JP5556032B2 - Pretreatment liquid, cartridge, ink jet recording apparatus and recording method, and ink recorded matter - Google Patents

Description

  The present invention relates to a pretreatment liquid, a cartridge containing the pretreatment liquid or ink jet ink, an ink jet recording apparatus equipped with the cartridge, an ink jet recording method using the pretreatment liquid, and an ink recorded matter.

When performing ink jet recording, it is well known to apply a pretreatment liquid to the surface of a recording medium before ejecting ink.
For example, Patent Document 1 proposes using a pretreatment liquid containing a quaternary ammonium salt as a cationic compound.
In such a pretreatment liquid, it is also conceivable to use a cationic fluorosurfactant as the cationic compound. However, when the pretreatment liquid is ejected to the surface of the recording medium by the ink jet method, there is a problem that if the pretreatment liquid contains a fluorosurfactant, ejection stability is lowered due to foaming.
On the other hand, Patent Document 2 proposes to use a fluorinated quaternary ammonium salt having a perfluoroalkenyl group as a developer. However, there is no description regarding the pretreatment liquid for inkjet recording.

  The present invention relates to a pretreatment liquid that causes less foaming even when ejected by an ink jet method, a cartridge that contains the pretreatment liquid or the ink and ink for ink jet in a container, an ink jet recording apparatus equipped with the cartridge, and the pretreatment liquid. It is an object of the present invention to provide an ink jet recording method and an ink recorded matter used.

（式中、Ｒ^１はＨ、炭素数１〜４の分岐していてもよい低級アルキル基又はフェニル基、Ｒ^２〜Ｒ^４は炭素数１〜１０の分岐していてもよい低級アルキル基、ＸはＳＯ_２又はＣＯ、ＹはＩ又はＢｒ、ｍは正の整数、ｎは４以上の整数を表し、Ｃ_ｎＦ_２ｎ−１は分岐構造を有する。）
２） １）に記載の前処理液、又は該前処理液とインクジェット用インクを容器中に収容したことを特徴とするカートリッジ。
３） ２）に記載のカートリッジが搭載され、インクジェット用インクに刺激を印加し飛翔させて画像を形成するインク飛翔手段を備えたインクジェット記録装置であって、インクジェットヘッドのノズルプレート面がシリコン樹脂を含有する撥インク層を有することを特徴とするインクジェット記録装置。
４） １）に記載の前処理液を用いる記録媒体表面の前処理工程、及びインクジェット用インクに刺激を印加し飛翔させて記録媒体に画像を形成するインク飛翔工程を含むことを特徴とするインクジェット記録方法。
５） 記録媒体上に、１）に記載の前処理液とインクジェット用インクを用いて形成された画像を有することを特徴とするインク記録物。 The above problems are solved by the following inventions 1) to 5).
1) A pretreatment liquid for treating the surface of a recording medium before performing inkjet recording on the recording medium, characterized by containing a fluorine-containing quaternary ammonium salt compound represented by the general formula (I) Pretreatment liquid.

(In the formula, R ¹ is H, a lower alkyl group having 1 to ⁴ carbon atoms which may be branched or a phenyl group, R ^{2 to} R ⁴ are lower alkyl groups having 1 to 10 carbon atoms which may be branched, X represents SO ₂ or CO, Y represents I or Br, m represents a positive integer, n represents an integer of 4 or more, and C _n F _2n-1 has a branched structure.)
2) A cartridge characterized in that the pretreatment liquid according to 1) or the pretreatment liquid and ink jet ink are contained in a container.
3) An ink jet recording apparatus equipped with the cartridge described in 2) and provided with ink flying means for forming an image by applying a stimulus to the ink for ink jet, and the nozzle plate surface of the ink jet head is made of silicon resin. An ink jet recording apparatus comprising an ink repellent layer.
4) Inkjet comprising a pretreatment step of the surface of the recording medium using the pretreatment liquid described in 1) and an ink flying step of forming an image on the recording medium by applying a stimulus to the inkjet ink and flying the ink. Recording method.
5) An ink recorded matter having an image formed on the recording medium using the pretreatment liquid described in 1) and the ink jet ink.

  According to the present invention, a pretreatment liquid that causes less foaming even when ejected by an ink jet method, a cartridge that contains the pretreatment liquid or ink and ink for ink jet in a container, an ink jet recording apparatus equipped with the cartridge, and the pretreatment An ink jet recording method using a liquid and an ink recorded matter can be provided.

1 is a diagram illustrating an example of an ink jet recording apparatus.

Hereinafter, the present invention will be described in detail.
In general, surfactants have foaming properties, and the same applies to fluorine-based surfactants. Therefore, foaming cannot be prevented when a pretreatment liquid containing a conventionally known fluorosurfactant is ejected by an ink jet method. In addition, since the surface tension is reduced by the action of fluorine, the wettability of the nozzle surface also increases, ink adheres to the periphery of the nozzle, non-uniform ink pool occurs, and the ink droplet ejection direction is bent. In some cases, a large variation may occur and the ejection stability may decrease.
Therefore, as a result of intensive studies on a pretreatment liquid that does not cause problems such as foaming even when ejected by an inkjet method, the present inventors have found that the foaming property of a fluorosurfactant is a hydrophobic group (fluorine group) and a hydrophilic group ( If the specific fluorine-containing quaternary ammonium salt compound represented by the above general formula (I) is contained in the pretreatment liquid, I found that the problem could be solved.

この「炭素鎖が分岐した側鎖状のＣ_ｎＦ_２ｎ−１基」の立体構造は塊状になる。このように塊状の疎水基が存在することで、界面活性剤の発泡性が抑制されると推測される。またフッ素の作用で撥水性が発揮され、ノズルプレートへのインク固着性が改善される。一方で表面張力の低下によりノズル面に対して濡れ性が上がり周辺部にインクが付着してインク吐出安定性が低下する可能性もあるが、一般式（Ｉ）で表される化合物を用いるとこのような問題も生じない。４級アンモニウム塩タイプであることによりノズル面に対し静電的な反発力を保持できるため、濡れ性を悪化させることなく吐出性が保持されると推測している。 A general fluorosurfactant has a perfluoroalkyl group represented by the following formula as a hydrophobic group.
CF ₃ CF ₂ (CF ₂ CF ₂ ) _m − (where m is an integer of 0 or more)
In this structure, the carbon atoms are arranged in a straight chain, and the perfluoroalkyl group is elongated in a straight chain.
On the other hand, the compound represented by the general formula (I) used in the present invention has a side chain-like C _n F _2n-1 group having a branched carbon chain, and particularly preferably a perfluoroalkenyl group. . This perfluoroalkenyl group is, for example, a hexafluoropropene oligomer and is exemplified by the following structure.

The three-dimensional structure of the “side-chain C _n F _2n-1 group having a branched carbon chain” is a lump. It is presumed that the foaming property of the surfactant is suppressed by the presence of the massive hydrophobic group. In addition, the water repellent is exhibited by the action of fluorine, and the ink fixing property to the nozzle plate is improved. On the other hand, there is a possibility that the wettability with respect to the nozzle surface increases due to the decrease in the surface tension and the ink adheres to the peripheral part and the ink ejection stability decreases. However, when the compound represented by the general formula (I) is used, Such a problem does not occur. Since it is possible to maintain an electrostatic repulsive force with respect to the nozzle surface by being a quaternary ammonium salt type, it is presumed that dischargeability is maintained without deteriorating wettability.

As a compound represented by general formula (I), the thing of the structure shown, for example in the following compound examples 1-54 is mentioned. All have a perfluoroalkenyl group.

The amount of the compound represented by formula (I) added to the pretreatment liquid is about 0.05 to 20% by weight, preferably 0.1 to 10% by weight, but is not particularly limited.
Since the compound represented by the general formula (I) has a property of being hardly soluble in water, it is desirable to use it by dissolving it in a water-soluble organic solvent. In addition, these compounds can be used alone or in admixture of two or more, or can be used in admixture with other surfactants.
The composition of the pretreatment liquid of the present invention is usually obtained by removing the chromatic colorant component from the inkjet ink and adding the compound represented by the general formula (I). Apparently it is colorless or light-colored, and the properties of the treatment liquid are almost the same as ink.
Therefore, the pretreatment liquid of the present invention can be ejected in the same manner as ink from an inkjet head and nozzles. It is also possible to apply the treatment liquid onto the recording medium with a roller or felt.

Examples of materials used in the pretreatment liquid and the inkjet ink according to the present invention are as follows.
Although there is no limitation in particular as a coloring agent used for an inkjet ink, For example, the pigments listed below are used suitably. Moreover, you may use these pigments in mixture of multiple types.
Carbon black, which is an inorganic black pigment, is carbon black produced by a furnace method or a channel method, having a primary particle size of 10 to 50 nm, a specific surface area of 50 to 400 square meters / g according to the BET method, and a DBP oil absorption amount. Having a volatile content of 0.5 to 10% and a pH value of 2 to 9 is preferable.
As such, for example, # 2200B, # 2300, # 2350, # 2400B, # 2450B, # 2600, # 2650, # 2700B, # 650B, # 750B, MA600, MCF88, # 850, # 900, # 900 950, # 960, # 970, # 980, # 990, # 1000, # 260, # 95, CF9, # 5, # 10, # 20, # 25, # 30, # 32, # 33, # 40, # 44, # 45, # 45L, # 47, # 50, # 52, MA7, MA8, MA11, MA14, MA77, MA100, MA100R, MA100S, MA220, MA200RB, MA230 (above, manufactured by Mitsubishi Chemical), Raven700, the same 760 ULTA, 780 ULTRA, 790 ULTRA, 820, 850, 860 ULTRA 880ULTRA, 890, 890H, 1000, 1020, 1035, 1040, 1060ULTRA, 1080ULTRA, 1100ULTRA, 1170, 1190ULTRA, 1200, 1250, 1255, 1500, 2000 , 2500 ULTRA, 3000 (above, manufactured by Columbian), REGAL99R, 250R, 300R, 330R, 400R, 415R, 500R, 660R, MOGAL L, MONARCH700, 800, 880, 900 1000, 1100, (above, manufactured by CABOT), Color Black FW1, FW2, FW2V, FW18, FW200, S150, S160, S170, NIPex35, 60, 70, 90, 150, 160 IQ, 170 IQ, 170 IQ, 180 IQ, PRINTEX 12, 25, 30, 31, 31, 35, 55, 60, 60 A, 75, 80, 85, 90, 95, 140U, 140V, 155C, 200, 300, 300IP, 301, SPECIAL BLACK4, 4A, 5, 6, 100, 250, 350, 550 (manufactured by Degussa) or the like can be used. However, the present invention is not limited to these.

Other inorganic pigments include iron oxide, titanium oxide, calcium carbonate, barium sulfate, aluminum hydroxide, barium yellow, bitumen, cadmium red, chrome yellow, metal powder, and the like, and organic pigments include azo, phthalocyanine, Anthraquinone, quinacridone, dioxazine, indigo, thioindigo, perylene, isoindolenone, aniline black, azomethine, rhodamine B lake pigment and the like can be mentioned.
More specifically, the following are listed for each color.
Examples of the yellow ink pigment include C.I. I. Pigment Yellow 1, 2, 2, 3, 12, 14, 16, 17, 17, 73, 74, 75, 83, 93, 95, 97, 98, 114, 128, 129, 151, 154, etc., but are not limited thereto.
Examples of the magenta ink pigment include C.I. I. Pigment Red 5, 7, 12, 48 (Ca), 48 (Mn), 57 (Ca), 57: 1, 112, 123, 168, 184, 202, etc. However, it is not limited to these.
Examples of the pigment for cyan ink include C.I. I. Pigment blue 1, 2, 3, 15: 3, 15:34, 16, 22, 22, 60, C.I. I. Examples thereof include, but are not limited to, Bat Blue 4 and 60.
In addition, the pigment contained in each ink used in the present invention may be newly produced for the present invention.

A chromatic colorant component is not used in the pretreatment liquid, but a light colorant equivalent to the recording medium can be used. Examples thereof include white inorganic pigments such as titanium oxide, calcium carbonate, barium sulfate, and aluminum hydroxide. By adding these to the pretreatment liquid, it is possible to further stabilize the ejection properties from the nozzles, and further improve the image density and color developability.
The colorant mentioned above can be used as a pretreatment liquid or an inkjet ink by dispersing in an aqueous medium using a polymer dispersant or a surfactant.
As a dispersant for dispersing such pigment powder, a normal water-soluble resin or a water-soluble surfactant can be used.

Specific examples of water-soluble resins include styrene, styrene derivatives, vinyl naphthalene derivatives, aliphatic alcohol esters of α, β-ethylenically unsaturated carboxylic acids, acrylic acid, acrylic acid derivatives, maleic acid, maleic acid derivatives, itacon. Examples thereof include block copolymers composed of two or more monomers selected from acids, itaconic acid derivatives, fumaric acid, fumaric acid derivatives and the like, random copolymers, or salts thereof.
These water-soluble resins are alkali-soluble resins that are soluble in an aqueous solution in which a base is dissolved. Among them, those having a weight average molecular weight of 3000 to 20000 are used in ink jet inks. It is particularly preferable because it has the advantage that it can be formed and can be easily dispersed.

  Specific examples of water-soluble surfactants include anionic surfactants such as higher fatty acid salts, alkyl sulfates, alkyl ether sulfates, alkyl ester sulfates, alkyl aryl ether sulfates, alkyl sulfonates, sulfosuccinates. Examples include acid salts, alkylallyl and alkylnaphthalene sulfonates, alkyl phosphates, polyoxyethylene alkyl ether phosphate esters, alkyl allyl ether phosphates, and the like. In addition, as nonionic surfactants, 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.

A water-soluble organic solvent is used in addition to the colorant for the purpose of making the pretreatment liquid and ink-jet ink according to the present invention have desired physical properties or preventing clogging of the nozzles of the recording head due to drying. Is preferred. The water-soluble organic solvent includes a wetting agent and a penetrating agent.
The wetting agent is added for the purpose of preventing clogging of the nozzles of the recording head due to drying. Specific examples of the wetting agent include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, propylene glycol, 1,3-butanediol, 1,3-propanediol, and 2-methyl-1,3-propane. Diol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, glycerin, 1,2,6-hexanetriol, 2-ethyl-1,3-hexanediol, 1,2 Polyhydric alcohols such as 1,4-butanetriol, 1,2,3-butanetriol, and petriol; ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene Polyhydric alcohol alkyl ethers such as glycol monobutyl ether, triethylene glycol monobutyl ether, tetraethylene glycol monomethyl ether and propylene glycol monoethyl ether; Polyhydric alcohol aryl ethers such as ethylene glycol monophenyl ether and ethylene glycol monobenzyl ether N-methyl-2-pyrrolidone, N-hydroxyethyl-2-pyrrolidone, 2-pyrrolidone, 1,3-dimethylimidazolidinone, nitrogen-containing heterocyclic compounds such as ε-caprolactam; formamide, N-methylformamide, Amides such as N, N-dimethylformamide; monoethanolamine, diethanolamine, triethanolamine, monoethylamine, diethylamine, triethylamine and the like Sulfur-containing compounds such as amines, dimethyl sulfoxide, sulfolane, thiodiethanol; propylene carbonate, ethylene carbonate, γ-butyrolactone, and the like. These solvents are used alone or in combination with water.

Further, the penetrant is added for the purpose of improving the wettability of the pretreatment liquid, the inkjet ink and the recording material, and adjusting the penetration speed.
As the penetrant, those represented by the following formulas (II) to (V) are preferable. That is, a polyoxyethylene alkylphenyl ether surfactant of the following formula (II), an acetylene glycol surfactant of the formula (III), a polyoxyethylene alkyl ether surfactant of the following formula (IV), and the following formula Since the polyoxyethylene polyoxypropylene alkyl ether surfactant (V) can reduce the surface tension of the liquid, it can improve wettability and increase the penetration rate.

（式中、Ｒは分岐していても良い炭素数６〜１４の炭化水素鎖、ｋは５〜２０の整数）

（式中、ｍ、ｎは０〜４０の整数）

（式中、Ｒは分岐していてもよい炭素数６〜１４の炭化水素鎖、ｎは５〜２０の整数）

（式中、Ｒは炭素数６〜１４の炭化水素鎖、ｍ、ｎは２０以下の自然数）

(Wherein R is an optionally branched hydrocarbon chain having 6 to 14 carbon atoms, k is an integer of 5 to 20)

(Where m and n are integers from 0 to 40)

(In the formula, R is an optionally branched hydrocarbon chain having 6 to 14 carbon atoms, and n is an integer of 5 to 20).

(Wherein R is a hydrocarbon chain having 6 to 14 carbon atoms, m and n are natural numbers of 20 or less)

  Other than the compounds of the above formulas (II) to (V), for example, diethylene glycol monophenyl ether, ethylene glycol monophenyl ether, ethylene glycol monoallyl ether, diethylene glycol monophenyl ether, diethylene glycol monobutyl ether, propylene glycol monobutyl ether, tetraethylene glycol chlorophenyl Use alkyl and aryl ethers of polyhydric alcohols such as ethers, nonionic surfactants such as polyoxyethylene polyoxypropylene block copolymers, fluorine-based surfactants, lower alcohols such as ethanol and 2-propanol However, diethylene glycol monobutyl ether is particularly preferable.

Conventionally known polymer particles can be added to the pretreatment liquid and inkjet ink according to the present invention. These polymer particles are used in the form of a resin emulsion, and are preferably at least one selected from polyurethane, styrene acrylic, and acrylic silicon. In particular, for a water-based pigment dispersion, a polyurethane-based resin emulsion is more preferable in terms of fixability on paper and the like.
The resin emulsion is present as an O / W type emulsion when used as a raw material for preparing an inkjet ink or after preparing a pretreatment liquid or an inkjet ink. Emulsions of polyurethane resins can be obtained by emulsifying normal polyurethane resins with relatively hydrophilic properties using emulsifiers, or by introducing functional groups that act as emulsifiers into the resin itself by means such as copolymerization. There is an emulsion of emulsifying resin. Any of them can be used, but care must be taken because there is a slight difference in the dispersion stability of the pigment and emulsion particles depending on the combination of the components of the inkjet ink.
In various combinations with pigments and dispersants, an anionic self-emulsifying polyurethane emulsion is always excellent in dispersion stability. In this case, the polyurethane resin is preferably a polycarbonate type rather than a polyester type, and more preferably an ether type than a polyester type or a polycarbonate type, in terms of pigment fixation and dispersion stability. The reason is not clear, but the non-ether type is often weak in solvent resistance, and the viscosity tends to aggregate when the ink is stored at high temperature. Although the reason is not clear, the processing time can be shortened by adding the resin emulsion to the aqueous pigment dispersion and the aqueous pigment ink, followed by heat treatment.

The surface tension of the pretreatment liquid and ink jet ink according to the present invention is preferably 20 to 60 dyne / cm, and 30 to 50 dyne / cm from the viewpoint of achieving both wettability with the recording medium and droplet formation. More preferably.
The viscosity of the pretreatment liquid and inkjet ink according to the present invention is preferably 1.0 to 20.0 cP, and more preferably 3.0 to 10.0 cP from the viewpoint of ejection stability.
The pH of the pretreatment liquid and ink jet ink according to the present invention is preferably 3 to 11, and more preferably 6 to 10 from the viewpoint of preventing corrosion of the metal member in contact with the liquid.

An antiseptic / antifungal agent can be added to the pretreatment liquid and ink-jet ink according to the present invention. By adding an antiseptic / antifungal agent, the growth of bacteria can be suppressed, and the storage stability and image quality stability can be improved. Examples of antiseptic / antifungal agents include benzotriazole, sodium dehydroacetate, sodium sorbate, 2-pyridinethiol-1-oxide sodium, isothiazoline-based compounds, sodium benzoate, and sodium pentachlorophenol.
A rust inhibitor may be added to the pretreatment liquid and ink jet ink according to the present invention. By adding a rust inhibitor, a film can be formed on the metal surface in contact with the head or the like to prevent corrosion. As the rust inhibitor, acidic sulfite, sodium thiosulfate, ammonium thiodiglycolate, diisopropylammonium nitrite, pentaerythritol tetranitrate, dicyclohexylammonium nitrite and the like can be used.
A pH adjuster can be added to the pretreatment liquid and ink jet ink according to the present invention. Examples of the pH adjuster include hydroxides of alkali metal elements such as lithium hydroxide, sodium hydroxide, potassium hydroxide, ammonium hydroxide, quaternary ammonium hydroxide, quaternary phosphonium hydroxide, lithium carbonate, Examples include alkali metal carbonates such as sodium carbonate and potassium carbonate, amines such as diethanolamine and triethanolamine, boric acid, hydrochloric acid, nitric acid, sulfuric acid, and acetic acid.

An antioxidant can be added to the pretreatment liquid and ink jet ink according to the present invention. Even when radical species that cause corrosion are generated by the addition of the antioxidant, the antioxidant can be eliminated, so that the corrosion can be prevented.
Typical examples of the antioxidant include phenolic compounds and amine compounds. Examples of the phenolic compounds include hydroquinone and gallate compounds, 2,6-di-tert-butyl-p-cresol, and stearyl. -Β- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 2,2'-methylenebis (4-methyl-6-tert-butylphenol), 2,2'-methylenebis (4-ethyl- 6-tert-butylphenol), 4,4′-thiobis (3-methyl-6-tert-butylphenol), 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-4-hydroxybenzyl) benzene, Hinders such as squirrel (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, tetrakis [methylene-3 (3 ′, 5′-di-tert-butyl-4-hydroxyphenyl) propionate] methane Examples of the amine compounds include N, N′-diphenyl-p-phenylenediamine, phenyl-β-naphthylamine, phenyl-α-naphthylamine, N, N′-β-naphthyl-p-phenylene. Examples include diamine, N, N'-diphenylethylenediamine, phenothiazine, N, N'-di-sec-butyl-p-phenylenediamine, 4,4'-tetramethyl-diaminodiphenylmethane, and the like.
In addition to the above, the sulfur compounds include dilauryl thiodipropionate, distearyl thiodipropionate, lauryl stearyl thiodipropionate, dimyristyl thiodipropionate, distearyl β, β′-thiodibutyrate, Examples include 2-mercaptobenzimidazole, dilauryl sulfide and the like, and phosphorus compounds include triphenyl phosphite, trioctadecyl phosphite, tridecyl phosphite, trilauryl trithiophosphite, diphenylisodecyl phosphite, trinonyl. Examples thereof include phenyl phosphite and distearyl pentaerythritol phosphite.

As a preparation method of the pretreatment liquid and ink jet ink according to the present invention, a conventionally known method of dispersing a colorant may be used. For example, first, the colorant is dispersed with a known disperser, and if necessary, coarse particles and the like are removed by centrifugation, filtration or the like to obtain a colorant dispersion (mill base). In addition, this process is unnecessary about the pre-processing liquid which does not contain a coloring agent. Next, a wetting agent, a penetrating agent, a surfactant, water, etc. are mixed and stirred so that they are uniformly mixed. Thereafter, a mill base, a pH adjusting agent, and a pH buffer material are added and stirred to obtain a pretreatment liquid or an inkjet ink.
The obtained pretreatment liquid or inkjet ink is preferably subjected to a filtration step in order to remove coarse particles derived from raw materials or generated in the production process. The filter pore diameter used for filtration is preferably 0.5 to 10 μm, and more preferably 3 to 7 μm from the viewpoint of production efficiency and ejection reliability of the pretreatment liquid or inkjet ink.

The pretreatment liquid and inkjet ink according to the present invention can be accommodated in a container and used as a cartridge. At that time, it is desirable to degas the pretreatment liquid and inkjet ink, and preferably the dissolved oxygen concentration is reduced. 5 ppm or less.
In addition, the cartridge can be mounted and used in an ink jet recording apparatus provided with an ink ejecting means for forming an image by applying a stimulus to ink jet ink and causing it to fly. At this time, even a recording apparatus having an ink repellent layer containing a silicon resin on the nozzle plate surface of the inkjet head can be suitably used.
In addition, the pretreatment liquid of the present invention is used to treat the surface of the recording medium (pretreatment step), and then to form an image on the recording medium by applying a stimulus to the ink jet ink and causing it to fly (ink flying step). ) It can be applied to an ink jet recording method.
At that time, after attaching the pretreatment liquid to the recording medium such as plain paper, the adhering liquid penetrates the recording medium, and apparently immediately after the liquid disappears on the surface of the recording medium, It is preferable to form an image by attaching an aqueous pigment ink containing an anionic or nonionic surfactant. Thereby, there is no blur of an image, it is excellent in the resolution, and a high density image is obtained.

FIG. 1 shows an example of an ink jet recording apparatus according to the present invention.
This apparatus includes an apparatus main body 101, a paper feed tray 102 for loading paper loaded in the apparatus main body 101, and a paper discharge tray 103 for stocking paper on which an image is recorded (formed) mounted on the apparatus main body 101. And. 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, a 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 at a position lower than the upper cover 111. On the upper surface of the cartridge loading section 104, operation keys and indicators are provided. An operation unit 105 such as is arranged. The cartridge loading section 104 has a front cover 115 that can be opened and closed to detach the cartridge.
Although not shown, this apparatus includes an ink jet head having a nozzle plate, a cartridge containing pretreatment liquid or ink for ink, and an ink repellent layer made of silicon resin or the like is provided on the discharge surface of the nozzle plate. Have. By applying a pulse voltage to the inkjet head in accordance with a recording signal, the pretreatment liquid and inkjet ink are ejected from the nozzle.

  EXAMPLES Hereinafter, although this invention is demonstrated in detail based on an Example, this invention is not limited by these Examples. In the examples, “part” is “part by weight”.

Example 1
(Preparation of pretreatment liquid 1)
After mixing the material of the following prescription and stirring for 30 minutes, it filtered with the membrane filter with the hole diameter of 0.5 micrometer, and also vacuum deaerated, and the pretreatment liquid 1 was obtained.

・ Glycerin 8.5 parts ・ Diethylene glycol 17.0 parts ・ 2-ethyl-1,3-hexanediol 2.0 parts ・ Surfactant of compound example 1 2.5 parts ・ Urethane resin emulsion (W-5661, Mitsui Chemicals) 23.7 parts ・ 2-pyrrolidone 2.0 parts ・ Pure water 44.3 parts

(Black mill base)
・ Carbon black (MONARCH880, manufactured by CABOT) 20 parts ・ Nonionic surfactant (RT-100, manufactured by Takemoto Yushi Co.) 5 parts ・ Pure water 80 parts

(Yellow mill base)
・ C. I. Pigment Yellow 74
(Yellow No. 34, manufactured by Dainichi Seika Co., Ltd.) 20 parts ・ Nonionic surfactant (RT-100, manufactured by Takemoto Yushi Co., Ltd.) 5 parts ・ Pure water 80 parts

(Magenta mill base creation)
・ C. I. Pigment Red 122 20 parts (Cromophthal JET Magenta DMQ, manufactured by Ciba Specialty Chemicals)
・ Nonionic surfactant (RT-100, manufactured by Takemoto Yushi Co., Ltd.) 5 parts ・ Pure water 80 parts

(Cyan mill base creation)
・ C. I. Pigment Blue 15.3
(Chromofine Blue A-220JC, manufactured by Dainichi Seika Co., Ltd.) 20 parts Nonionic surfactant (RT-100, Takemoto Yushi Co., Ltd.) 5 parts Pure water 80 parts

After premixing each of the above mixtures, the mixture is circulated and dispersed in a disk-type bead mill (Shinmaru Enterprises Co., Ltd .: KDL type, media: 0.3 mmφ zirconia balls used), and then subjected to centrifugal filtration with a centrifuge. Coarse particles and dust were removed to obtain aqueous black mill base A, yellow mill base A, magenta mill base A, and cyan mill base A having a volume average particle diameter of 70 nm.

(Preparation of ink)
Using each color mill base A obtained as described above, a mixture having the following formulation was prepared, stirred for 30 minutes, filtered through a membrane filter having a pore size of 0.5 μm, and further vacuum degassed to obtain an inkjet ink. .
(Black ink 1)
Black mill base A 40.0 parts Glycerin 8.5 parts Diethylene glycol 17.0 parts 2-ethyl-1,3-hexanediol 2.0 parts Anionic surfactant (alkylbenzenesulfonic acid sodium salt) 5 parts-Urethane resin emulsion (W-5661, manufactured by Mitsui Chemicals) 13.7 parts-2-pyrrolidone 2.0 parts-Pure water 14.3 parts

(Yellow ink 1)
-Yellow Mill Base A 50.0 parts-Glycerin 3.5 parts-Diethylene glycol 23.5 parts-2-Ethyl-1,3-hexanediol 2.0 parts-Anionic surfactant (alkylbenzenesulfonic acid sodium salt) 5 parts-Urethane resin emulsion (W-5661, manufactured by Mitsui Chemicals) 10.0 parts-Pure water 8.5 parts

(Magenta ink 1)
・ Magenta mill base A 60.0 parts ・ Glycerin 2.5 parts ・ Diethylene glycol 20.5 parts ・ 2-ethyl-1,3-hexanediol 2.0 parts ・ Anionic surfactant (alkylbenzenesulfonic acid sodium salt) 5 parts-Urethane resin emulsion (W-5661, manufactured by Mitsui Chemicals) 6.0 parts-Pure water 6.5 parts

(Cyan ink 1)
-Cyan mill base A 45.0 parts-Glycerin 4.5 parts-Diethylene glycol 24.5 parts-2-ethyl-1,3-hexanediol 2.0 parts-Anionic surfactant (alkylbenzenesulfonic acid sodium salt) 5 parts-Urethane resin emulsion (W-5661, manufactured by Mitsui Chemicals) 10.0 parts-Pure water 11.5 parts

The obtained pretreatment liquid 1 and each color ink 1 were filled in a cartridge.
Next, an ink jet printer (Ricoh Co., Ltd .: IPSiO GX5000) was remodeled, and five ink jet heads having an ink repellent layer containing silicon resin on the nozzle plate surface were mounted, and the cartridge was inserted. Using a PPC paper 4200 manufactured by Xerox Co., Ltd., a pretreatment liquid was first discharged, and then a print pattern chart was printed so as to discharge each color ink. When the image density of the obtained ink recording material was measured by Xrite, the density of the solid part was uniform, the blur of the edge part of the character was not seen, and the resolution of the fine line was good.
Further, when the cartridge of the pretreatment liquid 1 was confirmed, there was no unevenness in the discharge of the pretreatment liquid from the nozzles, and no bubbles were generated in the cartridge.

Example 2
(Pretreatment liquid 2)
After mixing the materials of the following formulation and stirring for 30 minutes, the mixture was filtered through a membrane filter having a pore size of 0.5 μm, and further vacuum degassed to obtain a pretreatment liquid 2.

・ Glycerin 8.5 parts ・ Diethylene glycol 17.0 parts ・ 2-ethyl-1,3-hexanediol 2.0 parts ・ Surfactant of compound example 28 2.5 parts ・ Urethane resin emulsion (W-5661, Mitsui Chemicals) 23.7 parts ・ 2-pyrrolidone 2.0 parts ・ Pure water 44.3 parts

The obtained pretreatment liquid 2 was filled in a cartridge.
Using the same printer as in Example 1, the pretreatment liquid 2 cartridge was mounted instead of the pretreatment liquid 1 cartridge, and the head was washed. Each color cartridge was the same as in Example 1. Next, as in Example 1, a PPC paper 4200 manufactured by Xerox Co., Ltd. was used, and a printing pattern chart was printed such that the pretreatment liquid was first ejected and then each color ink was ejected.
When the image density of the obtained ink recording material was measured by Xrite, the density of the solid part was uniform, the blur of the edge part of the character was not seen, and the resolution of the fine line was good.
Furthermore, when the cartridge of the pretreatment liquid 2 was confirmed, there was no unevenness in the discharge of the pretreatment liquid from the nozzles, and no bubbles were generated in the cartridge.

Example 3
(White mill base)
・ Titanium oxide (Taika) 20 parts ・ Nonionic surfactant (RT-100, Takemoto Yushi Co.) 5 parts ・ Pure water 80 parts

After premixing the above mixture, the mixture is circulated and dispersed in a disk-type bead mill (Shinmaru Enterprises Co., Ltd .: KDL type, media: 0.1 mmφ zirconia ball used), and then subjected to centrifugal filtration with a centrifuge to make it coarse. Particles and dust were removed to obtain an aqueous white mill base A having a volume average particle diameter of 70 nm.

(Pretreatment liquid 3)
After mixing the materials of the following formulation and stirring for 30 minutes, the mixture was filtered through a membrane filter having a pore size of 0.5 μm, and further vacuum degassed to obtain a pretreatment liquid 3.

・ White mill base A 40.0 parts ・ Glycerin 8.5 parts ・ Diethylene glycol 17.0 parts ・ 2-ethyl-1,3-hexanediol 2.0 parts ・ Surfactant of Compound Example 2 2.5 parts ・ Urethane resin Emulsion (W-5661, manufactured by Mitsui Chemicals) 13.7 parts 2-pyrrolidone 2.0 parts Pure water 14.3 parts

Next, the inkjet printer (manufactured by Ricoh: IPSiO GX3000) was remodeled, and a felt-shaped coating member was installed on the upstream side of the carriage holding the inkjet head so as to contact the recording medium. A tank was installed on the felt so that the pretreatment liquid was dripped in a timely manner. This tank was filled with the pretreatment liquid 3, and the felt was sufficiently impregnated with the pretreatment liquid.
Four color cartridges of ink 1 prepared in Example 1 were inserted into this modified machine. Next, a print pattern chart was printed using PPC paper 4200 manufactured by Xerox Corporation.
When the image density of the obtained ink recording material was measured by Xrite, the density of the solid part was uniform, the blur of the edge part of the character was not seen, and the resolution of the fine line was good.

Example 4
(Pretreatment liquid 4)
After mixing the materials of the following formulation and stirring for 30 minutes, the mixture was filtered through a membrane filter having a pore size of 0.5 μm, and further vacuum degassed to obtain a pretreatment liquid 4.
Next, the pretreatment liquid 4 was filled in a cartridge.

・ Glycerin 8.5 parts ・ Diethylene glycol 17.0 parts ・ 2-ethyl-1,3-hexanediol 2.0 parts ・ Surfactant of compound example 37 2.5 parts ・ Urethane resin emulsion (W-5661, Mitsui Chemicals) 23.7 parts ・ 2-pyrrolidone 2.0 parts ・ Pure water 44.3 parts

(Black mill base)
・ Carbon black (NIPex150, Degussa) 20 parts ・ Anionic surfactant (A-51-B, Takemoto Yushi Co.) 5 parts ・ Pure water 80 parts

(Yellow mill base)
・ C. I. Pigment Yellow 74
(Yellow No. 34, manufactured by Dainichi Seika Co., Ltd.) 20 parts ・ Anionic surfactant (A-51-B, manufactured by Takemoto Yushi Co., Ltd.) 5 parts ・ Pure water 80 parts

(Magenta mill base creation)
・ C. I. Pigment Red 122 20 parts (Cromophthal JET Magenta DMQ, manufactured by Ciba Specialty Chemicals)
・ Anionic surfactant (A-51-B, manufactured by Takemoto Yushi Co., Ltd.) 5 parts ・ Pure water 80 parts

(Cyan mill base creation)
・ C. I. Pigment Blue 15.3
(Chromofine Blue A-220JC, manufactured by Dainichi Seika Co., Ltd.) 20 parts ・ Anionic surfactant (A-51-B, manufactured by Takemoto Yushi Co., Ltd.) 5 parts ・ Pure water 80 parts

After premixing each of the above mixtures, the mixture is circulated and dispersed in a disk-type bead mill (Shinmaru Enterprises Co., Ltd .: KDL type, media: 0.3 mmφ zirconia balls used), and then subjected to centrifugal filtration with a centrifuge. Coarse particles and dust were removed to obtain aqueous black mill base B, yellow mill base B, magenta mill base B, and cyan mill base B having a volume average particle diameter of 70 nm.

(Preparation of ink)
Using each color mill base B obtained as described above, a mixture having the following formulation was prepared, stirred for 30 minutes, filtered through a membrane filter having a pore size of 0.5 μm, and further vacuum degassed to obtain an inkjet ink. .
(Black ink 2)
Black mill base B 40.0 parts Glycerin 8.5 parts Diethylene glycol 17.0 parts 2-ethyl-1,3-hexanediol 2.0 parts Anionic surfactant (alkylbenzenesulfonic acid sodium salt) 5 parts ・ Acrylic resin emulsion (J-450, manufactured by BASF) 13.7 parts ・ 2-pyrrolidone 2.0 parts ・ Pure water 15.3 parts

(Yellow ink 2)
-Yellow Mill Base B 50.0 parts-Glycerin 3.5 parts-Diethylene glycol 23.5 parts-2-Ethyl-1,3-hexanediol 2.0 parts-Anionic surfactant (alkylbenzenesulfonic acid sodium salt) 5 parts ・ Acrylic resin emulsion (J-450, manufactured by BASF) 10.0 parts ・ Pure water 9.5 parts

(Magenta ink 2)
-Magenta mill base B 60.0 parts-Glycerin 2.5 parts-Diethylene glycol 20.5 parts-2-ethyl-1,3-hexanediol 2.0 parts-Anionic surfactant (alkylbenzenesulfonic acid sodium salt) 5 parts Acrylic resin emulsion (J-450, manufactured by BASF) 6.0 parts Pure water 7.5 parts

(Cyan ink 2)
-Cyan mill base B 45.0 parts-Glycerin 4.5 parts-Diethylene glycol 24.5 parts-2-ethyl-1,3-hexanediol 2.0 parts-Anionic surfactant (alkylbenzenesulfonic acid sodium salt) 5 parts ・ Acrylic resin emulsion (J-450, manufactured by BASF) 10.0 parts ・ Pure water 12.5 parts

Each color ink 2 thus obtained was filled in a cartridge.
Next, the ink jet printer (IPSiO GX5000 manufactured by Ricoh) used in Example 1 was mounted with the pretreatment liquid 4 cartridge and each color ink 2 cartridge, and the head was washed. Next, in the same manner as in Example 1, a pretreatment liquid was first ejected onto a PPC paper 4200 manufactured by Xerox Co., Ltd., and then a printing pattern chart was printed so that each color ink was ejected. Was measured with Xrite.
In the obtained image, the density of the solid portion was uniform, the blur of the edge portion of the character was not seen, and the resolution of the fine lines was good.
When the cartridge of the pretreatment liquid 4 was confirmed, there was no unevenness in the discharge of the pretreatment liquid from the nozzles, and no bubbles were generated in the cartridge.

Examples 5-15
Except that the surfactant in the pretreatment liquid of Example 1 was changed to Compound Examples 7, 8, 9, 11, 14, 20, 24, 31, 42, 45, and 49, respectively, the same as in Example 1 A pretreatment liquid was prepared to obtain pretreatment liquids 5 to 15.
Each of the obtained pretreatment liquids was filled into a cartridge in the same manner as in Example 1, and the pretreatment liquid was first discharged onto the Xerox PPC paper 4200 using the same inkjet printer remodeling machine as in Example 1. A printing pattern chart was printed so as to eject each color ink 1 composition prepared in Example 1.
When the image density of the obtained ink recording material was measured by Xrite, the density of the solid part was uniform, the blur of the edge part of the character was not seen, and the resolution of the fine line was good.
Furthermore, when the cartridges of the respective pretreatment liquids were confirmed, there was no unevenness in the discharge of the pretreatment liquid from the nozzles, and no bubbles were generated in the cartridges.

Comparative Example 1
Each color ink 1 obtained in Example 1 was filled in a cartridge.
Next, the above cartridge is mounted on an ink jet printer (Ricoh Co., Ltd .: IPSiO GX5000) modified in the same manner as in Example 1, and a print pattern chart is printed on PPC paper 4200 made by Xerox Co., Ltd. Image density was measured with Xrite.
In the obtained image, the density of the solid portion was non-uniform, the density was low as a whole, blurring of the edge portion of the character was seen, and the image was poor in resolution.

Comparative Example 2
(Pretreatment liquid 5)
After mixing the materials of the following formulation and stirring for 30 minutes, the mixture was filtered through a membrane filter having a pore size of 0.5 μm, and further vacuum degassed to obtain a pretreatment liquid 5.

・ Glycerin 8.5 parts ・ Diethylene glycol 17.0 parts ・ 2-ethyl-1,3-hexanediol 2.0 parts ・ Surfactant of Compound Example 55 (fluorine surfactant having a linear carbon chain) 2・ 5 parts ・ Acrylic resin emulsion 23.7 parts ・ 2-pyrrolidone 2.0 parts ・ Pure water 44.3 parts

The obtained pretreatment liquid 5 was filled in a cartridge.
Next, the inkjet printer (IPSiO GX5000 manufactured by Ricoh Co., Ltd.) used in Example 1 was equipped with the pretreatment liquid 5 cartridge and the cartridges of each color ink 2 prepared in Example 4, and the head was washed. Next, in the same manner as in Example 1, a pretreatment liquid was first ejected onto Xerox PPC paper 4200, and then a print pattern chart was printed so as to eject each color ink, and the image density of the obtained ink record was measured with Xrite. did.
In the obtained image, the density of the solid portion was non-uniform, and the edge portion of the character was blurred at various places, resulting in an image having a low resolution as a whole. When the cartridge of the pretreatment liquid 5 was confirmed, unevenness was found in the discharge of the pretreatment liquid from the nozzles, and a large amount of bubbles were generated in the cartridge.

DESCRIPTION OF SYMBOLS 101 Main body 102 Paper feed tray 103 Paper discharge tray 104 Cartridge loading part 105 Operation part 111 Upper cover 112 Front cover front 115 Front cover

Japanese Patent No. 2711098 Japanese Patent Laid-Open No. 6-148942

Claims (5)

A pretreatment liquid for treating the surface of a recording medium before performing inkjet recording on the recording medium, comprising a fluorine-containing quaternary ammonium salt compound represented by the general formula (I) liquid.

(In the formula, R ¹ is H, a lower alkyl group having 1 to ⁴ carbon atoms which may be branched or a phenyl group, R ^{2 to} R ⁴ are lower alkyl groups having 1 to 10 carbon atoms which may be branched, X represents SO ₂ or CO, Y represents I or Br, m represents a positive integer, n represents an integer of 4 or more, and C _n F _2n-1 has a branched structure.)   A cartridge characterized by containing the pretreatment liquid according to claim 1 or the pretreatment liquid and ink-jet ink in a container.   An ink jet recording apparatus comprising the cartridge according to claim 2 and including an ink flying unit that forms an image by applying a stimulus to the ink for ink jet and the nozzle plate surface of the ink jet head contains a silicon resin. An ink jet recording apparatus comprising an ink repellent layer.   2. An ink jet recording comprising: a pretreatment step of a recording medium surface using the pretreatment liquid according to claim 1; and an ink flying step of forming an image on the recording medium by applying a stimulus to the ink jet ink to fly. Method.   An ink recorded matter comprising an image formed using the pretreatment liquid according to claim 1 and an inkjet ink on a recording medium.

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