Method for manufacturing an inkjet composition and inkjet recording method

Abstract

To provide an inkjet composition which can be suitably used for manufacture of a recorded article having a recording part that is excellent in discharge stability by an inkjet method and is excellent in color development property, and an inkjet recording method which can stably discharge droplets by an inkjet method, and can be suitably used for manufacture of a recorded article having a recording part that is excellent in color development property.SOLUTION: An inkjet composition contains water, a polyester resin having a sulfo group and a coloring material, wherein the coloring material is contained in particles composed of a material containing the polyester resin, and an abundance ratio of the sulfo group of the surface of the particles is higher than that at the center of the particles.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to an inkjet composition. Manufacturing method And regarding inkjet recording methods. [Background technology]

[0002] In recent years, the applications of inkjet printing have expanded, and it is now used not only as a printing press for offices and homes, but also for commercial printing, textile printing, and more.

[0003] Furthermore, inkjet printing is increasingly being applied to various recording media in addition to paper, such as fabrics, films, and cardboard.

[0004] Furthermore, while water-based inks are preferred for ease of use and safety, it is difficult to achieve sufficiently high film strength with water-based inks. For this reason, inkjet inks containing resin materials are used, but when ordinary polyester is used, there is a problem of reduced ejection stability due to the inkjet method.

[0005] To solve these problems, inkjet inks containing polyester resins with highly hydrophilic sulfo groups have been proposed (see, for example, Patent Document 1). [Prior art documents] [Patent Documents]

[0006] [Patent Document 1] Japanese Patent Publication No. 2020-158645 [Overview of the project] [Problems that the invention aims to solve]

[0007] While using such inkjet inks can improve ejection stability by the inkjet method, it comes with the problem of reduced color development. In particular, using polyester resins with a high proportion of sulfo groups can further improve ejection stability by the inkjet method, but in this case, the color development is especially poor.

[0008] In other words, there is a challenge in achieving both ejection stability and color development with the inkjet method. [Means for solving the problem]

[0009] This invention was made to solve the above-mentioned problems and can be realized in the following application examples.

[0010] A method for producing an inkjet composition according to an application example of the present invention is a method for producing an inkjet composition comprising water, a polyester resin having a sulfo group, and a colorant, An emulsion dispersion preparation step involves mixing a first composition containing the polyester resin and an organic solvent with a second composition containing water to prepare an emulsion dispersion. An organic solvent removal step to remove at least a portion of the organic solvent from the emulsion dispersion to obtain an aqueous dispersion of the polyester resin, The process includes a colorant mixing step in which, while heating, the aqueous dispersion of the polyester resin and the colorant are mixed to incorporate the colorant into particles composed of the material containing the polyester resin, The aforementioned colorant comprises at least one selected from the group consisting of sublimation dyes, oil dyes, and disperse dyes. In the inkjet composition, the colorant is contained in the particles which are made of a material containing the polyester resin. In the inkjet composition, the proportion of sulfo groups is higher on the surface of the particles than in the center of the particles.

[0012] An example of the application of the present invention is an inkjet recording method, and the inkjet composition of the present invention. Inkjet composition manufactured using a manufacturing methodIt has a discharging step of discharging by an inkjet method.

[0013] Also, in the inkjet recording method according to another application example of the present invention, after the discharging step, it further has a heating step of heating the recording medium to which the inkjet composition adheres.

[0014] Also, in the inkjet recording method according to another application example of the present invention, the heating temperature of the recording medium in the heating step is 100°C or more and 160°C or less.

Brief Description of Drawings

[0015] [Figure 1] FIG. 1 is a schematic perspective view of a recording apparatus of a preferred embodiment.

Modes for Carrying Out the Invention

[0016] Hereinafter, preferred embodiments of the present invention will be described in detail. <1> Inkjet Composition First, the inkjet composition of the present invention will be described.

[0017] The inkjet composition of the present invention contains water, a polyester resin having a sulfo group, and a coloring material. And the coloring material is contained in particles composed of a material containing the polyester resin, and the abundance ratio of the sulfo group is higher on the surface of the particles than at the center of the particles.

[0018] By satisfying these conditions, excellent ejection stability can be achieved by the inkjet method, and the color development of the recording portion by the inkjet composition can be improved. In particular, excellent color development can be achieved for various recording media. Furthermore, the fixation and adhesion strength of the recording portion formed using the inkjet composition can be improved. In addition, the water resistance of the recording material produced using the inkjet composition can be improved. Moreover, the inkjet composition of the present invention can be applied to a method of producing recording materials that does not have a transfer process, as will be detailed later, and is preferable from the viewpoint of improving the productivity of recording materials, reducing the production cost of recording materials, and conserving resources. Furthermore, because the colorant can be developed efficiently, sufficient color density can be ensured in the produced recording material even when the colorant content in the inkjet composition is low.

[0019] The following reasons are thought to explain why such excellent results can be obtained. In other words, the uneven distribution of sulfo groups on the surface of the particles increases the hydrophilicity of the particles, improving their dispersion stability in a water-containing dispersion medium. Therefore, it is believed that the ejection stability by the inkjet method is improved. Furthermore, since colorants are generally components with high lipophilicity, or in other words, low hydrophilicity, the colorants contained in the particles tend to be unevenly distributed near the less hydrophilic center of the particles, rather than near the highly hydrophilic surface. Therefore, the colorants are effectively retained within the particles, effectively preventing leakage into water, and effectively preventing the colorants from being included in the inkjet composition in a state with low dispersion stability. Consequently, the ejection stability of the inkjet composition by the inkjet method can be maintained in a suitable state, and the target area of ​​the recording medium can be suitably colored.

[0020] Furthermore, since the colorant is applied to the recording medium in a state where it suitably colors the resin material, the fixation of the recording portion in the manufactured recording can be made excellent, the unintentional detachment of the colorant from the recording can be effectively prevented, and the colorant can be stably retained on the recording. Therefore, even when subjected to heat treatments such as washing with hot water, heat drying in a dryer, or ironing, the unintentional dispersion of the colorant to the outside of the recording can be effectively prevented, and the durability of the recording can be made particularly excellent.

[0021] Furthermore, by heating the recording medium after applying the inkjet composition, the polyester resin softens and melts, and the sulfo groups that were unevenly distributed on the surface of the particles are incorporated into the recording area, increasing the uniformity of the sulfo group ratio in the recording area. As a result, the hydrophilicity of the recording area decreases, improving its water resistance and strength. In addition, as the polyester resin softens and melts, the distribution of the colorant in the recording area becomes more uniform, further improving the color development of the recording area. Furthermore, when dyes are included as colorants, the effects described above become even more pronounced.

[0022] In this specification, the term "inkjet composition" refers to a concept that includes not only the ink itself ejected by the inkjet method, but also the stock solution used to prepare the ink. In other words, the inkjet composition of the present invention may be ejected by the inkjet method as is, or it may be ejected by the inkjet method after treatment such as dilution. Examples of inkjet methods include charge deflection, continuous, piezo, bubble jet (registered trademark) and other on-demand methods.

[0023] <1-1>Water The inkjet composition of the present invention contains water. The water primarily serves to impart fluidity to the inkjet composition and functions, for example, as a particle dispersion medium. For the water used, for example, purified water such as RO water, distilled water, or ion-exchanged water may be used.

[0024] The lower limit of the water content in the inkjet composition is not particularly limited, but is preferably 30.0% by mass, more preferably 35.0% by mass, and even more preferably 40.0% by mass. The upper limit of the water content in the inkjet composition is not particularly limited, but is preferably 90.0% by mass, more preferably 85.0% by mass, and even more preferably 80.0% by mass.

[0025] This makes it possible to more reliably adjust the viscosity of the inkjet composition to a suitable value. Furthermore, it becomes easier to adjust the distribution of sulfo groups in the particles to a more favorable state, and the effects described above are exhibited more significantly.

[0026] <1-2> Colorants The inkjet composition of the present invention contains a colorant. The colorant is a component that colors the recording medium and significantly affects the appearance of the recorded material.

[0027] Examples of colorants include various pigments such as organic pigments and inorganic pigments, and various dyes. One or more of these can be selected and used in combination.

[0028] Examples of organic pigments include azo pigments such as azo lakes, insoluble azo pigments, condensed azo pigments, and chelate azo pigments; polycyclic pigments such as phthalocyanine pigments, perylene and perylene pigments; anthraquinone pigments, quinacridone pigments, dioxandine pigments, thioindigo pigments, isoindolinone pigments, and quinophthalone pigments; dye lakes such as basic dye lakes and acid dye lakes; nitro pigments, nitroso pigments, aniline black, and daylight fluorescent pigments.

[0029] Examples of inorganic pigments include titanium dioxide, iron oxide, and carbon black. For carbon black, those produced by known methods such as the contact method, furnace method, or thermal method can be used.

[0030] Examples of dyes include sublimation dyes, oil-based dyes, disperse dyes, fluorescent dyes, reactive dyes, acid dyes, sulfur dyes, vat dyes, and cationic dyes.

[0031] In particular, the colorant preferably contains at least one selected from the group consisting of sublimation dyes, oil dyes, and disperse dyes.

[0032] This allows the colorant to be more effectively incorporated near the center of the particles, resulting in a more pronounced effect than previously described. Furthermore, it improves the color development of the recording portion formed using the inkjet composition. Additionally, the improvement in color development is more pronounced even when the heat treatment of the recording medium is performed at relatively low temperatures and for relatively short periods. Therefore, it is advantageous from the viewpoint of energy conservation and improved productivity of recorded materials.

[0033] Examples of disperse dyes and sublimation dyes include CI Disperse Yellow 1, 3, 4, 5, 7, 9, 13, 23, 24, 30, 33, 34, 42, 44, 49, 50, 51, 54, 56, 58, 60, 61, 63, 64, 66, 68, 71, 74, 76, 79, 82, 83, 85, 86, 88, 90, 91, 93, 98, 99, 100, 104, 108, 114, 116, 118, 119, 122, 124, 126, 135, 140, 141, 149, 154, 160, 162, 163, 164, 165, 179, 180, 182, 183, 184, 18 6, 192, 198, 199, 201, 202, 204, 210, 211, 215, 216, 218, 224, 227, 231, 232; CI Disperse Orange 1, 3, 5, 7, 11, 13, 17, 20, 21, 25, 29, 30, 31, 32, 33, 37, 38, 42, 43, 44, 45, 46, 47, 48, 49, 50, 53, 54, 55, 56, 57, 58, 59, 60, 61, 66, 71, 73, 76, 78, 80, 89, 90, 91, 93, 96, 97, 119, 127, 130, 139, 142; CI Disperse Red 1, 4, 5, 7, 11, 12, 13, 15, 17, 27, 43, 44, 50, 52, 53, 54, 55, 56, 58, 59, 60, 65, 72, 73, 74, 75, 76, 78, 81, 82, 86, 88, 90, 91, 92, 93, 96, 103, 105, 106, 107, 108, 110, 111, 113, 117, 118, 121, 122, 126, 127, 128, 131, 132, 134, 135, 137, 143, 145, 146, 151, 152, 153, 154, 157, 159, 164, 167, 169, 177, 179, 181, 183, 184, 185, 188, 189, 190, 191, 192, 200, 201, 202, 203, 205, 206, 207, 210, 221, 224, 225, 227, 229, 239, 240, 257, 258, 277, 278, 279, 281, 288, 298, 302, 303, 310, 311, 312, 320, 324, 328, 364; CI Disperse Violet 1, 4, 8, 23, 26, 27, 28, 31, 33, 35, 36, 38, 40, 43, 46, 48, 50, 51, 52, 56, 57, 59, 61, 63, 69, 77; CIDisperse Green 9; CI Disperse Brown 1, 2, 4, 9, 13, 19; CI Disperse Blue 3, 7, 9, 14, 16, 19, 20, 24, 26, 27, 35, 43, 44, 54, 55, 56, 58, 60, 62, 64, 71, 72, 73, 75, 79, 81, 82, 83, 87, 91, 92, 93, 94, 95, 96, 102, 106, 108, 112, 113, 115, 118, 120, 122, 125, 128, 130, 139, 141, 142, 143, Examples include 146, 148, 149, 153, 154, 158, 165, 167, 171, 173, 174, 176, 181, 183, 185, 186, 187, 189, 197, 198, 200, 201, 205, 207, 211, 214, 224, 225, 257, 259, 267, 268, 270, 284, 285, 287, 288, 291, 293, 295, 297, 301, 315, 330, 333, 359, 360; and CI Disperse Black 1, 3, 10, 24.

[0034] Examples of oil-based dyes include CI Solvent Black 3, 7, 27, 29, 34; CI Solvent Yellow 14, 16, 19, 29, 56, 82; CI Solvent Red 1, 3, 8, 18, 24, 27, 43, 51, 72, 73, 132, 218; CI Solvent Violet 3; CI Solvent Blue 2, 5, 11, 70; CI Solvent Green 3, 7; and CI Solvent Orange 2.

[0035] Examples of fluorescent dyes include CI Disperse Red 364, CI Disperse Red 362, CI Batt Red 41, CI Disperse Yellow 232, CI Disperse Yellow 184, CI Disperse Yellow 82, and CI Disperse Yellow 43.

[0036] Examples of reactive dyes include CI Reactive Yellow 2, 3, 18, 81, 84, 85, 95, 99, 102 (yellow dyes), CI Reactive Orange 5, 9, 12, 13, 35, 45, 99 (orange dyes), CI Reactive Brown 2, 8, 9, 17, 33 (brown dyes), and CI Reactive Red 1, 3, 4, 13, 15, 24, 29, 31, 33, 120, 125, 151, 206, 218, 226. Examples include red dyes such as 245, violet dyes such as CI Reactive Violet 24, blue dyes such as CI Reactive Blue 2, 5, 10, 13, 14, 15, 15:1, 21, 49, 63, 71, 72, 75, 162, 176, CI Reactive Blue 4, 19, 198, green dyes such as CI Reactive Green 5, 8, 19, and black dyes such as CI Reactive Black 1, 8, 23, 39.

[0037] The lower limit of the colorant content in the inkjet composition is preferably 0.1% by mass, more preferably 0.2% by mass, and even more preferably 0.3% by mass. The upper limit of the colorant content in the inkjet composition is preferably 10.0% by mass, more preferably 7.0% by mass, and even more preferably 5.0% by mass.

[0038] This makes it possible to improve the color development and optical density of the recording area of ​​recording materials manufactured using inkjet compositions, and to more effectively prevent the occurrence of undesirable color unevenness in the recording material.

[0039] The colorants constituting the inkjet composition may be present in the particles in any part thereof, and may also include colorants that are not present in the particles.

[0040] However, the proportion of colorants not contained in the particles to the total colorants contained in the inkjet composition is preferably 10% by mass or less, more preferably 5% by mass or less, and even more preferably 1% by mass or less.

[0041] <1-3>Polyester resin having a sulfo group The inkjet composition of the present invention contains a polyester resin having a sulfo group in its molecule. Hereinafter, such a polyester resin having a sulfo group in its molecule will also be referred to as a "sulfo group-containing polyester resin." The sulfo group-containing polyester resin has the function of improving the fixability and durability of the recording area in recordings produced using the inkjet composition, as well as the function of improving the texture and feel. It also has the function of enhancing the color development of colorants.

[0042] Polyester is a general term for polymer materials having ester bonds in their main chain, but generally it includes a chemical structure formed by the dehydration condensation of a polyol component having multiple hydroxyl groups in the molecule and a polycarboxylic acid component having multiple carboxyl groups in the molecule.

[0043] A sulfo-group-containing polyester resin preferably has a sulfo group and contains a diol component and a dicarboxylic acid component. In addition to the diol component and the dicarboxylic acid component, the sulfo-group-containing polyester resin may also contain a trivalent or higher polyhydric alcohol component and a trivalent or higher polyhydric carboxylic acid component.

[0044] The sulfo group may be contained in any part of the sulfo group-containing polyester resin, for example, in the diol component, in the dicarboxylic acid component, or in any other part, but it is preferable that it be contained in the dicarboxylic acid component. In other words, it is preferable that the sulfo group-containing polyester resin contains a dicarboxylic acid component with a sulfonated chemical structure.

[0045] <1-3-1> Diol component Examples of diol components constituting the sulfo group-containing polyester resin include aliphatic diols such as 1,3-propanediol, methylpropanediol, neopentyl glycol, methylethylpropanediol, diethylpropanediol, butylethylpropanediol, ethylene glycol, 1,2-propanediol, 2,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, diethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, and cyclohexanedimethanol, as well as compounds in which sulfo groups have been introduced. One or more of these can be selected and used in combination.

[0046] <1-3-2> Dicarboxylic acid components The dicarboxylic acid component constituting the sulfo group-containing polyester resin only needs to have two or more carboxyl groups in its molecule.

[0047] The sulfo group-containing polyester resin may contain only one component as the dicarboxylic acid component, but it is preferable that it contains multiple components.

[0048] This increases the amorphous nature of the sulfo group-containing polyester resin, effectively preventing crystallization in the inkjet composition and in the recording section formed using the inkjet composition, thereby improving the storage stability of the inkjet composition and the reliability of the recorded material. In particular, when the dicarboxylic acid component includes aromatic dicarboxylic acids as described later, crystallization as described above is generally more likely to occur. However, by including multiple types of dicarboxylic acid components in the sulfo group-containing polyester resin, it is possible to effectively prevent crystallization while enjoying the benefits of using aromatic dicarboxylic acids as described later.

[0049] The dicarboxylic acid component constituting the sulfo group-containing polyester resin may be an aliphatic dicarboxylic acid, but it is preferable that it contains at least an aromatic dicarboxylic acid.

[0050] This allows for increased resin strength. Furthermore, for example, the hydrophobicity of the sulfo-group-containing polyester resin can be more effectively enhanced, and even when the inkjet composition is stored in a high-temperature environment, the sulfo-group-containing polyester resin can be more effectively prevented from unintentionally dissolving in a water-based dispersion medium. In addition, the water resistance of records produced using the inkjet composition can be improved. Moreover, when the inkjet composition contains a dye as a colorant, the affinity between the sulfo-group-containing polyester resin and the colorant can be increased, resulting in particularly excellent color development. Furthermore, the colorant can be suitably incorporated into the particles, and the effects described above are exhibited more significantly.

[0051] Examples of aromatic dicarboxylic acids include terephthalic acid, isophthalic acid, orthophthalic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, diphenic acid, and other aromatic dicarboxylic acids, as well as compounds to which a sulfo group has been introduced. Among these, terephthalic acid, isophthalic acid, and compounds to which a sulfo group has been introduced are preferred.

[0052] The lower limit of the proportion of aromatic dicarboxylic acid in the total dicarboxylic acid components constituting the sulfo group-containing polyester resin is preferably 0.4 mol%, more preferably 1.0 mol%, and even more preferably 1.4 mol%. The upper limit of the proportion of aromatic dicarboxylic acid in the total dicarboxylic acid components constituting the sulfo group-containing polyester resin is preferably 20.0 mol%, more preferably 15.0 mol%, and even more preferably 10.0 mol%.

[0053] This allows for a more favorable balance of sulfo group ratios on the surface and in the center of the particles, resulting in improved dispersion stability of the particles in the inkjet composition, storage stability of the inkjet composition, and color development in the recording area of ​​recordings produced using the inkjet composition. Furthermore, it allows for improved water resistance, oil resistance, and other properties of recordings produced using the inkjet composition.

[0054] Examples of aliphatic dicarboxylic acids include succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, fumaric acid, maleic acid, itaconic acid, hexahydrophthalic acid, tetrahydrophthalic acid, cyclohexanedicarboxylic acid, and compounds to which a sulfo group has been introduced.

[0055] When a sulfo-containing polyester resin contains multiple components as dicarboxylic acids, it is preferable that the dicarboxylic acids include terephthalic acid, isophthalic acid, and compounds in which a sulfo group has been introduced into terephthalic acid and / or isophthalic acid.

[0056] This results in the effect of increased compatibility and amorphousness due to the similar structure despite being different types of materials.

[0057] A sulfo-group-containing polyester resin in which the distribution of sulfo groups within the molecule is non-uniform can be suitably used. This allows for a suitable distribution of sulfo groups in the particles.

[0058] Furthermore, the inkjet composition may contain multiple types of sulfonated polyester resins with different degrees of sulfonation. Even with such a configuration, a suitable distribution of sulfonated groups in the particles can be achieved.

[0059] Polyester resins can be suitably synthesized by heating a mixture containing, for example, an ester compound of a diol component and a dicarboxylic acid component, and further containing components such as a catalyst as needed. Suitable ester compounds of the dicarboxylic acid component include, for example, methyl esters and ethyl esters. In such a method for producing polyester resins, a sulfo group-containing polyester resin can be produced by using a component containing a sulfo group as part of the monomer component.

[0060] A sulfo-containing polyester resin, in which the distribution of sulfo groups within the molecule is heterogeneous, can be suitably synthesized by a method comprising a first reaction step of heating a mixture containing an ester compound of a diol component and a dicarboxylic acid component, and optionally a catalyst, followed by a second reaction step of adding a monomer component containing sulfo groups to the reaction system and heating it. Here, by using a dicarboxylic acid component instead of an ester compound as the monomer component containing sulfo groups, the distribution of sulfo groups within the molecule can be made more favorable.

[0061] <1-3-3>Other ingredients The sulfo group-containing polyester resin may have components other than the diol and dicarboxylic acid components mentioned above. Examples of such components include trivalent or higher polyhydric alcohol components, trivalent or higher polyhydric carboxylic acid components, monovalent carboxylic acid components in which some of the hydroxyl groups of the diol component are esterified, and monovalent alcohol components in which some of the carboxyl groups of the dicarboxylic acid component are esterified.

[0062] However, the content of components other than the diol component and dicarboxylic acid component in the sulfo group-containing polyester resin is preferably 20.0% by mass or less, more preferably 10.0% by mass or less, and even more preferably 5.0% by mass or less.

[0063] <1-3-4> Other conditions The sulfo group-containing polyester resin preferably satisfies the following conditions.

[0064] The lower limit of the degree of sulfonation of the sulfo group-containing polyester resin is preferably 0.2 mol%, more preferably 0.5 mol%, and even more preferably 0.7 mol%. The upper limit of the degree of sulfonation of the sulfo group-containing polyester resin is preferably 10.0 mol%, more preferably 7.5 mol%, and even more preferably 5.0 mol%.

[0065] This allows for a more favorable balance of sulfo group ratios on the surface and in the center of the particles, resulting in improved dispersion stability of the particles in the inkjet composition, storage stability of the inkjet composition, and color development in the recording area of ​​recordings produced using the inkjet composition. Furthermore, it allows for improved water resistance, oil resistance, and other properties of recordings produced using the inkjet composition.

[0066] In this specification, the degree of sulfonation of a sulfo group-containing polyester resin refers to the proportion of monomers containing sulfo groups among all monomers constituting the sulfo group-containing polyester resin.

[0067] The lower limit of the acid value of the sulfo group-containing polyester resin is preferably 1.0 KOH mg / g, more preferably 1.5 KOH mg / g, and even more preferably 2.0 KOH mg / g. The upper limit of the acid value of the sulfo group-containing polyester resin is preferably 15 KOH mg / g, more preferably 10 KOH mg / g, and even more preferably 5.0 KOH mg / g.

[0068] The lower limit of the number-average molecular weight of the sulfo-containing polyester resin is preferably 1500, more preferably 3000, and even more preferably 10000. The upper limit of the number-average molecular weight of the sulfo-containing polyester resin is preferably 25000, more preferably 20000, and even more preferably 18000.

[0069] This makes it possible to achieve a higher level of balance between the fixation properties of sulfo-group-containing polyester resins to recording media and the durability of records produced using inkjet compositions. Furthermore, it is possible to improve the color development of colorants on various recording media.

[0070] The lower limit of the glass transition temperature of the sulfo group-containing polyester resin is preferably 0°C, more preferably 25°C, and even more preferably 40°C. The upper limit of the glass transition temperature of the sulfo group-containing polyester resin is preferably 90°C, more preferably 75°C, and even more preferably 70°C.

[0071] This makes it possible to achieve a higher level of both ease of fixing sulfo group-containing polyester resin to recording media and durability of recorded materials produced using inkjet compositions.

[0072] The lower limit of the sulfo group-containing polyester resin content in the inkjet composition is preferably 3.0% by mass, more preferably 4.0% by mass, and even more preferably 4.5% by mass. The upper limit of the sulfo group-containing polyester resin content in the inkjet composition is preferably 35.0% by mass, more preferably 30.0% by mass, and even more preferably 28.0% by mass.

[0073] The colorant content in the inkjet composition is X D [Mass %], the content of sulfo group-containing polyester resin in the inkjet composition is X P When expressed as [mass %], XP / X D The lower limit of X is preferably 4, more preferably 10, and even more preferably 15. P / X D The upper limit is preferably 300, more preferably 200, and even more preferably 100.

[0074] This makes it possible to improve the color development of the recording portion formed using the inkjet composition. Furthermore, it is possible to improve the fixation of the recording portion to the recording medium, and it is possible to more effectively prevent the unintentional release of colorant to the outside of the recording when the recording material manufactured using the inkjet composition is subjected to heat treatment such as washing with hot water, heat drying in a dryer, or ironing.

[0075] The sulfogroup-containing polyester resin constituting the inkjet composition only needs to have at least a portion of it consist of particles containing a colorant, and the inkjet composition may further contain, for example, sulfogroup-containing polyester resin particles that do not contain a colorant.

[0076] However, the proportion of sulfo-group-containing polyester resin that does not constitute the aforementioned particles to the total sulfo-group-containing polyester resin contained in the inkjet composition is preferably 10% by mass or less, more preferably 5% by mass or less, and even more preferably 1% by mass or less.

[0077] <1-4>Water-soluble organic solvents The inkjet composition may contain a water-soluble organic solvent.

[0078] This allows, for example, to suitably adjust the viscosity of the inkjet composition or to enhance its moisture retention. As a result, droplet ejection by the inkjet method can be performed more stably.

[0079] Examples of water-soluble organic solvents included in the inkjet composition include glycerin, propylene glycol, 2-pyrrolidone, and 1-(2-hydroxyethyl)-2-pyrrolidone.

[0080] By including these solvents, the excellent moisture retention ability slows down the evaporation rate, enabling more stable droplet dispensing.

[0081] The lower limit of the content of water-soluble organic solvents in the inkjet composition is not particularly limited, but is preferably 0% by mass, more preferably 1.0% by mass, and even more preferably 3.0% by mass. The upper limit of the content of water-soluble organic solvents in the inkjet composition is not particularly limited, but is preferably 30.0% by mass, more preferably 25.0% by mass, and even more preferably 20.0% by mass. This allows the effects of including the aforementioned water-soluble organic solvent to be more pronounced.

[0082] <1-5> Other ingredients Inkjet compositions may contain components other than those mentioned above. Hereafter, in this section, such components will also be referred to as "other components."

[0083] Other components include, for example, resin materials other than sulfo-containing polyester resins, various surfactants, various dispersants, emulsifiers, penetrating agents such as triethylene glycol monomethyl ether, triethylene glycol monobutyl ether, diethylene glycol monomethyl ether, 1,2-hexanediol, 1,2-pentanediol, 1,2-butanediol, and 3-methyl-1,5-pentanediol, drying inhibitors such as triethanolamine, pH adjusters, chelating agents such as ethylenediaminetetraacetate, preservatives / fungal agents, and rust inhibitors. As preservatives / fungal agents, for example, compounds having an isothiazolin ring structure in the molecule can be suitably used.

[0084] Furthermore, if the inkjet composition includes a polyester resin without sulfo groups as a resin material other than the sulfo group-containing polyester resin, then, for example, even if the sulfo group-containing polyester resin uniformly contains sulfo groups within the molecule, a suitable distribution of sulfo groups in the particles can be achieved.

[0085] Furthermore, if the inkjet composition contains a surfactant, the wettability of the inkjet composition with respect to the recording medium can be made more favorable, which is advantageous in obtaining better image quality.

[0086] Various surfactants can be used as surfactants in the inkjet composition, such as anionic surfactants, cationic surfactants, and nonionic surfactants.

[0087] More specifically, examples of surfactants included in inkjet compositions include acetylene-based surfactants, silicone-based surfactants, and fluorine-based surfactants.

[0088] The content of other components in the inkjet composition is preferably 6.0% by mass or less, and more preferably 5.0% by mass or less. If the other components include multiple types of components, it is preferable that the sum of their contents satisfies the above conditions.

[0089] <1-6> Other conditions As described above, in the inkjet composition of the present invention, the ratio of sulfo groups in particles composed of a material containing a sulfo group-containing polyester resin and a colorant is sufficient if it is higher on the surface of the particles than in the center of the particles, but it is preferable that the following conditions are met. That is, when measured by energy dispersive X-ray spectroscopy (EDX) with the measured atoms being C, N, O, Na, and S, the amount of S on the surface of the particles is greater than the amount of S inside the particles, preferably 1.2 times or more than the amount of S inside the particles, and more preferably 1.5 times or more. This allows the effects of the present invention, as described above, to be exhibited more clearly.

[0090] Energy dispersive X-ray spectroscopy (EDX) may also be performed on the cross-section of a coating film formed using an inkjet composition without heating it to 30°C or higher.

[0091] The lower limit of the surface tension of the inkjet composition at 25°C is not particularly limited, but is preferably 20 mN / m, more preferably 21 mN / m, and even more preferably 23 mN / m. The upper limit of the surface tension of the inkjet composition at 25°C is not particularly limited, but is preferably 50 mN / m, more preferably 40 mN / m, and even more preferably 30 mN / m.

[0092] This makes nozzle clogging in inkjet recording devices less likely, and improves the ejection stability of inkjet compositions. Furthermore, even if nozzle clogging occurs, the ability to recover by capping the nozzle, i.e., capping, can be improved.

[0093] Furthermore, the surface tension can be measured using the Wilhelmy method. For measuring surface tension, a surface tension meter such as the CBVP-7 manufactured by Kyowa Interface Science Co., Ltd. can be used.

[0094] The lower limit of the viscosity of the inkjet composition at 25°C is not particularly limited, but is preferably 2 mPa·s, more preferably 3 mPa·s, and even more preferably 4 mPa·s. The upper limit of the viscosity of the inkjet composition at 25°C is not particularly limited, but is preferably 30 mPa·s, more preferably 20 mPa·s, and even more preferably 10 mPa·s. This further improves the ejection stability of the inkjet composition.

[0095] The viscosity was measured at 25°C using a viscoelasticity tester such as the MCR-300 manufactured by Pysica, with a shear rate of 10 [s]. -1 ] to 1000[s -1 The viscosity can be measured by increasing the setting and reading the viscosity when the Shear Rate is 200.

[0096] When the inkjet composition of the present invention is an ink, the ink is typically applied to an inkjet recording device while stored in a container such as a cartridge, bag, or tank. In other words, the recording device according to the present invention is equipped with a container such as an ink cartridge that stores the ink as the inkjet composition of the present invention.

[0097] As described above, the inkjet composition of the present invention contains particles made of a material comprising a sulfo group-containing polyester resin and a colorant.

[0098] The lower limit of the average particle size is not particularly limited, but is preferably 20 nm, more preferably 50 nm, and even more preferably 80 nm. The upper limit of the average particle size is not particularly limited, but is preferably 300 nm, more preferably 200 nm, and even more preferably 150 nm.

[0099] This makes it easier to prepare inkjet compositions, and improves the dispersion stability of the particles in the inkjet composition, the storage stability of the inkjet composition, and the ejection stability of the inkjet composition by the inkjet method. It also improves the color development of the colorants.

[0100] In this specification, unless otherwise specified, the average particle size refers to the average particle size based on volume. The average particle size can be determined, for example, by measurement using Microtrac UPA (manufactured by Nikkiso Co., Ltd.).

[0101] <2> Method for manufacturing inkjet compositions Next, a method for producing the inkjet composition of the present invention will be described.

[0102] <2-1> Method 1 The inkjet composition of the present invention can be manufactured, for example, by the first method described below.

[0103] In other words, the first method comprises an emulsion suspension preparation step of mixing a first composition containing a sulfo group-containing polyester resin, a colorant, and an organic solvent with a second composition containing water to prepare an emulsion suspension, and an organic solvent removal step of removing at least a portion of the organic solvent from the emulsion suspension.

[0104] This makes it possible to suitably form particles composed of the aforementioned sulfo-group-containing polyester resin and colorant, in which the sulfo groups are distributed in a suitable state, and to efficiently manufacture an inkjet composition having the aforementioned excellent properties.

[0105] In the first method, a first composition containing a sulfo group-containing polyester resin, a colorant, and an organic solvent is prepared.

[0106] The first composition may be prepared by mixing each component simultaneously, or by mixing each component in two or more stages. However, it is preferable to use a mixture of two or more sulfo-group-containing polyester resins, either including the aforementioned heterogeneous polyester resin or having different sulfo-group content. This makes it easier for the polyester resin with a relatively high sulfo-group content to move to the outside of the polyester resin particles during the emulsification suspension preparation step described later, thus making it possible to obtain an inkjet composition containing polyester resin particles in which the sulfo-group ratio is higher on the surface of the particles than in the center of the particles.

[0107] For example, a mixture of a sulfo-containing polyester resin and a colorant may be prepared, and then the mixture may be mixed with an organic solvent to dissolve or disperse the sulfo-containing polyester resin and the colorant.

[0108] As an organic solvent, for example, one that has a solubility in water at 25°C of 0.1 g / 100 g H2O or more and 30 g / 100 g H2O or less can be preferably used.

[0109] Examples of such organic solvents include ethers such as tetrahydrofuran; ketones such as methyl ethyl ketone and methyl isopropyl ketone; and esters such as ethyl acetate and isopropyl acetate. One or more of these can be selected and used in combination.

[0110] Furthermore, the organic solvent is preferably one that dissolves or disperses the sulfo group-containing polyester resin and is easily removed in subsequent steps. Therefore, an organic solvent with a relatively low boiling point is preferred.

[0111] From this viewpoint, tetrahydrofuran, methyl ethyl ketone, and ethyl acetate are preferred as organic solvents, with tetrahydrofuran and methyl ethyl ketone being more preferred.

[0112] Furthermore, components other than sulfogroup-containing polyester resin, colorants, and organic solvents may be used in the preparation of the first composition. Examples of such components include basic compounds and emulsifiers.

[0113] <2-1-1> Emulsified suspension preparation process In the emulsion suspension preparation step, the first composition and the second composition containing water are mixed to prepare the emulsion suspension.

[0114] The emulsion suspension obtained in this manner is a dispersed state in which a sulfo-group-containing polyester resin, a colorant, and an organic solvent are dispersed in an aqueous dispersion medium.

[0115] The second composition may contain at least water, and may, for example, pure water or a liquid containing components other than water. Examples of such components include basic components.

[0116] The basic component may be mixed with the first composition prior to mixing the first composition with the second composition.

[0117] Examples of basic compounds include inorganic bases such as sodium hydroxide, potassium hydroxide, and ammonia, and organic bases such as diethylamine, triethylamine, and isopropylamine. One or more of these can be selected and used in combination.

[0118] The mixing of the first composition and the second composition may be carried out, for example, by supplying the second composition to the first composition, or by supplying the first composition to the second composition, but it is preferable to carry out the mixing by dropping the second composition onto the first composition. This allows for more favorable phase-inversion emulsification of the first composition.

[0119] Furthermore, it is preferable to mix the first composition and the second composition by supplying the second composition to the first composition while stirring the first composition. This allows for more favorable phase-inversion emulsification of the first composition.

[0120] The lower limit of the ratio of organic solvent to the total amount of organic solvent and water in the emulsion suspension at the end of the emulsion suspension preparation step is preferably 10% by mass, and more preferably 20%. The upper limit of the ratio of organic solvent to the total amount of organic solvent and water in the mixture at the end of the emulsion suspension preparation step is preferably 70% by mass, and more preferably 50%.

[0121] <2-1-2> Organic solvent removal process In the organic solvent removal step, at least a portion of the organic solvent is removed from the emulsified suspension.

[0122] This results in the formation of solid particles containing a colorant and a sulfo group-containing polyester resin corresponding to the particles constituting the inkjet composition of the present invention.

[0123] The organic solvent removal process can be carried out, for example, by heating the emulsion suspension or by placing the emulsion suspension under reduced pressure.

[0124] The dispersion obtained in the organic solvent removal step, in which solid particles containing a colorant and a sulfo-group-containing polyester resin are dispersed in an aqueous dispersion medium, may be used as is as the inkjet composition of the present invention, or the dispersion may be mixed with other components to form the inkjet composition of the present invention.

[0125] Furthermore, post-treatment steps such as washing and drying may be performed after the organic solvent removal step. This allows for the removal of unwanted components, making it possible to obtain an inkjet composition with a more reliably adjusted composition.

[0126] The particles contained in the dispersion obtained in the organic solvent removal process can be washed by, for example, using separation means such as a centrifuge, filter press, or belt filter to separate them from the dispersion to obtain a microparticle cake, then stirring and dispersing the microparticle cake in water, and finally dewatering it.

[0127] After dehydration, drying may be performed as needed. For the drying process, for example, mixed vacuum dryers such as ribocone dryers (manufactured by Okawara Seisakusho Co., Ltd.) and Nauter mixers (manufactured by Hosokawa Micron Corporation), and fluidized bed dryers such as fluidized bed dryers (manufactured by Okawara Seisakusho Co., Ltd.) and vibrating fluidized bed dryers (manufactured by Chuo Kako Kikai Co., Ltd.) can be used.

[0128] When dehydrating and drying the particles, the inkjet composition of the present invention described above can be obtained by mixing the washed particles with other components, including at least water.

[0129] In the organic solvent removal step, it is sufficient to remove at least a portion of the organic solvent contained in the emulsion suspension, particularly the organic solvent contained in the dispersed phase of the emulsion suspension; complete removal is not necessary. Even in such cases, the remaining organic solvent can usually be sufficiently removed by post-processing steps such as washing and drying. Furthermore, a small amount of organic solvent may remain in the final inkjet composition.

[0130] <2-2> Second method The inkjet composition of the present invention can be manufactured, for example, by the second method described below.

[0131] In other words, the second method comprises an emulsion dispersion preparation step of mixing a first composition containing a sulfo-group-containing polyester resin and an organic solvent with a second composition containing water to prepare an emulsion dispersion; an organic solvent removal step of removing at least a portion of the organic solvent from the emulsion dispersion to obtain an aqueous dispersion of the sulfo-group-containing polyester resin; and a colorant mixing step of mixing the aqueous dispersion of the sulfo-group-containing polyester resin with a colorant while heating to incorporate the colorant into particles composed of a material containing the sulfo-group-containing polyester resin.

[0132] This makes it possible to suitably form particles composed of the aforementioned sulfo-group-containing polyester resin and colorant, in which the sulfo groups are distributed in a suitable state, and to efficiently manufacture an inkjet composition having the aforementioned excellent properties.

[0133] In the second method, first, a first composition containing a sulfo group-containing polyester resin and an organic solvent is prepared.

[0134] The organic solvent is preferably one whose boiling point at 1 atmosphere is 90°C or lower, and more preferably one whose boiling point is 80°C or lower.

[0135] This allows for the effective removal of organic solvents in subsequent organic solvent removal steps, effectively preventing excess organic solvents from remaining in the final inkjet composition.

[0136] Examples of organic solvents include ethers such as tetrahydrofuran; ketones such as methyl ethyl ketone and methyl isopropyl ketone; and esters such as ethyl acetate and isopropyl acetate. One or more of these can be selected and used in combination.

[0137] Furthermore, components other than sulfogroup-containing polyester resin and organic solvents may be used in the preparation of the first composition. Examples of such components include basic compounds and emulsifiers.

[0138] <2-2-1> Emulsified Dispersion Preparation Process In the emulsion dispersion preparation step, the first composition and the second composition containing water are mixed to prepare the emulsion dispersion.

[0139] The emulsion dispersion obtained in this manner is in which a dispersed phase containing a sulfo-group-containing polyester resin and an organic solvent is dispersed in an aqueous dispersion medium.

[0140] The second composition may contain at least water, and may, for example, pure water or a liquid containing components other than water. Examples of such components include basic components.

[0141] The basic component may be mixed with the first composition prior to mixing the first composition with the second composition.

[0142] Examples of basic compounds include inorganic bases such as sodium hydroxide, potassium hydroxide, and ammonia, and organic bases such as diethylamine, triethylamine, isopropylamine, triethanolamine, and tripropanolamine. One or more of these can be selected and used in combination.

[0143] The mixing of the first composition and the second composition may be carried out, for example, by supplying the second composition to the first composition, or by supplying the first composition to the second composition, but it is preferable to carry out the mixing by dropping the second composition onto the first composition. This allows for more favorable phase-inversion emulsification of the first composition.

[0144] Furthermore, it is preferable to mix the first composition and the second composition by supplying the second composition to the first composition while stirring the first composition. This allows for more favorable phase-inversion emulsification of the first composition.

[0145] This process may be carried out, for example, while heating to a temperature below the boiling point of the organic solvent. This makes it possible to, for example, create a state in which sulfo groups are preferably concentrated near the surface of a dispersed phase containing a sulfo group-containing polyester resin and an organic solvent, and in a later step, particles with sulfo groups preferably concentrated near the surface can be preferably formed.

[0146] The lower limit of the ratio of organic solvent to the total amount of organic solvent and water in the emulsion dispersion at the end of the emulsion dispersion preparation step is preferably 10% by mass, and more preferably 20%. The upper limit of the ratio of organic solvent to the total amount of organic solvent and water in the emulsion dispersion at the end of the emulsion dispersion preparation step is preferably 70% by mass, and more preferably 50%.

[0147] <2-2-2> Organic Solvent Removal Process In the organic solvent removal step, at least a portion of the organic solvent is removed from the emulsion dispersion. This results in the formation of solid particles containing sulfo-group-containing polyester resin, and an aqueous dispersion of sulfo-group-containing polyester resin is obtained.

[0148] The organic solvent removal process can be carried out, for example, by heating the emulsion dispersion or by placing the emulsion dispersion under reduced pressure, but it is preferable to carry it out by heating the emulsion dispersion.

[0149] This makes it possible to create a state in which sulfo groups are preferably unevenly distributed near the surface of solid particles containing sulfo group-containing polyester resin, and to more preferably form particles with unevenly distributed sulfo groups near the surface that are contained in the final inkjet composition.

[0150] When heating the emulsion dispersion in this process, it is preferable to heat it at a temperature higher than the boiling point of the organic solvent and lower than the boiling point of water.

[0151] In the organic solvent removal step, it is sufficient to remove at least a portion of the organic solvent contained in the emulsion dispersion, particularly the organic solvent contained in the dispersed phase of the emulsion dispersion; complete removal is not necessary. Even in such cases, the remaining organic solvent can be sufficiently removed in subsequent steps. Furthermore, a small amount of organic solvent may remain in the final inkjet composition.

[0152] <2-2-3> Color material mixing process In the colorant mixing process, an aqueous dispersion of sulfo-group-containing polyester resin is mixed with the colorant to incorporate the colorant into particles composed of a material containing sulfo-group-containing polyester resin.

[0153] In order to efficiently incorporate the colorant into particles made of a material containing a sulfo group-containing polyester resin, this process is carried out while heating.

[0154] The lower limit of the heating temperature in this process is preferably 40°C, more preferably 45°C, and even more preferably 50°C. The upper limit of the heating temperature in this process is preferably 100°C, more preferably 98°C, and even more preferably 95°C. When heating in a heating container, the upper limit of the heating temperature in this process is preferably 200°C, more preferably 160°C, and even more preferably 130°C.

[0155] The lower limit of the heating time in this process is preferably 5 minutes, more preferably 10 minutes, and even more preferably 20 minutes. The upper limit of the heating time in this process is preferably 300 minutes, more preferably 240 minutes, and even more preferably 180 minutes.

[0156] In this process, heating is preferably carried out while stirring the mixture of the aqueous dispersion of sulfo group-containing polyester resin and the colorant.

[0157] In addition, in this process, components other than the colorant may be mixed with the aqueous dispersion of sulfo group-containing polyester resin along with the colorant.

[0158] The mixing with the aqueous dispersion of sulfo group-containing polyester resin may be carried out in two or more stages.

[0159] Furthermore, post-treatment steps such as washing and drying may be performed after the colorant mixing process. This allows for the removal of unwanted components, making it possible to obtain an inkjet composition with a more reliably adjusted composition.

[0160] The particles contained in the dispersion obtained in the colorant mixing process can be washed by, for example, using separation means such as a centrifuge, filter press, or belt filter to separate them from the dispersion to obtain a microparticle cake, then stirring and dispersing the microparticle cake in water, and finally dewatering it.

[0161] After dehydration, drying may be performed as needed. For the drying process, for example, mixed vacuum dryers such as ribocone dryers (manufactured by Okawara Seisakusho Co., Ltd.) and Nauter mixers (manufactured by Hosokawa Micron Corporation), and fluidized bed dryers such as fluidized bed dryers (manufactured by Okawara Seisakusho Co., Ltd.) and vibrating fluidized bed dryers (manufactured by Chuo Kako Kikai Co., Ltd.) can be used.

[0162] When dehydrating and drying the particles, the inkjet composition of the present invention described above can be obtained by mixing the washed particles with other components, including at least water.

[0163] <3> Inkjet recording method Next, the inkjet recording method of the present invention will be described.

[0164] The inkjet recording method of the present invention comprises an ejection step of ejecting the inkjet composition according to the present invention described above by an inkjet method.

[0165] This enables stable droplet ejection by the inkjet method and provides an inkjet recording method that can be suitably applied to the manufacture of recording materials having a recording area with excellent color development. In particular, it can exhibit excellent color development on various recording media. Furthermore, it can improve the fixation and adhesion strength of the recording area formed using the inkjet composition. In addition, it can improve the water resistance of recording materials manufactured using the inkjet composition.

[0166] In the inkjet recording method of the present invention, it is preferable to further include a heating step after the ejection step in which the recording medium to which the inkjet composition is attached is heated.

[0167] As a result, the sulfo-group-containing polyester resin softens and melts, and the sulfo-groups that were unevenly distributed on the surface of the particles constituting the inkjet composition are incorporated into the recording area, increasing the uniformity of the sulfo-group ratio within the recording area. Consequently, the hydrophilicity of the recording area decreases, improving its water resistance and strength. Furthermore, as the sulfo-group-containing polyester resin softens and melts, the distribution of the colorant within the recording area becomes more uniform, further improving the color development of the recording area.

[0168] <3-1>Discharge process In the ejection process, the inkjet composition is ejected by the inkjet method and applied to the recording medium. The ejection of the inkjet composition by the inkjet method can be performed using a known inkjet recording device. As for the ejection method, the piezo method or a method that ejects ink by generating bubbles by heating the ink can be used. Among these, the piezo method is preferred from the viewpoint of preventing deterioration of the inkjet composition.

[0169] In the ejection process, multiple inkjet compositions according to the present invention may be used in combination. More specifically, for example, multiple inkjet compositions with different colorant compositions and concentrations may be used in combination.

[0170] Furthermore, in the ejection process, inks other than the inkjet composition according to the present invention may be used in combination.

[0171] <3-2> Recording media The constituent materials of the recording medium are not particularly limited, but examples include resin materials such as polyurethane, polyethylene, polypropylene, polyester, polyamide, polyimide, and acrylic resin, as well as resin films, corrugated cardboard, plain paper, inkjet paper, glass, metal, ceramics, leather, wood, pottery, concrete, and fibers composed of at least one of these, as well as various natural fibers such as silk, wool, cotton, hemp, polyester, polyamide (nylon), acrylic, polyurethane, cellulose, linter, rayon, cupro, and acetate, synthetic fibers, and semi-synthetic fibers. One or more selected from these can be used in combination. Furthermore, the recording medium may have a three-dimensional shape such as a sheet, sphere, or rectangular prism.

[0172] If the recording medium is made of a material containing polyester, the adhesion between the recording medium and the recording section made of the inkjet composition of the present invention can be improved.

[0173] In particular, the recording medium is preferably made of cloth. While there is a great demand for dyeing woven fabrics, such as for printed T-shirts, and printing by ironing is widespread, recording materials with recording units on such woven fabrics require a certain texture, particularly smoothness, suppleness, and softness, as well as durability of the recording unit. The present invention can meet these requirements. Therefore, the effects of the present invention are more pronounced when the recording medium is woven fabric.

[0174] As for the fabric, various types of weaves can be used, such as plain weave, twill weave, satin weave, modified plain weave, modified twill weave, modified satin weave, variegated weave, patterned weave, single-layer weave, double weave, multi-layer weave, warp pile weave, weft pile weave, and leno weave.

[0175] Furthermore, the thickness of the fibers that make up the fabric can be, for example, between 10d and 100d.

[0176] Examples of fibers that make up the fabric include polyester fibers, nylon fibers, triacetate fibers, diacetate fibers, polyamide fibers, cellulose fibers, and blends using two or more of these fibers. Alternatively, blends of these fibers with regenerated fibers such as rayon or natural fibers such as cotton, silk, or wool may also be used.

[0177] Furthermore, this method can be suitably applied to various types of paper, including plain paper and inkjet-specific paper, as recording media. This makes it possible to obtain recording materials with excellent texture without the need for drying processes such as heating.

[0178] Furthermore, films that can be bent and stretched can also be suitably applied as recording media. This allows for the formation of a recording area that has low tackiness, excellent texture, and superior elasticity and adhesion to the recording media, among other effects of the present invention, to be exhibited more significantly.

[0179] <3-3>Heating process In this embodiment, after the ejection process described above, the recording medium to which the inkjet composition has been applied is heated.

[0180] As a result, the sulfo-group-containing polyester resin softens and melts, and the sulfo-groups that were unevenly distributed on the surface of the particles constituting the inkjet composition are incorporated into the recording area, increasing the uniformity of the sulfo-group ratio within the recording area. Consequently, the hydrophilicity of the recording area decreases, improving its water resistance and strength. Furthermore, as the sulfo-group-containing polyester resin softens and melts, the distribution of the colorant within the recording area becomes more uniform, further improving the color development of the recording area.

[0181] The lower limit of the heating temperature of the recording medium in this process is not particularly limited, but is preferably 70°C, more preferably 100°C, and even more preferably 110°C. The upper limit of the heating temperature of the recording medium in this process is not particularly limited, but is preferably 200°C, more preferably 170°C, and even more preferably 150°C.

[0182] This allows the effects of the aforementioned heating process to be more pronounced. Furthermore, the energy required for manufacturing the recording material can be reduced, thereby improving the productivity of the recording material. In addition, recording media with relatively low heat resistance can be suitably applied, further expanding the range of recording media options. Moreover, unintended discoloration, changes in optical density, etc., caused by heating after the manufacturing of the recording material, such as washing with hot water, heat drying in a dryer, or ironing, can be effectively prevented. Furthermore, if the heating temperature in this process is within the aforementioned range, deterioration of the texture of the recording area can be more effectively prevented.

[0183] Depending on the heating temperature of the recording medium in this process, the lower limit of the heating time for the recording medium in this process is preferably 0.1 seconds, more preferably 1 second, and even more preferably 5 seconds. The upper limit of the heating time for the recording medium in this process is preferably 300 seconds, more preferably 60 seconds, and even more preferably 30 seconds.

[0184] This allows the effects of the aforementioned heating process to be more pronounced. Furthermore, the energy required for manufacturing the recording material can be reduced, thereby improving the productivity of the recording material. In addition, recording media with relatively low heat resistance can be suitably applied, further expanding the range of recording media options. Moreover, unintended discoloration, changes in optical density, etc., caused by heating after the manufacturing of the recording material, such as washing with hot water, heat drying in a dryer, or ironing, can be effectively prevented. Furthermore, if the heating temperature in this process is within the aforementioned range, deterioration of the texture of the recording area can be more effectively prevented.

[0185] Furthermore, this process may be carried out by heating the surface of the recording medium to which the inkjet composition is attached while it is separated from the heating element, or by heating while the recording medium to which the inkjet composition is attached and the heating element are in close contact.

[0186] The heating process may be carried out simultaneously with the ejection process. More specifically, for example, the recording medium to which the inkjet composition will be applied may be preheated, and the heating process may be carried out again after the inkjet composition has come into contact with the recording medium. In this case, for example, heating may be carried out continuously before and after the application of the inkjet composition to the recording medium, or heating may be interrupted and then resumed.

[0187] Furthermore, the heating method in the heating process is not particularly limited; it may be carried out using contact methods such as rollers or presses, or non-contact methods such as furnaces, hot air, infrared radiation, microwaves, or lasers.

[0188] <4> Recording device Next, I will explain the recording device. Figure 1 is a schematic perspective view of a recording device according to a preferred embodiment.

[0189] In the following description, an on-carriage type printer, in which the ink cartridge is mounted on the carriage, will be used as an example of a recording device. In this embodiment, the recording device is not limited to an on-carriage type printer; for example, an off-carriage type printer, in which the ink cartridge is fixed externally, may also be used.

[0190] The recording device described below is a serial printer in which an inkjet head for recording is mounted on a carriage that moves in a predetermined direction, and droplets are ejected onto a recording medium by the movement of the inkjet head as the carriage moves. In the present invention, the recording device is not limited to a serial printer, and may be a line printer, for example. A line printer is a type of printer in which the inkjet head is formed to be wider than the width of the recording medium, and droplets are ejected onto the recording medium without the inkjet head moving.

[0191] In the drawings used in the following explanation, the scale of each component has been appropriately adjusted to ensure that each component is recognizable.

[0192] The recording device 1 is equipped with an inkjet head 2 that ejects the inkjet composition of the present invention described above towards the recording medium M by an inkjet method, and performs the inkjet recording method of the present invention described above.

[0193] This makes it possible to provide a recording device that has a recording section with excellent texture and can suitably produce recordings with excellent durability.

[0194] In particular, the recording device 1 shown in Figure 1 comprises an inkjet head 2, an ink cartridge 3, a carriage 4, a platen 5, a heating mechanism 6, a carriage movement mechanism 7, a media feeding mechanism 8, a guide rod 9, a linear encoder 10, and a control unit CONT.

[0195] The control unit CONT controls the operation of the entire recording device 1. The carriage 4 is equipped with an inkjet head 2 (described later) and has a removable ink cartridge 3 that supplies the inkjet composition to the inkjet head 2.

[0196] The platen 5 is located below the inkjet head 2, and the recording medium M is transported through it.

[0197] The heating mechanism 6 heats the recording medium M. By having a heating mechanism 6 that heats the recording medium M, the recording portion made of the inkjet composition can be suitably fixed to the recording medium M. In particular, the recording portion can be suitably fixed without using a separate device from the recording device 1.

[0198] The carriage movement mechanism 7 moves the carriage 4 in the media width direction of the recording medium M. The media feeding mechanism 8 transports the recording medium M in the media feeding direction. Here, the media width direction is the main scanning direction, which is the scanning direction of the inkjet head 2. The media feeding direction is the direction perpendicular to the main scanning direction and is the sub-scanning direction in which the recording medium M moves.

[0199] The inkjet head 2 is a means for depositing an inkjet composition onto a recording medium M, and has a plurality of nozzles (not shown) for ejecting the inkjet composition on the surface facing the recording medium M to which the ink is deposited. These plurality of nozzles are arranged in a row, thereby forming a nozzle surface on the nozzle plate surface.

[0200] One method for ejecting an inkjet composition from a nozzle is the piezo method, which simultaneously applies pressure and a recording information signal to the inkjet composition using a piezoelectric element, thereby ejecting and recording droplets of the inkjet composition.

[0201] In Figure 1, the ink cartridge 3 that supplies the inkjet composition to the inkjet head 2 consists of four independent cartridges. Each of the four cartridges is filled with, for example, a different type of inkjet composition. The ink cartridge 3 is detachably mounted to the inkjet head 2. In the example in Figure 1, there are four cartridges, but the number is not limited to this, and any desired number of cartridges can be installed.

[0202] The carriage 4 is mounted on a guide rod 9, which is a support member installed in the main scanning direction, and moves along the guide rod 9 in the main scanning direction by the carriage movement mechanism 7. In the example in Figure 1, the carriage 4 moves in the main scanning direction, but it is not limited to this, and may also move in the sub-scanning direction in addition to the main scanning direction.

[0203] The heating mechanism 6 is not particularly limited in its installation position, as long as it is provided in a position where it can heat the recording medium M. In the example shown in Figure 1, the heating mechanism 6 is installed on the platen 5, facing the inkjet head 2. When the heating mechanism 6 is installed facing the inkjet head 2, the adhesion site of the inkjet composition on the recording medium M can be reliably heated, and the inkjet composition adhering to the recording medium M can be efficiently dried.

[0204] Examples of heating mechanisms 6 include a printed heater mechanism that heats the recording medium M by bringing it into contact with a heat source, a mechanism that irradiates infrared rays or microwaves, which are electromagnetic waves with a maximum wavelength of approximately 2,450 MHz, and a dryer mechanism that blows hot air.

[0205] The control unit CONT controls various conditions for heating the recording medium M by the heating mechanism 6, such as the timing of heating, heating temperature, and heating time.

[0206] The recording device 1 may have a second heating mechanism (not shown) in addition to the heating mechanism 6. In that case, the second heating mechanism is installed downstream of the heating mechanism 6 in the transport direction of the recording medium M. This improves the drying of the inkjet composition adhering to the recording medium M. Any of the mechanisms described for the heating mechanism 6 can be used for the second heating mechanism.

[0207] The linear encoder 10 detects the position of the carriage 4 in the main scanning direction using a signal. The signal detected by the linear encoder 10 is transmitted to the control unit CONT as position information. Based on the position information from the linear encoder 10, the control unit CONT recognizes the scanning position of the inkjet head 2 and controls the recording operation, i.e., the ejection operation, etc., of the inkjet head 2. The control unit CONT is configured to variably control the movement speed of the carriage 4.

[0208] <4> Records Next, the recording device according to the present invention will be described.

[0209] The recording material according to the present invention has a recording section formed using the inkjet composition according to the present invention described above.

[0210] This makes it possible to provide a recording material having a recording area with excellent color development. Furthermore, it is possible to improve the fixation and adhesion strength of the recording area to the recording medium. Additionally, it is possible to improve the water resistance of the recording material. The aforementioned recording media can be suitably used.

[0211] Although preferred embodiments of the present invention have been described above, the present invention is not limited thereto.

[0212] For example, the inkjet composition of the present invention may be used for ejection in an inkjet method, and may not be applied to the method described above.

[0213] Furthermore, this method may also be applied to methods that have additional steps in addition to the steps described above.

[0214] In this case, pre-processing steps include, for example, a step of applying a coating layer to the recording medium.

[0215] Intermediate processing steps include, for example, a step of preheating the recording medium. Post-processing steps include, for example, cleaning the recording medium.

[0216] Furthermore, the inkjet composition of the present invention may be manufactured by any method and is not limited to the method described above. For example, the inkjet composition of the present invention may include particles formed by emulsion polymerization as particles containing a colorant and a sulfo group-containing polyester resin. [Examples]

[0217] Next, specific embodiments of the present invention will be described. <5> Polyester resin synthesis (Synthesis Example A1) Dimethyl terephthalate, dimethyl isophthalate, dimethyl 5-sodium sulfisoisophthalate, ethylene glycol, neopentyl glycol, and tetrabutoxytitanate were charged in predetermined proportions into an autoclave equipped with a thermometer and stirrer, and the transesterification reaction was carried out by heating at 180-230°C for 120 minutes. Then, the reaction system was heated to 250°C, and the system pressure was maintained at 1-10 mmHg, and the reaction was continued for 60 minutes to obtain a sulfo-containing polyester resin.

[0218] NMR analysis revealed that the obtained sulfo-containing polyester resin contained ethylene glycol (55 mol%) and neopentyl glycol (45 mol%) as diol components, and terephthalic acid (50 mol%), isophthalic acid (47 mol%), and 5-sodium sulfisoisophthalic acid (3 mol%) as dicarboxylic acid components. The number-average molecular weight of the sulfo-containing polyester resin was 3500, and its glass transition temperature was 58°C. Furthermore, the sulfo-containing polyester resin obtained in this synthesis example had a uniform distribution of sulfo groups within the molecule. In addition, the sulfur content (S) of the sulfo-containing polyester resin obtained in this synthesis example was 0.2 at% as determined by energy-dispersive X-ray analysis.

[0219] (Synthesis example A2) A sulfo-containing polyester resin was synthesized in the same manner as in Synthesis Example A1, except that the amount of each raw material used was changed. The sulfo-containing polyester resin obtained in this synthesis example had a uniform distribution of sulfo groups within the molecule. Furthermore, the sulfur element (S) content of the sulfo-containing polyester resin obtained in this synthesis example was 0.7 at% as determined by energy-dispersive X-ray analysis.

[0220] (Synthesis example A3) A polyester resin was synthesized in the same manner as in Synthesis Example A1, except that dimethyl 5-sodium sulfisophthalate was not used and the amounts of each other raw material were changed. The polyester resin obtained in this synthesis example did not have a sulfo group in its molecule and did not contain sulfur elements.

[0221] (Synthesis example A4) Dimethyl terephthalate, dimethyl isophthalate, ethylene glycol, neopentyl glycol, and tetrabutoxytitanate were charged in predetermined proportions into an autoclave equipped with a thermometer and stirrer, and the transesterification reaction was carried out by heating at 180-230°C for 120 minutes. Next, 5-sodium sulfisoisophthalic acid was added to the reaction system in predetermined proportions, and then the temperature was raised to 250°C, and the reaction was continued for 60 minutes at a system pressure of 1-10 mmHg to obtain a sulfo group-containing polyester resin.

[0222] NMR analysis revealed that the obtained sulfo-containing polyester resin contained ethylene glycol (55 mol%) and neopentyl glycol (45 mol%) as diol components, and terephthalic acid (50 mol%), isophthalic acid (47 mol%), and 5-sodium sulfisoisophthalic acid (3 mol%) as dicarboxylic acid components. The number-average molecular weight of the sulfo-containing polyester resin was 3500, and its glass transition temperature was 58°C. Furthermore, the sulfo-containing polyester resin obtained in this synthesis example had a heterogeneous distribution of sulfo groups within the molecule. In addition, the sulfur (S) content of the sulfo-containing polyester resin obtained in this synthesis example was 0.2 at% as determined by energy-dispersive X-ray analysis.

[0223] <6> Preparation of inkjet compositions (Example 1) The sulfo group-containing polyester resin synthesized in the above synthesis example A4 was dissolved in tetrahydrofuran at 60°C, and then three times the amount of water as tetrahydrofuran was added and stirred to obtain an emulsion dispersion.

[0224] Next, the emulsion dispersion was heated and stirred to 100°C to evaporate the tetrahydrofuran and obtain an aqueous dispersion of 30% by mass of a sulfo group-containing polyester resin.

[0225] Next, to 100.0 parts by mass of the aqueous dispersion of sulfo-containing polyester resin obtained as described above, 2.0 parts by mass of the sublimation dye CI Disperse Red 60, 6.0 parts by mass of propylene glycol, 1.0 part by mass of Silface SAG503A manufactured by Nisshin Chemical Co., Ltd., and 0.2 parts by mass of triethanolamine were added, and the mixture was stirred at 90°C for 2 hours to obtain an inkjet composition. The resulting mixture produced a vivid color, confirming that the polyester resin particles were dyed with the sublimation dye.

[0226] (Example 2) An inkjet composition was prepared in the same manner as in Example 1, except that instead of 100 parts by mass of the sulfo group-containing polyester resin synthesized in Synthesis Example A4, 50 parts by mass of the sulfo group-containing polyester resin synthesized in Synthesis Example A1 and 50 parts by mass of the sulfo group-containing polyester resin synthesized in Synthesis Example A2 were used, and instead of the sublimation dye CI Disperse Red 60 as a colorant, the oil-based dye CI Solvent Blue 5 was used.

[0227] (Example 3) An inkjet composition was prepared in the same manner as in Example 1, except that 50 parts by mass of the sulfo group-containing polyester resin synthesized in Synthesis Example A2 and 50 parts by mass of the sulfo group-containing polyester resin synthesized in Synthesis Example A3 were used instead of 100 parts by mass of the sulfo group-containing polyester resin synthesized in Synthesis Example A4.

[0228] (Example 4) An inkjet composition was prepared in the same manner as in Example 1, except that instead of 100 parts by mass of the sulfo group-containing polyester resin synthesized in Synthesis Example A4, 50 parts by mass of the sulfo group-containing polyester resin synthesized in Synthesis Example A1 and 50 parts by mass of the sulfo group-containing polyester resin synthesized in Synthesis Example A3 were used, and instead of the sublimation dye CI Disperse Red 60 as a colorant, the oil-based dye CI Solvent Blue 5 was used.

[0229] (Example 5) An inkjet composition was prepared in the same manner as in Example 1, except that 50 parts by mass of the sulfo-containing polyester resin synthesized in Synthesis Example A1 and 50 parts by mass of the sulfo-containing polyester resin synthesized in Synthesis Example A2 were used instead of 100 parts by mass of the sulfo-containing polyester resin synthesized in Synthesis Example A4.

[0230] (Comparative Example 1) An inkjet composition was prepared in the same manner as in Example 1, except that the sulfo-containing polyester resin synthesized in Synthesis Example A1 was used instead of the sulfo-containing polyester resin synthesized in Synthesis Example A4, and the oil-based dye CI Solvent Blue 5 was used as the colorant instead of the sublimation dye CI Disperse Red 60.

[0231] (Comparative Example 2) An inkjet composition was prepared in the same manner as in Example 1, except that the sulfo group-containing polyester resin synthesized in Synthesis Example A2 was used instead of the sulfo group-containing polyester resin synthesized in Synthesis Example A4.

[0232] (Comparative Example 3) An inkjet composition was prepared in the same manner as in Example 1, except that the polyester resin synthesized in Synthesis Example A3 was used instead of the sulfo group-containing polyester resin synthesized in Synthesis Example A4, and the oil-based dye CI Solvent Blue 5 was used as the colorant instead of the sublimation dye CI Disperse Red 60.

[0233] <7> evaluation <7-1>Discharge stability The inkjet compositions of the respective examples and comparative examples were each placed in a cartridge of a recording apparatus PX-M860F (manufactured by Seiko Epson Corporation), set in the recording apparatus, printed on 10 sheets of A4 plain paper with full coverage, and then printed on another 10 sheets of A4 plain paper with full coverage 30 minutes later. Immediately thereafter, a nozzle clogging pattern standard for the printer driver was printed, the number of clogged nozzles at this time was counted, and evaluation was performed according to the following criteria. It can be said that the fewer the number of clogged nozzles, the better the ejection stability.

[0234] A: The number of clogged nozzles is 0. B: The number of clogged nozzles is 1 or more and 9 or less. C: The number of clogged nozzles is 10 or more and 35 or less. D: The number of clogged nozzles is 36 or more.

[0235] <7-2>Color development property Regarding the inkjet compositions of the respective examples and comparative examples, each was ejected in a predetermined pattern toward a cotton fabric as a recording medium using a recording apparatus PX-M860F (manufactured by Seiko Epson Corporation).

[0236] Thereafter, an iron as a heating member was brought into contact with the side of the recording medium on which the inkjet composition was applied, and heat treatment at 150 °C for 5 seconds was performed to obtain a recorded matter.

[0237] [[ID=2X]] Also, using the standard ink of the recording apparatus PX-M860F (manufactured by Seiko Epson Corporation), printing was performed on plain paper (P paper manufactured by Fuji Xerox Co., Ltd.) in the same pattern as described above.

[0238] Regarding the recording portions formed using the inkjet compositions of the respective examples and comparative examples and the recording portions formed using the standard ink of the recording apparatus PX-M860F (manufactured by Seiko Epson Corporation), chromaticity (L * a * b *The saturation was measured and evaluated according to the following criteria. Higher saturation indicates superior color reproduction. For Examples 1, 3, 5 and Comparative Example 2, the recording area was compared with that formed using the standard magenta ink of the PX-M860F (manufactured by Seiko Epson Corporation). For Examples 2, 4 and Comparative Examples 1 and 3, the recording area was compared with that formed using the standard cyan ink of the PX-M860F (manufactured by Seiko Epson Corporation).

[0239] A: The color saturation is equivalent to or better than that of a recording area formed using standard ink. D: The color saturation is lower compared to the recording area formed using standard ink.

[0240] <7-3> Fixation The recordings according to each of the above examples and comparative examples, manufactured using cotton fabric as the recording medium as described in <7-2> above, were washed with laundry detergent (Lion Corporation, Top Clear Liquid) in a household washing machine (Toshiba Lifestyle Corporation, drum-type washer-dryer TW-Z9500L) in standard mode at 40°C using hot water. The rate of decrease in the OD value of the dyed area before and after washing was determined and evaluated according to the following criteria. A lower rate of decrease in the OD value indicates better fixation of the recording area to the recording medium by the inkjet composition. A level of B or higher was considered good.

[0241] A: The rate of decrease in OD value is less than 3%. B: The rate of decrease in OD value is 3% or more but less than 20%. The decrease in C:OD value is between 20% and 50%. D: The decrease in OD value is 50% or more.

[0242] Table 1 summarizes the composition of the inkjet compositions for each of the above examples and comparative examples, as well as the evaluation results described above. In the table, the sulfo-containing polyester resin synthesized in Synthesis Example A1 is denoted as "A1", the sulfo-containing polyester resin synthesized in Synthesis Example A2 as "A2", the polyester resin synthesized in Synthesis Example A3 as "A3", the sulfo-containing polyester resin synthesized in Synthesis Example A4 as "A4", CI Disperse Red 60 as "DR60", CI Solvent Blue 5 as "SB5", propylene glycol as "PG", Silface SAG503A manufactured by Nisshin Chemical Co., Ltd. as "SAG503A", and triethanolamine as "TEA". Furthermore, the inkjet compositions for each of the above examples all had a viscosity of 4 mPa·s or more and 10 mPa·s or less. The viscosity was measured using a viscoelasticity tester MCR-300 (manufactured by Pysica) at 25°C with a shear rate of 10 mPa·s. -1 ] to 1000[s -1 The viscosity was measured by increasing the viscosity and reading the viscosity at a Shear Rate of 200. In addition, the surface tension of the inkjet compositions in each of the above examples was within the range of 23 mN / m to 30 mN / m. The surface tension was measured using a surface tensile meter (CBVP-7, manufactured by Kyowa Interface Science Co., Ltd.) at 25°C by the Wilhelmy method. In addition, the average particle size of the pigment and sulfo-group-containing polyester resin particles in the inkjet compositions in each of the above examples was within the range of 100 nm to 300 nm. In addition, the sulfo-group-containing polyester resin contained in the inkjet compositions in each of the above examples had an acid value within the range of 1.0 KOH mg / g to 15 KOH mg / g, a number-average molecular weight within the range of 3000 to 20000, and a glass transition temperature within the range of 40°C to 80°C.

[0243] Furthermore, a 2 μm thick coating film formed at 25°C using the inkjet compositions of each of the above examples and comparative examples was cut with a cutter, and the cross-section was observed at 100,000x magnification using a scanning electron microscope (Hitachi Regulus 8220 ultra-high resolution field emission scanning electron microscope). In addition, sulfo-containing polyester resin particles with a diameter of approximately 20 nm to 400 nm were identified by line analysis of sulfur element S using energy-dispersive X-ray analysis, and the relative amount of S atoms on the surface and near the center was compared. The results obtained according to the following criteria are shown in the "Distribution of Sulfo Groups" column.

[0244] A: Surface S content > 1.5 × Internal S content B: Surface S content > 1.2 × Internal S content C: Surface S content > 1.0 × Internal S content D: Surface S amount ≤ 1.0 × Internal S amount

[0245] [Table 1]

[0246] As is clear from Table 1, the present invention yielded excellent results. In contrast, the comparative examples did not yield satisfactory results.

[0247] Furthermore, when the recording material was manufactured in the same manner as described above, except that paper made of cellulose fibers was used as the recording medium, the same results as described above were obtained. In addition, when the recording material was manufactured in the same manner as described above, except that the heating temperature in the heating process was changed within the range of 100°C to 160°C and the heating time was changed within the range of 0.2 seconds to 300 seconds, the same results as described above were obtained. [Explanation of symbols]

[0248] 1...Recording device, 2...Inkjet head, 3...Ink cartridge, 4...Carriage, 5...Platen, 6...Heating mechanism, 7...Carriage movement mechanism, 8...Media feeding mechanism, 9...Guide rod, 10...Linear encoder, M...Recording medium, CONT...Control unit

Claims

1. A method for producing an inkjet composition comprising water, a polyester resin having a sulfo group, and a colorant, An emulsion dispersion preparation step involves mixing a first composition containing the polyester resin and an organic solvent with a second composition containing water to prepare an emulsion dispersion. An organic solvent removal step to remove at least a portion of the organic solvent from the emulsion dispersion to obtain an aqueous dispersion of the polyester resin, The process includes a colorant mixing step in which, while heating, the aqueous dispersion of the polyester resin and the colorant are mixed to incorporate the colorant into particles composed of the material containing the polyester resin, The aforementioned colorant includes at least one selected from the group consisting of sublimation dyes, oil dyes, and disperse dyes. In the inkjet composition, the colorant is contained in the particles which are made of a material containing the polyester resin. A method for producing an inkjet composition, wherein the proportion of sulfo groups in the inkjet composition is higher on the surface of the particles than in the center of the particles.

2. An inkjet recording method comprising a dispensing step of dispensing the inkjet composition manufactured using the method described in claim 1 by an inkjet method.

3. The inkjet recording method according to claim 2, further comprising a heating step of heating a recording medium to which the inkjet composition is attached after the ejection step.

4. The inkjet recording method according to claim 3, wherein the heating temperature of the recording medium in the heating step is 70°C or more and 200°C or less.

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