Sublimation transfer toner

Abstract

This invention provides a sublimation transfer toner that offers improved dye density, enhanced friction fastness, improved dye dispersibility, and excellent low-temperature fixation properties for fabrics. [Solution] A sublimation transfer toner containing at least a binder component and a sublimable dye, wherein the binder component contains a polyester resin (A) and / or a vinyl resin (B), and when the binder component contains the polyester resin (A), the flow softening point of the polyester resin (A) is 90 to 125°C and the acid value of the polyester resin (A) is 11 to 45 mgKOH / g, and when the binder component contains the vinyl resin (B), the flow softening point of the vinyl resin (B) is 90 to 125°C and the acid value of the vinyl resin (B) is 11 to 45 mgKOH / g.

Description

[Technical Field]

[0001] The present invention relates to a toner for sublimation transfer. [Background Art]

[0002] Dyeing methods using an electrophotographic system for objects to be dyed such as hydrophobic fibers represented by polyester cloth can be broadly classified mainly into two types: the direct method and the sublimation transfer method. The direct method is a dyeing method in which after a toner is directly adhered to an object to be dyed, a dye contained in the toner is adhered to the object to be dyed by heat treatment, and deposits other than the dye (resin, release agent, etc.) are dissolved and removed by alkali washing. The sublimation transfer method is a dyeing method in which after a toner is adhered to an intermediate recording medium such as paper, the toner-adhered surface of the intermediate recording medium is overlapped with the object to be dyed, then heat press treatment (heating and pressure treatment) is performed to sublimation transfer the dye contained in the toner to the object to be dyed.

[0003] Of these two dyeing methods, the sublimation transfer method allows only the dye, among the plurality of components constituting the toner, to transfer from the intermediate recording medium to the fiber. That is, there is an advantage that toner components other than the dye do not adhere to the dyed cloth, so the steps of washing and drying the dyed cloth are unnecessary. Therefore, it is considered to be suitable for dyeing applications where texture is important, such as clothing (sports apparel, etc.) and interior goods (sheets, sofas, etc.).

[0004] In addition, since steps such as washing and drying are unnecessary, the dyeing process can be greatly reduced, and many advantages are obtained, including the advantage that a washing and drying line requiring large-scale space and operating energy is eliminated, and the advantage that a washing water treatment facility is unnecessary. Therefore, the sublimation transfer method is considered to be an excellent dyeing method also in that dyeing can be performed even in a small space.

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

[0006] In sublimation transfer printing, there are two methods: inkjet and electrophotography, with inkjet generally being the more common method. However, sublimation transfer dyeing using inkjet methods presents problems such as contamination of the work environment due to the volatilization of organic solvents, one of the components of the ink, caused by the heat generated during dye transfer. In contrast, electrophotography does not contain volatile components in the toner and does not contaminate the work environment, thus attracting attention in recent years.

[0007] As a toner used for dyeing by sublimation transfer in electrophotography, for example, Patent Document 1 discloses a toner containing a sublimable dye and a polyester resin, and states that by setting the storage modulus G' and loss modulus G'' in a dynamic viscoelasticity test within a specific numerical range, the peelability when peeling the intermediate recording medium from the object to be dyed can be improved. [Prior art documents] [Patent Documents]

[0008] [Patent Document 1] Japanese Patent Publication No. 2016-17228 [Overview of the project] [Problems that the invention aims to solve]

[0009] However, when using polyester resin as the binder resin in toners used for dyeing by sublimation transfer, it is difficult to create a sublimation transfer dyeing method that can efficiently dye fabrics and other materials to be dyed. There is a problem that even if the amount of disperse dye in the toner is increased, a sufficient dyeing density cannot be obtained. In addition, there is a problem that the friction fastness decreases due to the polyester resin transferred to the material to be dyed. To solve this, using styrene-acrylic resin as the binder resin reduces the affinity between the sublimable dye and the binder resin, making it possible to obtain a material to be dyed with a high dyeing density. On the other hand, when unused toner is stored, the sublimable dye bleeds out onto the surface of the toner particles, which is one of the causes of deterioration in the fluidity and electrostatic properties of the toner, and there is a problem with the dispersibility of the dye.

[0010] The object of the present invention is to provide a sublimation transfer toner that offers improved dye density of fabrics, improved friction fastness of fabrics, improved dye dispersibility, and excellent low-temperature fixation. [Means for solving the problem]

[0011] The inventors of this invention have diligently conducted research to solve the above problems and have completed the present invention. The present invention relates to a sublimation transfer toner containing at least a binder component and a sublimable dye, wherein the binder component contains a polyester resin (A) and / or a vinyl resin (B), and when the binder component contains the polyester resin (A), the flow softening point of the polyester resin (A) is 90 to 125°C and the acid value of the polyester resin (A) is 11 to 45 mgKOH / g, and when the binder component contains the vinyl resin (B), the flow softening point of the vinyl resin (B) is 90 to 125°C and the acid value of the vinyl resin (B) is 11 to 45 mgKOH / g. [Effects of the Invention]

[0012] The present invention provides a sublimation transfer toner that offers improved dye density of fabrics, improved friction fastness of fabrics, improved dye dispersibility, and excellent low-temperature fixation. [Modes for carrying out the invention]

[0013] The present invention will be described in detail below. The sublimation transfer toner of the present invention contains a binder component and a sublimable dye, wherein the binder component contains a polyester resin (A) and / or a vinyl resin (B).

[0014] The polyester resin (A) in the present invention is a polyester resin obtained by polycondensation of an alcohol component (x) and a carboxylic acid component (y).

[0015] Examples of alcohol components (x) include monoalcohols (x1), diols (x2), and polyols with a valency of 3 or higher (x3), while examples of carboxylic acid components (y) include monocarboxylic acids (y1) and polycarboxylic acids (y2). Of these, a polyester resin obtained by polycondensation of a component containing a diol (x2) and a polycarboxylic acid (y2) is preferred from the viewpoint of heat resistance and storage under high temperature and high humidity. These may be a single type or a combination of two or more types.

[0016] Examples of monoalcohols (x1) include linear or branched alkyl alcohols having 1 to 30 carbon atoms (methanol, ethanol, isopropanol, 1-decanol, dodecyl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, arachidyl alcohol, behenyl alcohol, and lignoceryl alcohol, etc.). Of these monoalcohols, from the viewpoint of heat-resistant storage under high temperature and high humidity, linear or branched alkyl alcohols having 8 to 24 carbon atoms are preferred, more preferably linear alkyl alcohols having 8 to 24 carbon atoms are preferred, even more preferably dodecyl alcohol, stearyl alcohol, arachidyl alcohol, behenyl alcohol and lignoceryl alcohol are preferred, and particularly preferred are stearyl alcohol and behenyl alcohol.

[0017] Examples of diols (x2) include linear aliphatic diols with 2 to 20 carbon atoms (ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,13-tridecanediol, 1,14-tetradecanediol, 1,18-octadecanediol, and 1,20-eicosanediol, etc.), and branched aliphatic diols. Examples include ols (1,2-propanediol, 1,2-butanediol, 1,2-pentanediol, and 3-methyl-1,5-pentanediol, etc.), alicyclic diols (hydrogenated bisphenol A, hydrogenated bisphenol F, and cyclohexanediol, etc.), alkylene oxide (AO) adducts of the above (linear aliphatic, branched aliphatic, and alicyclic) diols having 2 to 4 carbon atoms (2 to 30 moles added), and AO adducts of bisphenols (bisphenol A, bisphenol F, and bisphenol S, etc.) having 2 to 4 carbon atoms (2 to 30 moles added). Examples of AOs having 2 to 4 carbon atoms include ethylene oxide (EO), propylene oxide (PO), and butylene oxide. Of these diols, from the viewpoint of heat resistance and friction fastness under high temperature and high humidity conditions, 2-4 carbon atom AO adducts of bisphenols (such as bisphenol A, bisphenol F, and bisphenol S) (2-30 moles added) are preferred, and more preferably 2-4 carbon atom AO adducts of bisphenol A (2-30 moles added).

[0018] Examples of polyols with a valency of 3 or higher (x3) include polyhydric aliphatic alcohols with 3 to 36 carbon atoms that have a valency of 3 or higher (alkane polyols and their intramolecular or intermolecular dehydrated products [e.g., glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol, sorbitan, and polyglycerin]).

[0019] Based on the total number of moles of the alcohol component (x) that is a constituent component of the polyester resin (A), the content of the diol (x2) among the alcohol component (x) is preferably from 40 to 100 mol%, more preferably from 60 to 100 mol%, and still more preferably from 70 to 100 mol%, from the viewpoint of heat-resistant storage stability under high-temperature and high-humidity conditions.

[0020] Based on the total number of moles of the diol (x2) used, the content of the AO adduct (with 2 to 30 added moles) of bisphenol A having 2 to 4 carbon atoms among the diol (x2) is preferably 80 mol% or more, and more preferably 90 mol% or more, from the viewpoint of heat-resistant storage stability under high-temperature and high-humidity conditions.

[0021] Examples of the monocarboxylic acid (y1) include unsaturated monocarboxylic acids (e.g., (meth)acrylic acid ["(meth)acryl" means acrylic or methacrylic], crotonic acid, isocrotonic acid, cinnamic acid and the like), and saturated monocarboxylic acids (e.g., behenic acid, stearic acid, benzoic acid and the like). Among these monocarboxylic acids, saturated monocarboxylic acids are preferred from the viewpoint of heat-resistant storage stability under high-temperature and high-humidity conditions, and behenic acid and stearic acid are more preferred.

[0022] Examples of dicarboxylic acids among the polyvalent carboxylic acids (y2) include the following. Alkanedicarboxylic acids having 2 to 34 carbon atoms (including the carbon atom of the carbonyl group) {linear alkanedicarboxylic acids (succinic acid, adipic acid, sebacic acid, azelaic acid, dodecanedioic acid, 1,18-octadecanedicarboxylic acid, etc.) and branched alkanedicarboxylic acids (decylsuccinic acid, etc.), etc.}, alkenedicarboxylic acids having 4 to 34 carbon atoms (including the carbon atom of the carbonyl group) (alkenylsuccinic acids such as dodecenylsuccinic acid, pentadecenylsuccinic acid, octadecenylsuccinic acid, maleic acid, fumaric acid, citraconic acid, etc.), alicyclic dicarboxylic acids having 6 to 34 carbon atoms (including the carbon atom of the carbonyl group), aromatic dicarboxylic acids having 8 to 36 carbon atoms (phthalic acid, isophthalic acid, terephthalic acid, t-butylisophthalic acid, 2,6-naphthalenedicarboxylic acid, 4,4'-biphenyldicarboxylic acid, etc.) are mentioned. Among these dicarboxylic acids, from the viewpoint of heat-resistant storage stability under high-temperature and high-humidity conditions, aromatic dicarboxylic acids having 8 to 36 carbon atoms (phthalic acid, isophthalic acid, terephthalic acid, t-butylisophthalic acid, 2,6-naphthalenedicarboxylic acid, 4,4'-biphenyldicarboxylic acid, etc.) are preferred, more preferred are phthalic acid, isophthalic acid and terephthalic acid, and still more preferred are isophthalic acid and terephthalic acid.

[0023] Examples of trivalent or higher carboxylic acid components among polyvalent carboxylic acids (y2) include aromatic polycarboxylic acids having 9 to 20 carbon atoms (trimellitic acid, pyromellitic acid, etc.) and aliphatic tricarboxylic acids having 6 to 33 carbon atoms (hexanetricarboxylic acid, etc.). Among these trivalent or higher carboxylic acid components, trimellitic acid is preferred from the viewpoint of heat-resistant storage stability under high-temperature and high-humidity conditions.

[0024] As the carboxylic acid component (y), anhydrides of these carboxylic acids and lower alkyl (C1 to C4) esters (methyl esters, ethyl esters, isopropyl esters, etc.) may be used, or the anhydrides or lower alkyl esters may be used in combination with the above carboxylic acids.

[0025] In the present invention, the polyester resin (A) can be produced in the same manner as known methods for producing polyester resins. For example, a component containing an alcohol component (x) and a carboxylic acid component (y) can be reacted in an inert gas (such as nitrogen gas) atmosphere at a reaction temperature preferably 150 to 280°C, more preferably 160 to 250°C, and even more preferably 170 to 235°C. The reaction time is preferably 30 minutes or more, more preferably 2 to 40 hours, from the viewpoint of ensuring a polycondensation reaction. Reducing the pressure is also effective in improving the reaction rate at the end of the reaction.

[0026] An esterification catalyst can also be used at this time if necessary. Examples of esterification catalysts include tin-containing catalysts (e.g., dibutyltin oxide), antimony trioxide, titanium-containing catalysts [e.g., titanium alkoxide, potassium titanate oxalate, titanium terephthalate, titanium terephthalate alkoxide, catalysts described in Japanese Patent Publication No. 2006-243715 {titanium diisopropoxybis(triethanol aminate), titanium dihydroxybis(triethanol aminate), titanium monohydroxytris(triethanol aminate), titanylbis(triethanol aminate) and their intramolecular polycondensates, etc.}, and catalysts described in Japanese Patent Publication No. 2007-11307 (titanium tributoxyterephthalate, titanium triisopropoxyterephthalate and titanium diisopropoxyditeterephthalate, etc.)], zirconium-containing catalysts (e.g., zirconyl acetate), and zinc acetate. Of the above, titanium-containing catalysts are preferred from the viewpoint of resistance to hot offset and electrostatic stability.

[0027] The reaction ratio between the alcohol component (x) and the carboxylic acid component (y) is such that the molar ratio {[OH] / [COOH]} of the hydroxyl group of the alcohol component (x) to the carboxyl group of the carboxylic acid component (y) is preferably 1 / 1 to 1.5 / 1, more preferably 1 / 1 to 1.4 / 1, and even more preferably 1 / 1 to 1.3 / 1. The hydroxyl group is derived from the alcohol component (x).

[0028] When the binder component contains polyester resin (A), the flow softening point of polyester resin (A) is 90 to 125°C, and the acid value of polyester resin (A) is 11 to 45 mgKOH / g.

[0029] The flow softening point of the polyester resin (A) in the present invention is 90 to 125°C, preferably 95 to 115°C. If the flow softening point of polyester resin (A) is below 90°C, the dye dispersibility deteriorates, and if it exceeds 125°C, the low-temperature fixability deteriorates. The following describes the method for measuring the flow softening point [T1 / 2] of polyester resin (A) and vinyl resin (B), which will be described later. Using a constant test force extrusion type capillary rheometer flow tester {for example, Shimadzu Corporation, CFT-500D}, a 1g sample is heated at a heating rate of 6°C / min while a load of 1.96 MPa is applied by a plunger and extruded from a nozzle with a diameter of 1 mm and a length of 1 mm. A graph of the "plunger drop (flow value)" and "temperature" is drawn, and the temperature corresponding to half of the maximum value of the plunger drop is defined as the flow softening point [T1 / 2].

[0030] The flow softening points of polyester resin (A) and vinyl resin (B), described later, can be adjusted by controlling the weight-average molecular weight of the resin. Increasing the weight-average molecular weight of the resin raises the flow softening point, while decreasing it lowers the flow softening point.

[0031] The acid value of the polyester resin (A) in the present invention is 11 to 45 mgKOH / g, preferably 11 to 35 mgKOH / g, and more preferably 11 to 25 mgKOH / g. If the acid value of the polyester resin (A) is less than 11 mgKOH / g, the dyeing density and abrasion fastness of the fabric deteriorate, and if it exceeds 45 mgKOH / g, the heat resistance for storage under high temperature and high humidity deteriorates.

[0032] The hydroxyl value of the polyester resin (A) in the present invention is preferably 10.0 to 80.0 mgKOH / g, more preferably 15.0 to 75.0 mgKOH / g, and even more preferably 20.0 to 70.0 mgKOH / g, from the viewpoint of heat resistance storage under high temperature and high humidity. A value of 10.0 mgKOH / g or more results in good low-temperature fixation, and a value of 70.0 mgKOH / g or less results in good heat resistance storage under high temperature and high humidity.

[0033] The acid value and hydroxyl value of polyester resin (A) and vinyl resin (B), described below, can be measured by the method specified in JIS K0070.

[0034] The glass transition temperature of the polyester resin (A) in the present invention is preferably 50°C to 70°C, more preferably 55°C to 65°C, from the viewpoint of heat-resistant storage.

[0035] In the present invention, the glass transition temperature (Tg) of the polyester resin (A) and the vinyl resin (B) described below can be measured by the method specified in ASTM D3418-82 (DSC method). For measuring the glass transition temperature (Tg), for example, a DSC Q20 manufactured by TA Instruments Co., Ltd. can be used. The glass transition temperature (Tg) can be measured under the following conditions. <Measurement conditions> (1) Increase the temperature from 30°C to 150°C at a rate of 20°C / min. (2) Hold at 150°C for 10 minutes (3) Cool to -35°C at 20°C / min (4) Hold at -35°C for 10 minutes. (5) Heat up to 150°C at a rate of 20°C / min (6) The differential scanning calorimetry curve measured in process (5) is analyzed, and the position of the inflection point is defined as the glass transition temperature.

[0036] In the present invention, the number-average molecular weight (Mn) of the polyester resin (A) is preferably 1,900 to 9,000, more preferably 2,200 to 8,000, and even more preferably 2,500 to 7,000, from the viewpoint of low-temperature fixability and dye dispersibility.

[0037] In the present invention, the weight-average molecular weight (Mw) of the polyester resin (A) is preferably 7,000 to 90,000, more preferably 8,000 to 80,000, and even more preferably 9,000 to 70,000, from the viewpoint of low-temperature fixability and dye dispersibility.

[0038] In the present invention, the peak top molecular weight (Mp) of the polyester resin (A) is preferably 1,900 to 70,000, more preferably 2,500 to 70,000, and even more preferably 3,000 to 65,000, from the viewpoint of low-temperature fixability and dye dispersibility.

[0039] In the present invention, the Mn, Mw, and Mp of the polyester resin (A) and the vinyl resin (B) described later can be measured using GPC under the following conditions. The resin is dissolved in tetrahydrofuran (THF), and this is used as the sample solution. It is then measured using gel permeation chromatography (GPC) under the following conditions. Device: HLC-8320 [Manufactured by Tosoh Corporation] Columns: TSK GEL GMH6 (2 pieces) [Manufactured by Tosoh Corporation] Measurement temperature: 40℃ Sample solution: 0.25 wt% THF solution (undissolved components filtered through a glass filter) Solution injection volume: 100μL Detection device: Refractive index detector Reference material: Standard polystyrene (TSKstandard POLYSTYRENE) 12 points (molecular weight 500, 1050, 2800, 5970, 9100, 18100, 37900, 96400, 190000, 355000, 1090000, 2890000) [Manufactured by Tosoh Corporation]

[0040] The vinyl resin (B) in the present invention is a vinyl resin containing a monomer having a carboxylic acid group as a constituent monomer. The presence or absence of crystalline properties of vinyl resin (B) is not particularly limited, but it is preferably an amorphous vinyl resin. In addition to monomers having a carboxylic acid group as a constituent monomer, styrene monomer, (meth)acrylic acid ester monomer, sulfonic acid group-containing vinyl monomer, nitrile monomer, and vinyl ester monomer can be used in combination as constituent monomers. Of the above constituent monomers, it is preferable to include styrene monomer and / or (meth)acrylic acid ester monomer as constituent monomers. Using styrene monomer and / or (meth)acrylic acid ester monomer in combination is preferable because it makes it easier to control the glass transition temperature of vinyl resin (B) and its compatibility with polyester resin (A). In the present invention, "(meth)acrylic" means "acrylic" and / or "methacrylic," and "(meth)acrylo" means "acrylo" and / or "methacrylo." Furthermore, "amorphous" means that when the transition temperature of the sample is measured using the differential scanning calorimeter described below, there is no peak top temperature of the endothermic peak.

[0041] Monomers having a carboxylic acid group include monocarboxylic acids (including those with 3 to 15 carbon atoms, such as (meth)acrylic acid, crotonic acid, and cinnamic acid), dicarboxylic acids (including those with 4 to 15 carbon atoms, such as (anhydride) maleic acid, fumaric acid, itaconic acid, and citraconic acid), and dicarboxylic acid monoesters (monoalkyl (1 to 18 carbon atoms) esters of the above dicarboxylic acids, such as monoalkyl maleic acid esters, monoalkyl fumaric acid esters, monoalkyl itaconic acid esters, and monoalkyl citraconic acid esters). Among these monomers having a carboxylic acid group, monocarboxylic acids are preferred from the viewpoint of electrostatic stability, and (meth)acrylic acid is more preferred.

[0042] Examples of styrene monomers include styrene and alkylstyrenes with 1 to 3 carbon atoms in the alkyl group (e.g., α-methylstyrene, p-methylstyrene), and either one of each may be used or two or more may be used in combination. From a cost standpoint, styrene is preferred.

[0043] Examples of (meth)acrylic acid ester monomers include alkyl (meth)acrylates with 1 to 18 carbon atoms in the alkyl group [e.g., methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, and stearyl (meth)acrylate], hydroxylalkyl (meth)acrylates with 1 to 18 carbon atoms in the alkyl group [e.g., hydroxylethyl (meth)acrylate], and alkylamino group-containing (meth)acrylates with 1 to 18 carbon atoms in the alkyl group [e.g., dimethylaminoethyl (meth)acrylate and diethylaminoethyl (meth)acrylate]. Of these (meth)acrylic acid ester monomers, from the viewpoint of storage stability, preferably (meth)acrylic acid alkyl (meth)acrylates having 1 to 18 carbon atoms in the alkyl group and mixtures of two or more thereof, more preferably (meth)acrylic acid alkyl (meth)acrylates having 1 to 7 carbon atoms in the alkyl group and mixtures of two or more thereof, even more preferably (meth)acrylic acid alkyl (meth)acrylates having 1 to 5 carbon atoms in the alkyl group, and particularly preferably butyl acrylate.

[0044] Examples of vinyl monomers containing sulfonic acid groups include alkene sulfonic acid with 2 to 14 carbon atoms, styrene sulfonic acid, sulfo(hydroxy)alkyl(meth)acrylate with 5 to 18 carbon atoms, sulfo(hydroxy)alkyl(meth)acrylamide with 5 to 18 carbon atoms, and alkyl(3 to 18 carbon atoms) allyl sulfosuccinate.

[0045] Nitrile monomers include those with 3 to 20 carbon atoms, specifically acrylonitrile, methacrylonitrile, and cyanostyrene.

[0046] Examples of vinyl ester monomers include aliphatic vinyl esters (including those with 4 to 15 carbon atoms, such as vinyl acetate, vinyl propionate, and isopropenyl acetate), and aromatic vinyl esters (including those with 9 to 15 carbon atoms, such as methyl-4-vinylbenzoate).

[0047] The vinyl resin (B) can be obtained by known polymerization methods such as solution polymerization, bulk polymerization, suspension polymerization, and emulsion polymerization using the monomer having the carboxylic acid group and optionally styrene monomer, (meth)acrylic acid ester monomer, sulfonic acid group-containing vinyl monomer, nitrile monomer, and vinyl ester monomer, along with a radical polymerization initiator. Of these polymerization methods, those preferred from the viewpoint of manufacturing stability are solution polymerization, suspension polymerization, emulsion polymerization, and combinations thereof.

[0048] Examples of radical polymerization initiators include azo polymerization initiators (e.g., azobisisobutyronitrile, azobisvaleronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), and azobiscyanovaleric acid), inorganic peroxide polymerization initiators (e.g., hydrogen peroxide, ammonium persulfate, potassium persulfate, and sodium persulfate), and organic peroxide polymerization initiators (e.g., benzoyl peroxide, di-t-butyl peroxide, t-butyl-2-ethyl peroxyhexanate, t-butyl peroxybenzoate, 1,1-di-(t-butylperoxy)cyclohexane, di-t-butyl peroxyhexahydrophthalate, and 2,2-bis(4,4-di-t-butylperoxycyclohexyl)propane). Of these, preferred are 2,2'-azobis(2,4-dimethylvaleronitrile), di-t-butyl peroxide, t-butyl-2-ethylperoxyhexanate, 1,1-di-(t-butylperoxy)cyclohexane, di-t-butylperoxyhexahydrophthalate, and 2,2-bis(4,4-di-t-butylperoxycyclohexyl)propane. The amount of polymerization initiator used is preferably 0.01 to 5 parts by weight, more preferably 0.05 to 4 parts by weight, per 100 parts by weight of the total amount of monomer.

[0049] For solution polymerization, solvents such as cycloalkane solvents with 5 to 12 carbon atoms (cyclohexane and methylcyclohexane, etc.), aromatic solvents with 6 to 12 carbon atoms (benzene, toluene, xylene, ethylbenzene and cumene, etc.), ester solvents (ethyl acetate and butyl acetate, etc.), and ether solvents (methyl cellsolve, ethyl cellsolve and butyl cellsolve, etc.) are used. Of these, aromatic solvents having 6 to 12 carbon atoms are preferred, and more preferably toluene, xylene, and ethylbenzene.

[0050] Furthermore, when performing suspension polymerization or emulsion polymerization, polymerization can be carried out in water using inorganic acid dispersants (such as calcium carbonate and calcium phosphate), organic dispersants (such as polyvinyl alcohol and methylcellulose), and surfactants (s) described in Japanese Patent Application Publication No. 2002-284881.

[0051] The vinyl resin (B) in the present invention may be a graft copolymer obtained by further graft polymerization of multiple types of vinyl resins obtained by polymerizing them as described above. In this case, the multiple types of vinyl resins may differ from each other in at least one of their constituent monomers, weight-average molecular weight, and peak-top molecular weight.

[0052] If the binder component contains vinyl resin (B), the flow softening point of vinyl resin (B) is 90 to 125°C, and the acid value of vinyl resin (B) is 11 to 45 mgKOH / g.

[0053] The flow softening point of the vinyl resin (B) in the present invention is 90°C to 125°C, preferably 95°C to 115°C. If the flow softening point of vinyl resin (B) is below 90°C, the dye dispersibility deteriorates, and if it exceeds 125°C, the low-temperature fixability deteriorates.

[0054] The acid value of the vinyl resin (B) in the present invention is 11 to 45 mgKOH / g, preferably 11 to 35 mgKOH / g, and more preferably 11 to 25 mgKOH / g. If the acid value of vinyl resin (B) is less than 11 mg KOH / g, the dyeing density and abrasion fastness of the fabric deteriorate, and if it exceeds 45 mg KOH / g, the heat resistance for storage under high temperature and high humidity deteriorates.

[0055] In the present invention, the glass transition temperature of the vinyl resin (B) is preferably 50°C to 70°C, more preferably 55°C to 65°C, from the viewpoint of heat resistance for storage under high temperature and high humidity conditions and low temperature fixing properties.

[0056] In the present invention, the number-average molecular weight (Mn) of the vinyl resin (B) is preferably 2,000 to 60,000, more preferably 3,000 to 55,000, and even more preferably 4,000 to 50,000, from the viewpoint of low-temperature fixability and dye dispersibility.

[0057] In the present invention, the weight-average molecular weight (Mw) of the vinyl resin (B) is preferably 5,000 to 900,000, more preferably 10,000 to 800,000, and even more preferably 50,000 to 700,000, from the viewpoint of low-temperature fixability and dye dispersibility.

[0058] In the present invention, the peak top molecular weight (Mp) of the vinyl resin (B) is preferably 3,000 to 900,000, from the viewpoint of low-temperature fixability and dye dispersibility.

[0059] The binder component in the present invention is a binder component containing a polyester resin (A) and / or a vinyl resin (B), and may also contain known toner binder resins other than polyester resin (A) and vinyl resin (B) to the extent that it does not impair the effects of the present invention. That is, the binder component in the present invention may also contain, for example, a high softening point polyester resin (AH) other than polyester resin (A), a high softening point vinyl resin (BH) other than vinyl resin (B), epoxy resin, polycarbonate resin, and polyurethane resin as binder resins. When the above resins are included, it is preferable that the weight percentage of the above resins in the binder component is 70% by weight or less based on the weight of the binder component.

[0060] In the present invention, when the binder component includes a high-softening-point polyester resin (AH) and / or a high-softening-point vinyl resin (BH), the flow softening points of the high-softening-point polyester resin (AH) and the high-softening-point vinyl resin (BH) are preferably 126°C to 160°C, and more preferably 130°C to 160°C, from the viewpoint of dye dispersibility.

[0061] Furthermore, the constituent components of the high-softening-point polyester resin (AH) can be the same as those of the polyester resin (A), and the preferred components are also the same. The constituent monomers of the high-softening-point vinyl resin (BH) can be the same as those of the vinyl resin (B), and the preferred components are also the same.

[0062] There are no particular restrictions on the method for producing the binder component in the present invention, and polyester resin (A) and / or vinyl resin (B) can be produced by known kneading and grinding methods or powder mixing methods.

[0063] The sublimation transfer toner of the present invention may contain a release agent for the purpose of releasing the fixing portion in order to obtain a good fixed image in the electrophotographic process.

[0064] The release agent of the present invention can be any release agent known for toners, and is not particularly limited. From the viewpoint of friction fastness, it is preferable that it be at least one selected from the group consisting of natural waxes, petroleum waxes, and synthetic waxes. Examples of natural waxes include beeswax, carnauba wax, and montan wax; examples of petroleum waxes include paraffin wax, microcrystalline wax, and petrolatum; and examples of synthetic waxes include polyethylene wax, polypropylene wax, oxidized polyethylene wax, and oxidized polypropylene wax.

[0065] The release agent preferably has a melting point in the range of 60°C to 150°C, more preferably in the range of 60°C to 145°C, and even more preferably in the range of 65°C to 140°C. If the melting point of the release agent is 60°C or higher, the heat resistance of the toner is good, and if it is 150°C or lower, the release agent melts when the toner is fixed, allowing it to fully exhibit its release effect.

[0066] The release agent content in the toner is preferably 0.5 to 10.0% by weight, and more preferably 1.0 to 9.0% by weight. When the release agent content is within this range, good release agent dispersibility can be achieved, resulting in good adhesion and offset performance during printing on copiers and printers.

[0067] The main functions of the release agent for sublimation transfer toner are as follows: (1) and (2). Function (1): A function that peels toner off the fuser roller during the fixing process in electrophotographic printing. Function (2): In the heat sublimation transfer process, it separates from the binder component and forms a release film (layer) on the image surface, inhibiting the migration of the binder component (assisting in transferring only the sublimable dye from the paper to the fabric).

[0068] The sublimation transfer toner of the present invention contains a sublimable dye. Various additives such as charge control agents and fluidizers are mixed in as needed and used as toner. The binder component content in the toner is preferably 60-98% by weight based on the weight of the toner, and when magnetic powder is used, it is preferably 25-80% by weight based on the weight of the toner.

[0069] Sublimation dyes are not particularly limited as long as they are dyes that exhibit sublimation properties. For example, suitable yellow dyes include CI Disperse Yellow 54, suitable magenta dyes include CI Disperse Red 4 and 60, and suitable cyan dyes include CI Disperse Blue 56, 60, 60-2, 72, 359, and 360. In the case of black toner, a black dye formulated by mixing yellow, magenta, and cyan dyes can be used. Other colors such as blue, orange, red, and violet can also be added to the black dye. The sublimable dye content is preferably 1 to 40 parts by weight, and more preferably 2 to 15 parts by weight, per 100 parts by weight of the binder component in the present invention, from the viewpoint of dye dispersibility.

[0070] The charge control agent may contain either a positively charged charge control agent or a negatively charged charge control agent. Examples include nigrosine dyes, triphenylmethane-based dyes containing a tertiary amine as a side chain, quaternary ammonium salts, polyamine resins, imidazole derivatives, quaternary ammonium base-containing polymers, metal-containing azo dyes, copper phthalocyanine dyes, salicylic acid metal salts, benzyl acid boron complexes, sulfonic acid group-containing polymers, fluorine-containing polymers, halogen-substituted aromatic ring-containing polymers, and the like. The content of the charge control agent may be 0 to 20% by weight, preferably 0.1 to 10% by weight, and more preferably 0.5 to 7.5% by weight, based on the weight of the binder component in the present invention.

[0071] Examples of fluidizers include silica, titania, alumina, fatty acid metal salts, silicone resin particles, and fluororesin particles, and two or more may be used in combination. Silica is preferred from the viewpoint of the toner's electrostatic properties. Furthermore, hydrophobic silica is preferred from the viewpoint of the toner's transferability. The fluidizer content may be 0 to 10% by weight, preferably 0 to 5% by weight, and more preferably 0.1 to 4% by weight, based on the weight of the sublimation transfer toner of the present invention.

[0072] Furthermore, the total weight of the additives may be 3 to 70% by weight, preferably 4 to 58% by weight, and more preferably 5 to 50% by weight, based on the toner weight. By having the toner composition ratio within the above range, it is easy to obtain a toner with good electrostatic properties.

[0073] The sublimation transfer toner of the present invention preferably has no exposure of the sublimable dye on the toner surface, that is, it contains the sublimable dye internally. Furthermore, the sublimation transfer toner of the present invention is in the form of particles, and its volume average particle size (D50) is preferably 1 to 15 μm, more preferably 2 to 10 μm, and particularly preferably 3 to 8 μm. The volume-average particle size (D50) of the sublimation transfer toner of the present invention can be measured using a Coulter counter [for example, product name: Multisizer III (manufactured by Beckman Coulter, Inc.)].

[0074] In one-component developer toners, carrier particles are not necessary, but in two-component developer toners, carrier particles are required. An example of a carrier particle is a magnetic carrier particle, such as a ferrite carrier. A suitable carrier particle is one in which a ferrite core is coated with acrylic resin.

[0075] In the sublimation transfer toner of the present invention, the addition of a photocuring agent is unnecessary.

[0076] There are no particular limitations on the method for producing the sublimation transfer toner of the present invention. It may be produced by known kneading and grinding methods, suspension polymerization methods described in Japanese Patent Publication No. 36-10231, Japanese Unexamined Patent Publication No. 59-53856, and Japanese Unexamined Patent Publication No. 59-61842, emulsion polymerization methods such as soap-free polymerization methods which produce toner by directly polymerizing monomers in the presence of a water-soluble polymerization initiator, interfacial polymerization methods such as microcapsule manufacturing methods, in situ polymerization methods, coacervation methods, association polymerization methods such as those disclosed in Japanese Unexamined Patent Publication No. 62-106473 and Japanese Unexamined Patent Publication No. 63-186253 which involve aggregating at least one type of fine particles to obtain a toner of a desired particle size, dispersion polymerization methods characterized by monodispersion, or by dissolution suspension methods in which necessary resins are dissolved in a water-insoluble organic solvent and then tonerized in water. Of the above manufacturing methods, the kneading and grinding method and the association polymerization method, which aggregates at least one type of fine particle to obtain a toner with a desired particle size, are preferred from the viewpoint of toner particle size control and electrostatic stability.

[0077] For example, when obtaining toner by the kneading and grinding method, the components constituting the toner, excluding the fluidizer, are dry-blended using a Henschel mixer, Nauter mixer, or Banbury mixer. Then, they are melt-kneaded using a continuous mixing device such as a twin-screw kneader, extruder, continuous kneader, or three-roll machine. After that, they are coarsely ground using a mill, and finally, they are finely atomized using an air-jet mill. Further adjustment of the particle size distribution is performed using a classifier such as an elbow jet to obtain fine particles with a volume-average particle size (D50) of 4 to 12 μm. Finally, the fluidizer is mixed in using a mill to produce the toner.

[0078] For example, when obtaining toner by association polymerization, which involves agglomerating at least one type of fine particles to obtain a desired particle size, the toner can be produced by first obtaining a dispersion of resin particles using the following steps (1) to (3), and then removing the aqueous solvent. Step (1): Step to obtain resin particulate dispersion (resin particulate dispersion of polyester resin (A) (A0) and resin particulate dispersion of vinyl resin (B) (B0)) and additive dispersion (sublimable dye dispersion and mold release agent dispersion, etc.) Step (2): A step in which each resin microparticle dispersion and the additive dispersion are mixed to aggregate the resin microparticles and form aggregates of resin microparticles. Step (3): Step to obtain resin particles formed by fusing aggregates.

[0079] Aqueous solvents can be used as the dispersion medium for the dispersion. Any liquid containing water as an essential component can be used as the aqueous solvent, and as described later, water, aqueous solutions of organic solvents, aqueous solutions of surfactants (s), and mixtures of two or more of these can be used. In addition, organic solvents may be used to dissolve the resin in order to improve the dispersibility of the resin in the aqueous solvent.

[0080] Examples of organic solvents include aromatic hydrocarbon solvents, aliphatic or alicyclic hydrocarbon solvents, halogen solvents, ester or ester ether solvents, ether solvents, ketone solvents, alcohol solvents, amide solvents, sulfoxide solvents, heterocyclic compound solvents, and mixtures of two or more of these. Preferably, ethyl acetate, acetone, and methyl ethyl ketone are used.

[0081] To improve the dispersibility of the resin in an aqueous solvent, a neutralizing agent may be used to neutralize the carboxyl groups of the polyester resin (A) and vinyl resin (B). Examples of neutralizing agents include organic compounds such as ammonia and triethylamine, and inorganic compounds such as sodium hydroxide.

[0082] The amount of neutralizing agent used is preferably 1 to 150 moles, more preferably 5 to 100 moles, per 100 moles of carboxyl groups of polyester resin (A) and vinyl resin (B), from the viewpoint of dispersibility.

[0083] When dispersing polyester resin (A) and vinyl resin (B) in an aqueous solvent, known surfactants (s) and inorganic dispersants can be used as emulsifiers or dispersants. Using surfactants (s) and inorganic dispersants is preferable because it tends to reduce the volume-average particle size of the resin fine particles.

[0084] The surfactant (s) is not particularly limited and includes anionic surfactants (s-1), cationic surfactants (s-2), amphoteric surfactants (s-3), and nonionic surfactants (s-4). The surfactant (s) may also be a combination of two or more surfactants.

[0085] Examples of anionic surfactants (s-1) include carboxylic acids or their salts, sulfate esters, carboxymethylated salts, sulfonates, and phosphate esters. Examples of cationic surfactants (S-2) include quaternary ammonium salt type surfactants and amine salt type surfactants. Examples of amphoteric surfactants (S-3) include carboxylate-type amphoteric surfactants, sulfate-type amphoteric surfactants, sulfonate-type amphoteric surfactants, and phosphate-type amphoteric surfactants. Examples of nonionic surfactants (s-4) include AO-added nonionic surfactants and polyhydric alcohol-type nonionic surfactants. Specific examples of these surfactants (s) include those described in Japanese Patent Publication No. 2002-284881.

[0086] The amount of surfactant(s) used per 100 parts by weight of water as an aqueous solvent is preferably 0 to 300 parts by weight, more preferably 0.001 to 10 parts by weight, and even more preferably 0.01 to 5 parts by weight.

[0087] From the viewpoint of controlling the volume particle size and particle size distribution of the toner, the volume average particle size of the resin fine particles is preferably 0.05 to 1 μm, more preferably 0.07 to 0.5 μm, and even more preferably 0.09 to 0.3 μm. The volume-average particle size of resin microparticles can be measured using the dynamic light scattering particle size distribution analyzer "SZ-100" (manufactured by Horiba, Ltd.).

[0088] The amount of resin fine particles in 100 parts by weight of the dispersion is preferably 1 to 70 parts by weight (solid content of resin fine particles in the dispersion is 1 to 70% by weight), more preferably 5 to 65 parts by weight, and even more preferably 10 to 60 parts by weight, from the viewpoint of controlling the volume particle size and particle size distribution of the toner.

[0089] The following describes step (1). For example, an organic solvent solution containing a polyester resin (A) can be dispersed in an aqueous solvent, if necessary, in the presence of a suitable dispersant, and then the organic solvent can be removed to produce a dispersion. The dispersion method is not particularly limited, but known equipment such as low-speed shear, high-speed shear, friction, high-pressure jet, and ultrasonic dispersive systems can be used. A high-speed shear disperser is preferred to reduce the particle size of the fine particles in the dispersion to 0.05 to 1 μm. When using a high-speed shear disperser, the rotation speed is not particularly limited, but is preferably 1000 to 30000 rpm, more preferably 5000 to 20000 rpm. The dispersion time is not particularly limited, but in the case of a batch system, it is preferably 0.1 to 5 minutes. The temperature is preferably 5 to 200°C, more preferably 20 to 100°C. Dispersion equipment includes, for example, batch-type emulsifiers such as homogenizers (manufactured by IKA), Polytron (manufactured by Kinetica), and homomixers (manufactured by PRIMIX), as well as Ultraviscomil (manufactured by AIMEX), Ebara Milder (manufactured by Ebara Corporation), Filmix, and pipeline homomixers (manufactured by PRIMIX).

[0090] Step (2) is described below. The method for obtaining aggregates by agglomerating resin microparticles is not particularly limited, but one method is to add a flocculant to a dispersion. Examples of flocculants include metal salts of inorganic acids (such as sodium chloride, magnesium chloride, calcium chloride, aluminum chloride, aluminum sulfate, calcium sulfate, ammonium sulfate, aluminum nitrate, silver nitrate, copper sulfate, and sodium carbonate).

[0091] The temperature of the dispersion in step (2) above is preferably 5 to 100°C, more preferably 20 to 100°C, from the viewpoint of controlling the volume-average particle size and particle size distribution of the resin particles. Furthermore, in the step of forming aggregates in step (2), the pH of the dispersion is preferably 2 to 10, more preferably 3 to 6, from the viewpoint of controlling the volume-average particle size and particle size distribution of the resin particles.

[0092] Step (3) is described below. In step (3), the temperature at which the aggregates are fused is preferably 5 to 200°C, and more preferably 30 to 100°C, from the viewpoint of shape controllability of the resulting resin particles and toner. In step (3), the pH of the liquid used to fuse the aggregates is preferably 3 to 10, and more preferably 5 to 10.

[0093] The sublimation transfer toner of the present invention is fixed to a support (paper, polyester film, etc.) by a copier, printer, etc., to serve as a recording material. Known methods such as thermal roll fixing and flash fixing can be applied to fix the toner to the support.

[0094] The sublimation transfer toner of the present invention can be preferably used for developing electrostatic images or magnetic latent images in electrophotography, electrostatic recording, electrostatic printing, and the like. More preferably, it can be used for developing electrostatic images or magnetic latent images for full color. [Examples]

[0095] The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples.

[0096] <Manufacturing Example 1> Polyester resin (A-1) In a reaction vessel capable of heating, cooling, pressurizing, and depressurizing, 755.2 parts by weight of 2 molar EO adduct of bisphenol A (100 mol% in total alcohol content) was added and dissolved at 120°C. At 120°C, 2.5 parts by weight of titanium diisopropoxybis(triethanolamine), 256.0 parts by weight of terephthalic acid (88.0 mol% in total acid content), and 0.6 parts by weight of maleic anhydride (0.4 mol% in total carboxylic acid content) were added and the mixture was heated under reduced pressure towards 220°C. After esterification under reduced pressure at 220°C, the mixture was cooled to 175°C after confirming that the acid value was 1 mg KOH / g or less. Next, 39.2 parts by weight of trimellitic anhydride (11.6 mol% in total carboxylic acid content) was added, and after confirming that the acid value was 23 mg KOH / g, the mixture was removed. The physical properties of the obtained polyester resin (A-1) are shown in Table 1.

[0097] <Manufacturing Examples 2-5> Polyester resin (A-2)-(A-5) Polyester resins (A-2) to (A-5) were obtained in the same manner as in Production Example 1, except that the raw materials listed in Table 1 were used.

[0098] <Comparative Manufacturing Example 1> Polyester resin (A'-1) Polyester resin (A'-1) was obtained in the same manner as in Production Example 1, except that the raw materials listed in Table 1 were used (raw materials other than trimellitic anhydride were added at the beginning). The physical properties of the obtained polyester resin (A'-1) are shown in Table 1.

[0099] <Manufacturing Example 6> Polyester resin (AH) In a reaction vessel capable of heating, cooling, pressurizing, and depressurizing, 768.9 parts by weight of 2 molar EO adduct of bisphenol A (100 mol / mole ratio of the total alcohol) was added and dissolved at 120°C. At 120°C, 2.5 parts by weight of titanium diisopropoxybis(triethanolamine), 206.2 parts by weight of terephthalic acid (74.8 mol / mole ratio of the total acid component), 0.1 parts by weight of maleic anhydride (0.1 mol / mole ratio of the total acid component), and 80.0 parts by weight of trimellitic anhydride (25.1 mol / mole ratio of the total acid component) were added and the temperature was increased under reduced pressure toward 220°C. Esterilization was carried out under reduced pressure at 220°C, and after confirming the acid value of 1 mg KOH / g, the mixture was removed.

[0100] [Table 1]

[0101] <Manufacturing Example 7> 200 parts by weight of xylene was placed in an autoclave, purged with nitrogen, and then heated to 170°C under stirring and in a sealed state. A mixed solution of 715 parts by weight of styrene, 270 parts by weight of butyl acrylate, 15 parts by weight of acrylic acid, 1.5 parts by weight of di-t-butyl peroxide, and 100 parts by weight of xylene was added dropwise over 3 hours while controlling the autoclave temperature to 170°C, and polymerization was carried out. The mixture was then maintained at the same temperature for another hour to complete the polymerization. Polymer-1 was obtained by desolvent removal under reduced pressure at 4 kPa or less for 3 hours at the same temperature.

[0102] <Manufacturing Example 8> In a four-necked flask, 1376.3 parts by weight of water and 2.25 parts by weight of polyvinyl alcohol [Poval 95-88, manufactured by Kuraray Co., Ltd.] were added. A mixture consisting of 756.8 parts by weight of styrene, 213.5 parts by weight of butyl acrylate, and 3.7 parts by weight of 2,2-bis(4,4-di-t-butylperoxycyclohexyl)propane was added and stirred to form a suspension. After thoroughly purging the flask with nitrogen, the temperature was raised to 95°C to start polymerization. Polymerization was continued at the same temperature, and after confirming that the conversion rate reached 98% after 24 hours, the temperature was raised to 100°C and maintained at the same temperature for 2 hours to complete the polymerization. As a post-treatment, the product was filtered, washed with water, and dried to obtain polymer-2.

[0103] <Manufacturing Example 9> In a four-necked flask, 1131 parts by weight of water and 1.5 parts by weight of polyvinyl alcohol [(Kuraray Co., Ltd., Poval 95-88)] were added. A mixture consisting of 789 parts by weight of styrene, 210 parts by weight of butyl acrylate, 0.5 parts by weight of di-t-butyl peroxyhexahydroterephthalate, and 2.8 parts by weight of peroxy 2,2-bis(4,4-di-t-butylperoxycyclohexyl)propane was added and stirred to form a suspension. After thoroughly purging the flask with nitrogen, the temperature was raised to 98°C to start polymerization. Polymerization was continued at the same temperature, and after confirming that the conversion rate reached 98% after 24 hours, the temperature was raised to 100°C and maintained at the same temperature for 2 hours to complete the polymerization. As post-treatment, the product was filtered, washed with water, and dried to obtain polymer-3.

[0104] <Manufacturing Example 10> Vinyl Resin (B-1) 235 parts by weight of xylene was placed in an autoclave, and the temperature was raised to 135°C under a sealed state with stirring. After depressurization, the temperature was raised to 237°C under a sealed state with stirring. A mixed solution of 972 parts by weight of styrene, 28 parts by weight of acrylic acid, and 1.5 parts by weight of perbutyl D (di-t-butyl peroxide) as a polymerization initiator was added dropwise over 4 hours while controlling the autoclave temperature to 237°C, and polymerization was carried out. After addition, the dropping line was washed with 15 parts by weight of xylene. After holding at the same temperature for another 0.5 hours, desolventing was carried out at 237°C under reduced pressure of 0.5 to 2.5 kPa for 3 hours to obtain vinyl resin (B-1). The physical properties of the obtained vinyl resin (B-1) are shown in Table 2.

[0105] <Manufacturing Examples 11-14> Vinyl Resin (B-2)-(B-5) Vinyl resins (B-2) to (B-5) were obtained in the same manner as in Production Example 10, except that the raw materials listed in Table 2 were used.

[0106] <Manufacturing Example 15> Vinyl resin (BH) 236 parts by weight of xylene was placed in an autoclave, purged with nitrogen, and then heated to 139°C under stirring and in a sealed state. A mixed solution of 193.8 parts by weight of styrene, 52.5 parts by weight of butyl acrylate, 3.75 parts by weight of acrylic acid, 43 parts by weight of xylene, and 0.38 parts by weight of perbutyl D (di-t-butyl peroxide) was added dropwise over 1 hour while controlling the autoclave temperature to 139°C and polymerized. Next, the temperature was raised to 187°C. A mixed solution of 345.9 parts by weight of styrene, 16.5 parts by weight of butyl acrylate, 3.66 parts by weight of acrylic acid, 80 parts by weight of xylene, and 7.32 parts by weight of perbutyl D (di-t-butyl peroxide) was added dropwise over 2 hours while controlling the autoclave temperature to 187°C and polymerized. Next, the mixture was cooled to 70°C, and 60 parts by weight, 80 parts by weight, and 240 parts by weight of polymer-1, polymer-2, and polymer-3 were added. Then, the temperature was raised to 175°C, and desolvation was carried out under reduced pressure at 4 kPa or less for 3 hours to obtain vinyl resin (BH). Table 1 shows the physical properties of vinyl resin (BH). Note that the parts by weight of styrene, butyl acrylate, acrylic acid, and perbutyl D shown in Table 1 represent the total amount of each component added.

[0107] [Table 2]

[0108] <Example 1> Toner (T1) Using a Henschel mixer [FM10B, manufactured by Mitsui Miike Chemical Machinery Co., Ltd.], the toner binder, dye [CI Disperse Blue 56, manufactured by Huntsman Japan Co., Ltd.], release agent [HNP-9: paraffin wax, manufactured by Nippon Seiro Co., Ltd.], and charge control agent [TN-105: manufactured by Hodogaya Chemical Co., Ltd.] were pre-mixed according to the mixing ratio (parts by weight) shown in Table 3, and then kneaded in a twin-screw kneader [PCM-30, manufactured by Ikegai Co., Ltd.]. Next, the mixture was finely ground using a supersonic jet pulverizer LabJet [manufactured by Nippon Pneumatic Mfg. Co., Ltd.], and then classified using an airflow classifier [MDS-I, manufactured by Nippon Pneumatic Mfg. Co., Ltd.] to obtain toner particles with a particle size D50 of 7 μm. Next, 1.5 parts by weight of colloidal silica [Aerosil R972: manufactured by Nippon Aerosil Co., Ltd.] as a fluidizing agent was mixed with 119 parts by weight of toner particles in a sample mill to obtain sublimation transfer toner (T1).

[0109] <Examples 2-32> Toner (T2)-(T32) Sublimation transfer toners (T2) to (T32) were obtained in the same manner as in Example 1, except that the mixing ratios (parts by weight) were as shown in Tables 3 to 4.

[0110] <Comparative Example 1-2> Toner (T'1)-(T'2) Except for following the mixing ratio (parts by weight) listed in Table 4, comparative sublimation transfer toners (T'1) to (T'2) were obtained in the same manner as in Example 1.

[0111] <Low-temperature fixation> Toner is applied to the paper surface at a rate of 1.00 mg / cm². 2 The powder was applied evenly to the paper. The method used to apply the powder to the paper involved using a printer with the heat fuser removed. This paper was then passed through a soft roller at a fixing speed (heating roller peripheral speed) of 213 mm / second, with the heating roller temperature ranging from 80 to 180°C in 5°C increments. Next, the presence or absence of cold offset in the fixed image was visually inspected, and the cold offset occurrence temperature (MFT) was measured. A lower temperature at which cold offset occurs indicates superior low-temperature fixing performance. Under these evaluation conditions, a temperature of 120°C or lower is preferable.

[0112] <Dye dispersibility> The dye dispersibility (average particle size by domain number) of the dye in the toner was measured using the obtained toner according to the following measurement method. The toners obtained in the examples and comparative examples were embedded in thermosetting resin to form sample pieces, which were then ultrathinly sectioned to approximately 100 μm. The dye dispersed in the toner was stained with ruthenium tetroxide at a concentration of 1 for 3 minutes using a vacuum electron staining apparatus (VSC1R1H, manufactured by Philgen Co., Ltd.). The dispersion state of the dye, which appeared gray or black due to ruthenium tetroxide staining, was observed in the cross-section of the toner at a magnification of 10,000x using a transmission electron microscope (TEM, instrument name: H7500, manufactured by Hitachi High-Technologies Corporation), and the domain particle size of the dye in the toner was analyzed and calculated. Under these evaluation conditions, a score of ○ or higher is preferable.

[0113] [Judgment criteria] ◎: The average particle diameter by number of domains is 10 nm or less. ○: The average particle diameter by number of domains is greater than 10 nm and less than or equal to 50 nm. △: The average particle diameter by number of domains is greater than 50 nm and less than or equal to 200 nm. ×: The average particle size by number of domains is greater than 200 nm.

[0114] <Heat-resistant storage stability> 1 g of sublimation transfer toner and 0.013 g of Aerosil R972 (manufactured by Evonik Japan Co., Ltd.) were mixed in a shaker for 1 hour. The mixture was placed in a sealed container and left to stand for 24 hours in an atmosphere of 50°C and 50% relative humidity. The coagulation properties were measured using a powder tester to evaluate the heat resistance and storage properties. A lower cohesion test value, determined by the method described below, indicates superior heat resistance and storage properties. Under these evaluation conditions, a cohesion level of 10% or less is preferable. Equipment: POWDER TESTER model PT-X (manufactured by Hosokawa Micron) Sieve mesh sizes: 355μm, 250μm, 150μm Vibration width: 1mm Vibration time: 30 seconds Operating procedure: Place the sieves on the powder tester's vibrating platform in the following order: top 355μm, middle 250μm, and bottom 150μm. Place 1g of toner on the top sieve and vibrate for 30 seconds with a vibration amplitude of 1mm. Measure the weight of the toner remaining on each sieve. Cohesiveness: Calculated from the weight of toner used for measurement and the weight of remaining toner after sieving. Cohesion degree (%)=(U / N+M / N×3 / 5+L / N×1 / 5)×100 U: Weight of the top layer, M: Weight of the middle layer, L: Weight of the bottom layer, N: Weight of the sample (1g)

[0115] (Sublimation transfer onto polyester fabric) Tropical fabric was used as the polyester fabric for sublimation transfer dyeing. The toner fixing surface of each transfer paper was placed on top of each polyester fabric, and sandwiched between the press plates of a Hashima sublimation transfer press (machine name: HSP-5400). The press was heated at a temperature of 210°C, a pressure of 150 kg, and for 60 seconds. After cooling to room temperature, the sublimation transfer paper was peeled off the polyester fabric to obtain dyed polyester fabrics that had been sublimated by sublimation dye.

[0116] <Dye concentration> The image density of each color in specific locations on a dyed tropical fabric (polyester fiber) was measured using a densitometer (X-Rite, instrument name: spectrometer / densitometer). The spectral density was determined from the obtained values. Under these evaluation conditions, a value of 1.2 or higher is preferable.

[0117] <Friction fastness test> The abrasion fastness (dry friction) and (wet friction) of dyed tropical fabric (polyester fiber) was tested and determined according to the Type II test method of JIS L 0849. The abrasion tester has a table, and the fabric to be tested was attached to this table, with a cotton cloth attached to the tip of the arm (friction element) at the top of the abrasion tester. With a load of approximately 200g, the arm with the cotton cloth was rubbed back and forth over the fabric to be tested 100 times over a length of 100mm. After the rubbing was complete, the cotton cloth was removed from the arm, and the abrasion fastness value was determined by determining "staining" using a gray scale for staining. The value is expressed as a grade, with a higher grade indicating higher abrasion fastness. As part of the friction fastness test, a "dry test" and a "wet test" were conducted. In the "dry test," friction was performed using a dry cotton cloth. In the "wet test," friction was performed using a wet cotton cloth. In the wet test, the degree of wetting was set to approximately 100% according to JIS standards. In the wet test, after the friction was completed, the cotton cloth was removed from the arm and dried, and once dry, "staining" was determined using a grayscale for staining. Under these evaluation conditions, a grade of 4 or higher is preferable. Tables 3 and 4 show the evaluation results of the toners used in the examples.

[0118] [Table 3]

[0119] [Table 4] [Industrial applicability]

[0120] The sublimation transfer toner of the present invention offers excellent optical density improvement, friction fastness improvement, dye dispersibility, and low-temperature fixation properties for fabrics, making it suitable for use in applications such as dye printing treatment agents.

Claims

1. A sublimation transfer toner comprising at least a binder component and a sublimable dye, wherein the binder component comprises a polyester resin (A) and / or a vinyl resin (B), and when the binder component comprises the polyester resin (A), the flow softening point of the polyester resin (A) is 90 to 125°C and the acid value of the polyester resin (A) is 11 to 45 mgKOH / g, and when the binder component comprises the vinyl resin (B), the flow softening point of the vinyl resin (B) is 90 to 125°C and the acid value of the vinyl resin (B) is 11 to 45 mgKOH / g.

2. The sublimation transfer toner according to claim 1, further comprising a release agent, wherein the release agent is at least one selected from the group consisting of natural waxes, petroleum waxes, and synthetic waxes.

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