

  As the resin material used for the lid member, a resin material mixed with a filler, similar to the ink supply holding member, can be preferably used. Even when the above-mentioned resin material is used for the ink supply holding member and the lid member, moisture permeation from the resin material itself is unavoidable. Therefore, even when the above-described maze structure air communication port is provided, a certain amount of ink is used. Evaporation will occur.

(1-2) Mounting of Recording Head (Ink Cartridge) to Inkjet Recording Apparatus As shown in FIG. 2, the recording head H1001 includes a mounting guide H1560 and a headset for guiding the carriage mounting position of the inkjet recording apparatus main body. An engaging portion H1930 for mounting and fixing to the carriage by the lever is provided. Further, an abutting portion H1570 in the X direction (carriage scanning direction) for positioning at a predetermined mounting position of the carriage, an abutting portion H1580 in the Y direction (recording medium conveyance direction), and an abutting in the Z direction (ink ejection direction) Part H1590. By positioning by the abutting portion, the external signal input terminals H1302 on the electric wiring tapes H1300 and H1301 accurately make electrical contact with the contact pins of the electric connecting portion provided in the carriage.

(1-3) Recording Head Driving Method When a pulsed electric signal is applied to the metal wiring layer H2105 of the head of FIG. 5, the heat generating portion H2107 of the heat generating element substrate H2104 rapidly generates heat and comes into contact with this surface. Bubbles are generated in the ink. The meniscus is protruded by the pressure of the bubbles, and the ink is ejected through the ejection port H2109 of the head, becomes an ink droplet, and flies toward the recording medium.

[Inkjet recording device]
Next, a liquid discharge recording apparatus capable of mounting the above-described cartridge type recording head will be described. FIG. 8 is an explanatory diagram showing an example of a recording apparatus in which the liquid discharge recording head of the present invention can be mounted. In the recording apparatus shown in FIG. 8, the recording head H1001 shown in FIG. 2 is mounted on the carriage 102 so as to be replaceable, and each ejection is performed on the carriage 102 via an external signal input terminal on the recording head H1001. An electrical connection for transmitting a drive signal or the like to the unit is provided. FIG. 9 is an explanatory diagram showing an example of a recording apparatus in which the liquid discharge recording head of the present invention can be mounted. The recording apparatus illustrated in FIG. 9 is the same as the recording apparatus illustrated in FIG. 8 except that the recording apparatus includes two recording heads H1000 and H1001.

  The carriage 102 is guided and supported so as to reciprocate along a guide shaft 103 installed in the apparatus main body extending in the main scanning direction. The carriage 102 is driven by a main scanning motor 104 through driving mechanisms such as a motor pulley 105, a driven pulley 106, and a timing belt 107, and its position and movement are controlled. A home position sensor 130 is provided on the carriage 102. This makes it possible to know the position of the shielding plate 136 when the home position sensor 130 on the carriage 102 passes.

  A recording medium 108 such as a printing paper or a plastic thin plate is separated and fed one by one from an auto sheet feeder (ASF) 132 by rotating a pickup roller 131 from a paper feed motor 135 via a gear. Further, by the rotation of the conveyance roller 109, the conveyance roller 109 is conveyed (sub-scanned) through a position (printing unit) facing the discharge port surfaces of the recording heads H1000 and H1001. The conveyance roller 109 is performed via a gear by the rotation of the LF motor 134. At this time, the determination of whether or not the paper has been fed and the determination of the cueing position at the time of paper feeding are performed when the recording medium 108 passes through the paper end sensor 133. Further, the paper end sensor 133 is also used to finally determine the current recording position from the actual rear end where the rear end is located.

  The recording medium 108 is supported by a platen (not shown) on the back surface so that a flat print surface is formed in the print unit. In this case, the recording head H1001 mounted on the carriage 102 is held so that the discharge port surfaces thereof protrude downward from the carriage 102 and are parallel to the recording medium 108 between the two pairs of conveying rollers. . The recording head H1001 is mounted on the carriage 102 so that the direction in which the ejection ports are arranged in each ejection section intersects the scanning direction of the carriage 102 described above, and ejects liquid from these ejection port arrays for recording. I do.

  Hereinafter, although it demonstrates more concretely using an Example and a comparative example, this invention is not limited by the following Example, unless the summary is exceeded. In the following description, “parts” and “%” are based on mass unless otherwise specified.

（ｌ＝０〜２、ｍ＝１〜３、ｎ＝１〜３、但し、ｌ＋ｍ＋ｎ＝３〜４、ｍ≧１、置換基の置換位置は、４若しくは４’位であり、ＭはＮａである。） <Production of coloring material>
(Cyan dye 1)
Cyan dye 1 represented by the following formula was prepared as follows.

(L = 0-2, m = 1-3, n = 1-3, where l + m + n = 3-4, m ≧ 1, the substitution position of the substituent is the 4 or 4 ′ position, and M is Na. is there.)

  First, sulfolane, 4-sulfophthalic acid monosodium salt, ammonium chloride, urea, ammonium molybdate and copper (II) chloride are stirred, washed with methanol, water is added, and the solution is further added using an aqueous sodium hydroxide solution. The pH was adjusted to 11. Next, an aqueous hydrochloric acid solution was added while stirring the solution, and sodium chloride was gradually added thereto. The precipitated crystals were filtered, washed with a 20% aqueous sodium chloride solution, and subsequently methanol was added to separate the precipitated crystals. Furthermore, after washing with a 70% aqueous methanol solution and drying, copper phthalocyanine tetrasulfonic acid tetrasodium salt was obtained as blue crystals.

  Next, the copper phthalocyanine tetrasulfonic acid tetrasodium salt obtained above was gradually added to chlorosulfonic acid, and thionyl chloride was further added dropwise. The reaction solution was cooled, and the precipitated crystals were filtered to obtain a desired copper phthalocyanine tetrasulfonic acid chloride wet cake. This was suspended with stirring, and ammonia water and a compound of the following formula (α) were added. Water and sodium chloride were further added to precipitate crystals. The precipitated crystals were filtered, washed with an aqueous sodium chloride solution, again filtered, washed, and dried to obtain the coloring material of cyan dye 1 having the structure described above used in the examples.

  The compound represented by the above formula (α) was synthesized as follows. First, Lipar OH, cyanuric chloride, aniline-2,5-disulfonic acid monosodium salt was added to ice water, and an aqueous sodium hydroxide solution was added. Next, an aqueous sodium hydroxide solution was added to the reaction solution to adjust the pH to 10.0. To this reaction solution, 28% ammonia water and ethylenediamine were added. Subsequently, sodium chloride and concentrated hydrochloric acid were added dropwise to precipitate crystals. The precipitated crystals were collected by filtration and washed with a 20% aqueous sodium chloride solution to obtain a wet cake. Methanol and water were added to the obtained wet cake, filtered, washed with methanol, and dried to obtain a compound represented by the above formula (α).

(Magenta dye 1)
Magenta dye 1 represented by the following formula was produced as follows.

  A compound of the following formula (γ), sodium carbonate, and benzoyl acetate ethyl ester were reacted in xylene, and the reaction product was filtered and washed. This was sequentially charged with metaaminoacetanilide, copper acetate and sodium carbonate in N, N-dimethylformamide and reacted, and the reaction product was filtered and washed. Furthermore, it was sulfonated in fuming sulfuric acid, filtered and washed, and this was subjected to a condensation reaction with cyanuric chloride in the presence of sodium hydroxide. Anthranilic acid was added to the reaction solution, and a condensation reaction was performed in the presence of sodium hydroxide. This was filtered and washed to obtain a magenta dye 1 represented by the following formula used in Examples.

<Preparation of ink>
(Preparation of inks Y1, C1 and M1)
Using the cyan dye 1 and magenta dye 1 obtained above, various components listed in Table 2 were added in predetermined amounts in the table, and adjusted with water so that the total amount was 100 parts to prepare ink of each color. . Specifically, each component in Table 2 was mixed and sufficiently stirred to dissolve, and then pressure filtered through a micro filter (manufactured by Fuji Film) with a pore size of 0.2 μm to obtain cyan (C1), yellow (Y1 ) And magenta (M1) inks were prepared. These three types of ink before ink (hereinafter referred to as initial ink) and ink in an evaporated state (hereinafter referred to as these inks) are 10% and 15% on a mass basis. The ink density in a 25 ° C. environment was measured using a standard specific gravity meter. The results are also shown in Table 2. The ink evaporation operation for obtaining ink corresponding to 10% evaporation was performed by keeping the ink in a constant temperature and humidity state at a temperature of 30 ° C. and a humidity of 10%.

(Preparation of inks M2 to M6)
Further, magenta inks (M2 to M6) having the ink densities shown in Table 2 were produced in the same manner except that the amounts of M1 ethylene urea, 1,5-pentanediol and water prepared above were adjusted. Further, the ink density of each of the obtained five inks was measured in the same manner as described above for each of the initial ink, the ink corresponding to 10% evaporation, and the ink corresponding to 15% evaporation. Table 3 also shows the results. As is apparent from Table 3, all of these inks had initial ink densities higher than those of C1 and Y1.

<Examples 1 to 5 and Comparative Example 1>
The combinations of cyan ink C1, yellow ink Y1 and magenta ink M1 described in Table 2, cyan ink C1 and yellow ink Y1 described in Table 2, and magenta inks M2 to M6 described in Table 3 are shown in Table 4, respectively. Thus, ink sets 1 to 6 were prepared. Then, the obtained ink set was accommodated in each liquid chamber of the ink cartridge shown in FIGS. 2 and 3, and ink cartridges of Examples 1 to 5 and Comparative Example 1 were prepared. Ink cartridges 1 to 6 were prepared by storing the obtained ink in the initial state.

  Assuming that only the magenta ink of each ink set used above evaporates, a magenta ink corresponding to 10% evaporation is produced by evaporating each magenta ink constituting each ink set at a 10% evaporation rate. Then, an ink set in which magenta ink corresponding to 10% evaporation, cyan ink, and yellow ink were combined was created with the combinations shown in Table 4. Ink cartridges of Examples 1 to 5 and Comparative Example 1 were prepared by storing the obtained ink sets in the liquid chambers of the ink cartridges shown in FIGS. Ink cartridges 7 to 12 were prepared by storing magenta ink corresponding to 10% evaporation.

  Assuming that only the magenta ink of each ink set used above evaporates, a magenta ink corresponding to 15% evaporation was prepared by evaporating each magenta ink constituting each ink set at a 15% evaporation rate. Then, an ink set in which magenta ink corresponding to 15% evaporation, cyan ink, and yellow ink were combined was created with the combinations shown in Table 4. Ink cartridges of Examples 1 to 5 and Comparative Example 1 were prepared by storing the obtained ink sets in the liquid chambers of the ink cartridges shown in FIGS. Ink cartridges 13 to 18 were prepared by storing magenta ink corresponding to 15% evaporation. The ink supply holder (ink cartridge housing) is composed of a material made of a styrene-based material and a polyphenylene ether alloy containing 35% filler, and the ink absorber is made of polypropylene. Yes, as shown in FIG. 2 and FIG. 3, it is hermetically sealed with a lid forming material having an atmosphere communication path with a maze structure.

(Evaluation)
A 100% solid patch and gradation of CMYRGB (cyan, magenta, yellow, red, green, blue) using the ink cartridges 1 to 18 of Examples 1 to 5 and Comparative Example 1 and the recording apparatus shown in FIG. An image was output. In the obtained image, all the solid portions and gradation portions of the respective colors of the ink cartridges 1 to 6 in which the ink in the initial state is stored and the ink cartridges 7 to 18 in which the evaporated magenta ink is stored are stored. The color difference of the image was visually evaluated according to the following evaluation criteria. The obtained results are shown in Table 5.

○: Color difference is hardly understood.
Δ: There is a slight color difference.
X: Color difference is large.

<Examples 6 to 10 and Comparative Example 2>
Combinations of cyan ink C1, yellow ink Y1 and magenta ink M1 described in Table 2, cyan ink C1 and yellow ink Y1 described in Table 2, and magenta inks M2 to M6 described in Table 3 are shown in Table 6. Thus, ink sets 1 to 6 were prepared. Then, the obtained ink set was accommodated in each liquid chamber of the ink cartridge shown in FIGS. 2 and 3, and ink cartridges of Examples 6 to 10 and Comparative Example 2 were prepared. Ink cartridges 1 to 6 were prepared by storing the obtained ink in the initial state.

  Assuming that all the inks constituting each ink set used above evaporated uniformly, 10% evaporation equivalent ink was prepared by evaporating each ink constituting each ink set at a 10% evaporation rate. Then, an ink set in which magenta ink corresponding to 10% evaporation, cyan ink, and yellow ink were combined was created with the combinations shown in Table 6. Ink cartridges of Examples 6 to 10 and Comparative Example 2 were prepared by storing the obtained ink sets in the liquid chambers of the ink cartridges shown in FIGS. Ink cartridges 19 to 24 were prepared by storing these inks corresponding to 10% evaporation.

  Assuming the case where all the inks constituting each ink set used above evaporated uniformly, 15% evaporation equivalent ink was prepared by evaporating each ink constituting each ink set at a 15% evaporation rate. Then, an ink set in which magenta ink corresponding to 15% evaporation, cyan ink, and yellow ink were combined was created with the combinations shown in Table 6. Ink cartridges of Examples 6 to 10 and Comparative Example 2 were prepared by storing the obtained ink sets in the liquid chambers of the ink cartridges shown in FIGS. The ink cartridges 25 to 30 were prepared by storing these inks corresponding to 15% evaporation. The ink supply holder (ink cartridge housing) is composed of a material made of a styrene-based material and a polyphenylene ether alloy containing 35% filler, and the ink absorber is made of polypropylene. Yes, as shown in FIG. 2 and FIG. 3, it is hermetically sealed with a lid forming material having an atmosphere communication path with a maze structure.

(Evaluation)
100% solid patch and gradation image of CMYRGB (cyan, magenta, yellow, red, green, blue) using the initial and evaporative ink cartridges of Examples 6 to 10 and Comparative Example 2 and the recording apparatus shown in FIG. Was output. Then, the solid portions of the respective colors of the images of both the ink cartridges 1 to 6 that store the ink in the initial state and the ink cartridges 19 to 30 that store the ink evaporated at the evaporation rate of 10% or 15%. And the color difference of the gradation part was visually evaluated according to the following evaluation criteria. The results obtained are shown in Table 7.

○: Color difference is hardly understood.
Δ: There is a slight color difference.
X: Color difference is large.

<Examples 11 to 14>
10 is a form of an ink cartridge (a) having a liquid chamber structure in which the inside is divided into T-shapes, and the surface area βcm of the portion exposed to the atmosphere of each liquid chamber with respect to the volume αcm ³ of each liquid chamber Three types of ink cartridges of the form of FIGS. 2 and 3 were prepared in which the difference between the maximum value and the minimum value of the ratio β / α of ² was 0.4, 0.5, and 0.6, respectively. In these liquid chambers, the cyan ink C1, the yellow ink Y1, and the magenta ink M4 were accommodated as shown in Table 8, and ink cartridges 31 to 33 of Examples 11 to 13 were produced. 10 is an ink cartridge (b) having a structure in which each liquid chamber shown in FIG. 10 is divided in parallel, and the ink in each liquid chamber can evaporate with respect to the volume αcm ³ of each liquid chamber. An ink cartridge having the form shown in FIGS. 2 and 3 was prepared in which the difference between the maximum value and the minimum value of the ratio β / α of the surface area βcm ² was 0.8. In the same manner as described above, cyan ink C1, yellow ink Y1 and magenta ink M4 were respectively stored in these liquid chambers as shown in Table 8 to produce an ink cartridge 34 of Example 14.

  In any of the ink cartridges, the magenta ink M4 was accommodated in the liquid chamber having the largest β / α, and the yellow ink Y1 was accommodated in the liquid chamber having the smallest β / α. Further, assuming that only magenta ink was used extremely, 1 ml of magenta ink M4 was accommodated in each ink cartridge, and 10 ml of the other inks were accommodated. The ink supply holder (ink cartridge housing) is composed of a material made of a styrene-based material and a polyphenylene ether alloy containing 35% filler, and the ink absorber is made of polypropylene. Yes, as shown in FIG. 2 and FIG. 3, it is hermetically sealed with a lid forming material having an atmosphere communication path with a maze structure.

  Using these ink cartridges 31 to 34 of Examples 11 to 14, a 100% solid patch and gradation image of CMYRGB were output by the recording apparatus shown in FIG. 8 to obtain an image of the initial ink cartridge. After printing, the head part was capped with a separate recovery unit jig and left in a constant temperature and humidity chamber at 60 ° C. Dry for 10 days. After leaving, the ink cartridge was removed from the recovery unit jig, and a 100% solid patch of CMYRGB and a gradation image were output in the same manner as an image of the evaporated ink cartridge. The output images of the initial ink cartridge and the evaporated ink cartridge thus obtained were compared, and the color difference between the solid portion and the gradation portion of each color was visually evaluated according to the following evaluation criteria. The obtained results are shown in Table 9. Further, the evaporation rate of each ink was determined by the evaporation test from the absorbance measurement of each ink at the initial stage and after the evaporation, and is shown in Table 9.

  From the above results, it is clear that when the difference between the maximum value and the minimum value of β / α is 0.5 or less, the evaporation rates of the respective inks are relatively uniform, and the color difference between the initial output image and the output image after evaporation is small. . It is also clear that it is relatively preferable that the ink cartridge has a T-shaped division as the liquid chamber configuration.

[Evaluation of gray image using cyan ink, magenta ink and yellow ink]
(Preparation of inks M7 to M11)
Magenta inks (M7 to M11) having the ink densities shown in Table 10 were prepared in the same manner except that the amounts of ethylene urea, 1,5-pentanediol and water of the ink M1 were adjusted. All of these inks had initial densities higher than those of C1 and Y1.

<Examples 15 to 20>
The combinations of cyan ink C1, yellow ink Y1 and magenta ink M1 described in Table 2, cyan ink C1 and yellow ink Y1 described in Table 2, and magenta inks M7 to M11 described in Table 10 are shown in Table 11. Thus, an ink set was created by combining them. Then, the obtained ink set was accommodated in each liquid chamber of the ink cartridge shown in FIGS. 2 and 3, and ink cartridges of Examples 15 to 20 were produced. The ink cartridges 35 to 40 were prepared by storing the obtained ink in the initial state.

  Assuming that only the magenta ink of each ink set used above evaporates, a magenta ink corresponding to 10% evaporation is produced by evaporating each magenta ink constituting each ink set at a 10% evaporation rate. Then, an ink set was prepared by combining the magenta ink corresponding to 10% evaporation, the cyan ink, and the yellow ink in combinations shown in Table 11. The obtained ink sets were respectively stored in the liquid chambers of the ink cartridges shown in FIGS. 2 and 3 in the same manner as described above, thereby producing ink cartridges of Examples 15 to 20. The ink cartridges 41 to 46 were prepared by storing magenta ink corresponding to 10% evaporation.

  Assuming that only the magenta ink of each ink set used above evaporates, a magenta ink corresponding to 15% evaporation was prepared by evaporating each magenta ink constituting each ink set at a 15% evaporation rate. Then, an ink set was prepared by combining the magenta ink corresponding to 15% evaporation, the cyan ink, and the yellow ink in combinations shown in Table 11. The obtained ink sets were housed in the liquid chambers of the ink cartridges shown in FIGS. 2 and 3 in the same manner as described above, and ink cartridges of Examples 15 to 20 were produced. Ink cartridges 47 to 52 were prepared by storing magenta ink corresponding to 15% evaporation. The ink supply holder (ink cartridge housing) is composed of a material made of a styrene-based material and a polyphenylene ether alloy containing 35% filler, and the ink absorber is made of polypropylene. Yes, as shown in FIG. 2 and FIG. 3, it is hermetically sealed with a lid forming material having an atmosphere communication path with a maze structure.

(Evaluation)
Using the above-described ink cartridges 35 to 52 of Examples 15 to 20 and using the recording apparatus shown in FIG. 8, a gray solid patch image is output every 10% from 60% to 100% as a high image density gray image. . Further, a gray solid patch image was output every 10% from 10% to 50% as a low image density gray image. For the obtained image, the color difference between the images of both the ink cartridges 35 to 40 in which the ink in the initial state is stored and the ink cartridges 41 to 46 in which the evaporated magenta ink is stored is evaluated according to the following evaluation criteria. It evaluated visually. A professional photo paper PR101 manufactured by Canon Inc. was used as the recording medium. The obtained results are shown in Table 12.

○: Color difference is hardly understood.
Δ: There is a slight color difference.
X: Color difference is large.

尚、実施例１５〜２０の「初期状態（Ｎｏ３５〜４０）と、１０％蒸発相当Ｍインク収容（Ｎｏ４１〜４６）の色差」を、各色（ＣＭＹ）ベタと２次色（ＲＧＢ）ベタについて同様の評価をしたところ、何れも「色差がほとんど分からない」という結果となった。

It should be noted that the “color difference between the initial state (No. 35 to 40) and the 10% evaporation equivalent M ink storage (No. 41 to 46)” in Examples 15 to 20 is the same for each color (CMY) solid and secondary color (RGB) solid. As a result of the evaluation, all the results showed that “the color difference was hardly understood”.

<Examples 21 to 26>
Combinations of cyan ink C1, yellow ink Y1 and magenta ink M1 described in Table 2, cyan ink C1 and yellow ink Y1 described in Table 2, and magenta inks M7 to M11 described in Table 10 are respectively shown in Table 13. Thus, an ink set was created by combining them. Then, the obtained ink set was accommodated in each liquid chamber of the ink cartridge shown in FIGS. 2 and 3, and ink cartridges of Examples 21 to 6 were produced. The ink cartridges 35 to 40 were prepared by storing the obtained ink in the initial state.

  Assuming that all the inks constituting each ink set used above evaporated uniformly, 10% evaporation equivalent ink was prepared by evaporating each ink constituting each ink set at a 10% evaporation rate. Then, an ink set in which magenta ink corresponding to 10% evaporation, cyan ink, and yellow ink were combined was created with the combinations shown in Table 13. The obtained ink sets were housed in the liquid chambers of the ink cartridges shown in FIGS. 2 and 3 in the same manner as described above, and ink cartridges of Examples 21 to 26 were produced. The ink cartridges 53 to 58 were prepared by storing these inks corresponding to 10% evaporation.

  Assuming the case where all the inks constituting each ink set used above evaporated uniformly, 15% evaporation equivalent ink was prepared by evaporating each ink constituting each ink set at a 15% evaporation rate. Then, an ink set in which magenta ink corresponding to 15% evaporation, cyan ink, and yellow ink were combined was created with the combinations shown in Table 13. The obtained ink sets were housed in the liquid chambers of the ink cartridges shown in FIGS. 2 and 3 in the same manner as described above, and ink cartridges of Examples 21 to 26 were produced. The ink cartridges 59 to 64 were prepared by storing these inks corresponding to 15% evaporation. The ink supply holder (ink cartridge housing) is composed of a material made of a styrene-based material and a polyphenylene ether alloy containing 35% filler, and the ink absorber is made of polypropylene. Yes, as shown in FIG. 2 and FIG. 3, it is hermetically sealed with a lid forming material having an atmosphere communication path with a maze structure.

(Evaluation)
Using the initial and evaporative ink cartridges of Examples 21 to 26, the recording apparatus shown in FIG. 8 was used to output a gray solid patch image every 10% from 60% to 100% as a high image density gray image. Further, a gray solid patch image was output every 10% from 10% to 50% as a low image density gray image. Then, the color difference between the images of the ink cartridges 35 to 40 that store the ink in the initial state and the ink cartridges 53 to 64 that store the ink evaporated at the evaporation rate of 10% or 15% is shown below. It evaluated visually by the evaluation criteria. A professional photo paper PR101 manufactured by Canon Inc. was used as the recording medium. The obtained results are shown in Table 14.

○: Color difference is hardly understood.
Δ: There is a slight color difference.
X: Color difference is large.

尚、実施例２１〜２６の「初期状態（Ｎｏ３５〜４０）と、１０％蒸発相当Ｍインク収容（Ｎｏ５３〜５８）の色差」を、各色（ＣＭＹ）ベタと２次色（ＲＧＢ）ベタについて同様の評価をしたところ、何れも「色差がほとんど分からない」という結果となった。

It should be noted that the “color difference between the initial state (No. 35 to 40) and the 10% evaporation equivalent M ink storage (No. 53 to 58)” in Examples 21 to 26 is the same for each color (CMY) solid and secondary color (RGB) solid. As a result of the evaluation, all the results showed that “the color difference was hardly understood”.

<Examples 27 to 29>
10 is a form of an ink cartridge (a) having a liquid chamber structure in which the inside is divided into T-shapes, and the surface area βcm of the portion exposed to the atmosphere of each liquid chamber with respect to the volume αcm ³ of each liquid chamber Three types of ink cartridges of the form of FIGS. 2 and 3 were prepared in which the difference between the maximum value and the minimum value of the ratio β / α of ² was 0.4, 0.5, and 0.6, respectively. Then, the cyan ink C1, the yellow ink Y1, and the magenta ink M9 were respectively stored in the liquid chambers of these ink cartridges as shown in Table 15, and ink cartridges 65 to 67 of Examples 27 to 29 were produced. In any ink cartridge, the magenta ink M9 was accommodated in the liquid chamber having the largest β / α, and the yellow ink Y1 was accommodated in the liquid chamber having the smallest β / α. Further, assuming that only magenta ink was used extremely, 1 ml of magenta ink M9 was accommodated in each ink cartridge, and 10 ml of other inks were accommodated. The ink supply holder (ink cartridge housing) is composed of a material made of a styrene-based material and a polyphenylene ether alloy containing 35% filler, and the ink absorber is made of polypropylene. Yes, as shown in FIG. 2 and FIG. 3, it is hermetically sealed with a lid forming material having an atmosphere communication path with a maze structure.

  Using these ink cartridges 65 to 67 of Examples 27 to 29, the recording apparatus shown in FIG. 8 is used to output a gray solid patch image every 10% from 60% to 100% as a high image density gray image. did. Further, as a low image density gray image, a gray solid patch image was output every 10% from 10% to 50%, and an initial ink cartridge image was obtained. After printing, the head part was capped with a separate recovery unit jig and left in a constant temperature and humidity chamber at 60 ° C. Dry for 10 days. After leaving, the ink cartridge was removed from the recovery unit jig, and a gray solid patch image was output every 10% from 60% to 100% as a high image density gray image in the same manner as described above. Further, a gray solid patch image is output every 10% from 10% to 50% as a low image density gray image, and each is an image of the evaporating ink cartridge. The output images of the initial ink cartridge and the evaporated ink cartridge thus obtained were compared, and the color difference of the image was visually evaluated according to the following evaluation criteria. The obtained results are shown in Table 16. Further, the evaporation rate of each ink was determined by the evaporation test from the absorbance measurement of each ink in the initial stage and after the evaporation, and is shown in Table 16.

  From the above results, using the ink cartridge in the T-divided liquid chamber form, the evaporation rate of each ink is relatively uniform when the difference between the maximum value and the minimum value of β / α is 0.5 or less. It is clear that the color difference of the output image after evaporation is small.

[Evaluation of gray image using light cyan ink, light magenta ink and yellow ink]
(Preparation of ink LC1 and LM1)
Using the dyes prepared above, various components listed in Table 17 were added in predetermined amounts in the table, and ink was prepared by adjusting with water so that the total amount was 100 parts. Specifically, each component in Table 17 was mixed and sufficiently stirred and dissolved, and then pressure filtered through a microfilter (made by Fuji Film) having a pore size of 0.2 μm to obtain light cyan ink (LC1), light Each ink of magenta ink (LM1) was prepared. As shown in Table 17, the yellow ink is the same ink as the ink Y1 prepared previously. These three types of ink before evaporation, and 10% evaporation equivalent ink and 15% evaporation equivalent ink in a state where the ink reduction amount is 10% and 15% on a mass basis. About each, the density of the ink in 25 degreeC environment was measured using the standard specific gravity meter. The results are also shown in Table 17. The ink evaporation operation for obtaining ink corresponding to 10% evaporation was performed by maintaining the ink in a constant temperature and humidity state at a temperature of 30 ° C. and a humidity of 15%.

(Preparation of inks LM2 to LM6)
Further, light magenta inks (LM2 to LM6) having an initial density at 25 ° C. shown in Table 18 were prepared by adjusting the amount of solvent and water other than LM1 acetylenol E100 prepared above. Further, the ink density of each of the three types of inks obtained was measured for each of the ink corresponding to 10% evaporation and the ink corresponding to 15% evaporation in the same manner as described above. Table 18 also shows the results.

(Examples 30 to 35)
Of the light magenta inks LM1 to LM6, the light cyan ink LC1, and the yellow ink Y1 produced above, the one with the highest initial density is the yellow ink (see Tables 17 and 18). This is because the color material content is higher than that of other light inks. For this reason, when only the yellow ink Y1 of the above inks is evaporated, the difference in density appears remarkably. Therefore, assuming that only yellow ink has evaporated, yellow ink corresponding to 10% evaporation and yellow ink corresponding to 15% evaporation were produced. Using these inks, ink sets 68 to 73 according to Examples and Comparative Examples, which are composed of light cyan ink, light magenta ink, and black ink, were produced with combinations shown in Table 17. In addition, ink sets A to C having the combinations shown in Table 19 were prepared when composed of cyan ink, magenta ink, and yellow ink used together with these ink sets 68 to 73. In the table, BCI-6Bk represents BCI-6 black ink manufactured by Canon Inc., BCI-6C represents BCI-6 cyan ink manufactured by Canon Inc., and BCI-6M represents BCI-6M. Each represents BCI-6 magenta ink manufactured by Canon Inc.

  These ink sets 68 to 73 are accommodated in the respective liquid chambers of the ink cartridge shown in FIGS. 2 and 3, and the ink sets A to C used together therewith are the respective liquid chambers of the ink cartridge shown in FIGS. 2 and 3. These were used to form images, and the effects on color balance due to changes in ink properties were verified. Table 20 shows combinations of ink cartridges used in the examination. The ink cartridges 68 to 73 are ink cartridges in which the inks constituting the ink sets 68 to 73 are stored as inks in the initial state. In addition, assuming that the ink cartridge 74 contains the ink set A and the yellow ink Y1 of the three color inks of the ink set A evaporates 10%, the ink cartridge 75 contains the ink set B. Assuming that only the yellow ink Y1 of the three color inks of the ink set A evaporates by 15%, the ink cartridge 76 containing the ink set C was used. The ink supply holder (ink cartridge housing) is composed of a material made of a styrene-based material and a polyphenylene ether alloy containing 35% filler, and the ink absorber is made of polypropylene. Yes, as shown in FIG. 2 and FIG. 3, it is hermetically sealed with a lid forming material having an atmosphere communication path with a maze structure.

(Evaluation)
The ink cartridges 68 to 73 were mounted on the recording apparatus H1000 shown in FIG. 9, and the ink cartridges 74 to 76 used together were mounted on the recording apparatus H1001 shown in FIG. 9 to perform image formation. First, a color table was prepared in which the printing of each color was adjusted so as to form a gray line using yellow ink, light cyan ink, and light magenta ink in the initial state. Using this color table, a gray solid patch gradation image was output using light cyan ink, light magenta ink, and yellow ink contained in the ink cartridge. In each case, an image obtained when the cartridges 68 to 73 and the cartridge 74 containing the ink in the initial state are used, and the cartridge 75 containing the ink of the cartridges 68 to 73 and the ink Y1 corresponding to 10% evaporation. The color difference when compared with the image obtained when using the ink of the above, or the image obtained when using the cartridge 76 in which the ink in the cartridges 68 to 73 and the ink Y1 equivalent to 15% evaporation are stored The OD difference at the print density causing the maximum OD difference and the color difference at the print density causing the maximum color difference were evaluated according to the following evaluation criteria. The results are shown in Table 21. The OD value and hue were measured using Spectrolino manufactured by GretagMacbeth, and the color difference was calculated using them.

(OD difference)
○: The maximum OD difference is less than 0.1 compared to the initial value.
Δ: The maximum OD difference is 0.1 or more and less than 0.2 compared to the initial value.
X: The maximum OD difference is 0.2 or more compared to the initial value.
(Color difference)
○: The maximum color difference is less than 4 compared to the initial value.
Δ: Maximum color difference of 4 or more and less than 8 compared to the initial value.
X: The maximum color difference is 8 or more compared to the initial value.

尚、実施例３０〜３５の各色（淡Ｃ、淡Ｍ、Ｙ）ベタと２次色（ＲＧＢ）ベタについて、「初期と１０％蒸発後のＯＤ差」及び「初期と１０％蒸発後の色差」を、同様の評価をしたところ、何れも上記○評価相当という結果となった。

For each color (light C, light M, Y) solid and secondary color (RGB) solid in Examples 30 to 35, “OD difference after initial and 10% evaporation” and “color difference after initial and 10% evaporation”. ”Was evaluated in the same manner, all of the results were equivalent to the above ○ evaluation.

<Examples 36 to 41>
Next, assuming that the inks constituting the ink sets 68 to 73 and the ink set A are evenly evaporated, each ink is evaporated at a 10% evaporation rate under the above-described conditions, and the ink corresponding to 10% evaporation is obtained. Was made. Ink sets 74 to 85 composed of light cyan ink, light magenta ink, and black ink, which are used in Examples and Comparative Examples, in combination as shown in Table 22, using the obtained ink corresponding to 10% evaporation, and these Ink sets D and E composed of cyan ink, magenta ink, and yellow ink used together with the ink were prepared. BCI-6Bk is a BCI-6 black ink manufactured by Canon Inc., BCI-6C is a BCI-6 cyan ink manufactured by Canon Inc., and BCI-6M is a BCI-6 magenta manufactured by Canon Inc. Each represents ink.

  The ink sets 68 to 73 shown in Table 19 are stored in the liquid chambers of the ink cartridges shown in FIGS. 2 and 3, respectively, and the ink set A is stored in the liquid chambers of the ink cartridges shown in FIGS. Thus, ink cartridges 68 to 73 and an ink cartridge 74 composed of the initial state inks of Examples 36 to 41 and Comparative Example 6 shown in Table 23 were produced. Further, assuming that all of the inks constituting the ink sets 68 to 73 and the ink set A are uniformly evaporated by 10%, the ink sets 74 to 79 configured by ink corresponding to 10% evaporation shown in Table 22 are shown in FIG. The ink cartridges 77 to 82 were accommodated in the liquid chambers of the ink cartridge shown in FIG. Also, the ink set D shown in Table 7 used together with this was accommodated in each liquid chamber of the ink cartridge shown in FIGS. Further, assuming that all the ink sets are uniformly evaporated by 15%, the ink sets 80 to 85 shown in Table 22 are respectively accommodated in the liquid chambers of the ink cartridges shown in FIGS. 83-88. Also, the ink set E shown in Table 22 used together with this was accommodated in each liquid chamber of the ink cartridge shown in FIGS. The ink supply holder (ink cartridge housing) is composed of a material made of a styrene-based material and a polyphenylene ether alloy containing 35% filler, and the ink absorber is made of polypropylene. Yes, as shown in FIG. 2 and FIG. 3, it is hermetically sealed with a lid forming material having an atmosphere communication path with a maze structure.

(Evaluation)
The ink cartridges 68 to 73, 77 to 82, and 83 to 88 are mounted on the recording apparatus H1000 shown in FIG. 9, while the ink cartridges 74, 89, and 90 used together are included in the recording apparatus H1001 shown in FIG. It was mounted and image formation was performed. Using the color table described above, a gray solid patch gradation image was output using light cyan ink, light magenta ink, and yellow ink contained in these ink cartridges. In each case, an image obtained when the cartridges 68 to 73 and the cartridge 74 containing the ink in the initial state are used, and the cartridges 77 to 82 and the cartridge 89 containing the ink corresponding to 10% evaporation are used. Color difference when compared with the image obtained in this case, or the maximum OD when compared with the image obtained when using the cartridges 83 to 88 and the cartridge 90 containing the ink corresponding to 15% evaporation The OD difference at the print density causing the difference and the color difference at the print density causing the maximum color difference were evaluated based on the same evaluation criteria as described above. The results are shown in Table 24. The OD value and hue were measured using Spectrolino manufactured by GretagMacbeth, and the color difference was calculated using them.

尚、実施例３６〜４１の各色（淡Ｃ、淡Ｍ、Ｙ）ベタと２次色（ＲＧＢ）ベタについて、「初期と１０％蒸発後のＯＤ差」及び「初期と１０％蒸発後の色差」を、同様の評価をしたところ、何れも上記○評価相当という結果となった。

For each color (light C, light M, Y) solid and secondary color (RGB) solid of Examples 36 to 41, “OD difference after initial and 10% evaporation” and “color difference after initial and 10% evaporation”. ”Was evaluated in the same manner, all of the results were equivalent to the above ○ evaluation.

<Examples 42 to 45>
10 is a form of an ink cartridge (a) having a liquid chamber structure in which the inside is divided into T-shapes, and the surface on which the ink in each liquid chamber can evaporate with respect to the volume αcm ³ of each liquid chamber. ^Two types of ink cartridges of the form of FIG. 2 were prepared in which the difference between the maximum value and the minimum value of the ratio β / α of the area βcm ² was 0.4, 0.5, and 0.6. Then, the light cyan ink LC1, the yellow ink Y1, and the light magenta ink LM5 were accommodated in the liquid chambers as shown in Tables 25 and 26, respectively, and ink cartridges 91 to 94 of Examples 42 to 44 were produced.

10 is an ink cartridge (b) having a structure in which each liquid chamber shown in FIG. 10 is divided in parallel, and the ink in each liquid chamber can evaporate with respect to the volume αcm ³ of each liquid chamber. An ink cartridge of the form shown in FIG. 2 was prepared in which the difference between the maximum value and the minimum value of the ratio β / α of the surface area βcm ² was 0.8. Then, as described above, the light cyan ink LC1, yellow ink Y1, and light magenta ink LM6 were accommodated in the liquid chambers as shown in Table 25 and Table 26, respectively, and an ink cartridge 94 of Example 45 was produced.

  In any ink cartridge, the yellow ink Y1 was accommodated in the liquid chamber having the largest β / α, and the light magenta ink LM6 was accommodated in the liquid chamber having the smallest β / α. In addition, assuming that only yellow ink was used extremely, 1 ml of yellow ink Y1 was accommodated in each ink cartridge, and 10 ml of other inks was accommodated. The ink supply holder (ink cartridge housing) is composed of a material made of a styrene-based material and a polyphenylene ether alloy containing 35% filler, and the ink absorber is made of polypropylene. Yes, as shown in FIG. 2 and FIG. 3, it is hermetically sealed with a lid forming material having an atmosphere communication path with a maze structure.

  Using the yellow ink, light cyan ink, and light magenta ink of the ink cartridges 91 to 94 of Examples 42 to 45, the recording apparatus shown in FIG. The output was an initial ink cartridge image. After printing, the head part was capped with a separate recovery unit jig and left in a constant temperature and humidity chamber at 60 ° C. Dry for 10 days. After leaving, the ink cartridge was removed from the recovery unit jig, and a gray solid patch gradation image was similarly output using yellow ink, light cyan ink, and light magenta ink to obtain an image of the evaporated ink cartridge. The output images of the initial ink cartridge and the evaporated ink cartridge thus obtained were compared, and the color difference between the solid portion and gradation portion of each color was evaluated based on the above evaluation criteria. The results obtained are shown in Table 27. Further, the evaporation rate of each ink was determined by the evaporation test from the absorbance measurement of each ink at the initial stage and after the evaporation, and is shown in Table 27. The OD value and hue were measured using Spectrolino manufactured by GretagMacbeth, and the color difference was calculated using them.

  From the above results, it is clear that when the difference between the maximum value and the minimum value of β / α is 0.5 or less, the evaporation rates of the respective inks are relatively uniform, and the color difference between the initial output image and the output image after evaporation is small. . It is also clear that it is relatively preferable that the ink cartridge has a T-shaped division as the liquid chamber configuration.

It is the schematic explaining the relationship between the ink evaporation rate and ink density. FIG. 3 is a perspective view of a recording head (ink cartridge). FIG. 3 is an exploded view of a recording head (ink cartridge). FIG. 3 is a perspective view in which a recording element substrate is partially broken. It is a figure which shows the outline of the nozzle structure of a thermal inkjet head. It is a figure which shows Si substrate outline. FIG. 4 is a partial cross-sectional view of a recording head (ink cartridge). It is a figure which shows an inkjet recording device. It is a figure which shows an inkjet recording device. FIG. 6 is a perspective view showing a liquid chamber structure of an ink cartridge.

Claims (9)

An ink cartridge comprising an inkjet head and a plurality of liquid chambers containing different inks,
The minimum value A1 (g / ml) of the ink density of each ink accommodated in each of the plurality of liquid chambers, and the ink density of the ink obtained by evaporating 10% by mass of each ink accommodated in each of the plurality of liquid chambers. An ink cartridge, wherein the maximum value B1 (g / ml) satisfies (B1-A1) /A1≦0.100.   The maximum value B2 (g / ml) of ink density obtained by evaporating 15% by mass of each ink contained in the A1 and the plurality of liquid chambers satisfies (B2-A1) /A1≦0.070. The ink cartridge according to claim 1.   The minimum value C1 (g / ml) and the maximum value D1 (g / ml) of the ink density obtained by evaporating 10% by mass of each ink accommodated in each of the plurality of liquid chambers are (D1-C1) / C1. The ink cartridge according to claim 1, wherein ≦ 0.090 is satisfied.   The minimum value C2 (g / ml) and the maximum value D2 (g / ml) of the ink density obtained by evaporating 15% by mass of each ink contained in each of the plurality of liquid chambers are (D2-C2) / C2. The ink cartridge according to claim 2, wherein ≦ 0.060 is satisfied.   2. The ink according to claim 1, wherein a difference between an ink density of each ink contained in each of the plurality of liquid chambers and an ink density of an ink obtained by evaporating the ink by 10% by mass is 0.030 g / ml or less. cartridge.   3. The ink according to claim 2, wherein a difference between an ink density of each ink contained in each of the plurality of liquid chambers and an ink density of an ink obtained by evaporating the ink by 15 mass% is 0.020 g / ml or less. cartridge.   The ink cartridge according to claim 1, wherein the plurality of inks accommodated in the plurality of liquid chambers are yellow ink, magenta ink, and cyan ink, respectively. The difference between the maximum value and the minimum value of the ratio β / α of the area βcm ² of the surface in which the ink in the liquid chamber can evaporate with respect to the volume αcm ³ of each liquid chamber is 0.5 or less. The ink cartridge according to claim 1, wherein the ink cartridge is configured as follows. The ink cartridge according to claim 1, wherein a material of the liquid chamber contains polyphenylene ether.

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