Printing toner, manufacturing method thereof, and two-component developer

Abstract

To provide printing toner which can achieve both sublimation transfer efficiency and a heat-resistant storage property and can perform dyeing with high friction fastness for a dyed object, a manufacturing method of the same, and a two-component developer.SOLUTION: Printing toner has a toner particle including a polyester resin, a styrene acrylic resin, and a parting agent. The toner particle has a sea-island structure configured of a sea part including the styrene acrylic resin, a first island part including the polyester resin, and a second island part including the parting agent. The polyester resin of the first island part includes a sublimation dye. When SP values of the polyester resin, the styrene acrylic resin, and the parting agent are denoted as SP1, SP2, and SP3, respectively, a relation of the following formula (1) is satisfied: SP1>SP2>SP3 (1).SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present disclosure relates to a toner for textile printing suitable for sublimation transfer textile printing (dyeing using a sublimation transfer method), a method for producing the same, and a two-component developer. [Background technology]

[0002] Electrophotographic dyeing methods for dyeing substrates such as hydrophobic fibers, typified by polyester fabric, can be broadly divided into two types: (1) the direct method, in which toner is applied directly to the substrate, and then the dye in the toner is caused to adhere to the substrate by heat treatment, and resins other than the dye, release agents, etc., are dissolved and removed by alkaline washing; and (2) the sublimation transfer method, in which toner is applied to an intermediate recording medium, such as paper, and then the toner-adhered surface of the intermediate recording medium is placed over the substrate, and heat and pressure treatment are performed to sublimate and transfer the dye in the toner to the substrate.

[0003] Among these dyeing methods, the sublimation transfer method allows only the dye, one of the multiple components that make up the toner, to be transferred from the intermediate recording medium to the fibers of the object to be dyed, and in principle, no toner components other than the dye adhere to the object to be dyed (dyed cloth, woven fabric).For this reason, the sublimation transfer method is suitable for dyeing applications where texture is important, such as clothing (sports apparel, etc.) and interiors (seats, sofas, etc.), and is said to have the advantage of reducing the risk of rashes and eczema caused by components other than the dye in people with sensitive skin.

[0004] In addition, by eliminating the need for processes such as washing and drying, the dyeing process can be significantly reduced, and there are many other benefits, such as the benefit of not needing washing and drying lines that require large amounts of space and energy to operate, and the benefit of not needing treatment equipment for wash water, etc. For this reason, the sublimation transfer method is considered to be an advantageous dyeing method in that it can be used in small spaces.

[0005] As the dye in the toner used in the sublimation transfer method, disperse dyes and oil-soluble dyes that are suitable for dyeing hydrophobic fibers are used, and among these, easily sublimable dyes (sublimable dyes) that are particularly suitable for sublimation transfer to hydrophobic fibers by heat treatment are used.

[0006] In addition, there are two printing methods for the sublimation transfer method: inkjet printing and electrophotography, with inkjet printing being the mainstream. However, dyeing by sublimation transfer using the inkjet method has problems such as the organic solvent, one of the components of the ink, volatilizing due to the heat generated when transferring the dye, polluting the working environment. In contrast, electrophotography has been attracting attention in recent years because it does not pollute the working environment as there are no volatile components in the toner.

[0007] Incidentally, electrophotographic toners are known that have a sea-island structure in which toner particles have island portions (domains) dispersed in a sea portion (matrix). For example, Patent Document 1 discloses an electrophotographic toner in which a domain resin composition is dispersed in a matrix resin composition via a dispersion aid, the domain resin composition being a composition containing a colorant in the domain resin, the matrix resin composition having low miscibility with the domain resin, and the dispersion aid having miscibility with both the domain resin and the matrix resin and an Izod impact value higher than that of the matrix resin. [Prior art documents] [Patent documents]

[0008] [Patent Document 1] Japanese Patent Application Publication No. 5-88406 Summary of the Invention [Problem to be solved by the invention]

[0009] Resins used as binder resins for toners are broadly classified into polyester resins and styrene-acrylic resins. In the case of toners used in electrophotographic sublimation transfer methods, when polyester resins are used as binder resins, the polyester resins are highly miscible with sublimation dyes, so that a large amount of sublimation dye remains in the binder resin during sublimation transfer to the dyed object, making it difficult to improve the sublimation transfer efficiency. This results in the problem of difficulty in improving the dyeing density of the dyed object.

[0010] Furthermore, although the use of a styrene-acrylic resin as a binder resin can increase the sublimation transfer efficiency, the miscibility of the styrene-acrylic resin with the sublimation dye is low, which causes the sublimation dye to bleed out from the surface of the toner particles when the toner is stored in a high-temperature environment (a problem of reduced dye-bleed resistance), which in turn causes the problem of reduced heat-resistant storage stability of the toner.

[0011] Furthermore, dyeing using the sublimation transfer method in principle has high resistance to friction, and if only the sublimable dye is transferred to the item to be dyed during sublimation transfer to the item to be dyed, high resistance to friction can be achieved. However, if components other than the sublimable dye (especially resin components) are transferred to the item to be dyed, these components will be scraped off during friction, resulting in a problem of reduced resistance to friction.

[0012] The toner of the present disclosure has been discovered in view of the above circumstances, and its main object is to provide a textile printing toner that can achieve both sublimation transfer efficiency and heat-resistant storage stability and can dye an object with high abrasion fastness, a method for producing the same, and a two-component developer. [Means for solving the problem]

[0013] The toner for textile printing of the present disclosure, which has been made to solve the above problems, comprises: A toner having toner particles containing a polyester resin, a styrene-acrylic resin, and a release agent, the toner particles have a sea-island structure including a sea portion containing the styrene acrylic resin, a first island portion containing the polyester resin, and a second island portion containing the release agent; the polyester resin of the first island portion contains a sublimable dye; When the SP values ​​of the polyester resin, the styrene acrylic resin, and the release agent are SP1, SP2, and SP3, respectively, the relationship of the following formula (1) is satisfied. SP1>SP2>SP3 (1)

[0014] In the above-mentioned textile printing toner, the average dispersed diameter of the first island portions in the sea portion is preferably 0.3 μm or more and 2.5 μm or less.

[0015] In addition, it is preferable that the above-mentioned textile printing toner satisfies the relationship of the following formula (2). 2.0 ≧ SP1-SP2 ≧ 0.5 (2)

[0016] In the above-mentioned textile printing toner, the content ratio of the polyester resin to the styrene acrylic resin in the toner particles is preferably within a range of 1:9 to 3:7.

[0017] In the above-mentioned textile printing toner, the release agent is preferably a hydrocarbon wax, and the melting point thereof is preferably 70°C or higher and 110°C or lower.

[0018] In the above-mentioned textile printing toner, the average dispersion diameter of the second island portions in the sea portion is preferably 250 nm or more and 1500 nm or less.

[0019] In the above-mentioned textile printing toner, the content of the release agent in the toner particles is preferably 3% by mass or more and 10% by mass or less.

[0020] The two-component developer disclosed herein, which has been made to solve the above problems, contains the textile printing toner and a carrier.

[0021] The method for producing a toner for textile printing according to the present disclosure, which has been made to solve the above problems, comprises: a first melt-kneading step of melt-kneading a mixture containing the polyester resin and the sublimable dye to obtain a first melt-kneaded product; a second melt-kneading step of melt-kneading a mixture containing the first melt-kneaded product, the styrene-acrylic resin, and the release agent to obtain a second melt-kneaded product; a pulverization step of pulverizing the second molten kneaded product to obtain a pulverized product; and a classification step of classifying the pulverized product to obtain the toner particles.

[0022] In this specification, "external addition" means adding an additive so that it adheres to the outer surface (surface) of the substance to which it is added, and "internal addition" means adding an additive so that it is contained inside the substance to which it is added. [Effects of the Invention]

[0023] The textile printing toner and two-component developer of the present disclosure exhibit excellent effects such as excellent sublimation transfer efficiency and heat-resistant storage stability, and the ability to dye objects with high abrasion fastness. [Brief explanation of the drawings]

[0024] [Figure 1] FIG. 2 is a cross-sectional view schematically illustrating a toner particle according to the exemplary embodiment. [Figure 2] 1 is a cross-sectional view schematically illustrating how dye bleeding is suppressed in the toner particles according to the exemplary embodiment. [Figure 3] FIG. 2 is a cross-sectional view schematically illustrating a state in which the textile printing toner according to the present embodiment has been fixed to an intermediate recording medium as a toner layer. [Figure 4] FIG. 4 is a cross-sectional view schematically showing sublimation transfer from the toner layer to the object to be dyed in FIG. 3. [Figure 5] 1 is an SEM photograph of a textile printing toner in which the average dispersed diameter of the first island portions is about 0.3 μm. [Figure 6] 1 is an SEM photograph of a textile printing toner in which the average dispersed diameter of the first island portions is approximately 1.0 μm to 1.5 μm. [Figure 7] FIG. 1 is a cross-sectional view schematically illustrating a conventional textile printing toner. [Figure 8] FIG. 8 is a cross-sectional view schematically showing a state in which a sublimation dye bleeds out from the textile printing toner of FIG. 7. DETAILED DESCRIPTION OF THE INVENTION

[0025] The toner for textile printing, its manufacturing method, and two-component developer of the present disclosure will be described in detail below.

[0026] 1. Toner particles (toner cores) The toner particles according to this embodiment contain at least a polyester resin, a styrene-acrylic resin, and a release agent. The average primary particle diameter of the toner particles can be appropriately selected depending on the purpose, and may be, for example, 4 μm or more and 8 μm or less.

[0027] In the production of toner particles, a styrene-acrylic resin and a polyester resin containing a sublimable dye are mixed together to form a sea-island dispersion of the polyester resin within the styrene-acrylic resin, with the sublimable dye selectively incorporated into the first island regions of the polyester resin. This dispersion state can improve dye bleeding during high-temperature storage. Furthermore, since the majority of the toner components are styrene-acrylic resin when the toner is completely melted during thermal transfer, high sublimation transfer efficiency can be achieved. Additionally, by using a polyester resin containing a sublimable dye and selectively incorporating a release agent into the styrene-acrylic resin, it is possible to dye objects with high abrasion fastness without reducing dye bleed resistance.

[0028] 5 and 6 are photographs of toner particles according to this embodiment taken with a scanning electron microscope (SEM), with Fig. 5 being an SEM photograph of toner particles having a first island portion with an average dispersed diameter of about 0.3 μm, and Fig. 6 being an SEM photograph of toner particles having a first island portion with an average dispersed diameter of about 1.0 μm to 1.5 μm. In both SEM photographs, the sea-like portion is a styrene-acrylic resin, and the dispersed islands within it are a polyester resin, with a sublimable dye added internally to the polyester resin.

[0029] The toner particles according to this embodiment are in this dispersed state, that is, the toner particles according to this embodiment satisfy the following requirements (A) to (C): Requirements (A) and (B) are requirements relating to the configuration of the dispersed state, and requirement (C) is a requirement relating to the relationship of SP values ​​that the toner components must satisfy in order to achieve the dispersed state. (A) The toner particles have a sea-island structure composed of a sea portion containing the styrene acrylic resin, first island portions containing the polyester resin, and second island portions containing the release agent. (B) The polyester resin of the first island portion contains a sublimable dye. (C) When the SP values ​​of the polyester resin, the styrene acrylic resin, and the release agent are SP1, SP2, and SP3, respectively, the relationship of the following formula (1) is satisfied. SP1>SP2>SP3 (1)

[0030] In this embodiment, the sea portion is made of a styrene acrylic resin, the first island portion is made of a polyester resin containing a sublimable dye, and the second island portion is made of a release agent. However, the sea portion, the first island portion, and the second island portion may contain components other than these as long as the effects of the textile printing toner of the present disclosure are not impaired.

[0031] Here, the mechanism by which the textile printing toner according to this embodiment can achieve both sublimation transfer efficiency and heat-resistant storage stability and can dye an object with high abrasion fastness will be described with reference to the drawings.

[0032] FIG. 7 is a cross-sectional view of a conventional textile printing toner 100, in which a sublimable dye 300 and a release agent (wax) 400 are dispersed in a styrene-acrylic resin 200. As shown in FIG. 7, using the styrene-acrylic resin 200 as the binder resin can improve sublimation transfer efficiency, but the miscibility between the styrene-acrylic resin 200 and the sublimable dye 300 is low. This causes a problem in that the sublimable dye 300 bleeds out from the surface of the toner particles 100 when the toner is stored in a high-temperature environment (reducing dye-bleed resistance). FIG. 8 is a cross-sectional view of the textile printing toner of FIG. 7, in which the symbol 300a indicates the bleeding of the sublimable dye. This bleeding of the sublimable dye can cause problems such as a decrease in charge, a decrease in image density, and an increase in fogging.

[0033] Furthermore, dyeing using the sublimation transfer method inherently has high abrasion resistance. If only the sublimation dye is transferred to the substrate during sublimation transfer, high abrasion resistance can be achieved. However, if components other than the sublimation dye (especially resin components) are transferred to the substrate, they are scraped off during friction, resulting in a decrease in abrasion resistance. Therefore, it is important to properly form a release agent layer between the substrate and the toner layer on the intermediate recording medium during sublimation transfer. The formation of this release agent layer prevents the resin components from transferring to the substrate. In conventional textile printing toners, a release agent layer can be formed between the substrate and the toner layer on the intermediate recording medium by dispersing a large amount of release agent 400 in the resin, as shown in Figure 7. However, the release agent is compatible with some resins, locally reducing the resin viscosity. Furthermore, the release agent itself is easily mobile within the toner particles in high-temperature environments, which can lead to dye bleeding near the release agent. 8 shows a schematic diagram of how dye bleeding 300a is likely to occur near the release agent 400. On the other hand, if the content of the release agent in the toner particles is reduced, a sufficient release agent layer is not formed between the object to be dyed and the toner layer on the intermediate recording medium, resulting in a problem of reduced abrasion fastness.

[0034] In contrast, Figure 1 is a cross-sectional view schematically illustrating a toner particle 1 according to this embodiment, which has a sea-island structure in which first island regions 3 made of a polyester resin containing a sublimable dye and second island regions 4 made of a release agent are dispersed within a sea region 2 made of a styrene acrylic resin. Because polyester resins and sublimable dyes are highly miscible, it is possible to suppress dye bleeding that occurs when the toner particle is left in a high-temperature environment for a long period of time. Figure 2 is a cross-sectional view schematically illustrating how dye bleeding is suppressed in toner particle 1 according to this embodiment, and shows that bleeding 3a of the sublimable dye is suppressed.

[0035] Furthermore, in the toner particles according to this embodiment, the compatibility between the styrene acrylic resin, polyester resin, and release agent is controlled as required by requirement (C), and the release agent is selectively dispersed in the styrene acrylic resin, thereby containing a large amount of release agent. However, as shown in Figure 1, the sublimable dye in the first island portion 3 is unlikely to come into contact with the release agent in the second island portion 4. Therefore, since there is little contact between the sublimable dye and the release agent, it is possible to suppress dye bleeding that occurs when the toner particles are left in a high-temperature environment for a long period of time.

[0036] 3 is a cross-sectional view schematically showing a state in which the textile printing toner according to this embodiment has been fixed as a toner layer 60 onto transfer paper (plain paper) 70 as an intermediate recording medium. After the toner has been fixed onto the transfer paper 70, the styrene-acrylic resin and the polyester-based resin become compatible with each other, and the sublimable dye 62 is diffused throughout the toner layer 60, including the styrene-acrylic resin. Then, the release agent bleeds onto the surface of the toner layer 60, forming a release agent layer 50.

[0037] FIG. 4 is a cross-sectional view showing a schematic diagram of sublimation transfer from a toner layer 60 to a fabric 80 as a dyed object. The arrows in FIG. 4 indicate the sublimation of a sublimable dye 62 from the toner layer 60. During sublimation transfer to the fabric 80, the main component of the resin constituting the toner particles is a styrene-acrylic resin, resulting in good sublimation transfer efficiency and enabling high-concentration dyeing of the fabric 80. Furthermore, because the release agent layer 50 is properly formed, only the sublimable dye 62 migrates to the fabric 80, enabling dyeing of the fabric 80 with high rubbing fastness.

[0038] Next, each component constituting the toner particles will be described, but other optional components may be contained within a range that does not impair the effects of the textile printing toner of the present disclosure.

[0039] <Binder resin> The binder resin contained in the textile printing toner of the present disclosure includes a styrene-acrylic resin (styrene-acrylic copolymer resin) and a polyester resin.

[0040] The content of the binder resin in the toner particles (total amount of styrene acrylic resin and polyester resin) is not particularly limited and can be selected appropriately depending on the purpose. A guideline is 60% by mass or more and 95% by mass or less in the toner particles. If the binder resin content in the toner particles is less than 60% by mass, the viscoelastic properties required for a textile printing toner when fixing to an intermediate recording medium may not be obtained. If the binder resin content in the toner particles exceeds 95% by mass, the amounts of sublimation dye and release agent added, and the amounts of additives such as charge control agents added may become insufficient, and the effects of the textile printing toner of the present disclosure may not be fully obtained. The content of the binder resin in the toner particles is preferably 70% by mass or more and 93% by mass or less, and more preferably 80% by mass or more and 90% by mass or less.

[0041] In the textile printing toner according to this embodiment, when the SP values ​​of the polyester resin and the styrene acrylic resin are SP1 and SP2, respectively, it is preferable that the relationship of the following formula (2) is satisfied. 2.0 ≧ SP1-SP2 ≧ 0.5 (2)

[0042] By satisfying the relationship of the above formula (2), the compatibility between the polyester resin and the styrene-acrylic resin becomes appropriate, and the two resins form a clear boundary surface in the toner particles, while the two resins can be uniformly compatible when fixed to the intermediate recording medium, thereby further improving the sublimation transfer efficiency and dye bleed resistance. It is more preferable that SP1-SP2 is 1.0 or more and 1.6 or less.

[0043] The content ratio of the polyester resin to the styrene acrylic resin in the toner particles according to this embodiment is preferably within a range of 1:9 to 3:7, and more preferably within a range of 1.5:8.5 to 2.5:7.5. When the content ratio of the two resins is within the above range, sublimation transfer efficiency and dye bleed resistance can be further improved.

[0044] -Styrene acrylic resin- The styrene acrylic resin in the toner particles according to this embodiment constitutes the sea portion of the sea-island structure, as shown in FIG.

[0045] Styrene-acrylic resins can be produced by copolymerizing a styrene-based monomer and a (meth)acrylic monomer by a known method. Here, the term "(meth)acrylic monomer" encompasses both acrylic and methacrylic monomers.

[0046] Examples of polymerization methods for styrene-acrylic resins include bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization. The polymerization method can be selected and the polymerization conditions can be appropriately set depending on the molecular weight and physical properties of the resin to be obtained.

[0047] Examples of styrene-based monomers include styrene and styrene derivatives such as o-methylstyrene, m-methylstyrene, p-methylstyrene, α-methylstyrene, p-ethylstyrene, and 2,4-dimethylstyrene.

[0048] In the textile printing toner according to this embodiment, one of the above styrene-based monomers may be used alone, or two or more of them may be used in combination.

[0049] Examples of acrylic monomers include acrylic acid and acrylic acid derivatives such as methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, propyl acrylate, octyl acrylate, 2-chloroethyl acrylate, phenyl acrylate, and dodecyl acrylate.

[0050] Examples of methacrylic monomers include methacrylic acid, methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-octyl methacrylate, 2-ethylhexyl methacrylate, phenyl methacrylate, and methacrylic acid derivatives such as dimethylamino ester.

[0051] In the textile printing toner according to this embodiment, one of the above (meth)acrylic monomers may be used alone, or two or more of them may be used in combination.

[0052] The styrene-acrylic resin may contain other monomer components within the range that does not impair the effects of the toner for textile printing of the present disclosure. Examples of other monomer components include vinyl monomers such as maleic anhydride, maleic acid monomethyl ester, maleic acid monoethyl ester, maleic acid monophenyl ester, maleic acid monoallyl ester, and divinylbenzene.

[0053] The mass average molecular weight of the styrene acrylic resin is preferably 5,000 or more and 500,000 or less. If the mass average molecular weight is less than 5,000, the heat-resistant storage stability of the toner may be insufficient. If the mass average molecular weight exceeds 500,000, the fixability to the intermediate recording medium may be insufficient. The mass average molecular weight of the styrene acrylic resin is more preferably 10,000 or more and 200,000 or less.

[0054] The glass transition point (Tg) of the styrene-acrylic resin is preferably 50°C or higher and 70°C or lower. If the glass transition point is lower than 50°C, the heat-resistant storage stability of the toner may be insufficient. If the glass transition point is higher than 70°C, the low-temperature fixability to the intermediate recording medium is impaired, and when attempting to fix to the intermediate recording medium at high temperatures, partial sublimation of the sublimable dye occurs at that point, which may result in insufficient image density when transferred from the intermediate recording medium to the dyed object. The glass transition point of the styrene-acrylic resin is more preferably 52°C or higher and 67°C or lower, and even more preferably 55°C or higher and 65°C or lower.

[0055] The softening point (Tm) of the styrene acrylic resin is preferably 100°C or higher and 150°C or lower. If the softening point is lower than 100°C, the heat-resistant storage stability of the toner may be insufficient. If the softening point is higher than 150°C, the low-temperature fixability to the intermediate recording medium is impaired, and when attempting to fix to the intermediate recording medium at high temperatures, partial sublimation of the sublimable dye occurs at that point, which may result in insufficient image density when transferred from the intermediate recording medium to the dyed object. The softening point of the styrene acrylic resin is more preferably 110°C or higher and 145°C or lower, and even more preferably 120°C or higher and 140°C or lower.

[0056] When the softening point or glass transition point of the styrene-acrylic resin does not fall within the above range, it is preferable to adjust these points with the polyester resin used in combination so that the softening point and glass transition point are appropriate for the toner.

[0057] -Polyester resin- As shown in FIG. 1 , the polyester resin in the toner particles according to this embodiment constitutes first island portions in a sea-island structure. A sublimable dye is internally added to the polyester resin in the first island portions. The average dispersion diameter of the first island portions, composed of the polyester resin, in the sea portion composed of the styrene-acrylic resin is preferably 0.3 μm or more and 2.5 μm or less, and more preferably 1.0 μm or more and 2.0 μm or less. By setting the average dispersion diameter of the first island portions within the above range, sublimation transfer efficiency and dye-bleed resistance can be further improved. If the average dispersion diameter of the first island portions is below the lower limit, the polyester resin begins to partially dissolve in the styrene-acrylic resin, and the sublimable dye also migrates into the styrene-acrylic resin, which may result in a deterioration in dye-bleed resistance. If the average dispersion diameter of the first island portions exceeds the upper limit, the polyester resin is more likely to become the pulverized interface of the toner particles, which may increase the exposure of the sublimable dye to the toner particle surface, resulting in a deterioration in dye-bleed resistance. Furthermore, since the polyester resin and the styrene-acrylic resin are not sufficiently compatible with each other when fixed to the intermediate recording medium paper, the sublimation efficiency of the sublimable dye added to the polyester resin decreases, which may result in a decrease in transfer efficiency.

[0058] The polyester resin contained in the toner particles according to this embodiment is obtained by a polycondensation reaction between a carboxylic acid monomer containing terephthalic acid or isophthalic acid as a main component and a polyhydric alcohol containing ethylene glycol as a main component, for example.

[0059] The reaction conditions are the same as those used in the production of ordinary polyester resins, and for example, a polyester resin can be obtained by reacting a dicarboxylic acid monomer with a polyhydric alcohol in a nitrogen gas atmosphere, optionally in the presence of an esterification catalyst, at 190°C to 240°C. The reaction ratio of the polyhydric alcohol to the carboxylic acid monomer is preferably 1.3:1 to 1:1.2 in terms of the equivalent ratio of hydroxyl groups to carboxyl groups, [OH]:[COOH].

[0060] The dicarboxylic acid monomer used in the synthesis of the polyester resin contains terephthalic acid or isophthalic acid as a main component, and the molar content of terephthalic acid or isophthalic acid in the dicarboxylic acid monomer is preferably 70% or more and 100% or less, and more preferably 80% or more and 100% or less.

[0061] The dicarboxylic acid monomer may also contain an aromatic dicarboxylic acid or an aliphatic dicarboxylic acid other than terephthalic acid and isophthalic acid. Examples of aromatic dicarboxylic acids other than terephthalic acid and isophthalic acid include fumaric acid, and examples of aliphatic dicarboxylic acids include adipic acid, sebacic acid, succinic acid, and decanedicarboxylic acid. The dicarboxylic acid monomer may also contain an ester-forming derivative of terephthalic acid or isophthalic acid, an ester-forming derivative of an aromatic dicarboxylic acid other than terephthalic acid and isophthalic acid, or an ester-forming derivative of an aliphatic dicarboxylic acid. In the present disclosure, examples of the ester-forming derivative include an acid anhydride and an alkyl ester of a carboxylic acid. These dicarboxylic acid monomers may be used alone or in combination of two or more.

[0062] In the synthesis of polyester-based resins, trivalent or higher polycarboxylic acid monomers may be used together with the dicarboxylic acid monomers. Examples of trivalent or higher polycarboxylic acid monomers that can be used include trivalent or higher polycarboxylic acids such as trimellitic acid and pyromellitic acid, and ester-forming derivatives thereof. These trivalent or higher polycarboxylic acid monomers may be used alone or in combination of two or more.

[0063] The diol monomer used in the synthesis of the polyester resin contains ethylene glycol, butanediol, and bisphenol A as main components. Here, the molar content of ethylene glycol, butanediol, or bisphenol A in the diol monomer is preferably 70% or more and 100% or less, and more preferably 80% or more and 100% or less. The diol monomer may contain 1,3-propylene glycol, etc. These diol monomers may be used alone or in combination of two or more.

[0064] From the viewpoint of the fixability, storage stability, durability, etc. of the toner, the polyester resin preferably has a glass transition temperature (Tg) of 50° C. or more and 70° C. or less. If the glass transition temperature is outside this range, the balance between the fixability, storage stability, and durability of the toner may be lost.

[0065] Furthermore, from the viewpoint of achieving both low-temperature fixability and hot offset resistance of the toner, the polyester resin preferably has a softening point (Tm) of 100° C. or more and 150° C. or less. If the softening point is outside this range, the balance between the low-temperature fixability and hot offset resistance of the toner may be lost.

[0066] From the viewpoint of achieving both heat-resistant storage stability and low-temperature fixability of the toner, the polyester resin preferably has a peak top molecular weight (Mp) of 3,000 or more and 10,500 or less. If the peak top molecular weight is outside this range, the balance between the heat-resistant storage stability and low-temperature fixability of the toner may be lost. Here, the peak top molecular weight refers to the molecular weight showing the maximum peak height of the THF-soluble component in gel permeation chromatography (GPC) using tetrahydrofuran (THF) as the mobile phase and polystyrene as the standard.

[0067] Furthermore, from the viewpoint of the toner's chargeability, the polyester resin preferably has an acid value of 0 mgKOH or more and 60 mgKOH / g or less, and from the viewpoint of the toner's hot offset resistance, preferably has a hydroxyl value of 0 mgKOH / g or more and 50 mgKOH / g or less. If the acid value exceeds 60 mgKOH / g, the toner's chargeability may deteriorate, and if the hydroxyl value exceeds 50 mgKOH / g, the toner's hot offset resistance may become insufficient.

[0068] <Sublimable dye> In the textile printing toner according to this embodiment, the sublimation dye is incorporated into the first island portion (polyester resin). As the sublimation dye, a dye suitable for sublimation transfer is preferable.

[0069] The term "dye suitable for sublimation transfer" refers to a dye whose staining (polyester) test result in the heat treatment test (method C) in "Testing methods for color fastness to dry heat treatment [JIS L 0879:2005] (revised January 20, 2005, published by the Japanese Standards Association)" is usually grade 3 or 4 or lower, preferably grade 3 or lower. Among such dyes, well-known dyes include, for example, the following dyes:

[0070] Examples of yellow dyes include CI Disperse Yellow 3, 7, 8, 23, 39, 51, 54, 60, 71, and 86; CI Solvent Yellow 114 and 163; and the like.

[0071] Orange dyes include CI Disperse Orange 1, 1:1, 5, 20, 25, 25:1, 33, 56, 76, and the like.

[0072] Examples of brown dyes include CI Disperse Brown 2.

[0073] Red dyes include CI Disperse Red 11, 50, 53, 55, 55:1, 59, 60, 65, 70, 75, 93, 146, 158, 190, 190:1, 207, 239, 240; CI Vat Red 41, and the like.

[0074] Examples of violet dyes include CI Disperse Violet 8, 17, 23, 27, 28, 29, 36, and 57.

[0075] Examples of blue dyes include CI Disperse Blue 19, 26, 26:1, 35, 55, 56, 58, 64, 64:1, 72, 72:1, 81, 81:1, 91, 95, 108, 131, 141, 145, 359, and 360; and CI Solvent Blue 3, 63, 83, 105, and 111.

[0076] In the textile printing toner according to this embodiment, one of the above dyes may be used alone, or two or more may be used in combination. By combining two or more dyes, it is possible to obtain a hue that is completely different from the original dye. For example, a black dye can be obtained by blending a blue dye as the main dye with an appropriate amount of a yellow dye and a red dye. Furthermore, by combining two or more dyes, it is possible to fine-tune the color tone of blue, yellow, orange, red, violet, black, etc. to a more preferred color tone, or to obtain an intermediate color.

[0077] The content of the sublimation dye in the toner particles according to this embodiment can be appropriately selected depending on the purpose, but is preferably 2% by mass or more and 20% by mass or less, and more preferably 5% by mass or more and 15% by mass or less. If the content of the sublimation dye in the toner particles is less than the lower limit, the dye density may decrease. If the content of the sublimation dye in the toner particles exceeds the upper limit, poor dispersion of the sublimation dye may occur.

[0078] In the toner particles according to the present embodiment, the ratio of the sublimation dye to the styrene-acrylic resin and the polyester-based resin is preferably 60% to 100% of the sublimation dye in the polyester-based resin. If the ratio is 60% or less, the sublimation dye present in the styrene-acrylic resin is likely to cause dye bleeding during high-temperature storage, which may deteriorate the heat-resistant storage stability. The method for confirming the ratio of the sublimation dye is the same as the "Method for measuring the average dispersion diameter of island portions dispersed in toner particles" in the examples described later, and is confirmed using photographic data obtained by observing the cross section of the toner particles with a scanning transmission electron microscope.

[0079] <Release agent> The release agent in the toner particles according to this embodiment constitutes the second island portion in the sea-island structure, as shown in Fig. 1. As the release agent in the toner particles according to this embodiment, a release agent commonly used in the technical field can be used, and examples thereof include synthetic ester wax, carnauba wax, and hydrocarbon wax.

[0080] Among these, hydrocarbon waxes are preferred as the release agent in the toner particles according to the present embodiment. By using a hydrocarbon wax as the release agent, it is possible to obtain an appropriate compatibility between the release agent and the styrene-acrylic resin, and it is possible to more reliably make the release agent present in the styrene-acrylic resin.

[0081] The melting point of the release agent is preferably 70°C or higher and 110°C or lower, and more preferably 80°C or higher and 100°C or lower. When the melting point of the release agent is within the above range, a sufficient release agent layer is easily formed between the toner layer and the substrate during sublimation transfer from the intermediate recording medium to the substrate. This makes it possible to dye the substrate with higher abrasion fastness and further improve dye bleed resistance. If the melting point of the release agent is lower than 70°C, the heat resistance of the toner may deteriorate. If the melting point of the release agent is higher than 110°C, the release properties may be insufficient during fixation to the intermediate recording medium, which may cause hot offset. Furthermore, if the toner softens before the release agent layer is formed during sublimation transfer to the substrate, components other than the sublimable dye may migrate to the substrate, resulting in a decrease in the abrasion fastness of the substrate after sublimation transfer.

[0082] Hydrocarbon waxes include non-polar hydrocarbon waxes and polar hydrocarbon waxes.

[0083] Examples of non-polar hydrocarbon waxes include polyolefin waxes (low molecular weight polyethylene, low molecular weight polypropylene, polyolefin copolymers, etc.), paraffin wax, microcrystalline wax, and Fischer-Tropsch wax.

[0084] Examples of polar hydrocarbon waxes include oxides of non-polar hydrocarbon waxes such as oxidized polyethylene wax, and alcohols obtained by hydrolyzing the oxides.

[0085] Further, examples of polar hydrocarbon waxes include saturated straight-chain fatty acids such as palmitic acid, stearic acid, montanic acid, and long-chain alkylcarboxylic acids having even longer alkyl groups; unsaturated fatty acids such as brassidic acid, eleostearic acid, and valinaric acid; saturated alcohols such as stearyl alcohol, eicosyl alcohol, behenyl alcohol, carnaubyl alcohol, ceryl alcohol, melissyl alcohol, and long-chain alkyl alcohols having even longer alkyl groups; polyhydric alcohols such as sorbitol; fatty acid amides such as linoleic acid amide, oleic acid amide, and lauric acid amide; Examples of such bisamides include saturated fatty acid bisamides such as methylene bisstearic acid amide, ethylene biscapric acid amide, ethylene bislauric acid amide, and hexamethylene bisstearic acid amide; unsaturated fatty acid amides such as ethylene bisoleic acid amide, hexamethylene bisoleic acid amide, N,N'-dioleyl adipamide, and N,N'-dioleyl sebacic acid amide; aromatic bisamides such as m-xylene bisstearic acid amide and N,N'-distearyl isophthalic acid amide; and waxes obtained by grafting aliphatic hydrocarbon waxes with vinyl monomers such as styrene and acrylic acid.

[0086] In the toner for textile printing according to this embodiment, one of these release agents may be used alone, or two or more may be used in combination. Among these release agents, at least one hydrocarbon wax selected from the group consisting of polyolefin wax, paraffin wax, and Fischer-Tropsch wax is particularly preferred, as it has suitable compatibility with the styrene-acrylic resin binder resin, high bleeding properties of the release agent during fixing, and a high release effect.

[0087] The average dispersion diameter of the second island portions, which are composed of the release agent, in the sea portion composed of the styrene-acrylic resin is preferably 250 nm to 1,500 nm, more preferably 300 nm to 1,200 nm, and even more preferably 500 nm to 1,000 nm. If the average dispersion diameter of the second island portions is less than 250 nm, the release agent may bleed onto the toner particle surface when the toner is fixed to the intermediate recording medium, reducing the inherent effect of the release agent, which is to improve releasability from the fixing roller, and resulting in insufficient fixation to the intermediate recording medium. If the average dispersion diameter of the second island portions exceeds 1,500 nm, the exposed area of ​​the release agent on the toner particle surface increases, which may reduce the heat resistance of the toner.

[0088] In the textile printing toner according to this embodiment, when the SP values ​​of the polyester resin, the styrene acrylic resin, and the release agent are SP1, SP2, and SP3, respectively, it is more preferable that the relationship between the following formulas (3) and (4) is satisfied. 4.0 ≧ SP1-SP3 ≧ 3.0 (3) 3.3 ≧ SP2-SP3 ≧ 1.7 (4)

[0089] By satisfying the relationships of the above formulas (3) and (4), the polyester resin and the release agent can be easily formed as independent islands in the styrene-acrylic resin, and excessive compatibility of the release agent in the styrene-acrylic resin can be suppressed. As a result, it is possible to achieve both high sublimation transfer efficiency and suppression of deterioration of heat-resistant storage stability due to dye bleeding.

[0090] The content of the release agent in the toner particles according to this embodiment is preferably 3% by mass or more and 10% by mass or less, more preferably 3% by mass or more and 8% by mass or less, and even more preferably 4% by mass or more and 6% by mass or less. If the content of the release agent is less than 3% by mass, a sufficient release agent layer may not be formed when an image formed on an intermediate recording medium is thermally transferred to an object to be dyed, and components other than the sublimation dye may migrate to the object to be dyed, resulting in a decrease in the abrasion resistance of the object after sublimation transfer. If the content of the release agent exceeds 10% by mass, it becomes difficult for the release agent to be dispersed, increasing the exposed area of ​​the release agent on the toner particle surface and possibly reducing the heat resistance of the toner.

[0091] By having the melting point of the release agent in the toner particles within the above range and the content of the release agent in the toner particles within the above range, the toner particles have excellent heat-resistant storage stability. Furthermore, by forming a sufficient release agent layer between the toner layer and the object to be dyed during sublimation transfer to the object to be dyed, and suppressing the migration of the toner components to the fabric, the friction fastness of the object to be dyed after sublimation transfer can be sufficiently improved.

[0092] <Charge control agent> The toner particles according to the present embodiment preferably contain a charge control agent. The charge control agent is not particularly limited, but charge control agents commonly used in the art for controlling positive and negative charges can be used.

[0093] Examples of charge control agents for controlling positive charges include nigrosine dyes, basic dyes, quaternary ammonium salts, quaternary phosphonium salts, aminopyrine, pyrimidine compounds, polynuclear polyamino compounds, aminosilanes, nigrosine dyes and derivatives thereof, triphenylmethane derivatives, guanidine salts, and amidine salts.

[0094] Examples of charge control agents for negative charge control include oil-soluble dyes such as oil black and Spiron black, metal-containing azo compounds, azo complex dyes, metal naphthenate salts, metal complexes and metal salts of salicylic acid and its derivatives (metals include chromium, zinc, zirconium, etc.), boron compounds, fatty acid soaps, long-chain alkyl carboxylate salts, and resin acid soaps.

[0095] In the toner for textile printing according to this embodiment, one of the above charge control agents may be used alone, or two or more of them may be used in combination.

[0096] The content of the charge control agent in the toner particles can be appropriately selected according to the purpose, taking into consideration the type of binder resin, the presence or absence of other additives, the dispersion method, etc., and is not particularly limited, but is preferably 0.5% by mass to 3.0% by mass, and more preferably 0.7% by mass to 2.5% by mass. When the content of the charge control agent is within the above range, it is possible to form images with high image density and good image quality without impairing various physical properties of the toner.

[0097] 2.External additives The textile printing toner according to the present embodiment may have an external additive attached to the surface of the toner particles. Examples of the functions of the external additive include improving the powder fluidity, triboelectric charging property, heat-resistant storage stability, and cleaning property of the toner, and controlling the abrasion property of the photoreceptor surface.

[0098] The external additive is not particularly limited, and various external additives commonly used in the art can be used, and two or more external additives can be used in combination. For example, inorganic fine particles having an average primary particle diameter of 5 nm to 200 nm, such as silica, titanium oxide, or alumina, can be used as the external additive. These inorganic fine particles are more preferably hydrophobized by coating the surface with a surface treatment agent, such as a silane coupling agent, a titanium coupling agent, or a silicone oil, because this reduces the decrease in electrical resistance and charge amount in a high-humidity environment. Among these inorganic fine particles, silica particles having an average primary particle diameter of 15 nm or less are preferred because they can appropriately improve the fluidity and heat-resistant storage stability of toner particles.

[0099] Examples of silica particles as external additives include silica particles commonly used in the technical field, such as dry-process silica particles such as fumed silica obtained by burning silicon tetrachloride and arc-process silica in which silica is atomized in the gas phase using high energy such as plasma; wet-process silica particles such as precipitation-process silica synthesized under alkaline conditions using an aqueous sodium silicate solution as a raw material and gel-process silica synthesized under acidic conditions; colloidal silica particles obtained by polymerizing acidic silicic acid in an alkaline state; and sol-gel-process silica particles obtained by hydrolysis of an organic silane compound. These may be subjected to a hydrophobic treatment in which the surface is coated with a surface treatment agent such as a silane coupling agent in order to improve the electrical properties of the photoreceptor.

[0100] Methods for coating the surface with a silane coupling agent include surface treatments commonly used in the art using hexamethyldisilazane (HMDS), dimethyldichlorosilane (DDS), octylsilane (OTAS), polydimethylsiloxane (PDMS), and the like.

[0101] As the silica particles used as the external additive, commercially available hydrophobized silica particles may be used, or silica particles that have not been hydrophobized may be used after being subjected to a treatment.

[0102] The amount of external additive added is not particularly limited, and is usually 0.5 parts by mass or more and 3.0 parts by mass or less per 100 parts by mass of toner particles. If the amount of external additive added is less than 0.5 parts by mass, it becomes difficult to impart the effect of improving fluidity. If the amount of external additive added exceeds 3.0 parts by mass, fixability may decrease. The amount of external additive added is preferably 1.0 parts by mass or more and 2.5 parts by mass or less, and more preferably 1.2 parts by mass or more and 2.3 parts by mass or less per 100 parts by mass of toner particles.

[0103] 3.Method for manufacturing textile printing toner The method for producing a textile printing toner according to this embodiment includes a melt-kneading step S1 in which a mixture of toner raw materials is melt-kneaded to obtain a melt-kneaded product, a pulverizing step S2 in which the melt-kneaded product obtained in the melt-kneading step S1 is pulverized to obtain a pulverized product, a classification step S3 in which the pulverized product obtained in the pulverizing step S2 is classified to obtain toner particles, and an external addition step S4 in which an external additive is added to the toner particles obtained in the classification step S3.

[0104] In the melt-kneading step S1, toner raw materials such as binder resin, release agent, and sublimation dye are mixed in a mixer such as a Henschel mixer, and then kneaded using a kneader to obtain a melt-kneaded product.

[0105] In the production of the textile printing toner according to this embodiment, the melt-kneading step S1 preferably comprises two melt-kneading steps. Specifically, the melt-kneading step S1 preferably comprises a first melt-kneading step S11 in which a mixture containing a polyester resin and a sublimable dye is melt-kneaded to obtain a first melt-kneaded product, and a second melt-kneading step S12 in which a mixture containing the first melt-kneaded product, a styrene-acrylic resin, and a release agent is melt-kneaded to obtain a second melt-kneaded product. By melt-kneading the polyester resin and the sublimable dye in the first step, the sublimable dye can be selectively added to the first island portion composed of the polyester resin. Furthermore, by melt-kneading the styrene-acrylic resin and the release agent in the second step, the release agent can be selectively added to the styrene-acrylic resin. This makes it possible to more reliably form a sea-island structure that satisfies the above requirements (A) and (B), thereby further enhancing the effect that "both sublimation transfer efficiency and heat-resistant storage stability can be achieved, and an article can be dyed with high rubbing fastness."

[0106] Mixing is preferably dry, and any known mixer commonly used in the art can be used, such as a Henschel-type mixer such as Henschel Mixer (trade name, manufactured by Nippon Coke and Engineering Co., Ltd.), Super Mixer (trade name, manufactured by Kawata Corporation), or Mechano Mill (trade name, manufactured by Okada Seiko Co., Ltd.), as well as mixers such as Ang Mill (trade name, manufactured by Hosokawa Micron Corporation), Hybridization System (trade name, manufactured by Nara Machinery Works, Ltd.), or Cosmo System (trade name, manufactured by Kawasaki Heavy Industries, Ltd.).

[0107] The kneader may be a known device commonly used in the technical field, such as a twin-screw extruder, a three-roll mill, or a lab blast mill. Specific examples include single- or twin-screw extruders such as TEM-100B (trade name, manufactured by Toshiba Machine Co., Ltd.), PCM-65 / 87, or PCM-30 (all of which are trade names, manufactured by Ikegai Corporation), and open-roll type kneaders such as Kneadex (trade name, manufactured by Nippon Coke and Engineering Co., Ltd.). Among these, open-roll type kneaders are preferred because they exert a strong shear force during kneading and can highly disperse the toner materials.

[0108] In the pulverization step S2, the melt-kneaded product obtained in the melt-kneading step S1 is pulverized using a pulverizer. As the pulverizer, a known device commonly used in the technical field can be used, and examples thereof include a jet pulverizer that pulverizes using a supersonic jet stream, and an impact pulverizer that pulverizes a solidified material by introducing it into the space formed between a rotor and a stator (liner) that rotate at high speed.

[0109] In the classification step S3, the pulverized product obtained in the pulverization step S2 is classified using a classifier. A known device commonly used in the art can be used for classification. A classifier capable of removing excessively pulverized toner particles by centrifugal force and wind power, such as a rotary wind classifier, is preferred.

[0110] In the external addition step S4, the toner particles obtained in the classification step S3 are mixed with the external additives using a mixer, thereby adhering the external additives to the toner particles. The mixer may be a known device commonly used in the art. Examples include Henschel-type mixers such as Henschel Mixer (trade name, manufactured by Nippon Coke & Engineering Co., Ltd.), Super Mixer (trade name, manufactured by Kawata Corporation), and Mechano Mill (trade name, manufactured by Okada Seiko Co., Ltd.), as well as mixers such as Ang Mill (trade name, manufactured by Hosokawa Micron Corporation), Hybridization System (trade name, manufactured by Nara Machinery Works, Ltd.), and Cosmo System (trade name, manufactured by Kawasaki Heavy Industries, Ltd.).

[0111] 4. Two-component developer When performing two-component development, a two-component developer is prepared by mixing the toner for resist printing according to this embodiment and a carrier. Examples of the mixing device for mixing the toner for resist printing and the carrier include powder mixing devices such as a V-type mixer (trade name: V-5, manufactured by Tokuju Kousakusho Co., Ltd.).

[0112] Examples of the mixing ratio of the toner for resist printing and the carrier include 10:90 to 5:95 by mass ratio. As the carrier, carriers commonly used in the art can be used. It is also possible to use a coated carrier.

Examples

[0113] Hereinafter, based on examples and comparative examples, the toner for resist printing of the present disclosure and its manufacturing method will be specifically described.

[0114] 1. Measurement methods for various physical properties <Calculation method of SP value> The SP value is calculated by the method described in "POLYMER ENGINEERING AND SCIENCE, FEBRUARY, 1974, Vol. 14, No. 2, ROBERT F. FEDORS. (pages 147 - 154)" proposed by Fedors et al.

[0115] <Measurement method for average dispersion diameter of island parts dispersed in toner particles> The toner particles are embedded in an epoxy resin and sectioned with an ultramicrotome (manufactured by Reichert, product name: Ultracut N). The cross-section of the obtained toner particles is observed with a scanning transmission electron microscope (manufactured by Hitachi High-Technologies Corporation, model: S-4800). A random number (200 to 300) of first island parts (island parts composed of a polyester resin) are extracted from this electron microscope photograph data, and the equivalent circle diameter is obtained by image analysis using image analysis software (manufactured by Asahi Kasei Engineering Co., Ltd., trade name: A Image-kun), and this is taken as the average dispersion diameter. Also, for the second island part (island part composed of a release agent), the average dispersion diameter is obtained in the same manner.

[0116] <Measuring method for the melting point of release agents> Using a differential scanning calorimeter (Seiko Instruments Inc., model number: DSC220), 1 g of the sample is heated from 20°C to 200°C at a heating rate of 10°C / min, and then rapidly cooled from 200°C to 20°C. This operation is repeated twice to measure the DSC curve. The temperature of the endothermic peak corresponding to melting in the DSC curve measured in the second operation is taken as the melting point of the release agent.

[0117] <Method for measuring the softening point Tm of toner and resin> Using a flow property evaluation device (Shimadzu Corporation, Flow Tester, Model: CFT-100C), 1 g of sample is heated from an initial temperature of 40°C at a heating rate of 6°C / min while applying a load of 20 kgf / cm2 (9.8 × 105 Pa) and causing the sample to flow out of a die (nozzle diameter 1 mm, length 1 mm). The temperature at which half of the sample has flowed out is taken as the softening point, Tm.

[0118] 2. Raw material production <Production of polyester resin "Pes1"> A reaction vessel was charged with 432 parts by weight of terephthalic acid, 216 parts by weight of isophthalic acid, 44 parts by weight of adipic acid, 631 parts by weight of butanediol, and 0.5 parts by weight of tetrabutoxy titanate as a polymerization catalyst. The mixture was reacted at 210°C under a nitrogen stream for 5 hours while distilling off the resulting water and butanediol, followed by 1 hour of reaction under a reduced pressure of 5 to 20 mmHg. Next, 96 parts by weight of trimellitic anhydride was added, and the mixture was reacted for 1 hour under normal pressure, followed by reaction under a reduced pressure of 20 to 40 mmHg. The resin was extracted at the specified softening point. 180 parts by weight of butanediol was recovered. The resulting resin was cooled to room temperature and then pulverized into particles. This amorphous polyester resin was designated "Pes1." "Pes1" had a softening point (Tm) of 115°C and an SP value of 11.7.

[0119] <Production of polyester resin "Pes2"> A reaction vessel was charged with 432 parts by weight of terephthalic acid, 216 parts by weight of isophthalic acid, 30 parts by weight of adipic acid, 23 parts by weight of decanedicarboxylic acid, 217 parts by weight of ethylene glycol, 379 parts by weight of butanediol, and 0.5 parts by weight of tetrabutoxy titanate as a polymerization catalyst. The mixture was reacted at 210°C under a nitrogen stream for 5 hours while distilling off the resulting water, ethylene glycol, and butanediol. The reaction was then continued for 1 hour under a reduced pressure of 5 to 20 mmHg. Next, 96 parts by weight of trimellitic anhydride was added, and the mixture was reacted for 1 hour under normal pressure, followed by a reduced pressure of 20 to 40 mmHg. The resin was extracted at the specified softening point. A total of 201 parts by weight of ethylene glycol and butanediol was recovered. The resulting resin was cooled to room temperature and then pulverized into particles. This amorphous polyester resin was designated "Pes2." "Pes2" had a softening point Tm of 110°C and an SP value of 11.9.

[0120] <Production of polyester resin "Pes3"> A reaction vessel was charged with 432 parts by weight of terephthalic acid, 216 parts by weight of isophthalic acid, 15 parts by weight of adipic acid, 46 parts by weight of decanedicarboxylic acid, 1582 parts by weight of bisphenol A-EO adduct, and 0.5 parts by weight of tetrabutoxy titanate as a polymerization catalyst. The mixture was reacted at 210°C under a nitrogen stream for 5 hours while distilling off the water produced, followed by reaction at a reduced pressure of 5 to 20 mmHg for 1 hour. Next, 96 parts by weight of trimellitic anhydride was added, and the mixture was reacted at normal pressure for 1 hour, followed by reaction at a reduced pressure of 20 to 40 mmHg. The resin was extracted at the specified softening point. The resulting resin was cooled to room temperature and then pulverized into particles. This amorphous polyester resin was designated "Pes3." "Pes3" had a softening point (Tm) of 130°C and an SP value of 11.3.

[0121] <Production of styrene acrylic resin "St-Ac1"> 74 parts by weight of styrene, 26 parts by weight of n-butyl acrylate, and 1.0 part by weight of methacrylic acid were charged into a nitrogen-purged flask, and the internal temperature was raised to 120°C. Bulk polymerization was then carried out for 10 hours. Next, 80 parts by weight of xylene was added, and 20 parts by weight of a xylene solution in which 1.5 parts by weight of di-t-butyl peroxide had been uniformly dissolved was added continuously over 8 hours while maintaining the temperature at 130°C. The mixture was then flushed into a vessel at 90°C and 10 mmHg pressure. After distilling off the solvent, the mixture was coarsely crushed using a coarse crusher to obtain the styrene-acrylic resin "St-Ac1." "St-Ac1" had a softening point (Tm) of 140°C and an SP value of 10.4.

[0122] <Production of styrene acrylic resin "St-Ac2"> A styrene-acrylic resin "St-Ac2" was obtained in the same manner as "St-Ac1," except that the raw materials charged into the flask were changed to 74 parts by mass of styrene, 1 part by mass of n-butyl acrylate, and 18 parts by mass of methacrylic acid. "St-Ac2" had a softening point Tm of 150°C and an SP value of 11.1.

[0123] <Production of styrene acrylic resin "St-Ac3"> A styrene-acrylic resin "St-Ac3" was obtained in the same manner as "St-Ac1," except that the raw materials charged into the flask were changed to 60 parts by mass of styrene and 30 parts by mass of methacrylic acid. "St-Ac3" had a softening point Tm of 150°C and an SP value of 11.5.

[0124] <Production of styrene acrylic resin "St-Ac4"> A styrene-acrylic resin "St-Ac4" was obtained in the same manner as "St-Ac1," except that the raw materials charged into the flask were changed to 60 parts by mass of styrene and 84 parts by mass of dodecyl acrylate. "St-Ac4" had a softening point Tm of 120°C and an SP value of 9.7.

[0125] Here, the physical properties of the polyester resins and styrene-acrylic resins produced above, as well as the release agents used in the examples, are listed in Tables 1 to 3. In Table 3, "HNP-10" and "FNP-0090" are trade names manufactured by Nippon Seiro Co., Ltd., "PW725" is a trade name manufactured by Toyochem Co., Ltd., "550-P" is a trade name "Viscol 550-P" manufactured by Sanyo Chemical Industries, Ltd., and "WEP-8" and "WEP-2" are trade names manufactured by NOF Corporation.

[0126] [Table 1]

[0127] [Table 2]

[0128] [Table 3]

[0129] <Production of Resin-Coated Carriers> A coating resin solution was prepared by dissolving 0.375 parts by weight of coating resin 1 (a silicone-based resin manufactured by Shin-Etsu Chemical Co., Ltd., product name: KR240) and 0.375 parts by weight of coating resin 2 (manufactured by Shin-Etsu Chemical Co., Ltd., product name: KR251) in 12 parts by weight of toluene, adding and dispersing 0.0375 parts by weight of conductive particles (manufactured by Cabot Corporation, product name: VULCAN XC-72) and 0.0225 parts by weight of a coupling agent (manufactured by Toray Dow Corning Co., Ltd., product name: AY43-059). The surface of 100 parts by weight of a ferrite carrier core material with a volume average particle size of 40 μm was coated with 12.8 parts by weight of the coating resin solution by a dipping method. The resulting mixture was then cured at 200°C for 1 hour and sieved through a 150 μm mesh to produce a resin-coated carrier.

[0130] 3. Manufacture of toner and two-component developer [Example 1] <First melt-kneading step> The raw materials used in the first melt-kneading step are as follows: Binder resin: 70.0% by mass of the above polyester resin "Pes1" Sublimation dye: CI Disperse Red 60 30.0% by mass

[0131] The above raw materials were premixed for 5 minutes using a Henschel mixer (manufactured by Nippon Coke and Engineering Co., Ltd., model: FM20C), and then melt-kneaded under the following conditions using an open-roll type continuous kneader (manufactured by Nippon Coke and Engineering Co., Ltd., model: MOS320-1800) to obtain a first molten kneaded product. Heating roll supply temperature / discharge temperature: 130℃ / 100℃ -Cooling roll supply temperature / discharge temperature: 40℃ / 25℃ Heating roll and cooling roll: diameter 320 mm, effective length 1550 mm Roll gap on the supply and discharge sides: 0.3 mm Heating roll rotation speed / Cooling roll rotation speed: 75 rpm / 65 rpm Toner raw material supply rate: 5.0 kg / hour

[0132] <Second melt-kneading step> The raw materials used in the second melt-kneading step are as follows: Binder resin: 69.0% by mass of the above styrene acrylic resin "St-Ac1" 25.0% by mass of the first melt-kneaded product obtained in the "first melt-kneading step" Charge control agent: salicylic acid compound (manufactured by Orient Chemical Industries Co., Ltd., trade name: Bontron E-84) 1.0% by mass Mold release agent: Fischer-Tropsch wax (manufactured by Nippon Seiro Co., Ltd., product name: FT Wax FNP-0090, melting point (freezing point) 90°C) 5.0% by mass

[0133] The above raw materials were premixed for 5 minutes using a Henschel mixer (manufactured by Nippon Coke and Engineering Co., Ltd., model: FM20C), and then melt-kneaded under the following conditions using an open-roll type continuous kneader (manufactured by Nippon Coke and Engineering Co., Ltd., model: MOS320-1800) to obtain a second molten kneaded product. Heating roll supply temperature / discharge temperature: 130℃ / 100℃ -Cooling roll supply temperature / discharge temperature: 40℃ / 25℃ Heating roll and cooling roll: diameter 320 mm, effective length 1550 mm Roll gap on the supply and discharge sides: 0.3 mm Heating roll rotation speed / Cooling roll rotation speed: 75 rpm / 65 rpm Toner raw material supply rate: 5.0 kg / hour

[0134] <Coarse grinding and fine grinding process> The obtained second molten kneaded product was cooled with a cooling belt, and then coarsely pulverized using a power mill (manufactured by Dalton Co., Ltd., model: P-3) equipped with a φ2 mm screen to obtain a coarsely pulverized product. The obtained coarsely pulverized product was finely pulverized using a jet pulverizer (manufactured by Nippon Pneumatic Mfg. Co., Ltd., model: IDS-2) to obtain a finely pulverized product.

[0135] <Classification process> The resulting finely pulverized product was classified using an elbow jet classifier (manufactured by Nittetsu Mining Co., Ltd., model: EJ-LABO) to obtain toner particles having an average primary particle diameter of 6.7 μm.

[0136] <External addition process> 100 parts by mass of the obtained toner particles and 1.5 parts by mass of hydrophobic silica microparticles (average primary particle diameter 7 nm, dimethyldichlorosilane surface treatment, manufactured by Nippon Aerosil Co., Ltd., product name: R976S) were added to a Henschel mixer (manufactured by Nippon Coke and Engineering Co., Ltd., model: FM20C), and the peripheral speed at the outermost periphery of the tip of the stirring blade was set to 40 m / s, and the mixture was stirred and mixed for 1 minute to obtain a toner.

[0137] <Manufacturing process of two-component developer> The obtained toner and the resin-coated carrier prepared in the above "Production of resin-coated carrier" were mixed so that the toner concentration relative to the total amount of two-component developer was 7%, and mixed for 20 minutes in a V-type mixer (manufactured by Tokuju Kogyosho Co., Ltd., product name: V-5) to obtain a two-component developer with a toner concentration of 7%.

[0138] [Examples 2 to 5, 7 to 22] As shown in Table 4 below, toner particles, toner, and two-component developer were obtained in the same manner as in Example 1, except that the raw materials used to produce the toner particles (type of resin, composition ratio of resin, type of release agent) were changed. The concentration of the sublimable dye in the toner particles was adjusted to 7.5% by mass in all Examples.

[0139] [Example 6] As shown in Table 4 below, toner particles, toner, and two-component developer were obtained in the same manner as in Example 1, except that the raw materials used to manufacture the toner particles (type of resin, composition ratio of resin, type of release agent) were changed, and the "first melt-kneading step" was omitted and all raw materials were added in the "second melt-kneading step." The concentration of the sublimable dye in the toner particles was adjusted to 7.5% by mass.

[0140] [Comparative Examples 1 to 3] As shown in Table 4 below, toner particles, toner, and two-component developers were obtained in the same manner as in Example 1, except that the raw materials used to manufacture the toner particles (type of resin, composition ratio of resin, type of release agent) were changed, and the "first melt-kneading step" was omitted and all raw materials were added in the "second melt-kneading step." The concentration of the sublimable dye in the toner particles was adjusted to 7.5% by mass in all comparative examples.

[0141] [Table 4]

[0142] Table 4 lists the raw materials used in the production of toner particles (type of resin, composition ratio of resin, type of release agent), the physical properties of the toner particles, and whether or not a two-stage melt-kneading process was used during production. Note that "FT" in Table 4 for the wax type of release agent stands for Fischer-Tropsch wax.

[0143] 4. Evaluation <Evaluation 1: Evaluation method for density on fabric> The prepared two-component developer and toner were filled into the developing device and toner cartridge of a color multifunction printer (manufactured by Sharp Corporation, model: BP-20C25), respectively, and an A4 test document having a rectangular solid image measuring 20 mm in height and 50 mm in width was copied to form an image on an intermediate recording medium (manufactured by Sharp Corporation, product name: PPC paper SF-4AM3S).

[0144] Next, the intermediate recording medium on which the image was formed and a satin fabric as a polyester fabric were heat-treated at a temperature of 200°C for 1 minute, and the intermediate recording medium was peeled off from the fabric to obtain a dyed fabric dyed by the sublimation transfer method.

[0145] Next, the density of a specific dyed location of the obtained dyed product (the center of the above-mentioned "rectangular solid image 20 mm long and 50 mm wide") was measured using a densitometer (manufactured by X-Rite Corporation, trade name: spectrophotometer / densitometer X-Rite eXact).

[0146] From the measured concentration, the concentration on the fabric was evaluated according to the following criteria. ◎ (Excellent): Concentration is 1.3 or higher (suitable for practical use). ○ (Good): The density is 1.2 or more and less than 1.3 (suitable for practical use). △ (Acceptable): The concentration is 1.1 or more and less than 1.2 (practical use is possible). × (unacceptable): The concentration is less than 1.1 (unacceptable for practical use).

[0147] <Evaluation 2: Evaluation method for dry rub fastness> The prepared two-component developer and toner were filled into the developing device and toner cartridge of a color multifunction printer (manufactured by Sharp Corporation, model: BP-20C25), respectively, and a monochrome image with 100% coverage was formed on an intermediate recording medium (manufactured by Sharp Corporation, product name: PPC paper SF-4AM3S).

[0148] Next, the intermediate recording medium on which the image was formed and a satin fabric as a polyester fabric were heat-treated at a temperature of 200°C for 1 minute, and the intermediate recording medium was peeled off from the fabric to obtain a dyed fabric (hereinafter referred to as test fabric) dyed by the sublimation transfer method.

[0149] In accordance with JIS L 0849:2013 "Testing methods for color fastness to rubbing," a dry rubbing test (dry rubbing) was conducted on the test cloth using a Type II (Gakushin type) rubbing tester (manufactured by Tester Sangyo Co., Ltd., model: Gakushin type rubbing tester), and the staining on the white cloth was judged by comparing it with the stain gray scale, and the rubbing fastness was evaluated according to the following criteria.

[0150] The test cloth was attached to the table of the friction tester, and the cotton cloth was attached to the tip of the arm (friction element) at the top of the friction tester. The arm with the cotton cloth attached was rubbed back and forth 100 times over the test cloth (load of approximately 200 g, reciprocating distance of 100 mm). After the rub, the cotton cloth was removed from the arm, and the "staining" was judged using a gray scale for staining, thereby determining the value of the friction fastness. The value is expressed as a grade, with the higher the grade, the higher the friction fastness.

[0151] The measured values ​​of the rub fastness were evaluated according to the following criteria. ◎ (Excellent): Grade 4.5 or above (suitable for practical use). ○ (Good): Grade 4 or higher (suitable for practical use). △ (Acceptable): Grade 3 or above (suitable for practical use). × (Not acceptable): Grade 2 or below (not suitable for practical use).

[0152] <Evaluation 3: Evaluation method for heat-resistant storage stability of toner> The heat-resistant storage stability of the toner was evaluated based on the presence or absence of aggregates after high-temperature storage. 20 g of the prepared toner was placed in a 250 mL wide-mouthed cylindrical plastic container, which was then sealed and left to stand at 50°C for 72 hours. The toner was then removed and sieved through a 230-mesh sieve. The mass of the toner remaining on the sieve was measured, and the remaining amount, which is the ratio of this mass to the total mass of the toner, was calculated and evaluated according to the following criteria. The lower the remaining amount, the less blocking the toner was experiencing.

[0153] ◎ (Excellent): No aggregation, residual amount less than 0.5%. ◯ (Good): A small amount of aggregation, residual amount is 0.5% or more and less than 7%. △ (Fair): A large amount of aggregation, remaining amount is 7% or more but less than 12%. × (unacceptable): Large amount of aggregation, residual amount 12% or more.

[0154] [Table 5]

[0155] Table 5 shows the evaluation results of Examples and Comparative Examples. As is clear from these evaluation results, the textile printing toners of Examples 1 to 22, which are textile printing toners having toner particles containing a polyester resin, a styrene acrylic resin, and a release agent and which satisfy the following requirements (A) to (C), were able to achieve both sublimation transfer efficiency and heat-resistant storage stability, and were able to dye objects with high rubbing fastness. (A) The toner particles have a sea-island structure composed of a sea portion containing the styrene acrylic resin, first island portions containing the polyester resin, and second island portions containing the release agent. (B) The polyester resin of the first island portion contains a sublimable dye. (C) When the SP values ​​of the polyester resin, the styrene acrylic resin, and the release agent are SP1, SP2, and SP3, respectively, the relationship of the following formula (1) is satisfied. SP1>SP2>SP3 (1)

[0156] In contrast, Comparative Examples 1 to 3, which did not satisfy these requirements, were inferior to the Examples in the evaluation of the density on fabric or the heat-resistant storage stability of the toner. Comparative Example 1 is an example in which the SP value does not satisfy the relationship of the above formula (1). Comparative Example 2 is an example in which the toner particles do not contain a polyester-based resin, and Comparative Example 3 is an example in which the toner particles do not contain a styrene-acrylic resin. Furthermore, in Comparative Example 1, when the dispersion state was observed using the above-mentioned "method for measuring the average dispersion diameter of island portions dispersed in toner particles," the sublimation dye was not contained in the polyester-based resin, i.e., the above-mentioned requirement (B) was not satisfied.

[0157] Example 6 is an example in which the "first melt-kneading step" is omitted and all raw materials are added in the "second melt-kneading step", that is, an example in which toner particles are produced through a single melt-kneading step. Even in Example 6 in which toner particles are produced through a single melt-kneading step, the SP values ​​of each component satisfy the relationship of formula (1), and therefore the above requirements (A) to (C) are met. Example 16 is an example in which toner particles are produced through a two-stage melt-kneading step using the same raw materials as Example 6. Comparing Example 6 and Example 16, it can be seen that Example 16 in which toner particles are produced through a two-stage melt-kneading step is superior to Example 6 in which toner particles are produced through a single melt-kneading step in terms of the on-fabric concentration and the heat-resistant storage stability of the toner.

[0158] It can be seen that Examples 1 to 3, in which the average dispersed diameter of the first island portion (polyester-based resin) in the sea portion is 0.3 μm or more and 2.5 μm or less, are superior in the evaluation of the heat-resistant storage stability of the toner to Example 4, in which the average dispersed diameter is less than the above-mentioned lower limit, and are superior in the evaluation of the concentration on fabric to Example 5, in which the average dispersed diameter exceeds the above-mentioned upper limit.

[0159] It can be seen that Examples 1, 7, and 8, which satisfy the relationship of the following formula (2), are superior in the evaluation of the heat-resistant storage stability of the toner than Example 9, in which SP1-SP2 is less than the lower limit of the following formula (2), and are superior in the evaluation of the friction fastness than Example 10, in which SP1-SP2 exceeds the upper limit of the following formula (2). 2.0 ≧ SP1-SP2 ≧ 0.5 (2)

[0160] It can be seen that Examples 1, 11, and 12, in which the content ratio of polyester resin to styrene acrylic resin in the toner particles is within the range of 1:9 to 3:7, are superior in the evaluation of density on fabric to Example 13, in which the content ratio is outside the above range.

[0161] It can be seen that Examples 1, 14, and 15, in which the release agent is a hydrocarbon wax and whose melting point is 70°C or more and 110°C or less, are superior in the evaluation of friction fastness to Example 16, in which the melting point exceeds the above upper limit, and are superior in the evaluation of heat-resistant storage stability of the toner to Examples 17 and 18, in which the release agent is an ester wax.

[0162] It can be seen that Examples 1, 19, and 20, in which the average dispersed diameter of the second island portion (release agent) in the sea portion is 250 nm or more and 1500 nm or less, are superior in the evaluation of friction fastness to Example 21, in which the average dispersed diameter is below the above lower limit, and are superior in the evaluation of heat-resistant storage stability of the toner to Example 22, in which the average dispersed diameter exceeds the above upper limit.

[0163] It can be seen that Examples 1, 19, and 20, in which the content of release agent in the toner particles is 3% by mass or more and 10% by mass or less, are superior in the evaluation of friction fastness to Example 21, in which the content of release agent is less than the above lower limit, and are superior in the evaluation of heat-resistant storage stability of the toner to Example 22, in which the content of release agent exceeds the above upper limit.

[0164] The embodiments disclosed herein are illustrative in all respects and are not intended to be limiting. Therefore, the technical scope of the present disclosure should not be interpreted solely by the above-described embodiments, but should be defined based on the claims. Furthermore, all modifications within the scope and meaning equivalent to the claims are included. [Explanation of symbols]

[0165] 1 Toner particles 2 Kaifu (styrene acrylic resin) 3. First island (polyester resin containing sublimable dye) 3a Bleeding of sublimation dyes 4. Second island (release agent) 50 Release agent layer 60 toner layers 61 Compatible Resins 62 Sublimable dyes 70 Transfer paper (intermediate recording medium) 80 Fabric (material to be dyed)

Claims

1. A textile printing toner having toner particles containing a polyester resin, a styrene-acrylic resin, and a release agent, the toner particles have a sea-island structure including a sea portion containing the styrene-acrylic resin, a first island portion containing the polyester resin, and a second island portion containing the release agent; the polyester resin of the first island portion contains a sublimable dye; The textile printing toner is characterized in that, when the SP values ​​of the polyester resin, the styrene-acrylic resin, and the release agent are SP1, SP2, and SP3, respectively, the relationship of the following formula (1) is satisfied: SP1>SP2>SP3...(1)

2. The textile printing toner according to claim 1, 10. A textile printing toner, wherein the average dispersed diameter of the first island portions in the sea portion is 0.3 μm or more and 2.5 μm or less.

3. The textile printing toner according to claim 1 or 2, A textile printing toner characterized by satisfying the relationship of the following formula (2): 2.0 ≧ SP1-SP2 ≧ 0.5 ... (2)

4. The textile printing toner according to claim 1 or 2, The toner for textile printing is characterized in that the content ratio of the polyester resin to the styrene-acrylic resin in the toner particles is within a range of 1:9 to 3:

7.

5. The textile printing toner according to claim 1 or 2, The toner for textile printing, wherein the releasing agent is a hydrocarbon wax having a melting point of 70°C or higher and 110°C or lower.

6. The textile printing toner according to claim 1 or 2, The textile printing toner, wherein the average dispersion diameter of the second island portions in the sea portion is 250 nm or more and 1500 nm or less.

7. The textile printing toner according to claim 1 or 2, 1. A textile printing toner, wherein the content of the release agent in the toner particles is 3% by mass or more and 10% by mass or less.

8. A two-component developer comprising the textile printing toner according to claim 1 or 2 and a carrier.

9. 3. A method for producing the textile printing toner according to claim 1 or 2, comprising: a first melt-kneading step of melt-kneading a mixture containing the polyester resin and the sublimable dye to obtain a first melt-kneaded product; a second melt-kneading step of melt-kneading a mixture containing the first melt-kneaded product, the styrene-acrylic resin, and the release agent to obtain a second melt-kneaded product; a pulverization step of pulverizing the second molten kneaded product to obtain a pulverized product; a classification step of classifying the pulverized product to obtain the toner particles.

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