Inkjet treatment liquid, inkjet printing device and inkjet printing method

Abstract

The inkjet treatment liquid includes: emulsified particles containing silicone oil; and an aqueous medium, wherein the average particle diameter of the emulsified particles is 100 nm or more and 250 nm or less.

Description

Technical Field

[0001] The present invention relates to an inkjet processing liquid, an inkjet printing device and an inkjet printing method. Background Art

[0002] In the inkjet printing method, for example, an ink containing a pigment is used. In order to improve the color fastness to rubbing of a printed object (hereinafter sometimes referred to as a printed object) on which an image is formed, an ink containing a pigment is sometimes used together with a post-treatment liquid.

[0003] On the other hand, conventionally, a transport roller for inkjet recording apparatuses is known (for example, see Patent Document 1). In the transport roller described in Patent Document 1, a treatment liquid containing one or both of fullerene and a fullerene derivative is applied to the surface of the transport roller.

[0004] Prior art literature

[0005] Patent Literature

[0006] Patent Document 1: Japanese Patent Publication No. 2013-75524 Summary of the invention

[0007] An inkjet treatment liquid according to a first aspect of the present invention includes: emulsified particles containing silicone oil; and an aqueous medium, wherein the average particle size of the emulsified particles is 100 nm or more and 250 nm or less. BRIEF DESCRIPTION OF THE DRAWINGS

[0008] Figure 1 It is a side view showing an example of an inkjet printing apparatus according to a second embodiment of the present invention. DETAILED DESCRIPTION

[0009] In recent years, in inkjet printing technology, it is required to further improve the color fastness to rubbing of printed materials. It can be inferred that the color fastness to rubbing of printed materials varies depending on the concentration and type of silicone oil contained in the treatment liquid, the amount of treatment liquid ejected, etc. For example, in the case where the amount of treatment liquid ejected is small, it can be inferred that if the concentration of silicone oil is too low, the color fastness to rubbing of printed materials may be affected. Therefore, from the perspective of adjusting the concentration of silicone oil and selecting its type, it is advisable to understand the conditions for the characteristics of the inkjet treatment liquid that can produce printed materials with excellent color fastness to rubbing.

[0010] Here, it can be inferred that the color fastness to rubbing of the printed matter also changes depending on the average particle size of the emulsified particles contained in the silicone oil in the treatment liquid. For example, it can be inferred that when the average particle size of the emulsified particles is small, the color fastness to rubbing of the printed matter may be affected. Therefore, from the perspective of the average particle size of the emulsified particles in the treatment liquid, it is advisable to understand the conditions of the characteristics of the inkjet treatment liquid that can produce printed matter with excellent color fastness to rubbing.

[0011] In addition, when the average particle size of the emulsified particles in the treatment liquid is large, the meniscus becomes unstable when the treatment liquid is ejected from the treatment head of the inkjet printing device, and the ejection property sometimes deteriorates. Therefore, it is also required that the inkjet treatment liquid has excellent ejection property from the treatment head. In addition, it is more preferred if the inkjet treatment liquid can also suppress the deterioration of the touch of the printed object.

[0012] The inkjet treatment liquid of the present invention can suppress the deterioration of the touch of printed materials, can produce printed materials with excellent color fastness to rubbing, and has excellent discharge properties from the treatment head of an inkjet printing device.

[0013] The following describes the embodiments of the present invention. In addition, in this specification, unless otherwise specified, the volume median particle size (D 50 ) is a decimal particle size measured using a laser diffraction / scattering particle size distribution measuring device ("LA-950" manufactured by Horiba, Ltd.). 50 ". Unless otherwise specified, the "main component" of a material refers to the component with the largest content in the material based on mass. Unless otherwise specified, the "specific gravity" refers to the specific gravity at 25°C. Acrylic acid and methacrylic acid are sometimes collectively referred to as "(meth)acrylic acid". Each component described in this specification may be used alone or in combination of two or more.

[0014] [First embodiment: inkjet treatment liquid]

[0015] Next, the inkjet treatment liquid (hereinafter also referred to as the treatment liquid) according to the first embodiment of the present invention is described. The treatment liquid according to the first embodiment contains emulsified particles and an aqueous medium. The emulsified particles are dispersed in the aqueous medium of the treatment liquid. That is, the treatment liquid according to the first embodiment is an emulsion, more specifically, an oil-in-water (O / W) emulsion.

[0016] The treatment liquid involved in the first embodiment is suitable for use in, for example, an inkjet printing device and an inkjet printing method described later. The treatment liquid involved in the first embodiment is, for example, a treatment liquid for post-processing. Specifically, after an image is formed in an image forming area of ​​a printing object using ink, the treatment liquid involved in the first embodiment is used to post-process the image forming area.

[0017] <Emulsified particles>

[0018] The emulsified particles contained in the treatment liquid contain silicone oil. The silicone oil preferably contains at least ionic group-containing silicone oil. By containing ionic group-containing silicone oil, it is possible to produce printed materials with better wet friction color fastness. The silicone oil may also be silicone oil other than ionic group-containing silicone oil (hereinafter sometimes recorded as other silicone oil). Alternatively, the silicone oil may also contain both ionic group-containing silicone oil and other silicone oil. In this case, it may also be that one emulsified particle contains both ionic group-containing silicone oil and other silicone oil. Alternatively, it may also be that the emulsified particles contained in the treatment liquid are more than two kinds, for example, the first emulsified particle contains ionic group-containing silicone oil, and the second emulsified particle contains other silicone oil. By making the emulsified particles contain silicone oil, especially at least ionic group-containing silicone oil, the following first to fourth advantages are obtained.

[0019] The first advantage is explained. Silicone oil has the effect of reducing friction. By post-treating the printed object with a treatment liquid, the image formed on the printed object is coated with silicone oil, and the friction coefficient of the surface of the printed object is reduced. As a result, even if the image formed on the printed object is rubbed, it is difficult to fade, and a printed object with excellent color fastness to dry friction and color fastness to wet friction can be produced. In addition, by being coated with silicone oil that has the effect of reducing friction, the friction between the yarns of the printed object is reduced. As a result, the hardening of the printed object caused by image formation is alleviated, and the deterioration of the touch of the printed object is suppressed.

[0020] The second advantage is explained. Silicone oil has water resistance. By post-treating the printed object with a treatment liquid, the printed object is coated with water-resistant silicone oil, and the surface of the printed object is given water resistance. As a result, even if the image formed on the printed object is rubbed in a wet state, it is difficult to fade, and a printed object with excellent wet rubbing color fastness can be produced.

[0021] The third advantage is explained. It can be inferred that, especially in the case of containing at least ionic group-containing silicone oil, since the ionic group-containing silicone oil has ionic groups, ionic bonds are formed between the ionic groups and the printing object, and between the ionic groups and the ink ejected onto the printing object. By forming ionic bonds, the ionic group-containing silicone oil is difficult to be washed away from the printing object and the ink by water. As a result, a printed object with better wet rubbing color fastness can be produced.

[0022] The fourth advantage is described. In particular, in the case of containing at least ionic group-containing silicone oil, since the ionic group-containing silicone oil has ionic groups, the emulsified particles containing the ionic group-containing silicone oil are appropriately dispersed in the aqueous medium of the treatment liquid. Such a treatment liquid can be more appropriately ejected from the treatment head of the inkjet printing device. When the treatment liquid is ejected from the treatment head, the amount of treatment liquid used is reduced compared to the case where the printed material is immersed in the treatment liquid. Therefore, it is difficult for the printed object to become hard, and the deterioration of the touch of the printed material is further suppressed. In addition, when the treatment liquid is ejected from the treatment head, silicone oil with high viscosity can be used compared to the case where ink containing silicone oil as a base oil is ejected from the recording head. Therefore, a printed material with better color fastness to friction can be produced. The first to fourth advantages are described above.

[0023] The content percentage of silicone oil in the treatment liquid is preferably 5% by mass or more and 15% by mass or less. By making the content percentage of silicone oil more than 5% by mass, the deterioration of the touch of the printed material is further suppressed, and a printed material with better color fastness to friction can be produced. By making the content percentage of silicone oil less than 15% by mass, the ejection property of the treatment liquid from the processing head of the inkjet printing device can be further improved. In addition, in the case where the silicone oil contains at least ionic group-containing silicone oil, by making the content percentage of silicone oil less than 15% by mass, the excessive increase in the amount of ionic groups of the ionic group-containing silicone oil contained in the silicone oil is suppressed. As a result, it is possible to prevent the surface of the printed object from being difficult to be given appropriate waterproofness, and it is possible to suppress the reduction of the color fastness to friction of the printed material. In particular, if the content percentage of silicone oil is within this concentration range, although it also depends on the type of silicone oil, a printed material with excellent color fastness to friction can be produced.

[0024] The content percentage of the silicone oil in the treatment liquid is preferably 7% by mass or more, more preferably 9% by mass or more, and further preferably 10% by mass or more. In addition, the content percentage of the silicone oil in the treatment liquid is preferably 14% by mass or less, and more preferably 13% by mass or less. In particular, by setting the content percentage of the silicone oil in the treatment liquid to be within the range of 10% by mass or more and 13% by mass or less, a printed article having both better color fastness to dry rubbing and better color fastness to wet rubbing can be produced.

[0025] The content percentage of silicone oil in the treatment liquid refers to the percentage of the mass of silicone oil relative to the mass of the treatment liquid. In the case where the emulsified particles contain two or more silicone oils (for example, ionic group-containing silicone oil and other silicone oils), the content percentage of silicone oil refers to the percentage of the total mass of the two or more silicone oils relative to the mass of the treatment liquid.

[0026] The viscosity of silicone oil is preferably 500 mm 2 / s(mm 2 / sec) or more. If the viscosity of silicone oil is 500mm2 / s or more, the silicone oil is less likely to be separated from the printed material due to friction, and a printed material with better dry friction fastness and wet friction fastness can be produced. In addition, as already mentioned, the treatment liquid involved in the first embodiment has excellent ejection properties from the treatment head of the inkjet printing device. When the treatment liquid is ejected from the treatment head, the amount of treatment liquid used is reduced compared to the case where the printed material is immersed in the treatment liquid. Therefore, even if 500mm is used in the treatment liquid, 2 When the viscosity of the silicone oil is high, the printed object is less likely to become hard, and the deterioration of the touch of the printed object is further suppressed.

[0027] The upper limit of the viscosity of the silicone oil is not particularly limited. For example, the viscosity of the silicone oil is preferably 100,000 mm 2 / s or less, more preferably 6000mm 2 / s or less. The viscosity of silicone oil can be, for example, from 500 mm 2 / s、700mm 2 / s、900mm 2 / s、1000mm 2 / s、1100mm 2 / s、1200mm 2 / s、1500mm 2 / s、1700mm 2 / s、1800mm 2 / s、2000mm 2 / s、3000mm 2 / s、5700mm 2 / s and 6000mm 2 / s is within the range of 2 values ​​selected from the group consisting of.

[0028] The viscosity of silicone oil refers to the kinematic viscosity at 25° C. When the emulsified particles contain two or more silicone oils (for example, ionic group-containing silicone oil and other silicone oil), the viscosity of silicone oil refers to the viscosity of the mixture of the two or more silicone oils.

[0029] The viscosity of silicone oil is measured according to the method described in JIS (Japanese Industrial Standards) Z8803: 2011 (Liquid Viscosity Measurement Method). In addition, for example, the viscosity of silicone oil can be measured by extracting silicone oil from the treatment liquid with toluene, washing and drying, thereby separating silicone oil from the treatment liquid.

[0030] The average particle size of the emulsified particles (dispersed particle size in the aqueous medium) is 100 nm or more and 250 nm or less. By making the average particle size of the emulsified particles 100 nm or more and 250 nm or less, the inkjet processing liquid according to the first embodiment suppresses the deterioration of the touch of the printed material, can produce printed materials with excellent color fastness to friction, and has excellent ejection properties from the processing head of the inkjet printing device.

[0031] Specifically, if the average particle size of the emulsified particles is less than 100 nm, the color fastness to rubbing, especially the color fastness to wet rubbing, of the printed material is significantly reduced. This is believed to be because: if the particle size of the emulsified particles is too small, the specific surface area of ​​the treatment liquid increases, and the hydrophilicity becomes higher and the water resistance becomes lower. On the other hand, if the average particle size of the emulsified particles exceeds 250 nm, the ejection property of the treatment liquid from the treatment head is significantly deteriorated.

[0032] In addition, the average particle size of the emulsified particles is preferably 100 nm or more and 160 nm or less. Alternatively, the average particle size of the emulsified particles may be within a range of two values ​​selected from the group consisting of 100 nm, 105 nm, 110 nm, 115 nm, 120 nm, 125 nm, 130 nm, 135 nm, 140 nm, 145 nm, 150 nm, 155 nm, 160 nm, 170 nm, 180 nm, 190 nm, 200 nm, 210 nm, 220 nm, and 250 nm.

[0033] In the present specification, when the treatment liquid contains two or more emulsion particles having different average particle sizes, basically, "the average particle size of the emulsion particles is within a specific range" means "the average particle size of the two or more emulsion particles (the average particle size of the two or more emulsion particles added together is within a specific range). However, as described above, when the treatment liquid contains two or more emulsion particles having different average particle sizes, the average particle size of each emulsion particle is preferably 100 nm or more and 250 nm or less. In addition, it is more preferred that the difference in the average particle size of each emulsion particle is smaller. For example, when the treatment liquid contains two types of emulsion particles having different average particle sizes, the closer the average particle sizes of the two emulsion particles are, the more preferred. For example, the average particle sizes of the two different emulsion particles are preferably both within the range of 100 nm or more and 160 nm or less.

[0034] More specifically, in the case where the treatment liquid contains first emulsified particles and second emulsified particles having an average particle size different from that of the first emulsified particles, it is preferred that the average particle size of the first emulsified particles is 100 nm or more and 250 nm or less, and the average particle size of the second emulsified particles is 100 nm or more and 250 nm or less. Furthermore, it is more preferred that the average particle size of the first emulsified particles is 100 nm or more and 160 nm or less, and the average particle size of the second emulsified particles is 100 nm or more and 160 nm or less. Furthermore, it is further preferred that the difference between the average particle size of the first emulsified particles and the average particle size of the second emulsified particles is 0 nm or more and 30 nm or less.

[0035] The average particle size of the emulsified particles refers to the harmonic mean particle size calculated based on the scattered light intensity by the cumulant method (also referred to as the cumulant average particle size). The average particle size of the emulsified particles is measured according to the method described in ISO 13321:1996 (Particle size analysis-Photon correlation spectroscopy).

[0036] In addition, the emulsified particles may also contain components other than silicone oil. However, when the emulsified particles contain only silicone oil, it is possible to more reliably produce a printed article with excellent color fastness to rubbing, and it is possible to more reliably suppress the deterioration of the touch of the printed article.

[0037] As mentioned above, the silicone oil contained in the emulsified particles may be any one of the silicone oil containing ionic groups and other silicone oils. Alternatively, the silicone oil may contain both the silicone oil containing ionic groups and other silicone oils. In this case, one emulsified particle may contain both the silicone oil containing ionic groups and other silicone oils. Alternatively, the first emulsified particle may contain the silicone oil containing ionic groups, and the second emulsified particle may contain other silicone oils. The following describes the silicone oil containing ionic groups and other silicone oils.

[0038] (Silicone oil containing ionic groups)

[0039] Ionic group-containing silicone oil is a modified silicone oil, more specifically, an ionic group-modified silicone oil. Examples of the ionic group-modified silicone oil include modified silicone oils in which an ionic group is introduced into a side chain and modified silicone oils in which an ionic group is introduced into a terminal group.

[0040] The modified silicone oil having an ionic group introduced into the side chain has a first terminal group represented by the following formula (1a), a repeating unit represented by the following formula (1b), a repeating unit represented by the following formula (1c), and a second terminal group represented by the following formula (1d).

[0041]

[0042] The * in formula (1a) represents a dangling bond to the silicon atom in the repeating unit represented by formula (1b) or (1c). The * in formula (1d) represents a dangling bond to the oxygen atom in the repeating unit represented by formula (1b) or (1c). R in formula (1c) 1 The ionic group in the group containing an ionic group is preferably an amino group, a carboxyl group, a phenolic hydroxyl group or a silanol group.

[0043] The modified silicone oil having an ionic group introduced into the terminal group has a first terminal group represented by the following formula (2a), a repeating unit represented by the following formula (2b), and a second terminal group represented by the following formula (2c).

[0044]

[0045] The * in formula (2a) represents a dangling bond bonded to the silicon atom in the repeating unit represented by formula (2b). The * in formula (2c) represents a dangling bond bonded to the oxygen atom in the repeating unit represented by formula (2b). 2 And R in formula (2c) 3 Each independently represents a group containing an ionic group. As the ionic group in the group containing an ionic group, an amino group, a carboxyl group, a phenolic hydroxyl group or a silanol group is preferred.

[0046] The ionic group-containing silicone oil preferably contains at least one selected from the group consisting of amino-modified silicone oil, carboxyl-modified silicone oil, phenol-modified silicone oil and silanol-modified silicone oil. In addition, the ionic group-containing silicone oil is more preferably at least one selected from the group consisting of these. In addition, the ionic group-containing silicone oil is more preferably one of these. Amino-modified silicone oil, carboxyl-modified silicone oil, phenol-modified silicone oil and silanol-modified silicone oil each have an amino group, a carboxyl group, a phenolic hydroxyl group and a silanol group as an ionic group. Among these, the ionic group-containing silicone oil is more preferably a carboxyl-modified silicone oil.

[0047] In the case where the silicone oil contains at least ionic group-containing silicone oil, in order to make the emulsified particles more appropriately dispersed in the aqueous medium, the functional group equivalent of the ionic group-containing silicone oil is preferably more than 1000g / mol and less than 5500g / mol. The functional group equivalent is the molecular weight per 1mol of the functional group (ionic group). The functional group equivalent of the ionic group-containing silicone oil can be, for example, in the range of 2 values ​​selected from the group consisting of 1000g / mol, 1200g / mol, 1474g / mol, 1490g / mol, 1500g / mol, 2000g / mol, 3800g / mol, 3900g / mol, 4000g / mol, 5000g / mol, 5200g / mol and 5500g / mol.

[0048] When the silicone oil contains at least ionic group-containing silicone oil, the content percentage of the ionic group-containing silicone oil relative to the total mass of the silicone oil contained in the emulsified particles is preferably 30 mass % or more and 100 mass % or less, more preferably 40 mass % or more and 100 mass % or less, and particularly preferably 100 mass %.

[0049] (Other silicone oils)

[0050] The silicone oil contained in the treatment liquid may be only other silicone oil. Alternatively, by containing other silicone oil in addition to the ionic group-containing silicone oil, the viscosity of the silicone oil can be adjusted. As other silicone oils, for example, unmodified silicone oils can be cited. More specifically, dimethyl polysiloxane can be cited.

[0051] When other silicone oil is contained, the content percentage of other silicone oil relative to the total mass of silicone oil contained in the emulsified particles is preferably 50 mass % or more and 100 mass % or less, more preferably 50 mass % or more and 70 mass % or less, and further preferably 50 mass % or more and 60 mass % or less.

[0052] When the silicone oil contained in the treatment liquid contains both ionic group-containing silicone oil and other silicone oil, the silicone oil is preferably a combination of carboxyl-modified silicone oil and dimethylpolysiloxane. In this case, one emulsified particle may contain both carboxyl-modified silicone oil and dimethylpolysiloxane. Alternatively, the first emulsified particle may contain carboxyl-modified silicone oil, and the second emulsified particle as another emulsified particle may contain dimethylpolysiloxane.

[0053] When the silicone oil contained in the treatment liquid contains both the ionic group-containing silicone oil and other silicone oils, the ratio of the mass of the ionic group-containing silicone oil to the mass of the other silicone oil is preferably 0.5 or more and less than 1.0, more preferably 0.6 or more and 0.7 or less.

[0054] <Aqueous medium>

[0055] The aqueous medium contained in the treatment liquid is a medium with water as the main component. The aqueous medium can act as a solvent or as a dispersion medium. As specific examples of the aqueous medium, water or a mixed solution of water and a polar solvent can be cited. As examples of polar solvents contained in the aqueous medium, methanol, ethanol, isopropanol, butanol and methyl ethyl ketone can be cited. The content percentage of water in the aqueous medium is preferably 90% by mass or more, and particularly preferably 100% by mass. Relative to the mass of the treatment liquid, the content percentage of the aqueous medium is preferably 50% by mass or more and 90% by mass or less, and more preferably 55% by mass or more and 70% by mass or less.

[0056] <Other ingredients>

[0057] The treatment liquid may contain components other than the emulsified particles and the aqueous medium (hereinafter sometimes referred to as other components) as necessary. Examples of the other components include acids, bases, polyols, and dispersants.

[0058] (acid)

[0059] When the silicone oil contains at least an ionic group-containing silicone oil and the ionic group-containing silicone oil has an anionic group, the treatment liquid preferably contains an acid. The acid promotes the ionization of the anionic group, and the emulsified particles containing the ionic group-containing silicone oil are appropriately dispersed in the aqueous medium. As the acid, for example, strong acids and weak acids can be listed. As the strong acid, for example, hydrochloric acid, p-toluenesulfonic acid and sulfuric acid can be listed. As the weak acid, for example, benzoic acid and acetic acid can be listed. In order to promote the ionization of the anionic groups possessed by the silicone oil, a strong acid is preferably used as the acid. Specifically, hydrochloric acid, p-toluenesulfonic acid or sulfuric acid is more preferred. When the treatment liquid contains an acid, the percentage of the acid content converted into an acid amount at a concentration of 1 mol / L relative to the mass of the treatment liquid is preferably greater than 1% by mass and less than 5% by mass.

[0060] (Alkali)

[0061] When the silicone oil contains at least an ionic group-containing silicone oil and the ionic group-containing silicone oil has a cationic group, the treatment liquid preferably contains an alkali. The alkali promotes the ionization of the cationic group, and the emulsified particles containing the ionic group-containing silicone oil are appropriately dispersed in an aqueous medium. As the alkali, for example, sodium hydroxide can be cited. When the treatment liquid contains an alkali, the content percentage of the alkali converted into an alkali amount at a concentration of 1 mol / L relative to the mass of the treatment liquid is preferably 1% by mass or more and 5% by mass or less.

[0062] (Polyol)

[0063] By making the treatment liquid contain a polyol, the viscosity of the treatment liquid is appropriately adjusted. The polyol is preferably a diol or a triol. As the diol, for example, a diol compound can be mentioned. More specifically, ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol and tetraethylene glycol can be mentioned. As the triol, for example, glycerol can be mentioned. When the treatment liquid contains a polyol, the content percentage of the polyol relative to the mass of the treatment liquid is preferably 10 mass % or more and 40 mass % or less, more preferably 15 mass % or more and 35 mass % or less.

[0064] (Dispersant)

[0065] As the dispersant, for example, surfactants, resin dispersants and polysaccharides can be cited. However, it is preferred that the treatment liquid does not contain a dispersant and the emulsified particles are dispersed in the treatment liquid. As mentioned above, emulsified particles containing silicone oil, especially silicone oil containing ionic groups, are more appropriately dispersed in an aqueous medium. Therefore, even in the absence of a dispersant, the dispersed state of the emulsified particles can be appropriately maintained. There are many cases where the dispersant has a hydrophilic group. When the treatment liquid does not contain a dispersant having a hydrophilic group, the wet rubbing color fastness of the printed material treated with the treatment liquid is further improved.

[0066] <Method for producing treatment liquid>

[0067] An example of a method for producing a treatment liquid is described below. Silicone oil, an aqueous medium, and components added as needed (e.g., an acid or a base, and a polyol) are mixed and emulsified using a homogenizer. Thus, emulsified particles containing silicone oil are dispersed in the aqueous medium to obtain a treatment liquid.

[0068] In order to make the emulsification proceed well, a raw material emulsion containing emulsified particles may be prepared in advance, and the raw material emulsion, aqueous medium, and polyol added as needed are mixed to obtain a treatment liquid. The raw material emulsion contains, for example, silicone oil, a portion of the aqueous medium, and an acid or alkali added as needed. When the raw material emulsion is manufactured, the emulsification time is, for example, more than 5 minutes and less than 1 hour. The emulsification temperature is, for example, more than 5°C and less than 40°C. The content percentage of the raw material emulsion relative to the mass of the treatment liquid is, for example, more than 15% by mass and less than 50% by mass.

[0069] In addition, when two or more silicone oils, for example, ionic group-containing silicone oil and unmodified silicone oil, are used as raw materials, the two silicone oils may be mixed and emulsified to prepare emulsified particles containing both ionic group-containing silicone oil and unmodified silicone oil, thereby obtaining a treatment liquid. Alternatively, a raw material emulsion of ionic group-containing silicone oil and a raw material emulsion of unmodified silicone oil may be mixed to obtain a treatment liquid in which first emulsified particles containing ionic group-containing silicone oil and another second emulsified particles containing unmodified silicone oil are mixed.

[0070] The method for adjusting the average particle size of the emulsified particles contained in the treatment liquid to be within the range of 100 nm to 250 nm is not particularly limited. For example, when preparing the treatment liquid or the raw material emulsion, a properly adjusted amount of surfactant is added and mixed. Specifically, by increasing the amount of surfactant added, the average particle size of the emulsified particles can be further reduced. Examples of the surfactant include polyoxyethylene alkyl ethers.

[0071] [Second embodiment: inkjet printing device]

[0072] Below, refer to Figure 1 The inkjet printing device 10 according to the second embodiment of the present invention will be described. Figure 1 The components are mainly schematically shown. The size, number, etc. of the components shown in the figures can be changed as appropriate. Figure 1 It is a side view showing the main part of the inkjet printing apparatus 10 as an example of the inkjet printing apparatus according to the second embodiment. Figure 1 The inkjet printing device 10 shown in FIG. 1 is a flat-bed inkjet printing device.

[0073] The inkjet printing device 10 according to the second embodiment uses the treatment liquid according to the first embodiment to treat the printing object P. Since the treatment liquid according to the first embodiment is used, the inkjet printing device 10 can produce a printed object with excellent color fastness to friction and can suppress the deterioration of the touch of the printed object for the same reasons as described in the first embodiment. In addition, since the treatment liquid according to the first embodiment has excellent ejection properties from the treatment head, these effects can be reliably exerted according to the inkjet printing device according to the second embodiment.

[0074] Figure 1 The inkjet printing apparatus 10 shown in FIG. 1 includes a recording head 1, a processing head 2, and a mounting table 3. The recording head 1 includes a first recording head 1a, a second recording head 1b, a third recording head 1c, and a fourth recording head 1d.

[0075] The recording head 1 ejects ink toward the image forming area of ​​the printing object P. The first recording head 1a, the second recording head 1b, the third recording head 1c, and the fourth recording head 1d of the recording head 1 eject inks of different colors (e.g., yellow ink, magenta ink, cyan ink, and black ink), respectively. The recording head 1 is not particularly limited, and examples thereof include a piezoelectric head and a thermal inkjet head.

[0076] The processing head 2 discharges a processing liquid toward at least the image forming region of the printing object P. The processing liquid is the processing liquid according to the first embodiment. The processing head 2 is not particularly limited, and examples thereof include a piezoelectric head and a thermal inkjet head.

[0077] The printing object P is placed on the stage 3. A recording head 1 and a processing head 2 are arranged above the stage 3 so as to eject ink and a processing liquid onto the printing object P. The stage 3 is driven by a motor (not shown) to move in a direction from the recording head 1 toward the processing head 2 (for example, Figure 1 The printing object P on the mounting table 3 is transported by the horizontal movement of the mounting table 3.

[0078] The printing object P may be a woven fabric or a knitted fabric. Examples of the printing object P include cotton cloth, silk cloth, linen cloth, acetate cloth, rayon cloth, nylon cloth, polyurethane cloth, and polyester cloth.

[0079] When making a printed object, first, the stage 3 on which the printing object P is placed moves horizontally, and the printing object P is transported to a position facing the recording head 1. Ink is ejected from the recording head 1 to the image forming area of ​​the printing object P. In this way, an image is formed in the image forming area of ​​the printing object P using the ink. After the ink is ejected, the stage 3 on which the printing object P is placed moves further horizontally, and the printing object P is transported to a position facing the processing head 2. A processing liquid is ejected from the processing head 2 to at least the image forming area of ​​the printing object P. In this way, a processing film is formed on the image formed in the image forming area of ​​the printing object P using the processing liquid.

[0080] The processing head 2 may also spray the processing liquid only to the image forming area of ​​the printing object P. Alternatively, the processing head 2 may spray the processing liquid to an area wider than the image forming area of ​​the printing object P, or may spray the processing liquid to the entire surface of the printing object P. In order to reduce the amount of processing liquid used to suppress the deterioration of the touch of the printed object, it is preferred that the processing head 2 sprays the processing liquid only to the image forming area of ​​the printing object P. And, based on the same reason, it is more preferred that the processing head 2 sprays the processing liquid only to the area in the image forming area where the ink is sprayed by the recording head 1. Since the processing head 2 can accurately control the spraying position of the processing liquid, it is possible to spray the processing liquid only to the area after the ink has been sprayed. In order to accurately control the spraying position of the processing liquid, it is preferred that the distance between the processing head 2 and the printing object P is greater than 1 mm and less than 5 mm. In addition, in order to efficiently perform post-processing using the processing liquid, it is preferred that only the processing liquid is sprayed from the processing head 2.

[0081] After the treatment liquid is ejected from the treatment head 2 toward the printing object P, the mounting table 3 on which the printing object P is mounted further moves horizontally to transport the printing object P to a position facing the heating unit (not shown). The printing object P is heated by the heating unit, and the ink and the treatment liquid are dried. The heating temperature is, for example, not less than 120° C. and not more than 180° C. The heating time is, for example, not less than 1 minute and not more than 10 minutes. The volatile components contained in the ink and the treatment liquid evaporate by heating, thereby promoting the fixation of the ink and the treatment liquid on the printing object P. As a result, a printed object can be produced, that is, a printing object P after an image is formed using ink and treated with the treatment liquid.

[0082] The inkjet printing apparatus 10 according to the second embodiment has been described above. However, the inkjet printing apparatus of the present invention is not limited to the above-described inkjet printing apparatus 10, and may be modified as shown in the following modified examples, for example.

[0083] Regarding the first modified example, the inkjet printing apparatus 10 may include a sprayer for spraying the processing liquid instead of the processing head 2 for ejecting the processing liquid.

[0084] Regarding the second modification, the treatment using the treatment liquid may be performed by immersing the printing object P in a tank storing the treatment liquid. In the case of immersion, the discharge amount of the treatment liquid described later in the third embodiment corresponds to the application amount of the treatment liquid.

[0085] Regarding the third modification, in the above-described embodiment, the mounting table 3 is moved horizontally. However, the recording head 1 and the processing head 2 may be moved horizontally in a state where the mounting table 3 is fixed.

[0086] Regarding the fourth variation, the stage 3 may be horizontally moved along the conveying direction of the print object P, or the recording head 1 and the processing head 2 may be horizontally moved, and the recording head 1 and the processing head 2 may be horizontally moved in a direction parallel to the conveying direction of the print object P.

[0087] Regarding the fifth modification, the number of the recording heads 1 may be 1 to 3 or 5 or more.

[0088] The sixth modification may be a non-flatbed inkjet printing apparatus. As long as the recording head 1 and the processing head 2 are provided, the effect of using the processing liquid according to the first embodiment can be obtained regardless of the type of the inkjet printing apparatus.

[0089] [Third embodiment: inkjet printing method]

[0090] Next, continue to refer to Figure 1The inkjet printing method according to the third embodiment of the present invention is described. The inkjet printing method according to the third embodiment forms an image on the image forming area of ​​the printing object P using the processing liquid according to the first embodiment. In addition, the inkjet printing method according to the third embodiment forms an image on the image forming area of ​​the printing object P using the inkjet printing device 10 according to the second embodiment. Since the inkjet printing method according to the third embodiment uses the processing liquid according to the first embodiment, it is possible to produce a printed object with excellent color fastness to friction, and to suppress the deterioration of the touch of the printed object, for the same reasons as described in the first embodiment. In addition, since the processing liquid according to the first embodiment has excellent ejection properties from the processing head, these effects can be reliably exerted according to the inkjet printing method according to the third embodiment.

[0091] The inkjet printing method according to the third embodiment includes an inkjet step and a treatment step. In the inkjet step, ink is ejected from the recording head 1 to the image forming area of ​​the printing object P. In the treatment step, a treatment liquid is ejected from the treatment head 2 to at least the image forming area of ​​the printing object P. The treatment liquid is the treatment liquid according to the first embodiment. The treatment step is performed, for example, after the inkjet step. The inkjet printing method may also include a heating step as required.

[0092] In the ink jetting step, the ink jetting amount to the printing object P is, for example, 5 g / m 2 Above and 40g / m 2 the following.

[0093] In the treatment step, the amount of treatment liquid ejected to the printing object P is, for example, 10 g / m 2 Above and 120g / m 2 In order to improve the color fastness to dry rubbing, the treatment liquid spraying amount is preferably 15 g / m 2 Above and 30g / m 2 In order to improve not only the color fastness to dry rubbing but also the color fastness to wet rubbing, the treatment liquid spraying amount is more preferably 17 g / m 2 Above and 25g / m 2 Below. Above, refer to Figure 1 The inkjet printing method according to the third embodiment has been described.

[0094] [Ink used in the second and third embodiments]

[0095] The following describes the ink used in the second embodiment and the third embodiment. The ink contains, for example, a pigment and an aqueous medium. If necessary, the ink may also contain at least one selected from the group consisting of a surfactant, a polyol, and binder resin particles.

[0096] (pigment)

[0097] The pigment is dispersed in an aqueous medium, for example. From the viewpoint of obtaining an ink having excellent image density, hue, and color stability, the D 50 The diameter is preferably 30 nm to 250 nm, and more preferably 70 nm to 160 nm.

[0098] As pigments, for example, yellow pigments, orange pigments, red pigments, blue pigments, violet pigments and black pigments can be cited. As yellow pigments, for example, CI Pigment Yellow (74, 93, 95, 109, 110, 120, 128, 138, 139, 151, 154, 155, 173, 180, 185 and 193) can be cited. As orange pigments, for example, CI Pigment Orange (34, 36, 43, 61, 63 and 71) can be cited. As red pigments, for example, CI Pigment Red (122 and 202) can be cited. As blue pigments, for example, CI Pigment Blue (15, more specifically 15:3) can be cited. As violet pigments, for example, CI Pigment Violet (19, 23 and 33) can be cited. As black pigments, for example, CI Pigment Black (7) can be cited.

[0099] The content percentage of the pigment relative to the mass of the ink is preferably 1% by mass or more and 12% by mass or less, and more preferably 1% by mass or more and 7% by mass or less. By making the content percentage of the pigment 1% by mass or more, the image density of the printed material produced can be increased. In addition, by making the content percentage of the pigment 12% by mass or less, an ink with high fluidity can be obtained.

[0100] (Aqueous medium)

[0101] The aqueous medium contained in the ink has the same meaning as the aqueous medium contained in the treatment liquid described in the first embodiment. The content percentage of the aqueous medium relative to the mass of the ink is preferably 5 mass % to 70 mass %, more preferably 40 mass % to 60 mass %.

[0102] (Surfactant)

[0103] By making the ink contain a surfactant, the wettability of the ink to the printed object is improved. As surfactants, for example, anionic surfactants, cationic surfactants, nonionic surfactants and amphoteric surfactants can be listed. The surfactant contained in the ink is preferably a nonionic surfactant. The nonionic surfactant is preferably a surfactant having an acetylene glycol structure, and more preferably an acetylene glycol ethylene oxide adduct. The HLB value of the surfactant is preferably greater than 3 and less than 20, more preferably greater than 6 and less than 16, and further preferably greater than 7 and less than 10. The HLB value of the surfactant is calculated, for example, by the Griffin method and according to the formula "HLB value = 20×(sum of the formula weights of the hydrophilic part) / molecular weight". In order to improve the image concentration while suppressing image offset, the content percentage of the surfactant relative to the mass of the ink is preferably greater than 0.1 mass% and less than 5.0 mass%, and more preferably greater than 0.5 mass% and less than 2.0 mass%.

[0104] (Polyol)

[0105] By making the ink contain a polyol, the viscosity of the ink is appropriately adjusted. The polyol contained in the ink has the same meaning as the polyol contained in the treatment liquid described in the first embodiment. In the case where the ink contains a polyol, in order to appropriately adjust the viscosity of the ink, the content percentage of the polyol relative to the mass of the ink is preferably 5 mass% or more and 60 mass% or less, and more preferably 20 mass% or more and 50 mass% or less.

[0106] (Binder resin particles)

[0107] The binder resin particles exist in a state of being dispersed in an aqueous medium. The binder resin particles function as a binder for bonding the printing object and the pigment. Therefore, by making the ink contain the binder resin particles, a printed object with excellent pigment fixability can be obtained.

[0108] As the resin contained in the binder resin particles, polyurethane resin, (meth) acrylate resin, styrene-(meth) acrylate resin, styrene-maleic acid copolymer, vinyl naphthalene-(meth) acrylic acid copolymer and vinyl naphthalene-maleic acid copolymer can be listed. As the resin contained in the binder resin particles, polyurethane resin is preferably used. The content percentage of the polyurethane resin in the binder resin particles is preferably 80% by mass or more, more preferably 100% by mass.

[0109] The content percentage of the binder resin relative to the mass of the ink is preferably 1 mass % or more and 20 mass % or less, and more preferably 2 mass % or more and 10 mass % or less. If the content percentage of the binder resin particles is 1 mass % or more, a printing object with excellent pigment fixability can be obtained. On the other hand, if the content percentage of the binder resin particles is 20 mass % or less, the ink can be stably ejected onto the printing object.

[0110] (additive)

[0111] The ink may further contain known additives (more specifically, a dissolution stabilizer, an anti-drying agent, an antioxidant, a viscosity adjuster, a pH adjuster, an antifungal agent, etc.) as necessary.

[0112] (Ink Manufacturing Method)

[0113] The ink is produced by mixing the pigment, the aqueous medium, and components added as needed (eg, a surfactant, a polyol, and binder resin particles) using a mixer, for example, and the mixing time is, for example, 1 minute to 30 minutes.

[0114] [Summary of the Invention]

[0115] An inkjet treatment liquid according to a first aspect of the present invention includes: emulsified particles containing silicone oil; and an aqueous medium, wherein the average particle size of the emulsified particles is 100 nm or more and 250 nm or less.

[0116] The inkjet treatment liquid suppresses deterioration in the touch of printed materials, can produce printed materials with excellent color fastness to rubbing, and has excellent ejectability from a treatment head of an inkjet printing device.

[0117] In the inkjet processing liquid, the average particle size of the emulsified particles may be greater than or equal to 100 nm and less than or equal to 160 nm.

[0118] With this configuration, the inkjet processing liquid has better discharge properties from the processing head.

[0119] In the inkjet processing liquid, the emulsion particles may contain first emulsion particles and second emulsion particles having an average particle size different from that of the first emulsion particles, wherein the average particle size of the first emulsion particles is greater than 100 nm and less than 250 nm, and the average particle size of the second emulsion particles is greater than 100 nm and less than 250 nm.

[0120] By having this structure, even when containing two or more emulsified particles with different average particle sizes, the above-mentioned effect of suppressing the deterioration of the touch of the printed material, the effect of excellent color fastness to rubbing and the effect of ejection property can be reliably exerted.

[0121] In the inkjet processing liquid, the first emulsion particles may have an average particle size of 100 nm to 160 nm, and the second emulsion particles may have an average particle size of 100 nm to 160 nm.

[0122] By having this structure, even when containing two or more emulsified particles with different average particle sizes, the above-mentioned effect of suppressing the deterioration of the touch of the printed material, the effect of excellent color fastness to rubbing and the effect of ejection can be more reliably exerted.

[0123] In the inkjet processing liquid, a difference between an average particle size of the first emulsion particles and an average particle size of the second emulsion particles may be greater than or equal to 0 nm and less than or equal to 30 nm.

[0124] By having this structure, even when containing two or more emulsified particles with different average particle sizes, the above-mentioned effect of suppressing the deterioration of the touch of the printed material, the effect of excellent color fastness to rubbing and the effect of ejection properties can be further reliably exerted.

[0125] In the inkjet treatment liquid, the silicone oil may contain at least ionic group-containing silicone oil.

[0126] By containing at least an ionic group-containing silicone oil, a printed material having better color fastness to wet rubbing can be produced.

[0127] The inkjet processing liquid can be used for textile printing.

[0128] By using the inkjet treatment liquid for printing, the effect of suppressing the deterioration of the touch of the printed object and the effect of excellent color fastness to rubbing can be more effectively exerted.

[0129] The inkjet printing device involved in the second aspect of the present invention includes: a recording head that sprays ink toward an image forming area of ​​a printing object; and a processing head that sprays a processing liquid toward at least the image forming area of ​​the printing object, wherein the processing liquid is the inkjet processing liquid involved in the first aspect of the present invention.

[0130] Since the inkjet printing device uses the inkjet treatment liquid involved in the first aspect of the present invention, it is possible to produce printed articles with suppressed tactile deterioration and excellent color fastness to friction. In addition, since the inkjet treatment liquid has excellent ejection properties from the treatment head, the effect of the inkjet treatment liquid involved in the first embodiment of the present invention on printed articles can be reliably exerted.

[0131] The inkjet printing method involved in the third aspect of the present invention includes: an inkjet step of spraying ink from a recording head toward an image forming area of ​​a printing object; and a processing step of spraying a processing liquid from a processing head toward at least the image forming area of ​​the printing object, wherein the processing liquid is the inkjet processing liquid involved in the first aspect of the present invention.

[0132] Since the inkjet printing method uses the inkjet treatment liquid involved in the first aspect of the present invention, it is possible to produce printed articles with suppressed tactile deterioration and excellent color fastness to rubbing. In addition, since the inkjet treatment liquid has excellent ejection properties from the treatment head, the effect of the inkjet treatment liquid involved in the first embodiment of the present invention on printed articles can be reliably exerted.

[0133] Example

[0134] Hereinafter, the present invention will be further described in detail by way of examples, but the present invention is not limited to these examples.

[0135] In this embodiment, various printed articles were produced by changing the type and content percentage of silicone oil in the inkjet treatment liquid, the average particle size of the emulsified particles, and the ejection amount of the treatment liquid, and the color fastness to rubbing and the degree of suppression of tactile deterioration of the printed articles were evaluated. In addition, in this embodiment, the ejection properties of the treatment liquid from the nozzle corresponding to the average particle size of the emulsified particles of the silicone oil in the inkjet treatment liquid were also evaluated.

[0136] 1. Evaluation test of the color fastness to rubbing and the degree of inhibition of tactile deterioration of printed materials when the type of treatment liquid (type and content percentage of silicone oil in the treatment liquid and average particle size of emulsified particles) is changed

[0137] In this test, the spraying amount of the treatment liquid when making the printed material was set to 20 g / m 2 The types and percentages of silicone oil in the treatment solution and the average particle size of the emulsified particles were changed to produce various printed articles. The color fastness to rubbing and the degree of suppression of tactile deterioration of the various printed articles were then evaluated.

[0138] [Method for preparing treatment solution]

[0139] Treatment liquids (A-1) to (A-7) and (B-1) used in the evaluation test were prepared by the following method: The content percentage of the silicone oil was rounded off to the first decimal place.

[0140] <Preparation of Treatment Liquid (A-1)>

[0141] First, a raw material emulsion A contained in the treatment liquid (A-1) was prepared. Specifically, 300 g of amino-modified silicone oil ("KF-864" manufactured by Shin-Etsu Chemical Co., Ltd., viscosity: 1700 mm 2 / s, specific gravity: 0.98, functional group equivalent: 3800g / mol), 600g ion exchange water, and 100g hydrochloric acid (concentration: 1mol / L) were placed in a beaker. The contents of the beaker were stirred at a speed of 10000rpm for 15 minutes using a homogenizer ("ULTRA-TURRAX T25" manufactured by IKA) and allowed to stand for 30 minutes. Next, the contents of the beaker were filtered with a 120-mesh stainless steel filter to obtain a raw emulsion A. Emulsified particles of amino-modified silicone oil are dispersed in the raw emulsion A. The average particle size of the emulsified particles contained in the raw emulsion A is 150nm.

[0142] Next, a treatment liquid (A-1) was prepared using the raw material emulsion A prepared as described above. Specifically, 33.30 g of the raw material emulsion A (content percentage of amino-modified silicone oil: 30% by mass, content of amino-modified silicone oil: 9.99 g), 33.35 g of ion exchange water, and 33.35 g of propylene glycol were mixed to obtain a treatment liquid (A-1). In the treatment liquid (A-1), the content percentage of amino-modified silicone oil was 10% by mass.

[0143] <Preparation of Treatment Liquid (A-2)>

[0144] In the preparation of the treatment liquid (A-2), the raw material emulsion A prepared as described above was used. Specifically, 15.00 g of the raw material emulsion A (content percentage of amino-modified silicone oil: 30% by mass, content of amino-modified silicone oil: 4.50 g), 50.00 g of ion exchange water, and 35.00 g of propylene glycol were mixed to obtain the treatment liquid (A-2). In the treatment liquid (A-2), the content percentage of amino-modified silicone oil was 5% by mass.

[0145] <Preparation of Treatment Liquid (A-3)>

[0146] In the preparation of the treatment liquid (A-3), the raw material emulsion A prepared as described above was used. Specifically, 50.00 g of the raw material emulsion A (content percentage of amino-modified silicone oil: 30% by mass, content of amino-modified silicone oil: 15.00 g), 35.00 g of ion exchange water, and 15.00 g of propylene glycol were mixed to obtain the treatment liquid (A-3). In the treatment liquid (A-3), the content percentage of amino-modified silicone oil was 15% by mass.

[0147] <Preparation of Treatment Liquid (A-4)>

[0148] First, a raw emulsion B contained in the treatment liquid (A-4) was prepared. Specifically, 300 g of carboxyl-modified silicone oil ("X-22-3701E" manufactured by Shin-Etsu Chemical Co., Ltd., viscosity: 2000 mm2 / s, specific gravity: 0.98, functional group equivalent: 4000 g / mol), 600 g of ion exchange water, and 100 g of sodium hydroxide aqueous solution (concentration: 1 mol / L) were placed in a beaker. The contents of the beaker were stirred at a speed of 10,000 rpm for 15 minutes using a homogenizer ("ULTRA-TURRAX T25" manufactured by IKA) and allowed to stand for 30 minutes. Next, the contents of the beaker were filtered through a 120-mesh stainless steel filter to obtain raw emulsion B. Emulsified particles of carboxyl-modified silicone oil are dispersed in raw emulsion B. The average particle size of the emulsified particles contained in raw emulsion B is 120 nm.

[0149] Next, a treatment liquid (A-4) was prepared using the raw material emulsion B prepared as described above. Specifically, the treatment liquid (A-4) was obtained in the same manner as the treatment liquid (A-1) except that the raw material emulsion A (content percentage of amino-modified silicone oil: 30 mass %) was changed to the raw material emulsion B (content percentage of carboxyl-modified silicone oil: 30 mass %). In the treatment liquid (A-4), the content percentage of carboxyl-modified silicone oil was 10 mass %.

[0150] <Preparation of Treatment Liquid (A-5)>

[0151] First, a raw material emulsion C contained in the treatment liquid (A-5) was prepared. Specifically, 300 g of amino-modified silicone oil ("KF-877" manufactured by Shin-Etsu Chemical Co., Ltd., viscosity: 5700 mm 2 / s, specific gravity: 0.98, functional group equivalent: 5200g / mol), 600g of ion exchange water, and 100g of hydrochloric acid (concentration: 1mol / L) were placed in a beaker. The contents of the beaker were stirred at a speed of 10000rpm for 15 minutes using a homogenizer ("ULTRA-TURRAX T25" manufactured by IKA) and allowed to stand for 30 minutes. Next, the contents of the beaker were filtered with a 120-mesh stainless steel filter to obtain a raw emulsion C. Emulsified particles of amino-modified silicone oil are dispersed in the raw emulsion C. The average particle size of the emulsified particles contained in the raw emulsion C is 200nm.

[0152] Next, a treatment liquid (A-5) was prepared using the raw material emulsion C prepared as described above. Specifically, the treatment liquid (A-5) was obtained in the same manner as the treatment liquid (A-1) except that the raw material emulsion A (content percentage of amino-modified silicone oil: 30 mass %) was changed to the raw material emulsion C (content percentage of amino-modified silicone oil: 30 mass %). In the treatment liquid (A-5), the content percentage of amino-modified silicone oil was 10 mass %.

[0153] <Preparation of Treatment Liquid (A-6)>

[0154] First, a raw material emulsion D contained in the treatment liquid (A-6) was prepared. Specifically, an unmodified silicone oil (specifically dimethyl polysiloxane) ("KF96-3000cs" manufactured by Shin-Etsu Chemical Co., Ltd., viscosity: 3000 mm 2 / s, specific gravity: 0.97) 180 g and phenol-modified silicone oil ("KF2201" manufactured by Shin-Etsu Chemical Co., Ltd., viscosity: 97 m 2 / s, specific gravity: 0.99, functional group equivalent: 1474g / mol) 120g was mixed to obtain a viscosity of 1000mm 2 / s of mixture MD. 300g of mixture MD, 600g of ion exchange water, and 100g of sodium hydroxide aqueous solution (concentration 1mol / L) were placed in a beaker. Use a homogenizer ("ULTRA-TURRAXT25" manufactured by IKA) to stir the contents of the beaker at a speed of 10000rpm for 15 minutes, and let it stand for 30 minutes. Then, the contents of the beaker were filtered with a 120-mesh stainless steel filter to obtain a raw emulsion D. Emulsified particles containing unmodified silicone oil and phenol-modified silicone oil are dispersed in the raw emulsion D. The average particle size of the emulsified particles contained in the raw emulsion D is 160nm.

[0155] Next, a treatment liquid (A-6) was prepared using the raw material emulsion D prepared as described above. Specifically, the treatment liquid (A-6) was obtained in the same manner as the treatment liquid (A-1) except that the raw material emulsion A (content percentage of amino-modified silicone oil: 30 mass %) was changed to the raw material emulsion D (content percentage of a mixture of phenol-modified silicone oil and unmodified silicone oil: 30 mass %). In the treatment liquid (A-6), the content percentage of the mixture of phenol-modified silicone oil and unmodified silicone oil was 10 mass %.

[0156] <Preparation of Treatment Liquid (A-7)>

[0157] First, a raw material emulsion E contained in the treatment liquid (A-7) was prepared. Specifically, an unmodified silicone oil ("KF96-3000cs" manufactured by Shin-Etsu Chemical Co., Ltd., viscosity: 3000 mm 2 / s, specific gravity: 0.97) 180 g and silanol-modified silicone oil ("KF9701" manufactured by Shin-Etsu Chemical Co., Ltd., viscosity: 60 mm 2 / s, specific gravity: 0.977, functional group equivalent: 1500g / mol) 120g was mixed to obtain a viscosity of 1200mm 2 / s of mixture ME. 300g of mixture ME, 600g of ion exchange water, and 100g of sodium hydroxide aqueous solution (concentration 1mol / L) were placed in a beaker. The contents of the beaker were stirred at a speed of 10000rpm for 15 minutes using a homogenizer ("ULTRA-TURRAX T25" manufactured by IKA) and allowed to stand for 30 minutes. Next, the contents of the beaker were filtered through a 120-mesh stainless steel filter to obtain a raw emulsion E. Emulsified particles containing unmodified silicone oil and silanol-modified silicone oil are dispersed throughout the raw emulsion E. The average particle size of the emulsified particles contained in the raw emulsion E is 220nm.

[0158] <Preparation of Treatment Solution (B-1)>

[0159] First, a raw material emulsion F contained in the treatment liquid (B-1) was prepared. Specifically, 300 g of unmodified silicone oil ("KF96-3000cs" manufactured by Shin-Etsu Chemical Co., Ltd., viscosity: 3000 mm 2 / s, specific gravity: 0.97), 600g of ion exchange water, and 100g of hydrochloric acid (concentration: 1 mol / L) were placed in a beaker. The contents of the beaker were stirred at a speed of 10000rpm for 15 minutes using a homogenizer ("ULTRA-TURRAXT25" manufactured by IKA), and as a result, only emulsified particles with an average particle size of more than 1μm could be produced. Moreover, after stirring, the contents of the beaker were left to stand for 30 minutes, resulting in the separation of the aqueous phase and the oil phase, and the raw emulsion F could not be produced. As described above, since the raw emulsion F could not be produced, the treatment liquid (B-1) was not produced. In addition, since the treatment liquid (B-1) was not produced, the treatment liquid (B-1) was not evaluated.

[0160] The types of raw material emulsions, average particle sizes of emulsified particles, types of silicone oils and their content percentages, and viscosities of silicone oils in treatment liquids (A-1) to (A-7) and treatment liquid (B-1) are summarized in Table 1 below.

[0161]

[0162] In Table 1 and Table 4 described below, the meanings of the terms are as follows. "Amount" indicates the content percentage of silicone oil in the treatment liquid. "wt%" indicates mass%. "Viscosity" indicates the viscosity of silicone oil. When the emulsified particles contain two or more silicone oils, "viscosity" indicates the viscosity of a mixture of two or more silicone oils. "-" indicates that the raw material emulsion F could not be prepared and the preparation of the treatment liquid (B-1) was not implemented.

[0163] As shown in Table 1 above, the treatment liquids (A-1) to (A-7) all contain emulsified particles containing silicone oil; and an aqueous medium. In addition, the average particle size of the emulsified particles of the treatment liquids (A-1) to (A-7) is within the range of 100 nm to 250 nm. On the other hand, with respect to the treatment liquid (B-1), the raw material emulsion F could not be prepared.

[0164] [Measurement methods of various physical properties]

[0165] The average particle size of the emulsified particles in the raw material emulsion and the viscosity of the silicone oil are measured by the method described below.

[0166] <Measurement of Average Particle Diameter of Emulsified Particles>

[0167] The average particle size of the emulsified particles was measured using a laser diffraction particle size distribution measuring device ("ZETASIZER NANO ZS" manufactured by Malvern Instruments Ltd.) in accordance with the method described in ISO 13321:1996 (Particle size analysis-Photon correlation spectroscopy). The average particle size of the emulsified particles was measured using a measurement sample obtained by diluting the treatment liquid or the raw material emulsion (in the case of mixing two different raw material emulsions) 1000 times with water. In addition, the average particle size of the emulsified particles contained in the raw material emulsion and the average particle size of the emulsified particles contained in the treatment liquid are approximately the same as each other.

[0168] <Measurement of Viscosity of Silicone Oil>

[0169] The viscosity of the silicone oil was measured according to the method described in JIS Z8803:2011 (Method for measuring viscosity of liquid) at a temperature of 25° C. The viscosity of the silicone oil was measured using an Ubbelohde viscometer described in “6.2.3 Ubbelohde viscometer” of JIS Z8803:2011.

[0170] [Evaluation method]

[0171] Using each of the prepared treatment solutions, the color fastness to rubbing and the degree of inhibition of tactile deterioration of various printed articles were evaluated. Specifically, evaluation ink was prepared, and evaluation printed articles were prepared using the evaluation ink and each of the treatment solutions, and the color fastness to rubbing and the degree of inhibition of tactile deterioration of the evaluation printed articles were evaluated. The following describes the details of the method for preparing the evaluation ink, the method for preparing the evaluation printed article, and various evaluation methods.

[0172] <Method for preparing evaluation ink>

[0173] Inks a and b used for evaluation of the treatment liquid were prepared by the method shown below.

[0174] (Method for producing ink a)

[0175] 125 g of ion exchange water and 2 g of nonionic surfactant ("SURFYNOL (registered trademark) 440 manufactured by Nissin Chemical Industry Co., Ltd., content: acetylene glycol ethylene oxide adduct) were placed in a 1L three-necked flask equipped with a stirring blade. While stirring the contents of the flask, 165 g of propylene glycol, 100 g of black pigment dispersion ("AE2078F" manufactured by Sanyo Pigment Co., Ltd., content: CI Pigment Black 7, solid content concentration: 20% by mass), and 108 g of binder resin particle dispersion ("SUPERFLEX 470" manufactured by Daiichi Kogyo Seiyaku Co., Ltd., content: polyurethane dispersion, solid content concentration: 38% by mass) were added to the flask in sequence. The contents of the flask were stirred for 10 minutes to obtain ink a.

[0176] (Method for producing ink b)

[0177] 140 g of ion exchange water and 2 g of nonionic surfactant ("SURFYNOL (registered trademark) 440 manufactured by Nissin Chemical Industry Co., Ltd., content: acetylene glycol ethylene oxide adduct) were placed in a 1L three-necked flask equipped with a stirring blade. While stirring the contents of the flask, 225 g of propylene glycol, 83 g of black pigment dispersion ("ACAK1" manufactured by Dainichi Seika Industries Co., Ltd., content: CI Pigment Black 7, solid content concentration: 15% by mass), and 50 g of binder resin particle dispersion ("Eternacoll (registered trademark) UW-1527F" manufactured by Ube Industries, Ltd., content: polyurethane dispersion, solid content concentration: 40% by mass) were added to the flask in sequence. The contents of the flask were stirred for 10 minutes to obtain ink b.

[0178] <Method for preparing printed material for evaluation>

[0179] Printed articles for evaluation were produced using the inks and treatment liquids shown in Table 2. For example, in the evaluation of Example 1-1 in Table 2, treatment liquid (A-1) and ink a were used.

[0180] As the printing object, a broad-width cotton cloth (manufactured by Seisen Co., Ltd., size: A4 size, warp and weft cotton yarn number: 40 / 1, warp yarn density: 130 strands / inch, weft yarn density: 75 strands / inch, unit area weight: 122 g / m 2 ). An inkjet printer ("Colorio (registered trademark) PX-045A" manufactured by Seiko Epson Corporation) was used to prepare the print for evaluation. The first ink chamber of the first ink cartridge was filled with ink. The second ink chamber of the second ink cartridge was filled with a treatment liquid. The first ink cartridge and the second ink cartridge were installed in the inkjet printer. In addition, the ink filled in the first ink chamber was ejected from the recording head of the inkjet printer. The treatment liquid filled in the second ink chamber was ejected from the treatment head of the inkjet printer.

[0181] Use an inkjet printer to eject ink from the recording head onto the printed object, with the ink ejection amount reaching 20 g / m 2 Next, using an inkjet printer, a treatment liquid is ejected from a treatment head toward the printing object, and the amount of treatment liquid ejected is set to 20 g / m 2 In this way, a treatment film having the same size as the solid image was formed on the solid image of the ink using the treatment liquid. Next, the printed object was heated at 160° C. for 3 minutes to dry the ink and the treatment liquid, thereby obtaining a printed object for evaluation.

[0182] <Evaluation of color fastness to rubbing>

[0183] The solid image formed on the evaluation printed material was rubbed using a rubbing white cotton cloth according to the dry test and wet test of the friction tester II type (Gakushin type) method described in JIS L-0849:2013 (Test method for color fastness to rubbing). The coloring degree of the rubbing white cotton cloth after rubbing was evaluated according to the "Criteria for determination of color change and fading" described in Article 10 (Determination of color fastness) of JIS L-0801:2011 (General rules for test methods for color fastness). The coloring degree of the rubbing white cotton cloth was determined in 9 levels (level 1, level 1 to 2, level 2, level 2 to 3, level 3, level 3 to 4, level 4, level 4 to 5, and level 5 in descending order of the degree of contamination). The smaller the coloring degree of the rubbing white cotton cloth (closer to level 5), the better the color fastness to rubbing. The color fastness to dry rubbing and the color fastness to wet rubbing were evaluated according to the following criteria and the coloring degree of the rubbing white cotton cloth after the rubbing test. In addition, the determination result of the dry test is taken as the color fastness to dry rubbing, and the determination result of the wet test is taken as the color fastness to wet rubbing. The cases evaluated as A and B are considered to be qualified, and the cases evaluated as C are considered to be unqualified. The determined color fastness to rubbing and the evaluation results are summarized in Table 2 described below.

[0184] (Evaluation criteria for color fastness to dry rubbing)

[0185] Evaluation A: The color fastness to dry rubbing is grade 4 or higher.

[0186] Evaluation B: Color fastness to dry rubbing is level 3 to 4.

[0187] Evaluation C: Color fastness to dry rubbing is grade 3 or less.

[0188] (Evaluation criteria for color fastness to wet rubbing)

[0189] Evaluation A: Color fastness to wet rubbing is grade 3 or higher.

[0190] Evaluation B: Color fastness to wet rubbing is level 2 to 3.

[0191] Evaluation C: Color fastness to wet rubbing is grade 2 or less.

[0192] <Evaluation of the degree of suppression of deterioration in touch>

[0193] The unused printing object was folded in half along the warp (length direction), and the distance (loop height) between the lower fabric and the upper fabric of the fold was measured. The measured loop height of the unused printing object was set as the loop height before printing. Next, the area where the solid image of the evaluation print was formed was folded in half along the warp (length direction), and the loop height was measured. The measured loop height of the evaluation print was set as the loop height after printing. The loop height change rate before and after printing (unit: %) was calculated according to the formula "loop height change rate = 100 × loop height after printing / loop height before printing". The lower the loop height change rate, the less hard and swollen the printed object is after printing, which indicates that the deterioration of the touch of the printed object has been suppressed. Based on the loop height change rate, whether the deterioration of the touch of the printed object is suppressed is evaluated according to the following criteria. The cases evaluated as A and B are considered qualified, and the cases evaluated as C are considered unqualified. The measured loop height change rate and the evaluation results of the degree of suppression of tactile deterioration are summarized in Table 2 described below.

[0194] (Evaluation criteria for the degree of suppression of deterioration in tactile feel)

[0195] Evaluation A: The change rate of the ring height is 125% or less.

[0196] Evaluation B: The change rate of the ring height is more than 125% and less than 130%.

[0197] Evaluation C: The change rate of the ring height exceeded 130%.

[0198]

[0199] In the above Table 2 and the later described Table 3, the meanings of the terms are as follows. "Touch" indicates the evaluation of the degree of suppression of deterioration in the touch of the printed material. "Height" indicates the rate of change of the ring height before and after printing. "1-2", "2-3", "3-4" and "4-5" in the rubbing color fastness column respectively indicate that the degree of coloration of the white cotton cloth for friction is 1 to 2 levels, 2 to 3 levels, 3 to 4 levels, and 4 to 5 levels. "-" means that the raw material emulsion F cannot be prepared as described above, and the preparation of the treatment liquid (B-1) is not implemented, so the evaluation of the treatment liquid (B-1) cannot be implemented.

[0200] [Investigation]

[0201] As shown in Table 2, the evaluations of the color fastness to dry rubbing, the color fastness to wet rubbing, and the degree of suppression of tactile deterioration for the printed articles produced using the treatment liquids (A-1) to (A-7) were all A or B regardless of the type of ink. Therefore, it was determined that the inkjet treatment liquid of the present embodiment including the treatment liquids (A-1) to (A-7) could produce printed articles having excellent color fastness to rubbing and suppress tactile deterioration of the printed articles.

[0202] 2. Evaluation test of the color fastness to rubbing and the degree of suppression of tactile deterioration of printed materials when the ejection amount of the treatment liquid is changed

[0203] In this test, the treatment liquid (A-1) was used as the inkjet treatment liquid, and various evaluation prints were produced by changing the discharge amount of the treatment liquid. The color fastness to rubbing and the degree of suppression of tactile deterioration of the evaluation prints were evaluated.

[0204] <Method for preparing printed articles for evaluation of Example 1-1, Example 1-9 to Example 1-11, and Example 1-8>

[0205] Regarding the preparation of evaluation prints of Example 1-1, Example 1-9 to Example 1-11, and Example 1-8, the evaluation prints were prepared by the same method as the method for preparing the evaluation prints described in 1. above, except for the following changes. Specifically, the first ink chamber of the first ink cartridge was filled with the ink shown in Table 3 described later, and the second ink chamber of the second ink cartridge was filled with the treatment liquid (A-1). In each example, the discharge amount of the treatment liquid was set to the discharge amount shown in Table 3 described later. In addition, the discharge amount of the ink was not changed and was 20 g / m 2 .

[0206] <Method for preparing printed articles for evaluation of Examples 1-12>

[0207] Regarding the preparation of the evaluation prints of Examples 1-12, a print object having a solid image formed thereon was prepared by the same method as the method for preparing the evaluation prints described in 1. above, except for the following changes. Specifically, the first ink chamber of the first ink cartridge was filled with the ink shown in Table 3 described later, and the second ink chamber of the second ink cartridge was not filled with the treatment liquid. That is, the ejection amount of the treatment liquid was set to 0 g / m 2 , no treatment liquid was ejected from the treatment head. In addition, the ejection amount of ink did not change and was 20g / m 2 .

[0208] Next, the printed object with the solid image of ink formed thereon was immersed in the treatment liquid (A-1), and then taken out of the treatment liquid (A-1) and gently squeezed. Specifically, the pickup rate was 100% and the coating amount of the treatment liquid (A-1) was 120 g / m 2 The printed object was squeezed in the manner of . The squeezed printed object was heated at 160° C. for 3 minutes to dry the ink and the treatment liquid, thereby obtaining a printed object for evaluation.

[0209] <Evaluation of color fastness to rubbing and degree of suppression of deterioration in tactile feel>

[0210] The evaluation prints made using the treatment liquid (A-1) of Example 1-1, Example 1-9 to Example 1-12, and Example 1-8 were evaluated by the same method as the evaluation of the color fastness to rubbing described in 1. above and the same method as the evaluation of the degree of inhibition of tactile deterioration described in 1. above. The evaluation results are shown in Table 3 below. In addition, the evaluation results of the evaluation prints made using the treatment liquid (A-1) used in Example 1-1 and Example 1-8 are shown in Table 2 above, but for ease of understanding, they are shown again in Table 3 below.

[0211]

[0212] [Investigation]

[0213] As shown in Table 3 above, 2 Above and 120g / m 2 The printed articles produced with the following ejection amounts (including the coating amount) were evaluated as A or B in terms of color fastness to dry rubbing, color fastness to wet rubbing, and degree of suppression of tactile deterioration. 2 Above and 120g / m 2 By ejecting or applying the inkjet processing liquid of this embodiment in the following wide range of ejection amounts (including coating amounts), it is possible to produce printed materials with excellent color fastness to rubbing, and it is possible to suppress deterioration in the touch of the printed materials.

[0214] In addition, as shown in Table 3, the 2 Above and 30g / m 2 The print formed by the treatment liquid (A-1) with the following ejection amount was evaluated as A in terms of color fastness to dry rubbing. 2 Above and 30g / m 2 By discharging the inkjet processing liquid of this embodiment at the following discharge amount, it is possible to produce a printed material that is particularly excellent in color fastness to dry rubbing.

[0215] 3. Evaluation test of color fastness to rubbing and spraying properties when the average particle size of emulsified particles is changed

[0216] In this test, various printed articles were produced by changing the average particle size of the emulsified particles. Then, the color fastness to rubbing of the various printed articles produced was evaluated. At the same time, the ejection properties of the treatment liquid from the nozzle corresponding to the average particle size of the emulsified particles in each treatment liquid were also evaluated.

[0217] [Method for preparing treatment solution]

[0218] In this experiment, treatment liquids were used in which the average particle size of the emulsified particles of carboxyl-modified silicone oil or the average particle size of both the emulsified particles of carboxyl-modified silicone oil and the emulsified particles of unmodified silicone oil was changed to various values. The following is a detailed description of the preparation methods of the treatment liquids (C-1) to (C-6) and (D-1) to (D-4) used in this experiment.

[0219] <Preparation of Treatment Solution (C-1)>

[0220] When preparing the raw material emulsion B, 50 g of sodium hydroxide aqueous solution, 570 g of ion exchange water, and 80 g of a surfactant (polyoxyethylene alkyl ether) were added and stirred and mixed. Otherwise, the treatment liquid (C-1) was obtained by the same method as the preparation method of the treatment liquid (A-4) described in 1. The average particle size of the emulsified particles of the carboxyl-modified silicone oil of the treatment liquid (C-1) was 102 nm.

[0221] <Preparation of Treatment Solution (C-2)>

[0222] When preparing the raw material emulsion B, 50 g of sodium hydroxide aqueous solution, 590 g of ion exchange water, and 60 g of a surfactant (polyoxyethylene alkyl ether) were added and stirred and mixed. In addition, the treatment liquid (C-2) was obtained by the same method as the preparation method of the treatment liquid (A-4) described in 1. The average particle size of the emulsified particles of the carboxyl-modified silicone oil of the treatment liquid (C-2) was 137 nm.

[0223] <Preparation of Treatment Solution (C-3)>

[0224] When preparing the raw material emulsion B, 50 g of sodium hydroxide aqueous solution, 610 g of ion exchange water, and 40 g of a surfactant (polyoxyethylene alkyl ether) were added and stirred and mixed. In addition, the treatment liquid (C-3) was obtained by the same method as the preparation method of the treatment liquid (A-4) described in 1. The average particle size of the emulsified particles of the carboxyl-modified silicone oil in the treatment liquid (C-3) was 189 nm.

[0225] <Preparation of Treatment Solution (C-4)>

[0226] When preparing the raw material emulsion B, 50 g of sodium hydroxide aqueous solution, 630 g of ion exchange water, and 20 g of a surfactant (polyoxyethylene alkyl ether) were added and stirred and mixed. In addition, the treatment liquid (C-4) was obtained by the same method as the preparation method of the treatment liquid (A-4) described in 1. The average particle size of the emulsified particles of the carboxyl-modified silicone oil in the treatment liquid (C-4) was 247 nm.

[0227] <Preparation of Treatment Solution (C-5)>

[0228] The raw material emulsion used for preparing the treatment liquid (C-1) was referred to as the first raw material emulsion. The average particle size of the emulsified particles of the carboxyl-modified silicone oil contained in the first raw material emulsion was 102 nm.

[0229] Next, a second raw material emulsion containing unmodified silicone oil was prepared. Specifically, 300 g of unmodified silicone oil (specifically, dimethyl polysiloxane) ("KF96-3000cs" manufactured by Shin-Etsu Chemical Co., Ltd., viscosity: 3000 mm 2 / s, specific gravity: 0.97), 610g of ion exchange water, and 90g of surfactant (polyoxyethylene alkyl ether) were placed in a beaker. The contents of the beaker were stirred at a speed of 10000rpm for 15 minutes using a homogenizer ("ULTRA-TURRAXT25" manufactured by IKA) and left to stand for 30 minutes. Next, the contents of the beaker were filtered with a 120-mesh stainless steel filter to obtain a second raw material emulsion containing unmodified silicone oil. The average particle size of the emulsified particles of the unmodified silicone oil contained in the second raw material emulsion was 115nm.

[0230] A treatment liquid (C-5) was obtained by adding 33.31 g of ion exchange water and 33.35 g of propylene glycol to 16.67 g of the first raw material emulsion and 16.67 g of the second raw material emulsion. The average particle size of the emulsified particles in the treatment liquid (C-5) (the average particle size of the emulsified particles during mixing) was 106 nm.

[0231] <Preparation of Treatment Solution (C-6)>

[0232] The raw material emulsion used for preparing the treatment liquid (C-4) was referred to as the first raw material emulsion. The average particle size of the emulsified particles of the carboxyl-modified silicone oil contained in the first raw material emulsion was 247 nm.

[0233] Next, a second raw material emulsion containing unmodified silicone oil was prepared. Specifically, 300 g of unmodified silicone oil (specifically, dimethyl polysiloxane) ("KF96-3000cs" manufactured by Shin-Etsu Chemical Co., Ltd., viscosity: 3000 mm 2 / s, specific gravity: 0.97), 655g of ion exchange water, and 45g of surfactant (polyoxyethylene alkyl ether) were placed in a beaker. The contents of the beaker were stirred at a speed of 10000rpm for 15 minutes using a homogenizer ("ULTRA-TURRAXT25" manufactured by IKA) and left to stand for 30 minutes. Next, the contents of the beaker were filtered with a 120-mesh stainless steel filter to obtain a second raw material emulsion containing unmodified silicone oil. The average particle size of the emulsified particles of the unmodified silicone oil contained in the second raw material emulsion was 240nm.

[0234] A treatment liquid (C-6) was obtained by adding 33.31 g of ion exchange water and 33.35 g of propylene glycol to 16.67 g of the first raw material emulsion and 16.67 g of the second raw material emulsion. The average particle size of the emulsified particles in the treatment liquid (C-6) (the average particle size of the emulsified particles during mixing) was 245 nm.

[0235] <Preparation of Treatment Solution (D-1)>

[0236] When preparing the raw material emulsion B, 50 g of sodium hydroxide aqueous solution, 560 g of ion exchange water, and 90 g of surfactant (polyoxyethylene alkyl ether) were added and stirred and mixed. In addition, the treatment liquid (D-1) was obtained by the same method as the preparation method of the treatment liquid (A-4) described in 1. The average particle size of the emulsified particles of the carboxyl-modified silicone oil in the treatment liquid (D-1) was 75 nm.

[0237] <Preparation of Treatment Solution (D-2)>

[0238] When preparing the raw material emulsion B, 50 g of sodium hydroxide aqueous solution and 650 g of ion exchange water were added without adding a surfactant and stirred and mixed. Otherwise, the treatment liquid (D-2) was obtained by the same method as the preparation method of the treatment liquid (A-4) described in 1. The average particle size of the emulsified particles of the carboxyl-modified silicone oil in the treatment liquid (D-2) was 323 nm.

[0239] <Preparation of Treatment Solution (D-3)>

[0240] The raw material emulsion used for preparing the treatment liquid (D-1) was referred to as the first raw material emulsion. The average particle size of the emulsified particles of the carboxyl-modified silicone oil contained in the first raw material emulsion was 75 nm.

[0241] Next, a second raw material emulsion containing unmodified silicone oil was prepared. Specifically, 300 g of unmodified silicone oil (specifically, dimethyl polysiloxane) ("KF96-3000cs" manufactured by Shin-Etsu Chemical Co., Ltd., viscosity: 3000 mm 2 / s, specific gravity: 0.97), 580g of ion exchange water, and 120g of surfactant (polyoxyethylene alkyl ether) were placed in a beaker. The contents of the beaker were stirred at a speed of 10000rpm for 15 minutes using a homogenizer ("ULTRA-TURRAX T25" manufactured by IKA) and left to stand for 30 minutes. Next, the contents of the beaker were filtered with a 120-mesh stainless steel filter to obtain a second raw material emulsion containing unmodified silicone oil. The average particle size of the emulsified particles of the unmodified silicone oil contained in the second raw material emulsion was 86nm.

[0242] A treatment liquid (D-3) was obtained by adding 33.31 g of ion exchange water and 33.35 g of propylene glycol to 16.67 g of the first raw material emulsion and 16.67 g of the second raw material emulsion. The average particle size of the emulsified particles in the treatment liquid (D-3) (the average particle size of the emulsified particles during mixing) was 80 nm.

[0243] <Preparation of Treatment Solution (D-4)>

[0244] The raw material emulsion used for preparing the treatment liquid (D-2) was referred to as the first raw material emulsion. The average particle size of the emulsified particles of the carboxyl-modified silicone oil contained in the first raw material emulsion was 323 nm.

[0245] Next, a second raw material emulsion containing unmodified silicone oil was prepared. Specifically, 300 g of unmodified silicone oil (specifically, dimethyl polysiloxane) ("KF96-3000cs" manufactured by Shin-Etsu Chemical Co., Ltd., viscosity: 3000 mm 2 / s, specific gravity: 0.97), 680g of ion exchange water, and 20g of surfactant (polyoxyethylene alkyl ether) were placed in a beaker. The contents of the beaker were stirred at a speed of 10000rpm for 15 minutes using a homogenizer ("ULTRA-TURRAX T25" manufactured by IKA) and left to stand for 30 minutes. Next, the contents of the beaker were filtered with a 120-mesh stainless steel filter to obtain a second raw material emulsion containing unmodified silicone oil. The average particle size of the emulsified particles of the unmodified silicone oil contained in the second raw material emulsion was 350nm.

[0246] A treatment liquid (D-4) was obtained by adding 33.31 g of ion exchange water and 33.35 g of propylene glycol to 16.67 g of the first raw material emulsion and 16.67 g of the second raw material emulsion. The average particle size of the emulsified particles in the treatment liquid (D-4) (the average particle size of the emulsified particles during mixing) was 340 nm.

[0247] Next, printed materials for evaluation were prepared using the prepared treatment liquids (C-1) to (C-6) and treatment liquids (D-1) to (D-4), and the color fastness to rubbing thereof was evaluated.

[0248] <Method for preparing printed articles for evaluation of Examples 2-1 to 2-6 and Comparative Examples 2-1 to 2-4>

[0249] Regarding the preparation of printed articles of Examples 2-1 to 2-6 and Comparative Examples 2-1 to 2-4, evaluation printed articles were prepared by the same method as the method for preparing evaluation printed articles described in 1. above, except for the following changes. Specifically, the first ink chamber of the first ink cartridge was filled with the ink a described above, and the second ink chamber of the second ink cartridge was filled with any one of the treatment liquids (C-1) to (C-6) and (D-1) to (D-4) shown in Table 4 described later. The method for preparing the ink used was the same as the method described in 1. above. In each of the Examples and Comparative Examples, the discharge amount of the treatment liquid was set to 10 g / m 2 In addition, the ink ejection volume is 20g / m 2 .

[0250] <Evaluation of color fastness to rubbing>

[0251] The printed articles of Examples 2-1 to 2-6 and Comparative Examples 2-1 to 2-4 were evaluated by the same method as the evaluation of color fastness to rubbing described in 1. The evaluation results of the printed articles of each Example and each Comparative Example are summarized in Table 4 described below.

[0252] In this test, the ejection properties of the treatment liquids (C-1) to (C-6) and the treatment liquids (D-1) to (D-4) used in the examples and comparative examples from the treatment head were also evaluated. The method for evaluating the ejection properties is described in detail below.

[0253] <Evaluation of ejection properties>

[0254] The discharge properties of the processing liquid were evaluated using a discharge evaluation machine (KJ4B, manufactured by Kyocera Corporation) capable of checking the discharge of the processing liquid drop by drop from the nozzle using a camera image. The conditions of the discharge evaluation machine were set as follows.

[0255] (Conditions of the ejection evaluation machine)

[0256] Head temperature: 32℃

[0257] Spray volume of treatment liquid from the head: 10g / m 2

[0258] Drive frequency: 30kHz

[0259] The specific method for evaluating the ejection property is as follows. First, the camera position is adjusted using the ejection evaluation machine so that three nozzles can be seen in one field of view. Next, the ejection of the treatment liquid is started, and it takes 1 minute to visually confirm whether the treatment liquid is ejected normally through the camera image. After 1 minute, the nozzles that normally eject the treatment liquid are counted. Here, the nozzles that normally eject the treatment liquid refer to nozzles other than the nozzles that do not eject the treatment liquid normally (the nozzles that do not eject the treatment liquid straightly, the nozzles that do not eject the treatment liquid, the nozzles from which the treatment liquid overflows, etc.). Further, the camera position is moved, and another nozzle is used as the object, and the ejection property confirmation of the treatment liquid through the camera image for 1 minute is repeated in the same way. A total of 36 nozzles were confirmed at a total of 12 locations. Finally, the number of nozzles that normally eject the treatment liquid was totaled, and the ejection property of the treatment liquid was evaluated according to the following judgment criteria.

[0260] (Judgment Criteria)

[0261] A: 36

[0262] B: 34-35

[0263] C: 33 or less

[0264] Table 4 below summarizes the types of treatment liquids used in the examples and comparative examples (average particle size of emulsified particles, type of silicone oil, etc.), and the evaluation results of color fastness to rubbing and ejection properties.

[0265]

[0266] [Investigation]

[0267] As shown in Table 4, for Example 2-1 to Example 2-6, in which the average particle size of the emulsified particles of silicone oil (when two types of emulsified particles are contained, the average particle size of the two types of emulsified particles mixed) is within the range of 100 nm or more and 250 nm or less, the evaluations of color fastness to dry rubbing and color fastness to wet rubbing are all A or B. On the other hand, for the printed article of Comparative Example 2-1, in which the average particle size of the emulsified particles of 75 nm is used, and for the printed article of Comparative Example 2-3, in which the average particle size of the emulsified particles of 75 nm and 86 nm is used, the evaluations of color fastness to dry rubbing and color fastness to wet rubbing are poor, especially the evaluation of color fastness to wet rubbing is poor. It is speculated that this is because the hydrophilicity of the treatment liquid is improved, and the water resistance of the printed article is deteriorated. The ejection performance of the printed article of Comparative Example 2-2 using the treatment liquid (D-2) with an average particle size of 323 nm of emulsified particles and the printed article of Comparative Example 2-4 using the treatment liquid (D-4) with an average particle size of 323 nm and 350 nm of emulsified particles was significantly poor. It is speculated that this is because the meniscus becomes unstable when the particle size is large.

[0268] In other words, if the average particle size of the emulsified particles of the silicone oil in the treatment liquid (when it contains two types of emulsified particles, it is the average particle size of the emulsified particles on both sides) is greater than 100nm and less than 250nm, it is possible to produce printed materials with excellent sprayability of the treatment liquid and excellent color fastness to dry friction and color fastness to wet friction.

[0269] The embodiments and examples disclosed this time are illustrative in all points and should not be construed as limiting. The scope of the present invention is indicated by the claims rather than the above description, and includes all modifications within the meaning and scope equivalent to the claims.

[0270] Industrial Applicability

[0271] The processing liquid, inkjet printing device and inkjet printing method according to the present invention can be used to form printed objects.

[0272] Explanation of symbols

[0273] 1: Record header

[0274] 1a: First record header

[0275] 1b: Second recording head

[0276] 1c: Third record header

[0277] 1d: Fourth record header

[0278] 2: Processing header

[0279] 3: Loading table

[0280] 10: Inkjet printing device

[0281] P: Printing object

Claims

1. An inkjet treatment liquid, characterized in that Include: emulsified particles containing silicone oil; and an aqueous medium, The average particle size of the emulsified particles is greater than 100 nm and less than 250 nm, and the viscosity of the silicone oil is 700 nm. 2 / s~100000mm 2 / s, The silicone oil contains silicone oil containing ionic groups, The ionic group-containing silicone oil contains at least one selected from the group consisting of amino-modified silicone oil, carboxyl-modified silicone oil, phenol-modified silicone oil, and silanol-modified silicone oil.

2. The inkjet treatment liquid according to claim 1, characterized in that The average particle size of the emulsified particles is 100 nm or more and 160 nm or less.

3. The inkjet treatment liquid according to claim 1, characterized in that The emulsified particles include first emulsified particles and second emulsified particles having an average particle diameter different from that of the first emulsified particles, The average particle size of the first emulsified particles is 100 nm or more and 250 nm or less, The average particle size of the second emulsified particles is 100 nm or more and 250 nm or less.

4. The inkjet treatment liquid according to claim 3, characterized in that The average particle size of the first emulsified particles is 100 nm or more and 160 nm or less, The average particle size of the second emulsified particles is 100 nm or more and 160 nm or less.

5. The inkjet treatment liquid according to claim 3, characterized in that The difference between the average particle size of the first emulsified particles and the average particle size of the second emulsified particles is 0 nm or more and 30 nm or less.

6. The inkjet treatment liquid according to claim 1, wherein The ionic group-containing silicone oil is carboxyl-modified silicone oil.

7. The inkjet treatment liquid according to claim 1, characterized in that The silicone oil also contains unmodified silicone oil.

8. The inkjet treatment liquid according to claim 7, wherein The unmodified silicone oil is dimethyl polysiloxane.

9. The inkjet treatment liquid according to claim 7, wherein The ionic group-containing silicone oil is carboxyl-modified silicone oil.

10. The inkjet treatment liquid according to claim 3, characterized in that The silicone oil contains silicone oil containing ionic groups and unmodified silicone oil. The first emulsified particles contain silicone oil containing ionic groups, The second emulsified particles contain unmodified silicone oil.

11. The inkjet treatment liquid according to claim 1, wherein The silicone oil contains silicone oil containing ionic groups and unmodified silicone oil. The ratio of the mass of the ionic group-containing silicone oil to the mass of the unmodified silicone oil is 0.5 or more and less than 1.

0.

12. The inkjet treatment liquid according to claim 1, wherein For printing.

13. An inkjet printing method, characterized in that include: Ink jetting step, ejecting ink from the recording head toward the image forming area of ​​the printed object; as well as The processing step comprises ejecting an inkjet processing liquid from a processing head toward at least the image forming area of ​​the printing object, wherein: The inkjet processing liquid is the inkjet processing liquid according to any one of claims 1 to 12.

14. The inkjet printing method according to claim 13, characterized in that: The ink contains a pigment.

15. The inkjet printing method according to claim 13, characterized in that Also includes: The heating step heats at least the image forming area of ​​the printing object to which the ink and the processing liquid are ejected.

16. The inkjet printing method according to claim 13, characterized in that: Use the following inkjet printing device, the inkjet printing device comprises: A recording head ejects ink toward an image forming area of ​​a printed object; a processing head for ejecting the inkjet processing liquid toward at least the image forming area of ​​the printing object; and The ink cartridge is filled with the inkjet processing liquid.

17. The inkjet printing method according to claim 16, characterized in that: The ink contains a pigment.

18. The inkjet printing method according to claim 16, characterized in that: Also includes: The heating unit heats the printing object to which the ink and the processing liquid are ejected.

Images