JP2020007396A - White liquid composition, printing method, and printer - Google Patents

Abstract

To provide a white liquid composition that can achieve both excellent whiteness and heat resistance.SOLUTION: The present invention provides a white liquid composition containing a resin particle, the resin particle having a styrene-derived structural unit, a (meth) acryl compound-derived structural unit, 1,3-diethylbenzene.SELECTED DRAWING: None

Description

  The present invention relates to a white liquid composition, a printing method, and a printing device.

  In general, a system using titanium dioxide is used as a coloring material of the white ink for ink jet. Further, a white ink using hollow resin particles having a hollow inner layer as a white color material is also known. The hollow resin particles exhibit whiteness by utilizing the difference in the refractive index between the inner layer (air layer) and the outer shell resin. Such hollow resin particles are being used because they are superior to titanium dioxide in terms of whiteness and sedimentation.

  For example, an ink composition containing hollow resin particles and an agent for preventing the hollow resin particles from being transparent has been proposed (for example, see Patent Document 1).

  An object of the present invention is to provide a white liquid composition that can achieve both excellent whiteness and heat resistance.

  The white liquid composition of the present invention as a means for solving the above-mentioned problem is a white liquid composition containing resin particles, wherein the resin particles have a structural unit derived from styrene and a (meth) acrylic compound. And 1,3-diethylbenzene.

  According to the present invention, it is possible to provide a white liquid composition that can achieve both excellent whiteness and heat resistance.

FIG. 1 is a schematic diagram illustrating an example of a printing apparatus according to the present invention. FIG. 2 is a schematic diagram illustrating an example of another printing apparatus according to the present invention. FIG. 3 is an external perspective view illustrating an example of the ejection head in the printing apparatus of the present invention. FIG. 4 is an explanatory cross-sectional view in a direction orthogonal to the nozzle arrangement direction of the ejection head of FIG. FIG. 5 is a partial cross-sectional explanatory view in a direction parallel to the nozzle arrangement direction of the ejection head of FIG. FIG. 6 is an explanatory plan view of a nozzle plate of the ejection head of FIG. FIG. 7A is an explanatory plan view of each member constituting a flow path member of the ejection head of FIG. 3. FIG. 7B is an explanatory plan view of each member constituting the flow path member of the ejection head in FIG. 3. FIG. 7C is an explanatory plan view of each member constituting the flow path member of the ejection head in FIG. 3. FIG. 7D is an explanatory plan view of each member constituting the flow path member of the ejection head in FIG. 3. FIG. 7E is an explanatory plan view of each member constituting the flow path member of the ejection head in FIG. 3. FIG. 7F is an explanatory plan view of each member constituting the flow path member of the ejection head in FIG. 3. FIG. 8A is an explanatory plan view of each member constituting a common liquid chamber member of the ejection head of FIG. 3. FIG. 8B is an explanatory plan view of each member constituting the common liquid chamber member of the ejection head of FIG. 3. FIG. 9 is a block diagram showing an example of the white liquid composition circulation system according to the present invention. FIG. 10 is a sectional view taken along line A-A ′ of FIG. FIG. 11 is a sectional view taken along the line B-B 'of FIG.

(White liquid composition)
The white liquid composition of the present invention is a white liquid composition containing resin particles, wherein the resin particles have a structural unit derived from styrene, a structural unit derived from a (meth) acrylic compound, and 1,3-diethylbenzene. And, if necessary, other components.

  The white liquid composition of the present invention, in the prior art, because the hollow resin particles as a white color material contains a resin as a main component, the resin itself is dissolved when heat is applied in a drying step weakly to heat. This is based on the finding that sufficient whiteness cannot be obtained.

Therefore, the white liquid composition of the present invention contains resin particles obtained by crosslinking a copolymer having a structural unit derived from styrene and a structural unit derived from a (meth) acrylic compound with 1,3-diethylbenzene. Thereby, both excellent whiteness and heat resistance can be achieved.
In addition, by crosslinking the resin particles, the refractive index of the resin tends to decrease, and the whiteness tends to decrease slightly. Therefore, in the present invention, it is preferable to further add a fluorescent whitening agent and a fluorescent whitening enhancer.

<Resin particles>
The resin particles include a structural unit derived from styrene, a structural unit derived from a (meth) acrylic compound, and 1,3-diethylbenzene. More specifically, the resin particles include a structural unit represented by the following structural formula (1) and at least one type selected from structural units represented by the following structural formulas (2) to (4). It is preferable to include a structural unit and 1,3-diethylbenzene from the viewpoints of brightness and heat resistance of the resin particles, and include a structural unit represented by the following structural formula (1) and a structural unit represented by the following structural formula (2). It is more preferable to include a structural unit represented by the following formula, a structural unit represented by the following structural formula (4), and 1,3-diethylbenzene.
A copolymer is obtained by polymerizing a structural unit represented by the structural formula (1) with at least one structural unit selected from the structural units represented by the structural formulas (2) to (4). Is formed, and the obtained copolymer is crosslinked by 1,3-diethylbenzene which is a crosslinking agent.

The structural unit represented by the structural formula (1) is used mainly for the purpose of improving brightness. At least one structural unit selected from the structural units represented by the structural formulas (2) to (4) is used mainly for the purpose of improving heat resistance.
The ratio of the structural unit represented by the structural formula (1) in the resin particles and at least one structural unit selected from the structural units represented by the structural formulas (2) to (4) is white. When the liquid composition is used, at least one selected from the structural units represented by the structural formula (1) and the structural units represented by the structural formulas (4) to (4) included in the white liquid composition. The ratio is almost the same as that of one structural unit.
For the calculation of the ratio, the IR spectrum of the dried film of the resin particles was used, and the absorption band of 1600 cm ^-1 ± 10 cm ^-1 due to the C = C stretching vibration of the aromatic unit of the structural unit represented by the structural formula (1) was used. and the maximum value X, the structural formula (2) from the absorption band of the structural formula (4) derived from the carbonyl stretching vibration of the at least one structural unit selected from structural units represented by to 1730 cm ^-1 ± 10 cm ^-1 It can be calculated by taking a ratio (Y / X) with the maximum value Y, and this ratio (Y / X) is 3.0 or more and 6.0 or less, and preferably 3.0 or more and 5.5 or less. .
When the ratio (Y / X) is 3.0 or more, the heat resistance of the resin particles is improved, and as a result, a decrease in brightness caused by dissolution of the resin of the resin particles by energy such as heat can be suppressed. it can. On the other hand, when the ratio (Y / X) is 6.0 or less, the brightness of the resin particles is improved, and the sedimentability of the resin particles can be improved.
The ratio of the structural unit represented by the structural formula (1) and at least one structural unit selected from the structural units represented by the structural formulas (2) to (4) in the white liquid composition. (Y / X) is also preferably 3.0 or more and 6.0 or less.

  The amount of 1,3-diethylbenzene added to the resin particles is not particularly limited and can be appropriately selected depending on the intended purpose; however, it is preferably 0.01% by mass or more and 0.1% by mass or less.

  As the structural analysis of the resin particles, for example, a structural analysis using a micro FT-IR measuring apparatus (apparatus name: iN10MX / iZ10, manufactured by Thermo Fisher Scientific) and analysis software (OMNIC) is performed. It can be confirmed from 1) that the compound has the structural unit represented by the structural formula (4).

  As the resin particles, hollow resin particles are preferable. The hollow resin particles are hollow resin particles whose outer shell is formed of a resin.

<< hollow resin particles >>
The hollow resin particles have an inner layer formed of a hollow and an outer layer formed of a resin. The outer diameter is preferably 0.1 μm or more and 1 μm or less, and the inner diameter is preferably 0.04 μm or more and 0.8 μm or less.
Since the hollow resin particles have a hollow inner layer, the specific gravity of the white liquid composition is about 1, and does not settle with time unlike a metal oxide having a large specific gravity. In order to avoid sedimentation over time, the thickness of the resin of the hollow resin particles is preferably 10% or more and 20% or less based on the size of the entire hollow resin particles.

The volume average particle diameter of the hollow resin particles is preferably 0.4 μm or more and 0.6 μm or less. When the volume average particle diameter is 0.4 μm or more, it is possible to secure lightness even for a recording medium such as high quality paper. On the other hand, when the volume average particle diameter is 0.6 μm or less, it is possible to improve the sedimentation property and the ejection stability.
The volume average particle size of the hollow resin particles can be determined, for example, using a particle size distribution measuring device based on a dynamic light scattering method. Examples of the particle size distribution measuring device by the dynamic light scattering method include Nanotrac Wave-UT151 (Microtrac Bell Co., Ltd.), Nanotrac Wave-EX150 (Nikkiso Co., Ltd.), ELSZ-2, and DLS-. 8000 (all manufactured by Otsuka Electronics Co., Ltd.) and LB-550 (manufactured by Horiba, Ltd.).

  The method for preparing the hollow resin particles is not particularly limited, and a known method can be applied. For example, styrene, a (meth) acrylic compound, 1,3-diethylbenzene, a surfactant, a polymerization initiator, In addition, a so-called emulsion polymerization method in which a hollow resin emulsion is formed by stirring the aqueous dispersion medium while heating it under a nitrogen atmosphere can be applied.

  The thickness of the resin layer of the hollow resin particles is preferably from 30 nm to 100 nm, more preferably from 40 nm to 60 nm. By setting the thickness of the resin layer of the hollow resin particles to 30 nm or more, it is possible to suppress a decrease in brightness caused by dissolution of the resin of the hollow resin particles by energy such as heat. On the other hand, by setting the thickness of the resin layer of the hollow resin particles to 100 nm or less, it is possible to improve the sedimentation property and the ejection stability.

  The hollow ratio of the hollow resin particles is preferably from 30% to 60%, more preferably from 30% to 50%. By setting the hollow ratio of the hollow resin particles to 30% or more, it is possible to improve the sedimentation property and the ejection stability. On the other hand, by setting the hollow ratio of the hollow resin particles to 60% or less, a desired lightness can be exhibited without being affected by the base color of the recording medium. In addition, the hollow ratio of the hollow resin particles can be calculated by the following Equation 1.

[Formula 1]

  The glass transition temperature of the hollow resin particles is preferably 120 ° C or higher, more preferably 120 ° C or higher and 140 ° C or lower, further preferably 120 ° C or higher and 130 ° C or lower. By setting the glass transition temperature of the hollow resin particles to 120 ° C. or higher, it is possible to suppress a decrease in brightness caused by dissolution of the resin of the hollow resin particles by energy such as heat. On the other hand, by setting the glass transition temperature of the hollow resin particles to 140 ° C. or lower, a desired brightness can be exhibited without being affected by the undercolor of the recording medium.

  The content of the resin particles is preferably 5% by mass or more and 20% by mass or less, more preferably 8% by mass or more and 15% by mass or less based on the total amount of the white liquid composition. By setting the content of the resin particles to 5% by mass or more, it is possible to secure the film thickness of the white liquid composition even on a recording medium such as high quality paper. On the other hand, by setting the content of the hollow resin particles to 20% by mass or less, it is possible to improve the sedimentation property and the ejection stability.

<Fluorescent brightener>
The fluorescent whitening agent absorbs invisible ultraviolet rays on the short wavelength side and changes it into visible purple to blue light, and is also called a fluorescent dye. In the present invention, this fluorescent whitening agent is used for the purpose of improving lightness.
As the fluorescent whitening agent, a compound represented by the following structural formula (5) or (6) is used.

[Structural formula (5)]

[Structural formula (6)]

Those having the structural unit represented by the structural formula (5) are benzoxazoles or derivatives thereof, and those having the structural unit represented by the structural formula (6) are coumarins or derivatives thereof, and have hydrophilicity and Any hydrophobic material may be used.
The content of the fluorescent whitening agent is preferably from 0.001% by mass to 1% by mass, more preferably from 0.005% by mass to 0.2% by mass, based on the total amount of the white liquid composition. By setting the content of the fluorescent whitening agent to be 0.001% by mass or more, the desired brightness can be exhibited without being affected by the undercolor of the recording medium. On the other hand, when the content of the fluorescent whitening agent is 1% by mass or less, it is possible to suppress the concentration quenching phenomenon in which incident light is immediately absorbed or the fluorescence intensity is reduced due to collision between molecules.
As the fluorescent whitening agent, an appropriately synthesized one may be used, or a commercially available product may be used. Examples of the commercially available products include TINOPAL OB manufactured by BASF, Nikkafluor OB and Nikkabright PAW-L manufactured by Nippon Chemical Industry Co., Ltd., and Nikkafluor MCT manufactured by Nippon Chemical Industry Co., Ltd.

<Fluorescent whitening enhancer>
In the present invention, a fluorescent whitening enhancer may be used to improve the effect of the fluorescent whitening agent.
The fluorescent whitening enhancer enhances the effect of the fluorescent whitening agent by improving the dispersibility of the fluorescent whitening agent and transferring the fluorescent whitening agent to the surface. Specific examples include a polyether polyol compound.
The content of the fluorescent whitening enhancer is preferably from 0.2% by mass to 2% by mass, more preferably from 0.5% by mass to 2% by mass, based on the content of the white colorant. By setting the content of the fluorescent whitening enhancer to 0.2% by mass or more based on the content of the white color material, a desired lightness can be exhibited without being affected by the base color of the recording medium. On the other hand, by setting the content of the fluorescent whitening enhancer to 2% by mass or less based on the content of the white color material, the ejection stability can be improved.
As the fluorescent whitening enhancer, an appropriately synthesized one may be used, or a commercially available product may be used. Examples of the commercially available product include Optiact I-10 manufactured by San Nopco.

<Organic solvent>
As the organic solvent used in the present invention, a mixed SP value calculated from a solubility parameter (hereinafter, referred to as an SP value) of the organic solvent excluding water in the white liquid composition is 12.0 [cal / cm ³ ] ^0. it is preferable ^.5 or 15.0 [cal ^/ cm ^3] is ^0.5 or less. The dissolution of the resin of the hollow resin particles by the organic solvent can be suppressed by setting the mixed SP value of the organic solvent excluding water to 12.0 [cal / cm ³ ] ^0.5 or more. On the other hand, by setting the mixed SP value of the organic solvent excluding water to 15.0 [cal / cm ³ ] ^0.5 or less, it is possible to suppress the deterioration of fixability due to poor drying.
The mixed SP value of the organic solvent contained in the white liquid composition was calculated by the following equation.
Mixed SP value of organic solvent in white liquid composition [cal / cm ³ ] ^0.5
= [SP value of organic solvent A x volume fraction of organic solvent A] + ... + [SP value of organic solvent Z x volume fraction of organic solvent Z]
Further, the organic solvent in the present invention includes those classified as a penetrant or an antifoaming agent in function, but in the present invention, only those containing 3% by mass or more based on the whole white liquid composition are included. It is used in the calculation of the mixed SP value.

The organic solvent used in the present invention is not particularly limited, and a water-soluble organic solvent can be used. Examples thereof include ethers such as polyhydric alcohols, polyhydric alcohol alkyl ethers and polyhydric alcohol aryl ethers, nitrogen-containing heterocyclic compounds, amides, amines, and sulfur-containing compounds.
Specific examples of the water-soluble organic solvent include, for example, ethylene glycol, diethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 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-he Polyhydric alcohols such as sundiol, ethyl-1,2,4-butanetriol, 1,2,3-butanetriol, 2,2,4-trimethyl-1,3-pentanediol and petriol; ethylene glycol mono Polyhydric alcohol alkyl ethers such as ethyl 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; ethylene glycol monophenyl ether, ethylene glycol mono Polyhydric alcohol aryl ethers such as benzyl ether; 2-pyrrolidone, N-methyl-2-pyrrolidone, N-hydroxyethyl- Nitrogen-containing heterocyclic compounds such as -pyrrolidone, 1,3-dimethyl-2-imidazolidinone, ε-caprolactam, γ-butyrolactone; formamide, N-methylformamide, N, N-dimethylformamide, 3-methoxy-N, Amides such as N-dimethylpropionamide and 3-butoxy-N, N-dimethylpropionamide; amines such as monoethanolamine, diethanolamine and triethylamine; sulfur-containing compounds such as dimethylsulfoxide, sulfolane and thiodiethanol; 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.

Further, when an organic solvent having a hydrogen bond term of 3.0 [cal / cm ³ ] ^0.5 or more and 6.8 [cal / cm ³ ] ^0.5 or less and a boiling point of 150 ° C. or more and 300 ° C. or less is used. It is more preferable because the fixability is good.
The hydrogen bond term can be obtained by utilizing an atomic group summation method dealing with organic molecules proposed by Krevelen as atomic ^{(Krevelen, Properties of Polymer 3 rd} Edition, New York, see p200~p204).
As the organic solvent satisfying the above conditions, glycerin, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, isoprene glycol, and oxetane compounds are particularly preferable.

A polyol compound having 8 or more carbon atoms and a glycol ether compound are also preferably used. Specific examples of the polyol compound having 8 or more carbon atoms include 2-ethyl-1,3-hexanediol, 2,2,4-trimethyl-1,3-pentanediol, and the like.
Specific examples of the glycol ether compound 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 and ethylene glycol monobenzyl ether;

A polyol compound having 8 or more carbon atoms and a glycol ether compound are also preferably used.
Specific examples of the polyol compound having 8 or more carbon atoms include 2-ethyl-1,3-hexanediol, 2,2,4-trimethyl-1,3-pentanediol, and the like.
Specific examples of the glycol ether compound 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 and ethylene glycol monobenzyl ether;

  A polyol compound having 8 or more carbon atoms and a glycol ether compound can improve the permeability of a white liquid composition when paper is used as a recording medium.

  The content of the organic solvent in the white liquid composition is not particularly limited and may be appropriately selected depending on the intended purpose. % By mass or less, more preferably 20% by mass or more and 60% by mass or less.

<Water>
The content of water in the white liquid composition is not particularly limited and may be appropriately selected depending on the intended purpose. However, from the viewpoint of drying properties and ejection reliability of the white liquid composition, the content is 10% by mass to 90% by mass. The following is preferable, and 20 to 60% by mass is more preferable.

<Resin particles>
The type of the resin contained in the white liquid composition is not particularly limited and can be appropriately selected depending on the purpose. Examples thereof include a urethane resin, a polyester resin, an acrylic resin, a vinyl acetate resin, and a styrene resin. , Butadiene resin, styrene-butadiene resin, vinyl chloride resin, acryl-styrene resin, acryl-silicone resin and the like.
Resin particles made of these resins may be used. It is possible to obtain a white liquid composition by mixing resin particles with a material such as a coloring material or an organic solvent in a state of a resin emulsion in which water is dispersed as a dispersion medium. As the resin particles, appropriately synthesized ones or commercially available ones may be used. These may be used alone or in combination of two or more resin particles.
For the purpose of suppressing the collapse of the hollow resin particles due to impact or the like, the Rockwell hardness (JIS Z2245, JIS B7726) of the resin particles is preferably 80 or more and 130 or less, more preferably 80 or more and 110 or less.
The mixed SP value calculated from the SP value of the resin particles is preferably 8.0 [cal / cm ³ ] ^0.5 or more and 12.0 [cal / cm ³ ] ^0.5 or less. By setting the mixed SP value of the resin particles to 8.0 [cal / cm ³ ] ^0.5 or more, dissolution of the resin of the hollow resin particles by the resin particles can be suppressed. On the other hand, by setting the mixed SP value of the resin particles to 12.0 [cal / cm ³ ] ^0.5 or less, deterioration of the fixing property can be suppressed.
The mixed SP value of the resin particles contained in the white liquid composition can be calculated by the following equation.
Mixed SP value of resin particles in white liquid composition [cal / cm ³ ] ^0.5
= [SP value of resin particle A x volume fraction of resin particle A] + ... + [SP value of resin particle Z x volume fraction of resin particle Z]

The volume average particle size of the resin particles is not particularly limited and may be appropriately selected depending on the intended purpose. However, from the viewpoint of obtaining good fixing properties and high image hardness, the volume average particle size is preferably 10 nm or more and 1,000 nm or less, and 100 nm or less. The thickness is more preferably from 150 nm to 150 nm, and particularly preferably from 10 nm to 100 nm.
The volume average particle size can be measured, for example, using a particle size analyzer (Nanotrack Wave-UT151, manufactured by Microtrac Bell Inc.).

  The content of the resin is not particularly limited and can be appropriately selected depending on the intended purpose. From the viewpoint of fixability and storage stability of the white liquid composition, the content of the resin is 1% based on the total amount of the white liquid composition. The content is preferably from 30% by mass to 30% by mass, more preferably from 1% by mass to 20% by mass.

  The particle size of the solid content in the white liquid composition is not particularly limited and can be appropriately selected depending on the purpose.However, from the viewpoint of improving image quality such as ejection stability and image density, the maximum number of particles is calculated. The maximum frequency is preferably 20 nm or more and 1000 nm or less, more preferably 400 nm or more and 600 nm or less. The solid content includes resin particles and pigment particles. The particle size can be measured using a particle size analyzer (Nanotrack Wave-UT151, manufactured by Microtrac Bell Inc.).

<Lubricant>
The white liquid composition of the present invention preferably contains a wax or a siloxane compound as a lubricant for the purpose of imparting lubricity to the image area.
Among the above waxes, polyethylene wax and carnauba wax are preferred from the viewpoints of film formability and slipperiness when a white liquid composition is applied to an image area.
The melting point of the wax is preferably from 80 ° C to 140 ° C, more preferably from 100 ° C to 140 ° C. By setting the melting point to 80 ° C. or higher, the wax is less likely to melt or coagulate even in a room temperature (25 ° C.) environment, and the storage stability of the white liquid composition can be maintained. On the other hand, by setting the melting point to 140 ° C. or lower, the wax is sufficiently melted even at room temperature (25 ° C.), and it is possible to impart slipperiness to the white liquid composition.
The volume average particle diameter of the wax is preferably 0.01 μm or more, more preferably 0.01 μm or more and 0.1 μm or less. By setting the volume average particle diameter to 0.01 μm or more, the wax particles are easily oriented on the surface of the white liquid composition, and it is possible to provide the white liquid composition with lubricity.
Examples of the polyethylene wax include, as commercial products, Hitec series manufactured by Toho Chemical Industry Co., Ltd., and AQUACER series manufactured by BYK.
Examples of the carnauba wax include commercially available products, such as Cellosol 524 and Trasol CN manufactured by Chukyo Yushi Co., Ltd.
The content of the wax is preferably from 0.1% by mass to 5% by mass, more preferably from 0.1% by mass to 1% by mass, based on the total amount of the white liquid composition.
Examples of the siloxane compound include BYK307, BYK333, and BYK378 manufactured by BYK as commercial products.
The content of the siloxane compound is preferably from 0.1% by mass to 5% by mass, and more preferably from 0.1% by mass to 1% by mass, based on the total amount of the white liquid composition.

<Additives>
If necessary, a surfactant, an antifoaming agent, an antiseptic / antifungal agent, a rust inhibitor, a pH adjuster, and the like may be added to the white liquid composition.

<Surfactant>
As the surfactant, any of a silicone-based surfactant, a fluorine-based surfactant, an amphoteric surfactant, a nonionic surfactant, and an anionic surfactant can be used.
The silicone surfactant is not particularly limited and can be appropriately selected depending on the purpose. Among them, those which do not decompose even at a high pH are preferable, and include, for example, side chain-modified polydimethylsiloxane, both-terminal-modified polydimethylsiloxane, one-terminal-modified polydimethylsiloxane, and both-chain both-terminal-modified polydimethylsiloxane. Those having a polyoxyethylene group or a polyoxyethylene polyoxypropylene group are particularly preferable because they exhibit good properties as an aqueous surfactant. In addition, a polyether-modified silicone-based surfactant can also be used as the silicone-based surfactant, 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 the fluorine-based surfactant include a perfluoroalkylsulfonic acid compound, a perfluoroalkylcarboxylic acid compound, a perfluoroalkylphosphate ester compound, a perfluoroalkylethylene oxide adduct, and a perfluoroalkylether group in a side chain. Polyoxyalkylene ether polymer compounds are particularly preferred because of their low foaming properties. Examples of the perfluoroalkylsulfonic acid compound include perfluoroalkylsulfonic acid and perfluoroalkylsulfonic acid salt. Examples of the perfluoroalkylcarboxylic acid compound include perfluoroalkylcarboxylic acid and perfluoroalkylcarboxylic acid salt. Examples of the polyoxyalkylene ether polymer compound having a perfluoroalkyl ether group in a side chain include a sulfate salt of a polyoxyalkylene ether polymer having a perfluoroalkyl ether group in a side chain, and having a perfluoroalkyl ether group in a side chain. Salts of a polyoxyalkylene ether polymer are exemplified. The counter ions of the salts in these fluorinated surfactants include Li, Na, K, NH ₄ , NH ₃ CH ₂ CH ₂ OH, NH ₂ (CH ₂ CH ₂ OH) ₂ , and NH (CH ₂ CH ₂ OH) _{3 and the} like.
Examples of the amphoteric surfactant include lauryl aminopropionate, lauryl dimethyl betaine, stearyl dimethyl betaine, lauryl dihydroxyethyl betaine, and the like.
Examples of the nonionic surfactant include polyoxyethylene alkyl phenyl ether, polyoxyethylene alkyl ester, polyoxyethylene alkylamine, polyoxyethylene alkyl amide, polyoxyethylene propylene block polymer, sorbitan fatty acid ester, and polyoxyethylene sorbitan. Examples include fatty acid esters and ethylene oxide adducts of acetylene alcohol.
Examples of the anionic surfactant include polyoxyethylene alkyl ether acetate, dodecylbenzene sulfonate, laurylate, and polyoxyethylene alkyl ether sulfate.
These may be used alone or in combination of two or more.

The silicone-based surfactant is not particularly limited and can be appropriately selected depending on the intended purpose. Examples thereof include side-chain modified polydimethylsiloxane, both-terminal-modified polydimethylsiloxane, one-terminal-modified polydimethylsiloxane, Examples include polydimethylsiloxane modified at both ends of the chain, and a polyoxyethylene group having a modifying group, and a polyether-modified silicone surfactant having a polyoxyethylene polyoxypropylene group exhibiting good properties as an aqueous surfactant. preferable.
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, Big Chemie Co., Ltd., Shin-Etsu Chemical Co., Ltd., Dow Corning Toray Silicone Co., Ltd., Japan Emulsion Co., Ltd., Kyoeisha Chemical Co., Ltd.
The polyether-modified silicone-based surfactant is not particularly limited and may be appropriately selected depending on the intended purpose. For example, the polyalkylene oxide structure represented by the general formula (S-1) may be a dimethylpolysiloxane. Examples include those introduced into the side chain of the siloxane in the siloxane.

[General formula (S-1)]
(In the 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-mentioned polyether-modified silicone-based surfactant. For example, KF-618, KF-642, KF-643 (manufactured by Shin-Etsu Chemical Co., Ltd.), EMALEX-SS-5602, SS -1906EX (manufactured by Nippon Emulsion Co., Ltd.), FZ-2105, FZ-2118, FZ-2154, FZ-2161, FZ-2162, FZ-2163, FZ-2164 (manufactured by Dow Corning Toray Silicone Co., Ltd.), BYK -33, BYK-387 (manufactured by Big Chemie Co., Ltd.), TSF4440, TSF4452, and TSF4453 (manufactured by Toshiba Silicon Corporation).

As the fluorine-based surfactant, 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 the fluorine-based surfactant include a perfluoroalkyl phosphate ester compound, a perfluoroalkyl ethylene oxide adduct, and a polyoxyalkylene ether polymer compound having a perfluoroalkyl ether group in a side chain.
Among these, a polyoxyalkylene ether polymer compound having a perfluoroalkyl ether group in the side chain is preferable because of its low foaming property, and particularly, fluorine represented by the general formulas (F-1) and (F-2). A system surfactant is preferred.

[General formula (F-1)]
In the compound represented by the above 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.

General formula (F-2)
_{C n F 2n + 1- CH 2} CH (OH) CH 2 -O- (CH 2 CH 2 O) a -Y
In the compound represented by the general formula (F-2), Y is H, or _C m _{F 2m + 1} with m is an integer of 1 to 6, or _{CH 2 CH (OH) CH 2} -C m F 2m + 1 m is P is an integer of 1 to 19, or an integer of 4 to 6, or p is an integer of 1 to 19 at CpH _{2p + 1} . n is an integer of 1 to 6. a is an integer of 4 to 14.

  A commercially available product may be used as the above-mentioned fluorine-based surfactant. 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.); Fullard FC-93, FC-95, FC-98, FC-129, FC-135, FC-170C, FC-430, FC-431 (all manufactured by Sumitomo 3M Limited); Megafac F-470, F -1405, F-474 (all manufactured by DIC Corporation); 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 And 403N (manufactured by Daikin Industries, Ltd.). Among these, FS manufactured by Chemours Co., Ltd. is preferred because of its markedly improved printing quality, in particular, color development, paper permeability, wettability, and levelness. -3100, FS-34, FS-300, Neos Corporation FT-110, FT-250, FT-251, FT-400S, FT-150, FT-400SW, Omnova Polyfox PF-151N and Unidyne DSN-403N manufactured by Daikin Industries, Ltd. is particularly preferred.

  The content of the surfactant in the white liquid composition is not particularly limited and can be appropriately selected depending on the purpose. However, from the viewpoint of excellent wettability and ejection stability and improvement in image quality, 0 0.001% by mass or more and 5% by mass or less, more preferably 0.05% by mass or more and 5% by mass or less.

<Defoaming agent>
The defoaming agent is not particularly limited, and examples thereof include a silicone-based defoaming agent, a polyether-based defoaming agent, and a fatty acid ester-based defoaming agent. These may be used alone or in combination of two or more. Among these, silicone-based antifoaming agents are preferred because of their excellent foam breaking effect.

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

<Rust inhibitor>
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 the pH can be adjusted to 7 or more, and examples thereof include amines such as diethanolamine and triethanolamine.

The physical properties of the white liquid composition are not particularly limited and may be appropriately selected depending on the purpose. For example, the viscosity, surface tension, pH, and the like are preferably in the following ranges.
The viscosity of the white liquid composition at 25 ° C. is preferably 5 mPa · s or more and 30 mPa · s or less, and more preferably 5 mPa · s or more and 25 mPa · s or less, from the viewpoint of improving print density and character quality and obtaining good ejection properties. s or less is more preferable. Here, for the viscosity, for example, a rotary viscometer (manufactured by Toki Sangyo Co., Ltd., RE-80L) can be used. As measurement conditions, measurement can be performed at 25 ° C. with a standard cone rotor (1 ° 34 ′ × R24), a sample liquid amount of 1.2 mL, a rotation speed of 50 rpm, and 3 minutes.
The surface tension of the white liquid composition is preferably 35 mN / m or less at 25 ° C, more preferably 30 mN, from the viewpoint that the white liquid composition is suitably leveled on the recording medium and the drying time of the white liquid composition is shortened. / M or less is more preferable.
The pH of the white liquid composition is preferably from 7 to 12, and more preferably from 8 to 11, from the viewpoint of preventing corrosion of the metal member in contact with the liquid.

<Recording medium>
The recording medium used for recording is not particularly limited, and examples thereof include plain paper, glossy paper, special paper, cloth, film, OHP sheet, and general-purpose printing paper.

  The recording medium is not limited to one used as a general recording medium, and may be a building material such as wallpaper, flooring and tiles, a cloth for clothing such as a T-shirt, a textile, leather and the like. Further, by adjusting the configuration of the path for transporting the recording medium, ceramics, glass, metal, or the like can be used.

<Printed matter>
A printed material using the white liquid composition has an image formed on a recording medium using the white liquid composition of the present invention.
The printed matter can be printed by the printing apparatus and the printing method of the present invention.

  When a printed matter is prepared using the white liquid composition of the present invention, the thickness of the ink film forming the print layer is preferably 4 μm or more and 20 μm or less, more preferably 10 μm or more and 17 μm or less. When the thickness of the ink film is 4 μm or more, the desired brightness can be exhibited without being affected by the base color of the recording medium. On the other hand, when the thickness of the ink film is 20 μm or less, it is possible to maintain fixability and productivity.

(Printing method and printing device)
The printing method of the present invention includes a first printing step of printing the white liquid composition of the present invention on a recording medium, and a second printing step of printing color ink on the printed white liquid composition. And other steps as necessary.

  The printing apparatus of the present invention includes a white liquid composition of the present invention, a first printing unit that prints the white liquid composition on a recording medium, and a second printing unit that prints a color ink on the printed white liquid composition. Printing means, and other means as necessary.

The color ink contains a coloring material and a solvent, and further contains resin particles and other components as necessary.
The color ink means achromatic ink such as black ink and white ink, and chromatic ink such as yellow ink, magenta ink and cyan ink.

  The printing apparatus of the present invention includes a nozzle that discharges the white liquid composition, a plurality of individual liquid chambers that communicate with the nozzle, an inflow channel that allows the white liquid composition to flow into the individual liquid chamber, and the white liquid composition. A discharge head having an outflow channel for causing the white liquid composition to flow out of the individual liquid chamber, a circulation path for flowing the white liquid composition flowing out of the outflow channel into the inflow channel, and circulating the white liquid composition; And negative pressure means generating means for generating a negative pressure flowing out of the individual liquid chamber.

-Discharge head-
The discharge head includes a plurality of nozzles that discharge a white liquid composition, an individual liquid chamber that communicates with the nozzle, a common liquid chamber that supplies the white liquid composition to the individual liquid chamber, and a circulation that communicates with the individual liquid chamber. It has a flow path, a circulating common liquid chamber communicating with the circulating flow path, and pressure generating means for applying pressure to the white liquid composition in the individual liquid chamber, and further has other means as necessary.

The discharge head causes the white liquid composition to flow into the individual liquid chamber from the inflow channel, flows out of the individual liquid chamber to the outflow channel, and causes the white liquid composition to flow. By causing the white liquid composition in the discharge head to flow at least before discharging the white liquid composition, a separation state in which the hollow resin particles in the white liquid composition settle can be suppressed.
Further, it is preferable that a white liquid composition supply unit that supplies a white liquid composition to the individual liquid chamber via the inflow channel is connected to the ejection head. When the printing apparatus has a circulation unit, by connecting the outflow channel to the white liquid composition supply unit, the white liquid composition between the discharge head and the white liquid composition supply unit. Circulation is preferred. This is advantageous in that the amount of the waste white liquid composition due to the outflow from the outflow channel can be reduced.

  In the following, a case where black (K), cyan (C), magenta (M), and yellow (Y) are used will be described, but instead of or in addition to these, a white liquid composition or a coloring material is contained. Clear liquid compositions that do not may be used.

The white liquid composition of the present invention can be suitably used for various recording apparatuses using an ink jet recording method, for example, a printer, a facsimile apparatus, a copying apparatus, a combined printer / fax / copier machine, and a three-dimensional printing apparatus.
In the present invention, a recording device and a recording method are a device capable of discharging a white liquid composition, various processing liquids, and the like to a recording medium, and a method of performing recording using the device. The recording medium means a medium to which a white liquid composition or various processing liquids can be temporarily attached.
This recording apparatus includes not only a head portion for discharging a white liquid composition, but also means for feeding, transporting, and discharging a recording medium, and other devices such as a pre-processing device and a post-processing device. be able to.
The recording device and the recording method may include a heating unit used in the heating step and a drying unit used in the drying step. The heating means and the drying means include, for example, means for heating and drying the printing surface or the back surface of the recording medium. The heating means and the drying means are not particularly limited, and for example, a warm air heater or an infrared heater can be used. The drying temperature is preferably from 100 ° C to 200 ° C, more preferably from 120 ° C to 150 ° C. Heating and drying can be performed before printing, during printing, after printing, and the like.
Further, the recording apparatus and the recording method are not limited to those in which a significant image such as a character or a figure is visualized by the white liquid composition. For example, those that form a pattern such as a geometric pattern and the like that form a three-dimensional image are also included.
Further, the recording apparatus includes both a serial type apparatus that moves the ejection head and a line type apparatus that does not move the ejection head, unless otherwise limited.
Furthermore, this recording apparatus can use not only a desktop type but also a wide recording apparatus that can print on an A0 size recording medium, or a continuous paper wound in a roll shape as a recording medium. It also includes a simple continuous printer.
An example of the recording apparatus will be described with reference to FIGS. FIG. 1 is a perspective explanatory view of the device. FIG. 2 is a perspective explanatory view of the main tank. The image forming apparatus 400 as an example of the recording apparatus is a serial type image forming apparatus. A mechanism section 420 is provided inside an exterior 401 of the image forming apparatus 400. Each white liquid composition storage section 411 of the main tank 410 (410k, 410c, 410m, 410y) for each color of black (K), cyan (C), magenta (M), and yellow (Y) is made of, for example, aluminum laminate. It is formed of a packaging member such as a film. The white liquid composition storage section 411 is stored in, for example, a storage container case 414 made of plastics. Thus, the main tank 410 is used as a cartridge for each color.
On the other hand, a cartridge holder 404 is provided behind the opening when the cover 401c of the apparatus main body is opened. The main tank 410 is detachably mounted on the cartridge holder 404. As a result, the white liquid composition outlets 413 of the main tank 410 and the discharge heads 434 for each color communicate with each other via the supply tubes 436 for each color, and discharge the white liquid composition from the discharge head 434 to the recording medium. It becomes possible.

  Next, an example of the ejection head in the printing apparatus of the present invention will be described with reference to FIGS. 3, 4, 5, 6, 7A to 7F, 8A, and 8B. FIG. 3 is an external perspective view illustrating an example of the ejection head in the printing apparatus of the present invention. FIG. 4 is an explanatory cross-sectional view in a direction orthogonal to the nozzle arrangement direction of the ejection head of FIG. FIG. 5 is a partial cross-sectional explanatory view in a direction parallel to the nozzle arrangement direction of the ejection head of FIG. FIG. 6 is an explanatory plan view of a nozzle plate of the ejection head of FIG. 7A to 7F are plan explanatory views of each member constituting the flow path member of the ejection head of FIG. FIG. 8A and FIG. 8B are plan explanatory views of members constituting the common liquid chamber member of the ejection head of FIG.

  In the discharge head, a nozzle plate 1, a flow path plate 2, and a diaphragm member 3 as a wall member are laminated and joined, and a piezoelectric actuator 11 for displacing the diaphragm member 3, a common liquid chamber member 20, , A cover 29.

The nozzle plate 1 has a plurality of nozzles 4 for discharging a white liquid composition.
The flow path plate 2 is formed with an individual liquid chamber 6 communicating with the nozzle 4, a fluid resistance portion 7 communicating with the individual liquid chamber 6 serving as the inflow channel, and a liquid introduction portion 8 communicating with the fluid resistance portion 7. The flow path plate 2 is formed by laminating and joining a plurality of plate members 41 to 45 from the nozzle plate 1 side, and laminating and joining these plate members 41 to 45 and the diaphragm member 3 to form a flow path. A member 40 is configured.
The diaphragm member 3 has a filter part 9 as an opening through which the liquid introduction part 8 and the common liquid chamber 10 formed by the common liquid chamber member 20 pass.
The diaphragm member 3 is a wall member that forms a wall surface of the individual liquid chamber 6 of the flow path plate 2. The diaphragm member 3 has a two-layer structure (not limited), and is formed from a first layer forming a thin portion and a second layer forming a thick portion from the flow path plate 2 side. A deformable vibration region 30 is formed in a portion corresponding to the chamber 6.

Here, a plurality of nozzles 4 are arranged in a staggered manner on the nozzle plate 1 as shown in FIG.
As shown in FIG. 7A, the plate-like member 41 forming the flow path plate 2 has a through groove portion (meaning a groove-shaped through hole) 6a forming the individual liquid chamber 6, a fluid resistance portion 51, and the outflow flow. Through-groove portions 51a and 52a forming a circulation flow path 52 as a path are formed.
Similarly, in the plate-like member 42, as shown in FIG. 7B, a through groove 6b forming the individual liquid chamber 6 and a through groove 52b forming the circulation channel 52 are formed.
Similarly, in the plate-like member 43, as shown in FIG. 7C, a through-groove portion 6c forming the individual liquid chamber 6 and a through-groove portion 53a having the longitudinal direction of the nozzle array direction forming the circulation channel 53 are formed. .
Similarly, in the plate member 44, as shown in FIG. 7D, a through groove 6d forming the individual liquid chamber 6, a through groove 7a forming the fluid resistance part 7, a through groove 8a forming the liquid introducing part 8, A through groove 53b having a longitudinal direction in the nozzle arrangement direction that forms the flow path 53 is formed.
Similarly, as shown in FIG. 7E, the plate-like member 45 includes a through-groove portion 6e that forms the individual liquid chamber 6 and a through-groove portion 8b (the filter downstream side liquid) that has the longitudinal direction in the nozzle arrangement direction that forms the liquid introduction portion 8. ), And a through-groove portion 53c whose longitudinal direction is the nozzle arrangement direction that forms the circulation channel 53 is formed.
As shown in FIG. 7F, the diaphragm member 3 is formed with a vibration region 30, a filter portion 9, and a through groove portion 53d whose longitudinal direction is a nozzle arrangement direction constituting the circulation channel 53.
Thus, by forming the flow path member by laminating and joining a plurality of plate members, a complicated flow path can be formed with a simple configuration.

  With the above configuration, in the flow path member 40 including the flow path plate 2 and the vibration plate member 3, the fluid resistance portion 51, the circulation flow path 52, and the circulation along the surface direction of the flow path plate 2 communicating with each individual liquid chamber 6. A circulation channel 53 in the thickness direction of the channel member 40 communicating with the channel 52 is formed. Note that the circulation channel 53 communicates with a circulation common liquid chamber 50 described later.

On the other hand, the common liquid chamber member 20 has a common liquid chamber 10 to which a white liquid composition is supplied from the main tank and the white liquid composition cartridge and a circulation common liquid chamber 50.
As shown in FIG. 8A, the first common liquid chamber member 21 has a through hole 25a for a piezoelectric actuator, a through groove 10a to be a downstream common liquid chamber 10A, and a bottom groove 50a to be a circulation common liquid chamber 50. Are formed.
As shown in FIG. 8B, the second common liquid chamber member 22 is formed with a through hole 25b for a piezoelectric actuator and a groove 10b serving as the upstream common liquid chamber 10B. As shown in FIG. 3, the second common liquid chamber member 22 has a through hole 71 a serving as a supply port through the supply port 71 and one end of the common liquid chamber 10 in the nozzle arrangement direction.
The first common liquid chamber member 21 and the second common liquid chamber member 22 have through-holes through the other end (the end opposite to the through-hole 71 a) of the circulation common liquid chamber 50 in the nozzle arrangement direction and the circulation port 81. 81a and 81b are formed.
In FIGS. 8A and 8B, a groove having a bottom is shown by being painted (the same applies to the following drawings).
As described above, the common liquid chamber member 20 is constituted by the first common liquid chamber member 21 and the second common liquid chamber member 22, and the first common liquid chamber member 21 is joined to the diaphragm member 3 side of the flow path member 40. Then, the second common liquid chamber member 22 is laminated and joined to the first common liquid chamber member 21.

Here, the first common liquid chamber member 21 forms a downstream common liquid chamber 10A that is a part of the common liquid chamber 10 that communicates with the liquid introduction unit 8 and a circulation common liquid chamber 50 that communicates with the circulation channel 53. ing. Further, the second common liquid chamber member 22 forms an upstream common liquid chamber 10 </ b> B which is the remaining part of the common liquid chamber 10.
At this time, the downstream common liquid chamber 10A, which is a part of the common liquid chamber 10, and the circulation common liquid chamber 50 are arranged side by side in a direction orthogonal to the nozzle arrangement direction, and the circulation common liquid chamber 50 is It is located at the position projected into.
Thereby, the size (size) of the circulating common liquid chamber 50 is restricted by the size required for the flow path including the individual liquid chamber 6, the fluid resistance part 7, and the liquid introduction part 8 formed by the flow path member 40. Disappears.
The circulating common liquid chamber 50 and a part of the common liquid chamber 10 are arranged side by side, and the circulating common liquid chamber 50 is arranged at a position projected into the common liquid chamber 10 so as to be orthogonal to the nozzle arrangement direction. The width of the head in the direction can be suppressed, and the enlargement of the head can be suppressed. The common liquid chamber member 20 forms a common liquid chamber 10 to which a white liquid composition is supplied from a head tank or a white liquid composition cartridge and a circulation common liquid chamber 50.

On the other hand, a piezoelectric actuator 11 including an electromechanical transducer as driving means (actuator means, pressure generating means) for deforming the vibration area 30 of the diaphragm member 3 is provided on the side of the diaphragm member 3 opposite to the individual liquid chamber 6. Have been placed.
As shown in FIG. 5, the piezoelectric actuator 11 has a piezoelectric member 12 bonded on a base member 13, and the piezoelectric member 12 is grooved by half-cut dicing, and a required number of piezoelectric members 12 are formed. Are formed in a comb shape at a predetermined interval.
Here, the piezoelectric element 12A of the piezoelectric member 12 is a piezoelectric element that is driven by applying a drive waveform, and the piezoelectric element 12B is used as a simple support without providing a drive waveform. However, all the piezoelectric elements 12A and 12B are driven. It can also be used as a piezo element.
Then, the piezoelectric element 12A is joined to the convex portion 30a which is an island-shaped thick portion formed in the vibration region 30 of the diaphragm member 3. Further, the piezoelectric element 12B is joined to the convex portion 30b which is a thick portion of the diaphragm member 3.

The piezoelectric member 12 is formed by alternately laminating piezoelectric layers and internal electrodes. The internal electrodes are respectively drawn out to the end faces to provide external electrodes, and the flexible wiring member 15 is connected to the external electrodes.
In the ejection head configured as described above, for example, when the voltage applied to the piezoelectric element 12A is reduced from the reference potential, the piezoelectric element 12A contracts, and the vibration region 30 of the vibration plate member 3 moves down to reduce the volume of the individual liquid chamber 6. Expands, the white liquid composition flows into the individual liquid chamber 6.
Thereafter, the voltage applied to the piezoelectric element 12A is increased to extend the piezoelectric element 12A in the stacking direction, and to deform the vibrating region 30 of the diaphragm member 3 in the direction toward the nozzle 4 to contract the volume of the individual liquid chamber 6. Accordingly, the white liquid composition in the individual liquid chamber 6 is pressurized, and the white liquid composition is discharged from the nozzle 4.
Then, by returning the voltage applied to the piezoelectric element 12A to the reference potential, the vibration region 30 of the vibration plate member 3 is restored to the initial position, and the individual liquid chamber 6 expands to generate a negative pressure. The white liquid composition is filled from the chamber 10 into the individual liquid chamber 6. Then, after the vibration of the meniscus surface of the nozzle 4 is attenuated and stabilized, the operation shifts to the operation for the next ejection.
The method of driving the head is not limited to the above-described example (pull-push), but a pull or push may be performed depending on the drive waveform. Further, in the above-described embodiment, the laminated type piezoelectric element has been described as a means for applying the pressure fluctuation to the individual liquid chamber 6, but the present invention is not limited to this, and a thin film piezoelectric element may be used. Furthermore, a heater in which a heating resistor is arranged in the individual liquid chamber 6 to generate bubbles by the heat generated by the heating resistor to cause a pressure change, or a device which generates a pressure change by using an electrostatic force can be used. .

  Next, an example of a white liquid composition circulation system using the ejection head according to the present embodiment will be described with reference to FIG.

FIG. 9 is a block diagram illustrating an example of a white liquid composition circulation system.
As shown in FIG. 9, the white liquid composition circulation system includes a main tank, a discharge head, a supply tank, a circulation tank, a compressor, a vacuum pump, a liquid pump, a regulator (R), a supply-side pressure sensor, and a circulation-side pressure sensor. It is composed of The supply-side pressure sensor is connected between the supply tank and the discharge head and on the supply flow path side connected to the supply port 71 (see FIG. 3) of the discharge head. The circulation-side pressure sensor is connected between the discharge head and the circulation tank and on the side of the circulation flow path connected to the circulation port 81 (see FIG. 3) of the discharge head.
One of the circulation tanks is connected to a supply tank via a first liquid sending pump, and the other of the circulation tank is connected to a main tank via a second liquid sending pump. As a result, the white liquid composition flows into the discharge head from the supply tank through the supply port 71, is discharged from the circulation port, is discharged to the circulation tank, and is further discharged by the first liquid supply pump from the circulation tank to the supply tank. The white liquid composition circulates by sending the liquid composition.
Further, a compressor (not shown) is connected to the supply tank, and is controlled so that a predetermined positive pressure is detected by a supply-side pressure sensor. On the other hand, a vacuum pump (not shown) is connected to the circulation tank, and is controlled so that a predetermined negative pressure is detected by the circulation-side pressure sensor. Thus, the negative pressure of the meniscus can be kept constant while circulating the white liquid composition through the inside of the ejection head.
Also, when droplets are ejected from the nozzles of the ejection head, the amount of the white liquid composition in the supply tank and the circulation tank decreases. It is desirable to replenish the white liquid composition. The timing of refilling the white liquid composition from the main tank to the circulation tank is provided in the circulation tank, such as refilling the white liquid composition when the liquid level of the white liquid composition in the circulation tank falls below a predetermined height. It can be controlled by a detection result of a liquid level sensor or the like.

Next, circulation of the white liquid composition in the ejection head will be described. As shown in FIG. 3, a supply port 71 communicating with the common liquid chamber and a circulation port 81 communicating with the circulation common liquid chamber 50 are formed at an end of the common liquid chamber member 20. The supply port 71 and the circulation port 81 are respectively connected to a supply tank and a circulation tank (see FIGS. 10 and 11) for storing the white liquid composition via tubes. Then, the white liquid composition stored in the supply tank is supplied to the individual liquid chamber 6 via the supply port 71, the common liquid chamber 10, the liquid introduction section 8, and the fluid resistance section 7.
Further, while the white liquid composition in the individual liquid chamber 6 is ejected from the nozzle 4 by driving the piezoelectric member 12, a part or all of the white liquid composition remaining in the individual liquid chamber 6 without being ejected is The fluid is circulated to the circulation tank via the fluid resistance portion 51, the circulation flow channels 52 and 53, the circulation common liquid chamber 50, and the circulation port 81.
The circulation of the white liquid composition can be performed not only during the operation of the ejection head but also during the suspension of the operation. By circulating when the operation is stopped, the white liquid composition in the individual liquid chamber is constantly refreshed, and aggregation and sedimentation of components contained in the white liquid composition can be suppressed, which is preferable.

This recording device can include not only a portion for discharging the white liquid composition but also a device called a pre-processing device or a post-processing device.
As one mode of the pretreatment device and the posttreatment device, as in the case of the white liquid composition such as black (K), cyan (C), magenta (M), and yellow (Y), the pretreatment liquid and the posttreatment There is a mode in which a liquid storage section having a liquid and a liquid discharge head are added, and a pretreatment liquid and a post-treatment liquid are discharged by an ink jet recording method.
As another embodiment of the pre-processing device and the post-processing device, there is a mode in which a pre-processing device and a post-processing device other than the ink jet recording method, for example, by a blade coating method, a roll coating method, and a spray coating method are provided.

  The method of using the white liquid composition is not limited to the ink jet recording method, and can be widely used. In addition to the ink jet recording method, for example, a blade coating method, a gravure coating method, a bar coating method, a roll coating method, a dip coating method, a curtain coating method, a slide coating method, a die coating method, a spray coating method and the like can be mentioned.

The use of the white liquid composition of the present invention is not particularly limited and can be appropriately selected depending on the purpose. For example, the white liquid composition can be applied to printed matter, paints, coating materials, base materials, and the like. Further, it can be used not only as a white liquid composition to form two-dimensional characters and images, but also as a three-dimensional modeling material for forming a three-dimensional three-dimensional image (three-dimensional object).
As a three-dimensional modeling device for modeling a three-dimensional molded object, a known three-dimensional modeling device can be used, and is not particularly limited. For example, a device provided with a white liquid composition containing unit, a supplying unit, a discharging unit, a drying unit, and the like. Can be used. The three-dimensional structure includes a three-dimensional structure obtained by repeatedly applying a white liquid composition. Further, a molded product obtained by processing a structure in which a white liquid composition is provided on a base material such as a recording medium is also included. The molded product is obtained by subjecting a recording material or a structure formed in a sheet shape or a film shape to a molding process such as a heat drawing or a punching process. -It is suitably used for molding after decorating the surface, such as electronic equipment, meters of cameras and panels of operation units.

  Further, image forming, recording, printing, printing and the like in the terms of the present invention are all synonyms.

  A recording medium, a medium, and a printed material are all synonyms.

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

(Production Example 1)
<Preparation of hollow resin particles B>
-Synthesis of seed particle emulsion-
In a four-neck separable flask equipped with a stirrer, a thermometer, a cooler, and a dropping funnel, 726.0 parts by mass of deionized water, 5.0 parts by mass of methyl methacrylate, and 0.1 parts by mass of methacrylic acid were charged. And warmed with stirring. Next, when the internal temperature of the separable flask reached 70 ° C., 1.0 part by mass of a 10% by mass aqueous solution of ammonium persulfate was added, and the mixture was heated at 80 ° C. for 20 minutes.
On the other hand, 141.0 parts by mass of methyl methacrylate, 94.9 parts by mass of methacrylic acid, 5.0 parts by mass of sodium alkylbenzene sulfonate (Neogen SF-20, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) as an anionic emulsifier, and deionized water 120.0 parts by mass was emulsified with a homodisper to form a pre-emulsion, which was then charged into a dropping funnel.
Next, while maintaining the internal temperature of the separable flask at 80 ° C., the pre-emulsion obtained above was dropped uniformly over 3 hours, and at the same time, 10.0 parts by mass of a 10% by mass aqueous solution of ammonium persulfate was added to 3 parts by mass. It was dropped uniformly over time. After completion of the dropping, the mixture was aged at 80 ° C. for 3 hours, cooled, and filtered using a 120-mesh filter cloth to obtain a seed particle emulsion.

<Synthesis of hollow resin particles>
-First stage polymerization-
In a four-neck separable flask equipped with a stirrer, a thermometer, a cooler, and a dropping funnel, 188.2 parts by mass of deionized water was charged, and 66.0 parts by mass of the seed particle emulsion obtained above was added dropwise, The mixture was heated to 80 ° C. with stirring. On the other hand, 2.4 parts by mass of butyl acrylate, 1.1 parts by mass of butyl methacrylate, 19.5 parts by mass of methyl methacrylate, 0.7 parts by mass of methacrylic acid, sodium alkylbenzene sulfonate (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., Neogen SF- 20) 5.0 parts by mass and 55.3 parts by mass of deionized water were emulsified with a homodisper to prepare a pre-emulsion 1, which was then charged into a dropping funnel.
Next, while maintaining the internal temperature in the separable flask at 80 ° C., the pre-emulsion 1 obtained above was dropped uniformly over 30 minutes, and at the same time, 1.2 parts by mass of a 10% by mass aqueous solution of sodium persulfate. Was uniformly dropped over 30 minutes.

-2nd stage polymerization-
75.0 parts by mass of styrene, 0.5 parts by mass of 1,3-diethylbenzene, 5.0 parts by mass of sodium alkylbenzenesulfonate (Neogen SF-20, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), and 51.8 parts by mass of deionized water The resulting mixture was emulsified with a homodisper to obtain a pre-emulsion 2, which was then charged into a dropping funnel.
Next, while maintaining the internal temperature of the separable flask at 80 ° C., one hour after the completion of the dropping of the pre-emulsion 1, the pre-emulsion 2 obtained above was dropped uniformly over 60 minutes. At the same time, 3.5 parts by mass of a 10% by mass aqueous solution of sodium persulfate was dropped uniformly over 60 minutes.
After the completion of the dropping of the pre-emulsion 2, 7.5 parts by mass of 28% by mass aqueous ammonia was added dropwise to swell and dissolve the seed particles, and the mixture was aged at 80 ° C. for 1 hour. After cooling, filtration was performed using a 120-mesh filter cloth to obtain “hollow resin particles B”.

(Production Example 2)
-Preparation of hollow resin particles B'-
"Hollow resin particles B '" were obtained in the same manner as in Production Example 1 except that 1,3-diethylbenzene was not added to Pre-emulsion 2.

(Production Example 3)
-Preparation of hollow resin particles E-
"Hollow resin particles E" were obtained in the same manner as in Production Example 1 except that the amount of styrene in the second-stage polymerization was changed to 22.3 parts by mass.

(Production Example 4)
-Preparation of hollow resin particles E'-
In Production Example 3, "hollow resin particles E '" were obtained in the same manner as in Production Example 3, except that 1,3-diethylbenzene was not added to Preemulsion 2.

(Example 1)
<Preparation of white liquid composition>
First, an organic solvent, a fluorescent whitening agent, a fluorescent whitening enhancer, a surfactant, an antifoaming agent, a pH adjusting agent, a preservative / antifungal agent, and deionized water shown in Table 1 are stirred for 1 hour and uniformly mixed. did.
Next, the resin particles were added, and the mixture was further stirred for 1 hour to be uniformly mixed. Thereafter, a white color material was added, and the mixture was further stirred for 1 hour to be uniformly mixed. The obtained mixture was subjected to pressure filtration with a polyvinylidene fluoride membrane filter having an average pore diameter of 5 μm to remove coarse particles and dust to obtain a white liquid composition.

<Spectral ratio (Y / X)>
The maximum value X of 1600 cm ^-11 and the maximum value Y of 1730 cm ^-1 in the IR spectrum of the dried film of the obtained hollow resin particles were measured using a micro FT-IR measuring device (iN10MX / iZ10) manufactured by Thermo Fisher Scientific. ) And analysis software (OMNIC).

<Volume average particle size>
The volume average particle diameter of the hollow resin particles was measured by Nanotrac Wave EX-150 manufactured by Microtrac Bell.

<Glass transition temperature>
The glass transition temperature of the hollow resin particles was measured using a thermal analyzer (TA7000 series) manufactured by Hitachi High-Tech Science Corporation. In addition, the value of the glass transition temperature of the white liquid composition substantially coincided with the value of the glass transition temperature of the hollow resin particles, and thus the description is omitted.

<Structural analysis of hollow resin particles>
The structural analysis of the hollow resin particles is performed by using a microscopic FT-IR measuring device (device name: iN10MX / iZ10, manufactured by Thermo Fisher Scientific) and analysis software (OMNIC) to obtain the following structural formula ( It was confirmed from 1) that it had the structural unit represented by the structural formula (4).

<White color material>
-Hollow resin particles A (ROPAQUE ULTRA E, manufactured by Dow Chemical Company)-
-Ratio (Y / X) = 1.5
・ Resin structure: Structural formula (1) / Structural formula (2)
-Volume average particle diameter: 400 nm
・ Thickness of resin layer: 40 nm
-Hollow ratio: 51.0%
-Glass transition temperature (Tg) = 110.4 ° C
・ Cross-linking agent: None

-Hollow resin particles B (Production Example 1)-
-Ratio (Y / X) = 3.0
・ Resin structure: Structural formula (1) / Structural formula (2)
-Volume average particle diameter: 700 nm
-Thickness of resin layer: 60 nm
-Hollow ratio: 45.0%
-Glass transition temperature (Tg) = 111.7 ° C
・ Cross-linking agent: None

-Hollow resin particles B '(Production Example 2)-
-Ratio (Y / X) = 3.0
・ Resin structure: Structural formula (1) / Structural formula (2)
-Volume average particle diameter: 700 nm
-Thickness of resin layer: 60 nm
-Hollow ratio: 45.0%
-Glass transition temperature (Tg) = 115.3 ° C
・ Cross-linking agent (1,3-diethylbenzene): Available

-Hollow resin particles C (Sibinol X-213-913E-43, manufactured by Seiden Chemical Co., Ltd.)-
-Ratio (Y / X) = 4.9
-Resin structure: Structural formula (1) / Structural formula (2) / Structural formula (3) / Structural formula (4)
-Volume average particle diameter: 700 nm
-Thickness of resin layer: 100 nm
-Hollow ratio: 36.4%
-Glass transition temperature (Tg) = 119.3 ° C
・ Cross-linking agent (ethylene dimethacrylate, tetraethylene glycol methacrylate): Available

-Hollow resin particles D (ROPAQUE HT1432, manufactured by Dow Chemical Company)-
-Ratio (Y / X) = 5.1
・ Resin structure: Structural formula (1) / Structural formula (2) / Structural formula (4)
-Volume average particle diameter: 500 nm
-Thickness of resin layer: 60 nm
-Hollow rate = 32.0%
-Glass transition temperature (Tg) = 128.7 ° C
・ Cross-linking agent (1,3-diethylbenzene): Available

-Hollow resin particles E (Production Example 3)-
-Ratio (Y / X) = 6.0
・ Resin structure: Structural formula (1) / Structural formula (2)
-Volume average particle diameter: 700 nm
-Thickness of resin layer: 60 nm
-Hollow ratio: 30.1%
-Glass transition temperature (Tg) = 121.1 ° C
・ Cross-linking agent: None

-Hollow resin particles E '(Production Example 4)-
-Ratio (Y / X) = 6.0
・ Resin structure: Structural formula (1) / Structural formula (2)
-Volume average particle diameter: 700 nm
-Thickness of resin layer: 60 nm
-Hollow ratio: 30.1%
-Glass transition temperature (Tg) = 131.2 ° C
・ Cross-linking agent (1,3-diethylbenzene): Available

-Hollow resin particles F (SX868, manufactured by JSR Corporation)-
-Ratio (Y / X) = 9.3
-Volume average particle size = 600 nm
-Glass transition temperature (Tg) = 133.4 ° C
・ Cross-linking agent (ethylene dimethacrylate, tetraethylene glycol methacrylate): Available

-Organic solvent-
Organic solvent A (1,2-propanediol, manufactured by Tokyo Chemical Industry Co., Ltd., SP value = 14.3 (cal / cm ³ ) ^0.5 )
-Organic solvent B (manufactured by Tokyo Chemical Industry Co., Ltd., 1,2-butanediol, SP value = 13.1 (cal / cm ³ ) ^0.5 )

-Fluorescent whitening agent-
-Fluorescent brightener A (Nikkaburitsu PAW-L, manufactured by Nippon Chemical Industry Co., Ltd., hydrophilic benzoxazole fluorescent brightener)
・ Fluorescent whitening agent B (Nikkafluor OB, manufactured by Nippon Chemical Industry Co., Ltd., hydrophobic benzoxazole fluorescent whitening agent)
-Fluorescent whitening agent C (Nikkafluor MCT, manufactured by Nippon Chemical Industry Co., Ltd., hydrophobic coumarin fluorescent whitening agent)

-Fluorescent whitening enhancer-
-Fluorescent whitening enhancer (Optiact I-10, manufactured by San Nopco)

-Resin particles-
Resin particles (aqueous polyurethane resin, manufactured by Daiichi Kogyo Seiyaku Co., Ltd., Superflex 420, SP value = 11.6 (cal / cm ³ ) ^0.5 , solid content concentration: 38% by mass)

-Surfactant-
Shin-Etsu Silicone KF-640

-Antifoaming agent-
Shin-Etsu Silicone KM-72F

-PH adjuster-
2-Amino-2-ethyl-1,3-propanediol manufactured by Tokyo Chemical Industry Co., Ltd.

-Antiseptic / antifungal agent-
Abisia LV (S)

<Printing method>
Using the obtained white liquid compositions of Examples 1 to 14 and Comparative Examples 1 to 5, using an image forming apparatus (manufactured by Ricoh Co., Ltd., IPSiO GXe5500), a recording medium (manufactured by Oji Ftex Co., Ltd., Lumina color black 128 gsm) The printing was performed with a printing resolution of 1200 dpi × 1200 dpi and an adhesion amount of the white liquid composition of 2.4 mg / cm ² . Then, what was dried in a thermostat (ES-3, PR-3J) set at a predetermined temperature (120 ° C.) was used as a printed matter. The print chart used was a 3 cm square solid image formed in a dot pattern.
In Example 15, printing was performed in the same manner as in Examples 1 to 14 and Comparative Examples 1 to 5, except that the image forming apparatus having the ejection head having the circulation mechanism shown in FIGS. Was done.

  Next, various characteristics of the obtained white liquid compositions and printed materials of Examples 1 to 15 and Comparative Examples 1 to 5 were evaluated as follows. The results are shown in Tables 1 to 4.

<Image brightness>
The lightness (L ^* ) of the printed matter on which each of the obtained white liquid compositions was printed was measured with a spectrophotometer (939, manufactured by X-Rite). Note that the lightness is a usable level of 50 or more.

<Sedimentation>
The sedimentation of the hollow resin particles in each of the obtained white liquid compositions was measured as follows using a sedimentation measuring device (Terviscan Classic MA2000, manufactured by Eiko Seiki Co., Ltd.).
The white liquid composition is subjected to ultrasonic treatment (100 W, 40 minutes) using an ultrasonic cleaner (made by AS ONE Corporation, US-3) to make it uniform, and then a glass tube dedicated to the apparatus using a pipette. 5.5 mL of each white liquid composition was placed in a screw-mouth test tube (manufactured by AS ONE Corporation).
The measurement was performed after the liquid level of the white liquid composition in the glass tube was stabilized, and this time was defined as the sedimentation evaluation start time. Then, it left still at 25 degreeC and measured until 168 hours. The sedimentation of the hollow resin particles was confirmed by a deviation display based on the sedimentation evaluation start time.
The sedimentation was confirmed by integrating the backscattered light intensity peaks accompanying the sedimentation of the hollow resin particles (from 20 mm below the glass tube to the liquid surface), and the average value of the relative percentage change in supernatant after standing at 25 ° C. for 168 hours ( %), And the sedimentation property was evaluated according to the following evaluation criteria. The sedimentability is at a usable level of -2% or more.
[Evaluation criteria]
：: -2% or more △: -4% or more and less than -2% ×: more than -4%

<Discharge stability>
The resulting image forming apparatus each white liquid composition (manufactured by Ricoh Company, Ltd., IPSiO GXe5500) by printing a solid image of 10cm square resolution: 1200 dpi × 1200 dpi, the adhesion amount of the white liquid composition: condition 1 mg / cm ² The number of missing nozzles after printing 100 sheets was visually measured, and the ejection stability was evaluated according to the following evaluation criteria. If the number of missing nozzles is 5 or less, it is a practicable level.
[Evaluation criteria]
：: Number of nozzles with missing nozzles: 0 ○: Number of nozzles with missing nozzles: 2 or less △: Number of nozzles with missing nozzles: 3 or more and 5 or less ×: Number of nozzles with missing nozzles : 6 or more

Aspects of the present invention are, for example, as follows.
<1> A white liquid composition containing resin particles,
A white liquid composition, wherein the resin particles include a structural unit derived from styrene, a structural unit derived from a (meth) acrylic compound, and 1,3-diethylbenzene.
<2> The resin particles are a structural unit represented by the following structural formula (1) and at least one structural unit selected from structural units represented by the following structural formulas (2) to (4). And the 1,3-diethylbenzene. <1>.
<3> The resin particles are a structural unit represented by the structural formula (1), a structural unit represented by the structural formula (2), and a structural unit represented by the structural formula (4). The white liquid composition according to the item <2>, further comprising 1,3-diethylbenzene.
<4> The white liquid composition according to any one of <1> to <3>, wherein the resin particles are hollow resin particles.
<5> The white liquid composition according to <4>, wherein the glass transition temperature of the hollow resin particles is 120 ° C or higher.
<6> The white liquid composition according to any one of <4> to <5>, wherein the hollow resin particles have a volume average particle diameter of 0.4 μm or more and 0.6 μm or less.
<7> and the maximum value X of 1600 cm ^-1 ± 10 cm ^-1 in the IR spectrum of a dry film of the hollow resin particles, the ratio between the maximum value Y of ^{1730cm -1 ± 10cm -1 (Y /} X) is 3. The white liquid composition according to any one of <4> to <6>, which is 0 or more and 6.0 or less.
<8> The white liquid composition according to any one of <4> to <7>, wherein the hollow resin particles have a hollow ratio of 30% or more and 60% or less.
<9> The white liquid composition according to any one of <1> to <8>, further including a fluorescent whitening agent, wherein the fluorescent whitening agent includes at least one of benzoxazole and a benzoxazole derivative. .
<10> The white liquid composition according to any one of <1> to <9>, wherein the content of the fluorescent whitening agent is 0.001% by mass or more and 1% by mass or less.
<11> The white liquid composition according to any one of <1> to <10>, further including a fluorescent whitening enhancer, wherein the fluorescent whitening enhancer includes a polyether polyol compound.
<12> a first printing step of printing the white liquid composition according to any one of <1> to <11> on a recording medium;
A second printing step of printing a color ink on the printed white liquid composition;
Is a printing method characterized by including the following.
<13> The white liquid composition according to any one of <1> to <11>,
First printing means for printing the white liquid composition on a recording medium,
Second printing means for printing a color ink on the printed white liquid composition,
A printing apparatus comprising:
<14> a nozzle that discharges the white liquid composition, a plurality of individual liquid chambers that communicate with the nozzle, an inflow channel that allows the white liquid composition to flow into the individual liquid chamber, and the An ejection head having an outflow channel for outflow from the chamber,
A circulation path for causing the white liquid composition flowing out of the outflow channel to flow into and circulate in the inflow channel,
Negative pressure means generating means for generating a negative pressure for the white liquid composition to flow out of the individual liquid chamber,
<13> The printing apparatus according to <13>, wherein

  According to the white liquid composition according to any one of <1> to <11>, the printing method according to <12>, and the printing apparatus according to any one of <13> to <14>, And the object of the present invention can be achieved.

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 each color of black (K), cyan (C), magenta (M), yellow (Y) Main tank 411 White liquid composition storage section 413 White liquid composition discharge port 414 Storage container case 420 Mechanism section 434 Discharge head 436 Supply tube

JP-A-2006-28145

Claims (12)

A white liquid composition containing resin particles,
A white liquid composition, wherein the resin particles include a structural unit derived from styrene, a structural unit derived from a (meth) acrylic compound, and 1,3-diethylbenzene. The resin particles may include a structural unit represented by the following structural formula (1), at least one structural unit selected from structural units represented by the following structural formulas (2) to (4), and 1 2. The white liquid composition according to claim 1, comprising: 1,3-diethylbenzene.
  The resin particles include a structural unit represented by the structural formula (1), a structural unit represented by the structural formula (2), a structural unit represented by the structural formula (4), and 1,3. The white liquid composition according to claim 2, comprising-diethylbenzene.   The white liquid composition according to any one of claims 1 to 3, wherein the resin particles are hollow resin particles.   The white liquid composition according to claim 4, wherein the glass transition temperature of the hollow resin particles is 120C or higher.   The white liquid composition according to claim 4, wherein the hollow resin particles have a volume average particle diameter of 0.4 μm or more and 0.6 μm or less. Wherein the maximum value X of 1600 cm ^-1 ± 10 cm ^-1 in the IR spectrum of a dry film of the hollow resin particles, the ratio between the maximum value Y of ^{1730cm -1 ± 10cm -1 (Y /} X) is 3.0 or more 6 The white liquid composition according to any one of claims 4 to 6, which is not more than 0.0.   The white liquid composition according to any one of claims 1 to 7, further comprising a fluorescent whitening agent, wherein the fluorescent whitening agent contains at least one of benzoxazole and a benzoxazole derivative.   9. The white liquid composition according to claim 1, further comprising a fluorescent whitening enhancer, wherein the fluorescent whitening enhancer comprises a polyether polyol compound. A first printing step of printing the white liquid composition according to any one of claims 1 to 9 on a recording medium,
A second printing step of printing a color ink on the printed white liquid composition;
A printing method comprising: A white liquid composition according to any one of claims 1 to 9,
First printing means for printing the white liquid composition on a recording medium,
Second printing means for printing a color ink on the printed white liquid composition,
A printing apparatus comprising: A nozzle that discharges the white liquid composition, a plurality of individual liquid chambers that communicate with the nozzle, an inflow channel that allows the white liquid composition to flow into the individual liquid chamber, and an outflow path that causes the white liquid composition to flow out of the individual liquid chamber. A discharge head having an outflow channel for causing
A circulation path for causing the white liquid composition flowing out of the outflow channel to flow into and circulate in the inflow channel,
Negative pressure means generating means for generating a negative pressure for the white liquid composition to flow out of the individual liquid chamber,
The printing apparatus according to claim 11, comprising: