JP2009001741A - Recording ink, its manufacturing method, inkjet recording method and inkjet recording apparatus - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a recording ink little in foaming and excellent in storage stability and discharge stability, a manufacturing method of the recording ink, and the like. <P>SOLUTION: The recording ink comprises at least a pigment, water, a fluorine-based surfactant, a compound represented by general formula (1), polymer fine particles and a defoamant, wherein the polymer fine particles are urethane polymer fine particles, their content in the recording ink is 0.1-10 mass%, the defoamant is a silicone defoamant having a volume average particle size of ≤10 μm and its content in the recording ink is 0.005-3 mass%. The recording ink is prepared after filtration with a filter containing a glass fiber. In general formula (1) R<SP>1</SP>indicates any of a 1-20C alkyl, allyl and aralkyl group, L indicates an integer of 0-7 and n indicates an integer of 20-200. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a recording ink suitable for an ink jet recording system, a method for producing the recording ink, and an ink jet recording method and an ink jet recording apparatus using the recording ink.

  Inkjet printers using the inkjet recording method are rapidly spreading because they are small, inexpensive, and easy to color. In recent years, there has been a demand for recording high-quality ink recordings at high speed, and in order to meet this requirement, recording inks used in ink jet recording systems must satisfy various characteristics. For example, in order to record with high quality on plain paper, highly penetrable recording ink is suitable so that ink landed on plain paper does not spread. In order to cope with high-speed recording, the recording ink is required to have high permeability and quick drying. Furthermore, in order to ensure high reliability, a recording ink having good dispersion or dissolution stability, storage stability, and ejection stability is required. Among these, in terms of ejection stability, it is important to suppress bubbles generated in the recording ink. Further, the recording ink has a problem that bubbles are likely to be generated when the cartridge is filled, when the cartridge is attached to the head and when the ink is sucked after the attachment, during recording, and when recording is stopped, thereby causing ejection failure.

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。 In order to solve these problems, the applicant of the present application first contains a nonionic surfactant represented by the following general formula (1) as a dispersant, and the image sharpness, ejection stability, and An ink jet recording ink excellent in ink storage stability has been proposed (see Patent Document 1).

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.

However, the ejection stability of the ink for ink jet recording describes the ejected state after the ink jet printer equipped with the ink is left in a certain environment, and no foaming is disclosed. Since a surfactant is used to disperse the foam, there is a problem that foaming easily occurs.
In addition, the applicant of the present application has already proposed an ink for ink jet recording comprising the compound represented by the above general formula (1) and a silicone oil emulsion and having excellent image saturation and ink storage stability. (See Patent Document 2). However, even in this proposal, the silicone oil emulsion is intended to prevent aggregation of pigments and improve saturation, and has a problem that it easily foams.

Therefore, inks having various compositions have been proposed as a method for solving the ink ejection failure due to foaming. For example, an ink for inkjet recording has been proposed in which the foam stability after 5 minutes is 0 mm according to JIS K3362-1970 (see Patent Document 3). However, this proposal has a problem that it contains at least one of a lower alkyl alcohol having 5 or less carbon atoms and a nonionic surfactant and is not suitable for high-speed recording because of its low permeability to paper. is there.
In addition, an ink that contains a specific acetylene glycol-based surfactant and has high permeability and low foaming has been proposed (see Patent Document 4). However, certain acetylene glycol surfactants cause hydrophobic interaction with the colorant depending on the type of the colorant, so the drying speed does not improve, and when a pigment such as carbon black is used as the colorant. However, there is a problem that the pigment is likely to aggregate, nozzle clogging is likely to occur, and the ink jetting direction is likely to be bent.
In addition, an ink composition comprising a fluorosurfactant and a silicone antifoaming agent containing silica has been proposed (see Patent Document 5). However, this ink composition is a non-aqueous ink, and no aqueous ink is disclosed.
Further, an ink composition containing a self-emulsifying type or an emulsion type silicone antifoaming agent has been proposed (see Patent Document 6). However, when a pigment is used as the colorant of the ink composition, it is limited to a self-dispersing pigment or a polymer fine particle containing a pigment, and the use of a surfactant as a dispersant is disclosed. Not. Further, when the ink composition is filtered with a filter, the silicone antifoaming agent is reduced when passing through the filter, and the amount of the silicone antifoaming agent in the ink is reduced, so that foaming easily occurs. On the other hand, if the filter is not used, the nozzles may be clogged, resulting in ejection failure.

  Therefore, until now, no ink having a composition that has excellent storage stability and ejection stability and solves the problem of foaming in a recording ink and a related technique using a surfactant as a dispersant has not yet been provided. Is the current situation.

JP 2006-45436 A JP 2004-238573 A Japanese Examined Patent Publication No. 7-260149 JP 2000-144026 A Japanese Patent Laid-Open No. 2002-526631 JP 2004-59913 A

  An object of the present invention is to solve the above-described problems and achieve the following objects. That is, the present invention provides a recording ink having less foaming and excellent storage stability and ejection stability, a method for producing the recording ink, an ink jet recording method using the recording ink, and an ink jet recording apparatus. The purpose is to do.

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＞ ウレタン系ポリマー微粒子が、アニオン性自己乳化型エーテル系である前記＜１＞に記載の記録用インクである。
＜３＞ シリコーン消泡剤が、コンパウンド型シリコーン消泡剤、エマルジョン型シリコーン消泡剤、及び自己乳化型シリコーン消泡剤のいずれかである前記＜１＞から＜２＞のいずれかに記載の記録用インクである。
＜４＞ フッ素系界面活性剤が、下記一般式（２）で表される化合物を含有する前記＜１＞から＜３＞のいずれかに記載の記録用インクである。

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。
＜５＞ フッ素系界面活性剤の記録用インクにおける含有量が、０．１質量％〜１０質量％である前記＜１＞から＜４＞のいずれかに記載の記録用インクである。
＜６＞ ガラス繊維を含有するフィルターの孔径が０．５μｍ〜６μｍである前記＜１＞から＜５＞のいずれかに記載の記録用インクである。
＜７＞ 少なくとも、顔料と、水と、フッ素系界面活性剤と、下記一般式（１）で表される化合物と、ウレタン系ポリマー微粒子と、体積平均粒径１０μｍ以下のシリコーン消泡剤とを混合してなるインクを、ガラス繊維を含有するフィルターでろ過して調製することを特徴とする記録用インクの製造方法である。

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。
＜８＞ ウレタン系ポリマー微粒子が、アニオン性自己乳化型エーテル系である前記＜７＞に記載の記録用インクの製造方法である。
＜９＞ シリコーン消泡剤が、コンパウンド型シリコーン消泡剤、エマルジョン型シリコーン消泡剤、及び自己乳化型シリコーン消泡剤のいずれかである前記＜７＞から＜８＞のいずれかに記載の記録用インクの製造方法である。
＜１０＞ フッ素系界面活性剤が、下記一般式（２）で表される化合物を含有する前記＜７＞から＜９＞のいずれかに記載の記録用インクの製造方法である。

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。
＜１１＞ フッ素系界面活性剤の記録用インクにおける含有量が、０．１質量％〜１０質量％である前記＜７＞から＜１０＞のいずれかに記載の記録用インクの製造方法である。
＜１２＞ ガラス繊維を含有するフィルターの孔径が０．５μｍ〜６μｍである前記＜７＞から＜１１＞のいずれかに記載の記録用インクの製造方法である。
＜１３＞ 前記＜１＞から＜６＞のいずれかに記載の記録用インクに刺激を印加し、該記録用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。
＜１４＞ 刺激が、熱、圧力、振動及び光から選択される少なくとも１種である前記＜１３＞に記載のインクジェット記録方法である。
＜１５＞ 前記＜１＞から＜６＞のいずれかに記載の記録用インクに刺激を印加し、該記録用インクを飛翔させて画像を記録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。
＜１６＞ 刺激が、熱、圧力、振動及び光から選択される少なくとも１種である前記＜１５＞に記載のインクジェット記録装置である。 Means for solving the problems are as follows. That is,
<1> A recording ink containing at least a pigment, water, a fluorosurfactant, a compound represented by the following general formula (1), polymer fine particles, and an antifoaming agent,
The polymer fine particles are urethane polymer fine particles, and the content of the urethane polymer fine particles in the recording ink is 0.1% by mass to 10% by mass,
The antifoaming agent is a silicone antifoaming agent having a volume average particle size of 10 μm or less, and the content of the silicone antifoaming agent in the recording ink is 0.005% by mass to 3% by mass,
The recording ink is prepared by filtering with a filter containing glass fiber.

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 recording ink according to <1>, wherein the urethane-based polymer fine particles are anionic self-emulsifying ether-based.
<3> The silicone antifoaming agent according to any one of <1> to <2>, wherein the silicone antifoaming agent is one of a compound type silicone antifoaming agent, an emulsion type silicone antifoaming agent, and a self-emulsifying type silicone antifoaming agent. It is a recording ink.
<4> The recording ink according to any one of <1> to <3>, wherein the fluorosurfactant contains 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.
<5> The recording ink according to any one of <1> to <4>, wherein the content of the fluorosurfactant in the recording ink is 0.1% by mass to 10% by mass.
<6> The recording ink according to any one of <1> to <5>, wherein the filter containing glass fiber has a pore diameter of 0.5 μm to 6 μm.
<7> At least a pigment, water, a fluorosurfactant, a compound represented by the following general formula (1), urethane polymer fine particles, and a silicone antifoaming agent having a volume average particle size of 10 μm or less. It is a method for producing a recording ink, characterized in that a mixed ink is prepared by filtering with a filter containing glass fibers.

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.
<8> The method for producing a recording ink according to <7>, wherein the urethane polymer fine particles are anionic self-emulsifying ether type.
<9> The silicone antifoaming agent according to any one of <7> to <8>, wherein the silicone antifoaming agent is one of a compound type silicone antifoaming agent, an emulsion type silicone antifoaming agent, and a self-emulsifying type silicone antifoaming agent. This is a method for producing a recording ink.
<10> The method for producing a recording ink according to any one of <7> to <9>, wherein the fluorosurfactant contains 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.
<11> The method for producing a recording ink according to any one of <7> to <10>, wherein the content of the fluorosurfactant in the recording ink is 0.1% by mass to 10% by mass. .
<12> The method for producing a recording ink according to any one of <7> to <11>, wherein the filter containing glass fiber has a pore diameter of 0.5 μm to 6 μm.
<13> An ink jet comprising at least an ink flying step of recording an image by applying a stimulus to the recording ink according to any one of <1> to <6> and causing the recording ink to fly. It is a recording method.
<14> The inkjet recording method according to <13>, wherein the stimulus is at least one selected from heat, pressure, vibration, and light.
<15> An ink jet comprising at least ink flying means for recording an image by applying a stimulus to the recording ink according to any one of <1> to <6> and causing the recording ink to fly. It is a recording device.
<16> The inkjet recording apparatus according to <15>, wherein the stimulus is at least one selected from heat, pressure, vibration, and light.

The recording ink of the present invention comprises at least a pigment, water, a fluorine-based surfactant, a compound represented by the above general formula (1), polymer fine particles, and an antifoaming agent,
The polymer fine particles are urethane polymer fine particles, and the content of the urethane polymer fine particles in the recording ink is 0.1% by mass to 10% by mass,
The antifoaming agent is a silicone antifoaming agent having a volume average particle size of 10 μm or less, and the content of the silicone antifoaming agent in the recording ink is 0.005% by mass to 3% by mass,
Since the recording ink is prepared by filtering with a filter containing glass fiber, it has less foaming and is excellent in storage stability and ejection stability.

  The recording ink production method of the present invention comprises at least a pigment, water, a fluorosurfactant, a compound represented by the general formula (1), urethane polymer fine particles, and a volume average particle size of 10 μm. Since ink prepared by mixing the following silicone antifoaming agent is filtered through a filter containing glass fiber, recording ink with less foaming and excellent storage stability and ejection stability is efficiently produced. Can be manufactured.

  The ink jet recording method of the present invention includes at least an ink flying step of recording an image by applying energy to the recording ink of the present invention and causing the recording ink to fly. In the ink jet recording method of the present invention, in the ink flying step, energy is applied to the recording ink of the present invention, and the recording ink is ejected to record an image. As a result, there is little foaming, excellent storage stability and ejection stability, and high-quality image recording is possible.

  The ink jet recording apparatus of the present invention comprises at least ink flying means for recording an image by applying energy to the recording ink of the present invention and causing the recording ink to fly. In the ink jet recording apparatus, the ink flying means applies energy to the recording ink of the present invention and causes the recording ink to fly to record an image. As a result, there is little foaming, excellent storage stability and ejection stability, and high-quality image recording is possible.

  According to the present invention, the conventional problems can be solved, the foaming is less, the recording ink is excellent in storage stability and ejection stability, the method for producing the recording ink, and the recording ink. An ink jet recording method and an ink jet recording apparatus can be provided.

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。 (Recording ink and method for producing recording ink)
The recording ink of the present invention contains at least a pigment, water, a fluorosurfactant, a compound represented by the following general formula (1), polymer fine particles, and an antifoaming agent, and further requires a wetting agent. Depending on the case, it contains other components.

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 recording ink is prepared by filtering with a filter containing glass fibers.
The recording ink production method of the present invention comprises at least a pigment, water, a fluorosurfactant, a compound represented by the general formula (1), urethane polymer fine particles, and a volume average particle size of 10 μm. An ink obtained by mixing the following silicone antifoaming agent is prepared by filtering with a filter containing glass fibers.
The recording ink of the present invention is produced by the recording ink production method of the present invention.
The details of the method for producing the recording ink of the present invention will also be described below through the description of the recording ink of the present invention.

The recording ink of the present invention is prepared by filtering with a filter containing glass fibers. In general, as a filter material used for filtration of recording ink, there are polypropylene, polyethylene, polyethylene tetrafluoride, polyester and the like in addition to glass fiber. The rate at which coarse particles, impurities, dust, etc. in the recording ink are removed by filtration depends on the material and pore diameter of the filtration filter. At this time, when the solubility parameters of the recording ink and the filtration filter are close, the recording ink may be adsorbed on the filtration filter and removed.
Further, when a recording ink containing a silicone antifoaming agent is prepared and then filtered to remove impurities, dust, etc., the silicone antifoaming agent in the recording ink may be partially removed. In particular, when silica particles are contained in the silicone antifoaming agent, silica particles having a large particle size are removed by filtration, and the defoaming property of the recording ink is lowered. Further, silicone oil and silicone emulsion other than silica particles in the silicone antifoaming agent are also adsorbed to the filter and removed from the ink depending on the material of the filter, and the defoaming property is lowered.
Therefore, glass fiber is used as the material of the filter because it is difficult for the silicone antifoam used in the recording ink to be removed by adsorption onto the filter.
Examples of such a filter containing glass fiber include a glass fiber filter manufactured by Advantech Toyo Co., Ltd. and a glass fiber filter manufactured by Nippon Pole Co., Ltd.
The pore size of the filtration filter is preferably 0.5 μm to 6 μm, and more preferably 1.0 μm to 3 μm. When the pore diameter is less than 0.5 μm, the silicone antifoaming agent in the recording ink is removed by the filtration filter, and particles are removed more than necessary, which may shorten the life of the filtration filter. On the other hand, if the hole diameter exceeds 6 μm, impurities and dust in the recording ink cannot be removed, and clogging may occur at the nozzle when the recording ink is ejected from the head.

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 a colorant used in the present invention is dispersed with a compound represented by the following general formula (1). By using a 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.
By including a polyoxyethylene group as such 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 recording 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. .

-Fluorosurfactant-
When the fluorosurfactant is contained in the recording ink, the penetrability when the recording ink lands on a recording medium such as paper increases, preventing bleeding on the color boundary on the recording medium. it can. In general, a fluorosurfactant has high penetrability and can improve printing quality, but easily foams. Therefore, by using in the present invention, it is possible to obtain a recording ink with less foaming while maintaining high print quality.

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。 The fluorine-based surfactant is not particularly limited and may be appropriately selected depending on the intended purpose. For example, perfluoroalkyl sulfonate, perfluoroalkyl carboxylate, perfluoroalkyl phosphate, perfluoroalkyl Examples thereof include ethylene oxide adducts, perfluoroalkyl betaines, perfluoroalkylamine oxide compounds, and compounds represented by the following general formula (2). These may be used individually by 1 type and may use 2 or more types together. Among these, the compound represented by the following general formula (2) is particularly preferable from the viewpoint of high reliability.

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

  Commercially available products can be used as the fluorosurfactant. Examples of the commercially available products include S-144 and S-145 (both manufactured by Asahi Glass Co., Ltd.); FC-170C, FC-430, Fluorado -FC4430 (all manufactured by Sumitomo 3M); FSO, FSO-100, FSN, FSN-100, FS-300 (all manufactured by DuPont); FT-250, 251 (manufactured by Neos), etc. Is mentioned. Among these, FSO, FSO-100, FSN, FSN-100, and FS-300 manufactured by DuPont are particularly preferable from the viewpoint of good print quality and storage stability.

  The content of the fluorosurfactant in the recording ink is preferably 0.1% by mass to 10% by mass, and more preferably 0.1% by mass to 5% by mass. If the content is less than 0.1% by mass, a remarkable effect may not be obtained in improving the permeability. If the content exceeds 10% by mass, viscosity increase, aggregation, etc. may occur when stored at high temperature. This may cause problems with ejection stability.

-Polymer fine particles-
The polymer fine particles have a property of thickening or aggregating when ink is landed on a recording medium such as paper, and has an effect of promoting fixing on paper. In addition, depending on the type of polymer fine particles, a film is formed on paper, and the effect of improving the abrasion resistance of the printed matter is also obtained. Furthermore, the dispersion stability of the pigment is improved by adding polymer fine particles.
As the polymer fine particles, urethane polymer fine particles are used. The urethane-based polymer fine particles exist as an O / W emulsion when used as a raw material for pigment ink or after ink preparation.
In the emulsion of urethane polymer fine particles, normal urethane polymer fine particles having relatively hydrophilic properties are emulsified using an emulsifier on the outside, and the urethane polymer fine particles themselves have a functional group that functions as an emulsifier. And anionic self-emulsifying emulsions introduced by means such as polymerization. In the present invention, any of them can be carried out, but an emulsion of anionic self-emulsifying type urethane-based polymer fine particles is preferable because it is always excellent in dispersion stability in various combinations with pigments and dispersants. In this case, the ether type is more preferable than the polyester type or the polycarbonate type in terms of the fixing property and dispersion stability of the pigment. The reason for this is not clear, but many non-ether types are weak in solvent resistance, and it is thought that the ink tends to thicken and aggregate when stored at high temperatures.

The average particle diameter (D ₅₀ ) of the urethane polymer fine particles is preferably 200 nm or less, more preferably 100 nm or less, and still more preferably 80 nm or less. When the average particle diameter exceeds 200 nm, the nozzles of the ink jet recording apparatus may be clogged and discharge defects may easily occur.
The average particle diameter can be measured by a dynamic light scattering method using a Microtrac UPA manufactured by Nikkiso Co., Ltd. in an environment of 23 ° C. and 55% RH, for example.
Commercially available products can be used as the urethane polymer fine particles. Examples of the commercially available products include SF460, SF460S, SF420, SF110, SF300, SF361 (manufactured by Nihon Unicar Co., Ltd.); , Manufactured by Mitsui Chemicals Polyurethane Co., Ltd.).
The content of the urethane-based polymer fine particles in the recording ink is 0.1% by mass to 10% by mass, and preferably 0.1% by mass to 1% by mass. When the content is less than 0.1% by mass, the amount of polymer fine particles covering the pigment after landing on the recording medium is insufficient, and the scratch resistance may be reduced. In some cases, problems may arise in the storage stability and ejection stability of the ink.

-Antifoaming agent-
A silicone antifoaming agent is used as the antifoaming agent. Examples of the silicone antifoaming agent include a compound type silicone antifoaming agent, an emulsion type silicone antifoaming agent, and a self-emulsifying type silicone antifoaming agent. The compound-type silicone antifoaming agent is obtained by dispersing fine particles such as silica and alumina in an oil-type silicone antifoaming agent to improve antifoaming properties. The emulsion-type silicone antifoaming agent is obtained by increasing the dispersibility in water by making the compound-type antifoaming agent an O / W emulsion with an emulsifier. The self-emulsifying type silicone antifoaming agent contains silicone oil and silica and easily becomes an O / W type emulsion when diluted with water.
In the recording ink of the present invention, since a fluorosurfactant is used, the surface tension of the ink is lowered and bubbles are easily generated. Therefore, among the silicone antifoaming agents, compound type silicone antifoaming agents, silica emulsion defoaming agents and self-emulsifying silicone antifoaming agents containing silica particles having excellent defoaming properties are preferred.

The volume average particle size of the silicone antifoaming agent is 10 μm or less, preferably 1 μm to 10 μm. When the volume average particle diameter exceeds 10 μm, the silicone antifoaming agent may be removed from the recording ink in the filtration step during ink preparation. In addition, when a filter having a large pore size is used in the filtration process at the time of ink preparation and a silicone antifoaming agent having a volume average particle size larger than 10 μm remains in the ink, when the recording ink is discharged from the ink jet recording apparatus In addition, since the general nozzle diameter of the head is 20 μm to 30 μm, clogging may occur, resulting in ejection failure.
Further, when the silicone antifoaming agent having a volume average particle size of 10 μm or less is filtered through a glass fiber-containing filter having a pore size of 6 μm or less, silica having a particle size larger than 6 μm in the silicone antifoaming agent is removed by the filter. Silica having a diameter of 6 μm or less passes through the filter and improves the defoaming property of the ink. Further, silicone oil and silicone emulsion having a particle size other than silica in the silicone antifoaming agent larger than 6 μm also pass through the filter to improve the defoaming property of the ink. The reason for this is not clear, but silicone oil and silicone emulsion are different from solid silica, and it is considered that the filter can be passed by changing its shape.
Further, based on the same principle, it is estimated that clogging of the nozzle of the head is unlikely to occur if the silicone oil and the silicone emulsion in the silicone antifoaming agent are larger than 6 μm and smaller than 10 μm.
The volume average particle diameter of the silicone antifoaming agent can be measured by a dynamic light scattering method using Microtrac UPA manufactured by Nikkiso Co., Ltd. in an environment of 23 ° C. and 55% RH, for example.

As the silicone antifoaming agent, a commercially available product can be used. Examples of the commercially available product include KS-508, KS-531, KM-72, KM-72F, KM-90, and KM-98 (any , Manufactured by Shin-Etsu Chemical Co., Ltd.); SF-8427, SF-8428, SH-3749, SH-8400, FZ-2101, FZ-2104, FZ-2118, FZ-2203, FZ-2207 (all are Toray -Dow Corning Co., Ltd.); BYK-345, BYK-346, BYK-348 (manufactured by Big Chemie Japan Co., Ltd.), and the like.
The content of the silicone antifoaming agent in the recording ink is 0.005% by mass to 3% by mass, and preferably 0.01% by mass to 0.5% by mass. When the content is less than 0.005% by mass, improvement of the defoaming effect is insufficient, and when the content exceeds 3% by mass, problems may occur in the storage stability and ejection stability of the ink.

-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 such a thing, for example, no. 2300, no. 900, MCF-88, no. 33, no. 40, no. 45, no. 52, MA7, MA8, MA100, no. 2200B (Mitsubishi Chemical), Raven700, 5750, 5250, 5000, 3500, 1500 (Columbia), Regal 400R, 330R, 660R, MoguL, Monarch 700, 800, 880, 900, 1000, 1100, 1300, Monarch 1400 (manufactured by Cabot), color black FW1, FW2, FW2V, FW18, FW200, S150, S160, S170, Printex 35, U, the same V, the same 140 U, the same 140 V, the special black 6, the same 5, the same 4 A, the same 4 (manufactured by Degussa) and the like.

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, 2, 2, 3, 12, 14, 16, 17, 17, 73, 74, 75, 83, 93, 95, 97, 98, 114, 120, 128, 129, 138, 150, 151, 154, 155, 174, 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, 7, 12, 48 (Ca), 48 (Mn), 57 (Ca), 57: 1, 112, 122, 123, 146, 168, 176 184, 185, 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, 2, 3, 15, 15: 3, 15: 4, 15:34, 16, 22, 22, 60, 63, 66, C.I. I. Bat Blue 4, 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 recording 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.

-Wetting agent-
The recording ink of the present invention preferably contains a wetting agent. If the wetting agent is contained in the recording ink, it is possible to ensure water retention and wettability of the recording ink. As a result, even if the recording ink is stored for a long period of time, the aggregation of the colorant There is no increase in viscosity and excellent storage stability can be realized. Further, even when the nozzle tip of the ink jet printer is installed in an open state, it is possible to realize a recording ink that maintains the fluidity of the dried material for a long time. Further, nozzle clogging does not occur during printing or when restarting after interruption of printing, and high ejection stability can be obtained.

The wetting agent is not particularly limited and may be appropriately selected depending on the intended purpose.For example, polyhydric alcohols, polyhydric alcohol alkyl ethers, polyhydric alcohol aryl ethers, nitrogen-containing heterocyclic compounds, Examples include amides, amines, sulfur-containing compounds, propylene carbonate, and ethylene carbonate. These may be used alone or in combination of two or more.
Examples of the polyhydric alcohols include ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, 1,3-propanediol, 1,3-butanediol, 2,3-butanediol, 1,4-butanediol, 3-methyl-1,3-butanediol, 1,5-pentanediol, 1,6-hexanediol, 2-methyl-2,4-pentanediol, Examples include tetraethylene glycol, polyethylene glycol, glycerin, 1,2,6-hexanetriol, 1,2,4-butanetriol, 1,2,3-butanetriol, and petriol.
Examples of the polyhydric alcohol alkyl ethers include ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, tetraethylene glycol monomethyl ether, and propylene glycol monoethyl ether. It is done.
Examples of the polyhydric alcohol aryl ethers include ethylene glycol monophenyl ether and ethylene glycol monobenzyl ether.
Examples of the nitrogen-containing heterocyclic compound include N-methyl-2-pyrrolidone, N-hydroxyethyl-2-pyrrolidone, 2-pyrrolidone, 1,3-dimethylimidazolidinone, and ε-caprolactam.
Examples of the amides include formamide, N-methylformamide, N, N-dimethylformamide and the like.
Examples of the amines include monoethanolamine, diethanolamine, triethanolamine, monoethylamine, diethylamine, and triethylamine.
Examples of the sulfur-containing compounds include dimethyl sulfoxide, sulfolane, thiodiethanol, thiodiglycol, and the like.
Among these, 1,3-butyl glycol, diethylene glycol, triethylene glycol, and glycerin are particularly preferable in terms of preventing clogging due to drying of the ink and improving the saturation of the image.
The content of the wetting agent in the recording ink is preferably 0.1% by mass to 50% by mass, and more preferably 5% by mass to 40% by mass.

  The other components are not particularly limited and may be appropriately selected as necessary. For example, a pH adjuster, antiseptic / antifungal agent, chelating reagent, rust inhibitor, antioxidant, ultraviolet absorber, oxygen An absorber, a light stabilizer, etc. are mentioned.

  The pH adjuster is not particularly limited as long as the pH can be adjusted to 7 to 11 without adversely affecting the recording ink to be prepared, and can be appropriately selected according to the purpose. Examples include alcohol amines, alkali metal hydroxides, ammonium hydroxides, phosphonium hydroxides, alkali metal carbonates, and the like. If the pH exceeds 7 to 11, the amount of the ink jet head or ink supply unit that melts out is large, and problems such as ink deterioration, leakage, and ejection failure may occur.

  Examples of the antiseptic / antifungal agent include sodium dehydroacetate, sodium sorbate, 2-pyridinethiol-1-oxide sodium, sodium benzoate, sodium pentachlorophenol, and the like.

  Examples of the chelating reagent include sodium ethylenediaminetetraacetate, sodium nitrilotriacetate, sodium hydroxyethylethylenediaminetriacetate, sodium diethylenetriaminepentaacetate, sodium uramil diacetate, and the like.

  Examples of the rust inhibitor include acidic sulfite, sodium thiosulfate, ammonium thiodiglycolate, diisopropylammonium nitrite, pentaerythritol tetranitrate, dicyclohexylammonium nitrite, and benzotriazole.

  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.

  In the recording ink of the present invention, a pigment dispersion, a fluorosurfactant, water, polymer fine particles, an antifoaming agent, and other components as necessary are added, and at 20 to 30 ° C. for 1 to 3 hours. Stir to produce. 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 physical properties of the recording ink of the present invention are not particularly limited and may be appropriately selected depending on the intended purpose. For example, the number of coarse particles, viscosity, surface tension and the like are preferably in the following ranges.

  The number of coarse particles in the recording ink is preferably less than 50 and more preferably less than 30. The number of coarse particles in the present invention is a value obtained by measuring the number of coarse particles in 5.0 μl of ink with an Accusizer 780A manufactured by Particle Sizing Systems. The number of coarse particles is preferably within this range even when moisture in the recording ink is evaporated.

The viscosity of the recording ink is preferably 4 mPa · s to 20 mPa · s at 25 ° C., more preferably 4 mPa · s to 15 mPa · s. If the viscosity exceeds 20 mPa · s, it may be difficult to ensure ejection stability.
The static surface tension of the recording ink is preferably 35 mN / m or less, more preferably 30 mN / m or less at 25 ° C.

  There is no restriction | limiting in particular as coloring of the recording ink of this invention, According to the objective, it can select suitably, Yellow, magenta, cyan, black etc. are mentioned. When recording is performed using an ink set in which two or more of these colorings are used in combination, a multicolor image can be formed. When recording is performed using an ink set in which all colors are combined, a full color image is formed. be able to.

  The recording ink of the present invention uses an piezoelectric head as a pressure generating means for pressurizing ink in an ink flow path as an ink jet head, and deforms a diaphragm that forms the wall surface of the ink flow path to increase the volume in the ink flow path. A so-called piezo type that discharges ink droplets by changing (refer to 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. (Refer to Japanese Patent Application Laid-Open No. 61-59911), a diaphragm that forms the wall surface of an ink flow path and an electrode are arranged opposite to each other, and the diaphragm is deformed by an electrostatic force generated between the diaphragm and the electrode. Thus, a pre-printer equipped with any ink jet head such as an electrostatic type (see Japanese Patent Laid-Open No. 6-71882) that discharges ink droplets by changing the volume in the ink flow path. Can also be used well for printers.

  The recording ink of the present invention can be suitably used in various fields such as an ink jet recording ink, a fountain pen, a ballpoint pen, a magic pen, and a sign pen, and is particularly suitable for an image recording apparatus (printer or the like) using an ink jet recording method. For example, the recording paper and the recording ink can be heated at 50 to 200 ° C. before or after printing or printing, and can be used for a printer or the like having a function of promoting print fixing. The ink cartridge, the ink jet recording apparatus of the present invention, and the ink jet recording method can be particularly preferably used.

<Ink cartridge>
The ink cartridge contains the recording ink of the present invention in a container, and further includes other members and the like 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.

(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 by applying a stimulus to the recording ink of the present invention and causing the recording ink to fly.
The ink flying means is means for forming an image by applying a stimulus to the recording ink of the present invention and causing the recording ink to fly. The ink flying means is not particularly limited, and examples thereof include various nozzles for ejecting ink.

  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. Is 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, Examples include thermal actuators that use phase changes due to liquid film boiling using electrothermal transducers such as heating resistors, shape memory alloy actuators that use metal phase changes due to temperature changes, and electrostatic actuators that use electrostatic forces. .

  There are no particular restrictions on the manner in which the recording ink flies, and it varies depending on the type of the stimulus. For example, when the stimulus is “heat”, a recording signal is output to the recording ink in the recording head. Corresponding thermal energy is applied using, for example, a thermal head, bubbles are generated in the recording ink by the thermal energy, and the recording ink is formed into droplets from the nozzle holes of the recording head by the pressure of the bubbles. And a method of discharging and jetting. 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 the recording ink is ejected and ejected as droplets from the nozzle holes of the recording head.

The size of the recording 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 drive frequency is preferably 1 kHz or higher, and the resolution is preferably 300 dpi or higher.
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, the recording ink of the present invention is accommodated in an ink cartridge with reference to the drawings, and the ink cartridge is mounted on an ink jet printer and ejected and ejected as droplets from a fine ejection port to form an image on a recording medium. How to do will be described.

  The ink jet recording apparatus shown in FIG. 1 includes an apparatus main body 101, a paper feed tray 102 for loading paper loaded in the apparatus main body 101, and paper discharge for stocking paper loaded in the apparatus main body 101 and recorded with images. And a tray 103. 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. 2 and 3, in the apparatus main body 101, a carriage 133 is slidably held in the main scanning direction by a guide rod 131 and a stay 132, which are guide members 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 an 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 the 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.
A double-sided paper feeding unit 181 is detachably mounted on the back surface of the apparatus main body 101. The double-sided paper feeding unit 181 takes in the paper 142 returned by the reverse rotation of the transport belt 151, reverses it, and feeds it again between the counter roller 152 and the transport belt 151. Further, a manual paper feed unit 182 is provided on the upper surface of the double-sided paper feed unit 181.
In the ink jet recording apparatus configured as described above, the sheets 142 are separated and fed one by one from the sheet feeding unit, and the sheet 142 fed substantially vertically upward is guided by the guide 145, and the conveyance belt 151 and the counter roller 152. The leading end is guided by a conveying guide 153 and pressed against the conveying belt 151 by a leading end pressing roller 155, and the conveying direction is changed by approximately 90 °.
At this time, the conveying belt 151 is charged by the charging roller 156, and the sheet 142 is electrostatically attracted to the conveying belt 151 and conveyed. Therefore, by driving the recording head 134 according to the image signal while moving the carriage 133, ink droplets are ejected onto the stopped sheet 142 to record one line, and after the sheet 142 is conveyed by a predetermined amount, Record the next line. Upon receiving a recording end signal or a signal that the trailing edge of the paper 142 has reached the recording area, the recording operation is finished and the paper 142 is discharged onto the paper discharge tray 103.
When a near-end remaining amount of ink in the sub tank 135 is detected, a required amount of ink is supplied to the sub tank 135 from the ink cartridge.

  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 in the ink jet recording apparatus of the present invention will be described.
FIG. 4 is an enlarged view of elements of an ink jet head to which the present invention is applied, and FIG. 5 is an enlarged cross-sectional view of the main part of the head in the direction between channels.
This ink jet head includes 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. 4) and a frame 10 formed with a carving that becomes a common liquid chamber 12; The flow resistance plate 21, the flow path plate 20 having the communication port 23 communicating with the nozzle 31, the engraving that becomes the fluid resistance portion 21, the pressurized liquid chamber 22, the nozzle plate 30 that forms the nozzle 31, the convex portion 61, the diaphragm portion 62, and the ink. A diaphragm 60 having an inflow port 63, a laminated piezoelectric element 50 bonded to the diaphragm 60 via an adhesive layer 70, and a base 40 to which the laminated piezoelectric element 50 is fixed are provided. 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 and 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 on comb teeth by half-cut dicing and used as a drive unit 56 and a support unit 57 (non-drive unit) one by one (see FIG. 5).
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 provided with an electrode layer at the end of the laminated piezoelectric element and is wound around to join the Gnd electrode of the FPC (80). A driver IC (not shown) is mounted on the FPC (80), thereby controlling the drive voltage application to the drive unit 56.
The diaphragm 60 includes a thin film diaphragm portion 62, an island-shaped convex portion (island portion) 61 that joins the laminated piezoelectric element 50 that forms the driving portion 56 formed at the center portion of the diaphragm portion 62, and a support (not shown). A thick film portion including a beam to be joined to the portion and an opening to be an ink inflow port 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 engraving to be the fluid resistance portion 21 and the pressurized liquid chamber 22 and the through-hole to be the communication port 23 at a position relative to the nozzle 31 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 31 that are fine discharge ports for flying ink droplets. The inner shape (inner shape) of the nozzle 31 is formed in a horn shape (may be a substantially cylindrical shape or a substantially frustum shape). The diameter of the nozzle 31 is 20 μm to 35 μm on the ink droplet outlet side. The nozzle pitch of each row was 150 dpi.
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 31.
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 the recording medium using the recording ink 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.
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.
In the following Examples and Comparative Examples, the volume average particle size of the silicone antifoaming agent was measured by a dynamic light scattering method using a Microtrac UPA manufactured by Nikkiso Co., Ltd. in an environment of 23 ° C. and 55% RH.

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 (Production Example 1)
-Preparation of pigment dispersion-
After premixing the following composition, it was circulated and dispersed in a disk-type bead mill (manufactured by Shinmaru Enterprises, KDL type, media: zirconia balls having a diameter of 0.3 mm) to prepare a pigment dispersion.
・ C. I. Pigment Blue 15: 3 (Dainippon Seika Co., Ltd., Cyanine Blue A-292) 15 parts by mass Dispersant represented by the following general formula (1) (polyoxyethylene β-naphthyl ether)・ 12 parts by mass

However, in the said General formula (1), L = 0 and n represent 40.
・ Ion exchange water

(Production Example 2)
-Preparation of pigment dispersion-
C.I. as a cyan pigment I. Pigment Blue 15: 3 was subjected to low-temperature plasma treatment to prepare a pigment having a carboxylic acid group introduced. A dispersion of this in ion-exchanged water was desalted and concentrated with an ultrafiltration membrane to obtain a cyan pigment dispersion having a pigment concentration of 15% by mass.

ただし、前記一般式（２）中、ｍ＝６〜８、ｎ＝２６以上である。
・ウレタン系ポリマー微粒子（Ｗ５６６１、三井化学ポリウレタン株式会社製、アニオン性自己乳化型ポリエーテル系、平均粒径＝１０ｎｍ）・・・０．５質量部
・シリコーン消泡剤（ＫＭ−９０、信越化学工業株式会社製、自己乳化型、体積平均粒径＝７．５μｍ）・・・０．１質量部
・イオン交換水・・・残量（合計：１００質量部） Example 1
-Preparation of recording ink 1-
-Pigment dispersion liquid of Production Example 1 39 parts by mass-Glycerin ... 10 parts by mass-Diethylene glycol ... 20 parts by mass-Fluorine-based surfactant represented by the following general formula (2) ... 2 Parts by mass

However, in said general formula (2), it is m = 6-8, n = 26 or more.
・ Urethane-based polymer fine particles (W5661, manufactured by Mitsui Chemicals Polyurethane Co., Ltd., anionic self-emulsifying polyether type, average particle size = 10 nm)... 0.5 mass parts ・ Silicone antifoaming agent (KM-90, Shin-Etsu Chemical) Manufactured by Kogyo Co., Ltd., self-emulsifying type, volume average particle size = 7.5 μm) ... 0.1 part by mass ・ Ion-exchanged water: remaining amount (total: 100 parts by mass)

  First, a fluorosurfactant was added to glycerin and diethylene glycol. Next, urethane polymer fine particles were added, then ion exchange water was added, and after stirring for 30 minutes, the pigment dispersion and the silicone antifoaming agent were added and stirred for 1 hour. The obtained ink was filtered through a glass fiber filter having a pore diameter of 3 μm (Ultipore GF Plus, manufactured by Nippon Pole Co., Ltd.) to prepare recording ink 1.

ただし、前記一般式（２）中、ｍ＝１〜９、ｎ＝０〜２５である。
・ウレタン系ポリマー微粒子（Ｗ５０２５、三井化学ポリウレタン株式会社製、アニオン性自己乳化型ポリエーテル系、平均粒径＝１０ｎｍ）・・・０．５質量部
・シリコーン消泡剤（ＫＭ−９０、信越化学工業株式会社製、自己乳化型、体積平均粒径＝７．５μｍ）・・・０．１質量部
・イオン交換水・・・残量（合計：１００質量部） (Example 2)
-Preparation of recording ink 2-
-Pigment dispersion liquid of Production Example 1 39 parts by mass-Glycerin ... 10 parts by mass-Diethylene glycol ... 20 parts by mass-Fluorine-based surfactant represented by the following general formula (2) ... 2 Parts by mass

However, in the said General formula (2), it is m = 1-9 and n = 0-25.
・ Urethane polymer fine particles (W5025, manufactured by Mitsui Chemicals Polyurethanes, anionic self-emulsifying polyether type, average particle size = 10 nm) 0.5 parts by mass ・ Silicone antifoaming agent (KM-90, Shin-Etsu Chemical) Manufactured by Kogyo Co., Ltd., self-emulsifying type, volume average particle size = 7.5 μm) ... 0.1 part by mass ・ Ion-exchanged water: remaining amount (total: 100 parts by mass)

  First, a fluorosurfactant was added to glycerin and diethylene glycol. Next, urethane-based polymer fine particles were added, then ion-exchanged water was added, and after stirring for 30 minutes, a pigment dispersion and a silicone antifoaming agent were added and stirred for 1 hour. The obtained prepared ink was filtered through a glass fiber filter (Ultipore GF Plus, manufactured by Nippon Pole Co., Ltd.) having a pore diameter of 3 μm to prepare a recording ink 2.

ただし、前記一般式（２）中、ｍ＝１〜９、ｎ＝０〜２５である。
・ウレタン系ポリマー微粒子（ＳＦ４６０Ｓ、日本ユニカー株式会社製、アニオン性自己乳化型ポリカーボネート系、平均粒径＝３０μｍ）・・・０．５質量部
・シリコーン消泡剤（ＫＭ−９０、信越化学工業株式会社製、自己乳化型、体積平均粒径７．５μｍ）・・・０．１質量部
・イオン交換水・・・残量（合計：１００質量部） (Example 3)
-Preparation of recording ink 3-
-Pigment dispersion liquid of Production Example 1 39 parts by mass-Glycerin ... 10 parts by mass-Diethylene glycol ... 20 parts by mass-Fluorine-based surfactant represented by the following general formula (2) ... 2 Parts by mass

However, in the said General formula (2), it is m = 1-9 and n = 0-25.
・ Urethane-based polymer fine particles (SF460S, manufactured by Nihon Unicar Co., Ltd., anionic self-emulsifying polycarbonate system, average particle size = 30 μm) ... 0.5 parts by mass ・ Silicone antifoaming agent (KM-90, Shin-Etsu Chemical Co., Ltd.) Made by company, self-emulsifying type, volume average particle size 7.5 μm) ... 0.1 part by mass ・ Ion-exchanged water: remaining amount (total: 100 parts by mass)

  First, a fluorosurfactant was added to glycerin and diethylene glycol. Next, urethane polymer fine particles were added, then ion exchange water was added, and after stirring for 30 minutes, the pigment dispersion and the silicone antifoaming agent were added and stirred for 1 hour. The obtained blended ink was filtered through a glass fiber filter (Ultipore GF Plus, manufactured by Nippon Pole Co., Ltd.) having a pore diameter of 3 μm to prepare a recording ink 3.

ただし、前記一般式（２）中、ｍ＝６〜８、ｎ＝２６以上である。
・ウレタン系ポリマー微粒子（Ｗ５６６１、三井化学ポリウレタン株式会社製、アニオン性自己乳化型ポリエーテル系、平均粒径＝１０ｎｍ）・・・０．５質量部
・シリコーン消泡剤（ＫＭ−９０、信越化学工業株式会社製、自己乳化型、体積平均粒径７．５μｍ）・・・０．１質量部
・イオン交換水・・・残量（合計：１００質量部） Example 4
-Preparation of recording ink 4-
-Pigment dispersion liquid of Production Example 1 39 parts by mass-Glycerin ... 10 parts by mass-Diethylene glycol ... 20 parts by mass-Fluorine-based surfactant represented by the following general formula (2) ... 2 Parts by mass

However, in said general formula (2), it is m = 6-8, n = 26 or more.
・ Urethane-based polymer fine particles (W5661, manufactured by Mitsui Chemicals Polyurethane Co., Ltd., anionic self-emulsifying polyether-based, average particle size = 10 nm)... Manufactured by Kogyo Co., Ltd., self-emulsifying type, volume average particle size 7.5 μm) ... 0.1 part by mass

  First, a fluorosurfactant was added to glycerin and diethylene glycol. Next, urethane polymer fine particles were added, then ion exchange water was added, and after stirring for 30 minutes, the pigment dispersion and the silicone antifoaming agent were added and stirred for 1 hour. The obtained prepared ink was filtered through a glass fiber filter (MCG-045, manufactured by Advantech Toyo Co., Ltd.) having a pore diameter of 0.45 μm to prepare a recording ink 4.

ただし、前記一般式（２）中、ｍ＝１〜９、ｎ＝０〜２５である。
・ウレタン系ポリマー微粒子（Ｗ５６６１、三井化学ポリウレタン株式会社製、アニオン性自己乳化型ポリエーテル系、平均粒径＝１０ｎｍ）・・・０．５質量部
・シリコーン消泡剤（ＫＭ−９０、信越化学工業株式会社製、自己乳化型、体積平均粒径７．５μｍ）・・・０．０１質量部
・イオン交換水・・・残量（合計：１００質量部） (Example 5)
-Preparation of recording ink 5-
-Pigment dispersion liquid of Production Example 1 39 parts by mass-Glycerin ... 10 parts by mass-Diethylene glycol ... 20 parts by mass-Fluorine-based surfactant represented by the following general formula (2) ... 2 Parts by mass

However, in the said General formula (2), it is m = 1-9 and n = 0-25.
・ Urethane-based polymer fine particles (W5661, manufactured by Mitsui Chemicals Polyurethane Co., Ltd., anionic self-emulsifying polyether type, average particle size = 10 nm)... 0.5 mass parts ・ Silicone antifoaming agent (KM-90, Shin-Etsu Chemical) Manufactured by Kogyo Co., Ltd., self-emulsifying type, volume average particle size 7.5 μm)... 0.01 part by mass ・ Ion-exchanged water remaining amount (total: 100 parts by mass)

  First, a fluorosurfactant was added to glycerin and diethylene glycol. Next, urethane polymer fine particles were added, then ion-exchanged water was added, and after stirring for 30 minutes, a pigment dispersion and a silicone antifoaming agent were added and stirred for 1 hour. The obtained prepared ink was filtered through a glass fiber filter (Ultipore GF Plus, manufactured by Nippon Pole Co., Ltd.) having a pore diameter of 3 μm to prepare a recording ink 5.

ただし、前記一般式（２）中、ｍ＝６〜８、ｎ＝２６以上である。
・ウレタン系ポリマー微粒子（Ｗ５６６１、三井化学ポリウレタン株式会社製、アニオン性自己乳化型ポリエーテル系、平均粒径＝１０ｎｍ）・・・１０質量部
・シリコーン消泡剤（ＫＭ−９０、信越化学工業株式会社製、自己乳化型、体積平均粒径７．５μｍ）・・・０．５質量部
・イオン交換水・・・残量（合計：１００質量部） (Example 6)
-Preparation of recording ink 6-
-Pigment dispersion liquid of Production Example 1 39 parts by mass-Glycerin ... 10 parts by mass-Diethylene glycol ... 20 parts by mass-Fluorine-based surfactant represented by the following general formula (2) ... 2 Parts by mass

However, in said general formula (2), it is m = 6-8, n = 26 or more.
・ Urethane polymer fine particles (W5661, manufactured by Mitsui Chemicals Polyurethane Co., Ltd., anionic self-emulsifying polyether type, average particle size = 10 nm) ... 10 parts by mass ・ Silicone antifoaming agent (KM-90, Shin-Etsu Chemical Co., Ltd.) Made by company, self-emulsifying type, volume average particle size 7.5 μm) ... 0.5 parts by mass ・ Ion-exchanged water: remaining amount (total: 100 parts by mass)

  First, a fluorosurfactant was added to glycerin and diethylene glycol. Next, urethane polymer fine particles were added, then ion-exchanged water was added, and after stirring for 30 minutes, a pigment dispersion and a silicone antifoaming agent were added and stirred for 1 hour. The obtained prepared ink was filtered through a glass fiber filter (Ultipore GF Plus, manufactured by Nippon Pole Co., Ltd.) having a pore diameter of 3 μm to prepare a recording ink 6.

ただし、前記一般式（２）中、ｍ＝６〜８、ｎ＝２６以上である。
・ウレタン系ポリマー微粒子（Ｗ５６６１、三井化学ポリウレタン株式会社製、アニオン性自己乳化型ポリエーテル系、平均粒径＝１０ｎｍ）・・・０．５質量部
・シリコーン消泡剤（ＫＭ−９０、信越化学工業株式会社製、自己乳化型、体積平均粒径７．５μｍ）・・・２質量部
・イオン交換水・・・残量（合計：１００質量部） (Example 7)
-Preparation of recording ink 7-
-Pigment dispersion liquid of Production Example 1 39 parts by mass-Glycerin ... 10 parts by mass-Diethylene glycol ... 20 parts by mass-Fluorine-based surfactant represented by the following general formula (2) ... 12 Parts by mass

However, in said general formula (2), it is m = 6-8, n = 26 or more.
・ Urethane-based polymer fine particles (W5661, manufactured by Mitsui Chemicals Polyurethane Co., Ltd., anionic self-emulsifying polyether-based, average particle size = 10 nm)... Manufactured by Kogyo Co., Ltd., self-emulsifying type, volume average particle size 7.5 μm) 2 parts by mass

  First, a fluorosurfactant was added to glycerin and diethylene glycol. Next, urethane polymer fine particles were added, then ion-exchanged water was added, and after stirring for 30 minutes, a pigment dispersion and a silicone antifoaming agent were added and stirred for 1 hour. The obtained prepared ink was filtered through a glass fiber filter (Ultipore GF Plus, manufactured by Nippon Pole Co., Ltd.) having a pore diameter of 3 μm to prepare a recording ink 7.

ただし、前記一般式（２）中、ｍ＝１〜９、ｎ＝０〜２５である。
・ウレタン系ポリマー微粒子（Ｗ５６６１、三井化学ポリウレタン株式会社製、アニオン性自己乳化型ポリエーテル系、平均粒径＝１０ｎｍ）・・・０．５質量部
・シリコーン消泡剤（ＫＭ−７２Ｆ、信越化学工業株式会社製、エマルジョン型、体積平均粒径＝１７．４μｍ）・・・０．１質量部
・イオン交換水・・・残量（合計：１００質量部） (Comparative Example 1)
-Preparation of recording ink 8-
-Pigment dispersion liquid of Production Example 1 39 parts by mass-Glycerin ... 10 parts by mass-Diethylene glycol ... 20 parts by mass-Fluorine-based surfactant represented by the following general formula (2) ... 2 Parts by mass

However, in the said General formula (2), it is m = 1-9 and n = 0-25.
・ Urethane-based fine polymer particles (W5661, manufactured by Mitsui Chemicals Polyurethane Co., Ltd., anionic self-emulsifying type polyether, average particle size = 10 nm) 0.5 parts by mass ・ Silicone antifoaming agent (KM-72F, Shin-Etsu Chemical) Manufactured by Kogyo Co., Ltd., emulsion type, volume average particle diameter = 17.4 μm)... 0.1 mass part ・ Ion-exchanged water remaining amount (total: 100 mass parts)

  First, a fluorosurfactant was added to glycerin and diethylene glycol. Next, urethane polymer fine particles were added, then ion-exchanged water was added, and after stirring for 30 minutes, a pigment dispersion and a silicone antifoaming agent were added and stirred for 1 hour. The obtained blended ink was filtered through a glass fiber filter (Ultipore GF Plus, manufactured by Nippon Pole Co., Ltd.) having a pore diameter of 3 μm to prepare a recording ink 8.

ただし、前記一般式（２）中、ｍ＝６〜８、ｎ＝２６以上である。
・シリコーン消泡剤（ＫＭ−７２Ｆ、信越化学工業株式会社製、エマルジョン型、体積平均粒径＝１７．４μｍ）・・・０．１質量部
・イオン交換水・・・残量（合計：１００質量部） (Comparative Example 2)
-Preparation of recording ink 9-
-Pigment dispersion liquid of Production Example 1 39 parts by mass-Glycerin ... 10 parts by mass-Diethylene glycol ... 20 parts by mass-Fluorine-based surfactant represented by the following general formula (2) ... 2 Parts by mass

However, in said general formula (2), it is m = 6-8, n = 26 or more.
・ Silicone antifoaming agent (KM-72F, manufactured by Shin-Etsu Chemical Co., Ltd., emulsion type, volume average particle size = 17.4 μm) ... 0.1 part by mass ・ Ion-exchanged water: remaining amount (total: 100) Part by mass)

  First, a fluorosurfactant was added to glycerin and diethylene glycol. Next, ion-exchanged water was added, and after stirring for 30 minutes, a pigment dispersion and a silicone antifoaming agent were added and stirred for 1 hour. The obtained prepared ink was filtered through a glass fiber filter (Ultipore GF Plus, manufactured by Nippon Pole Co., Ltd.) having a pore diameter of 3 μm to prepare a recording ink 9.

ただし、前記一般式（２）中、ｍ＝１〜９、ｎ＝０〜２５である。
・ウレタン系ポリマー微粒子（Ｗ５６６１、三井化学ポリウレタン株式会社製、アニオン性自己乳化型ポリエーテル系、平均粒径＝１０ｎｍ）・・・０．５質量部
・シリコーン消泡剤（ＫＭ−７２Ｆ、信越化学工業株式会社製、エマルジョン型、体積平均粒径＝１７．４μｍ）・・・０．１質量部
・イオン交換水・・・残量（合計：１００質量部） (Comparative Example 3)
-Preparation of recording ink 10-
-Pigment dispersion liquid of Production Example 1 39 parts by mass-Glycerin ... 10 parts by mass-Diethylene glycol ... 20 parts by mass-Fluorine-based surfactant represented by the following general formula (2) ... 2 Parts by mass

However, in the said General formula (2), it is m = 1-9 and n = 0-25.
・ Urethane-based fine polymer particles (W5661, manufactured by Mitsui Chemicals Polyurethane Co., Ltd., anionic self-emulsifying type polyether, average particle size = 10 nm) 0.5 parts by mass ・ Silicone antifoaming agent (KM-72F, Shin-Etsu Chemical) Manufactured by Kogyo Co., Ltd., emulsion type, volume average particle diameter = 17.4 μm)... 0.1 mass part ・ Ion-exchanged water remaining amount (total: 100 mass parts)

  First, a fluorosurfactant was added to glycerin and diethylene glycol. Next, urethane polymer fine particles were added, then ion-exchanged water was added, and after stirring for 30 minutes, a pigment dispersion and a silicone antifoaming agent were added and stirred for 1 hour. The obtained prepared ink was filtered through a polypropylene filter (Profile Star, manufactured by Nippon Pole Co., Ltd.) having a pore diameter of 1.5 μm to prepare a recording ink 10.

ただし、前記一般式（２）中、ｍ＝６〜８、ｎ＝２６以上である。
・ウレタン系ポリマー微粒子（Ｗ５６６１、三井化学ポリウレタン株式会社製、アニオン性自己乳化型ポリエーテル系、平均粒径＝１０ｎｍ）・・・０．５質量部
・シリコーン消泡剤（ＫＭ−９０、信越化学工業株式会社製、自己乳化型、体積平均粒径＝７．５μｍ）・・・０．００１質量部
・イオン交換水・・・残量（合計：１００質量部） (Comparative Example 4)
-Preparation of recording ink 11-
-Pigment dispersion liquid of Production Example 1 39 parts by mass-Glycerin ... 10 parts by mass-Diethylene glycol ... 20 parts by mass-Fluorine-based surfactant represented by the following general formula (2) ... 2 Parts by mass

However, in said general formula (2), it is m = 6-8, n = 26 or more.
・ Urethane-based polymer fine particles (W5661, manufactured by Mitsui Chemicals Polyurethane Co., Ltd., anionic self-emulsifying polyether-based, average particle size = 10 nm)... Manufactured by Kogyo Co., Ltd., self-emulsifying type, volume average particle diameter = 7.5 μm)... 0.001 part by mass

  First, a fluorosurfactant was added to glycerin and diethylene glycol. Next, urethane polymer fine particles were added, then ion-exchanged water was added, and after stirring for 30 minutes, a pigment dispersion and a silicone antifoaming agent were added and stirred for 1 hour. The obtained prepared ink was filtered through a glass fiber filter having a pore diameter of 3 μm (Ultipore GF Plus, manufactured by Nippon Pole Co., Ltd.) to prepare a recording ink 11.

ただし、前記一般式（２）中、ｍ＝１〜９、ｎ＝０〜２５である。
・ウレタン系ポリマー微粒子（Ｗ５６６１、三井化学ポリウレタン株式会社製、アニオン性自己乳化型ポリエーテル系、平均粒径＝１０ｎｍ）・・・０．５質量部
・シリコーン消泡剤（ＫＭ−９０、信越化学工業株式会社製、自己乳化型、体積平均粒径＝７．５μｍ）・・・４質量部
・イオン交換水・・・残量（合計：１００質量部） (Comparative Example 5)
-Preparation of recording ink 12-
-Pigment dispersion liquid of Production Example 1 39 parts by mass-Glycerin ... 10 parts by mass-Diethylene glycol ... 20 parts by mass-Fluorine-based surfactant represented by the following general formula (2) ... 2 Parts by mass

However, in the said General formula (2), it is m = 1-9 and n = 0-25.
・ Urethane-based polymer fine particles (W5661, manufactured by Mitsui Chemicals Polyurethane Co., Ltd., anionic self-emulsifying polyether-based, average particle size = 10 nm)... Kogyo Co., Ltd., self-emulsifying type, volume average particle size = 7.5 μm) ... 4 parts by mass ・ Ion-exchanged water: remaining amount (total: 100 parts by mass)

  First, a fluorosurfactant was added to glycerin and diethylene glycol. Next, urethane polymer fine particles were added, then ion-exchanged water was added, and after stirring for 30 minutes, a pigment dispersion and a silicone antifoaming agent were added and stirred for 1 hour. The obtained prepared ink was filtered through a glass fiber filter (Ultipore GF Plus, manufactured by Nippon Pole Co., Ltd.) having a pore diameter of 3 μm to prepare a recording ink 12.

ただし、前記一般式（２）中、ｍ＝６〜８、ｎ＝２６以上である。
・ウレタン系ポリマー微粒子（Ｗ５６６１、三井化学ポリウレタン株式会社製、アニオン性自己乳化型ポリエーテル系、平均粒径＝１０ｎｍ）・・・０．０５質量部
・シリコーン消泡剤（ＫＭ−９０、信越化学工業株式会社製、自己乳化型、体積平均粒径＝７．５μｍ）・・・０．１質量部
・イオン交換水・・・残量（合計：１００質量部） (Comparative Example 6)
-Preparation of recording ink 13-
-Pigment dispersion liquid of Production Example 1 39 parts by mass-Glycerin ... 10 parts by mass-Diethylene glycol ... 20 parts by mass-Fluorine-based surfactant represented by the following general formula (2) ... 2 Parts by mass

However, in said general formula (2), it is m = 6-8, n = 26 or more.
・ Urethane polymer fine particles (W5661, manufactured by Mitsui Chemicals Polyurethane Co., Ltd., anionic self-emulsifying polyether type, average particle size = 10 nm) ... 0.05 parts by mass ・ Silicone antifoaming agent (KM-90, Shin-Etsu Chemical) Manufactured by Kogyo Co., Ltd., self-emulsifying type, volume average particle size = 7.5 μm) ... 0.1 part by mass ・ Ion-exchanged water: remaining amount (total: 100 parts by mass)

  First, a fluorosurfactant was added to glycerin and diethylene glycol. Next, urethane polymer fine particles were added, then ion-exchanged water was added, and after stirring for 30 minutes, a pigment dispersion and a silicone antifoaming agent were added and stirred for 1 hour. The obtained blended ink was filtered through a glass fiber filter (Ultipore GF Plus, manufactured by Nippon Pole Co., Ltd.) having a pore diameter of 3 μm to prepare a recording ink 13.

ただし、前記一般式（２）中、ｍ＝１〜９、ｎ＝０〜２５である。
・ウレタン系ポリマー微粒子（Ｗ５６６１、三井化学ポリウレタン株式会社製、アニオン性自己乳化型ポリエーテル系、平均粒径＝１０ｎｍ）・・・２０質量部
・シリコーン消泡剤（ＫＭ−９０、信越化学工業株式会社製、自己乳化型、体積平均粒径＝７．５μｍ）・・・０．１質量部
・イオン交換水・・・残量（合計：１００質量部） (Comparative Example 7)
-Preparation of recording ink 14-
-Pigment dispersion liquid of Production Example 1 39 parts by mass-Glycerin ... 10 parts by mass-Diethylene glycol ... 20 parts by mass-Fluorine-based surfactant represented by the following general formula (2) ... 2 Parts by mass

However, in the said General formula (2), it is m = 1-9 and n = 0-25.
・ Urethane polymer fine particles (W5661, manufactured by Mitsui Chemicals Polyurethane Co., Ltd., anionic self-emulsifying polyether type, average particle size = 10 nm) 20 parts by mass ・ Silicone antifoaming agent (KM-90, Shin-Etsu Chemical Co., Ltd.) Made by company, self-emulsifying type, volume average particle size = 7.5 μm) ... 0.1 part by mass ・ Ion-exchanged water: remaining amount (total: 100 parts by mass)

  First, a fluorosurfactant was added to glycerin and diethylene glycol. Next, urethane polymer fine particles were added, then ion-exchanged water was added, and after stirring for 30 minutes, a pigment dispersion and a silicone antifoaming agent were added and stirred for 1 hour. The obtained blended ink was filtered through a glass fiber filter (Ultipore GF Plus, manufactured by Nippon Pole Co., Ltd.) having a pore diameter of 3 μm to prepare a recording ink 14.

ただし、前記一般式（２）中、ｍ＝６〜８、ｎ＝２６以上である。
・スチレン−アクリル系ポリマー微粒子（Ｊ−４５０、ジョンソンポリマー社製、平均粒径＝６０ｎｍ）・・・２質量部
・シリコーン消泡剤（ＫＭ−９０、信越化学工業株式会社製、自己乳化型、体積平均粒径＝７．５μｍ）・・・０．１質量部
・イオン交換水・・・残量（合計：１００質量部） (Comparative Example 8)
-Preparation of recording ink 15-
-Pigment dispersion liquid of Production Example 1 39 parts by mass-Glycerin ... 10 parts by mass-Diethylene glycol ... 20 parts by mass-Fluorine-based surfactant represented by the following general formula (2) ... 2 Parts by mass

However, in said general formula (2), it is m = 6-8, n = 26 or more.
Styrene-acrylic polymer fine particles (J-450, manufactured by Johnson Polymer Co., Ltd., average particle size = 60 nm) 2 parts by mass Silicone defoaming agent (KM-90, manufactured by Shin-Etsu Chemical Co., Ltd., self-emulsifying type, Volume average particle diameter = 7.5 μm) ... 0.1 part by mass ・ Ion-exchanged water ... Remaining amount (total: 100 parts by mass)

  First, a fluorosurfactant was added to glycerin and diethylene glycol. Next, styrene-acrylic polymer fine particles were added, then ion-exchanged water was added, and after stirring for 30 minutes, the pigment dispersion and the silicone antifoaming agent were added and stirred for 1 hour. The obtained blended ink was filtered through a glass fiber filter (Ultipore GF Plus, manufactured by Nippon Pole Co., Ltd.) having a pore diameter of 3 μm to prepare a recording ink 15.

ただし、前記一般式（２）中、ｍ＝１〜９、ｎ＝０〜２５である。
・シリコーン消泡剤（ＫＭ−９０、信越化学工業株式会社製、自己乳化型、体積平均粒径＝７．５μｍ）・・・０．１質量部
・イオン交換水・・・残量（合計：１００質量部） (Comparative Example 9)
-Preparation of recording ink 16-
-Pigment dispersion liquid of Production Example 1 39 parts by mass-Glycerin ... 10 parts by mass-Diethylene glycol ... 20 parts by mass-Fluorine-based surfactant represented by the following general formula (2) ... 2 Parts by mass

However, in the said General formula (2), it is m = 1-9 and n = 0-25.
・ Silicone antifoaming agent (KM-90, manufactured by Shin-Etsu Chemical Co., Ltd., self-emulsifying type, volume average particle size = 7.5 μm) ... 0.1 part by mass ・ Ion-exchanged water ... Remaining amount (total: 100 parts by mass)

  First, a fluorosurfactant was added to glycerin and diethylene glycol. Next, ion-exchanged water was added, and after stirring for 30 minutes, a pigment dispersion and a silicone antifoaming agent were added and stirred for 1 hour. The obtained prepared ink was filtered through a glass fiber filter (Ultipore GF Plus, manufactured by Nippon Pole Co., Ltd.) having a pore diameter of 3 μm to prepare a recording ink 16.

ただし、前記一般式（２）中、ｍ＝６〜８、ｎ＝２６以上である。
・ウレタン系ポリマー微粒子（Ｗ５６６１、三井化学ポリウレタン株式会社製、アニオン性自己乳化型ポリエーテル系、平均粒径＝１０ｎｍ）・・・０．５質量部
・シリコーン消泡剤（ＫＭ−９０、信越化学工業株式会社製、自己乳化型、体積平均粒径＝７．５μｍ）・・・０．１質量部
・イオン交換水・・・残量（合計：１００質量部） (Comparative Example 10)
-Preparation of recording ink 17-
-Pigment dispersion liquid of Production Example 1 39 parts by mass-Glycerin ... 10 parts by mass-Diethylene glycol ... 20 parts by mass-Fluorine-based surfactant represented by the following general formula (2) ... 2 Parts by mass

However, in said general formula (2), it is m = 6-8, n = 26 or more.
・ Urethane-based polymer fine particles (W5661, manufactured by Mitsui Chemicals Polyurethane Co., Ltd., anionic self-emulsifying polyether-based, average particle size = 10 nm)... Manufactured by Kogyo Co., Ltd., self-emulsifying type, volume average particle size = 7.5 μm) ... 0.1 part by mass ・ Ion-exchanged water: remaining amount (total: 100 parts by mass)

  First, a fluorosurfactant was added to glycerin and diethylene glycol. Next, urethane polymer fine particles were added, then ion-exchanged water was added, and after stirring for 30 minutes, a pigment dispersion and a silicone antifoaming agent were added and stirred for 1 hour. The obtained prepared ink was filtered through a polypropylene filter (Profile Star, manufactured by Nippon Pole Co., Ltd.) having a pore diameter of 1.5 μm to prepare a recording ink 17.

ただし、前記一般式（２）中、ｍ＝１〜９、ｎ＝０〜２５である。
・ウレタン系ポリマー微粒子（Ｗ５６６１、三井化学ポリウレタン株式会社製、アニオン性自己乳化型ポリエーテル系、平均粒径＝１０ｎｍ）・・・０．５質量部
・シリコーン消泡剤（ＫＭ−９０、信越化学工業株式会社製、自己乳化型、体積平均粒径＝７．５μｍ）・・・０．１質量部
・イオン交換水・・・残量（合計：１００質量部） (Comparative Example 11)
-Preparation of recording ink 18-
-Pigment dispersion liquid of Production Example 1 39 parts by mass-Glycerin ... 10 parts by mass-Diethylene glycol ... 20 parts by mass-Fluorine-based surfactant represented by the following general formula (2) ... 2 Parts by mass

However, in the said General formula (2), it is m = 1-9 and n = 0-25.
・ Urethane-based polymer fine particles (W5661, manufactured by Mitsui Chemicals Polyurethane Co., Ltd., anionic self-emulsifying polyether type, average particle size = 10 nm)... 0.5 mass parts ・ Silicone antifoaming agent (KM-90, Shin-Etsu Chemical) Manufactured by Kogyo Co., Ltd., self-emulsifying type, volume average particle size = 7.5 μm) ... 0.1 part by mass ・ Ion-exchanged water: remaining amount (total: 100 parts by mass)

  First, a fluorosurfactant was added to glycerin and diethylene glycol. Next, urethane polymer fine particles were added, then ion-exchanged water was added, and after stirring for 30 minutes, a pigment dispersion and a silicone antifoaming agent were added and stirred for 1 hour. The obtained prepared ink was filtered through a hydrophilic PTFE membrane filter (H050A047, manufactured by Advantech Toyo Co., Ltd.) having a pore diameter of 0.50 μm, and a recording ink 18 was produced.

ただし、前記一般式（２）中、ｍ＝６〜８、ｎ＝２６以上である。
・ウレタン系ポリマー微粒子（Ｗ５６６１、三井化学ポリウレタン株式会社製、アニオン性自己乳化型ポリエーテル系、平均粒径＝１０ｎｍ）・・・０．５質量部
・シリコーン消泡剤（ＫＭ−９０、信越化学工業株式会社製、自己乳化型、体積平均粒径＝７．５μｍ）・・・０．１質量部
・イオン交換水・・・残量（合計：１００質量部） (Comparative Example 12)
-Preparation of recording ink 19-
-Pigment dispersion liquid of Production Example 1 39 parts by mass-Glycerin ... 10 parts by mass-Diethylene glycol ... 20 parts by mass-Fluorine-based surfactant represented by the following general formula (2) ... 2 Parts by mass

However, in said general formula (2), it is m = 6-8, n = 26 or more.
・ Urethane-based polymer fine particles (W5661, manufactured by Mitsui Chemicals Polyurethane Co., Ltd., anionic self-emulsifying polyether type, average particle size = 10 nm)... 0.5 mass parts ・ Silicone antifoaming agent (KM-90, Shin-Etsu Chemical) Manufactured by Kogyo Co., Ltd., self-emulsifying type, volume average particle size = 7.5 μm) ... 0.1 part by mass ・ Ion-exchanged water: remaining amount (total: 100 parts by mass)

  First, a fluorosurfactant was added to glycerin and diethylene glycol. Next, urethane polymer fine particles were added, then ion-exchanged water was added, and after stirring for 30 minutes, a pigment dispersion and a silicone antifoaming agent were added and stirred for 1 hour. The obtained prepared ink was filtered with a hydrophilic PTFE membrane filter (JMWP04700, manufactured by Nihon Millipore Corporation) having a pore diameter of 5.0 μm to prepare a recording ink 19.

ただし、前記一般式（２）中、ｍ＝１〜９、ｎ＝０〜２５である。
・ウレタン系ポリマー微粒子（Ｗ５６６１、三井化学ポリウレタン株式会社製、アニオン性自己乳化型ポリエーテル系、平均粒径＝１０ｎｍ）・・・０．５質量部
・シリコーン消泡剤（ＫＭ−９０、信越化学工業株式会社製、自己乳化型、体積平均粒径＝７．５μｍ）・・・０．１質量部
・イオン交換水・・・残量（合計：１００質量部） (Comparative Example 13)
-Preparation of recording ink 20-
-Pigment dispersion liquid of Production Example 1 39 parts by mass-Glycerin ... 10 parts by mass-Diethylene glycol ... 20 parts by mass-Fluorine-based surfactant represented by the following general formula (2) ... 2 Parts by mass

However, in the said General formula (2), it is m = 1-9 and n = 0-25.
・ Urethane-based polymer fine particles (W5661, manufactured by Mitsui Chemicals Polyurethane Co., Ltd., anionic self-emulsifying polyether type, average particle size = 10 nm)... 0.5 mass parts ・ Silicone antifoaming agent (KM-90, Shin-Etsu Chemical) Manufactured by Kogyo Co., Ltd., self-emulsifying type, volume average particle size = 7.5 μm) ... 0.1 part by mass ・ Ion-exchanged water: remaining amount (total: 100 parts by mass)

  First, a fluorosurfactant was added to glycerin and diethylene glycol. Next, urethane polymer fine particles are added, then ion exchange water is added, and after stirring for 30 minutes, a pigment dispersion and a silicone antifoaming agent are added and stirred for 1 hour to produce a recording ink 20. did.

(Comparative Example 14)
-Preparation of recording ink 21-
-Pigment dispersion liquid of Production Example 1-39 parts by mass-Glycerin-10 parts by mass-Diethylene glycol-20 parts by mass-Urethane polymer fine particles (W5661, manufactured by Mitsui Chemicals Polyurethanes, Inc., anionic self-emulsifying type Polyether-based, average particle size = 10 nm) ... 0.5 parts by mass Silicone defoaming agent (KM-90, manufactured by Shin-Etsu Chemical Co., Ltd., self-emulsifying type, volume average particle size = 7.5 μm)・ 0.1 parts by mass ・ Ion-exchanged water: remaining amount (total: 100 parts by mass)

  First, urethane-based polymer fine particles were added to glycerin and diethylene glycol, and then ion-exchanged water was added. After stirring for 30 minutes, the pigment dispersion and the silicone antifoaming agent were added and stirred for 1 hour. The obtained ink was filtered through a glass fiber filter having a pore diameter of 3 μm (Ultipore GF Plus, manufactured by Nippon Pole Co., Ltd.) to prepare a recording ink 21.

ただし、前記一般式（２）中、ｍ＝６〜８、ｎ＝２６以上である。
・ウレタン系ポリマー微粒子（Ｗ５６６１、三井化学ポリウレタン株式会社製、アニオン性自己乳化型ポリエーテル系、平均粒径＝１０ｎｍ）・・・０．５質量部
・シリコーン消泡剤（ＫＭ−９０、信越化学工業株式会社製、自己乳化型、体積平均粒径＝７．５μｍ）・・・０．１質量部
・イオン交換水・・・残量（合計：１００質量部） (Comparative Example 15)
-Preparation of recording ink 22-
-Pigment dispersion liquid of Production Example 2 ... 39 parts by mass-Glycerin ... 10 parts by mass-Diethylene glycol ... 20 parts by mass-Fluorine-based surfactant represented by the following general formula (2) ... 2 Parts by mass

However, in said general formula (2), it is m = 6-8, n = 26 or more.
・ Urethane-based polymer fine particles (W5661, manufactured by Mitsui Chemicals Polyurethane Co., Ltd., anionic self-emulsifying polyether-based, average particle size = 10 nm)... Manufactured by Kogyo Co., Ltd., self-emulsifying type, volume average particle size = 7.5 μm) ... 0.1 part by mass ・ Ion-exchanged water: remaining amount (total: 100 parts by mass)

  First, a fluorosurfactant was added to glycerin and diethylene glycol. Next, urethane polymer fine particles were added, then ion exchange water was added, and after stirring for 30 minutes, the pigment dispersion and the silicone antifoaming agent were added and stirred for 1 hour. The obtained ink was filtered through a glass fiber filter having a pore diameter of 3 μm (Ultipore GF Plus, manufactured by Nippon Pole Co., Ltd.) to prepare a recording ink 22.

ただし、前記一般式（２）中、ｍ＝６〜８、ｎ＝２６以上である。
・ウレタン系ポリマー微粒子（Ｗ５６６１、三井化学ポリウレタン株式会社製、アニオン性自己乳化型ポリエーテル系、平均粒径＝１０ｎｍ）・・・１２質量部
・シリコーン消泡剤（ＫＭ−９０、信越化学工業株式会社製、自己乳化型、体積平均粒径＝７．５μｍ）・・・０．１質量部
・イオン交換水・・・残量（合計：１００質量部） (Comparative Example 16)
-Preparation of recording ink 23-
-Pigment dispersion liquid of Production Example 2 ... 39 parts by mass-Glycerin ... 10 parts by mass-Diethylene glycol ... 20 parts by mass-Fluorine-based surfactant represented by the following general formula (2) ... 2 Parts by mass

However, in said general formula (2), it is m = 6-8, n = 26 or more.
・ Urethane polymer fine particles (W5661, manufactured by Mitsui Chemicals Polyurethane Co., Ltd., anionic self-emulsifying polyether type, average particle size = 10 nm) ... 12 parts by mass ・ Silicone antifoaming agent (KM-90, Shin-Etsu Chemical Co., Ltd.) Made by company, self-emulsifying type, volume average particle size = 7.5 μm) ... 0.1 part by mass ・ Ion-exchanged water: remaining amount (total: 100 parts by mass)

  First, a fluorosurfactant was added to glycerin and diethylene glycol. Next, urethane polymer fine particles were added, then ion exchange water was added, and after stirring for 30 minutes, the pigment dispersion and the silicone antifoaming agent were added and stirred for 1 hour. The obtained ink was filtered through a glass fiber filter having a pore diameter of 3 μm (Ultipore GF Plus, manufactured by Nippon Pole Co., Ltd.) to prepare a recording ink 23.

  Next, various characteristics of each of the obtained recording inks of Examples 1 to 7 and Comparative Examples 1 to 16 were evaluated as follows. The results are shown in Table 1.

<Bubbling test>
In an environment of 25 ° C., 5 ml of each recording ink is put in 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 standing for 5 minutes is as follows. 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

<Storage test>
Each recording ink was put in a sealed container and stored in an environment of 50 ° C. for 30 days. The ink viscosity before and after storage was measured and evaluated according to the following criteria. The ink viscosity was measured at 25 ° C. using an R-type viscometer (manufactured by Toki Sangyo Co., Ltd.).
〔Evaluation criteria〕
A: Viscosity change rate before and after storage is less than 5% B: Viscosity change rate before and after storage is 5% or more and less than 10% C: Viscosity change rate before and after storage is 10% or more

<Discharge stability test>
Each recording ink is filled in an ink jet printer (Ricoh Co., Ltd., IPSiO G707) as shown in FIGS. 1 to 3, and after printing 20,000 sheets of the following print pattern chart, the presence or absence of ejection failure is determined as follows. Evaluated by criteria. The print pattern was printed in the “plain paper, fast mode” of the ink jet printer with a chart in which the print area in the image area is the entire area of the paper and the print area of each color is 5%.
〔Evaluation criteria〕
A: Less than 5 non-ejection nozzles and all non-ejection nozzles recovered by cleaning B: 5 to less than 20 non-ejection nozzles and all non-ejection nozzles recovered by cleaning C: Non-ejection 20 or more nozzles or 1 or more nozzles that do not recover from non-ejection after cleaning

Since the recording ink of the present invention has less foaming and is excellent in storage stability and ejection stability, it can be suitably used in an ink jet recording apparatus and 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 perspective explanatory view showing an example of the ink jet recording apparatus of the present invention. FIG. 2 is a schematic configuration diagram showing an example of the ink jet recording apparatus of the present invention. FIG. 3 is a schematic enlarged view showing an example of an ink jet head in the ink jet recording apparatus of the present invention. FIG. 4 is an element enlarged view showing an example of an ink jet head in the ink jet recording apparatus of the present invention. FIG. 5 is an enlarged cross-sectional view of the main part in the channel-to-channel direction of an example of the inkjet head in the inkjet recording apparatus of the present invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 10 Frame 12 Common liquid chamber 20 Flow path plate 21 Fluid resistance part 22 Pressurized liquid chamber 23 Communication port 24 Partition 30 Nozzle plate 31 Nozzle 40 Base 50 Multilayer piezoelectric element 51 Piezoelectric layer 52 Internal electrode layer 53 External electrode 54 Individual electrode 55 Common Electrode 56 Drive part (movable part)
57 Supporting part 60 Diaphragm 61 Island-like convex part 62 Diaphragm part 63 Ink inlet 70 Adhesive layer 80 FPC
90 ink repellent layer 101 apparatus main body 102 paper feed tray 103 paper discharge tray 104 ink cartridge loading unit 105 operation unit 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 143 Feed roller 144 Separator pad 145 Guide 151 Transport belt 152 Counter roller 153 Transport guide 154 Pressing member 155 End pressure roller 156 Charging roller 157 Transport roller 158 Tension roller 161 Guide member 171 Separating claw 172 Discharge roller 173 Discharge roller 181 Double-sided paper feed unit 182 Manual paper feed unit

Claims (12)

A recording ink containing at least a pigment, water, a fluorine-based surfactant, a compound represented by the following general formula (1), polymer fine particles, and an antifoaming agent,
The polymer fine particles are urethane polymer fine particles, and the content of the urethane polymer fine particles in the recording ink is 0.1% by mass to 10% by mass,
The antifoaming agent is a silicone antifoaming agent having a volume average particle size of 10 μm or less, and the content of the silicone antifoaming agent in the recording ink is 0.005% by mass to 3% by mass,
A recording ink, wherein the recording ink is prepared by filtering with a filter containing glass fiber.

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 recording ink according to claim 1, wherein the urethane polymer fine particles are anionic self-emulsifying ether type.   The recording ink according to claim 1, wherein the silicone antifoaming agent is any one of a compound type silicone antifoaming agent, an emulsion type silicone antifoaming agent, and a self-emulsifying type silicone antifoaming agent. The recording ink according to any one of claims 1 to 3, wherein the fluorine-based surfactant contains 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 recording ink according to any one of claims 1 to 4, wherein the content of the fluorosurfactant in the recording ink is 0.1 mass% to 10 mass%.   6. The recording ink according to claim 1, wherein the filter containing glass fibers has a pore size of 0.5 to 6 [mu] m. At least a pigment, water, a fluorosurfactant, a compound represented by the following general formula (1), urethane polymer fine particles, and a silicone antifoaming agent having a volume average particle size of 10 μm or less are mixed. A method for producing a recording ink, wherein the ink is prepared by filtering with a filter containing glass fiber.

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 method for producing a recording ink according to claim 7, wherein the filter containing glass fibers has a pore size of 0.5 μm to 6 μm.   An ink jet recording method comprising at least an ink flying step of recording an image by applying a stimulus to the recording ink according to claim 1 and causing the recording ink to fly.   The inkjet recording method according to claim 9, wherein the stimulus is at least one selected from heat, pressure, vibration, and light.   7. An ink jet recording apparatus comprising at least ink flying means for recording an image by applying a stimulus to the recording ink according to claim 1 and causing the recording ink to fly.   The inkjet recording apparatus according to claim 11, wherein the stimulus is at least one selected from heat, pressure, vibration, and light.

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