JP2009138118A - Ink set, ink medium set, ink cartridge, inkjet recording apparatus, and inkjet recording method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an ink set with which color bleeding is improved even on not only regular paper but also coated paper for printing having low water absorbency and which has excellent defoaming property and discharge stability; and to provide an ink medium set or the like. <P>SOLUTION: The ink set is obtained by combining at least a pigment, first and second water soluble organic solvents, a surfactant, a specific derivative of oxyethylene β-naphtyl ether, and two or more kinds of inks containing water. The mass ratio of the first water soluble organic solvent to the second water soluble organic solvent is 1/1.1 to 1/1.9. The first water soluble organic solvent is glycerine, and the second water soluble organic solvent is ethylene glycol or the like. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to an ink set and an ink media set, and an ink cartridge, an ink jet recording apparatus, and an ink jet recording method using the ink set.

  Inkjet printers using the inkjet recording method are rapidly spreading because they are small, inexpensive, and easy to color. In recent years, it has been demanded to print a high-quality recorded matter at high speed. In order to meet this requirement, the ink used in the ink jet recording method must satisfy various characteristics. In particular, when printing at high speed, it is important to suppress color bleeding of ink on the recording medium and to maintain ejection stability. In this case, the reason why the ejection stability is deteriorated is that the ink is dried in the nozzle or the ink is a bubble, and it is necessary to improve this.

Therefore, the applicant of the present application uses a water-soluble organic solvent different in color inks other than black ink and black ink as an ink set that does not generate color bleeding not only in plain paper but also in coated paper with poor water absorption, An ink set in which the surface tension of the water-soluble organic solvent of the color ink is higher than the surface tension of the black ink has been proposed (see Patent Document 1).
However, in this proposal, although the difference in surface tension affects the color bleed, there is no disclosure about the combination and blending ratio of the water-soluble organic solvent that achieves both color bleed, saturation and ejection stability.

ただし、前記一般式（１）中、Ｒ^１は、炭素数１〜２０のアルキル基、アリル基、及びアラルキル基のいずれかを表す。Ｌは、０〜７の整数を表す。ｎは、２０〜２００の整数を表す。 The applicant of the present application has proposed an ink containing a compound represented by the following general formula (1) as a dispersant and having excellent image sharpness, ejection stability, ink storage stability, and the like (see Patent Document 2). ).

In the general formula (1), ^{R 1} represents any of an alkyl group, an allyl group, and an aralkyl group, having 1 to 20 carbon atoms. L represents an integer of 0 to 7. n represents an integer of 20 to 200.

The water-soluble organic solvent contained in the ink is usually used to improve moisture retention and image saturation, and in Patent Document 2, the water-soluble organic solvent used in the present invention is used. However, it is not shown which water-soluble organic solvent is effective for moisture retention and which water-soluble organic solvent is effective for improving the saturation of an image.
Patent Document 3 proposes an ink jet recording method in which color bleed does not occur on a recording medium that has little ink absorbability or no ink absorbability. However, this proposal has a problem that since the ultraviolet ray irradiation is used, the ink configuration that can be used is limited, the inkjet recording apparatus becomes complicated, and the cost increases.

  Therefore, the color bleed is improved not only for plain paper but also for printing paper with low water absorption, and no ink set and ink media set with excellent defoaming property and ejection stability have yet been provided. is there.

JP 2007-146135 A JP 2006-45436 A JP 2007-136988 A

  This invention is made | formed in view of this present condition, and makes it a subject to solve the said various problems in the past and to achieve the following objectives. That is, the present invention relates to an ink set and an ink media set which are improved in color bleed not only on plain paper but also on printing coated paper with low water absorbability, and excellent in defoaming properties and ejection stability, and the ink set. It is an object of the present invention to provide an ink jet recording apparatus, an ink jet recording method, and an ink cartridge.

ただし、前記一般式（１）中、Ｒ^１は、炭素数１〜２０のアルキル基、アリル基、及びアラルキル基のいずれかを表す。Ｌは、０〜７の整数を表す。ｎは、２０〜２００の整数を表す。
＜２＞ 界面活性剤が、下記一般式（２）で表される化合物である前記＜１＞に記載のインクセットである。

ただし、前記一般式（２）中、ｍは０〜１０の整数、ｎは０〜４０の整数を表す。
＜３＞ 界面活性剤が、下記一般式（３）で表される化合物である前記＜１＞に記載のインクセットである。

ただし、前記一般式（３）中、Ｒｆはフッ素含有基を表す。ｍは１〜２５の整数を表し、ｎは１〜４の整数を表し、ｐは１〜４の整数を表す。
＜４＞ 各インクの粘度差（最大粘度−最小粘度）が、０〜０．８ｍＰａ・ｓである前記＜１＞から＜３＞のいずれかに記載のインクセットである。
＜５＞ 各インクの２５℃における粘度が６ｍＰａ・ｓ〜２０ｍＰａ・ｓである前記＜１＞から＜４＞のいずれかに記載のインクセットである。
＜６＞ インクセットにおける各インクが、マゼンタインク、シアンインク、イエローインク、及びブラックインクの少なくともいずれかである前記＜１＞から＜５＞のいずれかに記載のインクセットである。
＜７＞ 記録用メディアに画像記録するのに用いられ、動的走査吸液計で測定した接触時間１００ｍｓにおける純水の該記録用メディアへの転移量が４ｍｌ／ｍ^２〜２６ｍｌ／ｍ^２であり、かつ接触時間４００ｍｓにおける純水の該記録用メディアへの転移量が５ｍｌ／ｍ^２〜２９ｍｌ／ｍ^２である前記＜１＞から＜６＞のいずれかに記載のインクセットである。
＜８＞ インクセットと、記録用メディアとからなるインクメディアセットにおいて、
前記インクセットが、少なくとも顔料、２種以上の水溶性有機溶剤、界面活性剤、下記一般式（１）で表される化合物、及び水を含有するインクを２種以上組み合わせてなり、
前記２種以上の水溶性有機溶剤が、第１の水溶性有機溶剤と、第２の水溶性有機溶剤とからなり、これらの質量比（第１：第２）が１：１．１〜１：１．９であり、
前記第１の水溶性有機溶剤がグリセリンであり、
前記第２の水溶性有機溶剤が、エチレングリコール、ジエチレングリコール、トリエチレングリコール、プロピレングリコール、ジプロピレングリコール、トリプロピレングリコール、１，３−ブタンジオール、２，３−ブタンジオール、１，４−ブタンジオール、３−メチル−１，３−ブタンジオール、１，５−ペンタンジオール、テトラエチレングリコール、１，６−ヘキサンジオール、２−メチル−２，４−ペンタンジオール、ポリエチレングリコール、１，２，４−ブタントリオール、及び１，２，６−ヘキサントリオールから選択される少なくとも１種であり、
前記記録用メディアが、動的走査吸液計で測定した接触時間１００ｍｓにおける純水の該記録用メディアへの転移量が４ｍｌ／ｍ^２〜２６ｍｌ／ｍ^２であり、かつ接触時間４００ｍｓにおける純水の該記録用メディアへの転移量が５ｍｌ／ｍ^２〜２９ｍｌ／ｍ^２であることを特徴とするインクメディアセットである。

ただし、前記一般式（１）中、Ｒ^１は、炭素数１〜２０のアルキル基、アリル基、及びアラルキル基のいずれかを表す。Ｌは、０〜７の整数を表す。ｎは、２０〜２００の整数を表す。
＜９＞ 前記＜１＞から＜７＞のいずれかに記載のインクセットの各インクを容器中に収容してなることを特徴とするインクカートリッジである。
＜１０＞ 前記＜１＞から＜７＞のいずれかに記載のインクセットの各インクに刺激を印加し、該インクを飛翔させて画像を記録するインク飛翔工程を少なくとも含むことを特徴とするインクジェット記録方法である。
＜１１＞ 前記＜１＞から＜７＞のいずれかに記載のインクセットの各インクに刺激を印加し、該インクを飛翔させて画像を形成するインク飛翔手段を少なくとも有することを特徴とするインクジェット記録装置である。
＜１２＞ 記録用メディア上に、前記＜１＞から＜７＞のいずれかに記載のインクジェットインクを用いて記録された画像を有してなることを特徴とするインク記録物である。 Means for solving the above problems are as follows. That is,
<1> An ink set comprising a combination of two or more inks containing at least a pigment, two or more water-soluble organic solvents, a surfactant, a compound represented by the following general formula (1), and water,
The two or more water-soluble organic solvents are composed of a first water-soluble organic solvent and a second water-soluble organic solvent, and the mass ratio (first: second) is from 1: 1.1 to 1. : 1.9,
The first water-soluble organic solvent is glycerin;
The second water-soluble organic solvent is ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,3-butanediol, 2,3-butanediol, 1,4-butanediol. 3-methyl-1,3-butanediol, 1,5-pentanediol, tetraethylene glycol, 1,6-hexanediol, 2-methyl-2,4-pentanediol, polyethylene glycol, 1,2,4- It is an ink set characterized by being at least one selected from butanetriol and 1,2,6-hexanetriol.

In the general formula (1), ^{R 1} represents any of an alkyl group, an allyl group, and an aralkyl group, having 1 to 20 carbon atoms. L represents an integer of 0 to 7. n represents an integer of 20 to 200.
<2> The ink set according to <1>, wherein the surfactant is a compound represented by the following general formula (2).

However, in the said General formula (2), m represents the integer of 0-10, n represents the integer of 0-40.
<3> The ink set according to <1>, wherein the surfactant is a compound represented by the following general formula (3).

However, in the general formula (3), Rf represents a fluorine-containing group. m represents an integer of 1 to 25, n represents an integer of 1 to 4, and p represents an integer of 1 to 4.
<4> The ink set according to any one of <1> to <3>, wherein a difference in viscosity (maximum viscosity−minimum viscosity) of each ink is 0 to 0.8 mPa · s.
<5> The ink set according to any one of <1> to <4>, wherein each ink has a viscosity at 25 ° C. of 6 mPa · s to 20 mPa · s.
<6> The ink set according to any one of <1> to <5>, wherein each ink in the ink set is at least one of magenta ink, cyan ink, yellow ink, and black ink.
<7> The recording medium used for image recording, by a dynamic scanning absorptometer at the transition amount ^4ml / ^{m 2 ~26ml} / m 2 of a contact time 100ms as measured in pure water of the recording medium There, and an ink set according the transfer amount to the recording medium of pure water at the contacting time 400ms is ^5ml / ^{m 2 ~29ml} / m 2 to any one of <1> to <6>.
<8> In an ink media set including an ink set and a recording medium,
The ink set is a combination of two or more inks containing at least a pigment, two or more water-soluble organic solvents, a surfactant, a compound represented by the following general formula (1), and water,
The two or more water-soluble organic solvents are composed of a first water-soluble organic solvent and a second water-soluble organic solvent, and the mass ratio (first: second) is from 1: 1.1 to 1. : 1.9,
The first water-soluble organic solvent is glycerin;
The second water-soluble organic solvent is ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,3-butanediol, 2,3-butanediol, 1,4-butanediol. 3-methyl-1,3-butanediol, 1,5-pentanediol, tetraethylene glycol, 1,6-hexanediol, 2-methyl-2,4-pentanediol, polyethylene glycol, 1,2,4- At least one selected from butanetriol and 1,2,6-hexanetriol;
Pure water wherein the recording medium is, in the dynamic transfer amount to the recording medium of pure water at the contacting time 100ms measured by scanning absorptometer is that ^{4ml / m 2 ~26ml / m 2} , and the contact time 400ms an ink media set, wherein the transition amount to the recording medium is ^{5ml / m 2 ~29ml / m 2} .

In the general formula (1), ^{R 1} represents any of an alkyl group, an allyl group, and an aralkyl group, having 1 to 20 carbon atoms. L represents an integer of 0 to 7. n represents an integer of 20 to 200.
<9> An ink cartridge, wherein each ink of the ink set according to any one of <1> to <7> is contained in a container.
<10> Inkjet comprising at least an ink flying step of recording an image by applying a stimulus to each ink of the ink set according to any one of <1> to <7> and causing the ink to fly It is a recording method.
<11> Inkjet comprising at least ink flying means for forming an image by applying a stimulus to each ink of the ink set according to any one of <1> to <7> and causing the ink to fly. It is a recording device.
<12> An ink recorded matter comprising an image recorded using the inkjet ink according to any one of <1> to <7> on a recording medium.

  According to the present invention, the conventional problems can be solved, and color bleeding is improved not only in plain paper but also in printing coated paper with low water absorbability, and excellent in defoaming properties and ejection stability. A set, an ink media set, and an ink cartridge, an ink jet recording apparatus, and an ink jet recording method using the ink set can be provided.

(Ink set)
The ink set of the present invention is a combination of two or more inks, and the ink comprises at least a pigment, two or more water-soluble organic solvents, a surfactant, a compound represented by the following general formula (1), and water. And further contains other components as required.

The ink set is used to record an image on a recording medium, and the transfer amount of pure water to the recording medium at a contact time of 100 ms measured by a dynamic scanning absorption meter is 4 ml / m ^{2 to} 26 ml / m. ^2, and it is preferable transfer amount to the recording medium of pure water at the contacting time 400ms is ^{5ml / m 2 ~29ml / m 2} . The transfer amount to the recording medium measured by the dynamic scanning absorption meter will be described in the ink media set.

ただし、前記一般式（１）中、Ｒ^１は、炭素数１〜２０のアルキル基、アリル基、及びアラルキル基のいずれかを表す。Ｌは、０〜７の整数を表す。ｎは、２０〜２００の整数を表す。 -Compound represented by the general formula (1)-
The pigment as the colorant of the ink used in the present invention is dispersed with a compound represented by the following general formula (1). Thus, by using the compound represented by the following general formula (1) as a dispersant, an aqueous pigment dispersion and an aqueous pigment ink having a small average particle size and excellent storage stability can be obtained.

In the general formula (1), ^{R 1} represents any of an alkyl group, an allyl group, and an aralkyl group, having 1 to 20 carbon atoms. L represents an integer of 0 to 7. n represents an integer of 20 to 200.

In the said General formula (1), n is an integer of 20-200, 20-100 are preferable and 30-50 are more preferable. When n is less than 20, the dispersion stability tends to decrease, and the ink containing a pigment having a large average particle diameter may not be obtained, so that satisfactory saturation may not be obtained. The viscosity of the ink becomes high, and it may be difficult to record with the ink jet recording method.
Thus, by including a polyoxyethylene group as a hydrophilic group, the charge on the pigment surface can be maintained well.
Examples of the alkyl group having 1 to 20 carbon atoms in R ¹ include a methyl group, an ethyl group, a propyl group, a butyl group, and an isopropyl group.
Examples of the aralkyl group in R ¹ include benzyl, phenethyl, 2-methylbenzyl, 3-methylbenzyl, 4-methylbenzyl and the like.
Examples of the compound represented by the general formula (1) include polyoxyethylene (n = 20) β-naphthyl ether, polyoxyethylene (n = 40) β-naphthyl ether, polyoxyethylene (n = 60) β- And naphthyl ether. Among these, polyoxyethylene (n = 40) β-naphthyl ether is particularly preferable.
The content of the compound represented by the general formula (1) is preferably 0.1 to 2.0 and more preferably 0.1 to 1.0 with respect to the pigment 1 in the ink on a mass basis. In the content range, an ink having a small average particle diameter can be provided. When the content is less than 0.1, the pigment may be insufficiently dispersed. When the content exceeds 2.0, the viscosity of the ink may be too high and recording by the ink jet method may be difficult. .

-Water-soluble organic solvent-
In the present invention, two or more types of water-soluble organic solvents are used, and the two or more types of water-soluble organic solvents comprise a first water-soluble organic solvent and a second water-soluble organic solvent, and their masses. The ratio (first: second) is from 1: 1.1 to 1: 1.9.
The first water-soluble organic solvent is glycerin, and the second water-soluble organic solvent is ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,3-butanediol, 2, 3-butanediol, 1,4-butanediol, 3-methyl-1,3-butanediol, 1,5-pentanediol, tetraethylene glycol, 1,6-hexanediol, 2-methyl-2,4-pentane It is at least one selected from diol, polyethylene glycol, 1,2,4-butanetriol, and 1,2,6-hexanetriol.

When the water-soluble organic solvent is as described above, excellent effects can be obtained in preventing nozzle clogging due to drying of ink, that is, preventing deterioration of ejection stability and improving the saturation of a formed image. Specifically, the discharge stability can be improved because the first water-soluble organic solvent is glycerin. In particular, nozzle clogging can be prevented even after the printer head is left unopened for a certain period of time without capping. The second water-soluble organic solvent is ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,3-butanediol, 2,3-butanediol, 1,4-butanediol. 3-methyl-1,3-butanediol, 1,5-pentanediol, tetraethylene glycol, 1,6-hexanediol, 2-methyl-2,4-pentanediol, polyethylene glycol, 1,2,4- By being at least one selected from butanetriol and 1,2,6-hexanetriol, the penetrability is increased and the color bleed is eliminated by keeping the pigment on the surface of the recording medium. A high print image can be obtained.
When the mass ratio (first: second) is from 1: 1.1 to 1: 1.9, the printing application is high in ejection stability and less water-absorbing and coated with an inorganic pigment. Color bleed can also be improved in industrial paper. If the second water-soluble organic solvent is less than 1.1 in the mass ratio, color bleeding may occur. On the other hand, when the number is more than 1.9, clogging occurs at the time of restart after the nozzle is installed in an open state, and bubbles are likely to be generated and the defoaming property is poor, so that high discharge stability may not be obtained. . In addition, when using 2 or more types of 2nd water-soluble organic solvents, those total amount is made into the 2nd water-soluble organic solvent amount.

ただし、前記一般式（２）中、ｍは０〜１０の整数、ｎは０〜４０の整数を表す。

ただし、前記一般式（３）中、Ｒｆはフッ素含有基を表す。ｍは１〜２５の整数を表し、ｎは１〜４の整数を表し、ｐは１〜４の整数を表す。
Ｒｆのフッ素含有基としては、例えばＣＦ_３、ＣＦ_２ＣＦ_３などが挙げられる。 -Surfactant-
By incorporating the surfactant into the ink, the coloring property of the ink is improved by improving the wettability of the ink on paper without impairing the stability of the pigment fine particles obtained using the nonionic dispersant. An image with little blur is obtained.
The surfactant is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably a fluorosurfactant, such as perfluoroalkyl sulfonate, perfluoroalkyl carboxylate, perfluoroalkyl phosphorus. Acid ester, perfluoroalkyl ethylene oxide adduct, perfluoroalkyl betaine, perfluoroalkylamine oxide compound, compound represented by the following general formula (2), compound represented by the following general formula (3), and the like It is done. Among these, the compound represented by the following general formula (2) and the compound represented by the following general formula (3) are particularly preferable because of good color developability and high reliability.

However, in the said General formula (2), m represents the integer of 0-10, n represents the integer of 0-40.

However, in the general formula (3), Rf represents a fluorine-containing group. m represents an integer of 1 to 25, n represents an integer of 1 to 4, and p represents an integer of 1 to 4.
Examples of the fluorine-containing group of Rf include CF ₃ and CF ₂ CF ₃ .

  As said surfactant, what was synthesize | combined suitably may be used and a commercial item may be used. Examples of the commercially available products include S-144 and S-145 (all manufactured by Asahi Glass Co., Ltd.); FC-170C, FC-430, Fluorard-FC4430 (all manufactured by Sumitomo 3M Co., Ltd.); 100, FSN, FSN-100, FS-300 (all manufactured by Dupont); FT-250, 251 (all manufactured by Neos Corporation), and the like. Among these, FSO, FSO-100, FSN, FSN-100, and FS-300 manufactured by Dupont are preferable because they can provide good print quality and storage stability. These surfactants that are nonionic fluorine-based surfactants can be used singly or in combination of two or more.

The amount of the surfactant added to the ink is preferably 0.1% by mass to 10% by mass, and more preferably 0.1% by mass to 5% by mass. When the addition amount is less than 0.1% by mass, there may be no significant effect on the improvement of permeability, and when it exceeds 10% by mass, viscosity increase, aggregation, etc. occur when stored at high temperature, Reliability may deteriorate.
The compounds represented by the general formulas (2) and (3) have high color developability and high reliability. However, when they are contained together with the compound represented by the general formula (1) in the ink, they are very easy to foam and defoaming. Because of this, foaming in the head of the ink jet printer deteriorates the ejection stability, making it difficult to use. However, the defoaming property could be improved by including the two or more water-soluble organic solvents in the above-described mass ratio.

-Pigment-
There is no restriction | limiting in particular as said pigment, According to the objective, it can select suitably, For example, any of an inorganic pigment and an organic pigment may be sufficient.
Examples of the inorganic pigment include titanium oxide, iron oxide, calcium carbonate, barium sulfate, aluminum hydroxide, barium yellow, cadmium red, chrome yellow, and carbon black. Among these, carbon black is preferable. In addition, as said carbon black, what was manufactured by well-known methods, such as a contact method, a furnace method, and a thermal method, is mentioned, for example.

Examples of the organic pigment include azo pigments, polycyclic pigments, dye chelates, nitro pigments, nitroso pigments, and aniline black. Among these, azo pigments and polycyclic pigments are more preferable.
Examples of the azo pigments include azo lakes, insoluble azo pigments, condensed azo pigments, and chelate azo pigments.
Examples of the polycyclic pigment include phthalocyanine pigments, perylene pigments, perinone pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, indigo pigments, thioindigo pigments, isoindolinone pigments, and quinofullerone pigments.
Examples of the dye chelates include basic dye chelates and acidic dye chelates.

There is no restriction | limiting in particular as a color of the said coloring agent, According to the objective, it can select suitably, For example, the thing for black, the thing for color, etc. are mentioned. These may be used individually by 1 type and may use 2 or more types together.
Examples of the black color include carbon black (CI pigment black 7) such as furnace black, lamp black, acetylene black, channel black, copper, iron (CI pigment black 11), oxidation, and the like. Examples thereof include metals such as titanium, organic pigments such as aniline black (CI pigment black 1), and the like.
The carbon black is carbon black produced by a furnace method or a channel method, a primary particle size is 15 nm to 40 nm, a specific surface area by a BET method is 50 to 300 m ² / g, and a DBP oil absorption is 40 to 150 ml. / 100 g, those having a volatile content of 0.5 to 10% and a pH value of 2 to 9 are preferred.
As the carbon black, a commercially available product can be used. 2300, no. 900, MCF-88, no. 33, no. 40, no. 45, no. 52, MA7, MA8, MA100, no. 2200B (all manufactured by Mitsubishi Chemical Corporation); Raven700, 5750, 5250, 5000, 3500, 1255 (all manufactured by Columbia); Regal400R, 330R, 660R, Mogu L, Monarch700, 800, 880, 900, 1000, 1100, 1300, Monarch 1400 (all manufactured by Cabot); Color Black FW1, FW2, FW2V, FW18, FW200, S150, S160, S170, Printex 35, U, V, 140U, 140V, Special Black 6, 5, 4A, and 4 (all manufactured by Degussa).

There is no restriction | limiting in particular as a pigment which can be used for yellow ink as the thing for said colors, According to the objective, it can select suitably, for example, C.I. I. Pigment yellow 1, C.I. I. Pigment yellow 2, C.I. I. Pigment yellow 3, C.I. I. Pigment yellow 12, C.I. I. Pigment yellow 13, C.I. I. Pigment yellow 14, C.I. I. Pigment yellow 16, C.I. I. Pigment yellow 17, C.I. I. Pigment yellow 73, C.I. I. Pigment yellow 74, C.I. I. Pigment yellow 75, C.I. I. Pigment yellow 83, C.I. I. Pigment yellow 93, C.I. I. Pigment yellow 95, C.I. I. Pigment yellow 97, C.I. I. Pigment yellow 98, C.I. I. Pigment yellow 114, C.I. I. Pigment yellow 120, C.I. I. Pigment yellow 128, C.I. I. Pigment yellow 129, C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 150, C.I. I. Pigment yellow 151, C.I. I. Pigment yellow 154, C.I. I. Pigment yellow 155, C.I. I. Pigment yellow 174, C.I. I. Pigment yellow 180, and the like.
The pigment that can be used in the magenta ink is not particularly limited and may be appropriately selected depending on the intended purpose. I. Pigment red 5, C.I. I. Pigment red 7, C.I. I. Pigment red 12, C.I. I. Pigment red 48 (Ca), C.I. I. Pigment red 48 (Mn), C.I. I. Pigment red 57 (Ca), C.I. I. Pigment red 57: 1, C.I. I. Pigment red 112, C.I. I. Pigment red 122, C.I. I. Pigment red 123, C.I. I. Pigment red 146, C.I. I. Pigment red 168, C.I. I. Pigment red 176, C.I. I. Pigment red 184, C.I. I. Pigment red 185, C.I. I. Pigment red 202, pigment violet 19, and the like.
The pigment that can be used in the cyan ink is not particularly limited and may be appropriately selected depending on the purpose. I. Pigment blue 1, C.I. I. Pigment blue 2, C.I. I. Pigment blue 3, C.I. I. Pigment blue 15, C.I. I. Pigment blue 15: 3, C.I. I. Pigment blue 15: 4, C.I. I. Pigment blue 15:34, C.I. I. Pigment blue 16, C.I. I. Pigment blue 22, C.I. I. Pigment blue 60, C.I. I. Pigment blue 63, C.I. I. Pigment blue 66; C.I. I. Bat Blue 4, C.I. I. Bat Blue 60 and the like.
In addition, the pigment contained in each ink used in the present invention may be newly produced for the present invention.
By using Pigment Yellow 74 as the yellow pigment, Pigment Red 122 and Pigment Bio Red 19 as the magenta pigment, and Pigment Blue 15 as the cyan pigment, it is possible to obtain a well-balanced ink having excellent color tone and light resistance.

The content of the pigment in the ink is preferably 0.1% by mass or more and 50.0% by mass or less, and more preferably 0.1% by mass or more and 20.0% by mass or less.
The average particle diameter (D ₅₀ ) of the pigment is preferably 150 nm or less, and more preferably 100 nm or less. In addition, the average particle diameter of the pigment in the present invention is a value measured by a dynamic light scattering method with Microtrack UPA manufactured by Nikkiso Co., Ltd. in an environment of 23 ° C. and 55% RH. This is because by reducing the amount of coarse particles of the pigment in the ink adhering to the nozzle plate, it is possible to prevent the ink repellent layer from being damaged due to the friction of the coarse particles in the ink during wiping. Further, it is possible to prevent irregular reflection of the pigment particles in the print image portion and provide a print image having a uniform density.

  The pigment is used as a water-based pigment dispersion by dispersing in water with the compound represented by the general formula (1). The aqueous pigment dispersion can be produced, for example, by the following method. First, the ratio of pigment to dispersant is determined. While dispersing a mixture of pigment and water with a known disperser such as a sand mill, roll mill, bead mill, nanomizer, homogenizer, etc., the dispersant was gradually added, and the viscosity became the smallest as the particle size decreased. Decide on the ratio. In addition, when dispersing by a bead mill, it is preferable to add a small amount of an antifoaming agent in order to suppress the generation of bubbles. The average particle diameter of the pigment can be controlled by the size of the beads to be added to the disperser, the dispersion time, etc. To make the average particle diameter 150 nm or less, the beads are 0.05 to 1.0 mm and the dispersion time is May be dispersed at 1 to 100 hours / L.

The other components are not particularly limited and may be appropriately selected as necessary. For example, an antifoaming agent, a pH adjuster, an antiseptic / antifungal agent, a rust inhibitor, an antioxidant, an ultraviolet absorber, Examples include oxygen absorbers and light stabilizers.
There is no restriction | limiting in particular as said antifoamer, According to the objective, it can select suitably, For example, a silicone type antifoamer, a polyether type antifoamer, a fatty-acid ester type | system | group antifoamer etc. are mentioned suitably. These may be used individually by 1 type and may use 2 or more types together. Among these, a silicone type antifoaming agent is preferable at the point which is excellent in the bubble-breaking effect.
Examples of the antiseptic / antifungal agent include 1,2-benzisothiazolin-3-one, sodium dehydroacetate, sodium sorbate, sodium 2-pyridinethiol-1-oxide, sodium benzoate, sodium pentachlorophenol, and the like. Can be mentioned.
The pH adjuster is not particularly limited as long as it can adjust the pH to 7 or more without adversely affecting the ink to be prepared, and any substance can be used according to the purpose. Examples of the pH adjuster include amines such as diethanolamine and triethanolamine, hydroxides of alkali metal elements such as lithium hydroxide, sodium hydroxide and potassium hydroxide; ammonium hydroxide and quaternary ammonium hydroxide. Quaternary phosphonium hydroxide, alkali metal carbonates such as lithium carbonate, sodium carbonate, potassium carbonate, and the like.
Examples of the rust inhibitor include acidic sulfite, sodium thiosulfate, ammonium thiodiglycolate, diisopropylammonium nitrite, pentaerythritol tetranitrate, and dicyclohexylammonium nitrite.
Examples of the antioxidant include phenol-based antioxidants (including hindered phenol-based antioxidants), amine-based antioxidants, sulfur-based antioxidants, phosphorus-based antioxidants, and the like.

  Each ink in the ink set of the present invention includes a pigment, two or more water-soluble organic solvents, a surfactant, a compound represented by the above general formula (1), water, and other components as necessary. And stirred for 1 to 3 hours at 20 ° C to 30 ° C. The dispersion can be performed by, for example, a sand mill, a homogenizer, a ball mill, a paint shaker, an ultrasonic disperser, etc., and stirring and mixing are performed by a stirrer using a normal stirring blade, a magnetic stirrer, a high-speed disperser, or the like. be able to.

The viscosity of each ink in the ink set of the present invention is preferably 6 mPa · s to 20 mPa · s, more preferably 6 mPa · s to 15 mPa · s at 25 ° C. If the viscosity exceeds 20 mPa · s, it may be difficult to ensure ejection stability.
The viscosity difference (maximum viscosity−minimum viscosity) of each ink is preferably 0 to 0.8 mPa · s. When the difference in viscosity exceeds 0.8 mPa · s, the amount of ink discharged from the inkjet head varies greatly between colors, and a good image may not be obtained.

  The ink set of the present invention can be suitably used in various fields, and can be suitably used in an image recording apparatus (printer or the like) using an ink jet recording method. The ink-jet ink set of the present invention, the ink cartridge of the present invention, the ink recorded matter, and the ink-jet printer of the present invention described below can be used for a printer or the like having the function of heating the ink-jet ink at 50 to 200 ° C. It can be particularly preferably used for a recording apparatus and an ink jet recording method.

(Ink media set)
The ink media set of the present invention comprises the ink set of the present invention and a recording medium.

<Recording media>
The recording medium includes, for example, a support and a coating layer on at least one surface of the support, and further includes other layers as necessary.

In the recording medium, the transfer amount of each ink of the ink set of the present invention to the recording medium at a contact time of 100 ms measured by a dynamic scanning absorption meter is 4 to 15 ml / m ² , 6 ˜14 ml / m ² is preferred. Further, the amount of transferred to the recording medium of the pure water is preferably ^{4~26ml / m 2, 8~25ml / m} 2 is more preferable.
If the transfer amount of the ink and pure water at the contact time of 100 ms is too small, beading is likely to occur. If it is too large, the ink dot diameter after recording becomes too smaller than the desired diameter. There is.
The transfer amount of each ink of the ink set of the present invention to the recording medium at a contact time of 400 ms measured with a dynamic scanning absorption meter is 7 to 20 ml / m ² , and preferably 8 to 19 ml / m ^2. . Further, the amount of transferred to the recording medium of the pure water is preferably ^{5~29ml / m 2, 10~28ml / m} 2 is more preferable.
If the amount of transfer at the contact time of 400 ms is too small, the drying property is insufficient, and thus spur marks may be easily generated. If the amount is too large, bleeding is likely to occur, and the gloss of the image area after drying is likely to occur. May become low.

  Here, the dynamic scanning absorptiometer (DSA, Papa-Pagi Technical Journal, Vol. 48, May 1994, pp. 88-92, Kuju Shigenori) absorbs liquid in a very short time. It is a device that can measure accurately. The dynamic scanning absorption meter reads the liquid absorption speed directly from the movement of the meniscus in the capillary, makes the sample a disk, and then scans the liquid absorption head in a spiral shape, and the scanning speed according to a preset pattern. Is automatically changed by a method in which the number of necessary points is measured with one sample. A liquid supply head for a paper sample is connected to a capillary via a Teflon (registered trademark) tube, and the position of the meniscus in the capillary is automatically read by an optical sensor. Specifically, the transfer amount of pure water or ink was measured using a dynamic scanning absorption meter (K350 series D type, manufactured by Kyowa Seiko Co., Ltd.). The transfer amount at the contact time of 100 ms and the contact time of 400 ms can be obtained by interpolation from the measured value of the transfer amount at the contact time adjacent to each contact time. The measurement was performed at 23 ° C. and 50% RH.

-Support-
The support is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include paper based on wood fibers, and sheet-like materials such as non-woven fabrics mainly composed of wood fibers and synthetic fibers. .
There is no restriction | limiting in particular as said paper, According to the objective, it can select suitably according to the objective, For example, wood pulp, waste paper pulp, etc. are used. Examples of the wood pulp include hardwood bleached kraft pulp (LBKP), softwood bleached kraft pulp (NBKP), NBSP, LBSP, GP, and TMP.
As the raw material of the used paper pulp, the white paper, ruled white, cream white, card, special white, medium white, imitation, fair white, Kent, white, as shown in the used paper standard quality specification table of the used paper recycling promotion center Art, special upper limit, another upper limit, newspaper, magazine, etc. are mentioned. Specifically, printer paper such as non-coating computer paper, thermal paper, and pressure-sensitive paper as information-related paper; OA waste paper such as PPC paper; coating of art paper, coated paper, fine coated paper, matte paper, etc. Paper: High quality paper, color quality, notebook, notepaper, wrapping paper, fancy paper, medium quality paper, newsprint, reprint paper, super paper, imitation paper, pure white roll paper, uncoated paper such as milk carton, etc. Examples of used paper and paperboard include chemical pulp paper and high-yield pulp-containing paper. These may be used individually by 1 type and may use 2 or more types together.

The waste paper pulp is generally produced from a combination of the following four steps.
(1) For disaggregation, waste paper is treated with mechanical force and chemicals with a pulper to loosen it into a fibrous form, and the printing ink is peeled off from the fiber.
(2) Dust removal is to remove foreign matter (plastic etc.) and dust contained in waste paper with a screen, cleaner or the like.
(3) In the deinking, the printing ink peeled off from the fiber using a surfactant is removed from the system by a flotation method or a cleaning method.
(4) Bleaching increases the whiteness of the fiber using an oxidizing action or a reducing action.
When mixing the used paper pulp, the mixing ratio of the used paper pulp in the total pulp is preferably 40% or less from the viewpoint of curling after recording.

  As the internal filler used for the support, for example, a conventionally known pigment is used as a white pigment. Examples of the white pigment include light calcium carbonate, heavy calcium carbonate, kaolin, clay, talc, calcium sulfate, barium sulfate, titanium dioxide, zinc oxide, zinc sulfide, zinc carbonate, satin white, aluminum silicate, diatomaceous earth, White inorganic pigments such as calcium silicate, magnesium silicate, synthetic silica, aluminum hydroxide, alumina, lithopone, zeolite, magnesium carbonate, magnesium hydroxide; styrene plastic pigment, acrylic plastic pigment, polyethylene, microcapsule, urea resin And organic pigments such as melamine resin. These may be used individually by 1 type and may use 2 or more types together.

  Examples of the internally added sizing agent used for making the support include neutral rosin sizing agents used for neutral papermaking, alkenyl succinic anhydride (ASA), alkyl ketene dimer (AKD), and petroleum resins. System sizing agents and the like. Among these, a neutral rosin sizing agent or alkenyl succinic anhydride is particularly preferable. The alkyl ketene dimer may be added in a small amount because of its high size effect, but the friction coefficient on the surface of the recording paper (media) is low and slippery, which is not preferable from the viewpoint of transportability during ink jet recording. There is.

-Coating layer-
The coating layer contains a pigment and a binder (binder), and further contains a surfactant and other components as necessary.
As the pigment, an inorganic pigment or a combination of an inorganic pigment and an organic pigment can be used.
Examples of the inorganic pigment include kaolin, talc, heavy calcium carbonate, light calcium carbonate, calcium sulfite, amorphous silica, titanium white, magnesium carbonate, titanium dioxide, aluminum hydroxide, calcium hydroxide, magnesium hydroxide, Examples thereof include zinc hydroxide and chlorite. Among these, kaolin is particularly preferable because it has excellent glossiness and can be made close to a paper for offset printing.
The kaolin includes delaminated kaolin, calcined kaolin, engineered kaolin by surface modification, etc. In consideration of gloss expression, the particle size distribution is such that the ratio of the particle size is 2 μm or less is 80% by mass or more. It is preferable that the kaolin which has occupies 50 mass% or more of the whole kaolin.
The amount of kaolin added is preferably 50 parts by mass or more with respect to 100 parts by mass of the total pigment in the coating layer. When the addition amount is less than 50 parts by mass, a sufficient effect on glossiness may not be obtained. The upper limit of the addition amount is not particularly limited, but is preferably 90 parts by mass or less from the viewpoint of coating suitability in consideration of the fluidity of kaolin, particularly the thickening under high shear force.
Examples of the organic pigment include water-soluble dispersions such as styrene-acrylic copolymer particles, styrene-butadiene copolymer particles, polystyrene particles, and polyethylene particles. Two or more of these organic pigments may be mixed.
The addition amount of the organic pigment is preferably 2 parts by mass to 20 parts by mass with respect to 100 parts by mass of the total pigment in the coating layer. Since the organic pigment is excellent in gloss expression and its specific gravity is smaller than that of an inorganic pigment, it is possible to obtain a coating layer that is bulky, high gloss, and has good surface coverage. If the addition amount is less than 2 parts by mass, the above effect is not obtained. If the addition amount exceeds 20 parts by mass, the fluidity of the coating liquid is deteriorated, leading to a decrease in coating operability, and economical in terms of cost. Not right.
The organic pigment has a solid type, a hollow type, a donut type, and the like in its form, but the average particle size is 0.2 μm in view of the balance of gloss development, surface coverage, and fluidity of the coating liquid. A hollow mold having a porosity of 40% or more is more preferable.

As the binder, an aqueous resin is preferably used.
As the aqueous resin, at least one of a water-soluble resin and a water-dispersible resin is preferably used. There is no restriction | limiting in particular as said water-soluble resin, According to the objective, it can select suitably, For example, modified products of polyvinyl alcohol, such as polyvinyl alcohol, anion modified polyvinyl alcohol, cation modified polyvinyl alcohol, acetal modified polyvinyl alcohol; Polyurethane; polyvinylpyrrolidone and polyvinylpyrrolidone and vinyl acetate copolymer, vinylpyrrolidone and dimethylaminoethyl / methacrylic acid copolymer, quaternized vinylpyrrolidone / dimethylaminoethyl / methacrylic acid copolymer, vinylpyrrolidone and Modified products of polyvinylpyrrolidone such as a copolymer of methacrylamidopropyl trimethylammonium chloride; Cellulo such as carboxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose Modified products of cellulose such as cationized hydroxyethyl cellulose; Synthetic resins such as polyester, polyacrylic acid (ester), melamine resin, or modified products thereof, polyester and polyurethane copolymer; poly (meth) acrylic acid, Examples include poly (meth) acrylamide, oxidized starch, phosphate esterified starch, self-modified starch, cationized starch, or various modified starches, polyethylene oxide, sodium polyacrylate, and sodium alginate. These may be used individually by 1 type and may use 2 or more types together.
Among these, polyvinyl alcohol, cation-modified polyvinyl alcohol, acetal-modified polyvinyl alcohol, polyester, polyurethane, a copolymer of polyester and polyurethane, and the like are particularly preferable from the viewpoint of ink absorbability.

The water-dispersible resin is not particularly limited and may be appropriately selected depending on the intended purpose. For example, polyvinyl acetate, ethylene-vinyl acetate copolymer, polystyrene, styrene- (meth) acrylate ester copolymer Polymer, (meth) acrylic acid ester polymer, vinyl acetate- (meth) acrylic acid (ester) copolymer, styrene-butadiene copolymer, ethylene-propylene copolymer, polyvinyl ether, silicone-acrylic copolymer Coalescence, etc. Further, it may contain a crosslinking agent such as methylolated melamine, methylolated urea, methylolated hydroxypropylene urea, or isocyanate, or may be a copolymer containing units such as N-methylolacrylamide and having a self-crosslinking property. A plurality of these water-based resins can be used simultaneously.
The amount of the aqueous resin added is preferably 2 parts by mass to 100 parts by mass and more preferably 3 parts by mass to 50 parts by mass with respect to 100 parts by mass of the pigment. The amount of the aqueous resin added is determined so that the liquid absorption characteristics of the recording medium fall within a desired range.

  When a water-dispersible colorant is used as the colorant, the cationic organic compound is not necessarily added, but is not particularly limited and can be appropriately selected and used depending on the purpose. For example, a primary to tertiary amine, quaternary ammonium salt monomer or oligomer that reacts with a sulfonic acid group, a carboxyl group, an amino group, or the like in a direct dye or acidic dye in water-soluble ink to form an insoluble salt. A polymer etc. are mentioned, Among these, an oligomer or a polymer is preferable.

Examples of the cationic organic compound include dimethylamine / epichlorohydrin polycondensate, dimethylamine / ammonia / epichlorohydrin condensate, poly (trimethylaminoethyl methacrylate / methyl sulfate), diallylamine hydrochloride / acrylamide copolymer, (Diallylamine hydrochloride / sulfur dioxide), polyallylamine hydrochloride, poly (allylamine hydrochloride / diallylamine hydrochloride), acrylamide / diallylamine copolymer, polyvinylamine copolymer, dicyandiamide, dicyandiamide / ammonium chloride / urea / formaldehyde condensate , Polyalkylene polyamine dicyandiamide ammonium salt condensate, dimethyl diallyl ammonium chloride, polydiallyl methylamine hydrochloride, poly (diallyl dimethyl ester) Ruammonium chloride), poly (diallyldimethylammonium chloride / sulfur dioxide), poly (diallyldimethylammonium chloride / diallylamine hydrochloride derivative), acrylamide / diallyldimethylammonium chloride copolymer, acrylate / acrylamide / diallylamine hydrochloride copolymer Products, ethyleneimine derivatives such as polyethyleneimine and acrylicamine polymer, and polyethyleneimine alkylene oxide modified products. These may be used individually by 1 type and may use 2 or more types together.
Among these, low molecular weight cationic organic compounds such as dimethylamine / epichlorohydrin polycondensate and polyallylamine hydrochloride and other relatively high molecular weight cationic organic compounds such as poly (diallyldimethylammonium chloride) It is preferable to use in combination. By using in combination, the image density can be improved and feathering can be further reduced as compared with the case of single use.
The cation equivalent of the cationic organic compound by colloid titration method (using polyvinyl potassium sulfate and toluidine blue) is preferably 3 to 8 meq / g. If the cation equivalent is within this range, good results can be obtained within the dry adhesion range.
Here, in the measurement of the cation equivalent by the colloid titration method, the cationic organic compound is diluted with distilled water to a solid content of 0.1% by mass, and pH adjustment is not performed.
The dry adhesion amount of the cationic organic compound is preferably 0.3 to 2.0 g / m ² . If the dry adhesion amount of the cationic organic compound is less than 0.3 g / m ² , sufficient image density improvement and feathering reduction effects may not be obtained.

There is no restriction | limiting in particular as said surfactant, Although it can select suitably according to the objective, Any of an anionic surfactant, a cationic surfactant, an amphoteric surfactant, and a nonionic surfactant can be used. Of these, nonionic active agents are particularly preferred. By adding the surfactant, the water resistance of the image is improved, the image density is increased, and bleeding is improved.
Examples of the nonionic activator include higher alcohol ethylene oxide adducts, alkylphenol ethylene oxide adducts, fatty acid ethylene oxide adducts, polyhydric alcohol fatty acid ester ethylene oxide adducts, higher aliphatic amine ethylene oxide adducts, and fatty acid amides. Ethylene oxide adduct, fat ethylene oxide adduct, polypropylene glycol ethylene oxide adduct, fatty acid ester of glycerol, fatty acid ester of pentaerythritol, fatty acid ester of sorbitol and sorbitan, fatty acid ester of sucrose, alkyl ether of polyhydric alcohol, And fatty acid amides of alkanolamines. These may be used individually by 1 type and may use 2 or more types together.
The polyhydric alcohol is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include glycerol, trimethylolpropane, pentaerythritol, sorbitol, and sucrose. As the ethylene oxide adduct, a product obtained by substituting a part of ethylene oxide with an alkylene oxide such as propylene oxide or butylene oxide is also effective as long as water solubility can be maintained. The substitution rate is preferably 50% or less. 4-15 are preferable and, as for HLB (hydrophilic / lipophilic ratio) of the said nonionic activator, 7-13 are more preferable.
The addition amount of the surfactant is preferably 10 parts by mass or less, more preferably 0.1 part by mass to 1.0 part by mass with respect to 100 parts by mass of the cationic organic compound.

Other components can be added to the coating layer as needed, as long as the object and effect of the present invention are not impaired. Examples of the other components include additives such as alumina powder, pH adjuster, preservative, and antioxidant.
There is no restriction | limiting in particular as a formation method of the said coating layer, According to the objective, it can select suitably, It can carry out by the method of impregnating or apply | coating a coating layer liquid on the said support body. The impregnation or coating method of the coating layer liquid is not particularly limited and may be appropriately selected depending on the intended purpose. For example, conventional size press, gate roll size press, film transfer size press, blade coater, rod coater It can be applied with various coating machines such as an air knife coater and a curtain coater. Among these, from the viewpoint of cost, a method of impregnating or adhering with a conventional size press, a gate roll size press, a film transfer size press or the like installed in a paper machine and finishing on-machine is preferable.

The adhesion amount of the coating layer liquid is not particularly limited and may be appropriately selected depending on the intended purpose, the solid content is preferably ^{0.5~20g / m 2, 1~15g / m} 2 Gayori preferable. If the adhesion amount is less than 0.5 g / m ² , the ink may not be sufficiently absorbed, and the ink may overflow and character bleeding may occur, and if it exceeds 20 g / m ² , the texture of the paper May be damaged, and it may be difficult to bend or to write with a writing instrument.
After the impregnation or coating, drying may be performed as necessary. In this case, the drying temperature is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably about 100 to 250 ° C. .
The recording medium may further include a back layer on the back surface of the support, another layer between the support and the coating layer, or another layer between the support and the back layer, and a protective layer on the coating layer. Can also be provided. Each of these layers may be a single layer or a plurality of layers.
The recording medium may be commercially available coated paper for offset printing, coated paper for gravure printing, etc. in addition to the inkjet recording medium, as long as the liquid absorption property is within the range of the present invention.

The basis weight of the recording medium is preferably 50 to 250 g / m ² . If it is less than 50 g / m ^2, may be the way the recording medium conveyance failure is likely to occur, such as clogged of the conveying path for lack stiffness, exceeds 250 g / m ^2, the stiffness is too large Therefore, the recording medium cannot be bent at the curved portion in the middle of the conveyance path, and the conveyance defect such as the recording medium clogging easily occurs.

(ink cartridge)
The ink cartridge of the present invention contains each ink in the ink set of the present invention in a container, and further includes other members appropriately selected as necessary.
The container is not particularly limited, and its shape, structure, size, material and the like can be appropriately selected according to the purpose. For example, at least an ink bag formed of an aluminum laminate film, a resin film, or the like Preferred examples include those possessed.

Next, the ink cartridge will be described with reference to FIGS. Here, FIG. 1 is a view showing an example of the ink cartridge of the present invention, and FIG. 2 is a view including a case (exterior) of the ink cartridge 200 of FIG.
As shown in FIG. 1, the ink cartridge 200 is filled into the ink bag 241 from the ink inlet 242 and exhausted, and then the ink inlet 242 is closed by fusion. In use, the needle of the apparatus main body is pierced into the ink discharge port 243 made of a rubber member and supplied to the apparatus.
The ink bag 241 is formed of a packaging member such as a non-permeable aluminum laminate film. As shown in FIG. 2, the ink bag 241 is usually housed in a plastic cartridge case 244 and is detachably attached to various ink jet recording apparatuses.

  The ink cartridge of the present invention contains each ink of the ink set of the present invention and can be used by being detachably attached to various ink jet recording apparatuses, and can be detachably attached to the ink jet recording apparatus of the present invention described later. It is particularly preferable to install and use.

(Inkjet recording method and inkjet recording apparatus)
The ink jet recording apparatus of the present invention includes at least ink flying means, and further includes other means appropriately selected as necessary, for example, stimulus generation means and control means.
The ink jet recording method of the present invention includes at least an ink flying step, and further includes other steps appropriately selected as necessary, for example, a stimulus generation step, a control step, and the like.
The ink jet recording method of the present invention can be preferably carried out by the ink jet recording apparatus of the present invention, and the ink flying step can be suitably carried out by the ink flying means. Moreover, the said other process can be suitably performed by the said other means.

-Ink flying process and ink flying means-
The ink flying step is a step of forming an image on a recording medium by applying a stimulus to each ink of the ink set of the present invention and causing the ink to fly.
The ink flying means is means for applying a stimulus to each ink of the ink set of the present invention and causing the ink to fly to form an image on a recording medium. There is no restriction | limiting in particular as this ink flying means, For example, an inkjet head etc. are mentioned.

  As the ink jet head, a piezoelectric element is used as a pressure generating means for pressurizing ink in the ink flow path, and a diaphragm that forms the wall surface of the ink flow path is deformed to change the volume in the ink flow path to eject ink droplets. A so-called piezo type (see Japanese Patent Laid-Open No. 2-51734), or a so-called thermal type that generates bubbles by heating ink in an ink flow path using a heating resistor (Japanese Patent Laid-Open No. 61-61). No. 59911), the diaphragm and the electrode forming the wall surface of the ink flow path are arranged opposite to each other, and the diaphragm is deformed by an electrostatic force generated between the diaphragm and the electrode, whereby the ink flow path inner volume is obtained. This includes any case of an electrostatic type in which ink droplets are ejected by changing the pressure (see Japanese Patent Laid-Open No. 6-71882).

  The stimulus can be generated, for example, by the stimulus generating means, and the stimulus is not particularly limited and can be appropriately selected according to the purpose, such as heat (temperature), pressure, vibration, light, etc. Can be mentioned. These may be used individually by 1 type and may use 2 or more types together. Among these, heat and pressure are preferable.

  Examples of the stimulus generating means include a heating device, a pressurizing device, a piezoelectric element, a vibration generating device, an ultrasonic oscillator, a light, and the like. Specifically, for example, a piezoelectric actuator such as a piezoelectric element, a heating resistor, etc. Examples include a thermal actuator that uses a phase change caused by film boiling of a liquid using an electrothermal transducer such as a body, a shape memory alloy actuator that uses a metal phase change caused by a temperature change, and an electrostatic actuator that uses an electrostatic force.

  There is no particular limitation on the mode of the ink flying, and it varies depending on the type of the stimulus. For example, when the stimulus is “heat”, the heat corresponding to the recording signal is applied to the ink in the recording head. A method of applying energy using, for example, a thermal head, generating bubbles in the ink by the thermal energy, and ejecting and ejecting the ink as droplets from the nozzle holes of the recording head by the pressure of the bubbles, etc. Can be mentioned. Further, when the stimulus is “pressure”, for example, by applying a voltage to a piezoelectric element bonded to a position called a pressure chamber in an ink flow path in the recording head, the piezoelectric element bends and the volume of the pressure chamber is increased. And a method of ejecting and ejecting the ink as droplets from the nozzle holes of the recording head.

  The size of the ink droplets to be ejected is preferably 3 pl to 40 pl, for example, and the ejection jet speed is preferably 5 m / s to 20 m / s. The frequency is preferably 1 kHz or more, and the resolution is preferably 300 dpi or more. The control means is not particularly limited as long as the movement of each means can be controlled, and can be appropriately selected according to the purpose. Examples thereof include devices such as sequencers and computers.

Next, an example of the ink jet recording apparatus used in the present invention will be described.
The ink jet recording apparatus shown in FIG. 3 stocks an apparatus main body 101, a paper feed tray 102 for loading paper loaded in the apparatus main body 101, and paper on which an image is recorded (formed) mounted on the apparatus main body 101. The sheet discharge tray 103 is provided. The upper surface of the upper cover 111 of the apparatus main body 101 is a substantially flat surface, and the front surface 112 of the front cover of the apparatus main body 101 is inclined obliquely rearward with respect to the upper surface. A paper discharge tray 103 and a paper feed tray 102 protruding toward the front side are provided. Further, an ink cartridge loading section 104 is provided on the end portion of the front surface 112 so as to protrude forward from the front surface 112 and lower than the upper cover 111. An operation key or the like is provided on the upper surface of the ink cartridge loading section 104. An operation unit 105 such as a display is arranged. The ink cartridge loading unit 104 has an openable / closable front cover 115 for attaching and detaching the ink cartridge.

  As shown in FIGS. 4 and 5, in the apparatus main body 101, a carriage 133 is slidably held in the main scanning direction by guide rods 131 and stays 132 that are horizontally mounted on left and right side plates (not shown). The main scanning motor (not shown) moves and scans in the carriage scanning direction of FIG.

  On the carriage 133, a recording head 134 composed of four ink jet heads for ejecting ink droplets of yellow, cyan, magenta, and black is arranged with a plurality of ink ejection openings in a direction intersecting with the main scanning direction to eject ink droplets. Wearing the direction downward. As a head constituting the recording head 134, a piezoelectric actuator such as a piezoelectric element, a thermal actuator that uses a phase change caused by film boiling of a liquid using an electrothermal transducer such as a heating resistor, and a metal phase change caused by a temperature change are used. A shape memory alloy actuator, an electrostatic actuator using an electrostatic force, or the like provided as energy generating means for discharging ink can be used.

  In addition, the carriage 133 is equipped with a sub tank 135 for each color for supplying ink of each color to the recording head 134. Ink is replenished and supplied to the sub tank 135 from an ink cartridge loaded in the ink cartridge loading unit 104 via an ink supply tube (not shown).

  On the other hand, as a paper feeding unit for feeding the paper 142 stacked on the paper stacking unit (pressure plate) 141 of the paper feed tray 102, half a month to separate and feed the paper 142 one by one from the paper stacking unit (pressure plate) 141. A separation pad 144 made of a material having a large coefficient of friction is provided opposite to the roller (sheet feeding roller) 143 and the sheet feeding roller 143, and the separation pad 144 is urged toward the sheet feeding roller 143 side.

  As a transport unit for transporting the paper 142 fed from the paper feed unit on the lower side of the recording head 134, a transport belt 151 for electrostatically attracting and transporting the paper 142, and a paper feed unit A counter roller 152 for transporting the paper 142 fed through the guide 145 while sandwiching it between the transport belt 151 and the paper 142 fed substantially vertically upward are changed by approximately 90 ° and copied onto the transport belt 151. A conveyance guide 153 for adjusting the pressure and a tip pressure roller 155 urged toward the conveyance belt 151 by a pressing member 154. In addition, a charging roller 156 that is a charging unit for charging the surface of the conveyance belt 151 is provided.

  Here, the conveyance belt 151 is an endless belt, and is configured to wrap around the conveyance roller 157 and the tension roller 158 and circulate in the belt conveyance direction. This transport belt 151 is, for example, a surface layer that is a sheet adsorbing surface formed of a pure resin material having a thickness of about 40 μm that is not subjected to resistance control, for example, ETFE pure material, and resistance control by carbon with the same material as this surface layer. And a back layer (medium resistance layer, ground layer). In addition, a guide member 161 is disposed on the back side of the conveyance belt 151 so as to correspond to a printing area by the recording head 134. Further, as a paper discharge unit for discharging the paper 142 recorded by the recording head 134, a separation claw 171 for separating the paper 142 from the transport belt 151, a paper discharge roller 172, and a paper discharge roller 173 are provided. A paper discharge tray 103 is provided below the paper discharge roller 172.

  The ink jet recording apparatus and the ink jet recording method of the present invention can be applied to various types of recording by the ink jet recording method, and are particularly suitable for, for example, an ink jet recording printer, a facsimile apparatus, a copying apparatus, and a printer / fax / copier multifunction machine. Can be applied to.

Next, the ink jet head will be described.
FIG. 6 is an enlarged view of elements of an ink jet head to which the present invention is applied, and FIG. 7 is an enlarged cross-sectional view of a main part in the direction between channels of the ink jet head.

  This ink jet head has an ink supply port (not shown) (supplying ink from the front surface direction to the back direction (back surface direction of the paper) in FIG. 6) and a frame 10 formed with a carving that becomes a common liquid chamber 12. The flow resistance plate 21, the engraving that forms the pressurized liquid chamber 22, the flow path plate 20 that forms the communication port 23 that communicates with the nozzle 41, the nozzle plate 30 that forms the nozzle 41, the convex portion 61, and the diaphragm portion 62. And a diaphragm 60 having an ink inlet 63, a laminated piezoelectric element 50 joined to the diaphragm 60 via an adhesive layer 70, and a base 40 to which the laminated piezoelectric element 50 is fixed. The base 40 is made of a barium titanate ceramic, and the laminated piezoelectric elements 50 are arranged in two rows and joined.

The laminated piezoelectric element 50 is composed of a lead zirconate titanate (PZT) piezoelectric layer 51 having a thickness of 10 to 50 μm / layer and an internal electrode layer 52 made of silver / palladium (AgPd) having a thickness of several μm / layer alternately. Are stacked. The internal electrode layer 52 is connected to the external electrode 53 at both ends. The laminated piezoelectric element 50 is divided onto comb teeth by half-cut dicing, and is used as a drive unit 56 and a support unit 57 (non-drive unit) one by one (see FIG. 7).
The outer end of one of the two external electrodes 53 (continuous to one end of the internal electrode layer 52 in the front or back direction (the back side of the paper) in the figure) is cut out so as to be divided by half-cut dicing. The length is limited by such processing, and these become a plurality of individual electrodes 54. The other is conductive without being divided by dicing, and becomes the common electrode 55.
An FPC 80 is soldered to the individual electrode 54 of the drive unit. The common electrode 55 is joined to the Gnd electrode of the FPC 80 by providing an electrode layer at the end of the laminated piezoelectric element 50 and turning it around. A driver IC (not shown) is mounted on the FPC 80, thereby controlling application of a drive voltage to the drive unit 56.

The diaphragm 60 includes a thin-film diaphragm portion 62, an island-shaped convex portion (island portion) 61 that is bonded to the laminated piezoelectric element 50 that is the driving portion 56 formed at the center portion of the diaphragm portion 62, and illustration is omitted. A thick film portion including a beam to be joined to the supporting portion and an opening to be an ink inlet 63 are formed by stacking two Ni plating films by an electroforming method. The diaphragm portion has a thickness of 3 μm and a width of 35 μm (one side).
The island-shaped convex portion 61 of the diaphragm 60 and the movable portion 56 of the laminated piezoelectric element 50, and the coupling of the diaphragm 60 and the frame 10 are bonded by patterning the adhesive layer 70 including a gap material.

  The flow path plate 20 was formed by using a silicon single crystal substrate, and patterning the engravings to be the fluid resistance portion 21 and the pressurized liquid chamber 22 and the through holes to be the communication ports 23 at positions relative to the nozzles 41 by an etching method. The portion left by etching becomes the partition wall 24 of the pressurized liquid chamber 22. Further, in this head, a portion for narrowing the etching width is provided, and this is used as the fluid resistance portion 21.

  The nozzle plate 30 is formed of a metal material, for example, an Ni plating film formed by an electroforming method, and has a large number of nozzles 41 that are fine discharge ports for causing ink droplets to fly. The internal shape (inner shape) of the nozzle 41 is formed in a horn shape (may be a substantially cylindrical shape or a substantially frustum shape). The diameter of the nozzle 41 is 20 μm to 35 μm on the ink droplet outlet side. The nozzle pitch of each row was 150 dpi.

  An ink repellent layer 90 is provided on the ink ejection surface (nozzle surface side) of the nozzle plate 30. In the present invention, in order to maintain sufficient ink repellency even for ink containing a fluorosurfactant, the ink repellent layer is composed of a structure containing a silicone resin. The structure containing a silicone resin is constituted by a silicone resin alone or a mixture with other components such as other resins and metals. For example, silicone resin fine particles dispersed in a fluororesin, silicone Examples thereof include a kneaded product of resin and polypropylene, and a eutectoid plating of silicone resin and Ni. In order to suppress the elution of the silicone resin, a mixture of the silicone resin and other components is more effective.

In the ink jet head configured as described above, a drive waveform (pulse voltage of 10 V to 50 V) is applied to the drive unit 56 in accordance with a recording signal, whereby a displacement in the stacking direction occurs in the drive unit 56, and the diaphragm 60. The pressurized liquid chamber 22 is pressurized via the pressure to increase the pressure, and ink droplets are ejected from the nozzle 41.
Thereafter, the ink pressure in the pressurizing liquid chamber 22 decreases with the end of ink droplet ejection, and negative pressure is generated in the pressurizing liquid chamber 22 due to the inertia of the ink flow and the discharge process of the drive pulse, and the ink is filled. Move to the process. At this time, the ink supplied from the ink tank flows into the common liquid chamber 12, passes from the common liquid chamber 12 through the ink inlet 63, passes through the fluid resistance portion 21, and is filled into the pressurized liquid chamber 22.
The fluid resistance portion 21 is effective in damping residual pressure vibration after ejection, but becomes resistant to refilling (refilling) due to surface tension. By appropriately selecting the fluid resistance portion, it is possible to balance the attenuation of the residual pressure and the refill time, and to shorten the time (drive cycle) until the transition to the next ink droplet ejection operation.

<Ink record>
The ink recorded matter has an image formed on each recording medium using each ink of the ink set of the present invention.
There is no restriction | limiting in particular as said recording medium, According to the objective, it can select suitably, For example, a plain paper, glossy paper, special paper, cloth, a film, an OHP sheet etc. are mentioned. These may be used individually by 1 type and may use 2 or more types together. Among these, the recording medium in the ink media set of the present invention is particularly preferable.
The ink recorded matter has high image quality, no bleeding, excellent temporal stability, and can be suitably used for various purposes as a material on which various prints or images are recorded.

  Examples of the present invention will be described below, but the present invention is not limited to these examples.

ただし、前記一般式（１）中、Ｌ＝０、ｎは４０を表す。
・イオン交換水・・・残量
上記の混合物をプレミックスした後、ディスクタイプのビーズミル（シンマルエンタープライゼス社ＫＤＬ型、メディア：直径０．３ｍｍのジルコニアボール使用）で循環分散して顔料分散液（ａ）を得た。 (Production Example 1)
<Preparation of pigment dispersion (a)>
・ C. I. Pigment Blue 15: 3 (Dainippon Seika Co., Ltd., Cyanine Blue A-292) 15 parts by mass A compound represented by the following general formula (1) (polyoxyethylene (n = 40) β-naphthyl) Ether) ... 12 parts by mass

However, in the said General formula (1), L = 0 and n represent 40.
・ Ion-exchanged water: remaining amount After premixing the above mixture, it is circulated and dispersed in a disk-type bead mill (Shinmaru Enterprises KDL type, media: zirconia balls with a diameter of 0.3 mm) to prepare a pigment dispersion. (A) was obtained.

ただし、前記一般式（２）中、ｍは２、ｎは１０を表す。
・イオン交換水・・・残量
上記の処方によりインクを調製し、１時間３０分間撹拌後、孔径０．８μｍのメンブランフィルターでろ過し、インクを得た。
インクの調合順序は、（１）グリセリン及びジエチレングリコール、（２）界面活性剤、（３）イオン交換水とし、３０分間撹拌した後、上記顔料分散液（ａ）を添加し、１時間撹拌してインクを作製した。 <Preparation of ink (1)>
Pigment dispersion (a): 40 parts by mass Glycerin: 12 parts by mass Diethylene glycol: 19.2 parts by mass Surfactant represented by the following general formula (2): 2 parts by mass Part

However, in said general formula (2), m represents 2 and n represents 10.
-Ion-exchanged water: remaining amount An ink was prepared according to the above formulation, stirred for 1 hour and 30 minutes, and then filtered through a membrane filter having a pore size of 0.8 µm to obtain an ink.
The order of ink preparation was (1) glycerin and diethylene glycol, (2) surfactant, (3) ion-exchanged water, stirred for 30 minutes, then added the pigment dispersion (a) and stirred for 1 hour. An ink was prepared.

ただし、前記一般式（１）中、Ｌ＝０、ｎは４０を表す。
・イオン交換水・・・残量
上記の混合物をプレミックスした後、ディスクタイプのビーズミル（シンマルエンタープライゼス社ＫＤＬ型、メディア：直径０．３ｍｍのジルコニアボール使用）で循環分散して顔料分散液（ｂ）を得た。 (Production Example 2)
<Preparation of pigment dispersion (b)>
・ C. I. Pigment Red 122 (FASTOGEN SUPER MAGENTA RG, manufactured by Dainippon Ink & Chemicals, Inc.) 15 parts by mass A compound represented by the following general formula (1) (polyoxyethylene (n = 40) β-naphthyl ether) ... 10 parts by mass

However, in the said General formula (1), L = 0 and n represent 40.
・ Ion-exchanged water: remaining amount After premixing the above mixture, it is circulated and dispersed in a disk-type bead mill (Shinmaru Enterprises KDL type, media: zirconia balls with a diameter of 0.3 mm) to obtain a pigment dispersion. (B) was obtained.

ただし、前記一般式（２）中、ｍは２、ｎは１０を表す。
・イオン交換水・・・残量
上記の処方によりインクを調製し、１時間３０分間撹拌後、孔径０．８μｍのメンブランフィルターでろ過し、インクを得た。
インクの調合順序は、（１）グリセリン及びジエチレングリコール、（２）界面活性剤、（３）イオン交換水とし、３０分間撹拌した後、上記顔料分散液（ｂ）を添加し、１時間撹拌してインクを作製した。 <Preparation of ink (2)>
Pigment dispersion (b): 40 parts by mass Glycerin: 12 parts by mass Diethylene glycol: 19.2 parts by mass Surfactant represented by the following general formula (2): 2 parts by mass Part

However, in said general formula (2), m represents 2 and n represents 10.
-Ion-exchanged water: remaining amount An ink was prepared according to the above formulation, stirred for 1 hour and 30 minutes, and then filtered through a membrane filter having a pore size of 0.8 µm to obtain an ink.
The order of ink preparation was (1) glycerin and diethylene glycol, (2) surfactant, (3) ion-exchanged water, stirred for 30 minutes, then added the pigment dispersion (b) and stirred for 1 hour. An ink was prepared.

ただし、前記一般式（１）中、Ｌ＝０、ｎは４０を表す。
・イオン交換水・・・残量
上記の混合物をプレミックスした後、ディスクタイプのビーズミル（シンマルエンタープライゼス社ＫＤＬ型、メディア：直径０．３ｍｍのジルコニアボール使用）で循環分散して顔料分散液（ｃ）を得た。 (Production Example 3)
<Preparation of pigment dispersion (c)>
・ C. I. Pigment Yellow 74 (Dainippon Seika Co., Ltd., Yellow No. 43) 15 parts by mass A compound represented by the following general formula (1) (polyoxyethylene (n = 40) β-naphthyl ether) ..10 parts by mass

However, in the said General formula (1), L = 0 and n represent 40.
・ Ion-exchanged water: remaining amount After premixing the above mixture, it is circulated and dispersed in a disk-type bead mill (Shinmaru Enterprises KDL type, media: zirconia balls with a diameter of 0.3 mm) to obtain a pigment dispersion. (C) was obtained.

ただし、前記一般式（２）中、ｍは２、ｎは１０を表す。
・イオン交換水・・・残量
上記の処方によりインクを調製し、１時間３０分間撹拌後、孔径０．８μｍのメンブランフィルターでろ過し、インクを得た。
インクの調合順序は、（１）グリセリン及びジエチレングリコール、（２）界面活性剤、（３）イオン交換水とし、３０分間撹拌した後、上記顔料分散液（ｃ）を添加し、１時間撹拌してインクを作製した。 <Preparation of ink (3)>
Pigment dispersion (c): 40 parts by mass Glycerin: 12 parts by mass Diethylene glycol: 19.2 parts by mass Surfactant represented by the following general formula (2): 2 parts by mass Part

However, in said general formula (2), m represents 2 and n represents 10.
-Ion-exchanged water: remaining amount An ink was prepared according to the above formulation, stirred for 1 hour and 30 minutes, and then filtered through a membrane filter having a pore size of 0.8 µm to obtain an ink.
The order of ink preparation was (1) glycerin and diethylene glycol, (2) surfactant, (3) ion-exchanged water, stirred for 30 minutes, then added the pigment dispersion (c) and stirred for 1 hour. An ink was prepared.

(Production Example 4)
<Preparation of ink (4)>
-Pigment dispersion (a)-40 parts by mass-Glycerin-12 parts by mass-Ethylene glycol-16.8 parts by mass-Polyoxyalkylene derivatives as surfactants (10 to 15 carbon atoms) ... 2 parts by mass-Ion-exchanged water ... remaining amount An ink was prepared according to the above formulation, stirred for 1 hour and 30 minutes, and then filtered through a membrane filter having a pore size of 0.8 µm to obtain an ink.
The ink was prepared in the order of (1) glycerin and ethylene glycol, (2) surfactant, (3) ion-exchanged water, stirred for 30 minutes, then added the pigment dispersion (a) and stirred for 1 hour. Ink was prepared.

(Production Example 5)
<Preparation of ink (5)>
-Pigment dispersion (b)-40 parts by mass-Glycerin-12 parts by mass-Ethylene glycol-16.8 parts by mass-Polyoxyalkylene derivatives as surfactants (C10-15) ... 2 parts by mass-Ion-exchanged water ... remaining amount An ink was prepared according to the above formulation, stirred for 1 hour and 30 minutes, and then filtered through a membrane filter having a pore size of 0.8 µm to obtain an ink.
The ink was prepared in the order of (1) glycerin and ethylene glycol, (2) surfactant, (3) ion-exchanged water, stirred for 30 minutes, then added with the pigment dispersion (b) and stirred for 1 hour. Thus, an ink was prepared.

(Production Example 6)
<Preparation of ink (6)>
-Pigment dispersion (c)-40 parts by mass-Glycerin-12 parts by mass-Ethylene glycol-16.8 parts by mass-Polyoxyalkylene derivatives as surfactants (C10-15) ... 2 parts by mass-Ion-exchanged water ... remaining amount An ink was prepared according to the above formulation, stirred for 1 hour and 30 minutes, and then filtered through a membrane filter having a pore size of 0.8 µm to obtain an ink.
The ink was prepared in the order of (1) glycerin and ethylene glycol, (2) surfactant, (3) ion-exchanged water, stirred for 30 minutes, then added with the pigment dispersion (c) and stirred for 1 hour. Thus, an ink was prepared.

ただし、前記一般式（３）中、ＲｆはＣＦ_２ＣＦ_３を表す。ｍは２、ｎは４、ｐは４を表す。
・イオン交換水・・・残量
上記の処方によりインクを調製し、１時間３０分間撹拌後、孔径０．８μｍのメンブランフィルターでろ過し、インクを得た。
インクの調合順序は、（１）グリセリン及びトリエチレングリコール、（２）界面活性剤、（３）イオン交換水とし、３０分間撹拌した後、上記顔料分散液（ａ）を添加し、１時間撹拌してインクを作製した。 (Production Example 7)
<Preparation of ink (7)>
Pigment dispersion (a): 40 parts by mass Glycerin: 5 parts by mass Triethylene glycol: 6 parts by mass Surfactant represented by the following general formula (3): 2 parts by mass Part

In the general formula (3), Rf represents _CF 2 CF _3. m represents 2, n represents 4, and p represents 4.
-Ion-exchanged water: remaining amount An ink was prepared according to the above formulation, stirred for 1 hour and 30 minutes, and then filtered through a membrane filter having a pore size of 0.8 µm to obtain an ink.
The ink was prepared in the order of (1) glycerin and triethylene glycol, (2) surfactant, (3) ion-exchanged water, stirred for 30 minutes, added with the pigment dispersion (a) and stirred for 1 hour. Thus, an ink was prepared.

ただし、前記一般式（３）中、ＲｆはＣＦ_２ＣＦ_３を表す。ｍは２、ｎは４、ｐは４を表す。
・イオン交換水・・・残量
上記の処方によりインクを調製し、１時間３０分間撹拌後、孔径０．８μｍのメンブランフィルターでろ過し、インクを得た。
インクの調合順序は、（１）グリセリン及びトリエチレングリコール、（２）界面活性剤、（３）イオン交換水とし、３０分間撹拌した後、上記顔料分散液（ｂ）を添加し、１時間撹拌してインクを作製した。 (Production Example 8)
<Preparation of ink (8)>
-Pigment dispersion (b)-40 parts by mass-Glycerin-5 parts by mass-Triethylene glycol-6.5 parts by mass-Surfactant represented by the following general formula (3)- 2 parts by mass

In the general formula (3), Rf represents _CF 2 CF _3. m represents 2, n represents 4, and p represents 4.
-Ion-exchanged water: remaining amount An ink was prepared according to the above formulation, stirred for 1 hour and 30 minutes, and then filtered through a membrane filter having a pore size of 0.8 µm to obtain an ink.
The ink was prepared in the order of (1) glycerin and triethylene glycol, (2) surfactant, (3) ion-exchanged water, stirred for 30 minutes, added with the pigment dispersion (b) and stirred for 1 hour. Thus, an ink was prepared.

ただし、前記一般式（３）中、ＲｆはＣＦ_２ＣＦ_３を表す。ｍは２、ｎは４、ｐは４を表す。
・イオン交換水・・・残量
上記の処方によりインクを調製し、１時間３０分間撹拌後、孔径０．８μｍのメンブランフィルターでろ過し、インクを得た。
インクの調合順序は、（１）グリセリン及びトリエチレングリコール、（２）界面活性剤、（３）イオン交換水とし、３０分間撹拌した後、上記の顔料分散液（ｃ）を添加し、１時間撹拌してインクを作製した。 (Production Example 9)
<Preparation of ink (9)>
-Pigment dispersion (c)-40 parts by mass-Glycerin-5 parts by mass-Triethylene glycol-6.5 parts by mass-Surfactant represented by the following general formula (3)- 2 parts by mass

In the general formula (3), Rf represents _CF 2 CF _3. m represents 2, n represents 4, and p represents 4.
-Ion-exchanged water: remaining amount An ink was prepared according to the above formulation, stirred for 1 hour and 30 minutes, and then filtered through a membrane filter having a pore size of 0.8 µm to obtain an ink.
The ink was prepared in the following order: (1) glycerin and triethylene glycol, (2) surfactant, (3) ion-exchanged water, stirred for 30 minutes, and then added the pigment dispersion (c) described above for 1 hour. The ink was prepared by stirring.

ただし、前記一般式（２）中、ｍは２、ｎは１０を表す。
・イオン交換水・・・残量
上記の処方によりインクを調製し、１時間３０分間撹拌後、孔径０．８μｍのメンブランフィルターでろ過し、インクを得た。
インクの調合順序は、（１）グリセリン及びプロピレングリコール、（２）界面活性剤、（３）イオン交換水とし、３０分間撹拌した後、上記顔料分散液（ａ）を添加し、１時間撹拌してインクを作製した。 (Production Example 10)
<Preparation of ink (10)>
Pigment dispersion (a): 40 parts by mass Glycerin: 15 parts by mass Propylene glycol: 19.2 parts by mass Surfactant represented by the following general formula (2): 2 Parts by mass

However, in said general formula (2), m represents 2 and n represents 10.
-Ion-exchanged water: remaining amount An ink was prepared according to the above formulation, stirred for 1 hour and 30 minutes, and then filtered through a membrane filter having a pore size of 0.8 µm to obtain an ink.
The ink was prepared in the order of (1) glycerin and propylene glycol, (2) surfactant, (3) ion-exchanged water, stirred for 30 minutes, added with the pigment dispersion (a) and stirred for 1 hour. Ink was prepared.

ただし、前記一般式（２）中、ｍは２、ｎは１０を表す。
・イオン交換水・・・残量
上記の処方によりインクを調製し、１時間３０分間撹拌後、孔径０．８μｍのメンブランフィルターでろ過し、インクを得た。
インクの調合順序は、（１）グリセリン及びプロピレングリコール、（２）界面活性剤、（３）イオン交換水とし、３０分間撹拌した後、上記顔料分散液（ｂ）を添加し、１時間撹拌してインクを作製した。 (Production Example 11)
<Preparation of ink (11)>
Pigment dispersion (b): 40 parts by mass Glycerin: 15 parts by mass Propylene glycol: 19.2 parts by mass Surfactant represented by the following general formula (2): 2 Parts by mass

However, in said general formula (2), m represents 2 and n represents 10.
-Ion-exchanged water: remaining amount An ink was prepared according to the above formulation, stirred for 1 hour and 30 minutes, and then filtered through a membrane filter having a pore size of 0.8 µm to obtain an ink.
The order of ink preparation was (1) glycerin and propylene glycol, (2) surfactant, (3) ion-exchanged water, stirred for 30 minutes, then added the pigment dispersion (b) and stirred for 1 hour. Ink was prepared.

ただし、前記一般式（２）中、ｍは２、ｎは１０を表す。
イオン交換水・・・残量
上記の処方によりインクを調製し、１時間３０分間撹拌後、孔径０．８μｍのメンブランフィルターでろ過し、インクを得た。
インクの調合順序は、（１）グリセリン及びプロピレングリコール、（２）界面活性剤、（３）イオン交換水とし、３０分間撹拌した後、上記顔料分散液（ｃ）を添加し、１時間撹拌してインクを作製した。 (Production Example 12)
<Preparation of ink (12)>
-Pigment dispersion (c)-40 parts by mass-Glycerin-15 parts by mass-Propylene glycol-19.2 parts by mass-Surfactant represented by the following general formula (2)-2 Parts by mass

However, in said general formula (2), m represents 2 and n represents 10.
Ion exchange water: remaining amount An ink was prepared according to the above formulation, stirred for 1 hour and 30 minutes, and then filtered through a membrane filter having a pore size of 0.8 μm to obtain an ink.
The order of ink preparation was (1) glycerin and propylene glycol, (2) surfactant, (3) ion-exchanged water, stirred for 30 minutes, then added the pigment dispersion (c) and stirred for 1 hour. Ink was prepared.

ただし、前記一般式（２）中、ｍは２、ｎは１０を表す。
・イオン交換水・・・残量
上記の処方によりインクを調製し、１時間３０分間撹拌後、孔径０．８μｍのメンブランフィルターでろ過し、インクを得た。
インクの調合順序は、（１）グリセリン及びジプロピレングリコール、（２）界面活性剤、（３）イオン交換水とし、３０分間撹拌した後、上記顔料分散液（ａ）を添加し、１時間撹拌してインクを作製した。 (Production Example 13)
<Preparation of ink (13)>
Pigment dispersion (a): 40 parts by mass Glycerin: 15 parts by mass Dipropylene glycol: 19.2 parts by mass Surfactant represented by the following general formula (2) 2 parts by mass

However, in said general formula (2), m represents 2 and n represents 10.
-Ion-exchanged water: remaining amount An ink was prepared according to the above formulation, stirred for 1 hour and 30 minutes, and then filtered through a membrane filter having a pore size of 0.8 µm to obtain an ink.
The ink was prepared in the order of (1) glycerin and dipropylene glycol, (2) surfactant, (3) ion-exchanged water, stirred for 30 minutes, added with the pigment dispersion (a) and stirred for 1 hour. Thus, an ink was prepared.

ただし、前記一般式（２）中、ｍは２、ｎは１０を表す。
・イオン交換水・・・残量
上記の処方によりインクを調製し、１時間３０分間撹拌後、孔径０．８μｍのメンブランフィルターでろ過し、インクを得た。
インクの調合順序は、（１）グリセリン及びジプロピレングリコール、（２）界面活性剤、（３）イオン交換水とし、３０分間撹拌した後、上記顔料分散液（ｂ）を添加し、１時間撹拌してインクを作製した。 (Production Example 14)
<Preparation of ink (14)>
-Pigment dispersion (b) ... 40 parts by mass-Glycerin ... 15 parts by mass-Dipropylene glycol ... 19.2 parts by mass-Surfactant represented by the following general formula (2) ... 2 parts by mass

However, in said general formula (2), m represents 2 and n represents 10.
-Ion-exchanged water: remaining amount An ink was prepared according to the above formulation, stirred for 1 hour and 30 minutes, and then filtered through a membrane filter having a pore size of 0.8 µm to obtain an ink.
The ink was prepared in the order of (1) glycerin and dipropylene glycol, (2) surfactant, (3) ion-exchanged water, stirred for 30 minutes, added with the pigment dispersion (b) and stirred for 1 hour. Thus, an ink was prepared.

ただし、前記一般式（２）中、ｍは２、ｎは１０を表す。
・イオン交換水・・・残量
上記の処方によりインクを調製し、１時間３０分間間撹拌後、孔径０．８μｍのメンブランフィルターでろ過し、インクを得た。
インクの調合順序は、（１）グリセリン及びジプロピレングリコール、（２）界面活性剤、（３）イオン交換水とし、３０分間撹拌した後、上記顔料分散液（ｃ）を添加し、１時間撹拌してインクを作製した。 (Production Example 15)
<Preparation of ink (15)>
-Pigment dispersion (c) ... 40 parts by mass-Glycerin ... 15 parts by mass-Dipropylene glycol ... 19.2 parts by mass-Surfactant represented by the following general formula (2) ... 2 parts by mass

However, in said general formula (2), m represents 2 and n represents 10.
-Ion-exchanged water: remaining amount An ink was prepared according to the above formulation, stirred for 1 hour and 30 minutes, and then filtered through a membrane filter having a pore size of 0.8 µm to obtain an ink.
The ink was prepared in the order of (1) glycerin and dipropylene glycol, (2) surfactant, (3) ion-exchanged water, stirred for 30 minutes, added with the pigment dispersion (c), and stirred for 1 hour. Thus, an ink was prepared.

ただし、前記一般式（２）中、ｍは２、ｎは１０を表す。
・イオン交換水・・・残量
上記処方によりインクを調製し、１時間３０分間撹拌後、孔径０．８μｍのメンブランフィルターでろ過し、インクを得た。
インクの調合順序は、（１）グリセリン及びトリプロピレングリコール、（２）界面活性剤、（３）イオン交換水とし、３０分間撹拌した後、上記顔料分散液（ａ）を添加し、１時間撹拌してインクを作製した。 (Production Example 16)
<Preparation of ink (16)>
Pigment dispersion (a): 40 parts by mass Glycerin: 15 parts by mass Tripropylene glycol: 19.2 parts by mass Surfactant represented by the following general formula (2) 2 parts by mass

However, in said general formula (2), m represents 2 and n represents 10.
-Ion-exchanged water: remaining amount An ink was prepared according to the above formulation, stirred for 1 hour and 30 minutes, and then filtered through a membrane filter having a pore size of 0.8 µm to obtain an ink.
The ink was prepared in the order of (1) glycerin and tripropylene glycol, (2) surfactant, (3) ion-exchanged water, stirred for 30 minutes, then added with the pigment dispersion (a) and stirred for 1 hour. Thus, an ink was prepared.

ただし、前記一般式（２）中、ｍは２、ｎは１０を表す。
・イオン交換水・・・残量
上記処方によりインクを調製し、１時間３０分間撹拌後、孔径０．８μｍのメンブランフィルターでろ過し、インクを得た。
インクの調合順序は、（１）グリセリン及びトリプロピレングリコール、（２）界面活性剤、（３）イオン交換水とし、３０分間撹拌した後、上記顔料分散液（ｂ）を添加し、１時間撹拌してインクを作製した。 (Production Example 17)
<Preparation of ink (17)>
-Pigment dispersion (b) ... 40 parts by mass-Glycerin ... 15 parts by mass-Tripropylene glycol ... 19.2 parts by mass-Surfactant represented by the following general formula (2) ... 2 parts by mass

However, in said general formula (2), m represents 2 and n represents 10.
-Ion-exchanged water: remaining amount An ink was prepared according to the above formulation, stirred for 1 hour and 30 minutes, and then filtered through a membrane filter having a pore size of 0.8 µm to obtain an ink.
The ink was prepared in the order of (1) glycerin and tripropylene glycol, (2) surfactant, (3) ion-exchanged water, stirred for 30 minutes, added with the pigment dispersion (b) and stirred for 1 hour. Thus, an ink was prepared.

ただし、前記一般式（２）中、ｍは２、ｎは１０を表す。
・イオン交換水・・・残量
上記の処方によりインクを調製し、１時間３０分間撹拌後、孔径０．８μｍのメンブランフィルターでろ過し、インクを得た。
インクの調合順序は、（１）グリセリン及びトリプロピレングリコール、（２）界面活性剤、（３）イオン交換水とし、３０分間撹拌した後、上記顔料分散液（ｃ）を添加し、１時間撹拌してインクを作製した。 (Production Example 18)
<Preparation of ink (18)>
-Pigment dispersion (c) ... 40 parts by mass-Glycerin ... 15 parts by mass-Tripropylene glycol ... 19.2 parts by mass-Surfactant represented by the following general formula (2) ... 2 parts by mass

However, in said general formula (2), m represents 2 and n represents 10.
-Ion-exchanged water: remaining amount An ink was prepared according to the above formulation, stirred for 1 hour and 30 minutes, and then filtered through a membrane filter having a pore size of 0.8 µm to obtain an ink.
The ink was prepared in the order of (1) glycerin and tripropylene glycol, (2) surfactant, (3) ion-exchanged water, stirred for 30 minutes, added with the pigment dispersion (c), and stirred for 1 hour. Thus, an ink was prepared.

ただし、前記一般式（２）中、ｍは２、ｎは１０を表す。
・イオン交換水・・・残量
上記の処方によりインクを調製し、１時間３０分間撹拌後、孔径０．８μｍのメンブランフィルターでろ過し、インクを得た。
インクの調合順序は、（１）グリセリン及び１，３−ブタンジオール、（２）界面活性剤、（３）イオン交換水とし、３０分間撹拌した後、上記顔料分散液（ａ）を添加し、１時間撹拌してインクを作製した。 (Production Example 19)
<Preparation of ink (19)>
-Pigment dispersion (a)-40 parts by mass-Glycerin-15 parts by mass-1,3-butanediol-19.2 parts by mass-Surfactant represented by the following general formula (2) ... 2 parts by mass

However, in said general formula (2), m represents 2 and n represents 10.
-Ion-exchanged water: remaining amount An ink was prepared according to the above formulation, stirred for 1 hour and 30 minutes, and then filtered through a membrane filter having a pore size of 0.8 µm to obtain an ink.
The order of ink preparation was (1) glycerin and 1,3-butanediol, (2) surfactant, (3) ion-exchanged water, stirred for 30 minutes, and then added the pigment dispersion (a). The ink was prepared by stirring for 1 hour.

ただし、前記一般式（２）中、ｍは２、ｎは１０を表す。
・イオン交換水・・・残量
上記の処方によりインクを調製し、１時間３０分間撹拌後、孔径０．８μｍのメンブランフィルターでろ過し、インクを得た。
インクの調合順序は、（１）グリセリン及び１，３−ブタンジオール、（２）界面活性剤、（３）イオン交換水とし、３０分間撹拌した後、上記顔料分散液（ｂ）を添加し、１時間撹拌してインクを作製した。 (Production Example 20)
<Preparation of ink (20)>
-Pigment dispersion (b)-40 parts by mass-Glycerin-15 parts by mass-1,3-butanediol-19.2 parts by mass-Surfactant represented by the following general formula (2) ... 2 parts by mass

However, in said general formula (2), m represents 2 and n represents 10.
-Ion-exchanged water: remaining amount An ink was prepared according to the above formulation, stirred for 1 hour and 30 minutes, and then filtered through a membrane filter having a pore size of 0.8 µm to obtain an ink.
The ink was prepared in the order of (1) glycerin and 1,3-butanediol, (2) surfactant, (3) ion-exchanged water, stirred for 30 minutes, and then added the pigment dispersion (b). The ink was prepared by stirring for 1 hour.

ただし、前記一般式（２）中、ｍは２、ｎは１０を表す。
・イオン交換水・・・残量
上記の処方によりインクを調製し、１時間３０分間撹拌後、孔径０．８μｍのメンブランフィルターでろ過し、インクを得た。
インクの調合順序は、（１）グリセリン及び１，３−ブタンジオール、（２）界面活性剤、（３）イオン交換水とし、３０分間撹拌した後、上記顔料分散液（ｃ）を添加し、１時間撹拌してインクを作製した。 (Production Example 21)
<Preparation of ink (21)>
-Pigment dispersion (c)-40 parts by mass-Glycerin-15 parts by mass-1,3-butanediol-19.2 parts by mass-Surfactant represented by the following general formula (2) ... 2 parts by mass

However, in said general formula (2), m represents 2 and n represents 10.
-Ion-exchanged water: remaining amount An ink was prepared according to the above formulation, stirred for 1 hour and 30 minutes, and then filtered through a membrane filter having a pore size of 0.8 µm to obtain an ink.
The ink was prepared in the order of (1) glycerin and 1,3-butanediol, (2) surfactant, (3) ion-exchanged water, stirred for 30 minutes, and then added the pigment dispersion (c). The ink was prepared by stirring for 1 hour.

ただし、前記一般式（２）中、ｍは２、ｎは１０を表す。
・イオン交換水・・・残量
上記の処方によりインクを調製し、１時間３０分間撹拌後、孔径０．８μｍのメンブランフィルターでろ過し、インクを得た。
インクの調合順序は、（１）グリセリン及び２，３−ブタンジオール、（２）界面活性剤、（３）イオン交換水とし、３０分間撹拌した後、上記顔料分散液（ａ）を添加し、１時間撹拌してインクを作製した。 (Production Example 22)
<Preparation of ink (22)>
-Pigment dispersion (a)-40 parts by mass-Glycerin-15 parts by mass-2,3-butanediol-19.2 parts by mass-Surfactant represented by the following general formula (2) ... 2 parts by mass

However, in said general formula (2), m represents 2 and n represents 10.
-Ion-exchanged water: remaining amount An ink was prepared according to the above formulation, stirred for 1 hour and 30 minutes, and then filtered through a membrane filter having a pore size of 0.8 µm to obtain an ink.
The order of ink preparation was (1) glycerin and 2,3-butanediol, (2) surfactant, (3) ion-exchanged water, stirred for 30 minutes, and then added the pigment dispersion (a). The ink was prepared by stirring for 1 hour.

ただし、前記一般式（２）中、ｍは２、ｎは１０を表す。
・イオン交換水・・・残量
上記の処方によりインクを調製し、１時間３０分間撹拌後、孔径０．８μｍのメンブランフィルターでろ過し、インクを得た。
インクの調合順序は、（１）グリセリン及び２，３−ブタンジオール、（２）界面活性剤、（３）イオン交換水とし、３０分間撹拌した後、上記顔料分散液（ｂ）を添加し、１時間撹拌してインクを作製した。 (Production Example 23)
<Preparation of ink (23)>
-Pigment dispersion (b)-40 parts by mass-Glycerin-15 parts by mass-2,3-butanediol-19.2 parts by mass-Surfactant represented by the following general formula (2) ... 2 parts by mass

However, in said general formula (2), m represents 2 and n represents 10.
-Ion-exchanged water: remaining amount An ink was prepared according to the above formulation, stirred for 1 hour and 30 minutes, and then filtered through a membrane filter having a pore size of 0.8 µm to obtain an ink.
The order of ink preparation was (1) glycerin and 2,3-butanediol, (2) surfactant, (3) ion-exchanged water, stirred for 30 minutes, and then added the pigment dispersion (b). The ink was prepared by stirring for 1 hour.

ただし、前記一般式（２）中、ｍは２、ｎは１０を表す。
・イオン交換水・・・残量
上記の処方によりインクを調製し、１時間３０分間撹拌後、孔径０．８μｍのメンブランフィルターでろ過し、インクを得た。
インクの調合順序は、（１）グリセリン及び２，３−ブタンジオール、（２）界面活性剤、（３）イオン交換水とし、３０分間撹拌した後、上記顔料分散液（ｃ）を添加し、１時間撹拌してインクを作製した。 (Production Example 24)
<Preparation of ink (24)>
-Pigment dispersion (c)-40 parts by mass-Glycerin-15 parts by mass-2,3-butanediol-19.2 parts by mass-Surfactant represented by the following general formula (2) ... 2 parts by mass

However, in said general formula (2), m represents 2 and n represents 10.
-Ion-exchanged water: remaining amount An ink was prepared according to the above formulation, stirred for 1 hour and 30 minutes, and then filtered through a membrane filter having a pore size of 0.8 µm to obtain an ink.
The order of ink preparation was (1) glycerin and 2,3-butanediol, (2) surfactant, (3) ion-exchanged water, stirred for 30 minutes, and then added the pigment dispersion (c). The ink was prepared by stirring for 1 hour.

ただし、前記一般式（２）中、ｍは２、ｎは１０を表す。
・イオン交換水・・・残量
上記の処方によりインクを調製し、１時間３０分間撹拌後、孔径０．８μｍのメンブランフィルターでろ過し、インクを得た。
インクの調合順序は、（１）グリセリン及び１，４−ブタンジオール、（２）界面活性剤、（３）イオン交換水とし、３０分間撹拌した後、上記顔料分散液（ａ）を添加し、１時間撹拌してインクを作製した。 (Production Example 25)
<Preparation of ink (25)>
-Pigment dispersion (a)-40 parts by mass-Glycerin-15 parts by mass-1,4-butanediol-19.2 parts by mass-Surfactant represented by the following general formula (2) ... 2 parts by mass

However, in said general formula (2), m represents 2 and n represents 10.
-Ion-exchanged water: remaining amount An ink was prepared according to the above formulation, stirred for 1 hour and 30 minutes, and then filtered through a membrane filter having a pore size of 0.8 µm to obtain an ink.
The ink preparation order was (1) glycerin and 1,4-butanediol, (2) surfactant, (3) ion-exchanged water, stirred for 30 minutes, and then added the pigment dispersion (a). The ink was prepared by stirring for 1 hour.

ただし、前記一般式（２）中、ｍは２、ｎは１０を表す。
・イオン交換水・・・残量
上記の処方によりインクを調製し、１時間３０分間撹拌後、孔径０．８μｍのメンブランフィルターでろ過し、インクを得た。
インクの調合順序は、（１）グリセリン及び１，４−ブタンジオール、（２）界面活性剤、（３）イオン交換水とし、３０分間撹拌した後、上記顔料分散液（ｂ）を添加し、１時間撹拌してインクを作製した。 (Production Example 26)
<Preparation of ink (26)>
Pigment dispersion (b): 40 parts by mass Glycerin: 15 parts by mass 1,4-butanediol: 19.2 parts by mass Surfactant represented by the following general formula (2) ... 2 parts by mass

However, in said general formula (2), m represents 2 and n represents 10.
-Ion-exchanged water: remaining amount An ink was prepared according to the above formulation, stirred for 1 hour and 30 minutes, and then filtered through a membrane filter having a pore size of 0.8 µm to obtain an ink.
The ink preparation order was (1) glycerin and 1,4-butanediol, (2) surfactant, (3) ion-exchanged water, stirred for 30 minutes, and then added the pigment dispersion (b). The ink was prepared by stirring for 1 hour.

ただし、前記一般式（２）中、ｍは２、ｎは１０を表す。
・イオン交換水・・・残量
上記の処方によりインクを調製し、１時間３０分間撹拌後、孔径０．８μｍのメンブランフィルターでろ過し、インクを得た。
インクの調合順序は、（１）グリセリン及び１，４−ブタンジオール、（２）界面活性剤、（３）イオン交換水とし、３０分間撹拌した後、上記顔料分散液（ｃ）を添加し、１時間撹拌してインクを作製した。 (Production Example 27)
<Preparation of ink (27)>
-Pigment dispersion (c)-40 parts by mass-Glycerin-15 parts by mass-1,4-butanediol-19.2 parts by mass-Surfactant represented by the following general formula (2) ... 2 parts by mass

However, in said general formula (2), m represents 2 and n represents 10.
-Ion-exchanged water: remaining amount An ink was prepared according to the above formulation, stirred for 1 hour and 30 minutes, and then filtered through a membrane filter having a pore size of 0.8 µm to obtain an ink.
The ink was prepared in the order of (1) glycerin and 1,4-butanediol, (2) surfactant, (3) ion-exchanged water, stirred for 30 minutes, and then added the pigment dispersion (c). The ink was prepared by stirring for 1 hour.

ただし、前記一般式（２）中、ｍは２、ｎは１０を表す。
・イオン交換水・・・残量
上記の処方によりインクを調製し、１時間３０分間撹拌後、孔径０．８μｍのメンブランフィルターでろ過し、インクを得た。
インクの調合順序は、（１）グリセリン及び３−メチル−１，３−ブタンジオール、（２）界面活性剤、（３）イオン交換水とし、３０分間撹拌した後、上記顔料分散液（ａ）を添加し、１時間撹拌してインクを作製した。 (Production Example 28)
<Preparation of ink (28)>
-Pigment dispersion (a)-40 parts by mass-Glycerin-15 parts by mass-3-Methyl-1,3-butanediol-19.2 parts by mass-Represented by the following general formula (2) 2 parts by weight of surfactant

However, in said general formula (2), m represents 2 and n represents 10.
-Ion-exchanged water: remaining amount An ink was prepared according to the above formulation, stirred for 1 hour and 30 minutes, and then filtered through a membrane filter having a pore size of 0.8 µm to obtain an ink.
The preparation order of the ink was (1) glycerin and 3-methyl-1,3-butanediol, (2) surfactant, (3) ion-exchanged water, stirred for 30 minutes, and then the pigment dispersion (a) Was added and stirred for 1 hour to prepare an ink.

ただし、前記一般式（２）中、ｍは２、ｎは１０を表す。
・イオン交換水・・・残量
上記の処方によりインクを調製し、１時間３０分間撹拌後、孔径０．８μｍのメンブランフィルターでろ過し、インクを得た。
インクの調合順序は、（１）グリセリン及び３−メチル−１，３−ブタンジオール、（２）界面活性剤、（３）イオン交換水とし、３０分間撹拌した後、上記顔料分散液（ｂ）を添加し、１時間撹拌してインクを作製した。 (Production Example 29)
<Preparation of ink (29)>
-Pigment dispersion (b) ... 40 parts by mass-Glycerin ... 15 parts by mass-3-Methyl-1,3-butanediol ... 19.2 parts by mass-Represented by the following general formula (2) 2 parts by weight of surfactant

However, in said general formula (2), m represents 2 and n represents 10.
-Ion-exchanged water: remaining amount An ink was prepared according to the above formulation, stirred for 1 hour and 30 minutes, and then filtered through a membrane filter having a pore size of 0.8 µm to obtain an ink.
The preparation order of the ink was (1) glycerin and 3-methyl-1,3-butanediol, (2) surfactant, (3) ion-exchanged water, stirred for 30 minutes, and then the pigment dispersion (b) Was added and stirred for 1 hour to prepare an ink.

ただし、前記一般式（２）中、ｍは２、ｎは１０を表す。
・イオン交換水・・・残量
上記の処方によりインクを調製し、１時間３０分間撹拌後、孔径０．８μｍのメンブランフィルターでろ過し、インクを得た。
インクの調合順序は、（１）グリセリン及び３−メチル−１，３−ブタンジオール、（２）界面活性剤、（３）イオン交換水とし、３０分間撹拌した後、上記顔料分散液（ｃ）を添加し、１時間撹拌してインクを作製した。 (Production Example 30)
<Preparation of ink (30)>
-Pigment dispersion (c)-40 parts by mass-Glycerin-15 parts by mass-3-Methyl-1,3-butanediol-19.2 parts by mass-Represented by the following general formula (2) 2 parts by weight of surfactant

However, in said general formula (2), m represents 2 and n represents 10.
-Ion-exchanged water: remaining amount An ink was prepared according to the above formulation, stirred for 1 hour and 30 minutes, and then filtered through a membrane filter having a pore size of 0.8 µm to obtain an ink.
The preparation order of the ink was (1) glycerin and 3-methyl-1,3-butanediol, (2) surfactant, (3) ion-exchanged water, stirred for 30 minutes, and then the pigment dispersion (c) Was added and stirred for 1 hour to prepare an ink.

ただし、前記一般式（２）中、ｍは２、ｎは１０を表す。
・イオン交換水・・・残量
上記の処方によりインクを調製し、１時間３０分間撹拌後、孔径０．８μｍのメンブランフィルターでろ過し、インクを得た。
インクの調合順序は、（１）グリセリン及び１，５−ペンタンジオール、（２）界面活性剤、（３）イオン交換水とし、３０分間撹拌した後、上記顔料分散液（ａ）を添加し、１時間撹拌してインクを作製した。 (Production Example 31)
<Preparation of ink (31)>
-Pigment dispersion (a)-40 parts by mass-Glycerin-15 parts by mass-1,5-pentanediol-19.2 parts by mass-Surfactant represented by the following general formula (2) ... 2 parts by mass

However, in said general formula (2), m represents 2 and n represents 10.
-Ion-exchanged water: remaining amount An ink was prepared according to the above formulation, stirred for 1 hour and 30 minutes, and then filtered through a membrane filter having a pore size of 0.8 µm to obtain an ink.
The ink preparation order was (1) glycerin and 1,5-pentanediol, (2) surfactant, (3) ion-exchanged water, stirred for 30 minutes, and then added the pigment dispersion (a). The ink was prepared by stirring for 1 hour.

ただし、前記一般式（２）中、ｍは２、ｎは１０を表す。
・イオン交換水・・・残量
上記の処方によりインクを調製し、１時間３０分間撹拌後、孔径０．８μｍのメンブランフィルターでろ過し、インクを得た。
インクの調合順序は、（１）グリセリン及び１，５−ペンタンジオール、（２）界面活性剤、（３）イオン交換水とし、３０分間撹拌した後、上記顔料分散液（ｂ）を添加し、１時間撹拌してインクを作製した。 (Production Example 32)
<Preparation of ink (32)>
-Pigment dispersion (b)-40 parts by mass-Glycerin-15 parts by mass-1,5-pentanediol-19.2 parts by mass-Surfactant represented by the following general formula (2) ... 2 parts by mass

However, in said general formula (2), m represents 2 and n represents 10.
-Ion-exchanged water: remaining amount An ink was prepared according to the above formulation, stirred for 1 hour and 30 minutes, and then filtered through a membrane filter having a pore size of 0.8 µm to obtain an ink.
The ink preparation order was (1) glycerin and 1,5-pentanediol, (2) surfactant, (3) ion-exchanged water, stirred for 30 minutes, and then added the pigment dispersion (b). The ink was prepared by stirring for 1 hour.

ただし、前記一般式（２）中、ｍは２、ｎは１０を表す。
・イオン交換水・・・残量
上記の処方によりインクを調製し、１時間３０分間撹拌後、孔径０．８μｍのメンブランフィルターでろ過し、インクを得た。
インクの調合順序は、（１）グリセリン及び１，５−ペンタンジオール、（２）界面活性剤、（３）イオン交換水とし、３０分間撹拌した後、上記顔料分散液（ｃ）を添加し、１時間撹拌してインクを作製した。 (Production Example 33)
<Preparation of ink (33)>
Pigment dispersion (c): 40 parts by mass Glycerin: 15 parts by mass 1,5-pentanediol: 19.2 parts by mass Surfactant represented by the following general formula (2) ... 2 parts by mass

However, in said general formula (2), m represents 2 and n represents 10.
-Ion-exchanged water: remaining amount An ink was prepared according to the above formulation, stirred for 1 hour and 30 minutes, and then filtered through a membrane filter having a pore size of 0.8 µm to obtain an ink.
The order of ink preparation was (1) glycerin and 1,5-pentanediol, (2) surfactant, (3) ion-exchanged water, stirred for 30 minutes, and then added the pigment dispersion (c). The ink was prepared by stirring for 1 hour.

ただし、前記一般式（２）中、ｍは２、ｎは１０を表す。
・イオン交換水・・・残量
上記の処方によりインクを調製し、１時間３０分間撹拌後、孔径０．８μｍのメンブランフィルターでろ過し、インクを得た。
インクの調合順序は、（１）グリセリン及びテトラエチレングリコール、（２）界面活性剤、（３）イオン交換水とし、３０分間撹拌した後、上記顔料分散液（ａ）を添加し、１時間撹拌してインクを作製した。 (Production Example 34)
<Preparation of ink (34)>
Pigment dispersion (a): 40 parts by mass Glycerin: 15 parts by mass Tetraethylene glycol: 19.2 parts by mass Surfactant represented by the following general formula (2) 2 parts by mass

However, in said general formula (2), m represents 2 and n represents 10.
-Ion-exchanged water: remaining amount An ink was prepared according to the above formulation, stirred for 1 hour and 30 minutes, and then filtered through a membrane filter having a pore size of 0.8 µm to obtain an ink.
The ink was prepared in the order of (1) glycerin and tetraethylene glycol, (2) surfactant, (3) ion-exchanged water, stirred for 30 minutes, added with the pigment dispersion (a) and stirred for 1 hour. Thus, an ink was prepared.

ただし、前記一般式（２）中、ｍは２、ｎは１０を表す。
・イオン交換水・・・残量
上記の処方によりインクを調製し、１時間３０分間撹拌後、孔径０．８μｍのメンブランフィルターでろ過し、インクを得た。
インクの調合順序は、（１）グリセリン及びテトラエチレングリコール、（２）界面活性剤、（３）イオン交換水とし、３０分間撹拌した後、上記顔料分散液（ｂ）を添加し、１時間撹拌してインクを作製した。 (Production Example 35)
<Preparation of ink (35)>
-Pigment dispersion (b) ... 40 parts by mass-Glycerin ... 15 parts by mass-Tetraethylene glycol ... 19.2 parts by mass-Surfactant represented by the following general formula (2) ... 2 parts by mass

However, in said general formula (2), m represents 2 and n represents 10.
-Ion-exchanged water: remaining amount An ink was prepared according to the above formulation, stirred for 1 hour and 30 minutes, and then filtered through a membrane filter having a pore size of 0.8 µm to obtain an ink.
The ink was prepared in the order of (1) glycerin and tetraethylene glycol, (2) surfactant, (3) ion-exchanged water, stirred for 30 minutes, added with the pigment dispersion (b) and stirred for 1 hour. Thus, an ink was prepared.

ただし、前記一般式（２）中、ｍは２、ｎは１０を表す。
・イオン交換水・・・残量
上記の処方によりインクを調製し、１時間３０分間撹拌後、孔径０．８μｍのメンブランフィルターでろ過し、インクを得た。
インクの調合順序は、（１）グリセリン及びテトラエチレングリコール、（２）界面活性剤、（３）イオン交換水とし、３０分間撹拌した後、上記顔料分散液（ｃ）を添加し、１時間撹拌してインクを作製した。 (Production Example 36)
<Preparation of ink (36)>
Pigment dispersion (c): 40 parts by mass Glycerin: 15 parts by mass Tetraethylene glycol: 19.2 parts by mass Surfactant represented by the following general formula (2) 2 parts by mass

However, in said general formula (2), m represents 2 and n represents 10.
-Ion-exchanged water: remaining amount An ink was prepared according to the above formulation, stirred for 1 hour and 30 minutes, and then filtered through a membrane filter having a pore size of 0.8 µm to obtain an ink.
The ink was prepared in the order of (1) glycerin and tetraethylene glycol, (2) surfactant, (3) ion-exchanged water, stirred for 30 minutes, added with the pigment dispersion (c) and stirred for 1 hour. Thus, an ink was prepared.

ただし、前記一般式（２）中、ｍは２、ｎは１０を表す。
・イオン交換水・・・残量
上記の処方によりインクを調製し、１時間３０分間撹拌後、孔径０．８μｍのメンブランフィルターでろ過し、インクを得た。
インクの調合順序は、（１）グリセリン及び１，６−ヘキサンジオール、（２）界面活性剤、（３）イオン交換水とし、３０分間撹拌した後、上記顔料分散液（ａ）を添加し、１時間撹拌してインクを作製した。 (Production Example 37)
<Preparation of ink (37)>
-Pigment dispersion (a)-40 parts by mass-Glycerin-15 parts by mass-1,6-hexanediol-19.2 parts by mass-Surfactant represented by the following general formula (2) ... 2 parts by mass

However, in said general formula (2), m represents 2 and n represents 10.
-Ion-exchanged water: remaining amount An ink was prepared according to the above formulation, stirred for 1 hour and 30 minutes, and then filtered through a membrane filter having a pore size of 0.8 µm to obtain an ink.
The ink was prepared in the order of (1) glycerin and 1,6-hexanediol, (2) surfactant, (3) ion-exchanged water, stirred for 30 minutes, and then added the pigment dispersion (a). The ink was prepared by stirring for 1 hour.

ただし、前記一般式（２）中、ｍは２、ｎは１０を表す。
・イオン交換水・・・残量
上記の処方によりインクを調製し、１時間３０分間撹拌後、孔径０．８μｍのメンブランフィルターでろ過し、インクを得た。
インクの調合順序は、（１）グリセリン及び１，６−ヘキサンジオール、（２）界面活性剤、（３）イオン交換水とし、３０分間撹拌した後、上記顔料分散液（ｂ）を添加し、１時間撹拌してインクを作製した。 (Production Example 38)
<Preparation of ink (38)>
-Pigment dispersion (b) ... 40 parts by mass-Glycerin ... 15 parts by mass-1,6-hexanediol ... 19.2 parts by mass-Surfactant represented by the following general formula (2) ... 2 parts by mass

However, in said general formula (2), m represents 2 and n represents 10.
-Ion-exchanged water: remaining amount An ink was prepared according to the above formulation, stirred for 1 hour and 30 minutes, and then filtered through a membrane filter having a pore size of 0.8 µm to obtain an ink.
The ink preparation order was (1) glycerin and 1,6-hexanediol, (2) surfactant, (3) ion-exchanged water, stirred for 30 minutes, and then added the pigment dispersion (b). The ink was prepared by stirring for 1 hour.

ただし、前記一般式（２）中、ｍは２、ｎは１０を表す。
・イオン交換水・・・残量
上記の処方によりインクを調製し、１時間３０分間撹拌後、孔径０．８μｍのメンブランフィルターでろ過し、インクを得た。
インクの調合順序は、（１）グリセリン及び１，６−ヘキサンジオール、（２）界面活性剤、（３）イオン交換水とし、３０分間撹拌した後、上記顔料分散液（ｃ）を添加し、１時間撹拌してインクを作製した。 (Production Example 39)
<Preparation of ink (39)>
-Pigment dispersion (c)-40 parts by mass-Glycerin-15 parts by mass-1,6-hexanediol-19.2 parts by mass-Surfactant represented by the following general formula (2) ... 2 parts by mass

However, in said general formula (2), m represents 2 and n represents 10.
-Ion-exchanged water: remaining amount An ink was prepared according to the above formulation, stirred for 1 hour and 30 minutes, and then filtered through a membrane filter having a pore size of 0.8 µm to obtain an ink.
The order of ink preparation was (1) glycerin and 1,6-hexanediol, (2) surfactant, (3) ion-exchanged water, stirred for 30 minutes, and then added the pigment dispersion (c). The ink was prepared by stirring for 1 hour.

ただし、前記一般式（２）中、ｍは２、ｎは１０を表す。
・イオン交換水・・・残量
上記の処方によりインクを調製し、１時間３０分間撹拌後、孔径０．８μｍのメンブランフィルターでろ過し、インクを得た。
インクの調合順序は、（１）グリセリン及び２−メチル−２，４−ペンタンジオール、（２）界面活性剤、（３）イオン交換水とし、３０分間撹拌した後、上記顔料分散液（ａ）を添加し、１時間撹拌してインクを作製した。 (Production Example 40)
<Preparation of ink (40)>
-Pigment dispersion (a)-40 parts by mass-Glycerin-15 parts by mass-2-methyl-2,4-pentanediol-19.2 parts by mass-Represented by the following general formula (2) 2 parts by weight of surfactant

However, in said general formula (2), m represents 2 and n represents 10.
-Ion-exchanged water: remaining amount An ink was prepared according to the above formulation, stirred for 1 hour and 30 minutes, and then filtered through a membrane filter having a pore size of 0.8 µm to obtain an ink.
The preparation order of the ink was (1) glycerin and 2-methyl-2,4-pentanediol, (2) surfactant, (3) ion-exchanged water, stirred for 30 minutes, and then the pigment dispersion (a) Was added and stirred for 1 hour to prepare an ink.

ただし、前記一般式（２）中、ｍは２、ｎは１０を表す。
・イオン交換水・・・残量
上記の処方によりインクを調製し、１時間３０分間撹拌後、孔径０．８μｍのメンブランフィルターでろ過し、インクを得た。
インクの調合順序は、（１）グリセリン及び２−メチル−２，４−ペンタンジオール、（２）界面活性剤、（３）イオン交換水とし、３０分間撹拌した後、上記顔料分散液（ｂ）を添加し、１時間撹拌してインクを作製した。 (Production Example 41)
<Preparation of ink (41)>
-Pigment dispersion (b) ... 40 parts by mass-Glycerin ... 15 parts by mass-2-Methyl-2,4-pentanediol ... 19.2 parts by mass-Represented by the following general formula (2) 2 parts by weight of surfactant

However, in said general formula (2), m represents 2 and n represents 10.
-Ion-exchanged water: remaining amount An ink was prepared according to the above formulation, stirred for 1 hour and 30 minutes, and then filtered through a membrane filter having a pore size of 0.8 µm to obtain an ink.
The preparation order of the ink was (1) glycerin and 2-methyl-2,4-pentanediol, (2) surfactant, (3) ion-exchanged water, stirred for 30 minutes, and then the pigment dispersion (b) Was added and stirred for 1 hour to prepare an ink.

ただし、前記一般式（２）中、ｍは２、ｎは１０を表す。
・イオン交換水・・・残量
上記の処方によりインクを調製し、１時間３０分間撹拌後、孔径０．８μｍのメンブランフィルターでろ過し、インクを得た。
インクの調合順序は、（１）グリセリン及び２−メチル−２，４−ペンタンジオール、（２）界面活性剤、（３）イオン交換水とし、３０分間撹拌した後、上記顔料分散液（ｃ）を添加し、１時間撹拌してインクを作製した。 (Production Example 42)
<Preparation of ink (42)>
-Pigment dispersion (c)-40 parts by mass-Glycerin-15 parts by mass-2-Methyl-2,4-pentanediol-19.2 parts by mass-Represented by the following general formula (2) 2 parts by weight of surfactant

However, in said general formula (2), m represents 2 and n represents 10.
-Ion-exchanged water: remaining amount An ink was prepared according to the above formulation, stirred for 1 hour and 30 minutes, and then filtered through a membrane filter having a pore size of 0.8 µm to obtain an ink.
The preparation order of the ink was (1) glycerin and 2-methyl-2,4-pentanediol, (2) surfactant, (3) ion-exchanged water, stirred for 30 minutes, and then the pigment dispersion (c) Was added and stirred for 1 hour to prepare an ink.

ただし、前記一般式（２）中、ｍは２、ｎは１０を表す。
・イオン交換水・・・残量
上記の処方によりインクを調製し、１時間３０分間撹拌後、孔径０．８μｍのメンブランフィルターでろ過し、インクを得た。
インクの調合順序は、（１）グリセリン及びポリエチレングリコール、（２）界面活性剤、（３）イオン交換水とし、３０分間撹拌した後、上記顔料分散液（ａ）を添加し、１時間撹拌してインクを作製した。 (Production Example 43)
<Preparation of ink (43)>
-Pigment dispersion (a) ... 40 parts by mass-Glycerin ... 15 parts by mass-Polyethylene glycol ... 19.2 parts by mass-Surfactant represented by the following general formula (2) ... 2 Parts by mass

However, in said general formula (2), m represents 2 and n represents 10.
-Ion-exchanged water: remaining amount An ink was prepared according to the above formulation, stirred for 1 hour and 30 minutes, and then filtered through a membrane filter having a pore size of 0.8 µm to obtain an ink.
The ink was prepared in the order of (1) glycerin and polyethylene glycol, (2) surfactant, (3) ion-exchanged water, stirred for 30 minutes, added with the pigment dispersion (a) and stirred for 1 hour. Ink was prepared.

ただし、前記一般式（２）中、ｍは２、ｎは１０を表す。
・イオン交換水・・・残量
上記の処方によりインクを調製し、１時間３０分間撹拌後、孔径０．８μｍのメンブランフィルターでろ過し、インクを得た。
インクの調合順序は、（１）グリセリン及びポリエチレングリコール、（２）界面活性剤、（３）イオン交換水とし、３０分間撹拌した後、上記の顔料分散液（ｂ）を添加し、１時間撹拌してインクを作製した。 (Production Example 44)
<Preparation of ink (44)>
-Pigment dispersion (b) ... 40 parts by mass-Glycerin ... 15 parts by mass-Polyethylene glycol ... 19.2 parts by mass-Surfactant represented by the following general formula (2) ... 2 Parts by mass

However, in said general formula (2), m represents 2 and n represents 10.
-Ion-exchanged water: remaining amount An ink was prepared according to the above formulation, stirred for 1 hour and 30 minutes, and then filtered through a membrane filter having a pore size of 0.8 µm to obtain an ink.
The ink was prepared in the order of (1) glycerin and polyethylene glycol, (2) surfactant, (3) ion-exchanged water, stirred for 30 minutes, then added with the pigment dispersion (b) and stirred for 1 hour. Thus, an ink was prepared.

ただし、前記一般式（２）中、ｍは２、ｎは１０を表す。
・イオン交換水・・・残量
上記の処方によりインクを調製し、１時間３０分間撹拌後、孔径０．８μｍのメンブランフィルターでろ過し、インクを得た。
インクの調合順序は、（１）グリセリン及びポリエチレングリコール、（２）界面活性剤、（３）イオン交換水とし、３０分間撹拌した後、上記顔料分散液（ｃ）を添加し、１時間撹拌してインクを作製した。 (Production Example 45)
<Preparation of ink (45)>
Pigment dispersion (c): 40 parts by mass Glycerin: 15 parts by mass Polyethylene glycol: 19.2 parts by mass Surfactant represented by the following general formula (2): 2 Parts by mass

However, in said general formula (2), m represents 2 and n represents 10.
-Ion-exchanged water: remaining amount An ink was prepared according to the above formulation, stirred for 1 hour and 30 minutes, and then filtered through a membrane filter having a pore size of 0.8 µm to obtain an ink.
The ink preparation order was (1) glycerin and polyethylene glycol, (2) surfactant, (3) ion-exchanged water, stirred for 30 minutes, then added the pigment dispersion (c) and stirred for 1 hour. Ink was prepared.

ただし、前記一般式（２）中、ｍは２、ｎは１０を表す。
・イオン交換水・・・残量
上記の処方によりインクを調製し、１時間３０分間撹拌後、孔径０．８μｍのメンブランフィルターでろ過し、インクを得た。
インクの調合順序は、（１）グリセリン及び１，２，４−ブタントリオール、（２）界面活性剤、（３）イオン交換水とし、３０分間撹拌した後、上記顔料分散液（ａ）を添加し、１時間撹拌してインクを作製した。 (Production Example 46)
<Preparation of Ink (46)>
-Pigment dispersion (a)-40 parts by mass-Glycerin-15 parts by mass-1,2,4-butanetriol-19.2 parts by mass-Interface represented by the following general formula (2) Activator ... 2 parts by mass

However, in said general formula (2), m represents 2 and n represents 10.
-Ion-exchanged water: remaining amount An ink was prepared according to the above formulation, stirred for 1 hour and 30 minutes, and then filtered through a membrane filter having a pore size of 0.8 µm to obtain an ink.
The ink was prepared in the order of (1) glycerin and 1,2,4-butanetriol, (2) surfactant, (3) ion-exchanged water, stirred for 30 minutes, and then added the pigment dispersion (a). And stirred for 1 hour to produce an ink.

ただし、前記一般式（２）中、ｍは２、ｎは１０を表す。
・イオン交換水・・・残量
上記の処方によりインクを調製し、１時間３０分間撹拌後、孔径０．８μｍのメンブランフィルターでろ過し、インクを得た。
インクの調合順序は、（１）グリセリン及び１，２，４−ブタントリオール、（２）界面活性剤、（３）イオン交換水とし、３０分間撹拌した後、上記顔料分散液（ｂ）を添加し、１時間撹拌してインクを作製した。 (Production Example 47)
<Preparation of ink (47)>
-Pigment dispersion (b) ... 40 parts by mass-Glycerin ... 15 parts by mass-1,2,4-butanetriol ... 19.2 parts by mass-Interface represented by the following general formula (2) Activator ... 2 parts by mass

However, in said general formula (2), m represents 2 and n represents 10.
-Ion-exchanged water: remaining amount An ink was prepared according to the above formulation, stirred for 1 hour and 30 minutes, and then filtered through a membrane filter having a pore size of 0.8 µm to obtain an ink.
The order of ink preparation was (1) glycerin and 1,2,4-butanetriol, (2) surfactant, (3) ion-exchanged water, stirred for 30 minutes, and then added the pigment dispersion (b) And stirred for 1 hour to produce an ink.

ただし、前記一般式（２）中、ｍは２、ｎは１０を表す。
・イオン交換水・・・残量
上記の処方によりインクを調製し、１時間３０分間撹拌後、孔径０．８μｍのメンブランフィルターでろ過し、インクを得た。
インクの調合順序は、（１）グリセリン及び１，２，４−ブタントリオール、（２）界面活性剤、（３）イオン交換水とし、３０分間撹拌した後、上記顔料分散液（ｃ）を添加し、１時間撹拌してインクを作製した。 (Production Example 48)
<Preparation of ink (48)>
-Pigment dispersion (c)-40 parts by mass-Glycerin-15 parts by mass-1,2,4-butanetriol-19.2 parts by mass-Interface represented by the following general formula (2) Activator ... 2 parts by mass

However, in said general formula (2), m represents 2 and n represents 10.
-Ion-exchanged water: remaining amount An ink was prepared according to the above formulation, stirred for 1 hour and 30 minutes, and then filtered through a membrane filter having a pore size of 0.8 µm to obtain an ink.
The ink was prepared in the order of (1) glycerin and 1,2,4-butanetriol, (2) surfactant, (3) ion-exchanged water, stirred for 30 minutes, and then added the pigment dispersion (c). And stirred for 1 hour to produce an ink.

ただし、前記一般式（２）中、ｍは２、ｎは１０を表す。
・イオン交換水・・・残量
上記の処方によりインクを調製し、１時間３０分間撹拌後、孔径０．８μｍのメンブランフィルターでろ過し、インクを得た。
インクの調合順序は、（１）グリセリン及び１，２，６−ヘキサントリオール、（２）界面活性剤、（３）イオン交換水とし、３０分間撹拌した後、上記顔料分散液（ａ）を添加し、１時間撹拌してインクを作製した。 (Production Example 49)
<Preparation of ink (49)>
-Pigment dispersion (a)-40 parts by mass-Glycerin-15 parts by mass-1,2,6-hexanetriol-19.2 parts by mass-Interface represented by the following general formula (2) Activator ... 2 parts by mass

However, in said general formula (2), m represents 2 and n represents 10.
-Ion-exchanged water: remaining amount An ink was prepared according to the above formulation, stirred for 1 hour and 30 minutes, and then filtered through a membrane filter having a pore size of 0.8 µm to obtain an ink.
The ink formulation order was (1) glycerin and 1,2,6-hexanetriol, (2) surfactant, (3) ion-exchanged water, stirred for 30 minutes, and then added the pigment dispersion (a) Then, the ink was prepared by stirring for 1 hour.

ただし、前記一般式（２）中、ｍは２、ｎは１０を表す。
・イオン交換水・・・残量
上記の処方によりインクを調製し、１時間３０分間撹拌後、孔径０．８μｍのメンブランフィルターでろ過し、インクを得た。
インクの調合順序は、（１）グリセリン及び１，２，６−ヘキサントリオール、（２）界面活性剤、（３）イオン交換水とし、３０分間撹拌した後、上記顔料分散液（ｂ）を添加し、１時間撹拌してインクを作製した。 (Production Example 50)
<Preparation of ink (50)>
-Pigment dispersion (b) ... 40 parts by mass-Glycerin ... 15 parts by mass-1,2,6-hexanetriol ... 19.2 parts by mass-Interface represented by the following general formula (2) Activator ... 2 parts by mass

However, in said general formula (2), m represents 2 and n represents 10.
-Ion-exchanged water: remaining amount An ink was prepared according to the above formulation, stirred for 1 hour and 30 minutes, and then filtered through a membrane filter having a pore size of 0.8 µm to obtain an ink.
The ink formulation order was (1) glycerin and 1,2,6-hexanetriol, (2) surfactant, (3) ion-exchanged water, stirred for 30 minutes, and then added the pigment dispersion (b) And stirred for 1 hour to produce an ink.

ただし、前記一般式（２）中、ｍは２、ｎは１０を表す。
・イオン交換水・・・残量
上記の処方によりインクを調製し、１時間３０分間撹拌後、孔径０．８μｍのメンブランフィルターでろ過し、インクを得た。
インクの調合順序は、（１）グリセリン及び１，２，６−ヘキサントリオール、（２）界面活性剤、（３）イオン交換水とし、３０分間撹拌した後、上記顔料分散液（ｃ）を添加し、１時間撹拌してインクを作製した。 (Production Example 51)
<Preparation of ink (51)>
-Pigment dispersion (c)-40 parts by mass-Glycerin-15 parts by mass-1,2,6-hexanetriol-19.2 parts by mass-Interface represented by the following general formula (2) Activator ... 2 parts by mass

However, in said general formula (2), m represents 2 and n represents 10.
-Ion-exchanged water: remaining amount An ink was prepared according to the above formulation, stirred for 1 hour and 30 minutes, and then filtered through a membrane filter having a pore size of 0.8 µm to obtain an ink.
The ink was prepared in the following order: (1) glycerin and 1,2,6-hexanetriol, (2) surfactant, (3) ion-exchanged water, stirred for 30 minutes, and then added the pigment dispersion (c) And stirred for 1 hour to produce an ink.

ただし、前記一般式（３）中、ＲｆはＣＦ_２ＣＦ_３を表す。ｍは２、ｎは４、ｐは４を表す。
・イオン交換水・・・残量
上記の処方によりインクを調製し、１時間３０分間撹拌後、孔径０．８μｍのメンブランフィルターでろ過し、インクを得た。
インクの調合順序は、（１）グリセリン及びジエチレングリコール、（２）界面活性剤、（３）イオン交換水とし、３０分間撹拌した後、上記顔料分散液（ａ）を添加し、１時間撹拌してインクを作製した。 (Production Example 52)
<Preparation of ink (52)>
Pigment dispersion (a): 40 parts by mass Glycerin: 15 parts by mass Diethylene glycol: 15 parts by mass Surfactant represented by the following general formula (3): 2 parts by mass

In the general formula (3), Rf represents _CF 2 CF _3. m represents 2, n represents 4, and p represents 4.
-Ion-exchanged water: remaining amount An ink was prepared according to the above formulation, stirred for 1 hour and 30 minutes, and then filtered through a membrane filter having a pore size of 0.8 µm to obtain an ink.
The order of ink preparation was (1) glycerin and diethylene glycol, (2) surfactant, (3) ion-exchanged water, stirred for 30 minutes, then added the pigment dispersion (a) and stirred for 1 hour. An ink was prepared.

ただし、前記一般式（３）中、ＲｆはＣＦ_２ＣＦ_３を表す。ｍは２、ｎは４、ｐは４を表す。
・イオン交換水・・・残量
上記の処方によりインクを調製し、１時間３０分間撹拌後、孔径０．８μｍのメンブランフィルターでろ過し、インクを得た。
インクの調合順序は、（１）グリセリン及びジエチレングリコール、（２）界面活性剤、（３）イオン交換水とし、３０分間撹拌した後、上記顔料分散液（ｂ）を添加し、１時間撹拌してインクを作製した。 (Production Example 53)
<Preparation of ink (53)>
Pigment dispersion (b): 40 parts by mass Glycerin: 15 parts by mass Diethylene glycol: 15 parts by mass Surfactant represented by the following general formula (3): 2 parts by mass

In the general formula (3), Rf represents _CF 2 CF _3. m represents 2, n represents 4, and p represents 4.
-Ion-exchanged water: remaining amount An ink was prepared according to the above formulation, stirred for 1 hour and 30 minutes, and then filtered through a membrane filter having a pore size of 0.8 µm to obtain an ink.
The order of ink preparation was (1) glycerin and diethylene glycol, (2) surfactant, (3) ion-exchanged water, stirred for 30 minutes, then added the pigment dispersion (b) and stirred for 1 hour. An ink was prepared.

ただし、前記一般式（３）中、ＲｆはＣＦ_２ＣＦ_３を表す。ｍは２、ｎは４、ｐは４を表す。
・イオン交換水・・・残量
上記の処方によりインクを調製し、１時間３０分間撹拌後、孔径０．８μｍのメンブランフィルターでろ過し、インクを得た。
インクの調合順序は、（１）グリセリン及びジエチレングリコール、（２）界面活性剤、（３）イオン交換水とし、３０分間撹拌した後、上記顔料分散液（ｃ）を添加し、１時間撹拌してインクを作製した。 (Production Example 54)
<Preparation of ink (54)>
-Pigment dispersion (c)-40 parts by mass-Glycerin-15 parts by mass-Diethylene glycol-15 parts by mass-Surfactant represented by the following general formula (3)-2 parts by mass

In the general formula (3), Rf represents _CF 2 CF _3. m represents 2, n represents 4, and p represents 4.
-Ion-exchanged water: remaining amount An ink was prepared according to the above formulation, stirred for 1 hour and 30 minutes, and then filtered through a membrane filter having a pore size of 0.8 µm to obtain an ink.
The order of ink preparation was (1) glycerin and diethylene glycol, (2) surfactant, (3) ion-exchanged water, stirred for 30 minutes, then added the pigment dispersion (c) and stirred for 1 hour. An ink was prepared.

ただし、前記一般式（３）中、ＲｆはＣＦ_２ＣＦ_３を表す。ｍは２、ｎは４、ｐは４を表す。
・イオン交換水・・・残量
上記の処方によりインクを調製し、１時間３０分間撹拌後、孔径０．８μｍのメンブランフィルターでろ過し、インクを得た。
インクの調合順序は、（１）グリセリン及びエチレングリコール、（２）界面活性剤、（３）イオン交換水とし、３０分間撹拌した後、上記顔料分散液（ａ）を添加し、１時間撹拌してインクを作製した。 (Production Example 55)
<Preparation of ink (55)>
Pigment dispersion (a): 40 parts by mass Glycerin: 10 parts by mass Ethylene glycol: 20 parts by mass Surfactant represented by the following general formula (3): 2 parts by mass

In the general formula (3), Rf represents _CF 2 CF _3. m represents 2, n represents 4, and p represents 4.
-Ion-exchanged water: remaining amount An ink was prepared according to the above formulation, stirred for 1 hour and 30 minutes, and then filtered through a membrane filter having a pore size of 0.8 µm to obtain an ink.
The ink was prepared in the order of (1) glycerin and ethylene glycol, (2) surfactant, (3) ion-exchanged water, stirred for 30 minutes, added with the pigment dispersion (a) and stirred for 1 hour. Ink was prepared.

ただし、前記一般式（３）中、ＲｆはＣＦ_２ＣＦ_３を表す。ｍは２、ｎは４、ｐは４を表す。
・イオン交換水・・・残量
上記の処方によりインクを調製し、１時間３０分間撹拌後、孔径０．８μｍのメンブランフィルターでろ過し、インクを得た。
インクの調合順序は、（１）グリセリン及びエチレングリコール、（２）界面活性剤、（３）イオン交換水とし、３０分間撹拌した後、上記顔料分散液（ｂ）を添加し、１時間撹拌してインクを作製した。 (Production Example 56)
<Preparation of ink (56)>
Pigment dispersion (b): 40 parts by mass Glycerin: 10 parts by mass Ethylene glycol: 20 parts by mass Surfactant represented by the following general formula (3): 2 parts by mass

In the general formula (3), Rf represents _CF 2 CF _3. m represents 2, n represents 4, and p represents 4.
-Ion-exchanged water: remaining amount An ink was prepared according to the above formulation, stirred for 1 hour and 30 minutes, and then filtered through a membrane filter having a pore size of 0.8 µm to obtain an ink.
The order of ink preparation was (1) glycerin and ethylene glycol, (2) surfactant, (3) ion-exchanged water, stirred for 30 minutes, then added the pigment dispersion (b) and stirred for 1 hour. Ink was prepared.

ただし、前記一般式（３）中、ＲｆはＣＦ_２ＣＦ_３を表す。ｍは２、ｎは４、ｐは４を表す。
・イオン交換水・・・残量
上記の処方によりインクを調製し、１時間３０分間撹拌後、孔径０．８μｍのメンブランフィルターでろ過し、インクを得た。
インクの調合順序は、（１）グリセリン及びエチレングリコール、（２）界面活性剤、（３）イオン交換水とし、３０分間撹拌した後、上記顔料分散液（ｃ）を添加し、１時間撹拌してインクを作製した。 (Production Example 57)
<Preparation of ink (57)>
Pigment dispersion (c): 40 parts by mass Glycerin: 10 parts by mass Ethylene glycol: 20 parts by mass Surfactant represented by the following general formula (3): 2 parts by mass

In the general formula (3), Rf represents _CF 2 CF _3. m represents 2, n represents 4, and p represents 4.
-Ion-exchanged water: remaining amount An ink was prepared according to the above formulation, stirred for 1 hour and 30 minutes, and then filtered through a membrane filter having a pore size of 0.8 µm to obtain an ink.
The order of ink preparation was (1) glycerin and ethylene glycol, (2) surfactant, (3) ion-exchanged water, stirred for 30 minutes, then added the pigment dispersion (c) and stirred for 1 hour. Ink was prepared.

ただし、前記一般式（２）中、ｍは２、ｎは１０を表す。
・イオン交換水・・・残量
上記の処方によりインクを調製し、１時間３０分間撹拌後、孔径０．８μｍのメンブランフィルターでろ過し、インクを得た。
インクの調合順序は、（１）グリセリン及びトリエチレングリコール、（２）界面活性剤、（３）イオン交換水とし、３０分間撹拌した後、上記顔料分散液（ａ）を添加し、１時間撹拌してインクを作製した。 (Production Example 58)
<Preparation of ink (58)>
Pigment dispersion (a): 40 parts by mass Glycerin: 8 parts by mass Triethylene glycol: 24 parts by mass Surfactant represented by the following general formula (2): 2 parts by mass Part

However, in said general formula (2), m represents 2 and n represents 10.
-Ion-exchanged water: remaining amount An ink was prepared according to the above formulation, stirred for 1 hour and 30 minutes, and then filtered through a membrane filter having a pore size of 0.8 µm to obtain an ink.
The ink was prepared in the order of (1) glycerin and triethylene glycol, (2) surfactant, (3) ion-exchanged water, stirred for 30 minutes, added with the pigment dispersion (a) and stirred for 1 hour. Thus, an ink was prepared.

ただし、前記一般式（２）中、ｍは２、ｎは１０を表す。
・イオン交換水・・・残量
上記の処方によりインクを調製し、１時間３０分間撹拌後、孔径０．８μｍのメンブランフィルターでろ過し、インクを得た。
インクの調合順序は、（１）グリセリン及びトリエチレングリコール、（２）界面活性剤、（３）イオン交換水とし、３０分間撹拌した後、上記顔料分散液（ｂ）を添加し、１時間撹拌してインクを作製した。 (Production Example 59)
<Preparation of ink (59)>
Pigment dispersion (b): 40 parts by mass Glycerin: 8 parts by mass Triethylene glycol: 24 parts by mass Surfactant represented by the following general formula (2): 2 parts by mass Part

However, in said general formula (2), m represents 2 and n represents 10.
-Ion-exchanged water: remaining amount An ink was prepared according to the above formulation, stirred for 1 hour and 30 minutes, and then filtered through a membrane filter having a pore size of 0.8 µm to obtain an ink.
The ink was prepared in the order of (1) glycerin and triethylene glycol, (2) surfactant, (3) ion-exchanged water, stirred for 30 minutes, added with the pigment dispersion (b) and stirred for 1 hour. Thus, an ink was prepared.

ただし、前記一般式（２）中、ｍは２、ｎは１０を表す。
・イオン交換水・・・残量
上記の処方によりインクを調製し、１時間３０分間撹拌後、孔径０．８μｍのメンブランフィルターでろ過し、インクを得た。
インクの調合順序は、（１）グリセリン及びトリエチレングリコール、（２）界面活性剤、（３）イオン交換水とし、３０分間撹拌した後、上記顔料分散液（ｃ）を添加し、１時間撹拌してインクを作製した。 (Production Example 60)
<Preparation of ink (60)>
Pigment dispersion (c): 40 parts by mass Glycerin: 8 parts by mass Triethylene glycol: 24 parts by mass Surfactant represented by the following general formula (2): 2 parts by mass Part

However, in said general formula (2), m represents 2 and n represents 10.
-Ion-exchanged water: remaining amount An ink was prepared according to the above formulation, stirred for 1 hour and 30 minutes, and then filtered through a membrane filter having a pore size of 0.8 µm to obtain an ink.
The ink was prepared in the order of (1) glycerin and triethylene glycol, (2) surfactant, (3) ion-exchanged water, stirred for 30 minutes, added with the pigment dispersion (c), and stirred for 1 hour. Thus, an ink was prepared.

ただし、前記一般式（２）中、ｍは２、ｎは１０を表す。
・イオン交換水・・・残量
上記処方のインクを調製し、ｐＨが９になるように水酸化リチウム１０質量％水溶液にて調整した。その後、平均孔径０．８μｍのメンブレンフィルターで濾過を行い、インクを作製した。 (Production Example 61)
<Preparation of pigment dispersion (61)>
C.I. as a cyan pigment I. Pigment cyan 15: 3 was subjected to low-temperature plasma treatment to prepare a pigment into which a carboxylic acid group was introduced. The dispersion in ion-exchanged water was desalted and concentrated with an ultrafiltration membrane to obtain a pigment dispersion (d) having a pigment concentration of 15% by mass.
<Preparation of ink (R)>
Pigment dispersion (d): 5 parts by mass Acrylic resin fine particles (Aquabrid 4720, manufactured by Daicel Chemical Industries, Ltd.): 4 parts by mass Glycerin: 7 parts by mass 3-methyl-1, 3-butanediol ... 21 parts by mass-2-ethyl-1,3-hexanediol ... 2 parts by mass-Surfactant represented by the following general formula (2) ... 1 part by mass

However, in said general formula (2), m represents 2 and n represents 10.
-Ion-exchanged water ... remaining amount The ink of the said prescription was prepared and it adjusted with lithium hydroxide 10 mass% aqueous solution so that pH might be set to nine. Then, it filtered with the membrane filter with an average hole diameter of 0.8 micrometer, and produced the ink.

ただし、前記一般式（２）中、ｍは２、ｎは１０を表す。
・イオン交換水・・・残量
上記処方のインクを調製し、ｐＨが９になるように水酸化リチウム１０質量％水溶液にて調整した。その後、平均孔径０．８μｍのメンブレンフィルターで濾過を行い、インクを作製した。 (Production Example 62)
<Preparation of pigment dispersion (e)>
C. of the pigment dispersion (d) I. Instead of Pigment Cyan 15: 3, C.I. I. Pigment Red 122 was used. Similar to the above example, the resulting surface-modified color pigment was easily dispersed in an aqueous medium upon stirring.
<Preparation of ink (62)>
-Pigment dispersion (e)-8 parts by mass-Acrylic resin fine particles (Aquabrid 4720, manufactured by Daicel Chemical Industries, Ltd.)-3.2 parts by mass-Glycerin-7 parts by mass-3-methyl- 1,3-butanediol ... 21 parts by mass-2-ethyl-1,3-hexanediol ... 2 parts by mass-Surfactant represented by the following general formula (2) ... 1 part by mass

However, in said general formula (2), m represents 2 and n represents 10.
-Ion-exchanged water ... remaining amount The ink of the said prescription was prepared and it adjusted with lithium hydroxide 10 mass% aqueous solution so that pH might be set to nine. Then, it filtered with the membrane filter with an average hole diameter of 0.8 micrometer, and produced the ink.

ただし、前記一般式（２）中、ｍは２、ｎは１０を表す。
・イオン交換水・・・残量
上記処方のインクを調製し、ｐＨが９になるように水酸化リチウム１０質量％水溶液にて調整した。その後、平均孔径０．８μｍのメンブレンフィルターで濾過を行い、インクを作製した。 (Production Example 63)
<Preparation of pigment dispersion (f)>
Similar to the pigment dispersion (d), a surface-modified yellow pigment was prepared. I. Pigment cyan 15: 3 instead of C.I. I. Pigment Yellow 128 was used. Similar to the above example, the resulting surface-modified color pigment was easily dispersed in an aqueous medium upon stirring.
<Preparation of ink (63)>
Pigment dispersion (f): 5.0 parts by mass Acrylic resin fine particles (Aquabrid 4720, manufactured by Daicel Chemical Industries, Ltd.): 4.0 parts by mass Glycerin: 7 parts by mass 3- Methyl-1,3-butanediol: 21 parts by mass 2-ethyl-1,3-hexanediol: 2 parts by mass Surfactant represented by the following general formula (2): 1 part by mass Part

However, in said general formula (2), m represents 2 and n represents 10.
-Ion-exchanged water ... remaining amount The ink of the said prescription was prepared and it adjusted with lithium hydroxide 10 mass% aqueous solution so that pH might be set to nine. Then, it filtered with the membrane filter with an average hole diameter of 0.8 micrometer, and produced the ink.

ただし、前記一般式（２）中、ｍは２、ｎは１０を表す。
・イオン交換水・・・残量
上記処方のインクを調製し、１時間３０分間撹拌後、孔径０．８μｍのメンブランフィルターでろ過し、インクを得た。
インクの調合順序は、（１）グリセリン及びトリプロピレングリコール、（２）界面活性剤、（３）イオン交換水とし、３０分間撹拌した後、上記顔料分散液（ｇ）を添加し、１時間撹拌してインクを作製した。 (Production Example 64)
<Preparation of pigment dispersion (g)>
In the same manner as in the pigment dispersion (a), except that 12 parts by mass of polyoxyethylene octyl ether was used instead of the compound represented by the general formula (1), a pigment dispersion (g) was obtained.
<Preparation of ink (64)>
-Pigment dispersion (g) ... 40 parts by mass-Glycerin ... 12 parts by mass-Tripropylene glycol ... 19.2 parts by mass-Surfactant represented by the following general formula (2) ... 2 parts by mass

However, in said general formula (2), m represents 2 and n represents 10.
-Ion-exchanged water-remaining amount After preparing the ink of the said prescription, stirring for 1 hour and 30 minutes, it filtered with the membrane filter with the hole diameter of 0.8 micrometer, and obtained the ink.
The ink was prepared in the order of (1) glycerin and tripropylene glycol, (2) surfactant, (3) ion-exchanged water, stirred for 30 minutes, added with the pigment dispersion (g) and stirred for 1 hour. Thus, an ink was prepared.

ただし、前記一般式（２）中、ｍは２、ｎは１０を表す。
・イオン交換水・・・残量
上記処方のインクを調製し、１時間３０分間撹拌後、孔径０．８μｍのメンブランフィルターでろ過し、インクを得た。
インクの調合順序は、（１）グリセリン及びトリプロピレングリコール、（２）界面活性剤、（３）イオン交換水とし、３０分間撹拌した後、上記顔料分散液（ｈ）を添加し、１時間撹拌してインクを作製した。 (Production Example 65)
<Preparation of pigment dispersion (h)>
In the pigment dispersion (b), a pigment dispersion (h) was obtained in the same manner except that 10 parts by mass of polyoxyethylene octyl ether was used instead of the compound represented by the general formula (1).
<Preparation of ink (65)>
-Pigment dispersion (h) ... 40 parts by mass-Glycerin ... 12 parts by mass-Tripropylene glycol ... 19.2 parts by mass-Surfactant represented by the following general formula (2) ... 2 parts by mass

However, in said general formula (2), m represents 2 and n represents 10.
-Ion-exchanged water-remaining amount After preparing the ink of the said prescription, stirring for 1 hour and 30 minutes, it filtered with the membrane filter with the hole diameter of 0.8 micrometer, and obtained the ink.
The ink was prepared in the order of (1) glycerin and tripropylene glycol, (2) surfactant, (3) ion-exchanged water, stirred for 30 minutes, added with the pigment dispersion (h) and stirred for 1 hour. Thus, an ink was prepared.

ただし、前記一般式（２）中、ｍは２、ｎは１０を表す。
・イオン交換水・・・残量
上記の処方によりインクを調製し、１時間３０分間撹拌後、孔径０．８μｍのメンブランフィルターでろ過し、インクを得た。
インクの調合順序は、（１）グリセリン及びトリプロピレングリコール、（２）界面活性剤、（３）イオン交換水とし、３０分間撹拌した後、上記顔料分散液（ｉ）を添加し、１時間撹拌してインクを作製した。 (Production Example 66)
<Preparation of pigment dispersion (i)>
In the pigment dispersion (c), a pigment dispersion (i) was obtained in the same manner except that 10 parts by mass of polyoxyethylene octyl ether was used instead of the compound represented by the general formula (1).
<Preparation of ink (66)>
-Pigment dispersion (i) ... 40 parts by mass-Glycerin ... 12 parts by mass-Tripropylene glycol ... 19.2 parts by mass-Surfactant represented by the following general formula (2) ... 2 parts by mass

However, in said general formula (2), m represents 2 and n represents 10.
-Ion-exchanged water: remaining amount An ink was prepared according to the above formulation, stirred for 1 hour and 30 minutes, and then filtered through a membrane filter having a pore size of 0.8 µm to obtain an ink.
The ink was prepared in the order of (1) glycerin and tripropylene glycol, (2) surfactant, (3) ion-exchanged water, stirred for 30 minutes, then added with the pigment dispersion (i) and stirred for 1 hour. Thus, an ink was prepared.

-Production of support-
A 0.3 mass% slurry having the following composition was made with a long paper machine to prepare a support having a basis weight of 79 g / m ² . In addition, in the size press process of the papermaking process, the oxidized starch aqueous solution was applied so that the solid content was 1.0 g / m ² per side.
-Hardwood bleached kraft pulp (LBKP): 80 parts by mass-Softwood bleached kraft pulp (NBKP): 20 parts by weight-Light calcium carbonate (trade name: TP-121, manufactured by Okutama Kogyo Co., Ltd.) ... 10 Part by mass-Aluminum sulfate-1.0 part by mass-Amphoteric starch (trade name: Cato3210, manufactured by NSC Japan)-1.0 part by weight-Neutral rosin sizing agent (trade name: NeuSize M-10) , Manufactured by Harima Chemicals Co., Ltd.) ... 0.3 parts by mass Yield improver (trade name: NR-11LS, manufactured by Hymo Co., Ltd.) ... 0.02 parts by mass

-Production of recording medium 1-
70 parts by mass of clay having a particle diameter of 2 μm or less as a pigment of 97% by mass, 30 parts by mass of heavy calcium carbonate having an average particle diameter of 1.1 μm, and styrene having a glass transition temperature (Tg) of −5 ° C. as an adhesive -Addition of 7 parts by weight of butadiene copolymer emulsion, 0.7 parts by weight of phosphate esterified starch, and 0.5 parts by weight of calcium stearate as an auxiliary agent, followed by addition of water to give a solid content concentration of 60% by weight A liquid was prepared.
The obtained coating solution is coated on both sides with a blade coater so that the solid content per side of the prepared support is 8 g / m ² , dried with hot air, and then subjected to a step super calendar process. “Recording medium 1” was produced.

-Recording media 2-
Coated paper for gravure printing (trade name: space DX, basis weight = 56 g / m ² , manufactured by Nippon Paper Industries Co., Ltd.)

-Recording media 3-
Offset coated paper (trade name: Aurora coat, basis weight = 104.7 g / m ² , manufactured by Nippon Paper Industries Co., Ltd.)

<Measurement of the amount of pure water transferred by dynamic scanning absorption meter>
About the recording media 1-3, the absorption curve of the pure water was measured using the dynamic scanning absorption meter (model: KS350D, Kyowa Seiko Co., Ltd. make). The absorption curve was plotted with a transition amount (mL / m ² ) and a square root of contact time √ (ms) to make a straight line with a certain slope, and the value of the transition amount of pure water after a certain time was measured by interpolation. . The measurement was performed under environmental conditions of 23 ° C. and 50% RH. The results are shown in Table 1.

(Examples 1-17 and Comparative Examples 1-6)
-Ink set-
As shown in Table 2-1 and Table 2-2 below, various properties of the ink set in which each ink and the recording media 1 to 2 were combined were evaluated as follows. The results are shown in Table 2-1 and Table 2-2.

<Measurement of ink viscosity>
The viscosity of each ink was measured at 25 ° C. using a R-500 viscometer (manufactured by Toki Sangyo Co., Ltd.) under conditions of cone 1 ° 34 ′ × R24, 60 rpm, 3 minutes later.

<Bubbling test>
In an environment of 25 ° C., 5 ml of each prepared ink was put into a test tube (inner diameter 10 mm, total length 160 mm), shaken up and down 30 times for 10 seconds, and the bubble height after 5 minutes of standing was determined according to the following criteria. evaluated.
〔Evaluation criteria〕
A: Bubble height is less than 3 cm B: Bubble height is 3 cm or more and less than 6 cm C: Bubble height is 6 cm or more

<Discharge stability test>
Each of the prepared inks was filled in the ink jet printer shown in FIGS. 3 to 5 (manufactured by Ricoh Co., Ltd., IPSiO G707) in the combinations shown in Table 1, and the ejection stability was evaluated by the following method. That is, in a 23 ° C., 50% RH environment, the printer head is left unopened for a certain period of time, and after printing 20,000 sheets of the following print pattern chart, the presence or absence of ejection failure is evaluated according to the following criteria. did. In the printing pattern, a chart in which the printing area of the image area is the entire area of the paper and the printing area of each color is 5% is printed in the plain paper fast mode of the printer.
〔Evaluation criteria〕
A: After 3 hours, less than 5 non-ejection nozzles and all non-ejection nozzles recovered by cleaning. B: After 2 hours, less than 5 non-ejection nozzles and all cleaning non-ejection nozzles. Recover C: After standing for 1 hour, less than 5 non-discharge nozzles and all non-discharge nozzles recovered by cleaning

<Evaluation of color bleed>
Each ink prepared was filled in the ink jet printer shown in FIGS. 3-5 (Ricoh Co., Ltd., IPSiO G707) with the combinations shown in Table 2-1 and Table 2-2, and yellow characters were printed on magenta. The degree of color bleed was visually observed and evaluated according to the following criteria.
〔Evaluation criteria〕
A: Clear printing without bleed B: Slight bleed is observed C: Bleeding occurs so that the outline of the character is not clear

(Examples 1, 4, 18, 19 and Comparative Examples 7-8)
-Ink media set-
As shown in Table 3 below, various characteristics were evaluated in the same manner as in Examples 1 to 17 and Comparative Examples 1 to 6 for the ink media set in which each ink and recording medium were combined. The results are shown in Table 3.

The ink set and the ink media set of the present invention have improved color bleed not only on plain paper but also on water-absorbing, coated paper for printing coated with an inorganic pigment, resulting in improved defoaming and ejection stability. Since an excellent and high-quality image can be obtained, it can be suitably used for an ink jet recording apparatus and an ink jet recording method.
The ink jet recording apparatus and the ink jet recording method of the present invention can be applied to various types of recording by the ink jet recording method, and are particularly suitable for, for example, an ink jet recording printer, a facsimile apparatus, a copying apparatus, and a printer / fax / copier multifunction machine. Can be applied to.

FIG. 1 is a schematic view showing an example of the ink cartridge of the present invention. FIG. 2 is a schematic view including the case of the ink cartridge of FIG. FIG. 3 is a perspective explanatory view of the ink jet recording apparatus of the present invention. FIG. 4 is a schematic configuration diagram illustrating the overall configuration of the ink jet recording apparatus of the present invention. FIG. 5 is a schematic enlarged view showing an example of the inkjet head of the present invention. FIG. 6 is an element enlarged view showing an example of the ink jet head of the present invention. FIG. 7 is an enlarged cross-sectional view of the main part in the channel-to-channel direction of an example of the ink jet head of the present invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 10 Frame 20 Flow path plate 30 Nozzle plate 40 Base 50 Laminated piezoelectric element 60 Vibrating plate 70 Adhesive layer 101 Apparatus main body 102 Paper feed tray 103 Paper discharge tray 104 Ink cartridge loading part 111 Upper cover 112 Front surface 115 Front cover 131 Guide rod 132 Stay 133 Carriage 134 Recording head 135 Sub tank 141 Paper placement unit 142 Paper 144 Separation pad 151 Conveyance belt 152 Counter roller 156 Charging roller 157 Conveyance roller 158 Densation roller 171 Separation claw 172 Paper ejection roller 173 Paper ejection roller 181 Double-sided paper feed unit 200 Ink cartridge 201 Ink cartridge 241 Ink bag 242 Ink inlet 243 Ink outlet 244 Cartridge exterior

Claims (11)

An ink set comprising a combination of two or more inks containing at least a pigment, two or more water-soluble organic solvents, a surfactant, a compound represented by the following general formula (1), and water,
The two or more water-soluble organic solvents are composed of a first water-soluble organic solvent and a second water-soluble organic solvent, and the mass ratio (first: second) is from 1: 1.1 to 1. : 1.9,
The first water-soluble organic solvent is glycerin;
The second water-soluble organic solvent is ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,3-butanediol, 2,3-butanediol, 1,4-butanediol. 3-methyl-1,3-butanediol, 1,5-pentanediol, tetraethylene glycol, 1,6-hexanediol, 2-methyl-2,4-pentanediol, polyethylene glycol, 1,2,4- An ink set comprising at least one selected from butanetriol and 1,2,6-hexanetriol.

In the general formula (1), ^{R 1} represents any of an alkyl group, an allyl group, and an aralkyl group, having 1 to 20 carbon atoms. L represents an integer of 0 to 7. n represents an integer of 20 to 200. The ink set according to claim 1, wherein the surfactant is a compound represented by the following general formula (2).

However, in the said General formula (2), m represents the integer of 0-10, n represents the integer of 0-40. The ink set according to claim 1, wherein the surfactant is a compound represented by the following general formula (3).

However, in the general formula (3), Rf represents a fluorine-containing group. m represents an integer of 1 to 25, n represents an integer of 1 to 4, and p represents an integer of 1 to 4.   The ink set according to any one of claims 1 to 3, wherein a difference in viscosity (maximum viscosity-minimum viscosity) of each ink is 0 to 0.8 mPa · s.   The ink set according to any one of claims 1 to 4, wherein each ink has a viscosity at 25 ° C of 6 mPa · s to 20 mPa · s.   The ink set according to any one of claims 1 to 5, wherein each ink in the ink set is at least one of magenta ink, cyan ink, yellow ink, and black ink. Used to image recording on a recording medium, a transfer amount is 4ml / m ² ~26ml / m ² of pure water of the recording medium at a contact time of 100ms measured by a dynamic scanning absorptometer, and the ink set according to any of claims 1 6 transition amount to the recording medium of the pure water is ^5ml / ^{m 2 ~29ml} / m 2 at a contact time 400 ms. In an ink media set consisting of an ink set and a recording medium,
The ink set is a combination of two or more inks containing at least a pigment, two or more water-soluble organic solvents, a surfactant, a compound represented by the following general formula (1), and water,
The two or more water-soluble organic solvents are composed of a first water-soluble organic solvent and a second water-soluble organic solvent, and the mass ratio (first: second) is from 1: 1.1 to 1. : 1.9,
The first water-soluble organic solvent is glycerin;
The second water-soluble organic solvent is ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,3-butanediol, 2,3-butanediol, 1,4-butanediol. 3-methyl-1,3-butanediol, 1,5-pentanediol, tetraethylene glycol, 1,6-hexanediol, 2-methyl-2,4-pentanediol, polyethylene glycol, 1,2,4- At least one selected from butanetriol and 1,2,6-hexanetriol;
Pure water wherein the recording medium is, in the dynamic transfer amount to the recording medium of pure water at the contacting time 100ms measured by scanning absorptometer is that ^{4ml / m 2 ~26ml / m 2} , and the contact time 400ms the ink media set, wherein the transition amount to the recording medium is ^{5ml / m 2 ~29ml / m 2} .

In the general formula (1), ^{R 1} represents any of an alkyl group, an allyl group, and an aralkyl group, having 1 to 20 carbon atoms. L represents an integer of 0 to 7. n represents an integer of 20 to 200.   An ink cartridge comprising the ink set according to any one of claims 1 to 7 accommodated in a container.   An ink jet recording method comprising at least an ink flying step of recording an image by applying a stimulus to each ink of the ink set according to claim 1 and causing the ink to fly.   8. An ink jet recording apparatus comprising at least ink flying means for forming an image by applying a stimulus to each ink of the ink set according to claim 1 and causing the ink to fly.

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