JP6848765B2 - Recorded material and ink for manufacturing recorded material - Google Patents

Description

The present invention relates to recorded materials and inks for producing recorded materials.

A method using titanium dioxide as a coloring material for white ink for inkjet is generally used. Further, an ink using hollow resin particles having a hollow inner layer as a coloring material is also known.

The hollow resin particles exhibit whiteness by utilizing the difference in refractive index between the inner layer and the outer shell resin. For example, an ink composition containing hollow resin particles and an anti-transparency agent for the hollow resin particles has been proposed (see, for example, Patent Document 1).
Further, multi-mode inks in which the particle sizes of the hollow resin particles differ by at least 0.1 μm have been proposed (see, for example, Patent Document 2).

An object of the present invention is to provide a recorded material having an image in which ^{the hollow resin can be suppressed from being crushed (decrease in brightness L *) and the fixability is good.}

The recording material of the present invention as a means for solving the above-mentioned problems is a recording material having a recording medium and an image on the recording medium, and the image is represented by the following general formula (1). that a structural unit, and includes a hollow resin comprising a copolymer having a structural unit represented by the following general formula (2), in the image, the absorbance at the maximum absorption wavelength in the wavelength 1,600cm ^-1 ± 10cm ^-1 The ratio (Y / X) when X is defined and the ^{absorbance at the maximum absorption wavelength at a wavelength of 1,730 cm -1} ± 10 cm ^-1 is Y is 3.0 or more and 6.0 or less.

According to the present invention, it is ^{possible to suppress crushing of the hollow resin (decrease in brightness L *} ), and it is possible to provide a recorded material having an image having good fixability.

FIG. 1 is a perspective explanatory view showing an example of an inkjet recording device. FIG. 2 is a perspective explanatory view showing an example of a main tank in an inkjet recording device.

本発明の記録物は、従来技術では、中空樹脂粒子は外殻樹脂のＳＰ値と近いＳＰ値を持つ有機溶剤と接触することにより、外殻樹脂が溶解し、中空樹脂粒子のつぶれ（明度Ｌ^＊の低下）が発生してしまうという問題があるという知見に基づくものである。
本発明の記録物は、記録媒体と、記録媒体上に設けた画像に加え、画像の上下に、下層、上層を有していてもよい。前記下層としては、例えば、記録媒体に前処理液が付与されることにより、形成されることができる。前記上層としては、例えば、画像上に後処理液が付与されることにより、形成されることができる。 (Recorded material)
The recording material of the present invention is a recording material having a recording medium and an image on the recording medium, and the image is a structural unit represented by the following general formula (1) and the following general formula (2). comprises a hollow resin comprising a copolymer having a structural unit represented by) in the image, the absorbance at the maximum absorption wavelength in the wavelength 1,600cm ^-1 ± 10cm ^-1 and X, wavelength 1,730cm ^-1 ± The ratio (Y / X) when the absorbance at the maximum absorption wavelength at 10 cm ^{-1 is Y is 3.0 or more and 6.0 or less.} When the ratio (Y / X) is 3.0 or more and 6.0 or less, good brightness can be obtained even when the image is heated.
When the ratio (Y / X) is 3.0 or more and 6.0 or less, and the rate of change in brightness before and after heating at 110 ° C. for 60 seconds is 25% or less, the recorded matter is described. Even when stored for a long period of time, the whiteness of the recorded material can be maintained, which is preferable.

In the document of the present invention, in the prior art, when the hollow resin particles come into contact with an organic solvent having an SP value close to the SP value of the outer shell resin, the outer shell resin is dissolved and the hollow resin particles are crushed (brightness L). It is based on the finding that there is a problem that ( ^{* decrease) occurs.}
In addition to the recording medium and the image provided on the recording medium, the recorded material of the present invention may have lower layers and upper layers above and below the image. The lower layer can be formed, for example, by applying a pretreatment liquid to a recording medium. The upper layer can be formed, for example, by applying a post-treatment liquid on the image.

<Image>
The image contains a hollow resin, preferably contains other resins, and further contains other components, if necessary.
The image can be formed with ink.

[Ratio (Y / X)]
In the image, in the IR spectrum, the absorbance at the maximum absorption wavelength in the wavelength 1,600cm ^-1 ± 10cm ^-1 and X, when the absorbance at the maximum absorption wavelength in the wavelength 1,730cm ^-1 ± 10cm ^-1 and the Y The 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 strength of the hollow resin can be improved, and as a result, the decrease in brightness caused by the dissolution of the hollow resin resin by energy such as heat can be suppressed. it can. Even after the image is formed, the pores formed by the hollow resin are maintained, and the decrease in brightness can be suppressed. On the other hand, when the ratio (Y / X) is 6.0 or less, the brightness of the image can be improved, and in addition, the sedimentation property of the hollow resin particles in the ink can be improved.
The absorbance can be measured using, for example, a microscopic FT-IR measuring device (device name: iN10MX / iZ10, manufactured by Thermo Fisher Scientific Co., Ltd.) and analysis software (OMNIC). When measuring the IR spectrum, an image (solid ink portion) can be cut out from the recorded material and measured as needed.

[Brightness change rate]
The rate of change in brightness before and after heating at 110 ° C. for 60 seconds in the image is preferably 25% or less, more preferably 21% or less. When the rate of change is 25% or less, good brightness can be obtained even when the image is heated.
The rate of change can be 25% or less because the brightness of the image and the strength of the hollow resin can be improved by setting the ratio (Y / X) to 3.0 or more and 6.0 or less. is there. In the present invention, a white image having a brightness (L ^* ) of 20 or more is defined as white.
The rate of change in brightness can be calculated from the initial value and the value after heating at 110 ° C. for 60 seconds using the following formula (1). The brightness (L ^* ) can be measured using, for example, a spectrocolorimeter (manufactured by X-Rite, apparatus name: 939).
Brightness change rate (%) = {(initial value-value after heating at -110 ° C. for 60 seconds) / initial value} x 100 ... Equation (1)

Since the image in the recorded material contains a hollow resin, pores can be formed in the image in the recorded material.
In the present invention, the pore means a hollow portion formed in the image of the recorded object.
The average value of the diameters of the pores in the image in the recorded material is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 0.04 μm or more and 0.8 μm or less.
For the average value of the diameters of the pores in the image in the recorded material, for example, the cross section of the recorded material is observed with a microscope, the diameters of 10 randomly selected holes are measured, and the average value is calculated. Can be used. If the holes are not perfect circles, the average diameter is calculated using the maximum diameter.
As the microscope, for example, JSM-6510 (manufactured by JEOL Ltd.) can be used.

前記共重合体における前記その他の構造単位としては、特に制限はなく、目的に応じて適宜選択することができ、例えば、α-メチルスチレンなどが挙げられる。 << Hollow resin >>
The hollow resin included in the image includes a copolymer having a structural unit represented by the following general formula (1) and a structural unit represented by the following general formula (2). The copolymer may further contain other structural units, if desired.
By having the structural unit, the brightness of the image and the strength of the hollow resin can be improved, and the pores in the image can be maintained.

The other structural unit in the copolymer is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include α-methylstyrene.

The copolymer can improve the brightness in the image by having the structural unit represented by the general formula (1), and by having the structural unit represented by the general formula (2). , The strength of the hollow resin can be improved.

The hollow resin particles contained in the ink have a hollow inner layer and a resin outer layer. Since the inner layer is hollow, the specific gravity of the ink is around 1, and it is possible to prevent sedimentation over time like titanium dioxide used as a white pigment.
The hollow resin particles contained in the ink correspond to the hollow resin contained in the image.

The hollow resin particles preferably have an outer diameter of 0.1 μm or more and 1 μm or less, and an inner diameter of 0.04 μm or more and 0.8 μm or less. When the outer diameter of the hollow resin particles is 0.1 μm or more and 1 μm or less, and the inner diameter of the hollow resin particles is 0.04 μm or more and 0.8 μm or less, pores can be formed in the image.
The average thickness of the resin in the hollow resin particles is preferably 10% or more and 20% or less with respect to the total size of the hollow resin particles from the viewpoint of preventing sedimentation over time. When the average thickness of the resin in the hollow resin particles is 10% or more and 20% or less with respect to the size of the entire hollow resin particles, pores can be formed in the image.

The ratio of the structural unit represented by the general formula (1) to the structural unit represented by the general formula (2) in the hollow resin in the image is the ratio of the structural unit represented by the general formula (2) in the hollow resin particles in the ink. The ratio of the structural unit represented by 1) to the structural unit represented by the general formula (2) is the same.

The ratio of the structural unit represented by the general formula (1) to the structural unit represented by the general formula (2) is the structural unit represented by the general formula (1) using the IR spectrum of the image. ^{Absorbance (X) at the maximum absorption wavelength at 1,600 cm -1} ± 10 cm ^-1 due to C = C expansion and contraction vibration of the aromatic of the above, and wavelength derived from the carbonyl expansion and contraction vibration of the structural unit represented by the general formula (2). It can be calculated by taking the ratio (Y / X) of the absorbance (Y) at the maximum absorption wavelength at 1,730 ^{cm -1} ± 10 cm ^-1.

The volume average particle diameter of the hollow resin particles contained in the ink is preferably 400 nm or more and 800 nm or less. When the volume average particle size is 400 nm or more, it is possible to secure brightness even for a recording medium such as high-quality paper, while when the volume average particle size is 800 nm or less, it is possible to secure brightness. It is possible to improve the sedimentation property and the discharge stability. The volume average particle diameter indicates the particle size at the point where the cumulative curve is 50% when the cumulative curve is obtained with the total volume of the group as 100%.
Examples of the measurement of the volume average particle size include a method using a laser scattering / diffraction type particle size measuring device.

The hollow resin particles are subjected to structural analysis using, for example, a microscopic FT-IR measuring device (device name: iN10MX / iZ10, manufactured by Thermo Fisher Scientific Co., Ltd.) and analysis software (OMNIC). It can be confirmed that the structural unit represented by 1) and the structural unit represented by the general formula (2) are possessed.

The content of the hollow resin particles is preferably 3% by mass or more and 14% by mass or less, and more preferably 5.0% by mass or more and 12.5% by mass or less with respect to the total amount of ink. When the content is 3% by mass or more, the brightness can be ensured even for a recording medium such as woodfree paper, and when it is 14% by mass or less, the settling property is improved and the ejection stability is improved. Can be improved.
The content of the hollow resin with respect to the total amount of the image is preferably 50% by mass or more and 100% by mass or less, and more preferably 60% by mass or more and 80% by mass or less. The hollow resin with respect to the total amount of the image can be measured using, for example, a microscopic FT-IR measuring device (device name: iN10MX / iZ10, manufactured by Thermo Fisher Scientific Co., Ltd.) and analysis software (OMNIC).

The method for preparing the hollow resin particles is not particularly limited, and a known method can be applied. For example, a vinyl monomer, a surfactant, a polymerization initiator, and an aqueous dispersion medium are heated in a nitrogen atmosphere. A so-called emulsion polymerization method, in which a hollow resin emulsion is formed by stirring while stirring, can be applied.

Examples of the vinyl monomer include a monofunctional vinyl monomer, a bifunctional vinyl monomer, and the trifunctional vinyl monomer. These may be used alone or in combination of two or more.

Examples of the monofunctional vinyl monomer include nonionic monoethylene unsaturated monomers.
Examples of the nonionic monoethylene unsaturated monomer include styrene, vinyltoluene, ethylene, vinyl acetate, vinyl chloride, vinylidene chloride, acrylonitrile, (meth) acrylamide, and (meth) acrylic acid ester. These may be used alone or in combination of two or more. Among these, (meth) acrylic acid ester is preferable.

Examples of the (meth) acrylic acid ester include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and benzyl (meth) acrylate. ) Acrylate, lauryl (meth) acrylate, oleyl (meth) acrylate, palmityl (meth) acrylate, stearyl (meth) acrylate and the like can be mentioned.

Examples of the bifunctional vinyl monomer include divinylbenzene, allyl methacrylate, ethylene glycol di (meth) acrylate, 1,5-butanediol di (meth) acrylate, and diethylene glycol di (meth) acrylate.

Examples of the trifunctional vinyl monomer include trimethylolpropane tri (meth) acrylate.

By copolymerizing the monofunctional vinyl monomer and the bifunctional vinyl monomer and highly cross-linking them, a hollow having not only light scattering characteristics but also heat resistance, solvent resistance, solvent dispersibility and the like. Resin particles can be obtained.

The surfactant may be any one that forms molecular aggregates such as micelles in water, and examples thereof include anionic surfactants, nonionic surfactants, cationic surfactants, and amphoteric surfactants. Can be mentioned. These may be used alone or in combination of two or more.

As the polymerization initiator, a known compound that can be used in water can be used, and examples thereof include hydrogen peroxide and potassium persulfate. These may be used alone or in combination of two or more.

Examples of the aqueous dispersion medium include water and water containing a hydrophilic organic solvent.

<< Other resins >>
The other resin is a resin other than the hollow resin, and is not particularly limited and may be appropriately selected depending on the intended purpose. For example, polyurethane resin, polyester resin, acrylic resin, vinyl acetate resin, styrene resin. Examples thereof include resins, butadiene resins, styrene-butadiene resins, vinyl chloride resins, acrylic styrene resins, and acrylic silicone resins. These may be used alone or in combination of two or more. Among these, acrylic silicone resin and polyurethane resin are preferable.

The other resin can be obtained by mixing with a material such as an organic solvent in the state of an emulsion of resin particles dispersed with water as a dispersion medium. As the resin particles, those synthesized as appropriate may be used, or commercially available products may be used. These may be used alone or in combination of two or more.

The glass transition temperature (Tg) of the other resin greatly contributes to the fixability of the image when the drying step is performed after recording.
Therefore, the glass transition temperature (Tg) of the resin is preferably 0 ° C. or lower as an acrylic silicone resin, more preferably −45 ° C. or higher and 0 ° C. or lower, and preferably 0 ° C. or lower as a polyurethane resin, and −45 ° C. or higher and 0. More preferably, it is below ° C.

When the ink contains the resin particles, the image containing the resin can be formed.

The volume average particle diameter 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 fixability and high image hardness, 10 nm or more and 1,000 nm or less are preferable. More than 200 nm is more preferable, and 10 nm or more and 100 nm or less is particularly preferable.
The volume average particle size can be measured using, for example, a particle size analyzer (Nanotrack Wave-UT151, manufactured by Microtrack Bell Co., Ltd.).

The content of the resin is not particularly limited and may be appropriately selected depending on the intended purpose. However, from the viewpoint of fixability and storage stability (precipitation resistance) of the ink, the content of the resin is 1 with respect to the total amount of the ink. It is preferably mass% or more and 10 mass% or less, and more preferably 3 mass% or more and 5 mass% or less.
The content of the resin with respect to the total amount of the image is preferably 21.4% by mass or more and 33.3% by mass or less, and more preferably 25% by mass or more and 30% by mass or less. The resin with respect to the total amount of the image can be measured using, for example, a microscopic FT-IR measuring device (device name: iN10MX / iZ10, manufactured by Thermo Fisher Scientific Co., Ltd.) and analysis software (OMNIC).

The image can be formed using an ink containing the hollow resin particles.
The ink preferably contains an organic solvent, water, and a resin, and further contains a coloring material and other components, if necessary.

<Organic solvent>
As the organic solvent, the mixed SP value calculated from the solubility parameter of the organic solvent in the ink (hereinafter, also referred to as “SP value”) is 11.0 (cal / cm ³ ) ^0.5 or more and 15 .5 (cal / cm ³ ) ^0.5 or less is preferable. When the mixed SP value is 11.0 (cal / cm ³ ) ^0.5 or more, dissolution of the resin in the hollow resin particles by the organic solvent can be suppressed. On the other hand, when the mixed SP value is 15.5 (cal / cm ³ ) ^0.5 or less, deterioration of fixability due to poor drying can be suppressed.
When calculating the mixed SP value in the organic solvent in the ink, the mixed SP value is calculated using an organic solvent other than water.
The SP value can be determined from the Hansen solubility parameter.

Further, the mixed SP value of the organic solvent contained in the ink can be calculated from the following formula.
Mixed SP value of organic solvent in ink ((cal / cm ³ ) ^0.5 ) = [SP value of organic solvent A x volume fraction of organic solvent A] + ... + [SP value of organic solvent n x Volume fraction of organic solvent n]

The organic solvent used in the present invention includes those classified as penetrants, antifoaming agents, etc. in terms of function, but in the present invention, only those contained in an amount of 3% by mass or more with respect to the entire ink. Considered in the calculation of the mixed SP value. When only one kind of organic solvent is used, the SP value of the one kind of organic solvent is used as the mixed SP value.

Examples of the organic solvent include ethers such as polyhydric alcohols, polyhydric alcohol alkyl ethers and polyhydric alcohol aryl ethers, nitrogen-containing heterocyclic compounds, amides, amine louis, and sulfur-containing compounds. These may be used alone or in combination of two or more.

Specific examples of the organic solvent include, for example, ethylene glycol, diethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, and 1,4-butanediol. , 2,3-Butandiol, 3-Methyl-1,3-Butandiol, 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, polyhydric alcohols such as petriol, 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 Polyhydric alcohol alkyl ethers such as, ethylene glycol monophenyl ether, polyhydric alcohol aryl ethers such as ethylene glycol monobenzyl ether, 2-pyrrolidone, N-methyl-2-pyrrolidone, N-hydroxyethyl-2-pyrrolidone, etc. Nitrogen-containing heterocyclic compounds such as 1,3-dimethyl-2-imidazolidinone, ε-caprolactam and γ-butyrolactone, formamide, N-methylformamide, N, N-dimethylformamide, 3-methoxy-N, N-dimethyl Amidos such as propionamide, 3-butoxy-N, N-dimethylpropionamide, amines such as monoethanolamine, diethanolamine and triethylamine, sulfur-containing compounds such as dimethylsulfoxide, sulfolane and thiodiethanol, propylene carbonate, ethylene carbonate and the like. Can be mentioned.
The organic solvent not only functions as a wetting agent but also has good drying properties. Therefore, the boiling point is preferably 300 ° C. or lower, more preferably 250 ° C. or lower.
Further, it is more preferable to use an organic solvent having a boiling point of 150 ° C. or higher and 300 ° C. or lower because the fixability is good.

The hydrogen bond term in the Hansen solubility parameter (HSP) of the organic solvent is preferably 3 (cal / cm ³ ) ^0.5 or more and 6.8 (cal / cm ³ ) ^0.5 or less.
The hydrogen bond term can be obtained by using the atomic group summation method in which the organic molecule proposed by Krevelen is treated as an atomic group (see Krevelen, Properties of Polymer 2nd Edition, New York, 154 (1976)).
Examples of the organic solvent satisfying the above conditions include glycerin, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, isoprene glycol, and an oxetane compound. ..
Examples of the oxetane compound include 3-ethyl-3-hydroxymethyloxetane.

Polyol compounds having 8 or more carbon atoms and glycol ether compounds are also preferably used. Specific examples of the polyol compound 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 and ethylene glycol monobenzyl ether can be mentioned.

The polyol compound having 8 or more carbon atoms and the glycol ether compound can improve the permeability of the ink when paper is used as the recording medium.

The content of the organic solvent in the ink is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 10% by mass or more and 60% by mass or less from the viewpoint of ink drying property and ejection reliability. More preferably, it is 20% by mass or more and 60% by mass or less.

<Wax>
The wax can impart slipperiness to the image.
As the wax, polyethylene wax and carnauba wax are particularly preferable from the viewpoint of film forming property, slipperiness, etc. when ink is applied to the image forming portion.

The melting point of the wax is preferably 80 ° C. or higher and 140 ° C. or lower, and more preferably 100 ° C. or higher and 140 ° C. or lower. When the melting point is 80 ° C. or higher, the wax is less likely to be excessively melted or solidified even in a room temperature environment, and the storage stability of the ink can be maintained. On the other hand, when the melting point is 140 ° C. or lower, the wax is sufficiently melted even in a room temperature environment, and slipperiness can be imparted to the ink.

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. When the volume average particle diameter is 0.01 μm or more, the wax particles are likely to be oriented on the image surface, and it is possible to impart slipperiness to the ink.
Examples of the measurement of the volume average particle size include a method using a laser scattering / diffraction type particle size measuring device.

As the polyethylene wax, for example, a commercially available product can be used, and examples of the commercially available product include a high-tech series manufactured by Toho Chemical Industry Co., Ltd. and an AQUACER series manufactured by BYK. These may be used alone or in combination of two or more.

As the carnauba wax, for example, a commercially available product can be used, and examples of the commercially available product include cellozole 524 and Torasoru CN manufactured by Chukyo Yushi Co., Ltd. These may be used alone or in combination of two or more.

The wax content is preferably 1% by mass or more and 10% by mass or less, and more preferably 1% by mass or more and 5% by mass or less with respect to the total amount of the image.

<Water>
The content of water in the ink is not particularly limited and may be appropriately selected depending on the intended purpose, but from the viewpoint of ink drying property and ejection reliability, it is preferably 10% by mass or more and 90% by mass or less, and 20% by mass. % To 60% by mass is more preferable.

<Physical characteristics of ink>
The physical characteristics of the ink are not particularly limited and may be appropriately selected depending on the intended purpose. For example, the viscosity, surface tension, pH and the like are preferably in the following ranges.
The viscosity of the ink at 25 ° C. is preferably 5 mPa · s or more and 30 mPa · s or less, 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, for the viscosity, for example, a rotary viscometer (manufactured by Toki Sangyo Co., Ltd., device name: RE-80L) can be used. As the measurement conditions, it is possible to measure at 25 ° C. with a standard cone rotor (1 ° 34'x R24), a sample liquid volume of 1.2 mL, a rotation speed of 50 rpm, and 3 minutes.
The dynamic surface tension of the ink is 20 mN / m or more under the conditions of a bubble lifetime of 1,500 ms and 25 ° C. from the viewpoint that the ink is suitably leveled on the recording medium and the drying time of the ink is shortened. It is preferably 35 mN / m or less. The dynamic surface tension is a value measured at 25 ° C. by the maximum foam pressure method, and can be measured using, for example, a dynamic surface tension meter SITA DinoTester (manufactured by SITA Mestechnik). The "bubble lifetime" is the life of bubbles generated by the maximum bubble pressure method, and is also called "surface life", and is the maximum bubble pressure from the time when a new interface is formed in the probe tip of the dynamic surface tension meter. Refers to the time until it becomes.
The pH of the ink is preferably 7 to 12, and more preferably 8 to 11 from the viewpoint of preventing corrosion of the metal member in contact with the liquid. The pH can be measured at an ink temperature of 25 ° C. using a pH meter (device name: HM-30R, manufactured by DKK-TOA CORPORATION).

The ink used for forming the image can be used as a white ink. When a transparent recording medium is used as the recording medium, a base is formed with white ink to obtain the image, and a color ink such as yellow, magenta, cyan, or black is used on the base image. Can be printed. When obtaining such a color ink, the color ink contains a coloring material.
Further, the white ink may be used not only as a base but also as a topcoat layer. For example, it is possible to print on the recording medium with color ink and apply white ink on the color ink to obtain an image.
The portion to which the white ink is applied may be the entire surface of the recording medium, or may be only the portion where the image is formed by using the color ink. Further, it may be a portion that overlaps with a portion that forms an image using color ink.
The color materials used for the color ink are as follows.

<Color material>
The coloring material is not particularly limited, and pigments and dyes can be used.
As the pigment, an inorganic pigment or an organic pigment can be used. These may be used alone or in combination of two or more. Moreover, you may use a mixed crystal.
As the pigment, for example, a black pigment, a yellow pigment, a magenta pigment, a cyan pigment, a white pigment, a green pigment, an orange pigment, a glossy color pigment such as gold or silver, a metallic pigment, or the like can be used.
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, and thermal method. Can be used.
Examples of organic pigments include azo pigments and polycyclic pigments (for example, phthalocyanine pigments, perylene pigments, perinone pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, indigo pigments, thioindigo pigments, isoindolinone pigments, quinophthalone pigments, etc.). , Dye chelate (for example, basic dye type chelate, acidic dye type chelate, etc.), nitro pigment, nitroso pigment, aniline black and the like can be used. Among these pigments, those having a good affinity with a solvent are preferably used. In addition, resin hollow particles and inorganic hollow particles can also be used.
As a specific example of the pigment, for black, carbon black (CI pigment black 7) such as furnace black, lamp black, acetylene black, channel black, or copper, iron (CI pigment black 11) , Metals such as titanium oxide, and organic pigments such as aniline black (CI 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 Carmin 6B), 60: 1, 63: 1, 63: 2, 64: 1, 81, 83, 88, 101 (Magenta), 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 Greens 1, 4, 7, 8, 10, 17, 18, 36, etc.
The dye is not particularly limited, and acid dyes, direct dyes, reactive dyes, and basic dyes can be used, and one type may be used alone or two or more types may be used in combination.
As the 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. Hood 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. Dilekdo 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.

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 viewpoint of improving image density, good fixability and ejection stability. It is as follows.

In order to disperse the pigment to obtain an ink, a method of introducing a hydrophilic functional group into the pigment to obtain a self-dispersing pigment, a method of coating the surface of the pigment with a resin and dispersing it, and a method of dispersing using a dispersant are used. The method, etc. can be mentioned.
As a method of introducing a hydrophilic functional group into a pigment to obtain a self-dispersing 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) so that the pigment can be dispersed in water. Can be mentioned.
Examples of the method of coating the surface of the pigment with a resin and dispersing the pigment include a method of encapsulating the pigment in microcapsules so that the pigment can be dispersed in water. This can be rephrased as a resin coating pigment. In this case, it is not necessary that all the pigments blended in the ink are coated with the resin, and the uncoated pigments and the partially coated pigments are 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 a high molecular weight dispersant represented by a surfactant.
As the dispersant, for example, an anionic surfactant, a cationic surfactant, an amphoteric surfactant, a nonionic surfactant and the like can be used depending on the pigment.
RT-100 (nonionic surfactant) manufactured by Takemoto Oil & Fat Co., Ltd. and a naphthalene sulfonate Na formalin condensate can also be suitably used as a dispersant.
The dispersant may be used alone or in combination of two or more.

<Pigment dispersion>
It is possible to obtain an ink by mixing a material such as water or an organic solvent with a pigment. It is also possible to produce an ink by mixing a material such as water or an organic solvent with a pigment dispersion obtained by mixing a pigment and other water or a dispersant.
The pigment dispersion is obtained by mixing and dispersing water, a pigment, a pigment dispersant, and other components as necessary, and adjusting the particle size. It is preferable to use a disperser for dispersion.
The particle size of the pigment in the pigment dispersion is not particularly limited, but the maximum frequency is 20 nm or more in terms of the maximum number because the dispersion stability of the pigment is good and the image quality such as ejection stability and image density is also high. It is preferably 500 nm or less, more preferably 20 nm or more and 150 nm or less. The particle size of the pigment can be measured using a particle size analyzer (Nanotrack Wave-UT151, manufactured by Microtrac Bell Co., Ltd.).
The content of the pigment in the pigment dispersion is not particularly limited and may be appropriately selected depending on the intended purpose. However, from the viewpoint of obtaining good ejection stability and increasing the image density, 0.1 mass is used. % Or more and 50% by mass or less are preferable, and 0.1% by mass or more and 30% by mass or less are more preferable.
If necessary, the pigment dispersion is preferably degassed by filtering coarse particles with a filter, a centrifuge, or the like.

<Other ingredients>
The other components include, if necessary, a surfactant, an antifoaming agent, an antiseptic / antifungal agent, a rust preventive, a pH adjuster and the like.

<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-based surfactant is not particularly limited and may be appropriately selected depending on the intended purpose. Among them, those that do not decompose even at high pH are preferable, and examples thereof include side chain modified polydimethylsiloxane, double-ended modified polydimethylsiloxane, single-ended modified polydimethylsiloxane, and side chain double-ended modified polydimethylsiloxane. Those having an oxyethylene group and a polyoxyethylene polyoxypropylene group are particularly preferable because they exhibit good properties as an aqueous surfactant. Further, as the silicone-based surfactant, a polyether-modified silicone-based surfactant can also be used, and examples thereof include a compound in which a polyalkylene oxide structure is introduced into the Si portion side chain of dimethylsiloxane.
Examples of the fluorine-based surfactant include a perfluoroalkyl sulfonic acid compound, a perfluoroalkyl carboxylic acid compound, a perfluoroalkyl phosphate compound, a perfluoroalkyl ethylene oxide adduct, and a perfluoroalkyl ether group in the side chain. A polyoxyalkylene ether polymer compound is particularly preferable because it has a low foaming property. Examples of the perfluoroalkyl sulfonic acid compound include perfluoroalkyl sulfonic acid and perfluoroalkyl sulfonic acid salt. Examples of the perfluoroalkylcarboxylic acid compound include perfluoroalkylcarboxylic acid and perfluoroalkylcarboxylic acid salt. The polyoxyalkylene ether polymer compound having a perfluoroalkyl ether group in the side chain includes a sulfate ester salt of a polyoxyalkylene ether polymer having a perfluoroalkyl ether group in the side chain and a perfluoroalkyl ether group in the side chain. Examples thereof include salts of polyoxyalkylene ether polymers. The counterions of the salts in these fluorine-based surfactants are Li, Na, K, NH ₄ , NH ₃ CH ₂ CH ₂ OH, NH ₂ (CH ₂ CH ₂ OH) ₂ , NH (CH ₂ CH ₂ OH). ₃ etc. can be mentioned.
Examples of the amphoteric tenside agent include laurylaminopropionate, lauryldimethylbetaine, stearyldimethylbetaine, and lauryldihydroxyethylbetaine.
Examples of the nonionic surfactant include polyoxyethylene alkylphenyl ether, polyoxyethylene alkyl ester, polyoxyethylene alkyl amine, polyoxyethylene alkyl amide, polyoxyethylene propylene block polymer, sorbitan fatty acid ester, and polyoxyethylene sorbitan. Examples thereof include fatty acid esters and ethylene oxide adducts of acetylene alcohols.
Examples of the anionic surfactant include polyoxyethylene alkyl ether acetate, dodecylbenzene sulfonate, lauryl salt, and salt of polyoxyethylene alkyl ether sulfate.
These may be used alone or in combination of two or more.

一般式（Ｓ−１）
（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 may be appropriately selected depending on the intended purpose. For example, side chain-modified polydimethylsiloxane, double-ended modified polydimethylsiloxane, one-ended modified polydimethylsiloxane, side. Examples thereof include polydimethylsiloxane modified at both ends of the chain, and a polyether-modified silicone-based surfactant having a polyoxyethylene group and a polyoxyethylene polyoxypropylene group as modifying groups exhibits good properties as an aqueous surfactant, and is particularly effective. preferable.
As such a surfactant, an appropriately synthesized one may be used, or a commercially available product may be used. As commercially available products, for example, they can be obtained from Big Chemie Co., Ltd., Shin-Etsu Chemical Co., Ltd., Toray Dow Corning Silicone Co., Ltd., Nippon Emulsion Co., Ltd., Kyoeisha Chemical Co., Ltd., and the like.
The above-mentioned 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) is dimethylpoly. Examples thereof include those introduced into the Si part side chain of siloxane.

General formula (S-1)
(However, 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 (Shinetsu Chemical Industry Co., Ltd.), EMALEX-SS-5602, SS- 1906EX (Nippon Emulsion Co., Ltd.), FZ-2105, FZ-2118, FZ-2154, FZ-2161, FZ-2162, FZ-2163, FZ-2164 (Toray Dow Corning Silicone Co., Ltd.), BYK-33, BYK-387 (Big Chemie Co., Ltd.), TSF4440, TSF4452, TSF4453 (Toshiba Silicon Co., Ltd.) and the like can be mentioned.

一般式（Ｆ−１）
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。
一般式（Ｆ-２）
Ｃ_ｎＦ_2ｎ+1−ＣＨ₂ＣＨ（ＯＨ）ＣＨ₂−Ｏ−（ＣＨ₂ＣＨ₂Ｏ）_ａ−Ｙ
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 fluorine-based surfactant, a compound having 2 to 16 carbon atoms substituted with fluorine is preferable, and a compound having 4 to 16 carbon atoms substituted with fluorine 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 the side chain. Among these, a polyoxyalkylene ether polymer compound having a perfluoroalkyl ether group in the side chain is preferable because it has low foaming property, and is particularly a fluorine-based compound represented by the general formula (F-1) and the general formula (F-2). Surfactants are preferred.

General formula (F-1)
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.
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 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. It is an integer, or CpH _{2p + 1} and p is an integer of 1-19. n is an integer of 1-6. a is an integer of 4 to 14.
Commercially available products may be used as the above-mentioned fluorine-based surfactant. Examples of this commercially available product 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.); Full Lard FC-93, FC-95, FC-98, FC-129, FC-135, FC-170C, FC-430, FC-431 (all manufactured by Sumitomo 3M Co., Ltd.); Megafuck F-470, F -1405, F-474 (all manufactured by Dainippon Ink and Chemicals Co., Ltd.); 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 The Chemours Company); 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 Omniova), Unidyne DSN-403N (manufactured by Daikin Industries, Ltd.) Among these, FS-3100, FS-34, FS- of Chemours Co., Ltd., from the viewpoint of remarkably improving good print quality, particularly color development, penetrability to paper, wettability, and leveling property. 300, FT-110, FT-250, FT-251, FT-400S, FT-150, FT-400SW manufactured by Neos Co., Ltd., Polyfox PF-151N manufactured by Omniova Co., Ltd. and Unidyne DSN-manufactured by Daikin Industries, Ltd. 403N is particularly preferable.

The content of the surfactant in the ink is not particularly limited and may be appropriately selected depending on the intended purpose. However, from the viewpoint of excellent wettability and ejection stability and improvement in image quality, 0.001 mass is used. % Or more and 5% by mass or less are preferable, and 0.05% by mass or more and 5% by mass or less are more preferable.

<Defoamer>
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, a silicone-based defoaming agent is preferable because it has an excellent defoaming effect.

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

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

<pH adjuster>
The pH adjusting agent 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.

前記有機溶剤の混合ＳＰ値としては、１０．４（ｃａｌ／ｃｍ^３）^０．５以上１６．０（ｃａｌ／ｃｍ^３）^０．５以下が好ましい。 (Ink for manufacturing recorded materials)
The ink for producing a recorded material of the present invention contains hollow resin particles containing a copolymer having a structural unit represented by the following general formula (1) and a structural unit represented by the following general formula (2), and organic. maximum and a solvent comprising water, and in the IR spectrum of the hollow resin particles, in the absorbance at the maximum absorption wavelength in the wavelength 1,600cm ^-1 ± 10cm ^-1 and X, wavelength 1,730cm ^-1 ± 10cm ^-1 The ratio (Y / X) when the absorbance at the absorption wavelength is Y is 3.0 or more and 6.0 or less, and is used for producing the recorded matter of the present invention.

The mixed SP value of the organic solvent is preferably 10.4 (cal / cm ³ ) ^0.5 or more and 16.0 (cal / cm ³ ) ^0.5 or less.

The ink for producing a recorded material contains hollow resin particles containing a copolymer having a structural unit represented by the general formula (1) and a structural unit represented by the general formula (2). It is possible to produce a recorded material having pores due to the hollow resin particles in the image. Therefore, the hollow resin in the recorded material can be configured to have a plurality of fine pores in the resin.

As the ink for producing the recorded material, the same ink as the ink can be used.

<Pretreatment liquid>
The pretreatment liquid contains a coagulant, an organic solvent, and water, and may contain a surfactant, an antifoaming agent, a pH adjuster, an antiseptic / antifungal agent, an anticorrosive agent, and the like, if necessary.
As the organic solvent, surfactant, defoaming agent, pH adjuster, antiseptic / antifungal agent, and rust preventive, the same materials as those used for ink can be used, and other materials used for known treatment liquids can be used. ..
The type of coagulant is not particularly limited, and examples thereof include water-soluble cationic polymers, acids, and polyvalent metal salts.

<Post-treatment liquid>
The post-treatment liquid is not particularly limited as long as it is possible to form a transparent layer. The post-treatment liquid is obtained by selecting and mixing organic solvents, water, resins, surfactants, antifoaming agents, pH adjusters, antiseptic and antifungal agents, rust preventives and the like, if necessary. Further, the post-treatment liquid may be applied to the entire area of the recording area formed on the recording medium, or may be applied only to the area where the ink image is formed.

<Recording medium>
The recording medium is not particularly limited, and plain paper, glossy paper, special paper, cloth, or the like can be used, but good image formation can be achieved even if a non-permeable base material is used.
The non-permeable base material is a base material having a surface having low water permeability and low absorbability, and includes a material that does not open to the outside even if there are many cavities inside, and more quantitatively. , A base material having a water absorption amount of 10 mL / m ² or less from the start of contact to 30 msec ^{1/2 in the Bristow method.}
As the non-permeable base material, for example, a plastic film such as a vinyl chloride resin film, a polyethylene terephthalate (PET) film, polypropylene, polyethylene, or a polycarbonate film can be preferably used.

The recording medium is not limited to that used as a general recording medium, and wallpaper, floor materials, building materials such as tiles, cloth for clothing such as T-shirts, textiles, leather and the like can be appropriately used. Further, ceramics, glass, metal, or the like can be used by adjusting the configuration of the path for transporting the recording medium.

The case where black (K), cyan (C), magenta (M), and yellow (Y) are used will be described below, but an ink containing the hollow resin particles in place of or in addition to these. May be used.

<Recording device, recording method>
The ink of the present invention can be suitably used for various recording devices by an inkjet recording method, for example, a printer, a facsimile device, a copying device, a printer / fax / copier multifunction device, a three-dimensional modeling device, and the like.
In the present invention, the recording device and the recording method are devices capable of ejecting ink, various processing liquids, and the like to a recording medium, and a method of recording using the device. The recording medium means a medium to which ink and various treatment liquids can adhere even temporarily.
This recording device can include not only a head portion for ejecting ink, but also means related to feeding, transporting, and discharging paper of a recording medium, and other devices called pretreatment devices and posttreatment devices. ..
The recording device and recording method may include a heating means used in the heating step and a drying means used in the drying step. The heating means and the drying means include, for example, means for heating and drying the print surface and the back surface of the recording medium. The heating means and the drying means are not particularly limited, but for example, a hot air heater and an infrared heater can be used. Heating and drying can be performed before printing, during printing, after printing, and the like.
The heating temperature is preferably 100 ° C. or higher and 200 ° C. or lower, and more preferably 120 ° C. or higher and 150 ° C. or lower.
Further, the recording device and the recording method are not limited to those in which significant images such as characters and figures are visualized by ink. For example, those that form patterns such as geometric patterns and those that form a three-dimensional image are also included.
Further, the recording device includes both a serial type device that moves the discharge head and a line type device that does not move the discharge head, unless otherwise specified.
Further, as this recording device, it is possible to use not only a desktop type but also a wide recording device capable of printing on an A0 size recording medium, or, for example, continuous paper wound in a roll shape as a recording medium. A continuous line printer is also included.
An example of the recording device will be described with reference to FIGS. 1 and 2. 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 mechanical unit 420 is provided in the exterior 401 of the image forming apparatus 400. Each ink 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, for example, a package of an aluminum laminated film or the like. It is formed of members. The ink container 411 is housed in, for example, a plastic container case 414. As a result, the main tank 410 is used as an ink 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. A main tank 410 is detachably attached to the cartridge holder 404. As a result, each ink ejection port 413 of the main tank 410 and the ejection head 434 for each color communicate with each other via the supply tube 436 for each color, and ink can be ejected from the ejection head 434 to the recording medium.

This recording device can include not only a portion that ejects ink, but also a device called a pretreatment device, a posttreatment device, and the like.
As one aspect of the pretreatment apparatus and the posttreatment apparatus, it has a pretreatment liquid and a posttreatment liquid as in the case of inks such as black (K), cyan (C), magenta (M), and yellow (Y). There is an embodiment in which a liquid accommodating portion and a liquid discharge head are added, and a pretreatment liquid or a posttreatment liquid is discharged by an inkjet recording method.
As another aspect of the pretreatment device and the posttreatment device, there is a mode in which a pretreatment device and a posttreatment device by, for example, a blade coating method, a roll coating method, and a spray coating method are provided other than the inkjet recording method.

The method of using the ink is not limited to the inkjet recording method, and can be widely used. In addition to the inkjet recording method, examples thereof include 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, and a spray coating method.

The use of the ink of the present invention is not particularly limited and may be appropriately selected depending on the intended purpose. For example, it can be applied to printed matter, paints, coating materials, base materials and the like. Further, it can be used not only as an ink 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 model).
A known three-dimensional modeling device can be used for modeling the three-dimensional object, and the device is not particularly limited, and for example, an device provided with ink accommodating means, supply means, ejection means, drying means, and the like is used. be able to. The three-dimensional model includes a three-dimensional model obtained by overcoating with ink. In addition, a molded product obtained by processing a structure in which ink is applied on a base material such as a recording medium is also included. The molded product is, for example, a recorded material or structure formed in the form of a sheet or a film, which has been subjected to a molding process such as heat stretching or punching. For example, an automobile, an OA device, or electricity. -Suitably used for molding after decorating the surface of electronic devices, meters of cameras, panels of operation parts, etc.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples.

The "absorbance" of the hollow resin particles in the ink, the "mixed SP value" of the organic solvent in the ink, and the content of the resin in the image were measured as follows.

(Absorbance)
The absorbance, absorbance at the maximum absorption wavelength in the wavelength 1,600cm ^-1 ± 10cm ^-1 of the hollow resin particles (X), the absorbance at the maximum absorption wavelength in the wavelength 1,730cm ^-1 ± 10cm ^-1 to (Y), The measurement was performed using a microscopic FT-IR measuring device (device name: iN10MX / iZ10, manufactured by Thermo Fisher Scientific Co., Ltd.) and analysis software (OMNIC). The ratio (Y / X) was calculated from the obtained values.

(Mixed SP value)
The mixed SP value of the organic solvent in the ink was calculated using the following formula. Only those containing 3% by mass or more of the organic solvent with respect to the entire image (ink) were considered in the calculation of the mixed SP value. In addition, water in the organic solvent was excluded from the above calculation.
Mixed SP value of organic solvent in ink ((cal / cm ³ ) ^0.5 ) = [SP value of organic solvent A x volume fraction of organic solvent A] + ... + [SP value of organic solvent n x Volume fraction of organic solvent n]

(Resin content for images)
The resin content with respect to the image was measured using a microscopic FT-IR measuring device (device name: iN10MX / iZ10, manufactured by Thermo Fisher Scientific Co., Ltd.) and analysis software (OMNIC).

(Preparation Example 1 of Hollow Resin Particles)
<Preparation of hollow resin particles B>
(1) Synthesis of seed particle emulsion In a four-neck separable flask equipped with a stirrer, a thermometer, a cooler, and a dropping funnel, deionized water (726.0 parts by mass) and methyl methacrylate (5.0 parts by mass). ) And methacrylic acid (0.1 part by mass) were charged and heated with stirring. Then, when the internal temperature in the separable flask reached 70 ° C., a 10 mass% ammonium persulfate aqueous solution (1.0 part by mass) was added, and the mixture was heated at 80 ° C. for 20 minutes. On the other hand, methyl methacrylate (141.0 parts by mass), methacrylic acid (94.9 parts by mass), and sodium alkylbenzene sulfonate (trade name: Neogen SF-20, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) as an anionic emulsifier. 0 parts by mass) and deionized water (120.0 parts by mass) were emulsified with a homodisper to form a pre-emulsion, and then charged into a dropping funnel.

Next, while maintaining the internal temperature in the separable flask at 80 ° C., the obtained pre-emulsion was uniformly added dropwise over 3 hours, and at the same time, a 10% by mass ammonium persulfate aqueous solution (10.0 parts by mass) was added. The mixture was uniformly added dropwise over 3 hours. 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 B.

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

-2nd stage polymerization-
Homo of styrene (254.8 parts by mass), sodium alkylbenzene sulfonate (trade name: Neogen SF-20, manufactured by Daiichi Kogyo Seiyaku Co., Ltd., 5.0 parts by mass), and deionized water (51.8 parts by mass). After emulsification with a disper to obtain pre-emulsion 2, the mixture was put into a dropping funnel. Then, while maintaining the internal temperature in the separable flask at 80 ° C., 1 hour after the dropping of the pre-emulsion 1 was completed, the obtained pre-emulsion 2 was uniformly dropped over 60 minutes, and at the same time. A 10 mass% sodium persulfate aqueous solution (3.5 parts by mass) was uniformly added dropwise over 60 minutes. After completion of the dropping of the pre-emulsion 2, 28% by mass of aqueous ammonia (7.5 parts by mass) was dropped and aged at 80 ° C. for 1 hour in order to swell and dissolve the seed particles. After cooling, the mixture was filtered using a 120-mesh filter cloth to obtain hollow resin particles B having a solid content concentration of 20% by mass.
The obtained hollow resin particles B were structurally analyzed using a microscopic FT-IR measuring device (device name: iN10MX / iZ10, manufactured by Thermo Fisher Scientific Co., Ltd.) and analysis software (OMNIC). It was confirmed that it had a structural unit represented by (1) and a structural unit represented by the following general formula (2). The ratio (Y / X) was 3.0.
When the volume average particle diameter of the obtained hollow resin particles B was measured using a particle size analyzer (device name: Nanotrack Wave-UT151, manufactured by Microtrack Bell Co., Ltd.), the outer diameter was 700 nm and the inner diameter was 700 nm. Was 600 nm.

(Preparation Example 2 of Hollow Resin Particles)
<Preparation of hollow resin particles C>
In Preparation Example 1 of hollow resin particles, the solid content concentration was 20.5 mass by mass in the same manner as in Preparation Example 1 of hollow resin particles, except that the styrene content in the second stage polymerization was changed to 39.0 parts by mass. The hollow resin particles C which are% were obtained.
When the structural analysis was performed in the same manner as in Preparation Example 1 of the hollow resin particles, it was found that the hollow resin particles had the structural unit represented by the general formula (1) and the structural unit represented by the general formula (2). Was confirmed. The ratio (Y / X) was 4.5.
When the volume average particle diameter of the obtained hollow resin particles C was measured using a particle size analyzer (device name: Nanotrack Wave-UT151, manufactured by Microtrac Bell Co., Ltd.), the outer diameter was 800 nm and the inner diameter was 800 nm. Was 700 nm.

(Preparation Example 3 of Hollow Resin Particles)
<Preparation of hollow resin particles D>
In Preparation Example 1 of hollow resin particles, the solid content concentration was 26% by mass in the same manner as in Preparation Example 1 of hollow resin particles, except that the styrene content in the second stage polymerization was changed to 22.3 parts by mass. A certain hollow resin particle D was obtained.
When the structural analysis was performed in the same manner as in Preparation Example 1 of the hollow resin particles, it was found that the hollow resin particles had the structural unit represented by the general formula (1) and the structural unit represented by the general formula (2). Was confirmed. The ratio (Y / X) was 6.0.
When the volume average particle diameter of the obtained hollow resin particles D was measured using a particle size analyzer (device name: Nanotrack Wave-UT151, manufactured by Microtrac Bell Co., Ltd.), the outer diameter was 500 nm and the inner diameter was 500 nm. Was 400 nm.

(Ink Preparation Example 1)
<Preparation of ink 1>
Hollow resin particles B 10.0% by mass (solid content concentration), 1,2-propanediol (manufactured by Tokyo Chemical Industry Co., Ltd.) 25.0% by mass, 1,2-butanediol (manufactured by Tokyo Chemical Industry Co., Ltd.) 8 .0% by mass, surfactant (trade name: KF-640, manufactured by Shin-Etsu Chemical Industry Co., Ltd.) 1.0% by mass, antifoaming agent (trade name: KF-353, manufactured by Shin-Etsu Chemical Industry Co., Ltd.) 0.5 Mass%, antibacterial agent (trade name: LV (S), manufactured by Abyssia) 0.1% by mass, pH adjuster (2-amino-2-ethyl-1,3-propanediol, manufactured by Tokyo Chemical Industry Co., Ltd.) The remaining amount of ion-exchanged water was added so as to have an appropriate amount and a total of 100% by mass, and the mixture was stirred for 1 hour and mixed uniformly to obtain a mixed solution. The obtained mixed solution was pressure-filtered with a polyvinylidene chloride membrane filter (trade name: Dismic 25CS080AS, manufactured by Advantech Co., Ltd.) having an average pore size of 5 μm to remove coarse particles and dust to obtain Ink 1. .. The pH was adjusted to 9-10. The pH was measured at an ink temperature of 25 ° C. using a pH meter (device name: HM-30R, manufactured by DKK-TOA CORPORATION).

(Ink Preparation Examples 2 to 20)
<Preparation of inks 2 to 20>
Ink 2 to 20 were obtained in the same manner as in Ink Preparation Example 1 except that the composition was changed to the composition shown in Tables 1 to 3 below in Ink Preparation Example 1. The compositions in Tables 1 to 3 below are shown in terms of solid content concentration (active ingredient).

In Tables 1 to 3 above, the product names of the ingredients and the names of the manufacturing companies are as follows.
-Hollow resin particles A: styrene-methylmethacrylate copolymer, manufactured by Dow Chemical Co., Ltd., trade name: ROPAQUE ULTRA E, ratio (Y / X): 1.5, outer diameter: 500 nm, inner diameter: 400 nm, solid content concentration 30% by mass
Hollow resin particles E: styrene-methylmethacrylate copolymer, manufactured by JSR Corporation, trade name: SX868, ratio (Y / X): 9.3, outer diameter: 700 nm, inner diameter: 500 nm, solid content concentration 20. 3% by mass
-Glycerin: manufactured by Sakamoto Yakuhin Kogyo Co., Ltd., SP value: 17.4 (cal / cm ³ ) ^0.5
・ 1,2-Propanediol: manufactured by Tokyo Chemical Industry Co., Ltd., SP value: 14.3 (cal / cm ³ ) ^0.5
-1,2-Butanediol: manufactured by Tokyo Chemical Industry Co., Ltd., SP value: 13.1 (cal / cm ³ ) ^0.5
-3-Ethyl-3-hydroxymethyloxetane: manufactured by Tokyo Chemical Industry Co., Ltd., SP value: 11.0 (cal / cm ³ ) ^0.5
-3-Methoxy-N, N-dimethylpropionamide: manufactured by Idemitsu Kosan Co., Ltd., SP value: 9.2 (cal / cm ³ ) ^0.5
-Acrylic silicone resin: manufactured by Toyochem Co., Ltd., trade name: RKP-02, Tg: -7 ° C
-Polyurethane resin A: manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., trade name: Superflex 420, Tg: -10 ° C, solid content concentration 38% by mass
-Polyurethane resin B: manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., trade name: Superflex 210, Tg: 41 ° C, solid content concentration of 35% by mass
-Polyethylene wax: manufactured by BYK, trade name: AQUACER-515
-Surfactant: Product name: KF-640, manufactured by Shin-Etsu Chemical Co., Ltd.-Defoamer: Product name: KF-353, manufactured by Shin-Etsu Chemical Co., Ltd.-Antibacterial agent: Product name: LV (S), Abyssia Manufactured by pH adjuster: manufactured by Tokyo Chemical Industry Co., Ltd., 2-amino-2-ethyl-1,3-propanediol

Using the obtained ink, "precipitation" was evaluated as follows. The results are shown in Table 4 below.

(Settling)
About 5 g of the obtained ink was placed in a glass tube (trade name: screw cap test tube, manufactured by AS ONE Corporation) and allowed to stand in an environment of 25 ° C. for 168 hours. Samples at 0 hours (initial value) and 168 hours (after storage) were subjected to a sedimentation measuring device (device name: Turbiscan MA2000, manufactured by Hidehiro Seiki Co., Ltd.), and the sedimentation rate was calculated. The smaller the sedimentation rate, the more sedimentation. The sedimentation rate is at a feasible level when the sedimentation rate is −2.0% or more.

(Examples 1 to 18 and Comparative Examples 1 to 2)
Using the obtained ink, an image was formed on a recording medium as described below to obtain a recorded material.
The cross section of the obtained recorded material was observed with a microscope (device name: JSM-6510, manufactured by JEOL Ltd.), the diameters of 10 randomly selected pores were measured, and the average value was obtained. The diameter of the pores in the image of the recorded material was determined. When the pores were not perfect circles, the average diameter was calculated using the maximum diameter.
The diameters of the pores in the image of the obtained recorded material are as follows.
-Recorded material containing hollow resin particles A: 400 nm
-Recorded material containing hollow resin particles B: 600 nm
-Recorded material containing hollow resin particles C: 700 nm
-Recorded material containing hollow resin particles D: 400 nm
-Recorded material containing hollow resin particles E: 500 nm

[Image formation]
The obtained ink is discharged onto a recording medium (trade name: Lumina Color Black 127 gsm, manufactured by Takeo Co., Ltd.) with a liquid ejection device (device name: IPSiO GXe5500, manufactured by Ricoh Co., Ltd.) at an adhesion amount of 600 mg / cm ² . After that, an initial sample (recorded material) was obtained by drying at 90 ° C. for 60 seconds using a constant temperature bath (device name: FX420P, manufactured by Kusumoto Kasei Co., Ltd.). As the print chart, a solid image of 3 cm square formed by a dot pattern was used.

-Measurement of absorbance of images-
^{The obtained initial sample was subjected to an IR spectrum wavelength of 1,600 cm -1} ± 10 cm using a microscopic FT-IR measuring device (device name: iN10MX / iZ10, manufactured by Thermo Fisher Scientific Co., Ltd.) and analysis software (OMNIC). absorbance at the maximum absorption wavelength in the ^-1 and (X), was measured absorbance at the maximum absorption wavelength (Y) at a wavelength of 1,730cm ^-1 ± 10cm ^-1. The ratio (Y / X) was calculated from the obtained absorbance (X) and absorbance (Y) values. The results are shown in Table 4 below.

Using the obtained recorded material, "fixability" was evaluated as follows. The results are shown in Table 4 below.

(Fixability)
The obtained initial sample was rubbed 5 times with a clock meter (manufactured by Daiei Kagaku Seiki Seisakusho Co., Ltd.) equipped with a cotton cloth. The image density before and after rubbing was measured using a spectrocolorimeter (manufactured by X-Rite, apparatus name: 939), and the fixing rate was calculated from the density difference before and after rubbing to evaluate "fixability".

(Brightness (L ^* ))
^{The brightness (L *} ) of the initial sample obtained by forming the image was measured using a spectrocolorimeter (manufactured by X-Rite, apparatus name: 939). Next, the initial sample was dried at 110 ° C. for 60 seconds using a constant temperature bath (device name: FX420P, manufactured by Kusumoto Kasei Co., Ltd.) to obtain a secondary sample. ^{The brightness (L *} ) of the obtained secondary sample was measured in the same manner as in the initial sample. ^{From the brightness (L *} ) of the obtained initial sample (initial value) and secondary sample (value after heating at 110 ° C. for 60 seconds), use the following formula (1) to determine the rate of change (%) in brightness. Calculated. The results are shown in Table 4 below.
Brightness change rate (%) = {(initial value-value after heating at -110 ° C. for 60 seconds) / initial value} x 100 ... Equation (1)

＜２＞ 前記中空樹脂の含有量が、画像全量に対して、５０質量％以上１００質量％以下である前記＜１＞に記載の記録物である。
＜３＞ 前記画像が、インクを用いて形成されてなり、
前記インクが、中空樹脂粒子を含有し、
前記中空樹脂粒子の含有量が、インク全量に対して、５．０質量％以上１２．５質量％以下である前記＜１＞から＜２＞のいずれかに記載の記録物である。
＜４＞ 前記画像が、アクリルシリコーン樹脂、及びポリウレタン樹脂をさらに含む前記＜１＞から＜３＞のいずれかに記載の記録物である。
＜５＞ 前記アクリルシリコーン樹脂の含有量が、２１．４質量％以上３３．３質量％以下であり、
前記ポリウレタン樹脂の含有量が、２１．４質量％以上３３．３質量％以下である前記＜４＞に記載の記録物である。
＜６＞ 前記画像が、インクを用いて形成されてなり、
前記アクリルシリコーン樹脂の含有量が、インク全量に対して、３質量％以上５質量％以下であり、
前記ポリウレタン樹脂の含有量が、インク全量に対して、３質量％以上５質量％以下である前記＜４＞から＜５＞のいずれかに記載の記録物である。
＜７＞ 前記アクリルシリコーン樹脂のガラス転移温度が、０℃以下であり、
前記ポリウレタン樹脂のガラス転移温度が、０℃以下である前記＜４＞から＜６＞のいずれかに記載の記録物である。
＜８＞ 前記画像が、有機溶剤をさらに含み、
前記有機溶剤の混合ＳＰ値が、１１．０（ｃａｌ／ｃｍ^３）^０．５以上１５．５（ｃａｌ／ｃｍ^３）^０．５以下である前記＜１＞から＜７＞のいずれかに記載の記録物である。
＜９＞ 前記中空樹脂の体積平均粒径が、４００ｎｍ以上８００ｎｍ以下である前記＜１＞から＜８＞のいずれかに記載の記録物である。
＜１０＞ 前記有機溶剤のハンセン溶解度パラメータ（ＨＳＰ）における水素結合項が、３（ｃａｌ／ｃｍ^３）^０．５以上６．８（ｃａｌ／ｃｍ^３）^０．５以下である前記＜８＞から＜９＞のいずれかに記載の記録物である。
＜１１＞ 前記有機溶剤が、グリセリン、１，２−プロパンジオール、１，３−プロパンジオール、１，２−ブタンジオール、１，３−ブタンジオール、イソプレングリコール、及びオキセタン化合物から選択される少なくとも１種である前記＜８＞から＜１０＞のいずれかに記載の記録物である。
＜１２＞ 前記オキセタン化合物が、３−エチル−３−ヒドロキシメチルオキセタンである前記＜１１＞に記載の記録物である。
＜１３＞ 前記有機溶剤の含有量が、画像全量に対して、１０質量％以上６０質量％以下である前記＜８＞から＜１２＞のいずれかに記載の記録物である。
＜１４＞ 前記画像が、ワックスをさらに含有する前記＜１＞から＜１３＞のいずれかに記載の記録物である。
＜１５＞ 前記ワックスが、ポリエチレンワックス、及びカルナバワックスの少なくともいずれかである前記＜１４＞に記載の記録物である。
＜１６＞ 前記ワックスの融点が、８０℃以上１４０℃以下である前記＜１４＞から＜１５＞のいずれかに記載の記録物である。
＜１７＞ 前記ワックスの体積平均粒径が、０．０１μｍ以上である前記＜１４＞から＜１６＞のいずれかに記載の記録物である。
＜１８＞ 前記ワックスの含有量が、画像全量に対して、１質量％以上１０質量％以下である前記＜１４＞から＜１７＞のいずれかに記載の記録物である。
＜１９＞ 前記画像が、界面活性剤をさらに含む前記＜１＞から＜１８＞のいずれかに記載の記録物である。
＜２０＞ 前記界面活性剤の含有量が、画像全量に対して、０．００１質量％以上５質量％以下である前記＜１９＞に記載の記録物である。
＜２１＞ 前記画像における、１１０℃にて６０秒間加熱した前後での明度の変化率が、２５％以下である前記＜１＞から＜２０＞のいずれかに記載の記録物である。
＜２２＞ 下記一般式（１）で表される構造単位、及び下記一般式（２）で表される構造単位を有する共重合体を含む中空樹脂粒子と、有機溶剤と、水と、を含み、
前記中空樹脂粒子のＩＲスペクトルにおいて、波長１，６００ｃｍ^−１±１０ｃｍ^−１における最大吸収波長における吸光度をＸとし、波長１，７３０ｃｍ^−１±１０ｃｍ^−１における最大吸収波長における吸光度をＹとしたときの比率（Ｙ／Ｘ）が、３．０以上６．０以下であり、
前記＜１＞から＜２１＞のいずれかに記載の記録物を製造するために用いられることを特徴とする記録物製造用のインクである。

＜２３＞ 前記有機溶剤の混合ＳＰ値が、１０．４（ｃａｌ／ｃｍ^３）^０．５以上１６．０（ｃａｌ／ｃｍ^３）^０．５以下である前記＜２２＞に記載の記録物製造用のインクである。 Examples of aspects of the present invention are as follows.
<1> A recording material having a recording medium and an image on the recording medium.
The image contains a hollow resin containing a copolymer having a structural unit represented by the following general formula (1) and a structural unit represented by the following general formula (2).
In the image, the absorbance at the maximum absorption wavelength in the wavelength 1,600cm ^-1 ± 10cm ^-1 and X, the ratio when the absorbance at the maximum absorption wavelength in the wavelength 1,730cm ^-1 ± 10cm ^-1 was Y (Y / X) is a recorded matter characterized in that it is 3.0 or more and 6.0 or less.

<2> The recorded material according to <1>, wherein the content of the hollow resin is 50% by mass or more and 100% by mass or less with respect to the total amount of the image.
<3> The image is formed by using ink.
The ink contains hollow resin particles and
The recorded material according to any one of <1> to <2>, wherein the content of the hollow resin particles is 5.0% by mass or more and 12.5% by mass or less with respect to the total amount of ink.
<4> The image is the record according to any one of <1> to <3>, which further contains an acrylic silicone resin and a polyurethane resin.
<5> The content of the acrylic silicone resin is 21.4% by mass or more and 33.3% by mass or less.
The record according to <4>, wherein the content of the polyurethane resin is 21.4% by mass or more and 33.3% by mass or less.
<6> The image is formed by using ink.
The content of the acrylic silicone resin is 3% by mass or more and 5% by mass or less with respect to the total amount of ink.
The record according to any one of <4> to <5>, wherein the content of the polyurethane resin is 3% by mass or more and 5% by mass or less with respect to the total amount of ink.
<7> The glass transition temperature of the acrylic silicone resin is 0 ° C. or lower.
The record according to any one of <4> to <6>, wherein the glass transition temperature of the polyurethane resin is 0 ° C. or lower.
<8> The image further contains an organic solvent and contains
Described in any of <1> to <7>, wherein the mixed SP value of the organic solvent is 11.0 (cal / cm ³ ) ^0.5 or more and 15.5 (cal / cm ³ ) ^{0.5 or less.} It is a record of.
<9> The recorded material according to any one of <1> to <8>, wherein the volume average particle diameter of the hollow resin is 400 nm or more and 800 nm or less.
<10> From the above <8>, in which the hydrogen bond term in the Hansen solubility parameter (HSP) of the organic solvent is 3 (cal / cm ³ ) ^0.5 or more and 6.8 (cal / cm ³ ) ^0.5 or less. It is the recorded matter according to any one of <9>.
<11> The organic solvent is at least one selected from glycerin, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, isoprene glycol, and an oxetane compound. The record according to any one of <8> to <10>, which is a species.
<12> The record according to <11>, wherein the oxetane compound is 3-ethyl-3-hydroxymethyloxetane.
<13> The recording according to any one of <8> to <12>, wherein the content of the organic solvent is 10% by mass or more and 60% by mass or less with respect to the total amount of the image.
<14> The image is the recording according to any one of <1> to <13>, which further contains wax.
<15> The record according to <14>, wherein the wax is at least one of polyethylene wax and carnauba wax.
<16> The recording according to any one of <14> to <15>, wherein the wax has a melting point of 80 ° C. or higher and 140 ° C. or lower.
<17> The recorded material according to any one of <14> to <16>, wherein the volume average particle diameter of the wax is 0.01 μm or more.
<18> The recording according to any one of <14> to <17>, wherein the content of the wax is 1% by mass or more and 10% by mass or less with respect to the total amount of the image.
<19> The image is the recording according to any one of <1> to <18>, which further contains a surfactant.
<20> The recording according to <19>, wherein the content of the surfactant is 0.001% by mass or more and 5% by mass or less with respect to the total amount of the image.
<21> The recorded material according to any one of <1> to <20>, wherein the rate of change in brightness of the image before and after heating at 110 ° C. for 60 seconds is 25% or less.
<22> Contains hollow resin particles containing a copolymer having a structural unit represented by the following general formula (1) and a structural unit represented by the following general formula (2), an organic solvent, and water. ,
In the IR spectrum of the hollow resin particles, the absorbance at the maximum absorption wavelength in the wavelength 1,600cm ^-1 ± 10cm ^-1 and X, when the absorbance at the maximum absorption wavelength in the wavelength 1,730cm ^-1 ± 10cm ^-1 and the Y The ratio (Y / X) of is 3.0 or more and 6.0 or less.
An ink for producing a recorded material, which is used for producing the recorded material according to any one of <1> to <21>.

<23> The recording product production according to <22>, wherein the mixed SP value of the organic solvent is 10.4 (cal / cm ³ ) ^0.5 or more and 16.0 (cal / cm ³ ) ^{0.5 or less.} Ink for.

According to the recording material according to any one of <1> to <21> and the ink for producing a recording material according to any one of <22> to <23>, the conventional problems can be solved. The object of the present invention can be achieved.

Japanese Unexamined Patent Publication No. 2014-028964 Japanese Patent No. 3747033

Claims (10)

A recording material having a recording medium and an image on the recording medium.
The image contains a hollow resin containing a copolymer having a structural unit represented by the following general formula (1) and a structural unit represented by the following general formula (2).
In the image, the absorbance at the maximum absorption wavelength in the wavelength 1,600cm ^-1 ± 10cm ^-1 and X, the ratio when the absorbance at the maximum absorption wavelength in the wavelength 1,730cm ^-1 ± 10cm ^-1 was Y (Y / A recorded material in which X) is 3.0 or more and 6.0 or less.

The recorded product according to claim 1, wherein the content of the hollow resin is 50% by mass or more and 100% by mass or less with respect to the total amount of the image. The image is formed with ink and
The ink contains hollow resin particles and
The recorded material according to any one of claims 1 to 2, wherein the content of the hollow resin particles is 5.0% by mass or more and 12.5% by mass or less with respect to the total amount of ink. The record according to any one of claims 1 to 3, wherein the image further includes an acrylic silicone resin and a polyurethane resin. The content of the acrylic silicone resin is 21.4% by mass or more and 33.3% by mass or less with respect to the total amount of the image.
The recorded product according to claim 4, wherein the content of the polyurethane resin is 21.4% by mass or more and 33.3% by mass or less with respect to the total amount of the image. The image is formed with ink and
The content of the acrylic silicone resin is 3% by mass or more and 5% by mass or less with respect to the total amount of ink.
The recorded material according to any one of claims 4 to 5, wherein the content of the polyurethane resin is 3% by mass or more and 5% by mass or less with respect to the total amount of ink. The glass transition temperature of the acrylic silicone resin is 0 ° C. or lower.
The record according to any one of claims 4 to 6, wherein the glass transition temperature of the polyurethane resin is 0 ° C. or lower. The recorded material according to any one of claims 1 to 7, wherein the rate of change in brightness before and after heating at 110 ° C. for 60 seconds in the image is 25% or less. It contains hollow resin particles containing a copolymer having a structural unit represented by the following general formula (1) and a structural unit represented by the following general formula (2), an organic solvent, and water.
In the IR spectrum of the hollow resin particles, the absorbance at the maximum absorption wavelength in the wavelength 1,600cm ^-1 ± 10cm ^-1 and X, when the absorbance at the maximum absorption wavelength in the wavelength 1,730cm ^-1 ± 10cm ^-1 and the Y The ratio (Y / X) of is 3.0 or more and 6.0 or less.
An ink for producing a recorded material, which is used for producing the recorded material according to any one of claims 1 to 8.

The ink for producing a recorded material according to claim 9, wherein the mixed SP value of the organic solvent is 10.4 (cal / cm ³ ) ^0.5 or more and 16.0 (cal / cm ³ ) ^{0.5 or less.}

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