JP5293193B2 - Image forming method using pretreatment liquid, pretreatment liquid, set with ink for ink jet recording, cartridge, ink jet recording apparatus, image formed product - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an image forming method excellent in smear resistance, a pretreatment liquid used thereof, and a set of the pretreatment liquid and inkjet recording ink. <P>SOLUTION: (1) In the method for forming the image, a recording medium surface is pretreated by using the pretreatment liquid containing water and a coagulant for the inkjet recording ink and then an image is formed on the recording medium surface by using the inkjet recording ink containing water and a pigment. At least one between the pretreatment liquid and the inkjet recording ink contains fluoroethylene/vinyl ether alternating copolymer. (2) In a set of the pretreatment liquid for a recording medium and the inkjet recording ink, the pretreatment liquid for the recording medium contains water, the coagulant for the inkjet recording ink and the fluoroethylene/vinyl ether alternating copolymer and the inkjet recording ink contains water, the pigment and the fluoroethylene/vinyl ether alternating copolymer. <P>COPYRIGHT: (C)2010,JPO&amp;INPIT

Description

  The present invention relates to an image forming method using a pretreatment liquid, a pretreatment liquid used therefor, a set of the pretreatment liquid and an ink for ink jet recording, a cartridge containing the pretreatment liquid or set in a container, and the cartridge The present invention relates to an ink jet recording apparatus equipped with an image forming material recorded on the ink jet recording apparatus.

Conventionally, after the surface of a recording medium is treated with a pretreatment liquid containing a flocculant such as citric acid, recording is performed using an ink containing a resin as a binder component, thereby causing the ink to aggregate on the surface of the recording medium. It is known to improve the concentration (Patent Document 1).
When the ink is agglomerated with such a pretreatment liquid, it is ideal to agglomerate only the color material in the ink and keep it on the surface of the recording medium, but in actuality, not only the color material but also the binding in the ink Since the agent resin is also agglomerated, the resin film-forming function is impaired. As a result, the ink on the surface of the recording medium becomes powdery, the binding force of the formed image is insufficient, and the printed image is easily lost due to rubbing of the image surface (smear resistance is reduced). there were.
Although Patent Document 2 describes an ink containing a fluoroethylene / vinyl ether alternating copolymer, there is no description regarding a pretreatment liquid.

JP 2008-126413 A JP 2008-050400 A

  The present invention relates to an image forming method in which defects due to rubbing or the like of a printed image are small (excellent smear resistance), a pretreatment liquid used therefor, a set of the pretreatment liquid and an ink jet recording ink, the pretreatment liquid Alternatively, it is an object of the present invention to provide a cartridge in which a set is contained in a container, an ink jet recording apparatus equipped with the cartridge, and an image formed product recorded by the ink jet recording apparatus.

The above problems are solved by the following inventions 1) to 11).
1) After pretreatment of the surface of the recording medium using a pretreatment liquid containing water and an ink jet recording ink aggregating agent, an image is formed on the surface of the recording medium using ink for ink jet recording containing water and a pigment. A method for forming an image, wherein at least one of the pretreatment liquid and the ink for inkjet recording contains a fluoroethylene / vinyl ether alternating copolymer.
2) The image forming method according to 1), wherein the ink for ink jet recording contains a resin that causes aggregation by the pretreatment liquid.
3) The image forming method according to 2), wherein the resin causing aggregation by the pretreatment liquid is an ether type polyurethane resin.
4) A recording medium pretreatment liquid comprising water, an aggregating agent for ink jet recording ink, and a fluoroethylene / vinyl ether alternating copolymer.
5) a recording medium pretreatment liquid comprising water, an ink jet recording ink flocculant and a fluoroethylene / vinyl ether alternating copolymer; an ink jet recording ink comprising water, a pigment and a fluoroethylene / vinyl ether alternating copolymer; A set of a pretreatment liquid for a recording medium and an ink for ink-jet recording, characterized by comprising:
6) The set of the pretreatment liquid for a recording medium and the ink for inkjet recording according to 5), wherein the ink for inkjet recording contains a resin that causes aggregation by the pretreatment liquid.
7) The set of the pretreatment liquid for a recording medium and the ink for ink jet recording according to 6), wherein the resin that causes aggregation by the pretreatment liquid is an ether type polyurethane resin.
8) A cartridge in which the pretreatment liquid for the recording medium described in 4) is contained in a container.
9) The recording medium pretreatment liquid and the ink jet recording ink constituting the set of the recording medium pretreatment liquid and the ink jet recording ink according to any one of 5) to 7) are contained in a container. Cartridge.
10) An ink jet recording apparatus equipped with the cartridge according to 8) or 9).
11) An image formed product printed by the ink jet recording apparatus described in 10).

Hereinafter, the present invention will be described in detail.
The image forming method of the present invention includes a pretreatment liquid containing a pretreatment liquid containing water and an ink for ink jet recording (hereinafter also simply referred to as “ink”), and an ink jet containing water and a pigment. When forming an image on the surface of the recording medium using the recording ink, a fluoroethylene / vinyl ether alternating copolymer (hereinafter referred to as alternating copolymer A) is used as at least one of the pretreatment liquid and the ink jet recording ink. It is characterized by including.
As described above, conventionally, there has been a problem that smear resistance is lowered when ink is aggregated using a pretreatment liquid containing an aggregating agent. On the other hand, since the alternating copolymer A used in the present invention is very stable with respect to the flocculant, it is possible to prevent a reduction in smear resistance.
Although the reason why the alternating copolymer A is stable with respect to the flocculant is not clear, the alternating copolymer A has a polar vinyl ether portion (a portion that provides dispersion stability in water) as a nonpolar portion. Since it is alternately sandwiched between fluoroethylenes, it is considered that the polar part is less likely to come into contact with the ions of the flocculant. On the other hand, in the case of other fluororesins such as fluoroethylene / vinyl ester resin and fluorinated alkyl resin, there is no or insufficient alternating structure, and the polar part is likely to come into contact with the ions of the flocculant Therefore, it is thought that it is easy to aggregate.

交互共重合体Ａの市販品としては、旭硝子社製のルミフロンＦＥ４３００、ＦＥ４５００、ＦＥ４４００などが挙げられる
交互共重合体Ａのインク中の添加量は、０．０５〜３０重量％程度、好ましくは０．５〜２０重量％、更に好ましくは１〜１０重量％である。
なお、交互共重合体Ａは水系樹脂であり、インク中に分散させたもの（樹脂エマルジョン）を用いてもよく、インクに可溶なものを用いてもよい。 The alternating copolymer A is a copolymer obtained by radical polymerization of fluoroethylene and a hydrocarbon vinyl ether, and is obtained by alternately polymerizing fluoroethylene units and vinyl ether units.
There is no particular limitation on the fluoroethylene units, can be appropriately selected depending on the intended purpose, for _{example, -CF 2 CF 2 -, -} CF 2 CF (CF 2) -, - CF 2 CFCl- and the like .
The vinyl ether unit is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include those represented by the following structural formula.

Examples of the commercial product of the alternating copolymer A include Lumiflon FE4300, FE4500, and FE4400 manufactured by Asahi Glass Co. The addition amount of the alternating copolymer A in the ink is about 0.05 to 30% by weight, preferably 0. 0.5 to 20% by weight, more preferably 1 to 10% by weight.
The alternating copolymer A is a water-based resin, and a dispersed resin (resin emulsion) may be used, or an ink soluble material may be used.

Further, when the alternating copolymer A and another resin that aggregates with a flocculant are used in combination, and the pigment is bound to the recording medium using the aggregation of the other resin, the image density is further improved. Can do. Other resins are also water-based resins, and those dispersed in ink (resin emulsion) may be used, or those soluble in ink may be used.
Other resins include polyurethane resin, polyester resin, polyepoxy resin, polyamide resin, polyether resin, silicon resin, polyolefin resin, polystyrene resin (styrene butadiene resin and styrene acrylic resin), polyvinyl ester resin, polyacrylic acid Resin, unsaturated carboxylic acid resin and the like. Furthermore, natural polymer compounds such as celluloses, rosins and natural rubbers may be used. Further, not only homopolymers composed of monomers of these resins but also copolymers composed of plural kinds of monomers may be used. Moreover, as a kind of emulsion, any of a single phase structure type, a core shell type, and a power feed type can be used.
The resin preferably has an average particle diameter D50 of 500 nm or less because it is difficult to clog the inkjet nozzle.

Among the above resins, a polyurethane resin is preferable, and a water dispersible polyurethane resin is particularly preferable. Examples of water-dispersible polyurethane resins include those in which a hydrophilic component necessary for stable dispersion in water is introduced in the main chain of the polyurethane skeleton, and water dispersions of polyurethane resins obtained by dispersing with an external emulsifier However, a self-dispersing type (self-emulsifying type) in which a hydrophilic component is introduced into the main chain is more preferable.
The self-emulsifying polyurethane resin is obtained by reacting a diisocyanate compound, a diol compound such as polyether diols, polyester diols, and polycarbonate diols with an acid group-containing diol compound such as a carboxylic acid group or a sulfonic acid group. There are ester type polyurethane resin, ether type polyurethane resin, carbonate type polyurethane resin and the like. Of these, ether type polyurethane resins are preferred because of their high cohesiveness and high image density improvement effect, and anionic and self-emulsifying ether type polyurethane resins are particularly preferred.

Examples of the diisocyanate compound include aliphatic diisocyanate compounds such as hexamethylene diisocyanate and 2,2,4-trimethylhexamethylene diisocyanate, isophorone diisocyanate, hydrogenated xylylene diisocyanate, 1,4-cyclohexane diisocyanate, 4,4′- Cycloaliphatic diisocyanate compounds such as dicyclohexylmethane diisocyanate, aromatic aliphatic diisocyanate compounds such as xylylene diisocyanate and tetramethylxylene diisocyanate, aromatic diisocyanate compounds such as toluylene diisocyanate and phenylmethane diisocyanate, modified products of these diisocyanates (carbodiimide, uretdione) Ureitomine-containing metamorphs, etc.).
Examples of the diol compound include polyether diols such as polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, polyhexamethylene ether glycol, polyethylene adipate, polybutylene adipate, polyneopentyl adipate, poly-3-methylpentyl adipate. Polyester diols such as polyethylene / butylene adipate and polyneopentyl / hexyl adipate, polylactone diols such as polycaprolactone diol, and polycarbonate diol. From the viewpoint of ink storage stability, polyether-based, polyester-based and polycarbonate-based diol compounds are preferable, polyether-based or polycarbonate-based are more preferable, and polyether-based are more preferable.
Examples of the acid group-containing diol compound include dimethylolacetic acid, dimethylolbutanoic acid, dimethylolpropionic acid, and dimethylolbutyric acid. Particularly preferred is dimethylolbutanoic acid.

The acid value of the polyurethane resin is preferably 50 to 100 KOH mg / g. Further, an ether type polyurethane resin in this range is preferable because the effect of improving the image density is further excellent.
The weight average molecular weight of the polyurethane resin is preferably 30000 or less, particularly 20000 or less from the viewpoint of ejection stability. As the molecular weight increases, the viscosity increases and ejection becomes difficult. On the other hand, if it is 10,000 or less, the coagulation effect of the polyurethane resin by the coagulant tends to be small.
Examples of commercially available polyurethane resins include Takeklac W5661, W5024, W-615, W-6010, W-6020, W-6061, and W-511 manufactured by Mitsui Chemicals, WS-6021, WS-5000, Examples include WS series such as WS-5100 and WS-4000, Hydran HW series, AP series, and VONDIC series manufactured by Dainippon Ink.

The pretreatment liquid of the present invention contains an ink flocculant. Here, the ink aggregating agent means an agent capable of destroying and aggregating the dispersion state of the pigment dispersion / resin in the ink.
Examples of the flocculant include water-soluble metal salts, long-chain alkyl isocyanate-modified polyethyleneimine, and acids.
The water-soluble metal salt is dissolved in water to be in an ionic state, and has a function of destroying and aggregating the surface charge of the pigment dispersion. Anions constituting the water-soluble metal salt include organic acid ions such as citric acid, tartaric acid, acetic acid, lactic acid, oxalic acid, fumaric acid, salicylic acid, benzoic acid, Cl, NO ₃ , I, Br, ClO _{3 and the} like. Inorganic ions may be mentioned. Examples of the cation include alkali metal ions such as Li, Na and K, divalent metal ions such as Ca, Cu, Ni, Mg, Zn and Ba, and trivalent metals such as Al, Fe and Cr. Ions.
Particularly, Ca and Mg salts have a large aggregation effect, and CaCl ₂ and MgCl ₂ are preferable.

The long-chain alkyl isocyanate-modified polyethyleneimine is obtained by grafting a long-chain alkyl isocyanate to a polyalkylimine, and the length of the alkyl group is preferably C6-C30, more preferably C10-C20 from the viewpoint of improving smear resistance. More preferably, it is C12-C20. If it is C6 or more, the image density tends to be improved.
Examples of long chain alkyl isocyanates include hexyl isocyanate, heptyl isocyanate, octyl isocyanate, decyl isocyanate, undecyl isocyanate, dodecyl isocyanate, tridecyl isocyanate, pentadecyl isocyanate, hexadecyl isocyanate, heptadecyl isocyanate, octadecyl isocyanate, docosanyl isocyanate , Nonadecyl isocyanate, and eicosyl isocyanate. In particular, when C18 octadecyl isocyanate is used, it has the highest image density and excellent smear resistance. As a commercial item, Nippon Shokubai Co., Ltd. RP-18W is mentioned.
Examples of the acid include organic acids such as citric acid, tartaric acid, acetic acid, lactic acid, oxalic acid, fumaric acid, salicylic acid, benzoic acid, and inorganic acids such as aluminum sulfate, among which lactic acid is preferable.

Further, when the pretreatment liquid contains the alternating copolymer A, the permeability of the resin in the ink is suppressed as much as possible, and the binding force of the pretreatment layer formed by the pretreatment to the recording medium surface is increased, and the pretreatment is performed. The adhesion between the layer and the image formed thereon can also be increased, and the image density can be improved.
The addition amount of the alternating copolymer A in the pretreatment liquid is 1 to 500 parts by weight, preferably 10 to 100 parts by weight, with respect to 100 parts by weight of the flocculant.
If necessary, the pretreatment liquid contains a wetting agent, surfactant, penetrating agent, pH adjuster, antiseptic / antifungal agent, chelating reagent, rust inhibitor, antioxidant, ultraviolet absorber, oxygen absorber, and light stability. Various additives such as an agent can be blended. Since these additives are the same as those for the pigment dispersion and the ink, details will be described later.
As a method for treating the surface of the recording medium with the pretreatment liquid, a known method such as an inkjet method, spraying, roll coating, or wire-bar can be used.

The ink of the present invention contains a pigment as a coloring material. Pigments are used from the viewpoint of fading due to light or water-based ink.
Carbon black is preferred as the black pigment. Examples thereof include ketjen black, furnace black, acetylene black, thermal black, and gas black. Further, a carbon black surface that has been oxidized or alkali-treated is also preferred. Carbon black coated with a resin, grafted or encapsulated can also be used.
Examples of the magenta pigment include Pigment Red 5, 7, 12, 48 (Ca), 48 (Mn), 57 (Ca), 57: 1, 112, 122, 123, 168, 184, 202, Pigment Violet 19, and the like. It is done.
Examples of the cyan pigment include pigment blue 1, 2, 3, 15, 15: 3, 15: 4, 16, 22, 60, and bat blue 4, 60.
Examples of the yellow pigment include pigment yellow 1, 2, 3, 12, 13, 14, 16, 17, 73, 74, 75, 83, 93, 95, 97, 98, 114, 120, 128, 129, 138, 150. 151, 154, 155, 180 and the like.
By using Pigment Yellow 74 as the yellow pigment, Pigment Red 122 and Pigment Violet 19 as the magenta pigment, and Pigment Blue 15 as the cyan pigment, it is possible to obtain a balanced ink with excellent color tone and light resistance.
The pigment concentration in the pigment dispersion or pigment ink is preferably 0.1 to 50% by weight, particularly preferably 0.1 to 30% by weight.

A pigment that has been surface-treated (for example, a pigment having a functional group or a pigment coated with a resin) may be used to disperse the pigment regardless of the surfactant. However, the pigment is dispersed using the surfactant. Is advantageous for improving the image density. This is presumably because the pigment aggregates because the surfactant whose ionicity is impaired by the flocculant contained in the pretreatment liquid is easily detached from the pigment.
As the dispersant for dispersing the pigment, various surfactants such as an anionic surfactant, a cationic surfactant, an amphoteric surfactant, and a nonionic surfactant can be used.
Examples of the anionic surfactant include alkyl sulfocarboxylates, α-olefin sulfonates, polyoxyethylene alkyl ether acetates, N-acyl amino acids and salts thereof, N-acyl methyl taurate, alkyl sulfate polyoxy Alkyl ether sulfate, alkyl sulfate polyoxyethylene alkyl ether phosphate, rosin acid soap, castor oil sulfate ester salt, lauryl alcohol sulfate ester salt, alkylphenol type phosphate ester, naphthalene sulfonate formalin condensate, alkyl type phosphate ester, Examples include alkylallylsulfone hydrochloride, diethylsulfosuccinate, and dioctylsulfosuccinate of diethylhexylsulfosuccinate.
Examples of the cationic surfactant include 2-vinylpyridine derivatives and poly-4-vinylpyridine derivatives.
Examples of amphoteric surfactants include lauryldimethylaminoacetic acid betaine, 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine, coconut oil fatty acid amidopropyldimethylaminoacetic acid betaine, polyoctylpolyaminoethylglycine and others Examples include imidazoline derivatives.

Nonionic surfactants include the following.
Ether systems such as polyoxyethylene nonyl phenyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene dodecyl phenyl ether, polyoxyethylene lauryl ether, polyoxyethylene oleyl ether, polyoxyethylene alkyl ether and polyoxyallylalkyl alkyl ether;
Polyoxyethylene oleic acid, polyoxyethylene oleate, polyoxyethylene distearate, sorbitan laurate, sorbitan monostearate, sorbitan monooleate, sorbitan sesquioleate, polyoxyethylene monooleate and polyoxyethylene stearate Ester systems such as
2,4,7,9-tetramethyl-5-decyne-4,7-diol, 3,6-dimethyl-4-octyne-3,6-diol and 3,5-dimethyl-1-hexyn-3-ol Acetylene glycol system such as

When the pigment is carbon black, an anionic surfactant naphthalenesulfonate formalin condensate is most preferred. In particular, when the pigment solid content is 20% by weight or more, the effect is remarkable as compared with other dispersants.
Carbon black having a BET surface area of 100 to 400 m ² / g and a primary particle diameter of 10 to 30 nm is particularly preferable because the density of the printed image is high and stable.
The addition amount of the dispersant needs to be appropriately selected depending on the kind of pigment, but 0.005 to 5 parts by weight is preferable with respect to 1 part by weight of the pigment. When the pigment is carbon black, even if 0.01 to 2 parts by weight with respect to 1 part by weight of the pigment, a uniform dispersion having no practical problem can be obtained, but most preferable is 0.02 to 1 part by weight of the pigment. 0.5 parts by weight. When the content is in the range of 0.01 to 2 parts by weight, the dispersibility of the pigment is improved and the aging stability of the pigment dispersion and the ink tends to be improved. Particularly in the range of 0.02 to 0.5 parts by weight, the temporal stability of the pigment dispersion and the ink is most improved.

  The dispersion medium of the pigment dispersion desirably contains water, but various organic solvents may be used in combination as necessary. For example, as water-soluble organic solvents, alcohols such as methanol, ethanol, 1-propanol and 2-propanol, polyhydric alcohols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol and glycerin, N-methylpyrrolidone, 2-pyrrolidone and the like Pyrrolidone derivatives, ketones such as acetone and methyl ethyl ketone, alkanolamines such as monoethanolamine, diethanolamine, and triethanolamine.

For pigment dispersions and inks, wetting agents, surfactants, penetrants, pH adjusters, antiseptic / antifungal agents, chelating reagents, rust inhibitors, antioxidants, UV absorbers, oxygen absorbers, light stabilizers Various additives such as can be blended.
Examples of the wetting agent are 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, other wetting agents and the like. These may be used alone or in combination of two or more.

Examples of polyhydric alcohols include glycerin, diethylene glycol, 1,3-butanediol, 3-methyl-1,3-butanediol, triethylene glycol, propylene glycol, dipropylene glycol, trimethylolpropane, trimethylolethane, Ethylene glycol, tripropylene glycol, tetraethylene glycol, hexylene glycol, polyethylene glycol, polypropylene glycol, 1,5-pentanediol, 1,6-hexanediol, glycerol, 1,2,6-hexanetriol, 1,2, Examples include 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, propylene glycol monoethyl ether, and the like. It is done.
Examples of polyhydric alcohol aryl ethers include ethylene glycol monophenyl ether and ethylene glycol monobenzyl ether.

Examples of the nitrogen-containing heterocyclic compound include 2-pyrrolidone, N-methyl-2-pyrrolidone, N-hydroxyethyl-2-pyrrolidone, 1,3-dimethylimidazolidinone, ε-caprolactam, γ-butyrolactone, and the like. Is mentioned.
Examples of amides include formamide, N-methylformamide, N, N-dimethylformamide, and the like.
Examples of amines include monoethanolamine, diethanolamine, triethanolamine, monoethylamine, diethylamine, triethylamine, and the like.
Examples of the sulfur-containing compounds include dimethyl sulfoxide, sulfolane, thiodiethanol, and the like.

Other humectants are preferably sugars. Examples of saccharides include monosaccharides, disaccharides, oligosaccharides (including trisaccharides and tetrasaccharides), polysaccharides, and the like. Specific examples include glucose, mannose, fructose, ribose, xylose, arabinose, galactose, maltose, cellobiose, lactose, sucrose, trehalose, maltotriose, and the like. Here, the polysaccharide means a saccharide in a broad sense, and is used to include a substance that exists widely in nature such as α-cyclodextrin and cellulose. Examples of derivatives of these saccharides include reducing sugars of the aforementioned saccharides (for example, sugar alcohols represented by the general formula: HOCH ₂ (CHOH) nCH ₂ OH (n = 2 to 5)), oxidized sugars ( For example, aldonic acid, uronic acid, etc.), amino acids, thioic acid and the like. Among these, sugar alcohols are preferable, and specific examples include maltitol and sorbit.
Among the above wetting agents, glycerin, diethylene glycol, triethylene glycol, 1,3-butanediol, 3-methyl-1,3-butanediol, 2-pyrrolidone, N-methyl from the viewpoint of storage stability and ejection stability. 2-pyrrolidone is particularly preferred.

The blending ratio of the pigment and the wetting agent has a great influence on the stability of ink ejection from the head. If the blending amount of the wetting agent is small even though the pigment solid content is high, the evaporation of water near the ink meniscus of the nozzle may progress, resulting in ejection failure.
The content of the wetting agent in the ink is about 20 to 35% by weight, but more preferably 22.5 to 32.5% by weight. Within this range, the results of ink drying, storage test, reliability test and the like are very good. If the content is less than 20% by weight, the ink may easily dry on the nozzle surface, resulting in ejection failure. If the content exceeds 35% by weight, the dryness on the paper surface is poor and the character quality on plain paper is poor. May decrease.

As the surfactant, those having a low surface tension and a high leveling property are used, depending on the type of pigment and the combination with the wetting agent. For example, fluorine-based surfactants and silicone-based surfactants can be mentioned, and fluorine-based surfactants are preferable.
As the fluorine-based surfactant, those having 2 to 16 carbon atoms substituted by fluorine are preferable, and those having 4 to 16 carbon atoms are more preferable. When the fluorine-substituted carbon number is less than 2, the effect of fluorine may not be obtained, and when it exceeds 16, problems such as ink storage stability may occur.
Examples of fluorosurfactants include perfluoroalkyl sulfonic acid compounds, perfluoroalkyl carboxylic acid compounds, perfluoroalkyl phosphate ester compounds, perfluoroalkyl ethylene oxide adducts, and perfluoroalkyl ether groups in the side chain. And polyoxyalkylene ether polymer compounds. Among these, a polyoxyalkylene ether polymer compound having a perfluoroalkyl ether group in the side chain is particularly preferable because of its low foaming property.

Examples of the perfluoroalkyl sulfonic acid compound include perfluoroalkyl sulfonic acid, perfluoroalkyl sulfonate, and the like.
Examples of the perfluoroalkyl carboxylic acid compound include perfluoroalkyl carboxylic acid and perfluoroalkyl carboxylate.
Examples of the perfluoroalkyl phosphate compound include perfluoroalkyl phosphate esters, perfluoroalkyl phosphate salts, and the like.
The polyoxyalkylene ether polymer compound having a perfluoroalkyl ether group in the side chain includes a polyoxyalkylene ether polymer having a perfluoroalkyl ether group in the side chain, and a polyoxyalkylene ether polymer having a perfluoroalkyl ether group in the side chain. And a salt of a polyoxyalkylene ether polymer having a perfluoroalkyl ether group in the side chain.
As counter ions of salts in these fluorosurfactants, Li, Na, K, NH ₄ , NH ₃ CH ₂ CH ₂ OH, NH ₂ (CH ₂ CH ₂ OH) ₂ , NH (CH ₂ CH ₂ OH) ₃ etc. are mentioned.
As a fluorine-type surfactant, what was synthesize | combined suitably may be used, or a commercial item may be used. Examples of commercially available products include DuPont FS-300, Neos FT-110, FT-250, FT-251, FT-400S, FT-150, FT-400SW, and OM-nova PF-151N. Is mentioned.

The silicone-based surfactant is not particularly limited and may be appropriately selected depending on the purpose, and those that do not decompose even at high pH are preferable. For example, side-chain modified polydimethylsiloxane, both-end modified polydimethylsiloxane, piece Examples include terminal-modified polydimethylsiloxane and side-chain both-end-modified polydimethylsiloxane, and those having a polyoxyethylene group or polyoxyethylene polyoxypropylene group as a modifying group exhibit good properties as an aqueous surfactant. preferable.
As a silicone type surfactant, you may use what was synthesize | combined suitably or may use a commercial item. Commercially available products can be easily obtained from, for example, Big Chemie, Shin-Etsu Silicone, Toray Dow Corning Silicone.
The content of the surfactant in the ink is preferably 0.01 to 3.0% by weight, and more preferably 0.5 to 2% by weight. If the content is less than 0.01% by weight, the effect of adding the surfactant may be lost. If the content exceeds 3.0% by weight, the permeability to the recording medium becomes higher than necessary, and the image density decreases. And strikethrough may occur.

The penetrant preferably contains at least one polyol compound having a solubility in water at 20 ° C. of 0.2 to 5.0% by weight. Examples of such a polyol compound include 2-ethyl-2-methyl-1,3-propanediol, 3,3-dimethyl-1,2-butanediol, and 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-1,2- Examples thereof include aliphatic diols such as diol and 2-ethyl-1,3-hexanediol.
Among these, 2-ethyl-1,3-hexanediol and 2,2,4-trimethyl-1,3-pentanediol are particularly preferable.

Other penetrants that can be used in combination are not particularly limited as long as they can be dissolved in the ink and adjusted to the desired physical properties, and can be appropriately selected according to the purpose. For example, diethylene glycol monophenyl ether, ethylene Examples thereof include alkyl and aryl ethers of polyhydric alcohols such as glycol monophenyl ether, ethylene glycol monoallyl ether, diethylene glycol monobutyl ether, propylene glycol monobutyl ether and tetraethylene glycol chlorophenyl ether, and lower alcohols such as ethanol.
The content of the penetrant in the ink is preferably 0.1 to 4.0% by weight. If the content is less than 0.1% by weight, quick-drying may not be obtained and a blurred image may be obtained. If the content exceeds 4.0% by weight, the dispersion stability of the colorant is impaired, and the nozzle is easily clogged. Or the permeability to the recording medium is unnecessarily high, and the image density may be lowered or the image may be broken through.

The pH adjuster is not particularly limited as long as it can adjust the pH to 7 to 11 without adversely affecting the ink to be prepared, and can be appropriately selected according to the purpose. And alkali metal hydroxides, ammonium hydroxides, phosphonium hydroxides, alkali metal carbonates, and the like. When the pH is less than 7 or exceeds 11, the amount of the ink-jet head or ink supply unit that melts out increases, and problems such as ink deterioration, leakage, and ejection failure may occur.
Examples of alcohol amines include diethanolamine, triethanolamine, 2-amino-2-ethyl-1,3-propanediol, and the like.
Examples of the alkali metal hydroxide include lithium hydroxide, sodium hydroxide, and potassium hydroxide.
Examples of the ammonium hydroxide include ammonium hydroxide, quaternary ammonium hydroxide, quaternary phosphonium hydroxide, and the like.
Examples of the alkali metal carbonate include lithium carbonate, sodium carbonate, and potassium carbonate.

Examples of the antiseptic / antifungal agent include sodium dehydroacetate, sodium sorbate, 2-pyridinethiol-1-oxide sodium, sodium benzoate, sodium pentachlorophenol, and the like.
Examples of the chelating reagent include sodium ethylenediaminetetraacetate, sodium nitrilotriacetate, sodium hydroxyethylethylenediaminetriacetate, sodium diethylenetriaminepentaacetate, sodium uramil diacetate, and the like.
Examples of the rust preventive include acidic sulfite, sodium thiosulfate, ammonium thiodiglycolate, diisopropylammonium nitrite, pentaerythritol tetranitrate, dicyclohexylammonium nitrite and the like.

Examples of the antioxidant include phenol-based antioxidants (including hindered phenol-based antioxidants), amine-based antioxidants, sulfur-based antioxidants, phosphorus-based antioxidants, and the like.
Examples of phenolic antioxidants (including hindered phenolic antioxidants) include butylated hydroxyanisole, 2,6-di-tert-butyl-4-ethylphenol, 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'-butylidenebis (3-methyl-6-tert-butylphenol), 3,9-bis [1,1-dimethyl-2- [β- (3-tert-butyl-4-hydroxy-5-methylphenyl) Propionyloxy] ethyl] -2,4,8,10-tetrixaspiro [5,5] undecane, 1,1,3-to Lis (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) Benzene, tetrakis [methylene-3- (3 ′, 5′-di-tert-butyl-4′-hydroxyphenyl) propionate] methane, and the like.

  Examples of amine-based antioxidants include phenyl-β-naphthylamine, α-naphthylamine, N, N′-di-sec-butyl-p-phenylenediamine, phenothiazine, N, N′-diphenyl-p-phenylenediamine, 2,6-di-tert-butyl-p-cresol, 2,6-di-tert-butylphenol, 2,4-dimethyl-6-tert-butyl-phenol, butylhydroxyanisole, 2,2'-methylenebis (4 -Methyl-6-tert-butylphenol), 4,4'-butylidenebis (3-methyl-6-tert-butylphenol), 4,4'-thiobis (3-methyl-6-tert-butylphenol), tetrakis [methylene- 3 (3,5-di-tert-butyl-4-dihydroxyphenyl) propionate And methane, 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, and the like.

Examples of the sulfur-based antioxidant include dilauryl-3,3′-thiodipropionate, distearyl thiodipropionate, lauryl stearyl thiodipropionate, dimyristyl-3,3′-thiodipropionate, distearyl. -Β, β'-thiodipropionate, 2-mercaptobenzimidazole, dilauryl sulfide and the like.
Examples of the phosphorus antioxidant include triphenyl phosphite, octadecyl phosphite, triisodecyl phosphite, trilauryl trithiophosphite, and trinonylphenyl phosphite.

Examples of the ultraviolet absorber include a benzophenone ultraviolet absorber, a benzotriazole ultraviolet absorber, a salicylate ultraviolet absorber, a cyanoacrylate ultraviolet absorber, and a nickel complex ultraviolet absorber.
Examples of benzophenone-based ultraviolet absorbers include 2-hydroxy-4-n-octoxybenzophenone, 2-hydroxy-4-n-dodecyloxybenzophenone, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone and the like can be mentioned.
Examples of the benzotriazole ultraviolet absorber include 2- (2′-hydroxy-5′-tert-octylphenyl) benzotriazole, 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- ( 2'-hydroxy-4'-octoxyphenyl) benzotriazole, 2- (2'-hydroxy-3'-tert-butyl-5'-methylphenyl) -5-chlorobenzotriazole and the like.
Examples of salicylate-based ultraviolet absorbers include phenyl salicylate, p-tert-butylphenyl salicylate, p-octylphenyl salicylate, and the like.
Examples of the cyanoacrylate ultraviolet absorber include ethyl-2-cyano-3,3′-diphenyl acrylate, methyl-2-cyano-3-methyl-3- (p-methoxyphenyl) acrylate, and butyl-2- And cyano-3-methyl-3- (p-methoxyphenyl) acrylate.
Examples of the nickel complex ultraviolet absorber include nickel bis (octylphenyl) sulfide, 2,2′-thiobis (4-tert-octylferrate) -n-butylamine nickel (II), 2,2′-thiobis ( 4-tert-octylferrate) -2-ethylhexylamine nickel (II), 2,2′-thiobis (4-tert-octylferrate) triethanolamine nickel (II), and the like.

The inkjet recording ink containing the pigment used in the present invention is a known method, for example, a pigment dispersion, water, a water-soluble organic solvent, a surfactant, etc., sand mill, ball mill, roll mill, bead mill, nanomizer, homogenizer, ultrasonic dispersion. It is obtained by stirring and mixing using a machine, etc., filtering coarse particles with a filter, a centrifugal separator or the like, and deaeration as necessary.
The concentration of the pigment in the ink is preferably 1 to 20% by weight based on the total amount of the ink. If it is less than 1% by weight, the image density is low, so that the printing is not clear. If it is more than 20% by weight, not only the viscosity of the ink tends to be high, but also nozzle clogging tends to occur.
The content of the water-soluble organic solvent is 50% by weight or less, preferably 5 to 40% by weight, more preferably 10 to 35% by weight, based on the total amount of the ink.
In addition, the ink may be blended with additives similar to the materials described for the additive to the pigment dispersion, if necessary.

The pretreatment liquid and inkjet recording ink can be stored in separate containers and used as cartridges.
Further, the pretreatment liquid of the present invention and the ink for ink jet recording may be accommodated in the same container to form a cartridge.
And it can print on a recording medium (for example, printing paper) using the inkjet recording device carrying these cartridges, and can obtain an image formation.
As a printing method, there are a continuous jet type and an on-demand type, and examples of the on-demand type include a piezo method, a thermal method, and an electrostatic method.

An example of the image forming method of the present invention and an ink jet recording apparatus for carrying out the method will be described with reference to the drawings.
The ink jet recording apparatus (1) shown in FIG. 1 is equipped with a cartridge (20) containing pretreatment liquid and ink, and the recording head from which pretreatment liquid and ink are loaded on a carriage (18). (Inkjet head). Here, the cartridge (20) is mounted in a state where the pretreatment liquid and the ink for each color are separated.
The recording head moves in the main scanning direction via the carriage (18) by driving the main scanning motor (26). That is, when the main scanning motor (26) is driven, the timing belt (23) travels, and the carriage (18) fixed to the timing belt (23) is guided and moved by the guide shafts (21) and (22). On the other hand, the recording medium is intermittently fed in the sub-scanning direction by driving the sub-scanning motor (17). In this way, while performing the main scanning of the recording head and the sub-scanning of the recording medium, after discharging the pretreatment liquid from the recording head to the recording medium, the ink is discharged from the recording head onto the surface of the recording medium. Form an image.

The recording head has a nozzle row that ejects a pretreatment liquid and a plurality of nozzle rows by color that eject ink of each color (for example, yellow ink, magenta ink, cyan ink, and black ink). The arrangement of the nozzle rows is arbitrary. For example, the nozzle row for discharging the pretreatment liquid and the plurality of nozzle rows for discharging the ink of each color are arranged in the sub-scanning direction, and the ink of each color is discharged. A plurality of nozzle rows are arranged so as to be aligned in the main scanning direction. In addition, a plurality of nozzle rows that discharge ink of each color may be arranged in the main scanning direction, and a nozzle row that discharges the pretreatment liquid may be arranged so as to be positioned before and after the main scanning direction. Good.
In the latter arrangement, since the pretreatment liquid discharge nozzles are provided before and after the main scanning direction, printing is possible both in the forward path and the backward path in which the recording head reciprocates on the carriage. In other words, it is possible to apply the pretreatment liquid first in both the forward path and the backward path, and then apply the ink from the top, or vice versa, resulting in an image density difference due to the difference in the moving direction of the recording head. Absent.
The ink jet recording apparatus can be replenished with pretreatment liquid and ink by replacing the cartridge. Further, this cartridge may be integrated with the recording head.

  Most preferably, the ink and the pretreatment liquid are discharged from the recording head in the same location. However, in the present invention, for example, the pretreatment liquid is thinned out and applied, and the ink is overlaid on the pretreatment liquid enlarged by bleeding or the like, or the pretreatment liquid is applied only to the contour portion of the image, and the ink is formed thereon. A sufficient effect can be obtained by overlapping a part of the above.

  According to the present invention, there is provided an image forming method with few defects due to rubbing or the like of printed images (excellent smear resistance), a pretreatment liquid used for the method, a set of the pretreatment liquid and an ink jet recording ink, It is possible to provide a cartridge in which a treatment liquid or set is contained in a container, an ink jet recording apparatus equipped with the cartridge, and an image formed product recorded by the ink jet recording apparatus.

1 shows an example of an ink jet recording apparatus.

EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated further more concretely, this invention is not limited by these Examples.
In Examples and Comparative Examples, pigment dispersions were prepared and inks were prepared using the pigment dispersions. Moreover, the pre-processing liquid was created, respectively. In the examples, “parts” and “%” are based on weight.

Example 1
<Preparation of pigment dispersion 1>
After pre-mixing materials with the following formulation, disperse for 5 minutes at a peripheral speed of 10 m / s and a liquid temperature of 10 ° C. using 0.3 mm zirconia beads with a disk-type bead mill (KDL type batch type manufactured by Shinmaru Enterprises). did. Subsequently, coarse particles were separated by a centrifugal separator (Model-3600, manufactured by Kubota Corporation) to obtain a carbon black pigment dispersion 1 having an average particle diameter of about 120 nm and a standard deviation of 51.2 nm.
(Pigment dispersion formulation)
・ Carbon black (manufactured by degussa: gas black, NIPEX150-IQ)
20 parts ・ Naphthalenesulfonic acid formalin condensate Na salt (10% aqueous solution) 30 parts ・ Distilled water 50 parts

<Creation of ink 1>
Ink 1 was prepared by mixing and stirring materials having the following formulation for 30 minutes.
(Ink formulation)
Pigment dispersion 1 (pigment concentration 20%) 40.0 parts Glycerol 5.5 parts 1,3-butanediol 16.5 parts 2-ethyl-1,3-hexanediol 2.0 parts Fluorine-based Surfactant (solid content 40%) 2.5 parts (DuPont: Zonyl FS-300)
Fluoroethylene / vinyl ether alternating copolymer (solid content 50%) 6.0 parts (Asahi Glass Co., Ltd .: Lumiflon FE4300, average particle size 150 nm,
MFT 30 ℃ or less)
・ 27.5 parts distilled water

<Preparation of pretreatment liquid 1>
The material of the following prescription was mixed and stirred to prepare Pretreatment Liquid 1.
(Pretreatment liquid formulation)
・ Calcium chloride aqueous solution (concentration 20%) 40.0 parts ・ Glycerin 5.5 parts ・ 1,3-butanediol 16.5 parts ・ 2-ethyl-1,3-hexanediol 2.0 parts ・ Fluorine-based surface activity Agent (solid content 40%) 2.5 parts (manufactured by DuPont, Zonyl FS-300)
Fluoroethylene / vinyl ether alternating copolymer (solid content 50%) 3.0 parts (manufactured by Asahi Glass Co., Ltd., Lumiflon FE4300: average particle diameter 150 nm,
MFT 30 ℃ or less)
・ Distilled water 30.5 parts

Example 2
<Preparation of pretreatment liquid 2>
The calcium chloride aqueous solution in the pretreatment liquid 1 of Example 1 was changed to 44.0 parts of octadecyl isocyanate-modified polyethyleneimine (manufactured by Nippon Shokubai Co., Ltd .: RP-18W, solid content 18%), and distilled water was changed to 26.5 parts. A pretreatment liquid 2 was prepared in the same manner as in Example 1 except for the above points.
Ink 1 prepared in Example 1 was used as ink 2.

Example 3
<Preparation of pretreatment liquid 3>
A pretreatment liquid 3 was prepared in the same manner as in Example 1 except that the calcium chloride aqueous solution in the pretreatment liquid 1 of Example 1 was changed to a lactic acid aqueous solution (solid content 30%).
Ink 1 prepared in Example 1 was used as ink 3.

Example 4
<Creation of ink 4>
Ink 4 was prepared by mixing and stirring materials having the following formulation for 30 minutes.
(Ink formulation)
Pigment dispersion 1 (pigment concentration 20%) 40.0 parts Glycerol 5.5 parts 1,3-butanediol 16.5 parts 2-ethyl-1,3-hexanediol 2.0 parts Fluorine-based Surfactant (solid content 40%) 2.5 parts (DuPont: Zonyl FS-300)
Fluoroethylene / vinyl ether alternating copolymer (solid content 50%) 6.0 parts (Asahi Glass Co., Ltd .: Lumiflon FE4300, average particle size 150 nm,
MFT 30 ℃ or less)
・ Distilled water 24.8 parts ・ Acrylic silicone resin (solid content 37%) 2.7 parts (Showa Polymers Co., Ltd .: Polysol 6312)
Note that the pretreatment liquid 1 prepared in Example 1 was used as the pretreatment liquid 4.

Example 5
<Creation of ink 5>
Other than the point that the acrylic silicone resin in the ink 4 of Example 4 was changed to 2.0 parts of styrene-butadiene resin (manufactured by Japan A & L: SR-113, solid content 48%) and distilled water was changed to 25.5 parts. In the same manner as in Example 4, ink 5 was prepared.
Note that the pretreatment liquid 1 prepared in Example 1 was used as the pretreatment liquid 5.

Example 6
<Creation of ink 6>
Except that the acrylic silicone resin in ink 4 of Example 4 was changed to 5.0 parts of styrene-acrylic resin (manufactured by Starlight PMC: T-YP198, solid content 20%) and distilled water was changed to 22.5 parts. Produced an ink 6 in the same manner as in Example 4.
Note that the pretreatment liquid 1 prepared in Example 1 was used as the pretreatment liquid 6.

Example 7
<Creation of ink 7>
The acrylic silicone resin in the ink 4 of Example 4 was changed to 4.4 parts of α-olefin-maleic anhydride resin (manufactured by Seiko PMC: T-YP115, solid content 23%), and distilled water was changed to 23.1 parts. Ink 7 was prepared in the same manner as in Example 4 except for the changes.
Note that the pretreatment liquid 1 prepared in Example 1 was used as the pretreatment liquid 7.

Example 8
<Creation of ink 8>
The point that the acrylic silicone resin in the ink 4 of Example 4 was changed to 2.2 parts of an ester type polyurethane resin (Dainippon Ink Co., Ltd .: APX-101H, solid content 45%), and distilled water was changed to 25.3 parts. Except for the above, ink 8 was prepared in the same manner as in Example 4.
Note that the pretreatment liquid 1 prepared in Example 1 was used as the pretreatment liquid 8.

Example 9
<Creation of ink 9>
The point that the acrylic silicone resin in the ink 4 of Example 4 was changed to 3.3 parts of carbonate type polyurethane resin (manufactured by Dainichi Seika Co., Ltd .: D-6300, solid content 30%), and distilled water was changed to 24.2 parts. Except for the above, an ink 9 was prepared in the same manner as in Example 4.
Note that the pretreatment liquid 1 prepared in Example 1 was used as the pretreatment liquid 9.

Example 10
<Creation of ether type polyurethane resin 1>
Into a four-necked flask equipped with a thermometer, a nitrogen gas inlet tube, a stirrer, and a reflux condenser, the raw material having the following formulation was added and reacted at 80 ° C. for 3 hours, and then 0.01 part of dibutyltin dilaurate was added and The reaction was carried out at 80 ° C. for 5 hours.
After allowing the reaction mixture to cool, 1 part of ethylenediamine was added and reacted for 1 hour to obtain a solution of ether type polyurethane resin 1 having an acid value of 70 KOHmg / mg and a number average molecular weight of 15,000. Thereafter, the solid content was adjusted to 20% with distilled water.
(Raw material formulation)
・ Methyl ethyl ketone 90 parts ・ Dimethylolpropionic acid 13 parts ・ Polylactone diol 52 parts ・ Isophorone diisocyanate 35 parts

<Creation of ink 10>
In the same manner as in Example 4, except that the acrylic silicone resin in the ink 4 of Example 4 was changed to 5 parts of the ether type polyurethane resin 1 (solid content 20%) and the distilled water was changed to 22.5 parts. Ink 10 was prepared.
Note that the pretreatment liquid 1 prepared in Example 1 was used as the pretreatment liquid 10.

Example 11
<Creation of ink 11>
Ink 11 was prepared in the same manner as in Example 10 except that the ratio of raw materials in ether type polyurethane resin 1 of Example 10 was adjusted and ether type polyurethane resin 2 having an acid value of 80 KOH mg / mg was prepared and used. .
Note that the pretreatment liquid 1 prepared in Example 1 was used as the pretreatment liquid 11.

Example 12
<Creation of ink 12>
Ink 12 was prepared in the same manner as in Example 10 except that the ratio of raw materials in ether type polyurethane resin 1 of Example 10 was adjusted and ether type polyurethane resin 3 having an acid value of 90 KOH mg / mg was prepared and used. .
Note that the pretreatment liquid 1 prepared in Example 1 was used as the pretreatment liquid 12.

Example 13
<Creation of ink 13>
Ink 13 was prepared in the same manner as in Example 10 except that the ratio of the raw materials in ether type polyurethane resin 1 of Example 10 was adjusted and ether type polyurethane resin 4 having an acid value of 100 KOH mg / mg was prepared and used. .
Note that the pretreatment liquid 1 prepared in Example 1 was used as the pretreatment liquid 13.

Example 14
<Creation of ink 14>
Ink 14 was prepared in the same manner as in Example 10 except that the ratio of raw materials in ether type polyurethane resin 1 of Example 10 was adjusted and ether type polyurethane resin 5 having an acid value of 40 KOH mg / mg was prepared and used. .
Note that the pretreatment liquid 1 prepared in Example 1 was used as the pretreatment liquid 14.

Example 15
<Creation of ink 15>
Ink 15 was prepared in the same manner as in Example 10, except that the ratio of the raw materials in ether type polyurethane resin 1 of Example 10 was adjusted and ether type polyurethane resin 6 having an acid value of 50 KOH mg / mg was prepared and used. .
Note that the pretreatment liquid 1 prepared in Example 1 was used as the pretreatment liquid 15.

Example 16
<Creation of ink 16>
The pigment dispersion 1 in the ink 1 of Example 1 was changed to 53.3 parts of pigment dispersion 2 (carboxyl group-grafted carbon black dispersion, manufactured by Cabot Corporation: CAB-O-JET300, solid content 15%), and distilled. Ink 16 was prepared in the same manner as in Example 1 except that the water was changed to 14.2 parts.
Note that the pretreatment liquid 1 prepared in Example 1 was used as the pretreatment liquid 16.

Example 17
<Preparation of pretreatment liquid 17>
A pretreatment liquid 17 was prepared in the same manner as in Example 1 except that the fluoroethylene / vinyl ether alternating copolymer was not added in the pretreatment liquid 1 of Example 1 and distilled water was changed to 33.5 parts. .
Ink 1 prepared in Example 1 was used as ink 17.

Example 18
<Creation of ink 18>
Ink 18 was prepared in the same manner as in Example 1 except that the fluoroethylene / vinyl ether alternating copolymer was not added to Ink 1 of Example 1 and the distilled water was changed to 33.5 parts.
Note that the pretreatment liquid 1 prepared in Example 1 was used as the pretreatment liquid 18.

Example 19
<Preparation of pretreatment liquid 19>
The calcium chloride aqueous solution in the pretreatment liquid 1 of Example 1 was changed to 44.0 parts of octadecyl isocyanate modified polyethyleneimine (manufactured by Nippon Shokubai Co., Ltd .: RP-18W, solid content 18%), and a fluoroethylene / vinyl ether alternating copolymer was changed to A pretreatment liquid 19 was prepared in the same manner as in Example 1 except that the distilled water was changed to 26.5 parts without adding it. Ink 1 prepared in Example 1 was used as ink 19.

Example 20
Instead of carbon black of Example 1 (pigment dispersion formulation), Pigment Red 122 (FASTOGEN SUPER MAGENTA RG, manufactured by Dainippon Ink Co., Ltd.) was used instead of Naphthalenesulfonic acid formalin condensate Na salt (10% aqueous solution) A pigment dispersion 3 was prepared in the same manner as in Example 1 except that polyoxyethylene (n = 40) -β-naphthyl ether (10% aqueous solution) was used, and this was used to prepare the ink of Example 20. Created.

Comparative Example 1
<Creation of ink 20>
Ink 20 was prepared in the same manner as in Example 1 except that the fluoroethylene / vinyl ether alternating copolymer was not added to Ink 1 of Example 1 and the distilled water was changed to 33.5 parts.
<Preparation of pretreatment liquid 20>
A pretreatment liquid 20 was prepared in the same manner as in Example 1 except that the fluoroethylene / vinyl ether alternating copolymer was not added to the pretreatment liquid 1 of Example 1 and the distilled water was changed to 33.5 parts. .

Comparative Example 2
<Creation of ink 21>
The alternating fluoroethylene / vinyl ether copolymer in Ink 1 of Example 1 was changed to 7.5 parts of a fluoroethylene / vinyl ester copolymer (Dainippon Ink Co., Ltd .: Fluorate FEM500, solid content adjusted to 40%) and distilled. Ink 21 was prepared in the same manner as in Example 1 except that the water was changed to 26.0 parts.
<Preparation of pretreatment liquid 21>
The fluoroethylene / vinyl ether alternating copolymer in the pretreatment liquid 1 of Example 1 is changed to 3.8 parts of a fluoroethylene / vinyl ester copolymer (Dainippon Ink Co., Ltd .: Fluorate FEM500, solid content adjusted 40%). A pretreatment liquid 21 was prepared in the same manner as in Example 1 except that the distilled water was changed to 29.7 parts.

Comparative Example 3
<Creation of ink 22>
Distilled water is obtained by changing the fluoroethylene / vinyl ether alternating copolymer in ink 1 of Example 1 to 7.5 parts of a fluorinated acrylic resin (Dainippon Ink Co., Ltd .: Aquafuran TE-5A, adjusted to 40% solid content). Ink 22 was prepared in the same manner as in Example 1 except that the value of was changed to 26.0 parts.
<Preparation of pretreatment liquid 22>
The fluoroethylene / vinyl ether alternating copolymer in the pretreatment liquid 1 of Example 1 was changed to 3.8 parts of a fluorinated acrylic resin (manufactured by Dainippon Ink Co., Ltd .: Aquafuran TE-5A, adjusted to 40% solid content), A pretreatment liquid 22 was prepared in the same manner as in Example 1 except that distilled water was changed to 29.7 parts.

Comparative Example 4
<Creation of ink 23>
The fluoroethylene / vinyl ether alternating copolymer in ink 1 of Example 1 was changed to 6.3 parts of styrene butadiene resin (manufactured by Japan A & L: SR-113, solid content 48%), and distilled water was changed to 27.2 parts. Ink 23 was prepared in the same manner as in Example 1 except for the changes.
<Preparation of pretreatment liquid 23>
The fluoroethylene / vinyl ether alternating copolymer in the pretreatment liquid 1 of Example 1 was changed to 3.1 parts of a styrene butadiene resin (manufactured by Japan A & L: SR-113, solid content 48%), and distilled water was 30.4. A pretreatment liquid 23 was prepared in the same manner as in Example 1 except that the part was changed to the part.

Comparative Example 5
<Creation of ink 24>
The fluoroethylene / vinyl ether alternating copolymer in ink 1 of Example 1 was changed to 6.7 parts of an ester type polyurethane resin (manufactured by Dainippon Ink Co., Ltd .: APX-101H, solid content 45%), and distilled water was 26.8. An ink 24 was prepared in the same manner as in Example 1 except that the part was changed to the part.
<Preparation of pretreatment liquid 24>
The alternating copolymer of fluoroethylene / vinyl ether in the pretreatment liquid 1 of Example 1 was changed to 3.3 parts of an ester type polyurethane resin (manufactured by Dainippon Ink Co., Ltd .: APX-101H, solid content 45%), and distilled water was added to 30 parts. A pretreatment liquid 24 was prepared in the same manner as in Example 1 except that the amount was changed to 2 parts.

Comparative Example 6
<Creation of ink 25>
The fluoroethylene / vinyl ether alternating copolymer in ink 1 of Example 1 was changed to 15.0 parts of styrene-acrylic resin (manufactured by Starlight PMC: T-YP198, solid content 20%), and 18.5 parts of distilled water was used. Ink 25 was prepared in the same manner as in Example 1 except that it was changed to.
<Preparation of pretreatment liquid 25>
The fluoroethylene / vinyl ether alternating copolymer in the pretreatment liquid 1 of Example 1 was changed to 7.5 parts of styrene-acrylic resin (manufactured by Starlight PMC: T-YP198, solid content 20%), and distilled water was changed to 26. A pretreatment liquid 25 was prepared in the same manner as in Example 1 except that the amount was changed to 0 part.

Comparative Example 7
<Creation of ink 26>
An ink 26 was prepared in the same manner as in Comparative Example 1 except that the dispersion 3 prepared in Example 20 was used.
Note that the pretreatment liquid 1 prepared in Comparative Example 1 was used as the pretreatment liquid 26.

The inks 1 to 25 and the pretreatment liquids 1 to 25 of the above examples and comparative examples were filled in a cartridge, mounted on an ink jet printer (see FIG. 1) manufactured by Ricoh, and a printing experiment was performed. Concentration and smear resistance were evaluated. The results are shown in Tables 1 and 2.
(1) Image density One sheet was printed on Xerox PPC paper 4024 (non-smooth paper), and the printed image was measured with an Xrite densitometer. Larger numbers are better.
(2) Smear resistance An image of 5 cm × 5 cm is printed on Xerox PPC paper 4024 (non-smooth paper), and the printed image surface is rubbed 5 times with a cotton cloth set on a clock meter (manufactured by Atlas). The image density of the ink transferred to the cotton cloth was measured with an Xrite densitometer. Smaller numbers are better.

As can be seen from Tables 1 and 2, in Examples 1 to 19 including the alternating copolymer A as the aqueous resin when the black pigment was used as the pigment, Comparative Example 1 and the alternating copolymer A including no aqueous resin were used. Compared to Comparative Examples 2 to 6 containing other water-based resins, the smear resistance is superior to non-smooth paper. In particular, in Examples 1 to 16 in which both the pretreatment liquid and the ink contain the alternating copolymer A, compared to Examples 17 to 19 in which only one of the pretreatment liquid and the ink contains the alternating copolymer A. The effect is even better. Similarly, when a magenta pigment is used as the pigment, Example 20 containing the alternating copolymer A as a water-based resin is superior in smear resistance to non-smooth paper as compared with Comparative Example 7 not containing a water-based resin. ing.
Also, with respect to image density, the examples are generally better than the comparative examples, and the examples 4 to 15 including the aggregated resin are superior to the examples 1 to 3 and 16 that do not include the aggregated resin. Yes. The image density of Example 16 is comparable to that of the comparative example because one of the reasons is that pigment dispersion 2 (carboxyl group-grafted carbon black dispersion) was used instead of pigment dispersion 1. .

1 Inkjet recording device 17 Sub-scanning motor 18 Carriage 20 Cartridge 26 Main scanning motor

Claims (11)

  A method of forming an image on a surface of a recording medium using an ink for ink jet recording containing water and a pigment after pretreating the surface of the recording medium using a pretreatment liquid containing water and a coagulant for ink jet recording ink An image forming method, wherein at least one of the pretreatment liquid and the inkjet recording ink contains a fluoroethylene / vinyl ether alternating copolymer.   The image forming method according to claim 1, wherein the ink for inkjet recording contains a resin that causes aggregation by the pretreatment liquid.   The image forming method according to claim 2, wherein the resin causing aggregation by the pretreatment liquid is an ether type polyurethane resin.   A pretreatment liquid for a recording medium comprising water, an aggregating agent for ink jet recording ink, and a fluoroethylene / vinyl ether alternating copolymer.   A recording medium pretreatment liquid containing water, an inkjet recording ink flocculant and a fluoroethylene / vinyl ether alternating copolymer, and an ink jet recording ink containing water, a pigment and a fluoroethylene / vinyl ether alternating copolymer A set of a recording medium pretreatment liquid and an inkjet recording ink.   6. The set of a pretreatment liquid for a recording medium and an ink for ink jet recording according to claim 5, wherein the ink for ink jet recording contains a resin that causes aggregation by the pretreatment liquid.   The set of a pretreatment liquid for a recording medium and an ink for ink jet recording according to claim 6, wherein the resin that causes aggregation by the pretreatment liquid is an ether type polyurethane resin.   A cartridge characterized in that the recording medium pretreatment liquid according to claim 4 is contained in a container.   A recording medium pretreatment liquid and an ink jet recording ink constituting a set of a recording medium pretreatment liquid and an ink jet recording ink according to any one of claims 5 to 7 are contained in a container. cartridge.   An ink jet recording apparatus on which the cartridge according to claim 8 is mounted.   An image formed matter printed by the ink jet recording apparatus according to claim 10.

Images