JP2009028990A - Filling liquid, cartridge for filling liquid, image recording method, and image recorder - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a filling liquid that is free from discharge failure in use even in a severe transport and storage environment by reducing a quantity of evaporation of a filling liquid that is in an equilibrium state, as much as possible, and to provide a cartridge for filling liquid, image recording method, and an image recorder. <P>SOLUTION: The filling liquid contains at least a humectant and fills the ink passage of the image recorder. The quantity of evaporation of the filling liquid that is in an equilibrium state in an environment with a temperature of 20°C and 60% humidity RH is 30% or less. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a filling liquid suitably used for various image recordings by an ink jet recording method, a filling liquid cartridge using the filling liquid, an image recording method, and an image recording apparatus.

In an image recording apparatus of a type that performs image recording by ejecting ink, ink is filled in the image recording apparatus before shipping, a print inspection is performed, and then the ink in the ink flow path is removed before shipping. . At that time, since a very small amount of ink remains in the ink flow path, there is a problem in that an ink discharge failure is likely to occur when the ink is received. In addition, in order to improve the initial filling property of ink at the time of arrival, the ink flow path is often stored and transported in a state where the filling liquid is filled.
Among such image recording apparatuses, inkjet recording apparatuses are widely used from personal use to business use because of their small size and low cost. Along with this, the ink used is changing from dye ink to pigment ink having high water resistance and high light resistance. Under such circumstances, various proposals have been made for the filling liquid filled in the ink flow path in order to improve the ink ejection reliability upon arrival.

  For example, Patent Document 1 proposes a filling liquid having a high solvent ratio in consideration of evaporation suppression, but does not show a specific composition of the filling liquid. In addition, it is described that the filling liquid preferably has a moisture composition of 50% or less. However, when it is transported overseas, changes in physical properties such as a decrease in liquid volume due to evaporation of the filling liquid and an increase in the viscosity of the remaining liquid. Therefore, it is insufficient to ensure the ink ejection reliability at the time of arrival.

  Patent Document 2 describes that a filling liquid containing polyoxyalkylene monoalkyl ether is suitable. However, even if this filling liquid is used, the filling liquid may be dried in the ink flow path depending on the storage in a harsh environment such as when exporting overseas and the storage period in a harsh environment such as a warehouse. When used, the initial filling of ink cannot be performed well, and ink ejection failure may occur.

  In addition, when the amount of solid content such as pigment is large in the ink used, it is important to suppress evaporation of the filling liquid during transportation or storage. In particular, in inks containing pigments and resin emulsions, if the filling liquid dries in the ink flow path, solid components remaining in trace amounts may form a film, and it is important to ensure moisture retention. It becomes a problem.

  Therefore, even under harsh transportation and storage environments, filling liquids and related technologies that do not cause defective discharge during use have not yet been provided, and further improvements and developments are desired. is there.

JP 2002-283590 A JP 2004-66599 A

  An object of the present invention is to solve the above-described problems and achieve the following objects. That is, the present invention reduces the amount of evaporation of the filling liquid in an equilibrium state as much as possible, thereby reducing the filling liquid that does not cause a discharge failure at the time of use even under more severe transportation and storage environments, and the filling liquid. It is an object of the present invention to provide a filling liquid cartridge, an image recording method, and an image recording apparatus that are used.

  As a result of intensive studies to solve the above problems, in order to suppress the evaporation of the filling liquid, the water content contained in the filling liquid is close to the equilibrium water content that can be retained by the moisturizing agent contained in the filling liquid. It is important to adjust to the amount. Therefore, it is important to balance the type of humectant contained in the filling liquid, the amount of humectant, and the amount of water in an equilibrium state. In addition, it is necessary to select a humectant to contain a humectant having a lower vapor pressure. In addition, it ensures fluidity when the filling liquid evaporates, and prevents aggregation of the pigment in the ink. It was also found that it is important to consider the equilibrium moisture content of the humectant.

ただし、前記一般式（１）中、Ｒｆはフッ素含有基を表す。ｍ、ｎ、及びｐは、それぞれ整数を表す。

ただし、前記一般式（２）中、ａ＋ｂは０〜２０の整数、ｘは１〜１０の整数、ｙは１〜１０の整数をそれぞれ表す。
＜８＞ 前記＜１＞から＜７＞のいずれかに記載の充填液がインクタンクからヘッドまでのインク流路に充填されており、該インク流路の充填液を、少なくとも顔料を含有するインクで置換充填してから画像記録を行うことを特徴とする画像記録方法である。
＜９＞ インクが、更に樹脂エマルジョンを含有する前記＜８＞に記載の画像記録方法である。
＜１０＞ インクの粘度が、２５℃で５ｍＰａ・ｓ〜１５ｍＰａ・ｓである前記＜８＞から＜９＞のいずれかに記載の画像記録方法である。
＜１１＞ インクジェット記録方法である前記＜８＞から＜１０＞のいずれかに記載の画像記録方法である。
＜１２＞ 前記＜１＞から＜７＞のいずれかに記載の充填液がインクタンクからヘッドまでのインク流路に充填されており、該インク流路の充填液を少なくとも顔料を含有するインクで置換充填してから画像記録を行うことを特徴とする画像記録装置である。
＜１３＞ インクジェット記録装置である前記＜１２＞に記載の画像記録装置である。
＜１４＞ 前記＜１＞から＜７＞のいずれかに記載の充填液を容器中に収容してなることを特徴とする充填液用カートリッジである。 The present invention is based on the above findings by the present inventors, and means for solving the above problems are as follows. That is,
<1> A filling liquid containing at least a humectant and filling an ink flow path of an image recording apparatus,
The filling liquid is characterized in that the evaporation amount in an equilibrium state in an environment of a temperature of 20 ° C. and a humidity of 60% RH is 30% or less.
<2> The filling liquid according to <1>, wherein an evaporation amount in an equilibrium state of the filling liquid is 15% or less.
<3> The filling liquid according to any one of <1> to <2>, wherein an evaporation amount in an equilibrium state in the filling liquid is 10% or less.
<4> The filling liquid according to any one of <1> to <3>, wherein the humectant contains at least glycerin.
<5> The filling liquid according to <4>, wherein the content of glycerin is 20% by mass to 90% by mass with respect to the total amount of the humectant.
<6> The filling liquid according to any one of <1> to <5>, further containing water and a surfactant.
<7> The filling liquid according to <6>, wherein the surfactant contains a compound represented by any one of the following general formulas (1) and (2).

However, in the general formula (1), Rf represents a fluorine-containing group. m, n, and p each represent an integer.

However, in said general formula (2), a + b represents the integer of 0-20, x represents the integer of 1-10, y represents the integer of 1-10, respectively.
<8> The filling liquid according to any one of <1> to <7> is filled in an ink flow path from an ink tank to a head, and the filling liquid in the ink flow path is used as an ink containing at least a pigment. The image recording method is characterized in that the image recording is performed after the replacement filling.
<9> The image recording method according to <8>, wherein the ink further contains a resin emulsion.
<10> The image recording method according to any one of <8> to <9>, wherein the ink has a viscosity of 5 mPa · s to 15 mPa · s at 25 ° C.
<11> The image recording method according to any one of <8> to <10>, which is an inkjet recording method.
<12> The filling liquid according to any one of <1> to <7> is filled in an ink flow path from an ink tank to a head, and the filling liquid in the ink flow path is made of an ink containing at least a pigment. An image recording apparatus is characterized in that image recording is performed after replacement filling.
<13> The image recording apparatus according to <12>, which is an inkjet recording apparatus.
<14> A cartridge for filling liquid, wherein the filling liquid according to any one of <1> to <7> is accommodated in a container.

The filling liquid of the present invention contains at least a humectant and is filled in the ink flow path of the image recording apparatus,
The amount of evaporation of the filling liquid in an equilibrium state in an environment of a temperature of 20 ° C. and a humidity of 60% RH is 30% or less.
In the filling liquid of the present invention, it is possible to ensure the discharge reliability at the time of arrival even under harsh transportation and storage environments by using a configuration that suppresses the evaporation amount in an equilibrium state of the filling liquid. Sometimes it does not cause defective discharge.

In the image recording apparatus of the present invention, the filling liquid of the present invention is filled in an ink flow path from an ink tank to a head, and the filling liquid in the ink flow path is replaced and filled with an ink containing at least a pigment. Record an image.
In the image recording apparatus of the present invention, since the filling liquid of the present invention is used, refillability is improved, and high speed and high image quality can be recorded.
In the image recording method of the present invention, the filling liquid of the present invention is filled in an ink flow path from an ink tank to a head, and the filling liquid in the ink flow path is replaced and filled with an ink containing at least a pigment. To record the image.
In the image recording method of the present invention, since the filling liquid of the present invention is used, refillability is improved, and high speed and high image quality can be recorded.

  Since the filling liquid cartridge of the present invention contains the filling liquid of the present invention in a container, the discharge reliability at the time of arrival can be ensured even under severe transportation and storage environments.

  According to the present invention, the conventional problems can be solved, and the amount of evaporation in the equilibrium state of the filling liquid can be reduced as much as possible, resulting in poor discharge during use even in more severe transportation and storage environments. And a filling liquid cartridge, an image recording method, and an image recording apparatus using the filling liquid can be provided.

(Filling liquid)
The filling liquid of the present invention is filled in the ink flow path of the image recording apparatus, contains at least a humectant, and contains water, a surfactant, and, if necessary, other components.
The ink flow path means a flow path from the ink tank to the head.

The amount of evaporation in an equilibrium state of the filling liquid at a temperature of 20 ° C. and a humidity of 60% RH is 30% or less, preferably 15% or less, and more preferably 10% or less. If the evaporation amount exceeds 30%, a small amount of ink remains in the ink flow path, or the viscosity of the filling liquid changes greatly, so that the initial filling property of the ink upon arrival may be lowered. is there.
Here, the measurement of the amount of water in the equilibrium state of the filling liquid is performed by leaving the filling liquid in a low-humidity state and sufficiently leaving it in an environment of temperature 20 ° C. and humidity 60% RH. It is calculated from the mass change at the time. Specifically, in a constant temperature and humidity chamber maintained at a temperature of 20 ° C. and a humidity of 60% RH, a certain amount of filling liquid is placed in a petri dish and the change in mass is measured over time. It is possible to calculate and calculate the mass when reaching.

  As the humectant, glycerin is particularly preferable from the viewpoint of a high equilibrium water content. When the glycerin is used alone, the viscosity of the filling liquid increases, and there is a high possibility that the initial filling property of the ink at the time of arrival will be lowered. Therefore, it is preferable to combine it with another moisturizing liquid having a low viscosity. Therefore, the content of the glycerin with respect to the total amount of the humectant is preferably 20% by mass to 90% by mass, and more preferably 40% by mass to 80% by mass. When the content is less than 20% by mass, the amount of equilibrium water that can be held by the filling liquid decreases, so that fluidity may be lacking and it may be difficult to ensure ink ejection stability. On the other hand, when the content exceeds 90% by mass, the viscosity of the filling liquid becomes too high, and the initial filling property of the ink upon arrival may be lowered.

  The humectant other than glycerin is not particularly limited and may be appropriately selected depending on the intended purpose. For example, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 3-methyl- 1,3-butanediol, 1,3-butanediol, 2,3-butanediol, 1,4-butanediol, 1,5-pentanediol, tetraethylene glycol, 1,6-hexanediol, 2-methyl- Examples include 2,4-pentanediol, polyethylene glycol, 1,2,4-butanetriol, 1,2,6-hexanetriol. These may be used individually by 1 type and may use 2 or more types together. Among these, diethylene glycol and triethylene glycol are particularly preferable.

  60 mass% or more is preferable and, as for content in the said filling liquid of the said moisturizer, 60 mass%-70 mass% are more preferable. If the content is less than 60% by mass, the remaining amount of ink may be fixed in the ink flow path due to evaporation of the filling liquid in a harsh environment such as when exported overseas or stored in a warehouse. In addition, since the viscosity of the filling liquid largely changes, the initial filling property of the ink upon arrival may be lowered.

ただし、前記一般式（１）中、Ｒｆはフッ素含有基を表す。ｍ、ｎ、及びｐは、それぞれ整数を表す。
Ｒｆのフッ素含有基としては、例えば炭素数１〜４のフルオロアルキル基などが挙げられる。該パーフルオロアルキル基としては、例えば、−ＣＦ_３、−ＣＦ_２ＣＦ_３、−Ｃ_３Ｆ_７、−Ｃ_４Ｆ_９、などが挙げられる。
ｍ、ｎ、及びｐは、それぞれ整数を表し、ｎ及びＰは、泡の発生を抑えるために等しい数であることが好ましく、いずれも１〜４がより好ましい。ｎ及びＰが５以上であると、保存性及び環境安全性に問題が生じることがある。また、ｍは求められる界面活性能により選択され、６〜２５が好ましい。
前記一般式（１）で現される界面活性剤としては、適宜合成したものを使用してもよいし、市販品を使用してもよい。該市販品としては、例えば、ＰＦ−１５１Ｎ（ＯＭＮＯＶＡ社製）、などが挙げられる。 -Surfactant-
There is no restriction | limiting in particular as said surfactant, Although it can select suitably according to the objective, The compound represented by either the following general formula (1) and (2) is preferable.

However, in the general formula (1), Rf represents a fluorine-containing group. m, n, and p each represent an integer.
As a fluorine-containing group of Rf, a C1-C4 fluoroalkyl group etc. are mentioned, for example. Examples of the perfluoroalkyl group include —CF ₃ , —CF ₂ CF ₃ , —C ₃ F ₇ , —C ₄ F ₉ , and the like.
m, n, and p each represents an integer, and n and P are preferably equal numbers in order to suppress the generation of bubbles, and more preferably 1 to 4. When n and P are 5 or more, a problem may occur in storage stability and environmental safety. M is selected according to the required surface activity and is preferably 6 to 25.
As the surfactant represented by the general formula (1), those appropriately synthesized may be used, or commercially available products may be used. As this commercial item, PF-151N (made by OMNOVA) etc. are mentioned, for example.

前記一般式（２）において、ａ＋ｂは０〜２０の整数、ｘは１〜１０の整数、ｙは１〜１０の整数が好ましく、ａ＋ｂは２〜２０の整数、ｘは１〜１０の整数、ｙは１〜１０の整数がより好ましい。
前記一般式（２）で表される界面活性剤としては、適宜合成したものを使用してもよいし、市販品を使用してもよい。該市販品としては、例えば、ソフタノールＥＰ７０２５（日本触媒株式会社製）、などが挙げられる。

In the general formula (2), a + b is an integer of 0-20, x is an integer of 1-10, y is preferably an integer of 1-10, a + b is an integer of 2-20, x is an integer of 1-10, y is more preferably an integer of 1 to 10.
As the surfactant represented by the general formula (2), a suitably synthesized surfactant or a commercially available product may be used. Examples of the commercially available product include Softanol EP7025 (manufactured by Nippon Shokubai Co., Ltd.).

These surfactants have a high effect of improving the wettability to the ink flow path when the ink is filled. When the ink used in the image recording apparatus is a pigment ink or a high-viscosity ink, the ink filling property is lower than that of other low-viscosity inks. However, the wettability can be increased by adding these surfactants. And the ink filling property can be improved. Further, since these have less foaming, there is no ink foaming in the flow path, and the effect of better filling is high. Since the compound represented by the general formula (1) has significantly less foaming, its effect is high. Furthermore, since these compounds do not cause aggregation or the like in the ink used, the subsequent ejection stability is also good.
0.05 mass%-3.0 mass% are preferable, and, as for content in the said filling liquid of the said surfactant, 0.8 mass%-2.0 mass% are more preferable.

  To the filling liquid of the present invention, a pH adjusting agent, a pH buffering agent, an antiseptic / antifungal agent, and the like can be further added as necessary, as long as the object and effects of the present invention are not hindered.

  Whether the ink used is a pigment ink or an ink containing a resin emulsion, the filling liquid of the present invention has no aggregation of pigment and resin when mixed at the initial filling, High reliability is ensured. In addition, the filling liquid of the present invention is effective in the case of a pigment ink that easily aggregates or thickens due to the residual filling liquid, and is particularly effective in a high-viscosity ink that emphasizes high-speed and high-quality. Therefore, even if it is stored for a long time in harsh temperature and humidity environment such as when exporting to overseas, it exhibits excellent effects without causing defective discharge at the time of arrival, and the ink described below is Particularly preferred.

<Ink>
The ink used in the present invention contains at least a colorant, water, and a resin emulsion, and further contains a wetting agent, a surfactant, a penetrating agent, and other components as necessary.

-Colorant-
The colorant is not particularly limited and may be appropriately selected depending on the purpose. A pigment is mainly used, but a dye may be contained within a range that does not deteriorate the weather resistance for the purpose of color tone adjustment. Absent.

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.

  Examples of the color are C.I. I. Pigment Yellow 1, 3, 12, 13, 14, 17, 24, 34, 35, 37, 42 (yellow iron oxide), 53, 55, 74, 81, 83, 95, 97, 98, 100, 101, 104 , 408, 109, 110, 117, 120, 128, 138, 150, 151, 153, 183, C.I. I. Pigment orange 5, 13, 16, 17, 36, 43, 51, C.I. I. Pigment Red 1, 2, 3, 5, 17, 22, 23, 31, 38, 48: 2, 48: 2 (Permanent Red 2B (Ca)), 48: 3, 48: 4, 49: 1, 52: 2, 53: 1, 57: 1 (Brilliant Carmine 6B), 60: 1, 63: 1, 63: 2, 64: 1, 81, 83, 88, 101 (Bengara), 104, 105, 106, 108 ( Cadmium red), 112, 114, 122 (quinacridone magenta), 123, 146, 149, 166, 168, 170, 172, 177, 178, 179, 185, 190, 193, 209, 219, C.I. I. Pigment violet 1 (rhodamine lake), 3, 5: 1, 16, 19, 23, 38, C.I. I. Pigment Blue 1, 2, 15 (phthalocyanine blue), 15: 1, 15: 2, 15: 3 (phthalocyanine blue), 16, 17: 1, 56, 60, 63, C.I. I. Pigment green 1, 4, 7, 8, 10, 17, 18, 36, and the like.

Among the pigments, a preferable form is that whose surface has been modified so that at least one hydrophilic group is bonded to the surface of the pigment directly or through another atomic group. Therefore, a specific functional group (a functional group such as a sulfone group or a carboxyl group) is chemically bonded to the surface of the pigment, or a wet oxidation process using at least one of hypohalous acid and a salt thereof. Or the like is used. Among these, a carboxyl group is bonded to the surface of the pigment and is dispersed in water. Since this pigment is surface-modified and has a carboxyl group bonded thereto, not only the dispersion stability is improved, but also high-quality printing quality is obtained and the water resistance of the recording medium after recording is further improved.
This form of ink is excellent in redispersibility after drying, so that recording is stopped for a long time, and even when the water content of the ink near the nozzles of the ink jet head evaporates, clogging does not occur and it is easy to perform with a simple cleaning operation. Can record. In addition, the pigment of this form has a particularly large synergistic effect when combined with a surfactant and a penetrating agent, which will be described later, and it is possible to obtain a more reliable and high-quality image.

  In addition to the above-described pigment, it is also preferable to use a polymer emulsion in which a pigment is contained in polymer fine particles. Examples of the polymer emulsion containing a pigment include those in which a pigment is encapsulated in polymer fine particles and those in which a pigment is adsorbed on the surface of the polymer fine particles. In this case, it is not necessary for all the pigments to be enclosed or adsorbed, and the pigments may be dispersed in the emulsion as long as the effects of the present invention are not impaired. Examples of the polymer that forms the polymer emulsion include vinyl polymers, polyester polymers, polyurethane polymers, and the like. Among these, vinyl polymers and polyester polymers are particularly preferable.

In the present invention, a pigment obtained by dispersing in an aqueous medium with a dispersant can be used in combination. There is no restriction | limiting in particular as said dispersing agent. A known dispersing agent used for preparing a conventionally known pigment dispersion can be used. For example, polyacrylic acid, polymethacrylic acid, acrylic acid-acrylonitrile copolymer, vinyl acetate-acrylic ester copolymer , Acrylic acid-acrylic acid alkyl ester copolymer, styrene-acrylic acid copolymer, styrene-methacrylic acid copolymer, styrene-acrylic acid-acrylic acid alkyl ester copolymer, styne-methacrylic acid-acrylic acid alkyl ester Copolymer, styrene-α-methylstyrene-acrylic acid copolymer, styrene-α-methylstyrene-acrylic acid copolymer-acrylic acid alkyl ester copolymer, styrene-maleic acid copolymer, vinylnaphthalene-malein Acid copolymer, vinyl acetate-ethylene copolymer, vinyl acetate Examples thereof include fatty acid vinyl ethylene copolymer, vinyl acetate-maleic acid ester copolymer, vinyl acetate-crotonic acid copolymer, vinyl acetate-acrylic acid copolymer m, and the like.
The weight average molecular weight of the copolymer as the dispersant is preferably 3,000 to 50,000, more preferably 5,000 to 30,000, and still more preferably 7,000 to 15,000.
The addition amount of the dispersant can be appropriately selected within a range in which the pigment is stably dispersed and the other effects of the present invention are not lost, but the mixing mass ratio (pigment: dispersant) is 1: 0. 0.06 to 1: 3 is preferable, and 1: 0.125 to 1: 3 is more preferable.

It is preferable that a carboxyl group is bonded to the dispersant. When a carboxyl group is bonded to the dispersant, not only the dispersion stability is improved, but also high-quality recording quality is obtained, and the water resistance of the recording medium after recording is further improved. Furthermore, the effect of preventing the ink from coming through can be obtained. In particular, when a pigment dispersed with a dispersant having a carboxyl group bonded thereto and a penetrant are used in combination, a sufficient drying speed can be obtained even when printing on a relatively high-size recording medium such as plain paper. Is obtained, and the effect that there is little show-through is obtained.
This is because the dissociation constant of carboxylic acid is small compared to other acid groups, so that after the pigment adheres to the recording medium, the pH of the ink decreases, and polyvalent metal ions such as calcium existing near the surface of the recording medium It is presumed that the solubility of the dispersant itself decreases due to the interaction of the above, and the dispersant itself and the pigment aggregate.

As the water-soluble surfactant as the dispersant, anionic surfactants include, for example, higher fatty acid salts, alkyl sulfates, alkyl ether sulfates, alkyl ester sulfates, alkyl aryl ether sulfates, alkyl sulfonates, Examples include sulfosuccinate, alkylallyl and alkylnaphthalene sulfonate, alkyl phosphate, polyoxyethylene alkyl ether phosphate ester, and alkyl allyl ether phosphate.
Examples of the cationic surfactant include alkylamine salts, dialkylamine salts, tetraalkylammonium salts, benzalkonium salts, alkylpyridinium salts, imidazolinium salts, and the like.
Examples of amphoteric surfactants include dimethylalkyl lauryl betaine, alkyl glycine, alkyl di (aminoethyl) glycine, imidazolinium betaine and the like.
Nonionic surfactants include, for example, polyoxyethylene alkyl ether, polyoxyethylene alkyl allyl ether, polyoxyethylene polyoxypropylene glycol, glycerin ester, sorbitan ester, sucrose ester, glycerin ester polyoxyethylene ether, sorbitan ester Polyoxyethylene ether, polyoxyethylene ether of sorbitol ester, fatty acid alkanolamide, polyoxyethylene fatty acid amide, amine oxide, polyoxyethylene alkylamine and the like.

  The amount of the colorant added to the ink is preferably 3% by mass to 15% by mass, and more preferably 4% by mass to 12% by mass.

-Resin emulsion-
A resin emulsion is added to the ink in order to improve image fixability. Here, the resin emulsion is obtained by dispersing resin fine particles in water as a continuous phase, and may contain a dispersant such as a surfactant as necessary. The content of resin fine particles as the dispersed phase component (content of resin fine particles in the resin emulsion) is generally preferably about 10% by mass to 70% by mass.
The particle diameter of the resin fine particles is preferably 10 nm to 1,000 nm, more preferably 20 nm to 300 nm in terms of volume average particle diameter, considering use in an image recording apparatus such as an ink jet recording apparatus.
The resin fine particle component of the dispersed phase is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include acrylic resins, vinyl acetate resins, styrene resins, butadiene resins, and styrene-butadiene resins. Examples thereof include resins, vinyl chloride resins, acrylic-styrene resins, acrylic-silicone resins, and among these, acrylic-silicone resins are particularly preferable from the viewpoint of good fixability.

As said resin emulsion, what was synthesize | combined suitably may be used and a commercial item may be used.
As this commercial item, for example, Microgel E-100, E-2002, E-5002 (styrene-acrylic resin emulsion, manufactured by Nippon Paint Co., Ltd.), Boncoat 5454 (styrene-acrylic resin emulsion, Dainippon) Ink Chemical Industry Co., Ltd.), Jonkrill 775 (styrene-acrylic resin emulsion, manufactured by Johnson Polymer Co., Ltd.), SAE1014 (styrene-acrylic resin emulsion, manufactured by Nippon Zeon Co., Ltd.), Cybinol SK-200 (acrylic resin emulsion) Seiden Chemical Co., Ltd.), Primal AC-22, AC-61 (acrylic resin emulsion, manufactured by Rohm and Haas), Nanoacryl SBCX-2821, 3689 (acrylic-silicone resin emulsion, Toyo Inn) Ltd. Manufacturing Co.), # 3070 (methyl methacrylate polymer resin emulsion, manufactured by Mikuni Color Ltd.), PESRESIN A210 (polyester resin emulsion, Takamatsu Yushi Co., Ltd.), and the like.

  The content of the resin emulsion in the ink is preferably 0.1% by mass to 30% by mass, more preferably 1% by mass to 20% by mass, and still more preferably 5% by mass to 15% by mass in terms of solid content.

-Wetting agent-
The wetting agent is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include polyhydric alcohols, polyhydric alcohol alkyl ethers, polyhydric alcohol aryl ethers, nitrogen-containing heterocyclic compounds, amides. , Amines, sulfur-containing compounds, propylene carbonate, ethylene carbonate and the like. 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.
The content of the wetting agent in the ink is preferably 10% by mass to 40% by mass, and more preferably 25% by mass to 35% by mass. When the amount of the wetting agent is small, the storage stability and ejection stability of the ink are deteriorated, and the nozzles are easily clogged. On the other hand, if the amount of the wetting agent is too large, the drying property is deteriorated, bleeding of characters and bleeding of the color boundary occur, and the image quality is deteriorated.

  The ink used in the present invention preferably contains a surfactant and a penetrating agent. The surfactant has a purpose of lowering a static surface tension particularly in the vicinity of 1,000 msec and promoting penetration into the paper when the ink lands on the paper as a recording medium. The penetrant has the purpose of lowering the more dynamic surface tension, particularly in the vicinity of 10 to 100 msec, and promoting the spread on the paper surface at the moment when the ink lands on the paper. By using these surfactants and penetrants together, it is possible to obtain an ink with more appropriate pixel spread and high penetrability into the paper (and hence quick-drying), resulting in a higher quality image. Is obtained at high speed.

-Surfactant-
The surfactant may be the same as that used for the filling liquid or may contain a different one. As such a surfactant, any of an amphoteric surfactant, a nonionic surfactant, and an anionic surfactant can be used. However, in order to further improve the image quality, fluorine having a high penetrating property is used. It is preferable to use a surface active agent or a silicone based surfactant. These may be used alone or in combination of two or more.
The content of the surfactant in the ink is preferably 0.01% by mass to 5.0% by mass, and more preferably 0.5% by mass to 3% by mass. When the content is less than 0.01% by mass, there is no effect of addition. When the content exceeds 5.0% by mass, the permeability to the recording medium is unnecessarily high, and the image density is lowered or the screen is lost. May occur.

-Penetration agent-
The penetrant preferably contains at least one polyol having a solubility in water at 20 ° C. of 0.2% by mass or more and less than 5.0% by mass. Among such polyols, as the aliphatic diol, for example, 2-ethyl-2-methyl-1,3-propanediol, 3,3-dimethyl-1,2-butanediol, 2,2-diethyl-1, 3-propanediol, 2-methyl-2-propyl-1,3-propanediol, 2,4-dimethyl-2,4-pentanediol, 2,5-dimethyl-2,5-hexanediol, 5-hexene- Examples include 1,2-diol and 2-ethyl-1,3-hexanediol. Among these, 2-ethyl-1,3-hexanediol, 2,2,4-trimethyl-1,3-pentanediol is particularly preferable.
Examples of other penetrants that can be used in combination include diethylene glycol monophenyl ether, ethylene glycol monophenyl ether, ethylene glycol monoallyl ether, diethylene glycol monophenyl ether, diethylene glycol monobutyl ether, propylene glycol monobutyl ether, and tetraethylene glycol chlorophenyl ether. .

  The addition amount of the penetrant in the ink is preferably 0.1% by mass to 4.0% by mass. If the addition amount is less than 0.1% by mass, quick drying may not be obtained and a blurred image may be obtained. On the other hand, when the added amount exceeds 4.0% by mass, the dispersion stability of the colorant is impaired, the nozzles are easily clogged, and the permeability to the recording medium is unnecessarily high. There are cases where problems such as deterioration of the image and occurrence of strikethrough may occur.

In addition to the above components, the ink may contain a pH adjuster, antiseptic / antifungal agent, chelating agent, antifoaming agent, and the like as necessary.
As the pH adjuster, any substance (for example, amines such as diethanolamine and triethanolamine, hydroxylation, etc.) can be used as long as the pH can be adjusted to a desired value without adversely affecting the prepared ink. Alkali metal hydroxides such as lithium, sodium hydroxide and potassium hydroxide, ammonium hydroxide, quaternary ammonium hydroxide, quaternary phosphonium hydroxide, alkali such as lithium carbonate, sodium carbonate and potassium carbonate Metal carbonates, etc.) can be used. In addition, when an appropriate amount of 2-amino-2-ethyl-1,3-propanediol is used, the dispersion stability of the pigment is further improved and reliability such as ejection stability is ensured.
The amount of the pH adjuster added to the ink is not particularly limited, and varies depending on the formulation system to be added and the desired pH value, and cannot be specified unconditionally, but is preferably 0.01% by mass to 2% by mass. 1 mass% to 1 mass% is more preferable.

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.
As the antifoaming agent, a silicone-based antifoaming agent is preferably used. Generally, silicone type antifoaming agents include oil type, compound type, self-emulsifying type, emulsion type, etc., but considering the use in water system, use of self-emulsifying type or emulsion type ensures reliability. This is preferable. In addition, modified silicone-based antifoaming agents such as amino-modified, carbinol-modified, methacryl-modified, polyether-modified, alkyl-modified, higher fatty acid ester-modified, alkylene oxide-modified, etc. may be used.

The viscosity of the ink is preferably 5 mPa · s to 15 mPa · s at 25 ° C. If the viscosity is less than 5 mPa · s, bleeding tends to occur on plain paper, and image quality during high-speed printing may be deteriorated. If it exceeds 15 mPa · s, there may be a problem in ejection stability.
There is no restriction | limiting in particular as coloring of the said ink, 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.

(Filler cartridge)
The cartridge for filling liquid of the present invention contains the above-mentioned filling liquid 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 the mechanism, structure, size, material and the like can be appropriately selected according to the purpose. For example, a filling liquid bag formed of an aluminum laminate film, a resin film, or the like Suitable examples include those having at least.

  One aspect of the filling liquid cartridge of the present invention will be described with reference to the drawings. A cartridge 1 for filling liquid shown in FIG. 1 has a filling liquid bag 2 for containing the filling liquid of the present invention, and a housing 3 for containing the filling liquid bag 2. The filling liquid bag 2 has a substantially rectangular flexible bag-shaped portion made of an aluminum laminate film, and is accommodated in a state where the filling liquid of the present invention is filled therein. The housing 3 is formed of a first housing 11, a second housing 12, and a third housing 13. In the filling liquid cartridge 1, the first housing 11 and the second housing 12 are fastened and fixed by a screw member 82.

  The cartridge for filling liquid of the present invention can be used by housing the filling liquid of the present invention in a container and detachably attaching it to various image recording apparatuses, and is detachable to the recording apparatus of the present invention described below. It is particularly preferable to use it mounted on.

(Image recording apparatus and image recording method)
In the image recording apparatus of the present invention, the filling liquid of the present invention is filled in an ink flow path from an ink tank to a head, and the filling liquid in the ink flow path is replaced and filled with an ink containing at least a pigment. And an image recording process for recording an image, and further include other processes as necessary.
In the image recording apparatus of the present invention, the filling liquid of the present invention is filled in an ink flow path from an ink tank to a head, and the filling liquid in the ink flow path is replaced and filled with an ink containing at least a pigment. It has an image recording means for recording an image, and further has other means as required.
The ink described above can be used as the ink.

The image recording method and the image recording apparatus of the present invention can be applied to various types of recording by the ink jet recording method. For example, an ink jet recording apparatus (ink jet printer), a facsimile apparatus, a copying apparatus, a printer / fax / copier multifunction machine, etc. In particular, the ink jet recording apparatus is particularly preferable.
Hereinafter, an ink jet recording apparatus and an ink jet recording method will be described in detail as a suitable example of the image recording apparatus and the image recording method of the present invention.

<Inkjet recording apparatus and inkjet recording method>
The ink jet recording apparatus used in the present invention includes at least ink flying means, and further includes other means appropriately selected as necessary, for example, stimulus generation means, control means, and the like.
The ink jet recording method used in the present invention includes at least an ink flying process, and further includes other processes appropriately selected as necessary, for example, a stimulus generation process, a control process, and the like.
The ink jet recording method can be preferably carried out by the ink jet recording apparatus, 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 ink and causing the ink to fly.
The ink flying means is means for forming an image by applying a stimulus to ink and causing the 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 change 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, electrostatic actuators that use electrostatic force, etc. It is done.

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

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

One aspect of carrying out the ink jet recording method by the ink jet recording apparatus will be described with reference to the drawings. The ink jet recording apparatus shown in FIG. 2 has an apparatus main body 101, a paper feed tray 102 for loading paper loaded in the apparatus main body, and a sheet for recording (forming) an image that is loaded in the apparatus main body. A paper discharge tray 103 and an ink cartridge loading unit 104 are provided. In FIG. 2, reference numeral 111 denotes an upper cover, and 112 denotes a front surface.
On the upper surface of the ink cartridge loading unit 104, an operation unit 105 such as operation keys and a display is arranged. The ink cartridge loading unit 104 has a front cover 115 that can be opened and closed for attaching and detaching the ink cartridge 201.

In the apparatus main body 101, as shown in FIGS. 3 and 4, a carriage 133 is slid 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). It is held movably and moved and scanned in the direction of the arrow in FIG. 4 by a main scanning motor (not shown).
The carriage 133 is provided with a recording head 134 composed of four ink jet recording heads that eject ink droplets of each color of yellow (Y), cyan (C), magenta (M), and black (Bk). Are arranged in a direction crossing the main scanning direction, and the ink droplet ejection direction is directed downward.
As the ink jet recording head constituting the recording head 134, a piezoelectric actuator such as a piezoelectric element, a thermal actuator using phase change due to liquid film boiling using an electrothermal transducer such as a heating resistor, a metal phase due to temperature change, etc. A shape memory alloy actuator using a change, an electrostatic actuator using an electrostatic force, or the like provided as energy generating means for discharging ink can be used.

In addition, the carriage 133 is equipped with a sub tank 135 for each color for supplying ink of each color to the recording head 134. The sub tank 135 is supplied with ink from the ink cartridge 201 loaded in the ink cartridge loading unit 104 via an ink supply tube (not shown) and is replenished.
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 feeding tray 102, a half-moon roller (feeding) that separates and feeds the paper 142 from the paper stacking unit 141 one by one. A separation pad 144 made of a material having a large coefficient of friction is provided facing the paper roller 143) and the paper feed roller 143, and the separation pad 144 is urged toward the paper feed roller 143 side.
As a transport unit for transporting the paper 142 fed from the paper feed unit below the recording head 134, a transport belt 151 for transporting the paper 142 by electrostatic adsorption and a guide 145 from the paper feed unit. The counter roller 152 for transporting the paper 142 fed via the transport belt 151 with the transport belt 151 and the paper 142 fed substantially vertically upward are changed by approximately 90 ° so as to follow the transport belt 151. For this purpose, a conveyance guide 153 and a tip pressure roller 155 urged toward the conveyance belt 151 by a pressing member 154 are provided. In addition, a charging roller 156 that is a charging unit for charging the surface of the conveyance belt 151 is provided.
The conveyance belt 151 is an endless belt, is stretched between the conveyance roller 157 and the tension roller 158, and can circulate in the belt conveyance direction. The transport belt 151 includes, for example, a surface layer serving as a sheet adsorption surface formed of a resin material having a thickness of about 40 μm that is not subjected to resistance control, for example, a copolymer of tetrafluoroethylene and ethylene (ETFE), and the same surface layer. It has a back layer (medium resistance layer, earth layer) that has been subjected to resistance control with carbon as a material. On the back side of the conveyance belt 151, a guide member 161 is arranged corresponding to a printing area by the recording head 134. Note that, 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 conveyance belt 151, a paper discharge roller 172, and a paper discharge roller 173 are provided. The paper discharge tray 103 is disposed 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. A manual paper feed unit 182 is provided on the upper surface of the duplex paper feed unit 181.
In this ink jet recording apparatus, the paper 142 is separated and fed one by one from the paper feed unit, and the paper 142 fed substantially vertically upward is guided by the guide 145 and between the transport belt 151 and the counter roller 152. It is sandwiched and conveyed. Further, the leading end is guided by the conveying guide 153 and pressed against the conveying belt 151 by the leading end pressure 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 paper 142 to record one line, and after the paper 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 sheet 142 has reached the recording area, the recording operation is terminated and the sheet 142 is discharged onto the 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 from the ink cartridge 201 to the sub tank 135.

  In this ink jet recording apparatus, when the ink in the ink cartridge 201 is used up, the casing of the ink cartridge 201 can be disassembled and only the filling liquid bag inside can be replaced. Further, the ink cartridge 201 can supply ink stably even when the ink cartridge 201 is placed vertically and has a front loading configuration. Therefore, the ink cartridge 201 can be replaced even when the upper portion of the apparatus main body 101 is closed, for example, when stored in a rack, or when an object is placed on the upper surface of the apparatus main body 101. Can be easily performed.

  In addition, although it demonstrated in the example applied to the serial type (shuttle type) inkjet recording device which a carriage scans, it can apply similarly to the line type inkjet recording device provided with the line type head.

Hereinafter, an ink jet head to which the present invention is applied will be described.
FIG. 5 is an enlarged view of elements of an ink jet head according to an embodiment of the present invention, and FIG. 6 is an enlarged cross-sectional view of the main part in the channel-to-channel direction of the head.
This ink jet head includes a frame 10 formed with an engraving serving as an ink supply port (not shown) and a common liquid chamber 1b, and a communication port 2c communicating with the fluid resistance portion 2a and the engraving serving as the pressurized liquid chamber 2b and the nozzle 3a. The formed flow path plate 20, the nozzle plate forming the nozzle 3 a, the vibration plate 60 having the convex portion 6 a, the diaphragm portion 6 b, and the ink inlet 6 c, and the vibration plate 60 bonded to each other through the adhesive layer 70. A laminated piezoelectric element 50 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 includes a lead zirconate titanate (PZT) piezoelectric layer having a thickness of 10 μm / 1 layer to 50 μm / 1 layer, and an internal electrode layer made of silver / palladium (AgPd) having a thickness of several μm / 1 layer. Are stacked alternately. The internal electrode layer is connected to the external electrode at both ends.
The laminated piezoelectric element 50 is divided on comb teeth by half-cut dicing, and is used as a drive unit 5f and a support unit 5g (non-drive unit) one by one. The length of the outside of the external electrode is limited by cutting or the like so as to be divided by half-cut dicing, and these become a plurality of individual electrodes. The other is not divided by dicing but is conductive and becomes a common electrode.
FPC 8 is soldered to the individual electrodes of the drive unit. The common electrode is joined to the Gnd electrode of the FPC 8 by providing an electrode layer at the end of the laminated piezoelectric element and turning it around. A driver IC (not shown) is mounted on the FPC 8 to control application of a driving voltage to the driving unit 5f.

The diaphragm 60 is joined to a thin film diaphragm portion 6b, an island-shaped convex portion (island portion) 6a that joins the laminated piezoelectric element 50 that is the driving portion 5f formed at the center portion of the diaphragm portion 6b, and a support portion. A thick film portion including a beam and an opening serving as an ink inflow port 6c are formed by stacking two layers of Ni plating films by electroforming. The diaphragm portion has a thickness of 3 μm and a width of 35 μm (one side).
The island-shaped convex part 6a of the diaphragm 60 and the movable part 5f 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.

As the flow path plate 20, a silicon single crystal substrate was used, and the engraving to be the fluid resistance portion 2a and the pressurized liquid chamber 2b and the through-hole to be the communication port 2c at the position with respect to the nozzle 3a were patterned by an etching method.
The portion left by etching becomes the partition wall 2d of the pressurized liquid chamber 2b. Further, in this head, a portion for narrowing the etching width is provided, and this is used as the fluid resistance portion 2a.
The nozzle plate 30 is formed of a metal material, for example, an Ni plating film formed by an electroforming method, and has a number of nozzles 3a that are fine discharge ports for causing ink droplets to fly. The inner shape (inner shape) of the nozzle 3a is formed in a horn shape (may be a substantially cylindrical shape or a substantially frustum shape). The diameter of the nozzle 3a is 20 μm to 35 μm on the ink droplet outlet side. The nozzle pitch of each row was 150 dpi.
The ink ejection surface (nozzle surface side) of the nozzle plate 30 is provided with a water-repellent treatment layer 3b that has been subjected to a water-repellent surface treatment (not shown). Ink, such as PTFE-Ni eutectoid plating, electrodeposition coating of fluororesin, vapor-deposited fluororesin (for example, fluorinated pitch, etc.), baking after solvent application of silicone resin and fluororesin A water-repellent film selected according to the physical properties is provided to stabilize the ink droplet shape and flight characteristics so as to obtain high-quality image quality. Among these, for example, various materials are known as the fluorine-based resin, but a modified perfluoropolyoxetane (manufactured by Daikin Industries, Ltd., trade name: OPTOOL DSX) has a thickness of 30 to 100 mm (3 nm). Good water repellency can be obtained by vapor deposition so as to be 10 nm to 10 nm).

The frame 10 that forms the engraving that becomes the ink supply port and the common liquid chamber 1b is made by resin molding.
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 5f in accordance with the recording signal, whereby displacement in the stacking direction occurs in the drive unit 5f, and the diaphragm 60 The pressurized liquid chamber 2b is pressurized through the pressure to increase the pressure, and ink droplets are ejected from the nozzle 3a.
Thereafter, the ink pressure in the pressurizing liquid chamber 2b is reduced with the end of ink droplet ejection, and negative pressure is generated in the pressurizing liquid chamber 2b 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 1b, passes from the common liquid chamber 1b through the ink inlet 6c, passes through the fluid resistance portion 2a, and is filled into the pressurized liquid chamber 2b.
The fluid resistance portion 2a is effective in damping the 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.

  Since the image recording method and the image recording apparatus of the present invention use the filling liquid of the present invention, it is possible to ensure ejection reliability at the time of arrival even under severe transportation and storage environments, and defective ejection during use. The refillability is excellent and a high quality image can be recorded.

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

ただし、前記一般式（２）中、ａ＋ｂは９〜１１、ｘは７、ｙは２．５を表す。
・ジエチレングリコール・・・６０質量％
・純水・・・残量 Example 1
-Preparation of filling liquid-
After the filling liquid having the following composition was stirred, it was filtered through a filter having an average pore size of 0.1 μm to prepare the filling liquid of Example 1.
-Surfactant (Nippon Shokubai Co., Ltd., Softanol EP7025) ... 1% by mass

However, in the said General formula (2), a + b represents 9-11, x represents 7, y represents 2.5.
・ Diethylene glycol: 60% by mass
・ Pure water: remaining amount

ただし、前記一般式（２）中、ａ＋ｂは９〜１１、ｘは７、ｙは２．５を表す。
・グリセリン・・・４５質量％
・ジエチレングリコール・・・１５質量％
・純水・・・残量 (Example 2)
-Preparation of filling liquid-
After the filling liquid having the following composition was stirred, it was filtered through a filter having an average pore size of 0.1 μm to prepare the filling liquid of Example 2.
-Surfactant (Nippon Shokubai Co., Ltd., Softanol EP7025) ... 1% by mass

However, in the said General formula (2), a + b represents 9-11, x represents 7, y represents 2.5.
・ Glycerin: 45% by mass
・ Diethylene glycol: 15% by mass
・ Pure water: remaining amount

ただし、前記一般式（２）中、ａ＋ｂは９〜１１、ｘは７、ｙは２．５を表す。
・グリセリン・・・１５質量％
・トリエチレングリコール・・・５５質量％
・純水・・・残量 (Example 3)
-Preparation of filling liquid-
After the filling liquid having the following composition was stirred, it was filtered through a filter having an average pore size of 0.1 μm to prepare the filling liquid of Example 3.
-Surfactant (Nippon Shokubai Co., Ltd., Softanol EP7025) ... 1% by mass

However, in the said General formula (2), a + b represents 9-11, x represents 7, y represents 2.5.
・ Glycerin: 15% by mass
・ Triethylene glycol: 55% by mass
・ Pure water: remaining amount

ただし、前記一般式（２）中、ａ＋ｂは９〜１１、ｘは７、ｙは２．５を表す。
・グリセリン・・・６０質量％
・純水・・・残量 Example 4
-Preparation of filling liquid-
After the filling liquid having the following composition was stirred, it was filtered through a filter having an average pore size of 0.1 μm to prepare the filling liquid of Example 4.
-Surfactant (Nippon Shokubai Co., Ltd., Softanol EP7025) ... 1% by mass

However, in the said General formula (2), a + b represents 9-11, x represents 7, y represents 2.5.
・ Glycerin ... 60% by mass
・ Pure water: remaining amount

(Example 5)
-Preparation of filling liquid-
After the filling liquid having the following composition was stirred, it was filtered through a filter having an average pore size of 0.1 μm to prepare the filling liquid of Example 5.
-Acetylene diol-based surfactant (manufactured by Nissin Chemical Industry Co., Ltd., Olphine STG) ... 0.1% by mass
・ Glycerin: 25% by mass
・ Diethylene glycol: 35% by mass
・ Pure water: remaining amount

ただし、前記一般式（１）中、ＲｆはＣＦ_２ＣＦ_３を表す。ｍ＝２１、ｎ＝ｐ＝４を表す。
・グリセリン・・・２５質量％
・ジエチレングリコール・・・３５質量％
・純水・・・残量 (Example 6)
-Preparation of filling liquid-
After the filling liquid having the following composition was stirred, it was filtered through a filter having an average pore size of 0.1 μm to prepare the filling liquid of Example 6.
-Fluorosurfactant (manufactured by OMNOVA, PF-151N) 2% by mass

In the general formula (1), Rf represents _CF 2 CF _3. m = 21 and n = p = 4.
・ Glycerin: 25% by mass
・ Diethylene glycol: 35% by mass
・ Pure water: remaining amount

(Comparative Example 1)
Pure water was used as the filling liquid of Comparative Example 1.

(Comparative Example 2)
-Preparation of filling liquid-
After the filling liquid having the following composition was stirred, it was filtered through a filter having an average pore size of 0.1 μm to prepare a filling liquid of Comparative Example 2.
-Acetylene glycol surfactant (Nissin Chemical Industry Co., Ltd., Surfynol 104E): 0.5% by mass
・ Pure water: remaining amount

(Comparative Example 3)
-Preparation of filling liquid-
After the filling liquid having the following composition was stirred, it was filtered through a filter having an average pore size of 0.1 μm to prepare a filling liquid of Comparative Example 3.
・ Glycerin ... 30% by mass
・ Pure water: remaining amount

ただし、前記一般式（２）中、ａ＋ｂは９〜１１、ｘは９、ｙは５を表す。
・ジエチレングリコール・・・５０質量％
・純水・・・残量 (Comparative Example 4)
-Preparation of filling liquid-
After the filling liquid having the following composition was stirred, it was filtered through a filter having an average pore size of 0.1 μm to prepare a filling liquid of Comparative Example 4.
・ Surfactant (Nippon Shokubai Co., Ltd., Softanol EP9050) 0.5% by mass

However, in said general formula (2), a + b represents 9-11, x represents 9, and y represents 5.
・ Diethylene glycol: 50% by mass
・ Pure water: remaining amount

<Measurement of evaporation in equilibrium>
1 g of each of the filling liquids of Examples 1 to 6 and Comparative Examples 1 to 4 was placed in a petri dish with a diameter of 2 cm in a constant temperature and humidity chamber maintained at a temperature of 20 ° C. and a humidity of 60% RH, and the mass The change was measured with time, and the amount of evaporation at equilibrium was obtained. The results are shown in Table 1.

(Production Example 1)
-Preparation of black ink-
An ink composition having the following formulation was prepared and sufficiently stirred at room temperature, followed by filtration with a membrane filter having an average pore size of 1.5 μm to prepare the black ink of Production Example 1.
・ Carbon black (KM-9036, manufactured by Toyo Ink Manufacturing Co., Ltd., self-dispersing pigment): 50% by mass
・ Glycerin: 10% by mass
・ 1,3-butanediol: 15% by mass
・ 2-ethyl-1,3-hexanediol: 2% by mass
・ 2-Pyrrolidone: 2% by mass
・ Surfactant (Dispanol TOC, manufactured by NOF Corporation) ... 1% by mass
・ Silicone antifoaming agent (manufactured by Shin-Etsu Chemical Co., Ltd., KS508) ... 0.1% by mass
・ Ion exchange water

ただし、前記一般式（２）中、ａ＋ｂは９〜１１、ｘは７、ｙは２．５を表す。
・アクリル−シリコーン系樹脂エマルジョン（ナノクリルＳＢＣＸ−２８２１、東洋インキ製造株式会社製）・・・１５質量％
・シリコーン消泡剤（ＫＳ５０８、信越化学工業株式会社製）・・・０．１質量％
・イオン交換水・・・残量 (Production Example 2)
-Preparation of black ink-
An ink composition having the following formulation was prepared and sufficiently stirred at room temperature, followed by filtration with a membrane filter having an average pore size of 1.5 μm to prepare the black ink of Production Example 2.
Carbon black (KM-9036, manufactured by Toyo Ink Manufacturing Co., Ltd., self-dispersing pigment): 35% by mass
・ Glycerin: 10% by mass
・ 1,3-butanediol: 15% by mass
・ 2-ethyl-1,3-hexanediol: 2% by mass
・ 2-Pyrrolidone: 2% by mass
-Surfactant (Nippon Shokubai Co., Ltd., Softanol EP7025) ... 1% by mass

However, in the said General formula (2), a + b represents 9-11, x represents 7, y represents 2.5.
・ Acrylic-silicone resin emulsion (Nanoacryl SBCX-2821, manufactured by Toyo Ink Manufacturing Co., Ltd.) ... 15% by mass
・ Silicone antifoaming agent (KS508, manufactured by Shin-Etsu Chemical Co., Ltd.) ... 0.1% by mass
・ Ion exchange water

(Production Example 3)
<Preparation of magenta ink>
-Preparation of polymer solution A-
After sufficiently replacing the inside of a 1 L flask equipped with a mechanical stirrer, thermometer, nitrogen gas introduction tube, reflux tube, and dropping funnel, 11.2 g of styrene, 2.8 g of acrylic acid, 12.0 g of lauryl methacrylate Then, 4.0 g of polyethylene glycol methacrylate, 4.0 g of styrene macromer, and 0.4 g of mercaptoethanol were mixed and heated to 65 ° C. Next, 100.8 g of styrene, 25.2 g of acrylic acid, 108.0 g of lauryl methacrylate, 36.0 g of polyethylene glycol methacrylate, 60.0 g of hydroxylethyl methacrylate, 36.0 g of styrene macromer, 3.6 g of mercaptoethanol, azobismethylvalero A mixed solution of 2.4 g of nitrile and 18 g of methyl ethyl ketone was dropped into the flask over 2.5 hours. After dropping, a mixed solution of 0.8 g of azobismethylvaleronitrile and 18 g of methyl ethyl ketone was dropped into the flask over 0.5 hours. After aging at 65 ° C. for 1 hour, 0.8 g of azobismethylvaleronitrile was added and further aging was performed for 1 hour. After completion of the reaction, 364 g of methyl ethyl ketone was added to the flask to obtain 800 g of a polymer solution A having a concentration of 50% by mass.

-Preparation of pigment-containing polymer fine particle water dispersion-
28 g of polymer solution A, 26 g of C.I. I. Pigment Red 122, 13.6 g of a 1 mol / L potassium hydroxide aqueous solution, 20 g of methyl ethyl ketone, and 13.6 g of ion-exchanged water were sufficiently stirred, and then kneaded using a roll mill. The obtained paste was put into 200 g of ion-exchanged water and sufficiently stirred, and then methyl ethyl ketone and water were distilled off using an evaporator to obtain an aqueous dispersion of magenta polymer fine particles.

ただし、前記一般式（２）中、ａ＋ｂは９〜１１、ｘは７、ｙは２．５を表す。
・アクリル−シリコーン系樹脂エマルジョン（ナノクリルＳＢＣＸ−２８２１、東洋インキ製造株式会社製）・・・１０質量％
・シリコーン消泡剤（ＫＳ５０８、信越化学工業株式会社製）・・・０．１質量％
・イオン交換水・・・残量 -Preparation of magenta ink-
An ink composition having the following formulation was prepared and sufficiently stirred at room temperature, followed by filtration through a membrane filter having an average pore size of 1.5 μm to prepare the magenta ink of Production Example 3.
-Polymer fine particle dispersion: 50% by mass
・ Glycerin: 8% by mass
・ 1,3-butanediol: 20% by mass
・ 2,2,4-trimethyl-1,3-pentanediol: 2% by mass
-Surfactant (Nippon Shokubai Co., Ltd., Softanol EP7025) ... 1% by mass

However, in the said General formula (2), a + b represents 9-11, x represents 7, y represents 2.5.
Acrylic-silicone resin emulsion (Nanoacryl SBCX-2821, manufactured by Toyo Ink Manufacturing Co., Ltd.) ... 10% by mass
・ Silicone antifoaming agent (KS508, manufactured by Shin-Etsu Chemical Co., Ltd.) ... 0.1% by mass
・ Ion exchange water

(Production Example 4)
<Preparation of yellow ink>
-Preparation of pigment-containing polymer fine particle water dispersion-
28 g of polymer solution A, 26 g of C.I. I. Pigment Yellow 97, 13.6 g of 1 mol / L potassium hydroxide aqueous solution, 20 g of methyl ethyl ketone, and 13.6 g of ion-exchanged water were sufficiently stirred, and then kneaded using a roll mill. The obtained paste was put into 200 g of ion-exchanged water and sufficiently stirred, and then methyl ethyl ketone and water were distilled off using an evaporator to prepare an aqueous dispersion of yellow polymer fine particles.

ただし、前記一般式（２）中、ａ＋ｂは９〜１１、ｘは７、ｙは２．５を表す。
・アクリル−シリコーン系樹脂エマルジョン（ナノクリルＳＢＣＸ−２８２１、東洋インキ製造株式会社製）・・・１０質量％
・シリコーン消泡剤（ＫＳ５０８、信越化学工業株式会社製）・・・０．１質量％
・イオン交換水・・・残量 -Preparation of yellow ink-
An ink composition having the following formulation was prepared and sufficiently stirred at room temperature, and then filtered through a membrane filter having an average pore size of 1.5 μm to prepare the yellow ink of Production Example 4.
・ Yellow polymer fine particle dispersion: 40% by mass
・ Glycerin: 8% by mass
・ 1,3-butanediol: 20% by mass
・ 2,2,4-trimethyl-1,3-pentanediol: 2% by mass
-Surfactant (Nippon Shokubai Co., Ltd., Softanol EP7025) ... 1% by mass

However, in the said General formula (2), a + b represents 9-11, x represents 7, y represents 2.5.
Acrylic-silicone resin emulsion (Nanoacryl SBCX-2821, manufactured by Toyo Ink Manufacturing Co., Ltd.) ... 10% by mass
・ Silicone antifoaming agent (KS508, manufactured by Shin-Etsu Chemical Co., Ltd.) ... 0.1% by mass
・ Ion exchange water

(Production Example 5)
<Preparation of cyan ink>
-Preparation of pigment-containing polymer fine particle water dispersion-
In Production Example 4, the pigment type was C.I. I. An aqueous dispersion of cyan polymer fine particles was prepared in the same manner as in Production Example 4 except that the pigment blue was changed to 15: 3.

ただし、前記一般式（１）中、ＲｆはＣＦ_２ＣＦ_３、ｍ＝２１、ｎ＝ｐ＝４を表す。
・アクリル−シリコーン系樹脂エマルジョン（ナノクリルＳＢＣＸ−２８２１、東洋インキ製造株式会社製）・・・１０質量％
・シリコーン消泡剤（ＫＳ５０８、信越化学工業株式会社製）・・・０．１質量％
・イオン交換水・・・残量 -Preparation of cyan ink-
An ink composition having the following formulation was prepared and sufficiently stirred at room temperature, and then filtered through a membrane filter having an average pore size of 1.5 μm to prepare the cyan ink of Production Example 5.
・ Cyan polymer fine particle dispersion: 40% by mass
・ Glycerin: 8% by mass
・ 1,3-butanediol: 20% by mass
・ 2,2,4-trimethyl-1,3-pentanediol: 2% by mass
-Fluorosurfactant represented by the following general formula (1): 1% by mass

In the general formula (1), Rf represents _{CF 2 CF 3, m = 21} , n = p = 4.
Acrylic-silicone resin emulsion (Nanoacryl SBCX-2821, manufactured by Toyo Ink Manufacturing Co., Ltd.) ... 10% by mass
・ Silicone antifoaming agent (KS508, manufactured by Shin-Etsu Chemical Co., Ltd.) ... 0.1% by mass
・ Ion exchange water

<Measurement of ink viscosity>
The viscosity of each ink obtained was measured at 25 ° C. using a viscometer (RL-500, manufactured by Toki Sangyo Co., Ltd.). The results are shown in Table 2.

(Examples 7-20 and Comparative Examples 5-12)
Using the obtained filling liquids of Examples 1 to 6 and Comparative Examples 1 to 4 and inks of Production Examples 1 to 5 in combinations shown in Table 3, the following evaluations (1) to (2) were performed. went. The results are shown in Table 3.

<Evaluation (1): Evaluation on refillability>
An ink jet printer (IPSiO G515, manufactured by Ricoh Co., Ltd.) was filled with each ink to perform printing, and it was confirmed that ink was ejected from all nozzles.
Next, after the ink was sucked from the nozzle surface by an external pump, each filling liquid was filled in the ink flow path. The filling liquid was filled until the ink content in the filling liquid sucked from the nozzle surface was 5% or less. The ink-containing concentration in the filling liquid was calculated from the absorbance measurement at 500 nm of the sucked liquid. Thereafter, the ink was filled again, and the refillability was evaluated based on the following criteria based on the number of nozzles that printed and did not discharge.
〔Evaluation criteria〕
◎: All nozzles discharge well ○: Non-discharge nozzles for all nozzles are less than 0.5% △: Non-discharge nozzles for all nozzles are 0.5% or more and less than 5% Discharge nozzle is 5% or more

<Evaluation (2): Evaluation of ejection stability after storage>
An ink jet printer (IPSiO G515, manufactured by Ricoh Co., Ltd.) was filled with each ink to perform printing, and it was confirmed that ink was ejected from all nozzles.
Next, after the ink was sucked from the nozzle surface by an external pump, the filling liquid was filled in the ink flow path. The filling liquid was filled until the ink content in the filling liquid sucked from the nozzle surface was 5% or less. The ink concentration in the filling liquid was calculated from the absorbance measurement at 450 nm of the sucked liquid. In this state, the printer was stored in an environment of 50 ° C. and 15% RH for 10 days or 20 days. Thereafter, the ink was filled again, and the refillability was evaluated in the same manner as in the above evaluation (1) from the number of nozzles that performed printing and did not discharge.

Since the filling liquid of the present invention reduces the evaporation amount as much as possible, it does not cause a discharge failure during use even under more severe transportation environment and storage environment. Therefore, the filling liquid ink cartridge and the image recording apparatus And an image recording method.
The image recording apparatus and the image recording method of the present invention can be applied to various types of recording by the ink jet recording method, and are particularly suitable for, for example, an ink jet recording printer, a facsimile apparatus, a copying apparatus, and a printer / fax / copier multifunction machine. Can be applied to.

FIG. 1 is a schematic view showing an example of the filling liquid cartridge of the present invention. FIG. 2 is an explanatory perspective view of the ink jet recording apparatus with the cover of the ink cartridge loading unit opened. FIG. 3 is a schematic configuration diagram illustrating the overall configuration of the ink jet recording apparatus. FIG. 4 is a schematic enlarged view showing an example of the ink jet head of the present invention. FIG. 5 is an element schematic enlarged view showing another example of the ink jet head of the present invention. FIG. 6 is an enlarged schematic cross-sectional view of a main part of the ink jet head of FIG.

Explanation of symbols

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

Claims (14)

A filling liquid containing at least a humectant and filling the ink flow path of the image recording apparatus,
The filling liquid, wherein the amount of evaporation in an equilibrium state in an environment of a temperature of 20 ° C. and a humidity of 60% RH is 30% or less.   The filling liquid according to claim 1, wherein an evaporation amount in an equilibrium state in the filling liquid is 15% or less.   The filling liquid according to claim 1, wherein an evaporation amount in an equilibrium state in the filling liquid is 10% or less.   The filling liquid according to any one of claims 1 to 3, wherein the humectant contains at least glycerin.   The filling liquid according to claim 4, wherein the glycerin content is 20% by mass to 90% by mass with respect to the total amount of the humectant.   Furthermore, the filling liquid in any one of Claim 1 to 5 containing water and surfactant. The filling liquid according to claim 6, wherein the surfactant contains a compound represented by any one of the following general formulas (1) and (2).

However, in the general formula (1), Rf represents a fluorine-containing group. m, n, and p each represent an integer.

However, in said general formula (2), a + b represents the integer of 0-20, x represents the integer of 1-10, y represents the integer of 1-10, respectively.   The filling liquid according to any one of claims 1 to 7 is filled in an ink flow path from an ink tank to a head, and the filling liquid in the ink flow path is replaced and filled with an ink containing at least a pigment. An image recording method comprising performing image recording.   The image recording method according to claim 8, wherein the ink further contains a resin emulsion.   The image recording method according to any one of claims 8 to 9, wherein the viscosity of the ink is 5 mPa · s to 15 mPa · s at 25 ° C.   The image recording method according to claim 8, which is an ink jet recording method.   The filling liquid according to any one of claims 1 to 7 is filled in an ink flow path from an ink tank to a head, and the filling liquid in the ink flow path is replaced and filled with an ink containing at least a pigment, and then an image is obtained. An image recording apparatus for performing recording.   The image recording apparatus according to claim 12, which is an ink jet recording apparatus.   A cartridge for filling liquid, wherein the filling liquid according to claim 1 is contained in a container.

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