JP7176215B2 - Liquid set, recording device, recording method, and recorded matter - Google Patents

Description

The present invention relates to a liquid set, recording apparatus, recording method, and recorded matter.

2. Description of the Related Art As a method for drying ink ejected onto a printing medium such as a recording medium, a method of blowing hot air onto the ink on the printing medium to dry the ink is known. Another known method is to irradiate the ink on the printing material with light including infrared rays to dry the ink. This method of drying by irradiating with light containing infrared rays has been attracting attention in recent years because it is superior to the method of drying by blowing hot air on the ink and can shorten the time required for drying the ink. ing.

In Patent Document 1, for the purpose of improving the drying speed of the ink, an ink for inkjet recording containing a coloring agent and water and an ink for inkjet recording containing an infrared absorbing agent are applied onto a recording medium before being discharged. and a treatment liquid to be ejected onto the inkjet ink set.

Patent Document 2 discloses a combination of one or more water-based colored inks and a water-based overcoat ink for the purpose of improving the weather resistance of a printed layer. , a resin, a UV absorber and water.

However, when the pretreatment liquid to be applied to the printed material contains an infrared absorbing agent and is heated by irradiating infrared rays, the printed material is directly heated, so there is a problem that deterioration such as deformation occurs in the printed material. In addition, when a post-treatment liquid containing an ultraviolet absorber is applied to a liquid composition such as an ink applied to a printed material and then heated, the ultraviolet absorber may be deactivated by heating, and in the presence of ultraviolet rays There is a problem that deterioration such as discoloration occurs in the layer formed by the liquid composition when used in .

The invention according to claim 1 is a pretreatment liquid that is applied to an object to be printed and contains first inorganic particles having a volume average particle diameter of 300 nm or more, wherein the first inorganic particles are metal particles. a certain pretreatment liquid, a liquid composition applied to a region of the substrate to which the pretreatment liquid has been applied, and a liquid composition applied to a region of the substrate to which the liquid composition has been applied; and a post-treatment liquid containing second inorganic particles having a volume average particle diameter of 200 nm or less , wherein the first inorganic particles account for 2.0 mass % or more of the total amount of the pre-treatment liquid5. The liquid set contains 0% by mass or less, and the second inorganic particles are contained in an amount of 2.0% by mass or more and 5.0% by mass or less with respect to the total amount of the post-treatment liquid .

The liquid set of the present invention exhibits an excellent effect of suppressing deterioration such as deformation in the printed material and suppressing deterioration such as discoloration in the layer formed by the liquid composition.

FIG. 1 is a perspective explanatory view showing an example of a recording apparatus. FIG. 2 is a perspective explanatory view showing an example of the main tank.

Embodiments of the present invention will be described below.

[Liquid set]
In the liquid set of the present embodiment, a pretreatment liquid containing first inorganic particles having a volume average particle diameter of 300 nm or more is applied to a printing material, and a pretreatment liquid is applied to the printing material. and a post-treatment liquid containing second inorganic particles having a volume average particle diameter of 200 nm or less, which is applied to the area of the substrate to which the liquid composition has been applied, and have The liquid set may be a set containing liquids other than the pre-treatment liquid, the liquid composition, and the post-treatment liquid. Also, the pretreatment liquid, the liquid composition, and the posttreatment liquid may each be one type of liquid or multiple types of liquids.

<< liquid composition >>
The liquid composition is a liquid applied to the area of the substrate to which the pretreatment liquid has been applied. This liquid contains additives such as an infrared absorbing agent, an organic solvent, water, a coloring material, a resin, and a surfactant as necessary. Note that the liquid composition is preferably ink. In the following description, the “liquid composition” is referred to as “ink” for convenience of explanation, but the application of the liquid composition is not limited to ink.

<Water>
The content of water in the ink is not particularly limited and can be appropriately selected according to the purpose. % or more and 60 mass % or less is more preferable.

<Organic solvent>
The organic solvent that can be used in this embodiment is not particularly limited, and a water-soluble organic solvent can be used. Examples thereof include polyhydric alcohols, ethers such as polyhydric alcohol alkyl ethers and polyhydric alcohol aryl ethers, nitrogen-containing heterocyclic compounds, amides, amines, and sulfur-containing compounds.
Specific examples of polyhydric alcohols include ethylene glycol, diethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, and 1,4-butane. Diol, 2,3-butanediol, 3-methyl-1,3-butanediol, triethylene glycol, polyethylene glycol, polypropylene glycol, 1,2-pentanediol, 1,3-pentanediol, 1,4-pentanediol , 2,4-pentanediol, 1,5-pentanediol, 1,2-hexanediol, 1,6-hexanediol, 1,3-hexanediol, 2,5-hexanediol, 1,5-hexanediol, glycerin, 1,2,6-hexanetriol, 2-ethyl-1,3-hexanediol, ethyl-1,2,4-butanetriol, 1,2,3-butanetriol, 2,2,4-trimethyl- 1,3-pentanediol, petriol and the like.
Examples of 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.
Examples of polyhydric alcohol aryl ethers include ethylene glycol monophenyl ether and ethylene glycol monobenzyl ether.
Nitrogen-containing heterocyclic compounds include 2-pyrrolidone, N-methyl-2-pyrrolidone, N-hydroxyethyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, ε-caprolactam, γ-butyrolactone and the like. mentioned.
Amides include formamide, N-methylformamide, N,N-dimethylformamide, 3-methoxy-N,N-dimethylpropionamide, 3-butoxy-N,N-dimethylpropionamide and the like.
Amines include monoethanolamine, diethanolamine, triethylamine, and the like.
Examples of sulfur-containing compounds include dimethylsulfoxide, sulfolane, thiodiethanol and the like.
Other organic solvents include propylene carbonate and ethylene carbonate.
It is preferable to use an organic solvent having a boiling point of 250° C. or less because it not only functions as a wetting agent but also provides good drying properties.

As the organic solvent, polyol compounds having 8 or more carbon atoms and glycol ether compounds are also preferably used. Specific examples of polyol compounds having 8 or more carbon atoms include 2-ethyl-1,3-hexanediol and 2,2,4-trimethyl-1,3-pentanediol.
Specific examples of glycol ether compounds include polyhydric alcohol alkyls such as ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, tetraethylene glycol monomethyl ether, and propylene glycol monoethyl ether. Ethers; polyhydric alcohol aryl ethers such as ethylene glycol monophenyl ether, ethylene glycol monobenzyl ether, and the like.

Also, the organic solvent contained in the ink preferably contains an alcohol with a boiling point of 240° C. or lower, more preferably an alcohol with a boiling point of 100° C. or higher. An alcohol with a boiling point of 240° C. or less functions as a humectant in the ink before it is ejected onto the substrate to improve the ejection stability of the ink, and after it is ejected onto the substrate, it improves the drying properties of the ink. Improve. Also, alcohol has excellent compatibility with the infrared absorbing agent contained in the ink. Therefore, precipitation of the infrared absorbing agent in the ink can be suppressed, and the ejection stability of the ink can be improved.
Alcohols having a boiling point of 240° C. or lower include alcohols that are liquid at 25° C. and 1 atm, including polyhydric alcohols. Alcohols having a boiling point of 240° C. or less include, for example, ethylene glycol (b.p. 197° C.), 1,2-propanediol (b.p. 187° C.), 1,3-propanediol (b.p. 213 ° C.), 1,2-butanediol (b.p. 192° C.), 1,3-butanediol (b.p. 207° C.), 1,4-butanediol (b.p. 230° C.), 2, 3-butanediol (bp 180°C), 3-methyl-1,3-butanediol (bp 204°C), 1,2-pentanediol (bp 206°C), 2,4 -pentanediol (b.p.202°C), 1,2-hexanediol (b.p.224°C), 2,5-hexanediol (b.p.218°C), 2,2,4-trimethyl- 1,3-pentanediol (b.p.232.degree. C.), 3-methoxy-3-methylbutanol (b.p.174.degree. C.) and the like. Alcohols having a boiling point of 240° C. or lower include glycol ethers such as dipropylene glycol monomethyl ether (b.p. 190° C.). Among these, 3-methoxy-3-methylbutanol (bp 174°C), 1,2-propanediol (bp 187°C), 1,3-butanediol (bp 207°C) , 1,2-hexanediol (b.p. 224° C.) is preferred. In addition, "b.p." shows a boiling point.

The content of the alcohol having a boiling point of 240° C. or less is 5.0% by mass or more, preferably 10.0% by mass or more, based on the total amount of the ink. Also, the content of the alcohol having a boiling point of 240° C. or less is preferably 40.0% by mass or less, more preferably 30.0% by mass or less, and 20.0% by mass or less relative to the total amount of the ink. is more preferable. If the content of the alcohol having a boiling point of 240° C. or less is 5.0% by mass or less, the drying property of the ink after being ejected onto the printing material becomes insufficient, resulting in abnormal images such as beading.

The content of the organic solvent in the ink is not particularly limited and can be appropriately selected according to the purpose. 20% by mass or more and 60% by mass or less is more preferable.

<Color material>
The coloring material is not particularly limited, and pigments and dyes can be used. An inorganic pigment or an organic pigment can be used as the pigment. These may be used individually by 1 type, and may use 2 or more types together. Mixed crystals may also be used as pigments.
Examples of pigments that can be used include black pigments, yellow pigments, magenta pigments, cyan pigments, white pigments, green pigments, orange pigments, glossy color pigments such as gold and silver, and metallic pigments.
As inorganic pigments, in addition to titanium oxide, iron oxide, calcium carbonate, barium sulfate, aluminum hydroxide, barium yellow, cadmium red, and chrome yellow, carbon black produced by known methods such as contact method, furnace method, thermal method, etc. can be used.
Organic pigments include azo pigments, polycyclic pigments (e.g., phthalocyanine pigments, perylene pigments, perinone pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, indigo pigments, thioindigo pigments, isoindolinone pigments, quinophthalone pigments, etc.). , dye chelates (eg, basic dye chelates, acid dye chelates, etc.), nitro pigments, nitroso pigments, aniline black, and the like. Among these pigments, those having good affinity with the solvent are preferably used. In addition, resin hollow particles and inorganic hollow particles can also be used.
Specific examples of pigments for black include carbon blacks (C.I. Pigment Black 7) such as furnace black, lamp black, acetylene black and channel black, or copper and iron (C.I. Pigment Black 11). , metals such as titanium oxide, and organic pigments such as aniline black (C.I. Pigment Black 1).
Further, for color, C.I. I. Pigment yellow 1, 3, 12, 13, 14, 17, 24, 34, 35, 37, 42 (yellow iron oxide), 53, 55, 74, 81, 83, 95, 97, 98, 100, 101, 104 , 108, 109, 110, 117, 120, 138, 150, 153, 155, 180, 185, 213, C.I. I. Pigment Orange 5, 13, 16, 17, 36, 43, 51, C.I. I. Pigment Red 1, 2, 3, 5, 17, 22, 23, 31, 38, 48:2, 48:2 (Permanent Red 2B (Ca)), 48:3, 48:4, 49:1, 52: 2, 53:1, 57:1 (brilliant carmine 6B), 60:1, 63:1, 63:2, 64:1, 81, 83, 88, 101 (red red), 104, 105, 106, 108 ( cadmium red), 112, 114, 122 (quinacridone magenta), 123, 146, 149, 166, 168, 170, 172, 177, 178, 179, 184, 185, 190, 193, 202, 207, 208, 209, 213, 219, 224, 254, 264, C.I. I. Pigment Violet 1 (rhodamine lake), 3, 5:1, 16, 19, 23, 38, C.I. I. Pigment Blue 1, 2, 15 (phthalocyanine blue), 15:1, 15:2, 15:3, 15:4 (phthalocyanine blue), 16, 17:1, 56, 60, 63, C.I. I. Pigment Green 1, 4, 7, 8, 10, 17, 18, 36, etc.
As dyes, acid dyes, direct dyes, reactive dyes, and basic dyes can be used without particular limitation, and may be used singly or in combination of two or more.
As a dye, for example, C.I. I. Acid Yellow 17, 23, 42, 44, 79, 142, C.I. I. Acid Red 52, 80, 82, 249, 254, 289, C.I. I. Acid Blue 9,45,249, C.I. I. Acid Black 1, 2, 24, 94, C.I. I. Food Black 1, 2, C.I. I. Direct Yellow 1, 12, 24, 33, 50, 55, 58, 86, 132, 142, 144, 173, C.I. I. Direct Red 1, 4, 9, 80, 81, 225, 227, C.I. I. Direct Blue 1, 2, 15, 71, 86, 87, 98, 165, 199, 202, C.I. I. Directed Black 19, 38, 51, 71, 154, 168, 171, 195, C.I. I. Reactive Red 14, 32, 55, 79, 249, C.I. I. Reactive Black 3, 4, 35 can be mentioned.
Among these colorants, pigments are preferably used, yellow pigments are more preferably used, and Pigment Yellow 74 is still more preferably used. Since these are easily degraded by ultraviolet rays, it is particularly preferable to use the liquid set of the present embodiment.

The content of the coloring material in the ink is preferably 0.1% by mass or more and 15% by mass or less, more preferably 1% by mass or more and 10% by mass, from the viewpoints of improving image density, good fixability, and ejection stability. It is below.

As a method of dispersing the pigment to obtain an ink, a method of introducing a hydrophilic functional group into the pigment to make it a self-dispersing pigment, a method of coating the surface of the pigment with a resin and dispersing the pigment, and a method of dispersing the pigment using a dispersant. method, etc.
As a method of making a self-dispersing pigment by introducing a hydrophilic functional group into a pigment, for example, a method of adding a functional group such as a sulfone group or a carboxyl group to a pigment (for example, carbon) to make it dispersible in water. is mentioned.
As a method of coating the surface of a pigment with a resin and dispersing it, there is a method of encapsulating the pigment in microcapsules to make it dispersible in water. This can be rephrased as a resin-coated pigment. In this case, all the pigments mixed in the ink need not be coated with a resin, and uncoated pigments or partially coated pigments may be dispersed in the ink as long as the effects of the present invention are not impaired. may be
Examples of the method of dispersing using a dispersant include a method of dispersing using a known low-molecular-weight dispersant and high-molecular-weight dispersant typified by surfactants.
As the dispersant, it is possible to use, for example, anionic surfactants, cationic surfactants, amphoteric surfactants, nonionic surfactants, etc. depending on the pigment.
As a dispersant, RT-100 (nonionic surfactant) manufactured by Takemoto Yushi Co., Ltd. and sodium naphthalenesulfonate formalin condensate can also be suitably used as a dispersant.
A dispersing agent may be used individually by 1 type, or may use 2 or more types together.

<Pigment dispersion>
Inks can be obtained by mixing materials such as water and organic solvents with pigments. Ink can also be produced by mixing a pigment, water, a dispersant, and the like to form a pigment dispersion, and then mixing materials such as water and an organic solvent.
The pigment dispersion is obtained by mixing and dispersing water, a pigment, a pigment dispersant, and optionally other components, and adjusting the particle size. Dispersion should be carried out using a disperser.
The particle diameter of the pigment in the pigment dispersion is not particularly limited, but the dispersion stability of the pigment is improved, and the image quality such as ejection stability and image density is improved. 500 nm or less is preferable, and 20 nm or more and 150 nm or less is more preferable. The particle size of the pigment can be measured using a particle size analyzer (Nanotrack Wave-UT151, manufactured by Microtrack Bell Co., Ltd.).
The content of the pigment in the pigment dispersion is not particularly limited and can be appropriately selected according to the purpose. 50% by mass or less is preferable, and 0.1% by mass or more and 30% by mass or less is more preferable.
It is preferable to filter coarse particles with a filter, a centrifugal separator, or the like, and deaerate the pigment dispersion, if necessary.

<Resin>
The type of resin contained in the ink is not particularly limited and can be appropriately selected according to the purpose. resins, styrene-butadiene-based resins, vinyl chloride-based resins, acrylic-styrene-based resins, acrylic-silicone-based resins, and the like.
Resin particles made of these resins may also be used. Ink can be obtained by mixing resin particles in a resin emulsion state in which water is dispersed as a dispersion medium with a material such as a coloring material or an organic solvent. As the resin particles, appropriately synthesized ones may be used, or commercially available products may be used. Moreover, these may be used individually by 1 type, or may be used in combination of 2 or more types of resin particles.

The volume average particle diameter of the resin particles is not particularly limited and can be appropriately selected according to the intended purpose. 200 nm or less is more preferable, and 10 nm or more and 100 nm or less is particularly preferable.
The volume average particle diameter can be measured, for example, using a particle size analyzer (Nanotrack Wave-UT151, manufactured by Microtrack Bell Co., Ltd.).

The content of the resin is not particularly limited and can be appropriately selected according to the purpose. However, from the viewpoint of fixability and storage stability of the ink, the content is 1% by mass or more and 30% by mass or less based on the total amount of the ink. is preferable, and 5% by mass or more and 20% by mass or less is more preferable.

The particle size of the solid content in the ink is not particularly limited, and can be appropriately selected according to the purpose. From the viewpoint of enhancing image quality such as ejection stability and image density, the maximum frequency of the particle size of the solid content in the ink is preferably 20 nm or more and 1000 nm or less, more preferably 20 nm or more and 150 nm or less, in terms of the maximum number. The solid content includes resin particles, pigment particles, and the like. The particle size can be measured using a particle size analyzer (Nanotrack Wave-UT151, manufactured by Microtrack Bell Co., Ltd.).

<Infrared absorber>
The ink preferably contains an infrared absorbing agent. When the ink contains an infrared absorbing agent, the efficiency of heating and drying the ink when irradiated with infrared rays is improved. However, since the ink is more likely to be heated, there are problems such as deterioration such as deformation in the printed material, and the ultraviolet absorber is deactivated by heating, and the layer formed by the ink when the printed material is used in the presence of ultraviolet rays. The problem of deterioration such as discoloration that occurs in is likely to occur. Therefore, when the ink contains an infrared absorbing agent, it is preferable to use the liquid set of the present embodiment.
The infrared absorbing agent is, for example, an infrared absorbing dye. The infrared absorbing agent is preferably a material having a maximum absorption wavelength between 700 nm and 1000 nm, and has a strong light absorption function based on charge transfer of organic dyes and metal complexes. In addition, when the maximum absorption wavelength at 700 nm or more and 1000 nm or less is 1, the infrared absorbent preferably has a maximum absorption wavelength at 380 nm or more and 700 nm or less of 0.5 or less, more preferably 0.4 or less. preferable.
Examples of infrared absorbing agents include cyanine dyes having an extended polymethine skeleton, phthalocyanine dyes having aluminum and zinc as the center, various naphthalocyanine compounds, nickel dithiolene complexes having a planar four-coordinate structure, squalium dyes, quinone compounds, Diimmonium compounds, azo compounds and the like are known. Such an infrared absorber may be appropriately synthesized or may be a commercially available product.市販品としては、例えば、ＱＣＲ Ｓｏｌｕｔｉｏｎｓ Ｃｏｒｐ社製のＮＩＲ７４６Ａ、ＮＩＲ７８２Ｅ、ＮＩＲ８１８Ｄ、ＮＩＲ８６９Ａ、ＮＩＲ８８０Ｄ、ＮＩＲ９１１Ａ、ＮＩＲ９８０Ａ、ＮＩＲ１０５４ＷＤ、ＮＩＲ１０５４Ｂ、ｌｕｍｉｎｏｃｈｅｍ社製のＬＵＷＳＩＲ４、ＬＵＮＩＲ５、ＬＵＮＩＲ８／１、ＬＵＮＩＲ６、ＡｍｅｒｉｃａｎＤｙｅＳｏｕｒｃｅ社製のＡＤＳ７７５ＭＩ , ADS775MP, ADS775PI, ADS775PP, ADS780HO, ADS798SM, ADS800AT, ADS815EI, ADS830AT, ADS1065A, ADS1075A, ADS780WS, ADS845MC and the like.

The content of the infrared absorbing agent in the ink is not particularly limited and can be appropriately selected according to the purpose. % or less, more preferably 0.5 mass % or more and 5.0 mass % or less, and even more preferably 0.8 mass % or more and 1.5 mass % or less.

In the ink, the content (by mass) of alcohol having a boiling point of 240° C. or less is preferably 5.0 to 30.0 relative to the content (by mass) of the infrared absorber. It is more preferably 0 or more and 30.0 or less, and even more preferably 10.0 or more and 20.0 or less. Within this range, precipitation of the infrared absorbing agent in the ink is suppressed, and the ejection stability of the ink can be improved.

<Additive>
Surfactants, antifoaming agents, antiseptic antifungal agents, anticorrosive agents, pH adjusters, etc. may be added to the ink as necessary.

<Surfactant>
Any of silicone surfactants, fluorine surfactants, amphoteric surfactants, nonionic surfactants, and anionic surfactants can be used as surfactants.
The silicone-based surfactant is not particularly limited and can be appropriately selected depending on the purpose. Among them, those that do not decompose even at high pH are preferred. Examples of silicone-based surfactants include side chain-modified polydimethylsiloxane, both-end-modified polydimethylsiloxane, single-end-modified polydimethylsiloxane, and side-chain both-end-modified polydimethylsiloxane. Those having a polyoxyethylene group or a polyoxyethylene-polyoxypropylene group as a modifying group are particularly preferred because they exhibit good properties as water-based surfactants. As the silicone-based surfactant, a polyether-modified silicone-based surfactant can also be used, and examples thereof include compounds in which a polyalkylene oxide structure is introduced into the side chain of the Si portion of dimethylsiloxane.
Examples of fluorine-based surfactants include perfluoroalkylsulfonic acid compounds, perfluoroalkylcarboxylic acid compounds, perfluoroalkylphosphoric acid ester compounds, perfluoroalkylethylene oxide adducts, and perfluoroalkyl ether groups in side chains. Polyoxyalkylene ether polymer compounds are particularly preferred due to their low foaming properties. Examples of perfluoroalkylsulfonic acid compounds include perfluoroalkylsulfonic acids, perfluoroalkylsulfonates, and the like. Examples of perfluoroalkylcarboxylic acid compounds include perfluoroalkylcarboxylic acids and perfluoroalkylcarboxylic acid salts. Examples of polyoxyalkylene ether polymer compounds having perfluoroalkyl ether groups in side chains include sulfuric acid ester salts of polyoxyalkylene ether polymers having perfluoroalkyl ether groups in side chains, and polyoxyalkylene ether polymers having perfluoroalkyl ether groups in side chains. Examples thereof include salts of oxyalkylene ether polymers. Counter ions of salts in these _{fluorosurfactants} include Li, Na, K, _NH4 , _NH3CH2CH2OH , _{NH2 ( CH2CH2OH} ) ₂ , and _{NH ( CH2CH2OH} ). ₃ and the like.
Examples of amphoteric surfactants include laurylaminopropionate, lauryldimethylbetaine, stearyldimethylbetaine, lauryldihydroxyethylbetaine and the like.
Nonionic surfactants include, for example, polyoxyethylene alkylphenyl ethers, polyoxyethylene alkyl esters, polyoxyethylene alkylamines, polyoxyethylene alkylamides, polyoxyethylene propylene block polymers, sorbitan fatty acid esters, polyoxyethylene sorbitan Examples include fatty acid esters and ethylene oxide adducts of acetylene alcohol.
Examples of anionic surfactants include polyoxyethylene alkyl ether acetates, dodecylbenzene sulfonates, laurates, and salts of polyoxyethylene alkyl ether sulfates.
These may be used individually by 1 type, or may use 2 or more types together.

（但し、一般式（Ｓ－１）式中、ｍ、ｎ、ａ、及びｂは、それぞれ独立に、整数を表わし、Ｒは、アルキレン基を表し、Ｒ’は、アルキル基を表す。）
上記のポリエーテル変性シリコーン系界面活性剤としては、市販品を用いることができ、例えば、ＫＦ－６１８、ＫＦ－６４２、ＫＦ－６４３（信越化学工業株式会社）、ＥＭＡＬＥＸ－ＳＳ－５６０２、ＳＳ－１９０６ＥＸ（日本エマルジョン株式会社）、ＦＺ－２１０５、ＦＺ－２１１８、ＦＺ－２１５４、ＦＺ－２１６１、ＦＺ－２１６２、ＦＺ－２１６３、ＦＺ－２１６４（東レ・ダウコーニング・シリコーン株式会社）、ＢＹＫ－３３、ＢＹＫ－３８７（ビックケミー株式会社）、ＴＳＦ４４４０、ＴＳＦ４４５２、ＴＳＦ４４５３（東芝シリコン株式会社）などが挙げられる。 The silicone-based surfactant is not particularly limited and can be appropriately selected depending on the intended purpose. Examples include polydimethylsiloxane modified at both ends, and polyether-modified silicone surfactants having polyoxyethylene groups or polyoxyethylene polyoxypropylene groups as modifying groups are particularly preferred because they exhibit good properties as water-based surfactants. .
As such a surfactant, an appropriately synthesized one may be used, or a commercially available product may be used. Commercially available products are available from, for example, BYK Chemie Co., Ltd., Shin-Etsu Chemical Co., Ltd., Dow Corning Toray Silicone Co., Ltd., Nihon Emulsion Co., Ltd., Kyoeisha Chemical Co., Ltd., and the like.
The above polyether-modified silicone-based surfactant is not particularly limited and can be appropriately selected according to the purpose. Examples include those introduced into the side chain of the Si portion of siloxane.

(However, in general formula (S-1), m, n, a, and b each independently represent an integer, R represents an alkylene group, and R' represents an alkyl group.)
Commercially available products can be used as the above polyether-modified silicone-based surfactants. 1906EX (Japan Emulsion Co., Ltd.), FZ-2105, FZ-2118, FZ-2154, FZ-2161, FZ-2162, FZ-2163, FZ-2164 (Dow Corning Toray Silicone Co., Ltd.), BYK-33, BYK-387 (BYK-Chemie Corporation), TSF4440, TSF4452, TSF4453 (Toshiba Silicon Co., Ltd.) and the like.

上記一般式（Ｆ－１）で表される化合物において、水溶性を付与するためにｍは０～１０の整数が好ましく、ｎは０～４０の整数が好ましい。

上記一般式（Ｆ－２）で表される化合物において、ＹはＨ、又はＣｍＦ_２ｍ＋１でｍは１～６の整数、又はＣＨ_２ＣＨ（ＯＨ）ＣＨ_２－ＣｍＦ_２ｍ＋１でｍは４～６の整数、又はＣｐＨ_２ｐ＋１でｐは１～１９の整数である。ｎは１～６の整数である。ａは４～１４の整数である。
上記のフッ素系界面活性剤としては市販品を使用してもよい。この市販品としては、例えば、サーフロンＳ－１１１、Ｓ－１１２、Ｓ－１１３、Ｓ－１２１、Ｓ－１３１、Ｓ－１３２、Ｓ－１４１、Ｓ－１４５（いずれも、旭硝子株式会社製）；フルラードＦＣ－９３、ＦＣ－９５、ＦＣ－９８、ＦＣ－１２９、ＦＣ－１３５、ＦＣ－１７０Ｃ、ＦＣ－４３０、ＦＣ－４３１（いずれも、住友スリーエム株式会社製）；メガファックＦ－４７０、Ｆ－１４０５、Ｆ－４７４（いずれも、大日本インキ化学工業株式会社製）；ゾニール（Ｚｏｎｙｌ）ＴＢＳ、ＦＳＰ、ＦＳＡ、ＦＳＮ－１００、ＦＳＮ、ＦＳＯ－１００、ＦＳＯ、ＦＳ－３００、ＵＲ、キャプストーンＦＳ－３０、ＦＳ－３１、ＦＳ－３１００、ＦＳ－３４、ＦＳ－３５（いずれも、Ｃｈｅｍｏｕｒｓ社製）；ＦＴ－１１０、ＦＴ－２５０、ＦＴ－２５１、ＦＴ－４００Ｓ、ＦＴ－１５０、ＦＴ－４００ＳＷ（いずれも、株式会社ネオス社製）、ポリフォックスＰＦ－１３６Ａ，ＰＦ－１５６Ａ、ＰＦ－１５１Ｎ、ＰＦ－１５４、ＰＦ－１５９（オムノバ社製）、ユニダインＤＳＮ－４０３Ｎ（ダイキン工業株式会社製）などが挙げられ、これらの中でも、良好な印字品質、特に発色性、紙に対する浸透性、濡れ性、均染性が著しく向上する点から、Ｃｈｅｍｏｕｒｓ社製のＦＳ－３１００、ＦＳ－３４、ＦＳ－３００、株式会社ネオス製のＦＴ－１１０、ＦＴ－２５０、ＦＴ－２５１、ＦＴ－４００Ｓ、ＦＴ－１５０、ＦＴ－４００ＳＷ、オムノバ社製のポリフォックスＰＦ－１５１Ｎ及びダイキン工業株式会社製のユニダインＤＳＮ－４０３Ｎが特に好ましい。 As the fluorosurfactant, a fluorine-substituted compound having 2 to 16 carbon atoms is preferable, and a fluorine-substituted compound having 4 to 16 carbon atoms is more preferable.
Examples of fluorine-based surfactants include perfluoroalkyl phosphate ester compounds, perfluoroalkyl ethylene oxide adducts, and polyoxyalkylene ether polymer compounds having perfluoroalkyl ether groups in side chains. Among these, a polyoxyalkylene ether polymer compound having a perfluoroalkyl ether group in a side chain is preferable because of its low foamability, and in particular, fluorine-based compounds represented by general formulas (F-1) and (F-2) Surfactants are preferred.

In the compound represented by the general formula (F-1), m is preferably an integer of 0 to 10 and n is preferably an integer of 0 to 40 in order to impart water solubility.

In the compound represented by the above general formula (F-2), Y is H, or CmF _2m+1 and m is an integer of 1 to 6, or CH ₂ CH(OH)CH ₂ -CmF _2m+1 and m is 4 to 6 Integer, or CpH _2p+1 where p is an integer from 1-19. n is an integer of 1-6. a is an integer from 4 to 14;
Commercially available products may be used as the fluorosurfactant. Examples of commercially available products include Surflon S-111, S-112, S-113, S-121, S-131, S-132, S-141, and S-145 (all manufactured by Asahi Glass Co., Ltd.); Fleurard FC-93, FC-95, FC-98, FC-129, FC-135, FC-170C, FC-430, FC-431 (both manufactured by Sumitomo 3M); Megafac F-470, F -1405, F-474 (both manufactured by Dainippon Ink and Chemicals); Zonyl TBS, FSP, FSA, FSN-100, FSN, FSO-100, FSO, FS-300, UR, Capstone FS-30, FS-31, FS-3100, FS-34, FS-35 (all manufactured by Chemours); FT-110, FT-250, FT-251, FT-400S, FT-150, FT- 400SW (all manufactured by Neos Co., Ltd.), Polyfox PF-136A, PF-156A, PF-151N, PF-154, PF-159 (manufactured by Omnova), Unidyne DSN-403N (manufactured by Daikin Industries, Ltd.) Among these, Chemours FS-3100, FS-34, FS- 300, FT-110, FT-250, FT-251, FT-400S, FT-150, FT-400SW manufactured by Neos Co., Ltd., Polyfox PF-151N manufactured by Omnova Co., Ltd. and Unidyne DSN- manufactured by Daikin Industries, Ltd. 403N is particularly preferred.

The content of the surfactant in the ink is not particularly limited and can be appropriately selected according to the purpose. % or more and 5 mass % or less is preferable, and 0.05 mass % or more and 5 mass % or less is more preferable.

<Antifoaming agent>
The antifoaming agent is not particularly limited, and examples thereof include silicone antifoaming agents, polyether antifoaming agents, and fatty acid ester antifoaming agents. These may be used individually by 1 type, or may use 2 or more types together. Among these, silicone-based antifoaming agents are preferred because of their excellent foam breaking effect.

<Preservative and antifungal agent>
The antiseptic and antifungal agent is not particularly limited, and examples thereof include 1,2-benzisothiazolin-3-one.

<Antirust agent>
The rust inhibitor is not particularly limited, and examples thereof include acidic sulfites and sodium thiosulfate.

<pH adjuster>
The pH adjuster is not particularly limited as long as it can adjust the pH to 7 or higher, and examples thereof include amines such as diethanolamine and triethanolamine.

<Physical properties of ink>
The physical properties of the ink are not particularly limited and can be appropriately selected depending on the intended purpose. For example, viscosity, surface tension, pH and the like are preferably within the following ranges.
The viscosity of the ink at 25° C. is preferably 5 mPa·s or more and 30 mPa·s or less, more preferably 5 mPa·s or more and 25 mPa·s or less, from the viewpoint of improving the print density and character quality and obtaining good ejection properties. more preferred. Here, the viscosity can be measured using, for example, a rotational viscometer (RE-80L manufactured by Toki Sangyo Co., Ltd.). Measurement conditions are 25° C., standard cone rotor (1°34′×R24), sample liquid volume 1.2 mL, rotation speed 50 rpm, 3 minutes.
The surface tension of the ink is preferably 35 mN/m or less, more preferably 32 mN/m or less at 25° C., because the ink is suitably leveled on the printed material and the drying time of the ink is shortened.
The pH of the ink is preferably from 7 to 12, more preferably from 8 to 11, from the viewpoint of preventing corrosion of metal members in contact with the liquid.

<<Pre-treatment liquid>>
The pretreatment liquid is applied to the material to be printed and contains first inorganic particles having a volume average particle diameter of 300 nm or more. In addition, if necessary, additives such as polyvalent metal salts, organic solvents, water, and surfactants are contained. The additives such as the organic solvent, water and surfactant are the same as the additives such as the organic solvent, water and surfactant used in the above-described liquid composition, so the description thereof is omitted.

<First inorganic particles>
The pretreatment liquid contains first inorganic particles having a volume average particle size of 300 nm or more. The first inorganic particles effectively shield infrared rays having a wavelength of 700 nm or more and 1200 nm or less, and function as infrared shielding particles. As a result, the first inorganic particle-containing layer formed by applying the pretreatment liquid containing the first inorganic particles onto the material to be printed can effectively reflect infrared rays. can suppress the heating effect on the Therefore, even if the material to be printed has the property of easily causing deterioration such as deformation when irradiated with infrared rays, deterioration such as deformation can be suppressed.

The volume average particle diameter of the first inorganic particles is 300 nm or more. The volume average particle diameter of the first inorganic particles is preferably 2000 nm or less, more preferably 1000 nm or less, and even more preferably 500 nm or less. When the volume average particle diameter of the first inorganic particles is 300 nm or more, infrared rays can be effectively reflected. The volume average particle diameter of the first inorganic particles can be measured, for example, using a particle size analyzer (Nanotrack Wave-UT151, manufactured by Microtrack Bell Co., Ltd.).

Materials constituting the first inorganic particles include, for example, metals such as aluminum, silver, iron, copper, nickel, and tungsten; metal oxides such as silver oxide; bricks; graphite; gypsum; Non-metals such as cement can be used, but metals are preferred. Among the metal particles, at least one selected from silver particles, aluminum particles, iron particles, and copper particles is more preferable, and silver particles are even more preferable. In addition, the material of the first inorganic particles may be of one type or of a plurality of types.

In addition, the first inorganic particles are preferably contained in an amount of 0.1% by mass or more and 20.0% by mass or less, and more preferably 1.0% by mass or more and 10.0% by mass or less, relative to the total amount of the pretreatment liquid. is more preferable, and more preferably 2.0% by mass or more and 5.0% by mass or less.

<Polyvalent metal salt>
The polyvalent metal salt agglomerates the coloring material contained in the ink applied onto the pretreatment liquid, suppresses color bleeding, and improves color developability. Examples of polyvalent metal salts include salts such as titanium compounds, chromium compounds, copper compounds, cobalt compounds, strontium compounds, barium compounds, iron compounds, aluminum compounds, calcium compounds, magnesium compounds, and nickel compounds.

The polyvalent metal salt is not particularly limited and can be appropriately selected depending on the purpose. Examples include titanium compounds, chromium compounds, copper compounds, cobalt compounds, strontium compounds, barium compounds, iron compounds, aluminum compounds, Examples include salts of calcium compounds, magnesium compounds, zinc compounds, nickel compounds, and the like. These may be used individually by 1 type, and may use 2 or more types together. Among these, salts of calcium compounds, magnesium compounds, and nickel compounds are preferable, and alkaline earth metal salts of calcium compounds and magnesium compounds are more preferable, since they can effectively aggregate the coloring material.

Specific examples of polyvalent metal salts include calcium carbonate, calcium nitrate, calcium chloride, calcium acetate, calcium sulfate, magnesium chloride, magnesium acetate, magnesium sulfate, barium sulfate, zinc sulfide, zinc carbonate, aluminum silicate, calcium silicate, and silicic acid. Examples include magnesium and aluminum hydroxide. Among these, calcium acetate is preferred.

The concentration of the polyvalent metal salt relative to the total amount of the pretreatment liquid is preferably 0.05 mol/kg or more and 0.5 mol/kg or less. Within this range, both excellent storage stability and suppression of color bleeding can be achieved.

<<Post-treatment liquid>>
The post-treatment liquid is applied to the area of the substrate to which the liquid composition has been applied, and contains second inorganic particles having a volume average particle size of 200 nm or less. Moreover, it contains additives such as resins, organic solvents, water, and surfactants as necessary. The resin, organic solvent, water, surfactant, and other additives are the same as the resin, organic solvent, water, and surfactant additives used in the above-described liquid composition. omitted.

<Second inorganic particles>
The post-treatment liquid contains second inorganic particles having a volume average particle size of 200 nm or less. The second inorganic particles effectively reflect ultraviolet rays with a wavelength of 280 nm or more and 400 nm or less, and function as ultraviolet shielding particles. As a result, the second inorganic particle-containing layer formed by applying the post-treatment liquid containing the second inorganic particles to the area of the substrate to which the liquid composition has been applied effectively reflects the ultraviolet rays. Therefore, deterioration such as discoloration can be suppressed in the layer formed by the liquid composition when used in the presence of ultraviolet rays. Therefore, even if the liquid composition contains an ultraviolet-degraded product, such as a coloring material, which has a property of easily causing deterioration such as discoloration when irradiated with ultraviolet rays, the deterioration can be suppressed. . In addition, even when the post-treatment liquid containing the second inorganic particles is applied onto the liquid composition such as the ink applied to the printed material and then heated, the inorganic substance is used as the ultraviolet shielding particles. , the deterioration of the ultraviolet shielding function is suppressed.

The volume average particle diameter of the second inorganic particles is 200 nm or less, preferably 100 nm or less, more preferably 80 nm or less, and even more preferably 50 nm or less. Moreover, the volume average particle diameter of the second inorganic particles is preferably 5 nm or more, more preferably 10 nm or more, and even more preferably 20 nm or more. When the volume average particle diameter of the second inorganic particles is 200 nm or less, ultraviolet rays can be effectively shielded. The volume average particle diameter of the second inorganic particles can be measured, for example, using a particle size analyzer (Nanotrack Wave-UT151, manufactured by Microtrack Bell Co., Ltd.).

Moreover, the material constituting the second inorganic particles is preferably a metal oxide. Among metal oxides, at least one selected from titanium oxide, zinc oxide, and cerium oxide is more preferable, and at least one selected from titanium oxide and zinc oxide is even more preferable. In addition, the material of the first inorganic particles may be of one type or of a plurality of types.

The second inorganic particles are preferably contained in an amount of 0.1% by mass or more and 20.0% by mass or less, and preferably 1.0% by mass or more and 10.0% by mass or less, relative to the total amount of the post-treatment liquid. is more preferable, and more preferably 2.0% by mass or more and 5.0% by mass or less.

<Substrate to be printed>
The material to be printed is not particularly limited, and plain paper, glossy paper, special paper, cloth, and the like can be used.
A non-permeable substrate is a substrate having a surface with low water permeability and low absorbency, and includes materials that do not open to the outside even if there are many cavities inside. More quantitatively, A substrate having a water absorption of 10 mL/m ² or less from the start of contact to 30 msec ^1/2 in the Bristow method.
As the impermeable substrate, for example, plastic films such as vinyl chloride resin films, polyethylene terephthalate (PET) films, polypropylene, polyethylene and polycarbonate films can be suitably used.

Examples of impermeable substrates using polypropylene and polyethylene include AR1025, AR1056, AR1082, EC1082, 1082D, 1073D, 1056D, 1025D, FR1073 (Asahi DuPont Flashspun Products Co., Ltd.), P2002, P2102, P2108, P2161, P2171, P2111, P4266, P5767, P3162, P6181, P8121, P1162, P1111, P1128, P1181, P1153, P1157, P1146, P1147, P1171 (Toyobo Co., Ltd.), YPI, Aquayupo, Superyupo, Ultrayupo, Newyupo, Yupo illumination paper, Yupo construction paper, Yupo high gloss, Yupo jet, metallic Yupo (Yupo Corporation) and the like.

When a liquid such as ink is applied to the permeable substrate, the liquid permeates into the interior of the substrate in addition to volatilizing from the surface. On the other hand, when a liquid such as ink is applied to an impermeable substrate, the liquid does not permeate the interior of the substrate, so it is important to increase the volatility from the surface. Therefore, it is preferable to increase the volatility from the surface by irradiating infrared rays. However, in the case of heating and drying by irradiating infrared rays, as described above, in the prior art, the print medium and the ultraviolet absorber may deteriorate. It is preferable to use the liquid set of the embodiment.

<Records>
A recorded material formed using the liquid set of the present embodiment is formed by laminating a first inorganic particle-containing layer, an intermediate layer, and a second inorganic particle-containing layer in this order from the printing material side on the printing material. The first inorganic particle-containing layer is a layer formed by drying or curing the pretreatment liquid applied to the printed material, and contains first inorganic particles having a volume average particle diameter of 300 nm or more. do.
The intermediate layer is a layer formed by drying or curing the liquid composition applied to the area of the printed material to which the pretreatment liquid has been applied.
The second inorganic particle-containing layer is a layer formed by drying or curing the post-treatment liquid applied to the area of the substrate to which the liquid composition is applied, and has a volume average particle size of 200 nm or less. contains the second inorganic particles.

<Recording device, recording method>
The liquid set of the present embodiment can be suitably used for various recording apparatuses using an inkjet recording method, such as printers, facsimile machines, copiers, printer/fax/copier complex machines, stereolithography machines, and the like.
In the present application, a recording apparatus and a recording method refer to an apparatus capable of applying a pretreatment liquid, a liquid composition, and a post-treatment liquid to an object to be printed, and a method of performing recording using the apparatus. The substrate to be printed means, for example, a recording medium, etc., to which the pretreatment liquid, the liquid composition, and the post-treatment liquid can adhere even temporarily.
This recording apparatus includes not only liquid composition applying means such as a head for applying the liquid composition to the printed material, but also means for feeding, conveying, and discharging the printed material, and applying a pretreatment liquid to the printed material. A pre-treatment liquid applying means, a post-treatment liquid applying means for applying the post-treatment liquid to the printed material, and the like can be included.
The recording apparatus and recording method have an infrared irradiation means used in an infrared irradiation step for irradiating light containing infrared light onto a region on the printed material to which the liquid composition is applied. When the infrared irradiation means irradiates the liquid composition applied to the printed material with infrared rays, the infrared absorbent contained in the ink absorbs the infrared rays to generate heat, and as a result, the liquid composition dries. In addition, the infrared rays have a wavelength of 700 nm or more and 1000 nm or less, and are preferably laser light. Examples of infrared irradiation means include light emitting diodes (LED), semiconductor lasers (LD), halogen lamps, and xenon lamps. Moreover, it is preferable that the infrared ray irradiation means is a means for irradiating infrared rays only to the area on the substrate to which the liquid composition is applied. As means for drying the area to which the liquid set is applied, known heating means and drying means can be used in addition to the infrared irradiation means. As known heating means and drying means, for example, hot air heaters and infrared heaters can be used. Moreover, heating and drying can be performed during printing, after printing, and the like.
In addition, when the ink is dried using the infrared irradiation means, the temperature of the substrate to be printed during the infrared irradiation step is preferably 50° C. or higher. The upper limit of the temperature of the printed material during the infrared irradiation step can be selected as appropriate, but is preferably 200° C. or lower in order to suppress thermal deformation of the printed material.
Moreover, the recording apparatus and recording method are not limited to those in which significant images such as characters and figures are visualized by the liquid composition. For example, it includes those that form patterns such as geometric patterns, and those that form three-dimensional images.
In addition, unless otherwise specified, the recording apparatus includes both a serial type apparatus in which the ejection head is moved and a line type apparatus in which the ejection head is not moved.
Furthermore, this recording device includes not only desktop printers, but also a continuous feed printer that can print on wide substrates that can print on A0 size substrates, and that uses continuous substrates that are wound up in a roll. be
An example of a recording apparatus will be described with reference to FIGS. 1 and 2. FIG. FIG. 1 is a perspective explanatory view of the device. FIG. 2 is a perspective explanatory view of the main tank. An image forming apparatus 400 as an example of a recording apparatus is a serial image forming apparatus. A mechanical unit 420 is provided inside the exterior 401 of the image forming apparatus 400 . Each ink container 411 of the main tank 410 (410k, 410c, 410m, 410y) for each color of black (K), cyan (C), magenta (M), and yellow (Y) is packed with, for example, an aluminum laminated film. It is made up of members. The ink containing portion 411 is housed, for example, in a container case 414 made of plastic. Thus, the main tank 410 is used as an ink cartridge for each color.
On the other hand, a cartridge holder 404 is provided on the far side of the opening when the cover 401c of the apparatus main body is opened. A main tank 410 is detachably attached to the cartridge holder 404 . As a result, each ink outlet 413 of the main tank 410 communicates with the ejection head 434 for each color via the supply tube 436 for each color, and ink can be ejected from the ejection head 434 onto the printing material.

This recording apparatus can include not only a portion that ejects ink, but also devices called pre-processing devices and post-processing devices.
As an aspect of the pre-treatment device and the post-treatment device, it has a pre-treatment liquid and a post-treatment liquid in the same manner as in the case of inks such as black (K), cyan (C), magenta (M), and yellow (Y). There is a mode in which a liquid container and a liquid ejection head are added, and the pretreatment liquid and the posttreatment liquid are ejected by an inkjet recording method.
As another aspect of the pre-treatment device and the post-treatment device, there is an aspect in which a pre-treatment device and a post-treatment device using a method other than the inkjet recording method, such as a blade coating method, a roll coating method, and a spray coating method, are provided.

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

<Preparation example of yellow pigment dispersion>
After premixing the following formulation mixture, the mixture was circulated and dispersed for 7 hours in a disk-type bead mill (KDL type by Shinmaru Enterprises, media: zirconia balls with a diameter of 0.3 mm) to obtain a yellow pigment dispersion.
・Pigment Yellow 74 (trade name: Fast Yellow 531, manufactured by Dainichiseika Kogyo Co., Ltd.) 15 parts ・Anionic surfactant (Pionin A-51-B, manufactured by Takemoto Oil Co., Ltd.) 2 parts by mass ・Ion-exchanged water 83 part by mass

<Ink preparation example>
(Ink 1)
Ink 1 was obtained by mixing and stirring each component in the following amounts and then filtering through a 5 μm filter (Minisart manufactured by Sartorius). When adding each component, the amount of ion-exchanged water was adjusted so that the total amount was 100% by mass.
・Yellow pigment dispersion (solid concentration: 15% by mass) 20.0% by mass
・ Resin particles (polyurethane resin, product name: Superflex 300, manufacturer: Daiichi Kogyo Seiyaku Co., Ltd., solid content concentration: 30% by mass) 20.0% by mass
· Infrared absorber (trade name: NIR746A, manufacturer: QCR Solutions Corp., maximum absorption wavelength: 746 nm) 1.0% by mass
・Surfactant (trade name: BYK-348, manufacturer: manufactured by BYK) 1.0% by mass
・ 1,2-propanediol (boiling point: 188 ° C.) 15.0% by mass
・Preservative (trade name: Proxel LV, manufacturer: Avecia) 0.1% by mass
・Remaining amount of high-purity water

(ink 2-5)
Inks 2 to 5 were prepared by changing the combination and amount of each component used in preparing ink 1 to the combination and amount shown in Table 1 below. The unit of each number in Table 1 is "% by mass", and the amount of high-purity water was adjusted so that the total amount was 100 parts by mass.

In addition, in the above Table 1, the product names of the components and the names of the manufacturers are as follows.
・Resin particles (acrylic-silicone resin, trade name: AE980, manufacturer: manufactured by ETEC, solid content concentration: 50% by mass)
・ Infrared absorber (trade name: ADS832WS, manufacturer: American Dye Source, maximum absorption wavelength: 830 nm)
・ Infrared absorber (trade name: NIR980A, manufacturer: QCR Solutions Corp., maximum absorption wavelength: 980 nm)
・Surfactant (trade name: FS300, manufacturer: manufactured by Dupont)
・ 1,3-butanediol (boiling point: 207 ° C.)
- 1,2-hexanediol (boiling point: 223°C)
· 3-methoxy-3-methylbutanol (boiling point: 174 ° C.)
・Glycerin (boiling point: 290°C)

In Table 1 above, all the infrared absorbents have a maximum absorption wavelength of 0.5 or less at 380 nm or more and 700 nm or less, where 1 is the maximum absorption wavelength at 700 nm or more and 1000 nm or less.

<Preparation example of pretreatment liquid>
(Pretreatment liquid 1)
After mixing and stirring each component in the following amounts, the mixture was filtered through a 5 μm filter (Minisart manufactured by Sartorius) to obtain a pretreatment liquid 1. When adding each component, the amount of ion-exchanged water was adjusted so that the total amount was 100% by mass.
・ 1,2-propanediol 10.0% by mass
・Surfactant (trade name: Emulgen LS-106, manufacturer: manufactured by Kao Corporation) 1.0% by mass
・Calcium carbonate monohydrate 2.0% by mass
・Silver particles (volume average particle diameter: 320 nm) 3.0% by mass
・Preservative (trade name: Proxel LV, manufacturer: Avecia) 0.1% by mass
・Remaining amount of deionized water

(Pretreatment solutions 2 to 7)
Pretreatment liquids 2 to 7 were prepared by changing the combination and addition amount of each component used in the preparation of pretreatment liquid 1 to the combination and addition amount shown in Table 2 below. The unit of each number in Table 2 below is "% by mass", and the amount of ion-exchanged water was adjusted so that the total amount was 100 parts by mass. For each first inorganic particle in Table 2 below, metal nanoparticles manufactured by SIGMA-ALDRICH were used.

<Preparation example of post-treatment liquid>
(Post-treatment liquid 1)
After mixing and stirring each component in the following amounts, the mixture was filtered through a 5 μm filter (Minisart manufactured by Sartorius) to obtain a post-treatment liquid 1. When adding each component, the amount of ion-exchanged water was adjusted so that the total amount was 100% by mass.
・ 1,2-propanediol 10.0% by mass
・Surfactant (trade name: Emulgen LS-106, manufacturer: manufactured by Kao Corporation) 1.0% by mass
・ Titanium oxide (trade name: TTO-55 (B), manufacturer: manufactured by Ishihara Sangyo Co., Ltd., volume average particle size: 40 nm) 3.0% by mass
・Preservative (trade name: Proxel LV, manufacturer: Avecia) 0.1% by mass
・Remaining amount of deionized water

(Post-treatment liquids 2 to 7)
Pretreatment liquids 2 to 7 were prepared by changing the combination and addition amount of each component used in the preparation of post-treatment liquid 1 to the combination and addition amount shown in Table 3 below. The unit of each number in Table 3 is "% by mass", and the amount of ion-exchanged water was adjusted so that the total amount was 100 parts by mass.

In addition, in the above Table 3, the product names of the components and the names of the manufacturers are as follows.
・ Titanium oxide (trade name: TTO-51 (A), manufacturer: manufactured by Ishihara Sangyo Co., Ltd., volume average particle size: 20 nm)
・ Titanium oxide (trade name: TTO-S-1, manufacturer: manufactured by Ishihara Sangyo Co., Ltd., volume average particle size: 75 nm)
・ Titanium oxide (trade name: TTO-V-3, manufacturer: manufactured by Ishihara Sangyo Co., Ltd., volume average particle size: 60 nm)
・ Titanium oxide (trade name: TTO-51 (A), manufacturer: manufactured by Ishihara Sangyo Co., Ltd., volume average particle size: 20 nm)
・ Zinc oxide (trade name: XZ-100F-LP, manufacturer: manufactured by Sakai Chemical Industry Co., Ltd., volume average particle size: 100 nm)
・ Titanium oxide (trade name: CR-EL, manufacturer: manufactured by Ishihara Sangyo Co., Ltd., volume average particle size: 250 nm)

(Examples 1 to 15, Comparative Examples 1 to 4)
The obtained ink, pretreatment liquid, and posttreatment liquid were used as a set of combinations described in Table 4 below. This set was evaluated for deformability of the printed material, discoloration of the layer formed from the liquid composition, and dryness of the recorded material according to the methods and evaluation criteria shown below. Table 4 shows the evaluation results.

[Deformability]
A modified machine of an inkjet printer IPSiO GX5000 (manufactured by Ricoh Co., Ltd.) is filled with ink, a pretreatment liquid, and a posttreatment liquid, respectively, and a polyvinyl chloride film (CPPVWP1300, manufactured by Sakurai Co., Ltd., hereinafter also referred to as "PVC film"). ), a solid image was formed at a resolution of 600 dpi. In addition, the modified inkjet printer has a pretreatment liquid application process in which the amount of pretreatment liquid applied to the PVC film is adjusted to 3 g/m ² immediately before the ink ejection process, and the applied pretreatment liquid and a pre-treatment liquid drying step of drying with hot air of 80° C. for 2 minutes. In addition, the modified inkjet printer has a post-treatment liquid application process in which a post-treatment liquid is applied to the area to which the ink has been applied by an inkjet method immediately after the ink ejection process, and a PVC film after the post-treatment liquid is applied. is passed through the infrared irradiation unit at a speed of 2 m / min, and a hot air drying process in which the PVC film after the infrared irradiation is dried with hot air at 70 ° C. for 1 minute. It is

Next, the printed PVC film was visually observed and evaluated according to the following criteria. When the evaluation was B or higher, it was judged to be practicable.
(Evaluation criteria)
A: Virtually no deformation of the PVC film is observed B: Some deformation of the PVC film is observed C: Deformation of the PVC film is clearly observed

[Discoloration]
First, a printed matter having a solid image was produced in the same manner as in the deformability evaluation.
Thereafter, the image density was measured using a reflection densitometer X-Rite eXact (manufactured by X-Rite) in an environment of 23° C. and 40% RH to measure the color characteristics of the initial image.
Next, a degraded image of the printed matter was produced using a xenon weatherometer Ci35AW manufactured by Atlas. A xenon weatherometer Ci35AW irradiates ultraviolet rays with a wavelength of 340 nm with an irradiance set to 0.35 mW/m ² , uses a B-Si/B-Si filter, sets the black panel temperature to 89 ° C., and uses a dry bulb The temperature was set at 70° C., the relative humidity was 50% RH, and irradiation was carried out for 24 hours. Thereafter, the image density was measured using a reflection densitometer X-Rite eXact (manufactured by X-Rite) under an environment of 23° C. and 40% RH to measure the color characteristics of the deteriorated image.
The color difference ΔE between the image density before exposure and the image density after exposure was calculated and evaluated according to the following criteria. When the evaluation was B or higher, it was judged to be practicable.
(Evaluation criteria)
A: ΔE is less than 35 B: ΔE is 35 or more and less than 40 C: ΔE is 40 or more

[Drying]
First, a printed matter having a solid image was produced in the same manner as in the deformability evaluation.
Next, a filter paper was pressed against the solid image formed on the PVC film, and the state of transfer to the filter paper was visually observed and evaluated according to the following criteria. A case where the evaluation was B or higher was judged to be a favorable case.
(Evaluation criteria)
A: Pigment transfer to filter paper is hardly observed B: Pigment transfer is observed to some extent C: Pigment is clearly transferred

400 Image forming apparatus 401 Exterior of image forming apparatus 401c Cover of apparatus main body 404 Cartridge holder 410 Main tank 410k, 410c, 410m, 410y For black (K), cyan (C), magenta (M), and yellow (Y) main tank 411 ink storage unit 413 ink discharge port 414 storage container case 420 mechanism unit 434 ejection head 436 supply tube

JP 2016-65137 A JP 2017-2255 A

Claims (19)

a pretreatment liquid applied to an object to be printed and containing first inorganic particles having a volume average particle diameter of 300 nm or more, wherein the first inorganic particles are metal particles;
a liquid composition applied to a region of the substrate to which the pretreatment liquid has been applied;
a post-treatment liquid applied to the area of the substrate to which the liquid composition has been applied and containing second inorganic particles having a volume average particle size of 200 nm or less ;
The first inorganic particles are contained in an amount of 2.0% by mass or more and 5.0% by mass or less with respect to the total amount of the pretreatment liquid,
A liquid set in which the second inorganic particles are contained in an amount of 2.0% by mass or more and 5.0% by mass or less with respect to the total amount of the post-treatment liquid . a pretreatment liquid applied to a material to be printed and containing first inorganic particles having a volume average particle diameter of 300 nm or more;
a liquid composition applied to a region of the substrate to which the pretreatment liquid has been applied;
a post-treatment liquid that is applied to the area of the substrate to which the liquid composition has been applied and that contains second inorganic particles having a volume average particle size of 200 nm or less ;
The second inorganic particles are metal oxide particles ,
The first inorganic particles are contained in an amount of 2.0% by mass or more and 5.0% by mass or less with respect to the total amount of the pretreatment liquid,
A liquid set in which the second inorganic particles are contained in an amount of 2.0% by mass or more and 5.0% by mass or less with respect to the total amount of the post-treatment liquid . a pretreatment liquid applied to a material to be printed and containing first inorganic particles having a volume average particle diameter of 300 nm or more;
a liquid composition applied to a region of the substrate to which the pretreatment liquid has been applied ;
a post-treatment liquid applied to the area of the substrate to which the liquid composition has been applied and containing second inorganic particles having a volume average particle size of 200 nm or less ;
The liquid composition contains an infrared absorber having a maximum absorption wavelength of 0.5 or less at 380 nm or more and 700 nm or less when the maximum absorption wavelength at 700 nm or more and 1000 nm or less is 1,
The first inorganic particles are contained in an amount of 2.0% by mass or more and 5.0% by mass or less with respect to the total amount of the pretreatment liquid,
A liquid set in which the second inorganic particles are contained in an amount of 2.0% by mass or more and 5.0% by mass or less with respect to the total amount of the post-treatment liquid . a pretreatment liquid applied to a material to be printed and containing first inorganic particles having a volume average particle diameter of 300 nm or more;
a liquid composition applied to a region of the substrate to which the pretreatment liquid has been applied ;
a post-treatment liquid applied to the area of the substrate to which the liquid composition has been applied and containing second inorganic particles having a volume average particle size of 200 nm or less ;
The liquid composition contains Pigment Yellow 74,
The first inorganic particles are contained in an amount of 2.0% by mass or more and 5.0% by mass or less with respect to the total amount of the pretreatment liquid,
A liquid set in which the second inorganic particles are contained in an amount of 2.0% by mass or more and 5.0% by mass or less with respect to the total amount of the post-treatment liquid . 5. The liquid set according to claim 1, wherein the first inorganic particles have a volume average particle diameter of 2000 nm or less. The liquid set according to any one of claims 1 to 5, wherein the second inorganic particles have a volume average particle size of 5 nm or more. The liquid set according to any one of claims 1 to 6, wherein the liquid composition contains alcohol having a boiling point of 240°C or less. 8. The liquid set according to any one of claims 1 to 7, wherein said first inorganic particles are at least one selected from silver particles, aluminum particles, iron particles and copper particles. 9. The liquid set according to any one of claims 1 to 8, wherein said second inorganic particles are at least one selected from titanium oxide particles and zinc oxide particles. A pretreatment liquid containing first inorganic particles having a volume-average particle diameter of 300 nm or more, wherein the first inorganic particles are metal particles. a granting means;
a liquid composition applying means for applying a liquid composition to the area of the substrate to which the pretreatment liquid has been applied;
post-treatment liquid applying means for applying a post-treatment liquid containing second inorganic particles having a volume average particle size of 200 nm or less to the area of the substrate to which the liquid composition has been applied ;
The first inorganic particles are contained in an amount of 2.0% by mass or more and 5.0% by mass or less with respect to the total amount of the pretreatment liquid,
The recording apparatus in which the second inorganic particles are contained in an amount of 2.0% by mass or more and 5.0% by mass or less with respect to the total amount of the post-treatment liquid . a pretreatment liquid applying means for applying a pretreatment liquid containing first inorganic particles having a volume average particle diameter of 300 nm or more to an object to be printed;
a liquid composition applying means for applying a liquid composition to the area of the substrate to which the pretreatment liquid has been applied;
post-treatment liquid applying means for applying a post- treatment liquid containing second inorganic particles having a volume average particle size of 200 nm or less to the area of the substrate to which the liquid composition has been applied ;
The second inorganic particles are metal oxide particles,
The first inorganic particles are contained in an amount of 2.0% by mass or more and 5.0% by mass or less with respect to the total amount of the pretreatment liquid,
The recording apparatus in which the second inorganic particles are contained in an amount of 2.0% by mass or more and 5.0% by mass or less with respect to the total amount of the post-treatment liquid . a pretreatment liquid applying means for applying a pretreatment liquid containing first inorganic particles having a volume average particle diameter of 300 nm or more to an object to be printed;
a liquid composition applying means for applying a liquid composition to the area of the substrate to which the pretreatment liquid has been applied;
post-treatment liquid applying means for applying a post-treatment liquid containing second inorganic particles having a volume average particle size of 200 nm or less to the area of the substrate to which the liquid composition has been applied ;
The liquid composition has an infrared absorber having a maximum absorption wavelength of 0.5 or less at 380 nm or more and 700 nm or less when the maximum absorption wavelength at 700 nm or more and 1000 nm or less is 1 ,
The first inorganic particles are contained in an amount of 2.0% by mass or more and 5.0% by mass or less with respect to the total amount of the pretreatment liquid,
The recording apparatus in which the second inorganic particles are contained in an amount of 2.0% by mass or more and 5.0% by mass or less with respect to the total amount of the post-treatment liquid . a pretreatment liquid applying means for applying a pretreatment liquid containing first inorganic particles having a volume average particle diameter of 300 nm or more to an object to be printed;
a liquid composition applying means for applying a liquid composition to the area of the substrate to which the pretreatment liquid has been applied;
post-treatment liquid applying means for applying a post-treatment liquid containing second inorganic particles having a volume average particle size of 200 nm or less to the area of the substrate to which the liquid composition has been applied ;
The liquid composition contains Pigment Yellow 74,
The first inorganic particles are contained in an amount of 2.0% by mass or more and 5.0% by mass or less with respect to the total amount of the pretreatment liquid,
The recording apparatus in which the second inorganic particles are contained in an amount of 2.0% by mass or more and 5.0% by mass or less with respect to the total amount of the post-treatment liquid . 14. The recording apparatus according to any one of claims 10 to 13, further comprising infrared irradiation means for irradiating a region to which the liquid composition is applied with light containing infrared rays. 15. The substrate according to any one of claims 10 to 14, wherein the substrate to be printed is a non-permeable substrate having a water absorption of 10 mL/ ^m2 or less from the start of contact to 30 msec ^1/2 in the Bristow method. recording device. A pretreatment liquid containing first inorganic particles having a volume-average particle diameter of 300 nm or more, wherein the first inorganic particles are metal particles. a granting step;
a liquid composition application step of applying a liquid composition to the area of the substrate to which the pretreatment liquid has been applied;
a post-treatment liquid application step of applying a post-treatment liquid containing second inorganic particles having a volume average particle diameter of 200 nm or less to the area of the substrate to which the liquid composition has been applied ;
The first inorganic particles are contained in an amount of 2.0% by mass or more and 5.0% by mass or less with respect to the total amount of the pretreatment liquid,
A recording method in which the second inorganic particles are contained in an amount of 2.0% by mass or more and 5.0% by mass or less with respect to the total amount of the post-treatment liquid . A pretreatment liquid applying step of applying a pretreatment liquid containing first inorganic particles having a volume average particle diameter of 300 nm or more to a material to be printed;
a liquid composition application step of applying a liquid composition to the area of the substrate to which the pretreatment liquid has been applied;
A post-treatment liquid containing second inorganic particles having a volume average particle diameter of 200 nm or less with respect to the area of the substrate to which the liquid composition is applied ,
a post-treatment liquid application step of applying a post-treatment liquid to the second inorganic particles, which are metal oxide particles ;
The first inorganic particles are contained in an amount of 2.0% by mass or more and 5.0% by mass or less with respect to the total amount of the pretreatment liquid,
A recording method in which the second inorganic particles are contained in an amount of 2.0% by mass or more and 5.0% by mass or less with respect to the total amount of the post-treatment liquid . A pretreatment liquid applying step of applying a pretreatment liquid containing first inorganic particles having a volume average particle diameter of 300 nm or more to a material to be printed;
a liquid composition application step of applying a liquid composition to the area of the substrate to which the pretreatment liquid has been applied;
a post-treatment liquid application step of applying a post-treatment liquid containing second inorganic particles having a volume average particle diameter of 200 nm or less to the area of the substrate to which the liquid composition has been applied ;
The liquid composition has an infrared absorber having a maximum absorption wavelength of 0.5 or less at 380 nm or more and 700 nm or less when the maximum absorption wavelength at 700 nm or more and 1000 nm or less is 1 ,
The first inorganic particles are contained in an amount of 2.0% by mass or more and 5.0% by mass or less with respect to the total amount of the pretreatment liquid,
A recording method in which the second inorganic particles are contained in an amount of 2.0% by mass or more and 5.0% by mass or less with respect to the total amount of the post-treatment liquid . A pretreatment liquid applying step of applying a pretreatment liquid containing first inorganic particles having a volume average particle diameter of 300 nm or more to a material to be printed;
a liquid composition application step of applying a liquid composition to the area of the substrate to which the pretreatment liquid has been applied;
a post-treatment liquid application step of applying a post-treatment liquid containing second inorganic particles having a volume average particle diameter of 200 nm or less to the area of the substrate to which the liquid composition has been applied ;
The liquid composition contains Pigment Yellow 74,
The first inorganic particles are contained in an amount of 2.0% by mass or more and 5.0% by mass or less with respect to the total amount of the pretreatment liquid,
A recording method in which the second inorganic particles are contained in an amount of 2.0% by mass or more and 5.0% by mass or less with respect to the total amount of the post-treatment liquid .

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