Contact member, drying apparatus, printing apparatus, and printing method

Abstract

To provide a contact member which prevents a component derived from a liquid composition, from being transferred from a contacted member to a contact member, even in a case where the contact member and the contacted member are used for a long period of time in a manner of being in contact with each other.SOLUTION: A contact member is configured to contact a contacted member to which a liquid composition is applied, the contact member including a surface layer (A) configured to contact the contacted member, where the surface layer (A) includes a support layer including alumite sulfate, the surface layer (A) has a root mean square height Sq of 1.0 μm or more, and the surface layer (A) has an orthogonal line roughness ratio of 0.7 or more.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a contact member, a drying apparatus, a printing apparatus, and a printing method. [Background technology]

[0002] Printing devices such as inkjet printers are equipped with transport members for transporting recording media such as continuous sheets and cut sheets. These transport members guide the recording media to means for applying a liquid composition such as ink, and means for heating and drying the applied liquid composition.

[0003] In recent years, with the aim of providing a highly productive water-repellent substrate that maintains superhydrophobicity, a water-repellent substrate has been proposed that comprises an aluminum substrate, an anodized layer provided on the surface of the aluminum substrate, and a water-repellent film provided on the surface of the anodized layer, wherein the anodized layer has a base layer integrated with the aluminum substrate and an uneven structure consisting of numerous pin-shaped protrusions arranged in parallel on the surface of the base layer (see, for example, Patent Document 1).

[0004] Furthermore, with the aim of resolving the problem of cracking, preventing the occurrence of image defects, and providing an image forming apparatus equipped with a heating roll that can be used for a long period of time, a fixing device for an image forming apparatus has been proposed that uses a heating roll with an anodized coating having micropores to fix an unfixed toner image on a recording medium (see, for example, Patent Document 2). [Overview of the project] [Problems that the invention aims to solve]

[0005] The present invention aims to provide a contact member that suppresses the transfer of components derived from a liquid composition from the contacted member to the contact member, even when used for a long period of time in a manner in which the contact member and the contacted member are in contact. [Means for solving the problem]

[0006] The present invention relates to a contact member that contacts a contacted member to which a liquid composition is applied. The contact member has a surface layer (A) that contacts the contacted member, and the surface layer (A) has a support layer containing sulfuric acid anodizing film. The root mean square height Sq in the surface layer (A) is 1.0 μm or more, and the orthogonal line roughness ratio in the surface layer (A) is 0.7 or more.

Effect of the Invention

[0007] According to the present invention, even when used for a long period of time in a manner in which the contact member and the contacted member are in contact, a contact member that suppresses the transfer of components derived from the liquid composition from the contacted member to the contact member can be provided.

Brief Description of the Drawings

[0008] [Figure 1] FIG. 1 is a schematic diagram showing an example of a printing apparatus using continuous paper. [Figure 2] FIG. 2 is a schematic diagram showing that the contacted member is in contact with the contact member. [Figure 3] FIG. 3 is an image showing the height in the surface layer (A) of Example 1. [Figure 4] FIG. 4 is an image showing the height in the surface layer (A) of Comparative Example 2. [Figure 5] FIG. 5 is an image showing the height profile in the cross section of the surface layer (A) of Example 1. [Figure 6] FIG. 6 is an image showing the height profile in the cross section of the surface layer (A) of Comparative Example 1. [Figure 7] FIG. 7 is an image showing the shape of the transfer portion when the contact member of Example 1 is used. [Figure 8] FIG. 8 is an image showing the shape of the transfer portion when the contact member of Comparative Example 1 is used.

Modes for Carrying Out the Invention

[0009] In a conventional transport member used in an image forming apparatus or the like, those that directly contact the area where the liquid composition is applied may sometimes cause problems with the transfer of the liquid composition onto the transport member. It is known that such transfer of the liquid composition onto the transport member becomes prominent when an ink with a slow drying rate, such as an aqueous ink or an ink containing a low-volatility solvent as a main component, is used as the liquid composition.

[0010] Also, in the prior art Patent Documents 1 and 2, when the contact member that contacts the contacted member where the liquid composition is applied is used for a long period in a manner where the contact member and the contacted member are in contact, there is a problem that components derived from the liquid composition are transferred from the contacted member to the contact member.

[0011] As a result of intensive studies, the inventors of the present invention have found that by providing a contact member that contacts the liquid composition with a surface layer (A) having a support layer containing sulfuric acid anodizing and adjusting the root mean square height Sq and the cross-line roughness ratio in the surface layer (A), it is possible to suppress the transfer of components derived from the liquid composition from the contacted member to the contact member.

[0012] Therefore, in the present invention, there is provided a contact member that contacts a contacted member to which a liquid composition is applied, the contact member having a surface layer (A) that contacts the contacted member, the surface layer (A) having a support layer containing sulfuric acid anodizing, the root mean square height Sq in the surface layer (A) being 1.0 μm or more, and the cross-line roughness ratio in the surface layer (A) being 0.7 or more, whereby even when used for a long period in a manner where the contact member and the contacted member are in contact, it is possible to obtain a contact member that suppresses the transfer of components derived from the liquid composition from the contacted member to the contact member.

[0013] Hereinafter, the present invention will be described.

[0014] (Contact member) The contact member of the present invention is a contact member that comes into contact with a member to be contacted to which a liquid composition has been applied, and has a surface layer (A) that comes into contact with a non-contact member, and may optionally have a base material, heating means, other members, etc. The surface layer (A) is preferably provided on a substrate described later.

[0015] The contact member may be a member that transports the contacted member (hereinafter sometimes referred to as a transport member) by contacting the contacted member described later, or it may be a member that does not transport the contacted member (hereinafter sometimes referred to as a non-transport member). When the contact member is a conveying member, there are no particular restrictions on the form of the conveying member, and it can be appropriately selected according to the purpose. For example, the contact member may be in the shape of a roller, and the contact member may rotate to convey the member to be contacted. When the contact member is a non-conveying member, there are no particular restrictions on the form of the non-conveying member, and it can be appropriately selected according to the purpose. For example, the contact member may be plate-shaped and heat or pressurize the contacted member while in contact with it. Specific examples of the non-conveying member include an iron and a platen.

[0016] <Surface layer (A)> In the present invention, the surface layer (A) is a layer that comes into contact with the member to be contacted, and has a support layer containing sulfuric acid anodized aluminum, and has the characteristics of a predetermined shape surface described later. The surface layer (A) preferably has fluororesin particles attached to the support layer, which will be described later.

[0017] <<Root Mean Square Height Sq>> In this invention, the root mean square height Sq of the surface layer (A) is 1.0 μm or more. The root mean square height Sq of the surface layer (A) is preferably 1.0 μm or more and 10.0 μm or less, more preferably 1.0 μm or more and 9.0 μm or less, and even more preferably 1.0 μm or more and 8.0 μm or less. The root mean square height Sq of the surface layer (A) being 1.0 μm or more is preferable because it reduces the contact area between the surface layer (A) and the member to be contacted, thereby suppressing the transfer of components derived from the liquid composition from the member to be contacted to the contacting member. The fact that the root mean square height Sq of the surface layer (A) is 10.0 μm or less improves the thermal conductivity of the contact member to the member to be contacted, which is effective when the contact member is used as a contact member having a heating means described later. In this disclosure, "components derived from the liquid composition" may refer to the liquid composition itself as described later, or to some of the components contained in the liquid composition (for example, colorants as described later).

[0018] There are no particular restrictions on the method for measuring the root mean square height Sq of the surface layer (A), and it can be appropriately selected depending on the purpose. For example, one method is to observe the surface layer (A) with a laser microscope (LEXT OLS4000, manufactured by Olympus) at a magnification of 20x and calculate it in accordance with JIS B0601:2013.

[0019] <<Orthogonal Line Roughness Ratio>> In this invention, the orthogonal line roughness ratio of the surface layer (A) is 0.7 or higher. The fact that the orthogonal line roughness ratio of the surface layer (A) is 0.7 or higher indicates that the occurrence of linear irregularities in a certain direction caused by turning and polishing processes, etc., on the surface layer (A) is suppressed. When a contact member having linear irregularities in a certain direction on the surface layer (A) is used, the shape of the contact surface between the surface layer (A) and the contacted member becomes linear, and the contact area per location becomes larger, making it easier for components derived from the liquid composition to be transferred from the contacted member to the contact member. As a result, the transfer area on the contacted member becomes linear, increasing the visibility of that area and making it easier to recognize it as a defect in the contacted member. On the other hand, if the orthogonal line roughness ratio of the surface layer (A) is 0.7 or more, and the root mean square height Sq of the surface layer (A) is 1.0 μm or more, the shape of the contact surface between the surface layer (A) and the contacted member becomes point-like, and the contact area per point becomes small, making it difficult for components derived from the liquid composition to be transferred from the contacted member to the contacting member. Furthermore, even if transfer occurs, the transferred area on the contacted member will be point-like with an inconsistent occurrence period, reducing the visibility of the area and making it difficult to recognize it as a defect in the contacted member.

[0020] There are no particular restrictions on the method for measuring the orthogonal line roughness ratio of the surface layer (A), and a suitable method can be selected depending on the purpose. For example, the following methods can be used. First, an arbitrary point on the surface layer (A) is designated as the measurement center point, and the linear roughness of the surface layer (A) in an arbitrary direction from the measurement center point is measured using a laser microscope (LEXT OLS4000, Olympus) at a magnification of 20x and a measurement length of 260 μm. Next, the linear roughness in the measurement direction in which the linear roughness is minimized, and the linear roughness in the direction perpendicular to the measurement direction in which the linear roughness is minimized are obtained. Furthermore, new measurement center points are designated at 100 μm intervals in a certain direction from the above measurement center point, and the linear roughness in the measurement direction in which the linear roughness is minimized, and the linear roughness in the direction perpendicular to the measurement direction in which the linear roughness is minimized are obtained in the same manner as the measurements at the above measurement center points. A total of five measurements are performed at the measurement center points, and Ra(Min.), which is the average of the linear roughness in the measurement direction in which the linear roughness is minimized, and Ra(90°), which is the average of the linear roughness in the direction perpendicular to the measurement direction in which the linear roughness is minimized, are obtained. Subsequently, the orthogonal line roughness ratio is obtained by calculating the ratio of Ra(Min.) to Ra(90°) [Ra(Min.) / Ra(90°)].

[0021] The ratio of the area of ​​the surface layer (A) to the area of ​​the contacted member is preferably 10% to 90%, more preferably 10% to 80%, even more preferably 10% to 50%, and particularly preferably 10% to 40%. In this specification, "area of ​​surface layer (A)" may be referred to as "observation area," "area in contact between surface layer (A) and the member to be contacted" as "contact area," and "ratio of the area in contact between surface layer (A) and the member to be contacted to the area of ​​surface layer (A)" as "contact area ratio." A contact area ratio of 90% or less is preferable because it reduces the contact area, thereby suppressing the transfer of components derived from the liquid composition from the contacted member to the contacting member. Since the contact area ratio is 10% or more, the thermal conductivity of the contact member to the contacted member is improved, which is effective when the contact member is used as a contact member having a heating means described later.

[0022] There are no particular restrictions on the method for measuring the contact area ratio, and it can be appropriately selected depending on the purpose. For example, the following methods can be used. First, the surface layer (A) is observed at 20x magnification using a laser microscope (LEXT OLS4000, manufactured by Olympus) to obtain a height profile. Next, the contact area is obtained from the acquired height profile, which is the cross-sectional area formed when the surface layer (A) is cut from the maximum height (the outermost surface of the surface layer (A)) with a plane parallel to the surface layer (A) at a depth of 5 μm. Then, the contact area ratio is obtained by calculating the ratio of the contact area to the observed area (contact area / observed area).

[0023] In the surface layer (A) of the present invention, there are no particular limitations on the method for achieving the above-mentioned root mean square height Sq, orthogonal line roughness ratio, and contact area ratio. However, one example is a method of performing blasting or the like on the substrate as described later as a pretreatment performed before the sulfuric acid anodizing treatment described later. By forming a random uneven shape on the surface of the substrate by blasting, and then generating a support layer containing sulfuric acid anodized aluminum by sulfuric acid anodizing treatment, while further forming the uneven shape, it becomes easy to make the root mean square height Sq of the surface layer (A) 1.0 μm or more, the orthogonal line roughness ratio of the surface layer (A) 0.7 or more, and the contact area ratio 10% to 90% or less.

[0024] There are no particular restrictions on the type of blasting agent used in the aforementioned blasting process, and it can be appropriately selected according to the purpose. Examples include glass beads (soda-lime glass), alumina beads, stainless steel beads, and zirconia beads. Among these, glass beads and alumina beads are preferred from the viewpoint of hardness. There are no particular restrictions on the shape of the blasting agent, and it can be appropriately selected according to the purpose. For example, blasting agents having shapes such as spheres, polygons, or cylinders can be suitably used. There are no particular restrictions on the particle size of the blasting agent, and it can be appropriately selected according to the purpose. For example, a central particle size of 50 μm or more and 1000 μm or less is preferred. There are no particular restrictions on the grit size of the blasting agent, and it can be set appropriately depending on the purpose. However, from the viewpoint of suppressing the drying energy required to prevent the transfer of components derived from the liquid composition from one contacted member to the other contacting member, it is preferable that it be less than 100.

[0025] <<Support layer>> The support layer in the present invention contains a layer containing sulfuric acid anodized aluminum (in other words, a sulfuric acid anodized aluminum film) as a constituent material, and may contain other constituent materials as needed. Here, "containing sulfuric acid anodized aluminum" indicates the presence of materials derived from sulfuric acid anodizing treatment, and "sulfuric acid anodizing treatment" refers to the process of anodic oxidation of aluminum in an aqueous sulfuric acid solution. In other words, a layer containing materials derived from sulfuric acid anodizing treatment is a layer that contains aluminum oxide and in which sulfur components can be detected.

[0026] Here, "detection of sulfur components" means, for example, that when sulfur components are mapped onto a cross-section of the supporting layer, data indicating the presence of sulfur components is obtained. There are no particular restrictions on the method for mapping sulfur components; it can be appropriately selected depending on the purpose. For example, one method is to perform EDS elemental analysis (UltraDry, manufactured by Thermo Fisher Scientific) on a cross-section of the supporting layer.

[0027] The inclusion of sulfuric acid anodized aluminum as a constituent material in the support layer improves the hardness of the surface layer (A) formed by the support layer. As a result, even when the contact member and the contacted member are used in contact for a long period of time (in other words, when frictional stress occurs between the contact member and the contacted member for a long period of time), the shape of the surface layer (A) is maintained (in other words, the root mean square height Sq of the surface layer (A) is maintained at 1.0 μm or more, and the orthogonal line roughness ratio of the surface layer (A) is maintained at 0.7 or more), providing a contact member that suppresses the transfer of components derived from the liquid composition from the contacted member to the contact member over a long period of time.

[0028] There are no particular restrictions on the method for confirming that a layer contains sulfuric acid anodized aluminum (in other words, a layer containing aluminum oxide and in which sulfur components can be detected), and an appropriate method can be selected depending on the purpose. For example, one method is to perform mapping of sulfur, aluminum, and oxygen components on the cross-section of the support layer, and obtain data indicating the presence of sulfur, aluminum, and oxygen components in the same region. Specifically, one method is to perform EDS elemental analysis (UltraDry, manufactured by Thermo Fisher Scientific) on the cross-section of the support layer to map sulfur, aluminum, and oxygen components.

[0029] As described above, the hardness of the support layer is improved by including sulfuric acid anodized aluminum as a constituent material. Specifically, it is preferable that the Vickers hardness of the contact member having the support layer is 400 Hv or more and 500 Hv or less. The Vickers hardness of the contact member is 400 Hv to 500 Hv, so that even when the contact member and the contacted member are used in contact for a long period of time (in other words, when frictional stress occurs between the contact member and the contacted member for a long period of time), the shape of the surface layer (A) is maintained (in other words, the root mean square height Sq of the surface layer (A) is maintained at 1.0 μm or more, and the orthogonal line roughness ratio of the surface layer (A) is maintained at 0.7 or more), and a contact member can be provided that suppresses the transfer of components derived from the liquid composition from the contacted member to the contact member over a long period of time.

[0030] There are no particular restrictions on the method for measuring the Vickers hardness of the contact member, and it can be appropriately selected according to the purpose. For example, it can be measured in accordance with the test method of JIS Z 2244.

[0031] -Fluororesin particles- In the present invention, the surface layer (A) preferably has fluororesin particles. More specifically, it is preferable that fluororesin particles are attached to and supported on the surface of the support layer. The presence of fluororesin particles in the surface layer (A) improves the lubricity between the contacted member and the contacting member, thereby suppressing the transfer of components derived from the liquid composition from the contacted member to the contacting member. Furthermore, as described above, the presence of fluororesin particles in the surface layer (A) having an uneven surface prevents the detachment of fluororesin particles from occurring even when frictional stress occurs between the contacting member and the contacted member, thus maintaining the above-mentioned transfer suppression effect over a long period of time.

[0032] The fluororesin particles are not particularly limited and can be appropriately selected depending on the purpose. Examples include tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA, melting point 300-310°C), polytetrafluoroethylene (PTFE, melting point 330°C), tetrafluoroethylene-hexafluoropropylene copolymer (FEP, melting point 250-280°C), ethylene-tetrafluoroethylene copolymer (ETFE, melting point 260-270°C), polyvinylidene fluoride (PVDF, melting point 160-180°C), polychlorotrifluoroethylene (PCTFE, melting point 210°C), and tetrafluoroethylene-hexafluoropropylene-perfluoroalkyl vinyl ether copolymer (EPE, melting point 290-300°C), as well as mixtures containing these polymers. Among these, polytetrafluoroethylene (PTFE) is preferred.

[0033] There are no particular limitations on the method for attaching the fluororesin particles to the support layer, and an appropriate method can be selected depending on the purpose. For example, one method is to immerse the member on which the support layer is formed in a dispersion containing fluororesin particles and then air dry it.

[0034] The amount of fluorine elements in the surface layer (A) (the ratio of fluorine atoms to the total amount of elements detected within the observation range) is preferably 5.0 atm% or more, and more preferably 10.0 atm% or more, when elemental analysis is performed. A fluorine content of 5.0 atm% or more in the surface layer (A) is preferable because it can suppress the transfer of components derived from the liquid composition from the contacted member to the contacting member.

[0035] There are no particular restrictions on the method for measuring the amount of fluorine element in the surface layer (A), and it can be appropriately selected depending on the purpose. For example, one method is to perform EDS elemental analysis under the following conditions. Specifically, spectrum analysis is performed under the following conditions, and the amount of fluorine element is determined by performing automatic quantification using analysis software. This is then performed in the same manner at five arbitrary locations, and the average value of the obtained values ​​is adopted as the amount of fluorine element. • Equipment: Carl Zeiss Merlin scanning electron microscope • EDS detector: UltraDry, an electronically cooled SDD detector manufactured by Thermo Fisher Scientific. • Acceleration voltage: 3.0kV WD: 13.0mm ·Take-out angle: 35.0deg. ·Magnification: 2000x • Conductive treatment: C-coat • Cumulative time: 10 seconds. • Total number of times: 100 • Drift correction: Yes • Analysis software: NORAN System 6, manufactured by Thermo Fisher Scientific.

[0036] The average thickness of the support layer is preferably 20.0 μm or more and 40.0 μm or less. The average thickness of the support layer is 20.0 μm or more, which improves the hardness of the surface layer (A) formed by the support layer. As a result, even when the contact member and the contacted member are used in a manner in which they are in contact for a long period of time (in other words, when frictional stress occurs between the contact member and the contacted member for a long period of time), the shape of the surface layer (A) is maintained (in other words, the root mean square height Sq of the surface layer (A) is maintained at 1.0 μm or more, and the orthogonal line roughness ratio of the surface layer (A) is maintained at 0.7 or more), and a contact member can be provided that suppresses the transfer of components derived from the liquid composition from the contacted member to the contact member over a long period of time. The average thickness of the support layer being 40.0 μm or less improves the thermal conductivity of the contact member to the member to be contacted, which is effective when the contact member is used as a contact member having a heating means described later.

[0037] There are no particular restrictions on the method for measuring the average thickness of the support layer, and it can be appropriately selected depending on the purpose. For example, it can be determined as follows. First, the sulfur, aluminum, and oxygen components are mapped in the cross-section of the contact member. Specific examples of methods for mapping the sulfur, aluminum, and oxygen components include performing EDS elemental analysis (UltraDry, Thermo Fisher Scientific). Next, the region where all sulfur, aluminum, and oxygen components are detected is identified as the support layer, and the length of the perpendicular line drawn from the surface of the support layer towards the substrate is determined within the support layer. Similarly, the length of the perpendicular line within the support layer is determined at 10 arbitrary locations, and the average value of these lengths is taken as the average thickness of the support layer.

[0038] <Base material> The contact member of the present invention may have a base material on the side where the surface layer (A) and the member to be contacted do not come into contact. In other words, the contact member of the present invention may have a base material and a surface layer (A) provided on the base material. The support layer is preferably formed by sulfuric acid anodizing treatment of the base material in the manufacturing process of the contact member. Therefore, the material constituting the base material preferably contains aluminum, more preferably magnesium, and even more preferably silicon. When aluminum is sulfuric acid anodized, aluminum oxide grows in a columnar shape, but by including magnesium together, the growth direction of the aluminum oxide can be disrupted. This generates stress within the aluminum oxide, making the surface of the formed support layer more uneven. Similarly, by including silicon, the growth direction of the aluminum oxide can be disrupted, generating stress within the aluminum oxide, and making the surface of the formed support layer more uneven. This uneven shape is preferable because it reduces the contact area between the surface layer (A) and the member to be contacted, thereby suppressing the transfer of components derived from the liquid composition from the member to be contacted to the contact member. Furthermore, this uneven shape is preferable because it provides a spacer effect that suppresses the detachment of fluororesin particles adhering to the support layer.

[0039] There are no particular restrictions on the shape of the base material, and it can be appropriately selected according to the purpose. For example, it is preferably a long metal rod, and more preferably a roller shape such as a cylindrical or cylindrical body with a circular cross-section (a cross-section perpendicular to the length direction). The base material having these shapes allows the contact member to be used as a conveying roller. When using a roller-shaped substrate, the diameter of the circle in the cross-section (the cross-section perpendicular to the longitudinal direction) of the contact member is preferably 50 mm or more and 600 mm or less. It is preferable that the diameter of the circle in the cross-section (the cross-section perpendicular to the longitudinal direction) of the contact member is 50 mm or more, as this reduces the pressure per unit area generated between the contact member and the member being contacted, thereby suppressing the transfer of the liquid composition. The diameter of the circle in the cross-section (the cross-section perpendicular to the longitudinal direction) of the contact member is 600 mm or less, which reduces excessive adhesion between the contact member and the contacted member and suppresses the transfer of the liquid composition, making it preferable.

[0040] <Heating means> The contact member may or may not have a heating means for applying heat to the contacted member via the surface layer (A). The heating means refers to a means of applying heat to the contacted member via the surface layer (A). If the contact member has a heating means, it is preferable that the contact member is a member that heats and dries the liquid composition applied to the contacted member by contacting the contacted member.

[0041] There are no particular restrictions on the heating means, and it can be appropriately selected according to the purpose. For example, when comparing the shortest length from a predetermined position of the heating means to the surface layer (A) with the shortest length from a predetermined position of the heating means to the contacted member, the shortest length from the predetermined position of the heating means to the surface layer (A) is shorter. For example, if the contact member is roller-shaped, the heating means is provided inside the roller-shaped base material and applies heat to the contacted member via the base material and the surface layer (A). In this configuration, the heating means applies heat to the contacted member via the surface layer (A), causing the surface layer (A) to become hot. When the contact member is used in an environment where the surface temperature of the contact member is high, the fluororesin particles generally soften and become more likely to detach from the surface of the contact member. However, in a configuration like this embodiment, where the fluororesin particles are attached to a support layer having an uneven shape, the detachment of the fluororesin particles is suppressed as described above, and the effect of suppressing the transfer of components derived from the liquid composition from the contacted member to the contact member is sustained.

[0042] The configuration in which the heating means is provided in the contact member of the present invention is not particularly limited and can be appropriately selected according to the purpose, but it is preferable that it is provided integrally with the surface layer (A) and other members constituting the contact member, such as the substrate. The heating means is not particularly limited, and various known means can be used, such as a heater and means for generating hot air.

[0043] If the contact member has the heating means, the temperature of the surface layer (A) is preferably 70°C or higher and 260°C or lower. The surface layer (A) is preferably 70°C or higher because it allows for efficient drying of the liquid composition applied to the contacted member. The temperature of the surface layer (A) being 260°C or lower is preferable because it suppresses the modification of the fluororesin particles.

[0044] <Liquid composition> The liquid compositions in the present invention are not particularly limited and can be appropriately selected depending on the purpose. Examples include ink, a pretreatment liquid applied to aggregate the colorants contained in the ink, a posttreatment liquid applied to protect the surface of the applied ink, and a liquid for forming an electrical circuit or the like with inorganic particles such as metal dispersed in it. These can be used in known compositions as appropriate.

[0045] <<Ink>> There are no particular restrictions on the ink, and it can be appropriately selected depending on the purpose, but it is preferable to use one that contains an organic solvent, water, colorant, resin, wax, additives, etc.

[0046] -Organic Solvents- There are no particular restrictions on the organic solvent, and it can be appropriately selected depending on the purpose. For example, water-soluble organic solvents, other organic solvents, etc., can be suitably used. Examples of the water-soluble organic solvents include polyhydric alcohols, ethers such as polyhydric alcohol alkyl ethers and polyhydric alcohol aryl ethers, nitrogen-containing heterocyclic compounds, amides, amines, and sulfur-containing compounds.

[0047] Specific examples of the aforementioned polyhydric alcohols include ethylene glycol, diethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 3-methyl-1,3-butanediol, triethylene glycol, polyethylene glycol, polypropylene glycol, 1,2-pentanediol, 1,3-pentanediol, and 1,4-pentanediol. Examples include 2,4-pentanediol, 1,5-pentanediol, 1,2-hexanediol, 1,6-hexanediol, 1,3-hexanediol, 2,5-hexanediol, 1,5-hexanediol, glycerin, 1,2,6-hexanetriol, 2-ethyl-1,3-hexanediol, ethyl-1,2,4-butanetriol, 1,2,3-butanetriol, 2,2,4-trimethyl-1,3-pentanediol, and petriol.

[0048] Specific examples of the polyhydric alcohol alkyl ethers include ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, tetraethylene glycol monomethyl ether, and propylene glycol monoethyl ether.

[0049] Specific examples of the aforementioned polyhydric alcohol aryl ethers include ethylene glycol monophenyl ether and ethylene glycol monobenzyl ether.

[0050] Specific examples of the nitrogen-containing heterocyclic compounds include 2-pyrrolidone, N-methyl-2-pyrrolidone, N-hydroxyethyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, ε-caprolactam, and γ-butyrolactone.

[0051] Specific examples of the aforementioned amides include formamide, N-methylformamide, N,N-dimethylformamide, 3-methoxy-N,N-dimethylpropionamide, and 3-butoxy-N,N-dimethylpropionamide.

[0052] Specific examples of the aforementioned amines include monoethanolamine, diethanolamine, and triethylamine.

[0053] Specific examples of the aforementioned sulfur-containing compounds include dimethyl sulfoxide, sulfolane, and thiodiethanol.

[0054] Specific examples of the aforementioned other organic solvents include propylene carbonate and ethylene carbonate.

[0055] In addition to the examples above, polyol compounds having 8 or more carbon atoms and glycol ether compounds can also be suitably used as the organic solvent. Specific examples of the polyol compounds having 8 or more carbon atoms include 2-ethyl-1,3-hexanediol and 2,2,4-trimethyl-1,3-pentanediol. Specific examples of the glycol ether compounds include polyhydric alcohol alkyl ethers such as ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, tetraethylene glycol monomethyl ether, and propylene glycol monoethyl ether; and polyhydric alcohol aryl ethers such as ethylene glycol monophenyl ether and ethylene glycol monobenzyl ether.

[0056] When the ink contains a resin, the organic solvent is preferably N,N-dimethyl-β-butoxypropionamide, N,N-dimethyl-β-ethoxypropionamide, 3-ethyl-3-hydroxymethyl oxetane, or propylene glycol monomethyl ether. These may be used individually or in combination of two or more. Among these, amide solvents such as 3-butoxy-N,N-dimethylpropionamide and 3-methoxy-N,N-dimethylpropionamide are more preferred from the viewpoint of promoting film formation of the resin and exhibiting high abrasion resistance.

[0057] The boiling point of the organic solvent is preferably between 180°C and 250°C. If the boiling point of the organic solvent is 180°C or higher, the evaporation rate during drying can be appropriately controlled, leveling can be performed sufficiently, and surface irregularities can be reduced, thereby improving gloss. If the boiling point of the organic solvent is 250°C or lower, problems such as poor drying properties and the need for long drying times can be resolved. With the increasing speed of printing technology in recent years, the drying time of the ink has become the rate-limiting factor, and it is necessary to shorten the drying time, so long drying times are undesirable.

[0058] There are no particular restrictions on the content of the organic solvent in the ink, and it can be set appropriately depending on the purpose. However, from the viewpoint of ink drying properties and ejection reliability, it is preferable that the content is 10% by mass or more and 60% by mass or less, and more preferably 20% by mass or more and 60% by mass or less, relative to the total amount of ink.

[0059] There are no particular restrictions on the content of the amides in the ink, and it can be set appropriately depending on the purpose, but it is preferably 0.05% by mass or more and 10% by mass or less, and more preferably 0.1% by mass or more and 5% by mass or less, relative to the total amount of ink.

[0060] -water- The water content in the ink is not particularly limited and can be set appropriately depending on the purpose, but from the viewpoint of ink drying properties and ejection reliability, it is preferably 10% to 90% by mass and more preferably 20% to 60% by mass relative to the total amount of ink.

[0061] -Colorants- There are no particular restrictions on the aforementioned coloring material, and it can be appropriately selected according to the purpose, and pigments (A) and dyes can be used.

[0062] --Pigment (A)-- As the pigment (A), inorganic or organic pigments can be used. These may be used individually or in combination of two or more. Mixed crystals may also be used as pigment (A). There are no particular restrictions on the pigment (A), and it can be appropriately selected according to the purpose. For example, black pigment, yellow pigment, magenta pigment, cyan pigment, white pigment, green pigment, orange pigment, glossy pigments such as gold and silver, and metallic pigments can be used. There are no particular restrictions on the inorganic pigments, and they can be appropriately selected depending on the purpose. For example, titanium dioxide, iron oxide, calcium carbonate, barium sulfate, aluminum hydroxide, barium yellow, cadmium red, chromium yellow, and carbon black produced by known methods such as the contact method, furnace method, and thermal method can be used. There are no particular restrictions on the organic pigments mentioned above, and they can be appropriately selected according to the purpose. Azo pigments, polycyclic pigments (e.g., phthalocyanine pigments, perylene pigments, perinone pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, indigo pigments, thioindigo pigments, isoindolinone pigments, quinophthalone pigments, etc.), dye chelates (e.g., basic dye type chelates, acid dye type chelates, etc.), nitro pigments, nitroso pigments, aniline black, etc. can be used. Of these pigments (A), those with good affinity for the solvent are preferably used. In addition, resin hollow particles and inorganic hollow particles can also be used.

[0063] Specific examples of the aforementioned pigment (A) include carbon blacks (CI Pigment Black 7) such as furnace black, lamp black, acetylene black, and channel black, metals such as copper, iron (CI Pigment Black 11), and titanium oxide, and organic pigments such as aniline black (CI Pigment Black 1). Specific examples of the aforementioned pigment (A) include, for color applications, CI Pigment Yellow 1, CI Pigment Yellow 3, CI Pigment Yellow 12, CI Pigment Yellow 13, CI Pigment Yellow 14, CI Pigment Yellow 17, CI Pigment Yellow 24, CI Pigment Yellow 34, CI Pigment Yellow 35, CI Pigment Yellow 37, CI Pigment Yellow 42 (yellow iron oxide), CI Pigment Yellow 53, CI Pigment Yellow 55, CI Pigment Yellow Low 74, CI Pigment Yellow 81, CI Pigment Yellow 83, CI Pigment Yellow 95, CI Pigment Yellow 97, CI Pigment Yellow 98, CI Pigment Yellow 100, CI Pigment Yellow 101, CI Pigment Yellow 104, CI Pigment Yellow 108, CI Pigment Yellow 109, CI Pigment Yellow 110, CI Pigment Yellow 117, CI Pigment Yellow 120, CI Pigment Yellow 138, CI Pigment Yellow 150, CI Pigment Yellow 153, CI Pigment Yellow 155, CI Pigment Yellow 180, CI Pigment Yellow 185, CI Pigment Yellow 213, CI Pigment Orange 5, CI Pigment Orange 13, CI Pigment Orange 16, CI Pigment Orange 17, CI Pigment Orange 36, CI Pigment Orange 43, CI Pigment Orange 51, CI Pigment Red 1, CI Pigment Red 2, CI Pigment Red 3, CI Pigment Red D5, CI Pigment Red 17, CI Pigment Red 22, CI Pigment Red 23, CI Pigment Red 31, CI Pigment Red 38, CI Pigment Red 48:2, CI Pigment Red 48:2 (Permanent Red 2B (Ca)), CI Pigment Red 48:3, CI Pigment Red 48:4, CI Pigment Red 49:1, CI Pigment Red 52:2, CI Pigment Red 53:1, CI Pigment Red 57:1 (Brilliant Carmine 6B), CIPigment Red 60:1, CI Pigment Red 63:1, CI Pigment Red 63:2, CI Pigment Red 64:1, CI Pigment Red 81, CI Pigment Red 83, CI Pigment Red 88, CI Pigment Red 101 (Bengara), CI Pigment Red 104, CI Pigment Red 105, CI Pigment Red 106, CI Pigment Red 108 (Cadmium Red), CI Pigment Red 112, CI Pigment Red 114, CI Pigment Red D122 (Quinacridone Magenta), CI Pigment Red 123, CI Pigment Red 146, CI Pigment Red 149, CI Pigment Red 166, CI Pigment Red 168, CI Pigment Red 170, Pigment Red 172, CI Pigment Red 177, CI Pigment Red 178, CI Pigment Red 179, CI Pigment Red 184, CI Pigment Red 185, CI Pigment Red 190, CI Pigment Red 193, CI Pigment Red CI Pigment Red 202, CI Pigment Red 207, CI Pigment Red 208, CI Pigment Red 209, CI Pigment Red 213, CI Pigment Red 219, CI Pigment Red 224, CI Pigment Red 254, CI Pigment Red 264, CI Pigment Violet 1 (Rhodamine Lake), CI Pigment Violet 3, 5:1, CI Pigment Violet 16, CI Pigment Violet 19, CI Pigment Violet 23, CI Pigment Violet 38, CI Pigment Blue 1, CI Pigment Blue 2, CI Pigment Blue 15 (Phthalocyanine Blue), CI Pigment Blue 15:1, CI Pigment Blue 15:2, CI Pigment Blue 15:3, CI Pigment Blue 15:4 (Phthalocyanine Blue), CI Pigment Blue 16, CI Pigment Blue 17:1, CI Pigment Blue 56, CI Pigment Blue 60, CI Pigment Blue 63, CI Pigment Green 1, CI Pigment Green 4, CIExamples include Pigment Green 7, CI Pigment Green 8, CI Pigment Green 10, CI Pigment Green 17, CI Pigment Green 18, and CI Pigment Green 36.

[0064] --dye-- There are no particular restrictions on the aforementioned dyes, and they can be appropriately selected according to the purpose. Acid dyes, direct dyes, reactive dyes, and basic dyes can be used, and they may be used individually or in combination of two or more. Specific examples of the aforementioned dyes include CI Acid Yellow 17, CI Acid Yellow 23, CI Acid Yellow 42, CI Acid Yellow 44, CI Acid Yellow 79, CI Acid Yellow 142, CI Acid Red 52, CI Acid Red 80, CI Acid Red 82, CI Acid Red 249, CI Acid Red 254, CI Acid Red 289, CI Acid Blue 9, CI Acid Red 45, CI Acid Red 249, CI Acid Black 1, CI Acid Black 2, CI Acid Black 24, CI Acid Black 94, CI Food Black 1, CI Food Black 2, CI Direct Yellow 1, CI Direct Yellow 12, CI Direct Yellow 24, CI Direct Yellow 33, CI Direct Yellow 50, CI Direct Yellow 55, CI Direct Yellow 58, CI Direct Yellow 86, CI Direct Yellow 132, CI Direct Yellow 142, CI Direct Yellow 144, CI Dye Rect Yellow 173, CI Direct Red 1, CI Direct Red 4, CI Direct Red 9, CI Direct Red 80, CI Direct Red 81, CI Direct Red 225, CI Direct Red 227, CI Direct Blue 1, CI Direct Blue 2, CI Direct Blue 15, CI Direct Blue 71, CI Direct Blue 86, CI Direct Blue 87, CI Direct Blue 98, CI Direct Blue 165, CI Direct Blue 199, CI Direct Blue 202, CI Direct Black 19, CI Direct Black 38, CI Direct Black 51, CI Direct Black 71, CI Direct Black 154, CI Direct Black 168, CI Direct Black 171, CI Direct Black 195, CI Reactive Red 14, CI Reactive Red 32, CI Reactive Red 55, CI Reactive Red 79, CI Reactive Red 249, CI Reactive Black 3, CIExamples include Reactive Black 4 and CI Reactive Black 35.

[0065] The content of the colorant in the ink is not particularly limited and can be set appropriately depending on the purpose, but from the viewpoint of improving image density and good fixation and ejection stability, it is preferably 0.1% by mass or more and 15% by mass or less, and more preferably 1% by mass or more and 10% by mass or less, relative to the total amount of ink.

[0066] There are no particular limitations on the method for dispersing the pigment (A) in the ink, and a suitable method can be selected depending on the purpose. Examples include a method of introducing hydrophilic functional groups into the pigment to make it a self-dispersible pigment, a method of coating the surface of the pigment with a resin and dispersing it, and a method of dispersing it using a dispersant.

[0067] One method for introducing hydrophilic functional groups into the aforementioned pigment to create a self-dispersible pigment is to add functional groups such as sulfone groups or carboxyl groups to the pigment (e.g., carbon) to make it dispersible in water.

[0068] Methods for coating and dispersing the surface of the aforementioned pigment with a resin include encapsulating the pigment in microcapsules to make it dispersible in water. The pigment obtained by this method can be called a resin-coated pigment. In this case, it is not necessary for all pigments incorporated into the ink to be coated with resin; uncoated pigments or partially coated pigments may be dispersed in the ink.

[0069] Methods for dispersion using the aforementioned dispersant include methods using known low-molecular-weight dispersants, such as surfactants, and high-molecular-weight dispersants. There are no particular restrictions on the dispersant, and it can be appropriately selected depending on the pigment used. For example, anionic surfactants, cationic surfactants, amphoteric surfactants, nonionic surfactants, etc., can be used. As the aforementioned dispersant, RT-100 (nonionic surfactant, manufactured by Takemoto Oil & Fat Co., Ltd.) and sodium naphthalene sulfonate formalin condensate can also be suitably used. The aforementioned dispersant may be used alone or in combination of two or more types.

[0070] The ink can be obtained by mixing the pigment (A) with materials such as water or the organic solvent. Alternatively, the ink can be obtained by mixing the pigment (A) with water or the dispersant to form a pigment dispersion, and then mixing that with materials such as water or the organic solvent.

[0071] The pigment dispersion can be obtained by mixing and dispersing the water, the pigment (A), the dispersant, and other components as needed, and adjusting the particle size. The dispersion may be performed using a disperser. There are no particular restrictions on the particle size of the pigment (A) in the pigment dispersion, and it can be set appropriately depending on the purpose. However, from the viewpoint of improving the dispersion stability of the pigment and improving the ejection stability and image quality such as image density, it is preferable that the maximum frequency in terms of the maximum number of particles be between 20 nm and 500 nm, and more preferably between 20 nm and 150 nm.

[0072] There are no particular restrictions on the method for measuring the particle size of pigment (A) in the pigment dispersion, and a suitable method can be selected depending on the purpose. For example, it can be measured using a particle size analyzer (NanoTrac Wave-UT151, manufactured by MicroTrac-Bell Co., Ltd.). The pigment content in the pigment dispersion is not particularly limited and can be set appropriately depending on the purpose, but from the viewpoint of obtaining good discharge stability and increasing image density, it is preferable that the pigment content be 0.1% by mass or more and 50% by mass or less, and more preferably 0.1% by mass or more and 30% by mass or less, relative to the total amount of the pigment dispersion. The pigment dispersion is preferably filtered to remove coarse particles and degassed using a filter, centrifuge, or the like, as needed.

[0073] -resin- The aforementioned resin is not particularly limited and can be appropriately selected depending on the purpose. Examples include urethane resin, polyester resin, acrylic resin, vinyl acetate resin, styrene resin, butadiene resin, styrene-butadiene resin, vinyl chloride resin, acrylic styrene resin, and acrylic silicone resin. Resin particles made from these resins may also be used. The ink can be obtained by mixing the resin emulsion, in which the resin particles are dispersed using water as a dispersion medium, with materials such as the colorant and the organic solvent. The resin particles may be synthesized as appropriate, or commercially available products may be used. Furthermore, these may be used individually or in combination of two or more types of resin particles.

[0074] Among these, urethane resin particles are preferred because they can form images with strong tackiness and improve image fixation. Furthermore, from the viewpoint of blocking resistance, it is even more preferable to use them in mixture with other resin particles. Furthermore, from the viewpoint of forming images with greater tack force and improved fixability, it is preferable that the urethane resin particles have a glass transition temperature (Tg) of -20°C to 70°C. Furthermore, among the aforementioned resins, acrylic resin particles made from acrylic resin are widely used because they have excellent discharge stability and are also inexpensive. It is preferable to use a mixture of elastic urethane resin particles and the aforementioned acrylic resin particles from the viewpoint of improving abrasion resistance.

[0075] There are no particular restrictions on the volume-average particle size of the resin particles, and it can be set appropriately depending on the purpose. However, from the viewpoint of obtaining good adhesion and high image hardness, it is preferable that the particle size is 10 nm to 1,000 nm, more preferably 10 nm to 200 nm, and even more preferably 10 nm to 100 nm. There are no particular restrictions on the method for measuring the volume-average particle size, and it can be appropriately selected depending on the purpose. For example, it can be measured using a particle size analyzer (NanoTrac Wave-UT151, manufactured by MicroTrac-Bell Co., Ltd.).

[0076] There are no particular restrictions on the resin content in the ink, and it can be set appropriately depending on the purpose. However, from the viewpoint of fixability and storage stability of the ink, it is preferable that the content be 1% by mass or more and 30% by mass or less, and more preferably 5% by mass or more and 20% by mass or less, relative to the total amount of ink.

[0077] There are no particular restrictions on the particle size of the solid particles in the ink, and it can be set appropriately depending on the purpose. However, from the viewpoint of improving ejection stability and image quality such as image density, the maximum frequency of solid particle size in the ink is preferably 20 nm to 1000 nm in terms of maximum number, and more preferably 20 nm to 150 nm. The solid particles in the ink include resin particles, pigment particles, etc. There are no particular restrictions on the method for measuring the particle size of the solid content in the ink, and a suitable method can be selected depending on the purpose. For example, it can be measured using a particle size analyzer (NanoTrac Wave-UT151, manufactured by MicroTrac-Bell Co., Ltd.).

[0078] -wax- The aforementioned ink can have improved abrasion resistance by containing wax. Furthermore, the gloss level can be improved by using the resin and the wax in combination. Polyethylene wax is preferred as the wax.

[0079] The polyethylene wax may be one that has been synthesized as appropriate, or a commercially available product may be used. Examples of commercially available polyethylene waxes include AQUACER531 (manufactured by Big Chemie Japan Co., Ltd.), Polylon P502 (manufactured by Chukyo Oils Co., Ltd.), Aqua Petro DP2502C (manufactured by Toyo Adore Co., Ltd.), and Aqua Petro DP2401 (manufactured by Toyo Adore Co., Ltd.). These may be used individually or in combination of two or more types.

[0080] There are no particular restrictions on the polyethylene wax content, and it can be set appropriately depending on the purpose, but it is preferably 0.05% by mass or more and 2% by mass or less, and more preferably 0.05% by mass or more and 0.5% by mass or less, relative to the total amount of ink. When the polyethylene wax content is between 0.05% by mass and 2% by mass, it is sufficiently effective in improving abrasion resistance and gloss. Furthermore, when the polyethylene wax content is 2% by mass or less, the storage stability and ejection stability of the ink become particularly good, making it more suitable for use in inkjet systems.

[0081] - Additives - There are no particular restrictions on the aforementioned additives, and they can be appropriately selected depending on the purpose. Examples include surfactants, defoamers, preservatives and antifungal agents, rust inhibitors, and pH adjusters.

[0082] --Surfactants-- There are no particular restrictions on the surfactant used as the additive, and it can be appropriately selected depending on the purpose. Examples include silicone-based surfactants, fluorine-based surfactants, amphoteric surfactants, nonionic surfactants, and anionic surfactants.

[0083] ---Silicone-based surfactants--- There are no particular limitations on the silicone-based surfactant, and it can be appropriately selected depending on the purpose, but it is preferable that it does not decompose even at high pH. Examples include side-chain modified polydimethylsiloxane, both-end modified polydimethylsiloxane, one-end modified polydimethylsiloxane, and both-end modified polydimethylsiloxane. Among these, from the viewpoint of exhibiting good properties as an aqueous surfactant, it is preferable that it has a polyoxyethylene group or a polyoxyethylene polyoxypropylene group as a modifying group.

[0084] Furthermore, a polyether-modified silicone surfactant can also be used as the silicone-based surfactant. There are no particular limitations on the polyether-modified silicone surfactant, and it can be appropriately selected depending on the purpose. For example, a polyalkylene oxide structure represented by the general formula (S-1) can be introduced into the Si side chain of dimethylpolysiloxane.

[0085] [ka] General formula (S-1) (However, in general formula (S-1), m, n, a, and b each represent an integer independently, R represents an alkylene group, and R' represents an alkyl group.)

[0086] As the aforementioned silicone-based surfactant, a suitably synthesized one may be used, or a commercially available product may be used. Commercially available silicone-based surfactants can be obtained from companies such as BIC Chemie Inc., Shin-Etsu Chemical Co., Ltd., Toray Dow Corning Silicone Co., Ltd., Nippon Emulsion Co., Ltd., and Kyoeisha Chemical Co., Ltd. Examples of commercially available polyether-modified silicone surfactants include KF-618, KF-642, KF-643 (all from Shin-Etsu Chemical Co., Ltd.), EMALEX-SS-5602, SS-1906EX (both from Nippon Emulsion Co., Ltd.), FZ-2105, FZ-2118, FZ-2154, FZ-2161, FZ-2162, FZ-2163, FZ-2164 (all from Toray Dow Corning Silicone Co., Ltd.), BYK-33, BYK-387 (both from BIC Chemie Co., Ltd.), and TSF4440, TSF4452, TSF4453 (both from Toshiba Silicone Corporation).

[0087] ---Fluorine-based surfactants--- There are no particular restrictions on the fluorinated surfactant, and it can be appropriately selected depending on the purpose, but compounds with 2 to 16 carbon atoms substituted with fluorine are preferred, and compounds with 4 to 16 carbon atoms substituted with fluorine are more preferred. Specific examples of the fluorinated surfactants include perfluoroalkyl sulfonic acid compounds, perfluoroalkyl carboxylic acid compounds, perfluoroalkyl phosphate ester compounds, perfluoroalkyl ethylene oxide adducts, and polyoxyalkylene ether polymer compounds having perfluoroalkyl ether groups in their side chains. Among these, polyoxyalkylene ether polymer compounds having perfluoroalkyl ether groups in their side chains are preferred from the viewpoint of low foaming ability, and fluorinated surfactants represented by the following general formulas (F-1) and (F-2) are more preferred.

[0088] [ka] General formula (F-1) In the compound represented by the above general formula (F-1), m is preferably an integer between 0 and 10, and n is preferably an integer between 0 and 40, in order to impart water solubility.

[0089] C n F 2n+1 -CH2CH(OH)CH2-O-(CH2CH2O) a-Y General formula (F-2) In the compound represented by the above general formula (F-2), Y is H or CmF 2m+1 m is an integer from 1 to 6, or CH2CH(OH)CH2-CmF 2m+1 m is an integer between 4 and 6, or CpH 2p+1 p is an integer between 1 and 19. n is an integer between 1 and 6. a is an integer between 4 and 14.

[0090] Examples of the perfluoroalkyl sulfonic acid compound include perfluoroalkyl sulfonic acid and perfluoroalkyl sulfonate salts. Examples of the perfluoroalkylcarboxylic acid compound include perfluoroalkylcarboxylic acids and perfluoroalkylcarboxylic acid salts. Examples of polyoxyalkylene ether polymer compounds having perfluoroalkyl ether groups in their side chains include sulfate ester salts of polyoxyalkylene ether polymers having perfluoroalkyl ether groups in their side chains, and salts of polyoxyalkylene ether polymers having perfluoroalkyl ether groups in their side chains. Examples of counterions for the salts of these fluorinated surfactants include Li, Na, K, NH4, NH3CH2CH2OH, NH2(CH2CH2OH)2, and NH(CH2CH2OH)3.

[0091] As the fluorine-based surfactant, a suitably synthesized one may be used, or a commercially available product may be used. Examples of commercially available fluorine-based surfactants include: Surflon S-111, S-112, S-113, S-121, S-131, S-132, S-141, S-145 (all manufactured by AGC Inc.); Flurad FC-93, FC-95, FC-98, FC-129, FC-135, FC-170C, FC-430, FC-431 (all manufactured by Sumitomo 3M Limited); Megafac F-470, F-1405, F-474 (all manufactured by DIC Corporation); Zonyl TBS, FSP, FSA, FSN-1 Examples include 00, FSN, FSO-100, FSO, FS-300, UR, Capstone FS-30, FS-31, FS-3100, FS-34, FS-35 (all manufactured by Chemors); FT-110, FT-250, FT-251, FT-400S, FT-150, FT-400SW (all manufactured by Neos Corporation); Polyfox PF-136A, PF-156A, PF-151N, PF-154, PF-159 (all manufactured by Omnova); and Unidyne DSN-403N (manufactured by Daikin Industries, Ltd.). Among these, Chemors' FS-3100, FS-34, and FS-300, Neos Corporation's FT-110, FT-250, FT-251, FT-400S, FT-150, and FT-400SW, Omnova's Polyfox PF-151N, and Daikin Industries, Ltd.'s Unidyne DSN-403N are preferred because they offer excellent print quality, particularly significantly improved color development, penetration into paper, wettability, and uniform dyeing.

[0092] ---Amphoteric surfactant--- The aforementioned amphoteric surfactant is not particularly limited and can be appropriately selected depending on the purpose. Examples include laurylaminopropionate, lauryldimethylbetaine, stearyldimethylbetaine, and lauryldihydroxyethylbetaine.

[0093] ---Nonionic surfactant--- The nonionic surfactant is not particularly limited and can be appropriately selected depending on the purpose. Examples include polyoxyethylene alkylphenyl ethers, polyoxyethylene alkyl esters, polyoxyethylene alkylamines, polyoxyethylene alkylamides, polyoxyethylene propylene block polymers, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, and ethylene oxide adducts of acetylene alcohols.

[0094] ---Anionic surfactants--- The anionic surfactant is not particularly limited and can be appropriately selected depending on the purpose. Examples include polyoxyethylene alkyl ether acetate, dodecylbenzene sulfonate, lauryl salt, and polyoxyethylene alkyl ether sulfate salts. These can be used individually or in combination of two or more types.

[0095] There are no particular restrictions on the content of the surfactant in the ink, and it can be set appropriately depending on the purpose. However, from the standpoint of excellent wettability and ejection stability, and improved image quality, it is preferable that the content be 0.001% by mass or more and 5% by mass or less, and more preferably 0.05% by mass or more and 5% by mass or less, relative to the total amount of ink.

[0096] --Antifoaming agent-- The surfactants used as other components can also be used as defoaming agents. There are no particular restrictions on the defoaming agent, and it can be appropriately selected depending on the purpose. Examples include silicone-based defoaming agents, polyether-based defoaming agents, and fatty acid ester-based defoaming agents. These may be used individually or in combination of two or more. Among these, silicone-based defoaming agents are preferred due to their excellent foam-breaking effect.

[0097] --Preservative and fungicidal agent-- There are no particular restrictions on the preservatives and fungicides used, and they can be appropriately selected depending on the purpose. For example, 1,2-benzisothiazolin-3-one is one such example.

[0098] --Rust Inhibitor-- There are no particular restrictions on the rust inhibitor, and it can be appropriately selected depending on the purpose. Examples include acidic sulfites and sodium thiosulfate.

[0099] --pH adjuster-- The pH adjusting agent is not particularly limited as long as it can adjust the pH to 7 or higher, and examples include amines such as diethanolamine and triethanolamine.

[0100] <Contacted member> There are no particular limitations on the contacted member in the present invention, and it can be appropriately selected according to the purpose. For example, ordinary paper, glossy paper, specialty paper, cloth, and other recording media can be used. Among these, low-permeability recording media (hereinafter sometimes referred to as low-absorption recording media) can be preferably used.

[0101] <<Low-penetration recording medium>> The aforementioned low-permeability recording medium refers to a recording medium having a surface with low water permeability, absorption, or adsorption, and may have numerous voids inside, including those in which these voids do not open to the outside. The low-permeability recording medium is not particularly limited and can be appropriately selected depending on the purpose. For example, it may have a support and a surface layer (B) provided on at least one side of the support, and may have other layers as needed. Note that the "surface layer (A)" in the contact member and the "surface layer (B)" in the non-contact member are different. For convenience, in this specification, the surface layer in the contact member will be referred to as "surface layer (A)," and the surface layer in the non-contact member will be referred to as "surface layer (B)." Details of "surface layer (B)" will be described later.

[0102] Specific examples of the low-permeability recording medium include coated paper used for commercial printing, and recording media such as paperboard obtained by blending waste paper pulp in the middle and back layers and applying a coating to the surface. Since the low-permeability recording medium has a stronger grip force compared to recording media such as plain paper and the friction generated between the contact members increases, it is likely to cause a problem that it becomes difficult to maintain the shape of the above surface layer (A). By using the contact member of the present invention in which the shape of the surface layer (A) is maintained, even when a low-permeability recording medium is used, it is possible to suppress the transfer of components derived from the liquid composition from the contacted member to the contact member over a long period of time.

[0103] In the low-permeability recording medium, the transfer amounts of pure water and ink to the low-permeability recording medium at a contact time of 100 ms measured by a dynamic scanning liquid absorption meter are 2 mL / m 2 35 mL / m or more 2 and preferably 2 mL / m 2 10 mL / m or more 2 and more preferably 10 mL / m or less. When the transfer amounts of pure water and ink to the low-permeability recording medium at a contact time of 100 ms measured by a dynamic scanning liquid absorption meter are 2 mL / m 2 or more, it is possible to solve the problem that beading is likely to occur. When the transfer amounts of pure water and ink to the low-permeability recording medium at a contact time of 100 ms measured by a dynamic scanning liquid absorption meter are 35 mL / m 2 or less, it is possible to solve the problem that the ink dot diameter after image formation becomes too small compared to the desired diameter.

[0104] In the low-permeability recording medium, the transfer amounts of pure water and ink to the low-permeability recording medium at a contact time of 400 ms measured by a dynamic scanning liquid absorption meter are 3 mL / m 2 40 mL / m or less and preferably 3 mL / m 2 10 mL / m or more 2 and more preferably 10 mL / m or less. 2 ​The transfer volume of pure water and ink to the low-permeability recording medium at a contact time of 400 ms, as measured by a dynamic scanning liquid absorption meter, was 3 mL / m². 2 This eliminates problems such as insufficient drying. The transfer volume of pure water and ink to the low-permeability recording medium at a contact time of 400 ms, as measured by a dynamic scanning liquid absorption meter, was 40 mL / m². 2 The following conditions can resolve issues such as a decrease in gloss in the image area after drying. The amount of pure water and ink transferred to the low-permeability recording medium at contact times of 100 ms and 400 ms can both be measured on the side of the low-permeability recording medium that has the surface layer (B).

[0105] Here, the dynamic scanning absorptometer (DSA, Journal of the Japan Society of Paper and Pulp Technology, Vol. 48, May 1994, pp. 88-92, Shigenori Kuga) is a device that can accurately measure the amount of liquid absorbed in an extremely short time. The dynamic scanning absorptometer automates the measurement by directly reading the rate of liquid absorption from the movement of the meniscus in the capillary, by using a disc-shaped sample and scanning the absorption head in a spiral motion over it, and by automatically changing the scanning speed according to a preset pattern, thereby performing the required number of measurements on a single sample. The liquid supply head to the paper sample is connected to a capillary via a Teflon® tube, and the position of the meniscus in the capillary is automatically read by an optical sensor. Specifically, the amount of pure water or ink transferred can be measured using a dynamic scanning liquid absorber (K350 series D type, manufactured by Kyowa Seikou Co., Ltd.).

[0106] The amount of pure water and ink transferred to the low-permeability recording medium at contact times of 100 ms and 400 ms can be determined by interpolation from the measured transfer amounts at neighboring contact times.

[0107] -Support- The support material is not particularly limited and can be appropriately selected depending on the purpose. Examples include paper mainly composed of wood fibers, and sheet-like materials such as nonwoven fabrics mainly composed of wood fibers and synthetic fibers. Note that the "support layer" in the contact member and the "support body" in the non-contact member are different. The average thickness of the support is not particularly limited and can be appropriately selected depending on the purpose, but 50 μm to 300 μm is preferred. The basis weight of the support is 45 g / m². 2 ~290g / m 2 It is preferable.

[0108] -Surface layer (B)- The surface layer (B) is not particularly limited and can be appropriately selected depending on the purpose. For example, it may contain a pigment (B), a binder, and optionally a surfactant and other components. Note that "pigment (A)" in the liquid composition and "pigment (B)" in the non-contact member are different. For convenience, in this specification, the pigment in the liquid composition is referred to as "pigment (A)," and the pigment in the non-contact member is referred to as "pigment (B)." Note that the "resin" or "resin particles" in the liquid composition are different from the "binder" in the non-contact member. For convenience, in this specification, the terms "resin" or "resin particles" are used in the liquid composition, and the term "binder" is used in the non-contact member.

[0109] --Pigment (B)-- As the pigment (B), an inorganic pigment or a combination of an inorganic pigment and an organic pigment can be used.

[0110] The inorganic pigment in pigment (B) is not particularly limited and can be appropriately selected depending on the purpose. Examples include kaolin, talc, heavy calcium carbonate, light calcium carbonate, calcium sulfite, amorphous silica, titanium white, magnesium carbonate, titanium dioxide, aluminum hydroxide, calcium hydroxide, magnesium hydroxide, zinc hydroxide, and chlorite. The amount of inorganic pigment added to the aforementioned pigment (B) is preferably 50 parts by mass or more per 100 parts by mass of the binder described later.

[0111] There are no particular restrictions on the organic pigment in pigment (B) and it can be appropriately selected depending on the purpose. Examples include water-soluble dispersions such as styrene-acrylic copolymer particles, styrene-butadiene copolymer particles, polystyrene particles, and polyethylene particles. The amount of organic pigment added to the pigment (B) is preferably 2 parts by mass or more and 20 parts by mass or less per 100 parts by mass of pigment (B) in the surface layer (B).

[0112] --binder-- As the binder, at least one of a water-soluble resin and a water-dispersible resin can be suitably used. The water-soluble resin used as the binder is not particularly limited and can be appropriately selected depending on the purpose. Examples include polyvinyl alcohol, cation-modified polyvinyl alcohol, acetal-modified polyvinyl alcohol, polyester, polyurethane, and the like.

[0113] --Surfactants-- The surfactants that may be included in the surface layer (B) as needed are not particularly limited and can be appropriately selected depending on the purpose. Examples include anionic surfactants, cationic surfactants, amphoteric surfactants, and nonionic surfactants.

[0114] There are no particular restrictions on the method for forming the surface layer (B), and it can be appropriately selected depending on the purpose. This can be done by impregnating or coating the support with the liquid constituting the surface layer (B). The amount of liquid adhering to the surface layer (B) is not particularly limited and can be appropriately selected according to the purpose, with a solid content of 0.5 g / m². 2 ~20g / m 2 Preferably, 1 g / m 2 ~15g / m 2 This is preferable.

[0115] (drying equipment) The drying apparatus of the present invention is an apparatus for drying a non-contact member to which a liquid composition has been applied by heating, and has the above-mentioned contact member, and may have other members as needed.

[0116] (Printing device) The printing apparatus of the present invention has means for dispensing a liquid composition, and may optionally have means for supplying a member to be contacted, means for recovering a member to be contacted, a transport path, and other means.

[0117] <Means for dispensing liquid composition> In this invention, the means for applying the liquid composition refers to a means for applying the liquid composition to a member to be contacted. The means for applying the liquid composition is not particularly limited and can be appropriately selected depending on the purpose. For example, an inkjet ejection head having multiple nozzle rows in which multiple nozzles are arranged, or various known methods such as spin coating, spray coating, gravure roll coating, reverse roll coating, and bar coating can be suitably used.

[0118] <Non-contact component supply means> In this invention, the non-contact member supply means refers to a means for supplying a non-contact member. The non-contact member supply process according to the present invention refers to the process of supplying a non-contact member. The non-contact member supply process can be carried out by the non-contact member supply means.

[0119] <Means for recovering contacted component and process for recovering contacted component> In this invention, the non-contact member recovery means refers to a means for recovering a non-contact member. The non-contact member recovery process according to the present invention refers to a process for recovering a non-contact member. The non-contact member retrieval process can be carried out by the non-contact member retrieval means.

[0120] <Transportation Route> In the present invention, the transport path refers to the path along which the contacted member supplied from the contacted member supply means is transported until it is recovered by the contacted member recovery means. Preferably, the length of the contacted member in the transport direction is longer than the length of the transport path.

[0121] Here, one embodiment of the printing apparatus according to the present invention will be described with reference to Figures 1 and 2. However, the applications of the printing apparatus according to the present invention are not limited in any way to these embodiments. In addition, the same reference numerals are used for identical components in each drawing, and redundant explanations may be omitted. Furthermore, the number, position, shape, etc. of the components described below are not limited to this embodiment, and can be set to a number, position, shape, etc. that is preferable for carrying out the present invention.

[0122] Figure 1 is a schematic diagram showing an example of a printing apparatus using continuous paper. Figure 2 is a schematic diagram showing that the contacted member is in contact with the contacting member. The printing apparatus 100 shown in Figure 1 includes a means for supplying the contact material 1, a means for applying the liquid composition 2, a heating element 3, a contact element 4, and a means for recovering the contact material 6. The printing apparatus 100 includes a drying apparatus 50, but the drying apparatus 50 may be an integrated apparatus with the printing apparatus 100, or it may be a separate, independent apparatus.

[0123] -Contacted member supply means- The contact member supply means 1 is driven to rotate and supply the contact member 7, which is wound into a roll and stored, to the transport path 8 within the printing device 100. The transport direction of the contact member 7 in the transport path 8 is indicated by arrow D. The contacted member supply means 1 transports the contacted member 7 at a high speed of 50 m / min or more by adjusting the rotational drive.

[0124] The contacted member 7 is a sheet-like object to be transported that is continuous in the transport direction D of the printing device 100, and specifically a recording medium such as continuous paper. The contacted member 7 is transported along a transport path 8 between the contacted member supply means 1 and the contacted member retrieval means 6. Furthermore, the length of the contacted member 7 in the transport direction D is at least longer than the length of the transport path 8 for the contacted member 7 provided between the contacted member supply means 1 and the contacted member retrieval means 6. In this embodiment, the printing device 100 uses a contacted member 7 that is continuous in the transport direction D of the printing device 100, and transports the contacted member 7 at high speed, so a large tension is applied to the contacted member 7 between the contacted member supply means 1 and the contacted member retrieval means 6.

[0125] -Method for imparting liquid composition- The liquid composition dispensing means 2 is an inkjet ejection head having multiple nozzle rows in which multiple nozzles are arranged, and the direction of ink ejection from the nozzles is set to face the transport path 8 of the contact member 7. As a result, the liquid composition dispensing means 2 sequentially ejects magenta (M), cyan (C), yellow (Y), and black (K) inks as a liquid composition to the contact member 7. Note that the colors of the ejected inks are not limited to these, and may also be white, gray, silver, gold, green, blue, orange, violet, or other colors. In this embodiment, the case where the liquid composition is ink was described as an example, but as mentioned above, other liquid compositions may also be used. Furthermore, in this embodiment, as an example, a case in which the liquid composition is applied to the contacted member 7 by an inkjet ejection head has been described, but as mentioned above, it may be applied by other means.

[0126] -Heating component- The heating element 3 heats and dries the liquid composition applied to the contacted member 7 from the back side of the surface of the contacted member 7 that has the applied liquid composition. The means for heating the liquid composition are not particularly limited, but various known means can be used, such as blowing hot air or drying the back surface of the contacted member 7 by bringing it into contact with a flat heater or the like.

[0127] Furthermore, the heating element 3 is provided near the contact element 4, which will be described later. As a result, when the printing device 100 is in use, the surface temperature of the contact element 4 may become high (for example, 70°C to 260°C). When a contact element with fluororesin particles attached is used in an environment where the surface temperature of the contact element is high, the fluororesin particles generally soften and become more likely to detach from the surface of the contact element. However, with the configuration of this embodiment, as described above, the detachment of fluororesin particles is suppressed, and a significant effect can be obtained in suppressing the transfer of components derived from the liquid composition from the contacted element to the contact element.

[0128] In this application, "heating means" and "heating member" are clearly distinguished terms. As described above, the heating means is a means of applying heat to the contacted member via the surface layer (A), and is provided as one of the means of constituting the contact member. On the other hand, the heating element is a component that is incorporated into the drying or printing apparatus as a separate component from the contact element.

[0129] -Contact member- The contact member 4 is a cylindrical or cylindrical roller that conveys the member to be contacted 7 while changing the conveying direction D of the member to be contacted 7.

[0130] As described above, in the printing apparatus 100 of this embodiment, the contacted member supply means 1 transports the contacted member 7 at a speed of 50 m / min or more. When transporting at such high speed, as shown in Figure 1, when the transport direction of the contacted member 7 is changed by the contact member 4, a large pressure is applied between the contact member 4 and the contacted member 7. This causes an increase in friction in the contact member 4 due to the application of pressure, but with the configuration of this embodiment, as described above, the shape of the surface layer (A) is maintained (in other words, the root mean square height Sq of the surface layer (A) is maintained at 1.0 μm or more, and the orthogonal line roughness ratio of the surface layer (A) is maintained at 0.7 or more), and the transfer of components derived from the liquid composition from the contacted member to the contact member can be suppressed for a long period of time.

[0131] As described above, the printing apparatus 100 of this embodiment transports the contacted member 7 that is continuous in the transport direction D of the printing apparatus 100, so a large tension is applied to the contacted member 7 between the contacted member supply means 1 and the contacted member retrieval means 6. In such a case, as shown in Figure 2, when the transport direction of the contacted member 7, which is subjected to a large tension, is changed by the contact member 4, a large pressure is applied between the contact member 4 and the contacted member 7. Therefore, an increase in friction occurs in the contact member 4 due to the application of pressure. However, with the configuration of this embodiment, as described above, the shape of the surface layer (A) is maintained (in other words, the root mean square height Sq of the surface layer (A) is maintained at 1.0 μm or more, and the orthogonal line roughness ratio of the surface layer (A) is maintained at 0.7 or more), and the transfer of components derived from the liquid composition from the contacted member to the contact member can be suppressed for a long period of time.

[0132] Furthermore, if the contact member 4 is a roller-shaped conveying roller, as shown in Figure 1, the conveying direction of the contacted member 7 is changed when the contacted member 7 wraps around the conveying roller. In this case, the winding ratio of the contacted member 7 around the conveying roller is preferably 10% or more, more preferably 15% or more, and even more preferably 20% or more. When the winding ratio of the contacted member 7 with respect to the conveyor roller is 10% or more, the pressure per unit area generated between the conveyor roller and the contacted member 7 decreases, and the friction generated in the conveyor roller is reduced. Furthermore, the winding ratio of the contacted member 7 with respect to the conveying roller is preferably 90% or less, more preferably 70% or less, and even more preferably 50% or less. By having a winding ratio of the contacted member 7 with respect to the conveying roller of 90% or less, the contacted member 7 can be conveyed effectively.

[0133] The "winding ratio" in this embodiment will be explained using Figure 2. As shown in Figure 2, when the contacted member 7 is in contact with the roller-shaped contact member 4 by being wrapped around it, the "winding ratio" is the ratio of the circumference X of the contact member 4 between 9a and 9b on the side where the contacted member 7 and the contact member 4 are in contact, when one end of the contacted member that separates from the contact member is 9a and the other end is 9b, to the total circumference of the contact member 4.

[0134] Furthermore, the contact member 4 shown in Figure 2 does not have a heating means for applying heat to the contacted member 7 via the surface layer (A), but it may have one. If the contact member 4 has a heating means, the surface temperature of the contact member may become high (for example, 70°C to 260°C) when the printing device 100 is in use. In such an environment where the surface temperature of the contact member is high, when a contact member with fluororesin particles attached is used, the fluororesin particles generally soften and become more likely to detach from the surface of the contact member. However, with the configuration of this embodiment, as described above, the detachment of fluororesin particles is suppressed, and a significant effect can be obtained in suppressing the transfer of components derived from the liquid composition from the contacted member to the contact member.

[0135] -Method for recovering contacted component- The contacted member retrieval means 6 rotates to wind up the contacted member 7, on which an image has been formed by applying the liquid composition, and stores it in a roll shape.

[0136] (Printing method) The printing method of the present invention comprises a liquid composition application step and a contact step, and may optionally include a drying step and other steps.

[0137] <Liquid composition application process> In the present invention, the liquid composition application step refers to the step of applying a liquid composition to a member to be contacted. The liquid composition application step can be carried out by the liquid composition application means.

[0138] <Contact process> In the present invention, the contact step refers to a step in which the contact member and the non-contact member to which the liquid composition has been applied come into contact. The contact step may also be a conveying step in which the contact member conveys the contacted member by bringing into contact the surface of the contacted member to which the liquid composition has been applied.

[0139] <Drying process> The drying step according to the present invention refers to a step in which, after the liquid composition application step, the applied liquid composition is dried by heating it using a heating member. If the heating means is incorporated in the contact member, the drying may be performed by the contact member.

[0140] Here, an embodiment of the printing method according to the present invention will be described with reference to Figures 1 and 2. However, the applications of the printing method of the present invention are not limited in any way to these embodiments. In addition, the same reference numerals are used for identical components in each drawing, and redundant explanations may be omitted. Furthermore, the number, position, shape, etc. of the components described below are not limited to this embodiment, and can be set to a number, position, shape, etc. that is preferable for carrying out the present invention.

[0141] -Liquid composition application process- The liquid composition application step is a step of applying a liquid composition such as ink to the contact member 7 supplied from the contact member supply means 1. As a result, a region on the contact member 7 to which the liquid composition has been applied is formed.

[0142] -Drying process- The drying process involves drying the applied liquid composition by heating it using the heating element 3 after the liquid composition application process. It is preferable to dry the liquid composition to the extent that the contacted member 7 no longer feels sticky. As mentioned above, if a heating means is incorporated into the contact member 4, the drying process may be performed by the contact member.

[0143] -Conveying Process- In this embodiment, a conveying process will be described as an example of a contact process. The conveying process is a process in which the contacted member 7 is conveyed by contacting the contacted member 7 with the contacting member 4 after the drying process. The conveying process may be performed either before or after the liquid composition application process. Furthermore, it is preferable that the contacting member 4 contacts the surface of the contacted member 7 to which the liquid composition has been applied. [Examples]

[0144] The following describes embodiments of the present invention, but the present invention is not limited in any way to these embodiments.

[0145] <Example of preparation of self-dispersing black pigment dispersion> Carbon black (NIPEX160, manufactured by degussa, BET specific surface area 150m²) 2 20g of the compound represented by the following structural formula (1), with an average primary particle size of 20nm, pH 4.0, and DBP oil absorption of 620g / 100g, along with 20 mmol of this compound and 200 mL of ion-exchanged high-purity water, were mixed at room temperature using a Silverson mixer (6,000 rpm). If the pH of the resulting slurry was higher than 4, 20 mmol of nitric acid was added. After stirring for 30 minutes, 20 mmol of sodium nitrite dissolved in a small amount of ion-exchanged high-purity water was slowly added to the mixture. Furthermore, the mixture was heated to 60°C while stirring and reacted for 1 hour. A modified pigment was produced by adding the compound represented by the following structural formula (1) to carbon black. Next, the pH was adjusted to 10 with an aqueous NaOH solution, and the mixture was stirred for 30 minutes to obtain a modified pigment dispersion. The dispersion, which contained a pigment bonded to at least one geminal bisphosphonate group or a sodium geminal bisphosphonate salt, was subjected to ultrafiltration using a dialysis membrane with ion-exchanged high-purity water, and further ultrasonic dispersion was performed to obtain a self-dispersing black pigment dispersion having bisphosphonate groups as hydrophilic functional groups with a pigment solid content of 16% by mass.

[0146] [ka]

[0147] <Examples of liquid composition (ink) preparation> A mixture of 50.00% by mass of a self-dispersing black pigment dispersion (pigment solids concentration 16%), 2.22% by mass of polyethylene wax AQUACER531 (non-volatile content 45% by mass, manufactured by BIC Chemie Japan), 30.00% by mass of 3-ethyl-3-hydroxymethyl oxetane, 10.0% by mass of propylene glycol monopropyl ether, 2.00% by mass of a silicone-based surfactant (TEGO Wet 270, manufactured by Tomoe Engineering Co., Ltd.), and deionized water (remaining amount) was mixed and stirred for 1 hour. The mixture was then filtered through a membrane filter with an average pore size of 1.2 μm to obtain a liquid composition (ink).

[0148] <Examples of contact component manufacturing> (Example 1) A hollow aluminum roller substrate (A5052, manufactured by Misumi Corporation) with a diameter of 80 mm was subjected to blasting by spraying a polygonal alumina blasting agent with a grit of 60 and a central particle size of 256 μm at 0.3 MPa. Next, the substrate was subjected to anodizing treatment in a sulfuric acid aqueous solution (sulfuric acid anodizing treatment). More specifically, electrodes were attached to the ends of the hollow roller substrate, and it was immersed in a 15 wt% sulfuric acid aqueous solution adjusted to 0°C, with a metal rod as the anode at 1.0 A / dm 2Electrolytic treatment was performed for 1 hour at a current density to precipitate a sulfuric acid anodized film (a layer containing aluminum oxide and in which sulfur components can be detected), forming a support layer with an average thickness of 29.5 μm. The surface was thoroughly washed with pure water, and after being immersed in PTFE dispersion (Fluon, manufactured by AGC Inc.) prepared to a solid content concentration of 10%, it was air-dried once. After air-drying, the hollow roller was rotated at a speed of 10 rpm, and polished once by pressing fluororesin fibers (Tommy Firec, manufactured by Tomoegawa Paper Co., Ltd.) against it and wiping it off. The hollow roller thus obtained was integrated with a halogen lamp to form the contact member of Example 1.

[0149] (Examples 2-14) In Example 1, contact members for Examples 2 to 14 were obtained in the same manner as in Example 1, except that the various conditions in the blasting process and the presence or absence of the fluororesin particle adhesion step were changed as shown in Tables 1 to 3 below.

[0150] (Comparative Example 1) In Comparative Example 1, the contact member was obtained in the same manner as in Example 1, except that blast processing was not performed.

[0151] (Comparative Examples 2-3) In Example 1, contact members of Comparative Examples 2 and 3 were obtained in the same manner as in Example 1, except that instead of blasting, irregularities were formed in the direction of substrate transport using a lathe. Comparative Example 2 was machined on a lathe so that the surface appeared to be substantially smooth, while Comparative Example 3 was machined on a lathe so that streaky irregularities on the surface were visible.

[0152] (Comparative Example 4) The contact member of Comparative Example 4 was obtained in the same manner as in Example 1, except that the anodizing treatment in an aqueous sulfuric acid solution (sulfuric acid anodizing treatment) was not performed.

[0153] Next, for the contact members of Examples 1 to 14 and Comparative Examples 1 to 4, the ratio of the area in contact between the surface layer (A) and the contacted member to the area of ​​the surface layer (A) (contact area ratio), the root mean square height Sq of the surface layer (A), the orthogonal line roughness ratio of the surface layer (A), the amount of fluorine element in the surface layer (A), the average thickness of the support layer, and the Vickers hardness of the contact member were determined according to the following methods, and the results are shown in Tables 1 to 3 below. For reference, images showing the height of the surface layer (A) in Example 1 (see Figure 3), the height of the surface layer (A) in Comparative Example 2 (see Figure 4), the height profile in the cross-section of the surface layer (A) in Example 1 (see Figure 5), and the height profile in the cross-section of the surface layer (A) in Comparative Example 1 (see Figure 6) are included. However, the straight lines in Figures 5 and 6 represent planes parallel to the surface layer (A) from the maximum height (the outermost surface of the surface layer (A)) to a depth of 5 μm.

[0154] [Method for measuring contact area ratio] First, the surface layer (A) was observed at 20x magnification using a laser microscope (Olympus LEXT OLS4000) to obtain a height profile. Next, the contact area, which is the cross-sectional area formed when the surface layer (A) is cut from the maximum height (the outermost surface of the surface layer (A)) at a depth of 5 μm, was obtained. Subsequently, the contact area ratio was obtained by calculating the ratio of the contact area to the observed area (contact area / observed area).

[0155] [Method for measuring root mean square height (Sq)] The surface layer (A) was observed at 20x magnification using a laser microscope (Olympus LEXT OLS4000) and calculated according to JIS B0601:2013.

[0156] [Method for measuring the orthogonal line roughness ratio] First, an arbitrary point on the surface layer (A) was set as the measurement center point, and the linear roughness of the surface layer (A) in an arbitrary direction from the measurement center point was measured using a laser microscope (LEXT OLS4000, Olympus) at a magnification of 20x and a measurement length of 260 μm. Next, the linear roughness in the measurement direction in which the linear roughness was minimized, and the linear roughness in the direction perpendicular to the measurement direction in which the linear roughness was minimized were obtained. Furthermore, new measurement center points were set at 100 μm intervals in a certain direction from the above measurement center point, and the linear roughness in the measurement direction in which the linear roughness was minimized, and the linear roughness in the direction perpendicular to the measurement direction in which the linear roughness was minimized were obtained in the same manner as the measurements at the above measurement center points. A total of five measurements were performed at the measurement center points, and Ra(Min.), which is the average of the linear roughness in the measurement direction in which the linear roughness was minimized, and Ra(90°), which is the average of the linear roughness in the direction perpendicular to the measurement direction in which the linear roughness was minimized, were obtained. Subsequently, the orthogonal line roughness ratio was obtained by calculating the ratio of Ra(Min.) to Ra(90°) [Ra(Min.) / Ra(90°)].

[0157] [Method for measuring the amount of fluorine element] Spectrum analysis was performed on the surface layer (A) under the following conditions, and the amount of fluorine was determined by automatic quantification using analysis software. The same procedure was performed at five arbitrary locations, and the average value of the obtained values ​​was adopted as the amount of fluorine. • Equipment: Carl Zeiss Merlin scanning electron microscope • EDS detector: UltraDry, an electronically cooled SDD detector manufactured by Thermo Fisher Scientific. • Acceleration voltage: 3.0kV WD: 13.0mm ·Take-out angle: 35.0deg. ·Magnification: 2000x • Conductive treatment: C-coat • Cumulative time: 10 seconds. • Total number of times: 100 • Drift correction: Yes • Analysis software: NORAN System 6, manufactured by Thermo Fisher Scientific.

[0158] [Method for measuring average thickness] First, the sulfur, aluminum, and oxygen components were mapped in the cross-section of the contact member using EDS elemental analysis (Thermo Fisher Scientific, UltraDry). Next, the region where all three components were detected was identified as the support layer, and the length of the perpendicular line drawn from the surface of the support layer towards the substrate was determined within the support layer. Similarly, the length of the perpendicular line within the support layer was determined at 10 arbitrary locations, and the average value of these lengths was taken as the average thickness of the support layer.

[0159] [Method for measuring Vickers hardness] Measurements were taken in accordance with the test method of JIS Z 2244.

[0160] Next, the degree to which components derived from the liquid composition were transferred from the contacted member to the contact members of Examples 1 to 14 and Comparative Examples 1 to 4 (hereinafter sometimes referred to as "transferability") was evaluated using the contact members in their initial state and after the durability test, according to the method described below. Furthermore, the shape (area and aspect ratio) of the transfer area and the heat transfer properties of the contact material were evaluated according to the following method.

[0161] [Evaluation of transferability (initial state)] A modified printing device was created by incorporating the contact members of Examples 1-14 and Comparative Examples 1-4 into an inkjet printing system (RICOH Pro VC60000, manufactured by Ricoh Co., Ltd.). The inkjet head, which is the liquid composition application means, applied the liquid composition (ink) to the recording medium (Magno Satin 300gsm, manufactured by Sappi, a low-penetration recording medium), which is the contacted material, at an ink application rate of 0.9 μL / cm². 2 The material was extruded in this manner to form a solid image. Next, a drying process was carried out in which a drying roller with a surface temperature of 120°C was brought into contact with the surface of the contacted member that was not coated with the liquid composition, thereby drying the liquid composition while transporting the contacted member. At this time, the drying energy (°C·sec.) is defined as the value calculated by the following formula: "(temperature of the contacted member during the drying process - temperature of the contacted member before the drying process) (°C) × contact time between the contacted member and the drying roller (sec.)". Next, the contact member, whose surface layer (A) temperature was raised to 120°C by the incorporated heating means (halogen lamp), was brought into contact with the surface of the member to be contacted, to which the liquid composition had been applied, 10 times under the condition that each contact time was 0.2 seconds. The above series of steps was performed while changing the contact time (sec.) between the contacted member and the drying roller by adjusting the transport speed of the contacted member. The drying energy required to eliminate the transfer of components derived from the liquid composition from the contacted member to the contacting member was determined and evaluated according to the following evaluation criteria. The evaluation results are shown in Tables 1 to 3. (Evaluation Criteria) A: Required drying energy is less than 20°C·sec. B: Required drying energy is 20°C·sec. or more and less than 35°C·sec. C: Required drying energy is 35°C·sec. or higher and less than 50°C·sec. D: Required drying energy is 50°C·sec. or higher.

[0162] [Evaluation of transferability (after durability test)] A modified printing device was created by incorporating the contact members of Examples 1-14 and Comparative Examples 1-4 into an inkjet printing system (RICOH Pro VC60000, manufactured by Ricoh Co., Ltd.). In this device, a motor was installed as the drive source for the contact members, and the contact members were configured to rotate independently of the transport mechanism of the printing device. Next, a durability test was conducted to test the wear between the contact members and non-contact members by rotating the contact members at 500 rpm for 18 hours in the same direction as the transport while transporting the recording medium (Lumi Art Gloss 200gsm, manufactured by Stora Enso) with a tension of 40 N and 1 mpm. Using the contact members after the durability test, the drying energy required to eliminate the transfer of components derived from the liquid composition from the contacted member to the contacting member was determined using the same method as in the [Evaluation of Transferability (Initial State)] described above, and evaluated using the same evaluation criteria. The evaluation results are shown in Tables 1-3.

[0163] [Evaluation of the shape of the transfer area] In the above [evaluation of transferability (initial state)], transfer was intentionally induced by setting the drying energy to 9.2°C·sec. Next, the images with white spots due to transfer were observed at 20x magnification using a laser microscope (Olympus LEXT OLS4000). The obtained observed images were then binarized using the MaxEntropy algorithm and particle analysis was performed on analysis software (National Institutes of Health ImageJ) to calculate the average area and aspect ratio per white spot, and evaluated according to the following criteria. The evaluation results are shown in Tables 1-3. (Evaluation criteria regarding the area of ​​white space) A: 1000 μm 2 less than B: 1000 μm 2 More than 5000μm 2 less than C: 5000 μm 2 More than 10000μm 2 less than D: 10000 μm 2 That's all. (Evaluation criteria regarding aspect ratio of white areas) A: 0.8 or higher B: 0.7 or higher, less than 0.8 C: 0.6 or higher, less than 0.7 D: Less than 0.6

[0164] For reference, images showing the shape of the transfer area when using the contact member of Example 1 (see Figure 7) and images showing the shape of the transfer area when using the contact member of Comparative Example 1 (see Figure 8) are included.

[0165] [Evaluation of heat transfer properties] The surface temperature of the contact members in Examples 1-14 and Comparative Examples 1-4 was heated to 140°C, and the paper surface temperature was measured using an infrared thermometer after contact with the contacted member (Lumi Art Gloss 200gsm, manufactured by Stora Enso) for 0.4 seconds, and evaluated according to the following criteria. More specifically, the paper surface temperature at a position 12 mm from the start of the nip was measured using an infrared thermometer when the contacted member was transported at 30 mm / s. The evaluation results are shown in Tables 1-3. (Evaluation Criteria) A: 79℃ or higher B: 75℃ or higher and less than 79℃ C: 70°C to less than 75°C D: Below 70℃

[0166] [Table 1]

[0167] [Table 2]

[0168] [Table 3]

[0169] Examples of the present invention are as follows: <1> A contact member that comes into contact with a member to be contacted to which a liquid composition has been applied, wherein the contact member has a surface layer (A) that comes into contact with the member to be contacted, the surface layer (A) has a support layer containing sulfuric acid anodized aluminum, the root mean square height Sq of the surface layer (A) is 1.0 μm or more, and the orthogonal line roughness ratio of the surface layer (A) is 0.7 or more. <2> The root mean square height Sq of the surface layer (A) is 10.0 μm or less. <1> This is the contact member described in [reference]. <3> The ratio of the area of ​​the surface layer (A) to the area of ​​the contacted member is 10% or more and 90% or less. <1> from <2> It is a contact member as described in any of the above. <4> The surface layer (A) has fluororesin particles attached to the support layer. <1> from <3> It is a contact member as described in any of the above. <5> The amount of fluorine in the surface layer (A) is 5.0 atm% or more. <1> from <4> It is a contact member as described in any of the above. <6> The Vickers hardness of the contact member is 400 Hv or more and 500 Hv or less. <1> from <5> It is a contact member as described in any of the above. <7> The average thickness of the support layer is 20 μm or more and 40 μm or less. <1> from <6> It is a contact member as described in any of the above. <8> The contact member comprises a base material and the surface layer (A) provided on the base material, and the base material contains aluminum. <1> from <7> It is a contact member as described in any of the above. <9> The roller shape has a diameter of 50 mm or more and 600 mm or less. <1> from <8> It is a contact member as described in any of the above. <10> The contact member has a heating means for applying heat to the contacted member via the surface layer (A). <1> from <9> It is a contact member as described in any of the above. <11> The temperature of the surface layer (A) is 70°C or higher and 260°C or lower. <1> from <10> It is a contact member as described in any of the above. <12> The contacted member is a recording medium. <1> from <11> It is a contact member as described in any of the above. <13> <1> from <12> A drying apparatus having a contact member as described in any of the above, characterized in that it dries a contact member to which a liquid composition has been applied. <14> A liquid composition application means for applying a liquid composition to a member to be contacted, <1> from <12> A printing apparatus characterized by having a contact member as described in any of the above. <15> The system comprises a contact member supply means for supplying the contact member, a contact member retrieval means for retrieving the contact member, and a transport path which is the path through which the contact member supplied from the contact member supply means is transported until it is retrieved by the contact member retrieval means, wherein the length of the contact member in the transport direction is longer than the length of the transport path. <14> This is the printing device described in [reference]. <16> The transport speed of the contacted member is 50 m / min or more. <14> from <15> It is a printing device as described in any of the following. <17> A liquid composition application step in which a liquid composition is applied to a member to be contacted, and <1> from <12> The printing method is characterized by having a contact step in which a contact member described in any of the above comes into contact with the contacted member to which the liquid composition has been applied.

[0170] The aforementioned <1> From the above <12> Contact member as described in any of the above, <13> The drying apparatus described above, <14> From the above <16> The printing apparatus described above, <17> The printing method described herein can solve the problems of the past and achieve the objectives of the present invention. [Explanation of Symbols]

[0171] 1 Contacted member supply means 2. Means for imparting liquid composition 3. Heating element 4 Contact members 6. Means for recovering the contacted member 7 Contacted member 8. Transport Route 9a End portion of the contacted member that separates from the contacting member 9b End portion of the contacted member that separates from the contacting member 50 Drying equipment 100 Printing equipment [Prior art documents] [Patent Documents]

[0172] [Patent Document 1] Patent No. 6641990 [Patent Document 2] Special Announcement No. 9-114294

Claims

1. A contact member that comes into contact with a contact member to which a liquid composition has been applied, The contact member has a surface layer (A) that contacts the member to be contacted, The surface layer (A) has a support layer containing sulfuric acid anodized aluminum, The root mean square height Sq of the surface layer (A) is 4.75 μm or more and 10.0 μm or less. The orthogonal line roughness ratio in the surface layer (A) is 0.74 or more and 0.82 or less. The amount of fluorine in the surface layer (A) is 5.0 atm% or more. The ratio of the area of ​​the surface layer (A) to the area of ​​the contacted member is 16.0% or more and 34.0% or less. A contact member characterized in that the average thickness of the support layer is 20 μm or more and 31 μm or less.

2. The contact member according to claim 1, wherein the surface layer (A) has fluororesin particles attached to the support layer.

3. The contact member according to any one of claims 1 to 2, wherein the Vickers hardness of the contact member is 400 Hv or more and 500 Hv or less.

4. The contact member has a base material and the surface layer (A) provided on the base material, The contact member according to any one of claims 1 to 3, wherein the base material contains aluminum.

5. A contact member according to any one of claims 1 to 4, wherein the contact member has a roller shape with a diameter of 50 mm or more and 600 mm or less.

6. The contact member according to any one of claims 1 to 5, wherein the contact member has a heating means for applying heat to the contacted member via the surface layer (A).

7. The contact member according to any one of claims 1 to 6, wherein the temperature of the surface layer (A) is 70°C or higher and 260°C or lower.

8. The contact member according to any one of claims 1 to 7, wherein the contacted member is a recording medium.

9. A drying apparatus having a contact member according to any one of claims 1 to 8, characterized in that it dries a contact member to which a liquid composition has been applied.

10. A liquid composition application means for applying a liquid composition to a member to be contacted, A printing apparatus characterized by having a contact member according to any one of claims 1 to 8.

11. A means for supplying the member to be contacted, A means for recovering the contacted member, The system includes a transport path which is the path through which the contacted member supplied from the contacted member supply means is transported until it is collected by the contacted member collection means. The printing apparatus according to claim 10, wherein the length of the contacted member in the transport direction is longer than the length of the transport path.

12. The printing apparatus according to any one of claims 10 to 11, wherein the transport speed of the contacted member is 50 m / min or more.

13. A liquid composition application step in which a liquid composition is applied to a member to be contacted, and A printing method characterized by having a contact step in which a contact member according to any one of claims 1 to 8 comes into contact with the contacted member to which the liquid composition has been applied.

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