JP6965632B2 - Records, how to use them, and how to manufacture records - Google Patents

Description

The present invention relates to a recorded material, a method of using the recorded material, and a method of producing the recorded material.

Compared to other recording methods, the inkjet recording method has a simple process, is easy to make into full color, and can obtain high-resolution images even with a device with a simple configuration. , Is expanding into the fields of commercial printing and industrial printing.

In the field of commercial printing, it is common to process printed matter with a post-processing machine such as a bookbinding machine or a folding machine, and it is required that the processing environment can be widely supported. In addition, there are various usage environments for recorded materials, and it is required to have good scratch resistance and blocking resistance under a wide range of environments.

It is an object of the present invention to provide a recorded material having excellent scratch resistance in a low humidity environment while suppressing the occurrence of troubles in transporting recorded materials with less generation of static electricity even in a low humidity environment.

The recorded material of the present invention as a means for solving the above-mentioned problems is a recorded material having a recording medium and a recording layer containing an organic solvent, a coloring material, and a resin on the recording medium. The resin contains an acrylic resin and a urethane resin, and the mass ratio of the urethane resin content (mass%) and the acrylic resin content (mass%) to the total amount of the recording layer (urethane resin / acrylic resin). However, 0. 4 or more and 0.7 or less, the acrylic resin is an acrylic silicone resin, and the organic solvent contains hexanediol and propylene glycol.

It is possible to provide a recorded material having excellent scratch resistance in a low humidity environment while suppressing the occurrence of troubles in transporting the recorded material with less generation of static electricity even in a low humidity environment.

FIG. 1 is a perspective explanatory view showing an example of a serial type image forming apparatus. FIG. 2 is a perspective explanatory view showing an example of the main tank of the apparatus of FIG. FIG. 3 is a schematic view showing a peak area A and a peak area B.

(How to use recorded materials)
The method of using the recorded material of the present invention is a method of using a recorded material having a recording medium and a recording layer containing an organic solvent, a coloring material, and a resin on the recording medium, wherein the resin is acrylic. The mass ratio (urethane resin / acrylic resin) of the content of the urethane resin (mass%) to the content of the acrylic resin (mass%) with respect to the total amount of the recording layer containing the resin and the urethane resin is 0. .1 or more and 0.7 or less, the organic solvent contains hexanediol and propylene glycol, and the recorded material is used at a relative humidity of 40% or less.

(Recorded material)
The recording material of the present invention is a recording material having a recording medium and a recording layer containing an organic solvent, a coloring material, and a resin on the recording medium, and the resin is an acrylic resin and a urethane resin. The mass ratio (urethane resin / acrylic resin) of the content of the urethane resin (mass%) to the content of the acrylic resin (mass%) with respect to the total amount of the recording layer is 0.1 or more and 0.7. The organic solvent is as follows, and contains hexanediol and propylene glycol.

In addition, the present inventors have obtained the following findings.
When the recorded material is used in a low humidity environment with a relative humidity of 40% or less, troubles in transporting the recorded material due to the generation of static electricity are likely to occur, but the image (recording layer) contains propylene glycol and hexanediol. Therefore, it is expected that the moisture in the image or the recording medium is retained and the generation of static electricity is suppressed. The propylene glycol is expected to have the above effect in the image, and the hexanediol is expected to have the above effect in the recording medium. The recorded material transport trouble in the present invention includes, for example, a step of ejecting the recorded material, a process of winding the recorded material, a step of making a crease in the recorded material, a step of cutting the recorded material, and a recorded material. Includes those generated in the process of transportation.

In addition, images containing acrylic resin and urethane resin are expected to improve scratch resistance in all environments.
Images containing the urethane resin tend to have higher scratch resistance because the urethane resin has lower hardness and higher elasticity than the acrylic resin.
On the other hand, the image containing the urethane resin is more likely to absorb moisture in a high temperature and high humidity environment than the image containing the acrylic resin, and the tack force of the image is likely to increase, which causes a problem of transfer between images. It will be easier. However, in a low humidity environment, it has a moisturizing effect and maintains the elasticity of the image, so that it is possible to suppress a decrease in scratch resistance. The moisturizing effect of the urethane resin in a low humidity environment is also expected to be effective in suppressing troubles in transporting recorded materials due to the generation of static electricity.

Therefore, by including acrylic resin and urethane resin in a specific mass ratio in the image, the acrylic resin and urethane resin in the image are contained in a specific mass ratio to obtain an image containing propylene glycol and hexanediol. As a result, it was found that troubles in transporting recorded materials due to the generation of static electricity in a low humidity environment can be suppressed, and recorded materials with high image fixability can be obtained in both low humidity and high temperature and high humidity environments. ..

Further, the method of using the recording material of the present invention is a method of using a recording material having a recording medium and a recording layer containing an organic solvent and a coloring material on the recording medium, and the recording layer is used. when measured by Fourier transform infrared absorption spectroscopy, from the spectrum 692cm ^-1 and the area up to 707cm ^-1, the minimum point and spectrum 660 cm ^-1 or more 690 cm ^-1 or less in between: spectrum 710 cm ^-1 or more 740 cm ^-1 The area A of the peak region surrounded by the tangent line connecting the minimum points between them, ^{the region from spectrum 1,731 cm -1} to 1,750 cm ^-1 , and the spectrum 1,660 cm ^-1 or more and 1,690 cm ^-1 or less. The area ratio (B / A) of the area B of the peak region surrounded by the tangent line connecting the minimum point between the minimum points and the minimum points between 1,760 cm ^-1 or more and 1,790 cm ^{-1 or less in the spectrum is 0.3 or more.} 1.0 or less, the organic solvent contains hexanediol and propylene glycol, and the recorded material is used at a relative humidity of 40% or less.

The recorded material used in the method of using the recorded material of the present invention is preferably used at a relative humidity of 40% or less, preferably at a relative humidity of 30% or less, and further, has a temperature of 30 ° C. or more and a relative humidity of 80. It is preferable that it can be used in% or more.
The temperature in a low temperature environment is preferably 0 ° C. or higher and 25 ° C. or lower.

<Recording layer>
The recording layer contains an organic solvent, a coloring material, and a resin, and further contains wax and other components, if necessary.
The recording layer can be formed by using an ink containing an organic solvent, a coloring material, and a resin, and if necessary, an ink containing wax and other components.

<< Resin >>
The resin contains an acrylic resin and a urethane resin, and further contains other resins, if necessary.

The resin is preferably, for example, a water-dispersible dispersion.
Examples of the acrylic resin include acrylic silicone resin and styrene acrylic resin. These may be used alone or in combination of two or more. Among these, an acrylic silicone resin is preferable from the viewpoint of scratch resistance.
Examples of the urethane resin include polycarbonate urethane resin, polyester urethane resin, and polyether urethane resin. These may be used alone or in combination of two or more. Among these, polycarbonate urethane resin is preferable from the viewpoint of scratch resistance of images and storage stability of ink. The polycarbonate urethane resin may have a polycarbonate structure in the structure, and means that the polycarbonate urethane resin is also included.

As the resin, a commercially available product may be used, or a synthetic product may be used. As the commercially available product, for example, as an acrylic resin, the product name is Cymac (manufactured by Toa Synthetic Co., Ltd.), and the product name is Boncoat (DIC). (Manufactured by Co., Ltd.), Aquabrid (manufactured by DIC CORPORATION); as urethane resin Product name: U-coat (manufactured by Sanyo Kasei Kogyo Co., Ltd.), Product name: Takelac (manufactured by Mitsui Chemicals, Inc.), Product name as polycarbonate urethane resin: Takelac W-4000, trade name: Takelac W-6010, trade name: Takelac W-6110 (all manufactured by Mitsui Chemicals, Inc.) and the like can be mentioned. These may be used alone or in combination of two or more.

The Martens hardness of the resin is preferably ^{10 N / mm 2 or less from the viewpoint of scratch resistance.}
Examples of the Martens hardness of the urethane resin, from the viewpoint of abrasion resistance, preferably from 10 N / mm ² or less, 0.1 N / mm ² or more 10 N / mm ² or less being more preferred.
As for the Martens hardness, a resin particle solution is coated on a support such as slide glass (trade name: white plate glass S1111, manufactured by Matsunami Glass Ind. Co., Ltd.) so as to have an average thickness of 10 μm or more, and at 60 ° C. After pre-drying for 3 hours, it is dried at 100 ° C. for 6 hours to obtain a resin film. The obtained resin film was pushed by a Vickers indenter with a force of 1.0 mN for 10 seconds using a microhardness meter (device name: HM-2000, manufactured by Fischer Instruments Co., Ltd.), held for 5 seconds, and then held for 5 seconds. It can be measured by pulling out in 10 seconds with a force of 1.0 mN.

The resin is preferably dispersed as resin particles in the ink.

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

The resin in the recording layer is not particularly limited and may be appropriately selected depending on the intended purpose. For example, measurement may be performed using NMR, differential scanning calorimetry (DSC), differential thermal analysis (DTA), or the like. Can be done.

The content of the resin is preferably 30% by mass or more and 80% by mass or less, more preferably 50% by mass or more and 60% by mass or less, based on the total amount of the recording layer.

The content of the acrylic resin is preferably 10% by mass or more and 60% by mass or less, more preferably 30% by mass or more and 50% by mass or less, based on the total amount of the recording layer.
The content of the urethane resin is preferably 5% by mass or more and 30% by mass or less, more preferably 10% by mass or more and 30% by mass or less, based on the total amount of the recording layer.

[Mass ratio (urethane resin / acrylic resin)]
The mass ratio (urethane resin / acrylic resin) of the urethane resin content (mass%) to the acrylic resin content (mass%) is 0.1 or more and 0.7 or less, and the image resistance of the image. From the viewpoint of scratch resistance, ink ejection stability, and storage stability, 0.4 or more and 0.7 or less are preferable.

<< Organic Solvent >>
The organic solvent contains propylene glycol (1,2-propanediol) and hexanediol, and further contains other organic solvents as needed.

Examples of the hexanediol include 1,2-hexanediol, 1,6-hexanediol, 1,3-hexanediol, 2,5-hexanediol, and 1,5-hexanediol. These may be used alone or in combination of two or more. Of these, 1,2-hexanediol is preferred.

-Other organic solvents-
The other organic solvent is not particularly limited and may be appropriately selected depending on the intended purpose. For example, polyhydric alcohols other than propylene glycol and hexanediol; polyhydric alcohol alkyl ethers and polyhydric alcohol aryl ethers. Examples thereof include ethers; nitrogen-containing heterocyclic compounds; amides; amines; sulfur-containing compounds and the like. These may be used alone or in combination of two or more. Among these, 1,6-hexanediol and 3-ethyl-3-hydroxymethyloxetane are preferable.

The content (residual concentration) of the organic solvent in the recording layer ^{is preferably 21 mg / m 2} or more and 120 mg / m ² or less, and more preferably 33 mg / m ² or more and 90 mg / m ² or less, based on the total amount of the recording layer. , 45 mg / m ² or more and 71 mg / m ² or less is particularly preferable.
The content (residual concentration) of the propylene glycol in the recording layer ^{is preferably 20 mg / m 2} or more and 80 mg / m ² or less, more preferably 30 mg / m ² or more and 60 mg / m ² or less, based on the total amount of the recording layer. , 40 mg / m ² or more and 50 mg / m ² or less is particularly preferable.
The content (residual concentration) of the hexanediol in the recording layer is preferably 1 mg / m ² or more and 40 mg / m ² or less, more preferably 3 mg / m ² or more and 30 mg / m ² or less, based on the total amount of the recording layer. 5, 5 mg / m ² or more and 21 mg / m ² or less is particularly preferable.

The organic solvent in the recording layer can be quantified by a gas chromatography method by extracting a recording layer having a certain area into a high boiling point solvent.

The content of the organic solvent is preferably 10% by mass or more and 60% by mass or less, more preferably 20% by mass or more and 40% by mass or less, based on the total amount of the ink.

<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, black pigment, yellow pigment, magenta pigment, cyan pigment, white pigment, green pigment, orange pigment, glossy color pigment such as gold or silver, metallic pigment and 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 Carmine 6B), 60: 1, 63: 1, 63: 2, 64: 1, 81, 83, 88, 101 (Bengara), 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. Food Black 1, 2, C.I. I. Direct Yellow 1,12,24,33,50,55,58,86,132,142,144,173, C.I. I. Direct Red 1,4,9,80,81,225,227, C.I. I. Direct Blue 1,2,15,71,86,87,98,165,199,202, C.I. I. 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 the 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 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.

The color material in the recording layer is not particularly limited and can be appropriately selected depending on the intended purpose, and can be measured by using, for example, the MALDI method.

[Mass ratio (resin / coloring material)]
The mass ratio (resin / coloring material) of the resin content (mass%) to the coloring material content (mass%) is 0.50 or more and 3.5 or less from the viewpoint of scratch resistance. It is preferable, 0.50 or more and 3.0 or less is more preferable, and 0.6 or more and 3.0 or less is particularly preferable.

[Area ratio (B / A)]
When the recording layer of the recorded material of the present invention is measured by Fourier transform infrared absorption spectroscopy (hereinafter, also referred to as “FTIR”), the spectrum is in ^{the region from 692 cm -1} to 707 cm ^-1 , and the spectrum is 710 cm ^{−. 1} or 740 cm ^-1 or less of the minimum point and the tangent line connecting the minimum point between the spectrum 660 cm ^-1 or more 690 cm ^-1 or less, the area of the peak region surrounded by a between, and from the spectrum 1,731Cm ^-1 1, an area of up to 750 cm ^-1, the tangent connecting the minimum point between the 1,790Cm ^-1 below the minimum point and spectral 1,760Cm ^-1 or more between the spectral 1,660Cm ^-1 or more 1,690Cm ^-1 or less, The area ratio (B / A) of the area B of the peak region surrounded by is 0.3 or more and 1.0 or less, preferably 0.6 or more and 1.0 or less. When the area ratio (B / A) is 0.3 or more and 1.0 or less, both scratch resistance in a low humidity environment and a high temperature and high humidity environment are compatible, and static electricity is generated in a low humidity environment. It is also effective in preventing the occurrence of recording troubles due to suppression.

For the measurement of the recording layer by the Fourier transform infrared absorption spectrum method, the ATR (Attented Total Reflection) method of the Fourier transform infrared spectrophotometer can be used. Specifically, the surface of the recording layer of the recorded material can be determined from the spectrum measured by the ATR method using a diamond indenter using, for example, an apparatus name: Spectrum One (manufactured by PerkinElmer).

FIG. 3 is a schematic view showing a peak area A and a peak area B.
As shown in FIG. 3, the peak area A, from the spectrum 692cm ^-1 and the area up to 707cm ^-1, the minimum point and spectrum 660 cm ^-1 or more 690 cm ^-1 or less in between: spectrum 710 cm ^-1 or more 740 cm ^-1 It can be calculated from the tangent line connecting the minimum points between them and the peak area surrounded by the device name: Spectrum One (manufactured by PerkinElmer). The peak area B is ^{the minimum point between the spectrum 1,731 cm -1} to 1,750 cm ^-1 and the spectrum 1,660 cm ^-1 or more and 1,690 cm ^-1 or less, and the spectrum 1,760 cm ^-1 or more. It can be calculated in the same manner as the peak area A from the tangent line connecting the minimum points between 1,790 cm and ^{1 and the peak region surrounded by.}

<< Wax >>
Further, in the present invention, wax may be contained in the recording layer in order to further improve the scratch resistance.
The wax can reduce the coefficient of dynamic friction on the surface of the recording layer, and when combined with a urethane resin in particular, the scratch resistance of the image can be dramatically improved. This is because the urethane resin contained in order to improve the scratch resistance of the image can suppress the increase in the dynamic friction coefficient, the force received by the image is reduced, and the mechanical strength of the urethane resin is fully exhibited. Therefore, it is presumed that the scratch resistance can be dramatically improved.

As the wax, a water-dispersible wax emulsion is preferable.
Examples of the wax include polyethylene wax and paraffin wax. These may be used alone or in combination of two or more. Among these, polyethylene wax is preferable from the viewpoint of ink storage stability.

As the wax, a commercially available product can be used. As the commercially available product, for example, trade name: HYTEC E-8237 (polyethylene wax, melting point: 106 ° C., average particle size: 80 nm, manufactured by Toho Chemical Industry Co., Ltd.) , Product name: AQUACER531 (polyethylene wax, melting point: 130 ° C, manufactured by Big Chemie), Product name: AQUACER515 (polyethylene wax, melting point: 135 ° C, manufactured by Big Chemie), Product name: AQUACER537 (paraffin, melting point: 110 ° C, manufactured by Big Chemie) (Manufactured by the company) and the like. These may be used alone or in combination of two or more.

The melting point of the wax is preferably 70 ° C. or higher and 170 ° C. or lower, and more preferably 100 ° C. or higher and 140 ° C. or lower. When the melting point is 70 ° C. or higher, the images are not sticky, image transfer does not occur even if the images are overlapped, and when the melting point is 170 ° C. or lower, the images are melted by the frictional heat when the images are rubbed and slip. Since the property is obtained, the scratch resistance is good.

The volume average particle diameter of the wax is preferably 200 nm or less, more preferably 20 nm or more and 150 nm or less. When the volume average particle diameter is 200 nm or less, the ink does not get caught in the nozzle or the filter in the head, and good ejection stability can be obtained.
The volume average particle size can be measured using, for example, a particle size analyzer (Microtrack MODEL UPA9340, manufactured by Nikkiso Co., Ltd.).

The wax content is preferably 0.09% by mass or more and 0.5% by mass or less in terms of solid content with respect to the total amount of the recording layer. When the content is 0.09% by mass or more and 0.5% by mass or less, it is sufficiently effective in reducing the dynamic friction coefficient of the obtained recording layer (ink film) surface, and also the storage stability of the ink and the storage stability of the ink. It is unlikely to adversely affect the discharge stability.

<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.

The water is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include pure water such as ion-exchanged water, ultra-filtered water, reverse osmosis water and distilled water; and ultrapure water. .. These may be used alone or in combination of two or more.

<Additives>
If necessary, a surfactant, a defoaming agent, an antiseptic / antifungal agent, a rust preventive, a pH adjuster, or the like may be added to the ink.

<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, and polydimethylsiloxane is used as a modifying group. 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 side chain of dimethylsiloxane.
Examples of the fluorine-based surfactant include a perfluoroalkyl sulfonic acid compound, a perfluoroalkyl carboxylic acid compound, a perfluoroalkyl phosphate ester 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 counter ions 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). _3rd grade can be mentioned.
Examples of amphoteric surfactants include laurylaminopropionate, lauryl dimethyl betaine, stearyl dimethyl betaine, and lauryl dihydroxyethyl betaine.
Examples of the nonionic surfactant include polyoxyethylene alkyl phenyl ether, polyoxyethylene alkyl ester, polyoxyethylene alkyl amine, polyoxyethylene alkyl amide, polyoxyethylene propylene block polymer, sorbitan fatty acid ester, and polyoxyethylene sorbitan. Examples thereof include a fatty acid ester and an ethylene oxide adduct of acetylene alcohol.
Examples of the anionic surfactant include polyoxyethylene alkyl ether acetate, dodecylbenzene sulfonate, lauryl salt, salt of polyoxyethylene alkyl ether sulfate, and the like.
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 or a polyoxyethylene polyoxypropylene group as a modifying group 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−}ＣＨ_２ＣＨ（ＯＨ）ＣＨ_２−Ｏ−（ＣＨ_２ＣＨ_２Ｏ）_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ＣｎＦ_２ｎ＋１でｎは１〜６の整数、又はＣＨ_２ＣＨ（ＯＨ）ＣＨ_２−ＣｎＦ_２ｎ＋１でｎは４〜６の整数、又はＣｐＨ_２ｐ＋１でｐは１〜１９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 fluorosurfactant include a perfluoroalkyl phosphate ester compound, a perfluoroalkylethylene 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 CnF _{2n + 1} and n is an integer of 1 to 6, or CH ₂ CH (OH) CH _2- CnF _{2n + 1} and n is 4 to 6. It is an integer, or CpH _{2p + 1} and p is an integer of 1-19. 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, the Chemours FS-3100, FS-34, and FS- 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 Co., 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.

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 (RE-80L manufactured by Toki Sangyo Co., Ltd.) can be used. As the measurement conditions, it is possible to measure at 25 ° C. with a standard cone rotor (1 ° 34'× R24), a sample liquid volume of 1.2 mL, a rotation speed of 50 rpm, and 3 minutes.
The surface tension of the ink is preferably 35 mN / m or less, more preferably 32 mN / m or less at 25 ° C. from the viewpoint that the ink is preferably leveled on the recording medium and the drying time of the ink is shortened.
The pH of the ink is preferably 7 to 12, more preferably 8 to 11, from the viewpoint of preventing corrosion of the metal member in contact with the liquid.

[Manufacturing method of recording layer]
As a method for producing the recording layer, for example, an ink produced by stirring and mixing the water, the organic solvent, the resin particles, the coloring material, and if necessary, the wax and the additive is used. It can be obtained by recording. As the stirring and mixing, for example, a sand mill, a homogenizer, a ball mill, a paint shaker, an ultrasonic disperser, a stirrer using a normal stirring blade, a magnetic stirrer, a high-speed disperser and the like can be used.

<Recording medium>
The recording medium used for recording is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include plain paper, glossy paper, special paper, cloth, and general-purpose printing paper.

<Recorded material>
The ink recording material of the present invention comprises an image formed by using the ink of the present invention on a recording medium.
It can be recorded by an inkjet recording device and an inkjet recording method to obtain a recorded material.

Further, the recorded material is a recorded material having a recording medium and a recording layer containing an organic solvent and a coloring material on the recording medium, and the recording layer is subjected to a Fourier transform infrared absorption spectrum method. when measured, the tangential line connecting the region from the spectrum 692cm ^-1 to 707cm ^-1, the minimum point between 690 cm ^-1 or less the minimum point and spectrum 660 cm ^-1 or more between the spectrum 710 cm ^-1 or more 740 cm ^-1 or less Area A of the peak region surrounded by, ^{and the minimum point between the spectrum 1,731 cm -1} to 1,750 cm ^-1 and the spectrum 1,660 cm ^-1 or more and 1,690 cm ^-1 or less, and the spectrum 1, the tangent line connecting the minimum points between 760 cm ^-1 or more 1,790Cm ^-1 or less, the area ratio of the area B of the peak area enclosed (B / a) is, is 0.3 to 1.0, wherein The organic solvent comprises hexanediol and propylene glycol.

<Ink container>
The ink used to form the recording layer in the recorded material is preferably contained in an ink container.
The ink container comprises ink contained in the container and further has other members appropriately selected as needed.
The container is not particularly limited, and its shape, structure, size, material, etc. can be appropriately selected according to the purpose. For example, at least an ink bag made of an aluminum laminate film, a resin film, or the like can be selected. Those having are preferably mentioned.

(Manufacturing method of recorded materials)
The method for producing a recorded material of the present invention is a method for producing a recorded material having a recording medium and a recording layer containing an organic solvent, a coloring material, and a resin on the recording medium. The resin contains an acrylic resin and a urethane resin, and the mass ratio (urethane resin / acrylic) of the content of the urethane resin (mass%) to the content of the acrylic resin (mass%) with respect to the total amount of the recording layer. Resin) is 0.1 or more and 0.7 or less, the organic solvent contains hexanediol and propylene glycol, and the recorded material is conveyed at a relative humidity of 40% or less, which is further necessary. Other steps are included depending on the situation.
Further, the method for producing a recorded material of the present invention is a method for producing a recorded material having a recording medium and a recording layer containing an organic solvent and a coloring material on the recording medium. When the recording layer is measured by the Fourier transform infrared absorption spectrum method, the region ^{from 692 cm -1} to 707 cm ^{-1 in the spectrum, the minimum point between 710 cm -1} or more and 740 cm ^-1 or less in the spectrum, and 660 cm ^-1 or more in the spectrum. The area A of the peak region surrounded by the tangent line connecting the minimum points between 690 cm ^{-1 and below, the region from spectrum 1,731 cm -1} to 1,750 cm ^-1 , and the spectrum 1,660 cm ^-1 or more 1, 690 cm ^-1 minimum point between the following and spectral 1,760Cm ^-1 or more 1,790Cm ^-1 and tangential connecting the minimum points between the following, the area ratio of the area B of the peak area surrounded the (B / a) , 0.3 or more and 1.0 or less, the organic solvent contains hexanediol and propylene glycol, and the recorded material is transported at a relative humidity of 40% or less, further including, if necessary. Including other steps.

As the recorded matter, the same recorded matter as in the method of using the recorded matter of the present invention can be used.
The process of being conveyed is preferably carried out by the conveying means.
The transporting means is not particularly limited and may be appropriately selected depending on the intended purpose. For example, known transporting means such as a transport roller and a transport belt can 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.
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 mechanism portion 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. The main tank 410 is detachably attached to the cartridge holder 404. As a result, each ink discharge port 413 of the main tank 410 and the discharge head 434 for each color communicate with each other via the supply tube 436 for each color, and ink can be discharged from the discharge 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 device and the posttreatment device, 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, but 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 molding processing such as heat stretching or punching. For example, an automobile, an OA device, or an electric machine. -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 area ratio (B / A) of the recorded material obtained below in the recording layer and the residual concentration of the organic solvent (propylene glycol, hexanediol) in the recording layer in the recorded material were determined as follows. rice field.

(Area ratio (B / A))
The surface of the obtained image was measured in spectrum by the ATR method using a diamond indenter using a device name: Spectrum One (manufactured by PerkinElmer). Surrounded from the spectrum 692cm ^-1 and the area up to 707cm ^-1, the tangent line connecting the minimum points between 690 cm ^-1 or less the minimum point and spectrum 660 cm ^-1 or more between the spectrum 710 cm ^-1 or more 740 cm ^-1 or less, by Area A of the peak region, ^{and the minimum point between the spectrum 1,731 cm -1} to 1,750 cm ^-1 and the spectrum 1,660 cm ^-1 or more and 1,690 cm ^-1 or less, and the spectrum 1,760 cm ^-1 or more. The area B of the peak region surrounded by the tangent line connecting the minimum points between 1,790 cm and ¹ or less was calculated, and then the area ratio (B / A) was calculated.

(Residual concentration of organic solvent (propylene glycol, hexanediol) in the recording layer in the recorded material)
The organic solvent (propylene glycol, hexanediol) in the recording layer was quantified by a gas chromatography method by extracting a recording layer having a certain area into a high boiling point solvent.

(Production Example 1 of Pigment Dispersion)
<Preparation of cyan pigment dispersion>
A cyan pigment dispersion was obtained in the same manner as in the method described in − Method A− of [Pigment Surface Modification Treatment] of JP2012-207202A.
Specifically, C.I. I. Pigment Blue 15: 3 (trade name: Chromofine Blue, manufactured by Dainichiseika Kogyo Co., Ltd.), 20 mmol of the compound of the following structural formula (1), and 200 mL of ion-exchanged water in a Silverson mixer at room temperature (25 ° C). Mix at (6,000 rpm (0.6% by mass)) to obtain a slurry. If the pH of the resulting slurry is higher than 4, 20 mmol of nitric acid is added. After 30 minutes, sodium nitrite (20 mmol) dissolved in a small amount of ion-exchanged water was slowly added to the slurry. Further, the mixture was heated to 60 ° C. with stirring and reacted for 1 hour. The C.I. I. A modified pigment having the compound of the following structural formula (1) added to the surface of Pigment Blue 15: 3 was obtained. Then, the pH was adjusted to 10 with an aqueous NaOH solution to obtain a modified pigment dispersion after 30 minutes. Ultrafiltration using a dialysis membrane is performed using the modified pigment dispersion and ion-exchanged water, and further ultrasonic dispersion is performed to have a bisphosphonic acid group as a hydrophilic functional group having a pigment concentration of 15% by mass. A cyan pigment dispersion (self-dispersion type) was obtained.
Structural formula (1)

(Production Example 2 of Pigment Dispersion)
<Preparation of magenta pigment dispersion>
In Production Example 1 of the pigment dispersion, C.I. I. Pigment Blue 15: 3 20g C.I. I. Pigment Red 122 (trade name: Toner Magenta EO02, manufactured by Clariant Japan Co., Ltd.) A magenta pigment dispersion having a pigment concentration of 15% by mass was prepared in the same manner as in Production Example 1 of the pigment dispersion except that the pigment was changed to 20 g. bottom.

(Production Example 3 of Pigment Dispersion)
<Preparation of yellow pigment dispersion>
In Production Example 1 of the pigment dispersion, C.I. I. Pigment Blue 15: 3 20g C.I. I. Pigment Yellow 74 (trade name: First Yellow 531; manufactured by Dainichiseika Kogyo Co., Ltd.) A yellow pigment dispersion having a pigment concentration of 15% by mass in the same manner as in Production Example 1 of the pigment dispersion except that it was changed to 20 g. Was produced.

(Ink Preparation Example 1)
<Preparation of ink 1>
Cyan pigment dispersion 15.0% by mass, propylene glycol (1,2-propanediol, trade name: industrial propylene glycol, manufactured by ADEKA Co., Ltd.) 25.0% by mass, 1,2-hexanediol (trade name: 1) , 2-Hexanediol, manufactured by Tokyo Kasei Kogyo Co., Ltd.) 5.0% by mass, acrylic silicone resin particle liquid (solid content concentration: 30) containing acrylic silicone resin particles (trade name: Cymac US480, manufactured by Toa Synthetic Co., Ltd.) Polyurethane urethane resin particle liquid (solid content concentration: 30% by mass) containing 6.0% by mass) and polycarbonate urethane resin particles (trade name: Takelac W6110, manufactured by Mitsui Chemicals, Inc.) 4.0% by mass, poly Ether-modified siloxane copolymer (trade name: TEGO Wet270, manufactured by Tomoe Kogyo Co., Ltd.) 2.0% by mass, and the remaining amount of ion-exchanged water was added so that the total was 100% by mass. Ink 1 was obtained by filtering using a 0.8 μm membrane filter (trade name: DISMIC-25cs, manufactured by Advantech).

(Ink Preparation Examples 2 to 18)
<Preparation of inks 2 to 18>
Ink 2 to 18 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 4 below in Ink Preparation Example 1.

In Tables 1 to 4, the product names of the ingredients and the names of the manufacturers are as follows.
<Organic solvent>
Propylene glycol: ADEKA Co., Ltd., 1.2-propanediol, trade name: industrial propylene glycol, 1.2-hexanediol: Tokyo Kasei Kogyo Co., Ltd., trade name: 1.2-hexanediol, 1. 6-Hexanediol: manufactured by Ube Kosan Co., Ltd., trade name: 1.6-hexanediol, 3-ethyl-3-hydroxymethyloxetane: manufactured by Ube Kosan Co., Ltd., trade name: EHO

<Resin particles>
<< Acrylic resin particles >>
-Acrylic silicone resin particles: manufactured by Toagosei Co., Ltd., product name: Cymac US480
-Styrene acrylic resin particles: manufactured by Showa Denko KK, trade name: Polysol AP-1120
<< Urethane resin particles >>
-Polycarbonate urethane resin particles: manufactured by Mitsui Chemicals, Inc., trade name: Takelac W6110, Martens hardness: 10N / mm ²
-Polyester urethane resin particles: manufactured by Mitsui Chemicals, Inc., trade name: Takelac WS5984, Martens hardness: 1N / mm ²
-Polyether urethane resin particles: manufactured by Mitsui Chemicals, Inc., trade name: Takelac W5661 Martens hardness: 5N / mm ²
The resin particles were diluted with ion-exchanged water and added so that the solid content concentration was 30% by mass.

<Wax>
-Polyethylene wax liquid: manufactured by Big Chemie, trade name: AQUACER531, melting point 130 ° C
The wax was diluted with ion-exchanged water and added so that the solid content concentration was 30% by mass.

(Examples 1 to 12 and Comparative Examples 1 to 6)
The obtained ink was filled in an inkjet printer (device name: IPSIO GX5500, manufactured by Ricoh Corporation). Next, paper (trade name: Lumi Art Gloss 90 gsm, manufactured by Stora Enso) is set in the inkjet printer, the amount of ink adhered is 1.12 ^{mg / cm 2} (700 mg / A4), and 1,200 dpi × 1, A solid image (recording layer) was recorded at a resolution of 200 dpi, and then dried at 100 ° C. for 1 minute to obtain a recorded material.

Using the obtained recorded material, "transportability of recorded material in low humidity environment", "scratch resistance in low humidity environment", "resistance in high temperature and high humidity environment" as follows. "Blocking property" was evaluated. The results are shown in Table 5 below.

<Transportability of recorded materials in a low humidity environment>
A means for transporting the recorded material in the same environment after leaving the obtained recorded material in a low humidity environment (25 ° C., relative humidity 40% and 30%; 15 ° C., relative humidity 10%) for 24 hours. It was folded in three using a paper folding machine (device name: EPF-200, manufactured by Max Co., Ltd.). 300 sheets were continuously processed, the number of troubles in transporting recorded materials was observed, and "transportability of recorded materials in a low humidity environment" was evaluated based on the following evaluation criteria. In addition, B or more is an allowable range.
-Evaluation criteria-
A: 0 times B: 1 time or more 2 times or less C: 3 times or more

<Scratch resistance in low humidity environment>
The obtained recorded material was left to stand in a low humidity environment (25 ° C., relative humidity 40% and 30%; 15 ° C., relative humidity 10%) for 24 hours, and then cut into 1.2 cm squares in the same environment. Using the above paper (trade name: Lumi Art Gloss 90 gsm, manufactured by Stora Enso), the solid part is rubbed 20 times with a load of 400 g to remove ink adhesion stains on the paper with a reflective color spectrophotometric densitometer. Measurement was performed using (manufactured by X-Rite), the density obtained by subtracting the background color of the rubbed paper was calculated, and "scratch resistance in a low humidity environment" was evaluated based on the following evaluation criteria. In addition, B or more is an allowable range.
-Evaluation criteria-
A: Concentration is less than 0.10 B: Concentration is 0.10 or more and less than 0.20 C: Concentration is 0.20 or more

<Blocking resistance in high temperature and high humidity environment>
The obtained recorded material was left to stand in a high temperature and high humidity environment (32 ° C., relative humidity 80%) for 24 hours, and then the images were overlapped so as to be in contact with each other, and a load of ^{0.5 kg / cm 2 was applied.} It was left in the same environment for 24 hours, and then the presence or absence of transfer was confirmed. A or more is the allowable range.
-Evaluation criteria-
A: No transfer B: With transfer

Examples of aspects of the present invention are as follows.
<1> A method of using a recording material having a recording medium and a recording layer containing an organic solvent, a coloring material, and a resin on the recording medium.
The resin contains an acrylic resin and a urethane resin.
When the mass ratio (urethane resin / acrylic resin) of the urethane resin content (mass%) and the acrylic resin content (mass%) with respect to the total amount of the recording layer is 0.1 or more and 0.7 or less. can be,
The organic solvent contains hexanediol and propylene glycol.
A method of using a recorded material, wherein the recorded material is used at a relative humidity of 40% or less.
<2> The method of using the recorded material according to <1>, wherein the urethane resin is a polycarbonate urethane resin.
<3> The method of using the recorded material according to any one of <1> to <2>, wherein the acrylic resin is an acrylic silicone resin.
<4> The mass ratio (resin / coloring material) of the content (mass%) of the resin and the content (mass%) of the coloring material with respect to the total amount of the recording layer is 0.50 or more and 3.5 or less. This is the method of using the recorded material according to any one of <1> to <3>.
<5> The method of using the recorded material according to any one of <1> to <4>, wherein the recorded material is used at a relative humidity of 30% or less.
<6> The method of using the recorded material according to any one of <1> to <5>, wherein the content of the acrylic resin is 5% by mass or more and 30% by mass or less with respect to the total amount of the recording layer.
<7> The method of using the recorded material according to any one of <1> to <6>, wherein the content of the acrylic resin is 6% by mass or more and 20% by mass or less with respect to the total amount of the recording layer.
<8> The method of using the recorded material according to any one of <1> to <7>, wherein the content of the urethane resin is 1% by mass or more and 10% by mass or less with respect to the total amount of the recording layer.
<9> The method of using the recorded material according to any one of <1> to <8>, wherein the content of the urethane resin is 1% by mass or more and 4% by mass or less with respect to the total amount of the recording layer.
<10> The method of using the recorded material according to any one of <1> to <9>, wherein the content of the urethane resin is 3% by mass or more and 4% by mass or less with respect to the total amount of the recording layer.
<11> The method of using the recorded material according to any one of <1> to <10>, wherein the mass ratio (urethane resin / acrylic resin) is 0.4 or more and 0.7 or less.
<12> The method of using the recorded material according to any one of <1> to <11>, wherein the recording layer further contains wax.
<13> The method of using the recorded material according to <12>, wherein the wax is polyethylene wax.
<14> The method of using the recorded material according to any one of <1> to <13>, wherein the recorded material is further used at a temperature of 30 ° C. or higher and a relative humidity of 80% or higher.
<15> The method for using the recorded material according to any one of <1> to <14>, wherein the hexanediol is 1,2-hexanediol.
<16> A method of using a recorded material having a recording medium and a recording layer containing an organic solvent and a coloring material on the recording medium.
When the recording layer is measured by the Fourier transform infrared absorption spectroscopy,
Surrounded from the spectrum 692cm ^-1 and the area up to 707cm ^-1, the tangent line connecting the minimum points between 690 cm ^-1 or less the minimum point and spectrum 660 cm ^-1 or more between the spectrum 710 cm ^-1 or more 740 cm ^-1 or less, by Area A of the peak region, ^{and the minimum point between the spectrum 1,731 cm -1} to 1,750 cm ^-1 and the spectrum 1,660 cm ^-1 or more and 1,690 cm ^-1 or less, and the spectrum 1,760 cm ^-1 or more. The area ratio (B / A) of the area B of the peak region surrounded by the tangent line connecting the minimum points between 1,790 cm and ^{-1 is 0.3 or more and 1.0 or less.}
The organic solvent contains hexanediol and propylene glycol.
A method of using a recorded material, wherein the recorded material is used at a relative humidity of 40% or less.
<17> A recording material having a recording medium and a recording layer containing an organic solvent, a coloring material, and a resin on the recording medium.
The resin contains an acrylic resin and a urethane resin.
When the mass ratio (urethane resin / acrylic resin) of the urethane resin content (mass%) and the acrylic resin content (mass%) with respect to the total amount of the recording layer is 0.1 or more and 0.7 or less. can be,
The organic solvent is a recorded material containing hexanediol and propylene glycol.
<18> The recorded material according to <17>, wherein the urethane resin is a polycarbonate urethane resin.
<19> The recorded material according to any one of <17> to <18>, wherein the acrylic resin is an acrylic silicone resin.
<20> A recording material having a recording medium and a recording layer containing an organic solvent and a coloring material on the recording medium.
When the recording layer is measured by the Fourier transform infrared absorption spectroscopy,
Surrounded from the spectrum 692cm ^-1 and the area up to 707cm ^-1, the tangent line connecting the minimum points between 690 cm ^-1 or less the minimum point and spectrum 660 cm ^-1 or more between the spectrum 710 cm ^-1 or more 740 cm ^-1 or less, by Area A of the peak region, ^{and the minimum point between the spectrum 1,731 cm -1} to 1,750 cm ^-1 and the spectrum 1,660 cm ^-1 or more and 1,690 cm ^-1 or less, and the spectrum 1,760 cm ^-1 or more. The area ratio (B / A) of the area B of the peak region surrounded by the tangent line connecting the minimum points between 1,790 cm and ^{-1 is 0.3 or more and 1.0 or less.}
The organic solvent is a recorded material containing hexanediol and propylene glycol.
<21> A method for producing a recording material, which comprises a recording medium and a recording material containing an organic solvent, a coloring material, and a resin on the recording medium.
The resin contains an acrylic resin and a urethane resin.
When the mass ratio (urethane resin / acrylic resin) of the urethane resin content (mass%) and the acrylic resin content (mass%) with respect to the total amount of the recording layer is 0.1 or more and 0.7 or less. can be,
The organic solvent contains hexanediol and propylene glycol.
A method for producing a recorded material, which comprises a step of transporting the recorded material at a relative humidity of 40% or less.
<22> A method for producing a recording material, which comprises a recording medium and a recording material containing an organic solvent, a coloring material, and a resin on the recording medium.
The resin contains an acrylic resin and a urethane resin.
When the mass ratio (urethane resin / acrylic resin) of the urethane resin content (mass%) and the acrylic resin content (mass%) with respect to the total amount of the recording layer is 0.1 or more and 0.7 or less. can be,
The organic solvent contains hexanediol and propylene glycol.
A method for producing a recorded material, which comprises a step of transporting the recorded material at a relative humidity of 40% or less.

The method of using the recorded material according to any one of <1> to <16>, the recorded material according to any one of <17> to <20>, and any of the above <21> to <22>. According to the method for producing a recorded material described above, it is possible to solve the above-mentioned problems in the past and achieve the above-mentioned object of the present invention.

Claims (10)

A method of using a recording material having a recording medium and a recording layer containing an organic solvent, a coloring material, and a resin on the recording medium.
The resin contains an acrylic resin and a urethane resin.
The mass ratio (urethane resin / acrylic resin) of the content of the urethane resin (mass%) to the content of the acrylic resin (mass%) with respect to the total amount of the recording layer is 0. 4 or more and 0.7 or less,
The acrylic resin is an acrylic silicone resin.
The organic solvent contains hexanediol and propylene glycol.
A method of using a recorded material, wherein the recorded material is used at a relative humidity of 40% or less. The method for using a recorded material according to claim 1, wherein the urethane resin is a polycarbonate urethane resin. The method for using a recorded material according to any one of claims 1 to 2, wherein the recording layer contains a polyether-modified siloxane copolymer. A claim that the mass ratio (resin / coloring material) of the content (mass%) of the resin and the content (mass%) of the coloring material with respect to the total amount of the recording layer is 0.50 or more and 3.5 or less. The method of using the recorded material according to any one of Items 1 to 3. The method for using a recorded material according to any one of claims 1 to 4, wherein the recorded material is used at a relative humidity of 30% or less. The method for using a recorded material according to any one of claims 1 to 5, wherein the recorded material is further used at a temperature of 30 ° C. or higher and a relative humidity of 80% or higher. A recording material having a recording medium and a recording layer containing an organic solvent, a coloring material, and a resin on the recording medium.
The resin contains an acrylic resin and a urethane resin.
The mass ratio (urethane resin / acrylic resin) of the urethane resin content (mass%) to the acrylic resin content (mass%) with respect to the total amount of the recording layer is 0.4 or more and 0.7 or less. can be,
The acrylic resin is an acrylic silicone resin.
A recorded material, wherein the organic solvent contains hexanediol and propylene glycol. The recording according to claim 7, wherein the recording layer contains a polyether-modified siloxane copolymer. A method for producing a recording material, which comprises a recording medium and a recording material containing an organic solvent, a coloring material, and a resin on the recording medium.
The resin contains an acrylic resin and a urethane resin.
The mass ratio (urethane resin / acrylic resin) of the urethane resin content (mass%) to the acrylic resin content (mass%) with respect to the total amount of the recording layer is 0.4 or more and 0.7 or less. can be,
The acrylic resin is an acrylic silicone resin.
The organic solvent contains hexanediol and propylene glycol.
A method for producing a recorded material, which comprises a step of transporting the recorded material at a relative humidity of 40% or less. The method for producing a recorded material according to claim 9, wherein the recording layer contains a polyether-modified siloxane copolymer.

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