JP2006169289A - Cyan ink, method for ink-jet recording, recording unit, ink cartridge and apparatus for ink-jet recording - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a cyan ink preparing prints having excellent gas resistance and good color developing properties and preservable over a long period. <P>SOLUTION: The cyan ink is obtained by using a phthalocyanine dye. A specific dye is further contained in the cyan ink and the weight ratio of the dye content of the phthalocyanine dye to the total dye content of the specific dye is (9.9:0.1) to (7:3). <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a cyan ink that is excellent in gas resistance and can provide a recorded matter that can be stored for a long period of time, and an ink jet recording method, a recording unit, an ink cartridge, and an ink jet recording apparatus using the cyan ink.

  Recent advances in inkjet recording technology have made it possible to output full-color images comparable to silver halide photography. In order to output such a high-quality full-color image, dye inks of three colors of cyan (C), magenta (M), and yellow (Y) are often used.

Copper phthalocyanine dyes widely used as cyan dyes are excellent in color developability and light resistance, but easily deteriorated by oxidizing gases such as ozone, NO _x , SO _x , and H ₂ S present in the air. In other words, it has the disadvantage of poor gas resistance. For this reason, the recorded matter formed with the ink containing the phthalocyanine dye loses its original bluish color and becomes reddish over time when stored in a normal environment such as a room. In reality, it is still not as good as silver halide photography in terms of preservation.

  In addition, because of the relationship between halftone gradation and hue adjustment, C, M, and Y composite black may be applied to image forming black (K). As a result, the black color tone is shifted to redness, and the quality of the color image is extremely deteriorated.

  As means for solving the above problems, it has been studied to impart gas resistance to phthalocyanine dyes (see, for example, Patent Documents 1 to 3). However, at present, none of these have achieved a hue, light resistance and gas resistance at the same time.

Furthermore, it has been studied to solve the above problem by improving the ink composition (for example, see Patent Document 4). However, when a water-based ink contains an anti-fading agent or the like, there may be a problem in safety.
Japanese Patent Laid-Open No. 3-103484 JP-A-4-39365 JP 2000-303009 A JP-A-8-003497

  As a result of diligent studies to solve the above problems, the present inventors have added a gas-resistant dye to a low-gas-resistant phthalocyanine dye, whereby the gas resistance of cyan ink using a phthalocyanine dye is added. Found to improve.

  Accordingly, an object of the present invention is to provide a recorded material that has excellent gas resistance, good color developability, and can be stored for a long time without causing problems such as nozzle clogging even when used as an ink for ink jet recording. It is to provide a cyan ink that can be used.

  The above object is achieved by the present invention described below. That is, the present invention is a cyan ink using a phthalocyanine dye, and the cyan ink further includes at least one kind of dyes represented by the following general formulas (I), (II), and (III): And the weight ratio of the dye content of the phthalocyanine dye in the ink to the total amount of the dyes represented by the following general formulas (I), (II) and (III) is 9.9: 0.1-7 : 3.

（上記一般式（Ｉ）中、Ｒ_１、Ｒ_２は各々独立的に置換もしくは未置換の炭素数１〜４のアルキル基を表し、少なくともＲ_１、Ｒ_２のうちいずれかは１つの水酸基を有する。Ｒ_３は水素原子もしくは、置換もしくは未置換のフェニル基を表す。Ｘ_１はカルボキシル基及びその対イオン、又はスルホン酸もしくはその対イオンを表す。ｌは１〜２の整数を表す。Ｍはスルホン酸基の対イオンであり、水素原子、アルカリ金属、アンモニウム或いは有機アンモニウムのいずれかを表す。）

(In the general formula (I), R ₁ and R ₂ each independently represents a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, and at least _one of R ₁ and R ₂ represents one hydroxyl group. R ₃ represents a hydrogen atom or a substituted or unsubstituted phenyl group, X ₁ represents a carboxyl group and its counter ion, or a sulfonic acid or its counter ion, and l represents an integer of 1 to 2. M Is a counter ion of a sulfonic acid group and represents a hydrogen atom, an alkali metal, ammonium, or organic ammonium.)

（上記一般式（ＩＩ）中、Ｒ_４、Ｒ_５は各々独立的に水素原子、炭素数１〜４のアルキル基、炭素数１〜４のアルコキシ基、炭素数２〜４のアルカノイルアミノ基を表し、Ｒ_４、Ｒ_５のうちいずれかは炭素数１〜４のアルコキシ基を有する。Ｒ_６は水素原子もしくは、置換もしくは未置換のフェニル基、ベンゾイル基、ベンジル基を表す。Ｘ_２はカルボキシル基及びその対イオン、又はスルホン酸もしくはその対イオンを表す。ｍは１〜２の整数を表す。Ｍはスルホン酸基の対イオンであり、水素原子。アルカリ金属、アンモニウム或いは有機アンモニウムのいずれかを表す。）

(In the general formula (II), R ₄ and R ₅ each independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or an alkanoylamino group having 2 to 4 carbon atoms. Any one of R ₄ and R ₅ has an alkoxy group having 1 to 4 carbon atoms, R ₆ represents a hydrogen atom, a substituted or unsubstituted phenyl group, a benzoyl group, or a benzyl group, and X ₂ represents a carboxyl group A group and a counter ion thereof, or a sulfonic acid or a counter ion thereof, m represents an integer of 1 to 2, M is a counter ion of a sulfonic acid group, and is a hydrogen atom, either an alkali metal, ammonium, or organic ammonium. Represents.)

（上記一般式（ＩＩＩ）中、Ｒ_７、Ｒ_８、Ｒ_９は各々独立的に炭素数１〜４のアルキル基を表す。Ｒ_１０は水素原子もしくは、置換もしくは未置換のフェニル基を表す。Ｘ_３はカルボキシル基及びその対イオン、又はスルホン酸もしくはその対イオンを表す。ｎは１〜２の整数を表す。ｐ、ｑは０〜１の整数を表し（０の場合の置換基は水素原子）、ｐ＋ｑは１もしくは２である。Ｍはスルホン酸基の対イオンであり、水素原子、アルカリ金属、アンモニウム或いは有機アンモニウムのいずれかを表す。）

(In the general formula (III), R ₇ , R ₈ and R ₉ each independently represents an alkyl group having 1 to 4 carbon atoms. R ₁₀ represents a hydrogen atom or a substituted or unsubstituted phenyl group. X ₃ represents a carboxyl group and its counter ion, or sulfonic acid or its counter ion, n represents an integer of 1 to 2, p and q represent an integer of 0 to 1 (the substituent in the case of 0 is hydrogen) Atom), p + q is 1 or 2. M is a counter ion of the sulfonic acid group, and represents any of a hydrogen atom, an alkali metal, ammonium, or organic ammonium.)

  According to the present invention, it is possible to provide a cyan ink that has excellent gas resistance, good color developability, and can produce a recorded material that can be stored for a long time.

  Next, the present invention will be described in more detail with reference to preferred embodiments. In the present invention, when the compound is a salt, the salt is dissociated into ions in the ink, but is expressed as “contains a salt” for convenience.

  The cyan ink according to the present invention is a cyan ink containing a phthalocyanine dye, and further contains at least one of the black dyes represented by the general formulas (I), (II) and (III). It is characterized by. By using a phthalocyanine dye and a black dye in combination, a cyan ink capable of producing a recorded material having excellent gas resistance is obtained.

The cyan ink according to the present invention uses a Gretag Spectrolino (trade name; manufactured by Gretag) to measure a ^* and b ^* in the L ^* a ^* b ^* display system defined by the CIE, and is represented by the following formula. The hue angle (H °) is defined as cyan ink having a hue angle between 215 and 265.
When a ^* ≧ 0 and b ^* ≧ 0 (first quadrant), H ° = tan−1 (b ^* / a ^* )
When a ^* ≦ 0 and b ^* ≧ 0 (second quadrant), H ° = 180 + tan−1 (b ^* / a ^* )
When a ^* ≦ 0 and b ^* ≦ 0 (third quadrant), H ° = 180 + tan−1 (b ^* / a ^* )
When a ^* ≧ 0 and b ^* ≦ 0 (fourth quadrant), H ° = 360 + tan−1 (b ^* / a ^* )
Hereinafter, each component constituting the cyan ink according to the present invention will be described.

<Phthalocyanine dye>
The cyan ink according to the present invention preferably uses a copper phthalocyanine dye as the phthalocyanine dye. The copper phthalocyanine dye is preferably water-soluble. I. Direct blue (hereinafter abbreviated as DB) 86, 199 and the like. A plurality of these can be used in combination.

  The weight ratio of the dye content of the phthalocyanine dye and the total amount of the dyes represented by the general formulas (I), (II) and (III) is preferably 9.9: 0.1-7: 3, Preferably it is 9: 1-7: 3. The weight ratio of the dye content of the phthalocyanine dye in the ink exceeds 9.9, and the weight ratio of the dye content to the total amount of the dyes represented by the general formulas (I), (II) and (III) is With an ink smaller than 0.1, sufficient gas resistance cannot be obtained. In contrast, the weight ratio of the dye content of the phthalocyanine dye in the ink is smaller than 7, and the weight of the dye content with respect to the total amount of the dyes represented by the general formulas (I), (II) and (III). An ink having a ratio larger than 3 is not preferable because the hue angle of a recorded matter printed with the ink is out of the above range and cannot be said to be a cyan ink practically.

  <Dye of general formula (I)>

（上記一般式（Ｉ）中、Ｒ_１、Ｒ_２は各々独立的に置換もしくは未置換の炭素数１〜４のアルキル基を表し、少なくともＲ_１、Ｒ_２のうちいずれかは１つの水酸基を有する。Ｒ_３は水素原子もしくは、置換もしくは未置換のフェニル基を表す。Ｘ_１はカルボキシル基及びその対イオン、又はスルホン酸もしくはその対イオンを表す。ｌは１〜２の整数を表す。Ｍはスルホン酸基の対イオンであり、水素原子、アルカリ金属、アンモニウム或いは有機アンモニウムのいずれかを表す。）
上記一般式（Ｉ）中のＲ_１〜Ｒ_３について詳述すると、Ｒ_１、Ｒ_２は各々独立的に置換もしくは未置換の炭素数１〜４のアルキル基を表し、Ｒ_１、Ｒ_２のうち少なくともいずれかは１つの水酸基を有し、アルキル基の置換基としては、例えば、炭素数１〜４の直鎖状若しくは分岐鎖状のアルコキシル基、アミノ基、或いはハロゲン原子（フッ素、塩素、臭素等）等が挙げられる。Ｒ_３は、例えば、水素原子、置換もしくは未置換のフェニル基等が挙げられる。フェニル基の置換基としては例えば、炭素数１〜４の直鎖状若しくは分岐鎖状のアルキル基、スルホン基、若しくはこれらの塩、カルボキシル基若しくはその塩等が挙げられる。又、上記式中のＸ_１について詳述すると、Ｘ_１は、例えば、−ＣＯＯＭや−ＳＯ_３Ｍ等が挙げられる。Ｍとしては、水素原子、アルカリ金属（例えば、Ｌｉ、Ｎａ等）、アンモニウム（ＮＨ_４）、有機アンモニウム（Ｎ（Ｒ_１１）_４）等であるもの、Ｒ_１１が、メチル基或いはエチル基等であるものが挙げられる。

(In the general formula (I), R ₁ and R ₂ each independently represents a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, and at least _one of R ₁ and R ₂ represents one hydroxyl group. R ₃ represents a hydrogen atom or a substituted or unsubstituted phenyl group, X ₁ represents a carboxyl group and its counter ion, or a sulfonic acid or its counter ion, and l represents an integer of 1 to 2. M Is a counter ion of a sulfonic acid group and represents a hydrogen atom, an alkali metal, ammonium, or organic ammonium.)
The R _{1 to} R ₃ in the general formula (I) will be described in detail. R ₁ and R ₂ each independently represents a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, and R ₁ and R ₂ At least one of them has one hydroxyl group, and examples of the substituent of the alkyl group include a linear or branched alkoxyl group having 1 to 4 carbon atoms, an amino group, or a halogen atom (fluorine, chlorine, Bromine) and the like. Examples of R ₃ include a hydrogen atom and a substituted or unsubstituted phenyl group. Examples of the substituent of the phenyl group include a linear or branched alkyl group having 1 to 4 carbon atoms, a sulfone group, a salt thereof, a carboxyl group, or a salt thereof. Further, X ₁ in the above formula will be described in detail. Examples of X ₁ include —COOM and —SO ₃ M. M is a hydrogen atom, an alkali metal (eg, Li, Na, etc.), ammonium (NH ₄ ), organic ammonium (N (R ₁₁ ) ₄ ), or the like, and R ₁₁ is a methyl group or an ethyl group. Some are listed.

  The exemplary compounds 1-5 are shown below as specific examples of the dye represented by formula (I) used in the present invention. In addition, compounds having a structure described in WO 00/43451 can also be used. However, the dye represented by the general formula (I) used in the present invention is not limited thereto. Two or more dyes exemplified below may be used at the same time.

＜一般式（ＩＩ）の染料＞

<Dye of general formula (II)>

（上記一般式（ＩＩ）中、Ｒ_４、Ｒ_５は各々独立的に水素原子、炭素数１〜４のアルキル基、炭素数１〜４のアルコキシ基、炭素数２〜４のアルカノイルアミノ基を表し、Ｒ_４、Ｒ_５のうちいずれかは炭素数１〜４のアルコキシ基を有する。Ｒ_６は水素原子もしくは、置換もしくは未置換のフェニル基、ベンゾイル基、ベンジル基を表す。Ｘ_２はカルボキシル基及びその塩、又はスルホン酸もしくはその塩を表す。ｍは１〜２の整数を表す。Ｍはスルホン酸基の対イオンであり、水素原子。アルカリ金属、アンモニウム或いは有機アンモニウムのいずれかを表す。）
上記一般式（ＩＩ）中のＲ_６について詳述すると、Ｒ_６としては、例えば、水素原子、置換もしくは未置換のフェニル基等が挙げられる。フェニル基の置換基としては例えば、炭素数１〜４の直鎖状若しくは分岐鎖状のアルキル基、スルホン基、若しくはこれらの塩、カルボキシル基若しくはその塩等が挙げられる。Ｘ_２としては、例えば、−ＣＯＯＭや−ＳＯ_３Ｍ等が挙げられる。但し、Ｍが、水素原子、アルカリ金属（例えば、Ｌｉ、Ｎａ等）、アンモニウム（ＮＨ_４）、有機アンモニウム（Ｎ（Ｒ_１２）_４）等であるもの、Ｒ１２が、メチル基或いはエチル基等であるものが挙げられる。

(In the general formula (II), R ₄ and R ₅ each independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or an alkanoylamino group having 2 to 4 carbon atoms. Any one of R ₄ and R ₅ has an alkoxy group having 1 to 4 carbon atoms, R ₆ represents a hydrogen atom, a substituted or unsubstituted phenyl group, a benzoyl group, or a benzyl group, and X ₂ represents a carboxyl group Represents a group and a salt thereof, or a sulfonic acid or a salt thereof, m represents an integer of 1 to 2, M represents a counter ion of a sulfonic acid group, a hydrogen atom, and represents an alkali metal, ammonium, or organic ammonium. .)
When R ₆ in the general formula (II) is described in detail, examples of R ₆ include a hydrogen atom, a substituted or unsubstituted phenyl group, and the like. Examples of the substituent of the phenyl group include a linear or branched alkyl group having 1 to 4 carbon atoms, a sulfone group, a salt thereof, a carboxyl group, or a salt thereof. The X _2, for example, -COOM and -SO ₃ M and the like. However, M is a hydrogen atom, an alkali metal (for example, Li, Na, etc.), ammonium (NH ₄ ), organic ammonium (N (R ₁₂ ) ₄ ), etc., and R12 is a methyl group or an ethyl group. Some are listed.

  Illustrative compounds 6 to 9 show specific examples of the dye represented by formula (II) used in the present invention. The dye represented by the general formula (II) used in the present invention is not limited to these. Two or more dyes listed below may be used at the same time.

＜一般式（ＩＩＩ）の染料＞

<Dye of general formula (III)>

（上記一般式（ＩＩＩ）中、Ｒ_７、Ｒ_８、Ｒ_９は各々独立的に炭素数１〜４のアルキル基を表す。Ｒ_１０は水素原子もしくは、置換もしくは未置換のフェニル基を表す。Ｘ_３はカルボキシル基及びその塩、又はスルホン酸もしくはその塩を表す。ｎは１〜２の整数を表す。ｐ、ｑは０〜１の整数を表し（０の場合の置換基は水素原子）、ｐ＋ｑは１もしくは２である。Ｍはスルホン酸基の対イオンであり、水素原子、アルカリ金属、アンモニウム或いは有機アンモニウムのいずれかを表す。）
上記一般式（ＩＩＩ）中のＲ_１０について詳述すると、例えば、水素原子、置換もしくは未置換のフェニル基等が挙げられる。フェニル基の置換基としては、例えば、炭素数１〜４の直鎖状若しくは分枝鎖状のアルキル基、スルホン基若しくはこれらの塩、カルボキシル基若しくはその塩等が挙げられる。Ｘ_３としては、例えば、−ＣＯＯＭや−ＳＯ_３Ｍ等が挙げられる。但し、Ｍが、水素原子、アルカリ金属（例えば、Ｌｉ、Ｎａ等）、アンモニウム（ＮＨ_４）、有機アンモニウム（Ｎ（Ｒ_１３）等であるもの、Ｒ_１３が、メチル基或いはエチル基等であるものが挙げられる。

(In the general formula (III), R ₇ , R ₈ and R ₉ each independently represents an alkyl group having 1 to 4 carbon atoms. R ₁₀ represents a hydrogen atom or a substituted or unsubstituted phenyl group. X ₃ represents a carboxyl group and a salt thereof, or a sulfonic acid or a salt thereof, n represents an integer of 1 to 2, p and q represent an integer of 0 to 1 (the substituent in the case of 0 is a hydrogen atom). P + q is 1 or 2. M is a counter ion of the sulfonic acid group and represents a hydrogen atom, an alkali metal, ammonium, or organic ammonium.)
When R ₁₀ in the general formula (III) is described in detail, examples thereof include a hydrogen atom, a substituted or unsubstituted phenyl group, and the like. Examples of the substituent of the phenyl group include a linear or branched alkyl group having 1 to 4 carbon atoms, a sulfone group or a salt thereof, a carboxyl group or a salt thereof. Examples of X ₃ include —COOM and —SO ₃ M. However, M is a hydrogen atom, an alkali metal (eg, Li, Na, etc.), ammonium (NH ₄ ), organic ammonium (N (R ₁₃ ), etc., and R ₁₃ is a methyl group or an ethyl group. Things.

  Illustrative compounds 10 to 13 show specific examples of the dye represented by formula (III) used in the present invention. The dye represented by the general formula (III) used in the present invention is not limited to these. Two or more dyes listed below may be used at the same time.

＜水性媒体＞
本発明にかかるシアンインクは、主溶媒として、水を含むことが好ましい。水は、イオン交換水、限外濾過水、逆浸透水、蒸留水等の純水又は超純水を用いることができる。紫外線照射又は過酸化水素添加などにより滅菌処理した水を用いることが黴やバクテリアの発生を防止してインクの長期保存を可能とする点で好ましい。水の含有量は、シアンインク全体に対して３０〜９５重量％が好ましい。

<Aqueous medium>
The cyan ink according to the present invention preferably contains water as a main solvent. As the water, pure water or ultrapure water such as ion exchange water, ultrafiltration water, reverse osmosis water, or distilled water can be used. It is preferable to use water sterilized by ultraviolet irradiation or addition of hydrogen peroxide in order to prevent generation of wrinkles and bacteria and enable long-term storage of the ink. The water content is preferably 30 to 95% by weight based on the entire cyan ink.

<Penetration promoter>
The cyan ink of the present invention preferably further contains a penetration accelerator. Examples of penetration enhancers include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, ethylene Glucol mono-iso-propyl ether, ethylene glycol mono-iso-propyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol mono-t-butyl ether, ethylene glycol mono-n-butyl ether, triethylene glycol mono -N-butyl ether, diethylene glycol mono-t-butyl ether, 1-methyl-1-methoxy Butanol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene mono-n-propylene ether, propylene mono-iso-propyl ether, propylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, dipropylene Examples thereof include alkyl ethers of polyhydric alcohols such as glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, and dipropylene glycol mono-iso-propyl ether. A plurality of these penetration enhancers can be used in combination.

  The content of the penetration accelerator is preferably 1 to 40% by weight, more preferably 3 to 30% by weight, based on the whole cyan ink.

<Surfactant>
The cyan ink according to the present invention preferably further contains a surfactant from the viewpoints of promoting ink penetration, ejection stability, and forming a high-quality image. Examples of the surfactant include an anionic surfactant (for example, sodium dodecylbenzenesulfonate, sodium laurate, ammonium salt of polyoxyethylene alkyl ether sulfate, etc.), a nonionic surfactant (for example, polyoxyethylene alkyl). Ethers, polyoxyethylene alkyl esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene alkyl phenyl ethers, polyoxyethylene alkyl amines, polyoxyethylene alkyl amides, etc.) and acetylene glycol surfactants (2, 4, 7, 9, -tetramethyl-5-decyne-4,7-diol, 3,6-dimethyl-4-octyne-3,6-diol, 3,5-dimethyl-1,3-ol, etc.). The acetylene glycol surfactants are acetylenol EH (manufactured by Kawaken Fine Chemical), Surfynol 82, 104, 440, 485, or TG (manufactured by Air Products and Chemicals. Inc), Orphine STG and Olphine E1010 (manufactured by Nisshin Chemical). Is mentioned. A plurality of these surfactants can be used in combination.

  The surfactant content is preferably 0.2 to 5% by weight, more preferably 0.5 to 2% by weight, based on the entire cyan ink.

<Wetting agent>
The cyan ink according to the present invention preferably further contains a wetting agent composed of a high boiling point organic solvent. Examples of the wetting agent comprising a high-boiling organic solvent include ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, polypropylene glycol, propylene glycol, butylene glycol, 1,2,6-hexanetriol, thioglycol, hexylene glycol, Polyhydric alcohols such as glycerin, trimethylolethane, trimethylolpropane; urea; 2-pyrrolidone, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, formamide, acetamide, dimethyl sulfoxide, sorbit Sorbitan, acetin, diacetin, triacetin, sulfolane, etc., among which glycerin, ethylene glycol, diethylene glycol, and urea are particularly preferable. A plurality of these wetting agents can be used in combination.

  The content of the wetting agent is preferably 0.1 to 20% by weight, more preferably 3.0 to 10.0% by weight, based on the entire cyan ink.

<Water-soluble organic solvent>
The cyan ink according to the present invention can contain a water-soluble organic solvent as necessary. The water-soluble organic solvent is preferably a low boiling point organic solvent from the viewpoint of quick drying of the ink. Examples of the low boiling point organic solvent include methanol, ethanol, n-propyl alcohol, iso-propyl alcohol, n-butanol, sec-butanol, tert-butanol, n-pentanol and the like. Alcohol is preferred. A plurality of these water-soluble organic solvents can be used in combination.

<Additives>
In addition, the cyan ink according to the present invention can be used as necessary for preventing clogging, preserving agents, antifungal agents, pH adjusting agents, dissolution aids, antioxidants, surface tension adjusting agents, viscosity adjusting agents, and dielectric constant adjustments. Additives such as agents and oxygen absorbers can be included. A plurality of these additives can be used in combination.

  The content of the additive is preferably added so that the surface tension is 20 to 40 mN / m, preferably 25 to 35 mN / m, from the viewpoint of ensuring the permeability to the recording medium. Further, from the viewpoint of stable ejection characteristics from the head, it is preferable to add such that the viscosity at a temperature of 20 ° C. is less than 5 mPa · s.

<Recording medium>
As the recording medium on which an image is formed using the cyan ink according to the present invention, any recording medium can be used as long as the recording medium performs recording with ink attached.

<Inkjet recording method>
An ink jet recording method in which ink is ejected from an orifice according to a recording signal and recording is performed on a recording medium using the cyan ink according to the present invention can be preferably used. In particular, thermal energy is applied to the ink. Thus, an inkjet recording method for recording on a recording medium can be more preferably used.

<Recording unit>
As a recording unit suitable for performing recording using the cyan ink according to the present invention, a recording unit having a recording head having an ink storage portion in which these inks are stored may be mentioned. Examples thereof include a recording unit that applies thermal energy corresponding to a signal and generates ink droplets by the energy.

<Ink cartridge>
Examples of the ink cartridge suitable for performing recording using the cyan ink according to the present invention include an ink cartridge having an ink storage portion in which these inks are stored.

<Inkjet recording apparatus>
As a recording apparatus suitable for recording using the cyan ink according to the present invention, thermal energy corresponding to a recording signal is applied to ink in a recording head having an ink storage section in which these inks are stored. And an apparatus for generating ink droplets by the energy.

  Below, the schematic structure of the mechanism part of the inkjet recording device used by this embodiment is demonstrated. The main body of the recording apparatus according to the present embodiment includes a paper feed unit, a paper transport unit, a carriage unit, a paper discharge unit, a cleaning unit, and an exterior unit that protects these parts and has a design from the role of each mechanism. The outline of these will be described below.

  FIG. 1 is a perspective view of a recording apparatus applied in this embodiment. 2 and 3 are diagrams for explaining the internal mechanism of the recording apparatus main body. FIG. 2 is a perspective view from the upper right part, and FIG. 3 is a side sectional view of the recording apparatus main body. is there.

  When paper feeding is performed in the recording apparatus applied in the present embodiment, first, only a predetermined number of recording media in the paper feeding unit including the paper feeding tray M2060 is transferred to the nip part constituted by the paper feeding roller M2080 and the separation roller M2041. Sent. The sent recording medium is separated at the nip portion, and only the uppermost recording medium is conveyed. The recording medium sent to the paper transport unit is guided by the pinch roller holder M3000 and the paper guide flapper M3030, and is sent to the roller pair of the transport roller M3060 and the pinch roller M3070. A roller pair composed of a conveyance roller M3060 and a pinch roller M3070 is rotated by driving of the LF motor E0002, and the recording medium is conveyed on the platen M3040 by this rotation.

  When an image is formed on a recording medium in the carriage unit, the recording head H1001 (FIG. 4) is disposed at a target image forming position, and ink is ejected onto the recording medium in accordance with a signal from the electric substrate E0014. Although the detailed configuration of the recording head H1001 will be described later, in the recording apparatus of the present embodiment, a recording medium is scanned by the carriage M4000 in the column direction while recording is performed by the recording head H1001, and a recording medium is detected by the conveyance roller M3060. An image is formed on the recording medium by alternately repeating the sub-scan transported in the row direction.

  The recording medium on which the image has been finally formed is sandwiched between nips of the first paper discharge roller M3110 and the spur M3120 at the paper discharge unit, conveyed, and discharged to the paper discharge tray M3160.

  For the purpose of cleaning the recording head H1001 before and after image recording in the cleaning unit, if the pump M5000 is operated in a state where the cap M5010 is in close contact with the ink discharge port of the recording head H1001, it is unnecessary from the recording head H1001. Ink or the like is sucked. Further, by sucking the ink remaining in the cap M5010 with the cap M5010 opened, consideration is given to preventing the remaining ink from adhering and the subsequent adverse effects.

<Recording head configuration>
The configuration of the head cartridge H1000 will be described below. The head cartridge H1000 in this embodiment has a recording head H1001, a means for mounting the ink tank H1900, and a means for supplying ink from the ink tank H1900 to the recording head, and is detachable from the carriage M4000. Mounted on.

  FIG. 4 is a diagram illustrating a state in which the ink tank H1900 is attached to the head cartridge H1000 applied in the present embodiment. The recording apparatus of the present embodiment forms an image with yellow, magenta, cyan, black, light magenta, light cyan, and green ink, and therefore, ink tanks H1900 are also prepared for seven colors independently. In the above, the ink according to the present invention is used as at least one kind of ink. As shown in the figure, each is detachable from the head cartridge H1000. The ink tank H1900 can be attached and detached while the head cartridge H1000 is mounted on the carriage M4000.

  FIG. 5 is an exploded perspective view of the head cartridge H1000. In the figure, a head cartridge H1000 includes a first recording element substrate H1100 and a second recording element substrate H1101, a first plate H1200, a second plate H1400, an electric wiring substrate H1300, a tank holder H1500, and a flow path forming member H1600. , Filter H1700, seal rubber H1800, and the like.

  The first recording element substrate H1100 and the second recording element substrate H1101 are Si substrates, and a plurality of recording elements (nozzles) for ejecting ink are formed on one side thereof by a photolithography technique. Electric wiring such as Al for supplying electric power to each recording element is formed by a film forming technique, and a plurality of ink flow paths corresponding to individual recording elements are also formed by a photolithography technique. Further, an ink supply port for supplying ink to the plurality of ink flow paths is formed to open on the back surface.

  FIG. 6 is an enlarged front view for explaining the configuration of the first recording element substrate H1100 and the second recording element substrate H1101. H2000 to H2600 are printing element rows (hereinafter also referred to as nozzle rows) corresponding to different ink colors, and the first printing element substrate H1100 has a nozzle row H2000 supplied with yellow ink and a supply of magenta ink. The nozzle row for three colors is configured, that is, the nozzle row H2100 to be supplied and the nozzle row H2200 to which cyan ink is supplied. The second recording element substrate H1101 includes a nozzle row H2300 supplied with light cyan ink, a nozzle row H2400 supplied with black ink, a nozzle row H2500 supplied with orange ink, and a nozzle supplied with light magenta ink. Nozzle rows for four colors of the row H2600 are configured.

Each nozzle row is composed of 768 nozzles arranged at an interval of 1200 dpi (dot / inch; reference value) in the conveyance direction of the recording medium, and ejects approximately 2 picoliters of ink droplets. The opening area at each nozzle outlet is set to approximately 100 square μm ² . Further, the first recording element substrate H1100 and the second recording element substrate H1101 are bonded and fixed to the first plate H1200. Here, the first recording element substrate H1100 and the second recording element substrate H1101 are attached. An ink supply port H1201 for supplying ink is formed.

  Further, a second plate H1400 having an opening is bonded and fixed to the first plate H1200, and the second plate H1400 includes the electric wiring substrate H1300, the first recording element substrate H1100, and the second recording element substrate H1100. The electric wiring substrate H1300 is held so that the recording element substrate H1101 is electrically connected.

  The electrical wiring substrate H1300 applies an electrical signal for ejecting ink from each nozzle formed on the first recording element substrate H1100 and the second recording element substrate H1101, and the first recording element substrate Electrical wiring corresponding to the H1100 and the second recording element substrate H1101, and an external signal input terminal H1301 for receiving an electrical signal from the recording apparatus main body located at the end of the electrical wiring. The external signal input terminal H1301 is positioned and fixed on the back side of the tank holder H1500.

  On the other hand, in a tank holder H1500 that holds the ink tank H1900, a flow path forming member H1600 is fixed by, for example, ultrasonic welding to form an ink flow path H1501 that communicates from the ink tank H1900 to the first plate H1200.

  A filter H1700 is provided at the ink tank side end of the ink flow path H1501 that engages with the ink tank H1900, and can prevent dust from entering from the outside. Further, a seal rubber H1800 is attached to the engaging portion with the ink tank H1900 so that ink can be prevented from evaporating from the engaging portion.

  Further, as described above, the tank holder portion composed of the tank holder H1500, the flow path forming member H1600, the filter H1700, and the seal rubber H1800, the first recording element substrate H1100, the second recording element substrate H1101, and the first plate. The head cartridge H1000 is configured by bonding the recording head unit H1001 including the H1200, the electric wiring substrate H1300, and the second plate H1400 by bonding or the like.

  Here, as an embodiment of the recording head, a bubble jet (registration) that performs recording using an electrothermal transducer (recording element) that generates thermal energy for causing film boiling to the ink in response to an electrical signal. A trademark type recording head has been described with an example.

  About this typical structure and principle, for example, what is performed using the basic principle disclosed in US Pat. Nos. 4,723,129 and 4,740,796 is preferable. . This method can be applied to both the so-called on-demand type and the continuous type. In particular, in the case of the on-demand type, it corresponds to a sheet or liquid flow path in which liquid (ink) is held. By applying at least one drive signal that corresponds to the recorded information and gives a rapid temperature rise exceeding the nucleate boiling to the electrothermal transducer arranged in a manner, heat energy is generated in the electrothermal transducer, This is effective because film boiling occurs on the heat acting surface of the recording head, and as a result, bubbles in the liquid (ink) corresponding to the drive signal on a one-to-one basis can be formed. By the growth and contraction of the bubbles, liquid (ink) is ejected through the ejection opening to form at least one droplet. When this drive signal is in a pulse shape, bubbles are grown and contracted immediately and appropriately, so that it is possible to achieve the discharge of liquid (ink) with particularly excellent responsiveness, which is more preferable.

  Further, as a form of the ink jet recording apparatus using the second mechanical energy, a nozzle forming substrate having a plurality of nozzles, a pressure generating element made of a piezoelectric material and a conductive material disposed opposite to the nozzles, and this pressure An on-demand ink jet recording head that includes ink that fills the periphery of the generating element, displaces the pressure generating element by an applied voltage, and discharges a small droplet of ink from a nozzle can be exemplified.

  Further, the ink jet recording apparatus is not limited to the one in which the head and the ink tank are separated as described above, but may be one in which they are integrated so as not to be separated. The ink tank is integrated with the head so as to be separable or inseparable from the head and mounted on the carriage, and is provided at a fixed portion of the apparatus so that ink is supplied to the recording head via an ink supply member, for example, a tube. The thing of the form to supply may be sufficient. Further, when the ink tank is provided with a configuration for applying a preferable negative pressure to the recording head, a configuration in which an absorber is disposed in the ink storage portion of the ink tank, or a flexible ink storage bag and the same A form having a spring portion that applies a biasing force in the direction of expanding the internal volume can be employed. In addition to the serial recording method as described above, the recording apparatus may take the form of a line printer in which recording elements are aligned over a range corresponding to the entire width of the recording medium.

  Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples. However, the present invention is not limited to the following Examples unless it exceeds the gist. Unless otherwise noted, “parts” and “%” indicate parts by weight and% by weight, respectively.

(Examples 1-6 and Comparative Examples 1-3)
The components shown in Table 1 below were mixed, sufficiently stirred and dissolved, and then subjected to pressure filtration using a 0.20 μm Teflon (registered trademark) filter. Inks of Examples 1 to 6 and Comparative Examples 1 to 3 Were prepared respectively.

＜評価＞
実施例１〜６及び比較例１〜３の各シアンインクについて、耐ガス性、及び色相角を評価した。

<Evaluation>
About each cyan ink of Examples 1-6 and Comparative Examples 1-3, gas resistance and a hue angle were evaluated.

-Gas resistance It has an on-demand type multi-recording head that discharges ink by applying thermal energy according to recording signals to the cyan inks of Examples 1 to 6 and Comparative Examples 1 to 3 obtained above. Mounted on the inkjet recording apparatus BJ F890 (manufactured by Canon) and created a print duty pattern in which the optical density OD (Optical Density) measured using Gretag Spectrolino (manufactured by Gretag) is in the range of 2.2 to 2.5. Then, solid printing was performed on the recording medium GP301N (manufactured by Canon) to create a recorded matter. Thereafter, the recorded matter was left in a room temperature room for 3 days. Thereafter, the recorded matter was put into an ozone atmosphere environment having a temperature of 45 ° C., a relative humidity of 55% RH, and an ozone concentration of 3 ppm, and a gas resistance test was conducted. For each of the gas resistance tests conducted for 2 hours, the color change (ΔE *) from before the gas resistance test was calculated from the following formula and evaluated according to the following evaluation criteria. Further, the degree of hue change of the solid part before and after the test was visually evaluated according to the following criteria. The results are shown in Table 2 below.
ΔE ^* = {(ΔL ^* ) ² + (Δa ^* ) ² + (Δb ^* ) ² } ^1/2
(In the formula, ΔL ^* , Δa ^*, and Δb ^* mean differences in coordinates of L ^* , a ^*, and b ^* in the L ^* a ^* b ^* color system before and after the gas resistance test.)
A: ΔE ^* is less than 15 and gas resistance is good B: ΔE ^* is 15 or more and less than 20 and there is no practical problem C: ΔE ^* is 20 or more and unpractical level ・ Hue angle A recorded material was prepared in the same manner as the gas test, and the recorded material was left in a room temperature room for 3 days. Thereafter, L ^* , a ^*, and b ^* were measured for each recorded matter using Gretag Spectrolino (manufactured by Gretag), and the hue angle (H °) was calculated by the following formula, and evaluated according to the following evaluation criteria. The results are shown in Table 2 below.

When a ^* ≧ 0 and b ^* ≧ 0 (first quadrant), H ° = tan−1 (b ^* / a ^* )
When a ^* ≦ 0 and b ^* ≧ 0 (second quadrant), H ° = 180 + tan−1 (b ^* / a ^* )
When a ^* ≦ 0 and b ^* ≦ 0 (third quadrant), H ° = 180 + tan−1 (b ^* / a ^* )
When a ^* ≧ 0 and b ^* ≦ 0 (fourth quadrant), H ° = 360 + tan−1 (b ^* / a ^* )
○: H ° is 215 or more and 265 or less and good level as cyan ink ×: H ° is less than 215 or larger than 265 and inferior as cyan ink

表２から明らかなように、実施例１〜６のシアンインクは、いずれも優れた耐ガス性を有し、且つ色相角も本発明が定義するシアンインクの範囲内にある。これに対し、一般式（Ｉ）、（ＩＩ）及び（ＩＩＩ）で表される染料を含まない比較例１のシアンインクでは、耐ガス性は著しく低い。又、比較例２にみられるように、一般式（Ｉ）、（ＩＩ）及び（ＩＩＩ）で表される染料のうち１種類以上を含んだシアンインクであっても、前記染料含有量の重量比が９．９：０．１〜７：３を外れたインクでは耐ガス性は良好であるが、色相角が前記範囲を外れ、シアンインクとして用いるには実用上問題がある。一般式（Ｉ）、（ＩＩ）及び（ＩＩＩ）で表される染料以外の染料を用いた比較例３のシアンインクは、色相角は前記範囲内にあるものの、十分な耐ガス性が得られなかった。

As is apparent from Table 2, the cyan inks of Examples 1 to 6 all have excellent gas resistance, and the hue angle is within the range of the cyan ink defined by the present invention. In contrast, the cyan ink of Comparative Example 1 that does not contain the dyes represented by the general formulas (I), (II), and (III) has extremely low gas resistance. Further, as seen in Comparative Example 2, even if the cyan ink contains one or more dyes represented by the general formulas (I), (II) and (III), the weight of the dye content Ink with a ratio out of 9.9: 0.1 to 7: 3 has good gas resistance, but the hue angle is out of the above range, and there is a problem in practical use as a cyan ink. The cyan ink of Comparative Example 3 using a dye other than the dyes represented by the general formulas (I), (II) and (III) has sufficient gas resistance although the hue angle is within the above range. There wasn't.

1 is a perspective view of a recording apparatus according to an embodiment of the present invention. FIG. 3 is a perspective view of a mechanism unit of the recording apparatus according to the embodiment of the invention. 1 is a cross-sectional view of a recording apparatus in an embodiment of the present invention. FIG. 5 is a perspective view showing a state where an ink tank is mounted on the head cartridge applied in the embodiment of the present invention. It is a disassembled perspective view of the head cartridge applied in the embodiment of the present invention. FIG. 3 is a front view showing a recording element substrate in a head cartridge applied in an embodiment of the present invention.

Explanation of symbols

M2041 Separation roller M2060 Paper feed tray M2080 Paper feed roller M3000 Pinch roller holder M3030 Paper guide flapper M3040 Platen M3060 Transport roller M3070 Pinch roller M3110 Paper discharge roller M3120 Spur M3160 Paper discharge tray M4000F Carriage M5000 Pump M500P Head cartridge H1001 Recording head H1100 First recording element substrate H1101 Second recording element substrate H1200 First plate H1201 Ink supply port H1300 Electrical wiring substrate H1301 External signal input terminal H1400 Second plate H1500 Tank holder H1501 Ink channel H1600 Flow path forming member H1700 Luther H1800 seal rubber H1900 ink tank H2000 yellow nozzle row H2100 magenta nozzle row H2200 cyan nozzle row H2300 light cyan nozzle row H2400 black nozzle row H2500 green nozzle row H2600 light magenta nozzle row

Claims (7)

A cyan ink using a phthalocyanine dye, wherein the cyan ink further contains at least one of the dyes represented by the following general formulas (I), (II), and (III); That the weight ratio of the dye content of the phthalocyanine dye of the formula (I), (II) and (III) below is 9.9: 0.1 to 7: 3 Characteristic cyan ink.

(In the general formula (I), R ₁ and R ₂ each independently represents a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, and at least _one of R ₁ and R ₂ represents one hydroxyl group. R ₃ represents a hydrogen atom or a substituted or unsubstituted phenyl group, X ₁ represents a carboxyl group and its counter ion, or a sulfonic acid or its counter ion, and l represents an integer of 1 to 2. M Is a counter ion of a sulfonic acid group and represents a hydrogen atom, an alkali metal, ammonium, or organic ammonium.)

(In the general formula (II), R ₄ and R ₅ each independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or an alkanoylamino group having 2 to 4 carbon atoms. Any one of R ₄ and R ₅ has an alkoxy group having 1 to 4 carbon atoms, R ₆ represents a hydrogen atom, a substituted or unsubstituted phenyl group, a benzoyl group, or a benzyl group, and X ₂ represents a carboxyl group A group and a counter ion thereof, or a sulfonic acid or a counter ion thereof, m represents an integer of 1 to 2, M is a counter ion of a sulfonic acid group, and is a hydrogen atom, either an alkali metal, ammonium, or organic ammonium. Represents.)

(In the general formula (III), R ₇ , R ₈ and R ₉ each independently represents an alkyl group having 1 to 4 carbon atoms. R ₁₀ represents a hydrogen atom or a substituted or unsubstituted phenyl group. X ₃ represents a carboxyl group and a salt thereof, or a sulfonic acid or a counter ion thereof, n represents an integer of 1 to 2, p and q represent an integer of 0 to 1 (the substituent in the case of 0 is a hydrogen atom) ), P + q is 1 or 2. M is a counter ion of the sulfonic acid group, and represents a hydrogen atom, an alkali metal, ammonium, or organic ammonium.)   The weight ratio of the dye content of the phthalocyanine dye and the total amount of the dyes represented by the general formulas (I), (II) and (III) is 9: 1 to 7: 3. The cyan ink according to 1.   3. An ink jet recording method for performing recording on a recording medium by ejecting ink from an orifice in accordance with a recording signal, wherein the ink is the cyan ink according to claim 1 or 2.   The inkjet recording method according to claim 3, wherein recording is performed on a recording medium by applying thermal energy to the ink.   3. A recording unit comprising an ink containing portion containing ink and a recording head for discharging the ink, wherein the ink is the cyan ink according to claim 1 or 2.   An ink cartridge comprising an ink containing portion containing ink, wherein the ink is the cyan ink according to claim 1.   3. An ink jet recording apparatus comprising a recording unit having an ink containing portion containing ink and a head portion for discharging the ink, wherein the ink is the cyan ink according to claim 1 or 2. Inkjet recording device.

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