Sublimation transfer toner

Abstract

The present invention provides a sublimation transfer toner that can prevent contamination of the photoreceptor, improve the friction fastness of sublimation-transferred fabrics, and have high heat resistance for storage. [Solution] A sublimation transfer toner containing a copolymer (W) having a segment (A) derived from a polyolefin and a segment (B) derived from a vinyl monomer, and a sublimable dye, wherein the SP value difference (SP(B)-SP(A)) between the segment (A) derived from the polyolefin and the segment (B) derived from the vinyl monomer is 1.5 to 5.0.

Description

[Technical Field]

[0001] This invention relates to a toner for sublimation transfer. [Background technology]

[0002] A method for manufacturing dyed fabrics using sublimation dyes is known. In this method, first, an image of toner containing sublimation dye is formed on a photoreceptor, the toner formed on the photoreceptor is transferred to a sheet-like substrate, and then the toner is fixed to the sheet-like substrate by heat. After that, the sheet-like substrate and the fabric are placed on top of each other, and the sheet-like substrate is heated to dye the fabric with the sublimation dye contained in the toner of the sheet-like substrate.

[0003] In this method, a heating press or vacuum heating machine is used to sublimate the sublimable dye in the toner and dye the fabric. The heating conditions are set to 190-210°C and 100-600 g / cm³, taking into account the sublimation temperature of the sublimable dye. 2 A duration of 1 minute is common, and this condition is known to be the best for sublimating sublimable dyes and dyeing fabrics.

[0004] By the way, even with this type of printing method, it is necessary to have high friction fastness for the printed fabric. Friction fastness evaluates the degree of color transfer (staining) to other garments due to friction between clothing, such as when wearing multiple layers. For example, if you wear navy blue jeans and a white shirt, you might experience some navy blue color transfer around the hem of your shirt. This is because the friction between the jeans and shirt during wear causes the color to transfer from the jeans (navy blue) to the shirt (white). This type of accident is likely to occur in areas where clothing rubs against each other, so high friction fastness is necessary.

[0005] However, conventional methods often result in insufficient friction fastness. One reason for this is that when toner fixed to a sheet-like substrate is heated to sublimate the sublimable dye in the toner and transfer it to the fabric, the toner melts and adheres to the fabric. When toner transfers to the fabric, it not only reduces friction fastness but also deteriorates the texture of the fabric itself and makes it difficult to peel the sheet-like substrate from the fabric after sublimation transfer.

[0006] As a toner used for dyeing by sublimation transfer in an electrophotographic system, for example, Patent Document 1 describes a toner containing at least one sublimable dispersible dye and a binder resin. In a flow rate test in which this toner is flowed downward through a hole with a diameter of 1 mm and a length of 1 mm while a pressure of 4.90 MPa is applied to it with a plunger and the temperature is raised at 5°C / min, the temperature at which half of the toner flows out is T 1 / 2 The optimal temperature range is 150°C to 175°C, and the loss tangent tanδ of this toner at 130°C is 0.35 or less.

[0007] Furthermore, in electrophotographic methods, there are also known methods (Patent Documents 2-4) that use a heated roller or heated belt to fix the electrostatic latent image visualized with toner. In this method, the toner is moved onto the electrostatic latent image on the photoreceptor, then further moved onto a support (paper, polyester film, etc.), and finally fixed to the support by a heated roller fixing method or the like to become a recording material. [Prior art documents] [Patent Documents]

[0008] [Patent Document 1] Patent No. 6250218 [Patent Document 2] Patent No. 6795570 [Patent Document 3] Patent No. 6626871 [Patent Document 4] Patent No. 5341167 [Overview of the project] [Problems that the invention aims to solve]

[0009] However, conventional sublimation transfer toners have poor dispersion of the release agent, which can lead to photoreceptor contamination due to the release agent being exposed on the toner surface. In addition, the poor dispersion of the release agent resulted in insufficient friction fastness of the fabric and poor heat resistance of the toner when dye was sublimated onto the fabric. In other words, with conventional sublimation transfer toners, it was difficult to prevent photoreceptor contamination due to the release agent being exposed on the toner surface, improve the friction fastness of the fabric, and further enhance the heat resistance of the toner.

[0010] This invention has been made in view of these problems, and aims to provide a sublimation transfer toner that can prevent contamination of the photoreceptor, improve the friction fastness of the sublimation-transferred fabric, and have high heat resistance for storage. [Means for solving the problem]

[0011] The inventors of this invention have diligently studied and conducted research to solve the above problems, and as a result, have completed this invention. The present invention relates to a sublimation transfer toner containing a copolymer (W) having a segment (A) derived from a polyolefin and a segment (B) derived from a vinyl monomer, and a sublimable dye, wherein the SP value difference (SP(B)-SP(A)) between the segment (A) derived from the polyolefin and the segment (B) derived from the vinyl monomer is 1.5 to 5.0. [Effects of the Invention]

[0012] The present invention provides a sublimation transfer toner that can prevent photoreceptor contamination, improve the friction fastness of sublimation-transferred fabrics, and have high heat resistance for storage. [Modes for carrying out the invention]

[0013] The sublimation transfer toner of the present invention is a sublimation transfer toner containing a copolymer (W) having a segment (A) derived from a polyolefin, a segment (B) derived from a vinyl monomer, and a sublimable dye, wherein the difference in SP value between the segment (A) derived from the polyolefin and the segment (B) derived from the vinyl monomer (SP(B)-SP(A)) is 1.5 to 5.0. The sublimation transfer toner of the present invention will be sequentially described below.

[0014] The sublimation transfer toner of the present invention comprises a copolymer (W) having a segment (A) derived from a polyolefin and a segment (B) derived from a vinyl monomer. The copolymer (W) is a copolymer obtained by polymerizing a polyolefin and a vinyl monomer.

[0015] The copolymer (W) has a function of dispersing a release agent. That is, by improving the dispersion state of the release agent in the toner, exposure of the release agent to the toner surface can be suppressed, and the release agent can be uniformly eluted during sublimation transfer, thereby suppressing resin transfer and improving the friction fastness of fabrics.

[0016] The segment (B) derived from a vinyl monomer is a segment not derived from a polyolefin and does not contain a polyolefin. More specifically, the vinyl monomer preferably contains a styrene monomer as an essential constituent monomer. That is, the segment (B) derived from a vinyl monomer is preferably a polymer having styrene as an essential constituent monomer.

[0017] For the segment (B), a styrene monomer is used as an essential constituent monomer, and a (meth)acrylic acid ester monomer, a carboxyl group-containing vinyl monomer, a nitrile monomer, and a vinyl ester monomer can be further used in combination as constituent monomers. In the present invention, "(meth)acryl" means "acryl" and / or "methacryl", and "(meth)acrylo" means "acrylo" and / or "methacrylo".

[0018] Examples of the styrene monomer include styrene and alkylstyrenes in which the alkyl group has 1 to 3 carbon atoms (e.g., α-methylstyrene, p-methylstyrene). One of these may be used alone, or two or more thereof may be used in combination. Styrene is preferred from the viewpoint of cost.

[0019] Examples of the (meth)acrylic acid ester monomer include alkyl (meth)acrylates in which the alkyl group has 1 to 18 carbon atoms [e.g., methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate (butyl (meth)acrylate), 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, etc.], hydroxylalkyl (meth)acrylates in which the alkyl group has 1 to 18 carbon atoms [e.g., hydroxylethyl (meth)acrylate, etc.], and alkylamino group-containing (meth)acrylates in which the alkyl group has 1 to 18 carbon atoms [e.g., dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, etc.]. From the viewpoint of storage stability among these (meth)acrylic acid ester monomers, preferred are alkyl (meth)acrylates in which the alkyl group has 1 to 18 carbon atoms and mixtures of two or more thereof; more preferred are alkyl (meth)acrylates in which the alkyl group has 1 to 7 carbon atoms and mixtures of two or more thereof; and still more preferred are alkyl (meth)acrylates in which the alkyl group has 1 to 5 carbon atoms (alkyl (having 1 to 5 carbon atoms) esters of (meth)acrylic acid).

[0020] Examples of the carboxyl group-containing vinyl monomer include monocarboxylic acids [including those having 3 to 15 carbon atoms, such as (meth)acrylic acid, crotonic acid and cinnamic acid, etc.], dicarboxylic acids [including those having 4 to 15 carbon atoms, such as (anhydrous) maleic acid, fumaric acid, itaconic acid and citraconic acid, etc.], and monoester of dicarboxylic acids [monoalkyl (having 1 to 18 carbon atoms) esters of the above dicarboxylic acids, such as monoalkyl maleate, monoalkyl fumarate, monoalkyl itaconate and monoalkyl citraconate, etc.], and the like. Of these carboxyl group-containing vinyl monomers, (meth)acrylic acid, dicarboxylic acid monoesters, (anhydride) maleic acid, fumaric acid, and mixtures of two or more thereof are preferred from the viewpoint of electrostatic stability, and (meth)acrylic acid, maleic acid monoesters, and mixtures of two or more thereof are preferred.

[0021] Nitrile monomers include those with 3 to 20 carbon atoms, specifically (meth)acrylonitrile and cyanostyrene. Of these, acrylonitrile and methacrylonitrile are preferred.

[0022] 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).

[0023] The weight percentage of styrene monomer in the monomers constituting segment (B) is preferably 60 to 99% by weight, based on the total weight of the monomers constituting segment (B).

[0024] Segment (B) may use a crosslinking agent in an amount of 0.0001 to 0.1% by weight relative to the above constituent monomers. Examples of crosslinking agents include divinylbenzene, divinylnaphthalene, divinyl ether, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, 1,3-butylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, propylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, and tetramethylolmethane tetra(meth)acrylate.

[0025] The polyolefin that constitutes segment (A) is a homopolymer or copolymer of olefins having 2 to 7 carbon atoms. Examples of olefins having 2 to 7 carbon atoms include ethylene, propylene, 1-butene, isobutylene, 1-hexene, and mixtures thereof.

[0026] In particular, in segment (A) derived from polyolefin, it is preferable that the polyolefin is polyethylene and / or polypropylene.

[0027] Furthermore, the polyolefin forming segment (A) may be a modified polyolefin having terminal double bonds.

[0028] From the viewpoint of durability, the molecular weight of the polyolefin that forms segment (A) is preferably a number-average molecular weight (Mn) of 1,000 to 10,000, and more preferably a number-average molecular weight (Mn) of 1,500 to 9,000.

[0029] As the polyolefin for segment (A), the aforementioned olefins having 2 to 7 carbon atoms may be polymerized by known methods, or commercially available polyolefins [such as the Sanwax series and the Viscol series (both manufactured by Sanyo Chemical Industries, Ltd.)] may be used.

[0030] The weight percentage of segments (A) derived from polyolefins in the copolymer (W) is preferably 5 to 30% by weight, and more preferably 10 to 25% by weight, based on the weight of the copolymer (W). If the weight percentage of segment (A) in the copolymer (W) is less than 5% by weight, the dispersibility of the release agent may deteriorate. If the weight percentage of segment (A) in the copolymer (W) exceeds 30% by weight, the heat resistance of the toner may deteriorate.

[0031] The peak-top molecular weight (Mp) of the copolymer (W) is preferably 3,000 to 8,000, and more preferably 4,500 to 7,000.

[0032] In the present invention, the peak top molecular weight (Mp) of the copolymer (W) and the vinyl resin (C) and polyester resin (D) described below 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% by weight THF solution (undissolved components filtered out using 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]

[0033] The difference in SP values ​​(SP(B)-SP(A)) between the segment (A) derived from polyolefin and the segment (B) derived from vinyl monomer is 1.5 to 5.0, preferably 2.0 to 4.5, and more preferably 2.5 to 4.0. If this SP value difference is less than 1.5, contamination of the photoreceptor or deterioration of the dispersibility of the release agent may occur. If this SP value difference exceeds 5.0, the compatibility between the polyolefin and the vinyl monomer deteriorates, which can make it difficult to produce the copolymer (W).

[0034] From the viewpoints of preventing contamination of the photoreceptor and dispersibility of the release agent, the SP value (SP(A)) of the segment (A) derived from polyolefin is preferably from 8.0 to 9.0, and more preferably from 8.2 to 8.8.

[0035] From the viewpoint of heat-resistant storage stability, the SP value (SP(B)) of the segment (B) derived from a vinyl monomer is preferably 10.5 to 13.5, more preferably 10.5 to 13.0, and still more preferably 11.0 to 12.5.

[0036] The SP value (SP(A)) of the segment (A) derived from polyolefin and the SP value (SP(B)) of the segment (B) derived from a vinyl monomer can be calculated by the following method.

[0037] The SP value in the present invention means a value calculated by the Fedors method, that is, a value calculated by formula (28) described on page 153 of Polymer Engineering and Science, February, 1974, Vol. 14, No. 2, pp. 147 to 154, using the numerical values described on page 152 (Table 5) (heat of evaporation and molar volume of atoms or functional groups at 25°C). Specifically, the calculation can be performed by applying the numerical values corresponding to the types of atoms and atomic groups in the molecular structure from Δe described in Tables 1-1 and 1-2 below, which are parameters of the Fedors method, i and Δv i to the following mathematical formula. SP value=(ΣΔe i / ΣΔv i ) 1 / 2 In the formula, ΣΔe i (unit: cal / mol) is cohesive energy density (unit: cal / mol), and ΣΔv i is molar volume (unit: cm 3 / mol).]

[0038]

Table 1-1

[0039] [Table 1-2]

[0040] Furthermore, when two or more monomers are used as constituent monomers, the SP value of the constituent units derived from each monomer is calculated using the method described above, and the weighted average value based on the weight fraction of each monomer is used as the SP value of the segment.

[0041] Copolymer (W) can be obtained by polymerizing a vinyl monomer that will form segment (B) in the presence of a polyolefin that will form segment (A). Copolymer (W) can be obtained, for example, by dissolving a polyolefin in toluene or xylene heated to 100°C to 200°C, simultaneously or separately adding the constituent monomers of segment (B) and a radical polymerization initiator dropwise, polymerizing, and then distilling off the solvent. The polymerization temperature is preferably 60 to 230°C, more preferably 110 to 200°C. The polymerization time is preferably 1 to 30 hours, more preferably 2 to 10 hours. The copolymer (W) obtained by the above polymerization method is obtained because the monomer composition containing vinyl monomers polymerizes starting from radicals generated in the polyolefin, resulting in a copolymer (W) having segments (A) derived from the polyolefin and segments (B) derived from the vinyl monomer.

[0042] Examples of radical polymerization initiators include azo polymerization initiators (e.g., azobisisobutyronitrile, azobisvaleronitrile, and azobiscyanovaleric acid) and organic peroxide polymerization initiators (e.g., benzoyl peroxide, di-t-butyl peroxide, 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 di-t-butyl peroxide, 1,1-di-(t-butylperoxy)cyclohexane, di-t-butyl peroxyhexahydrophthalate, 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, based on 100 parts by weight of the total amount of monomer.

[0043] When copolymerizing copolymer (W) in solution, 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, preferred are aromatic solvents having 6 to 12 carbon atoms, and more preferably toluene, xylene, and ethylbenzene.

[0044] Furthermore, when polymerizing the copolymer (W) using suspension polymerization, polymerization can be carried out in water using inorganic acid dispersants (such as calcium carbonate and calcium phosphate) and organic dispersants (such as polyvinyl alcohol and methylcellulose).

[0045] The sublimation transfer toner of the present invention preferably contains a binder (toner binder). Examples of the binder include vinyl resin (C) and / or polyester resin (D). The vinyl resin (C) is distinguished from copolymer (W) in that it is not a copolymer with segment (A).

[0046] Vinyl resin (C) is a vinyl resin containing styrene monomer as a constituent monomer. The crystalline nature of vinyl resin (C) is not particularly limited, but it is preferably an amorphous vinyl resin. In addition to styrene monomer, (meth)acrylic acid ester monomer, carboxyl group-containing vinyl monomer, sulfonic acid group-containing vinyl monomer, nitrile monomer, and vinyl ester monomer can also be used as constituent monomers. Of the above constituent monomers, it is preferable to include (meth)acrylic acid ester monomer and / or carboxyl group-containing vinyl monomer as constituent monomers. Using (meth)acrylic acid ester monomer and / or carboxyl group-containing vinyl monomer in combination is preferable because it makes it easier to control the glass transition temperature of vinyl resin (C).

[0047] The styrene monomer used in the vinyl resin (C) can be the same as that used in the segment (B), and either one type may be used or two or more types may be used in combination. From a cost standpoint, styrene is preferred.

[0048] As the (meth)acrylic acid ester monomer used in the vinyl resin (C), the same (meth)acrylic acid ester monomer as in segment (B) can be used. The preferred (meth)acrylic acid ester monomer used in the vinyl resin (C) is the same as that for segment (B), but n-butyl acrylate is particularly preferred.

[0049] As the carboxyl group-containing vinyl monomer used in the vinyl resin (C), the same carboxyl group-containing vinyl monomer as in segment (B) can be used. Among these carboxyl group-containing vinyl monomers, monocarboxylic acids are preferred from the viewpoint of electrostatic stability, and (meth)acrylic acid is more preferred.

[0050] Examples of sulfonic acid group-containing vinyl monomers used in vinyl resin (C) 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.

[0051] For the vinyl resin (C), the same nitrile monomer as that used in segment (B) can be used.

[0052] For vinyl resin (C), the same vinyl ester monomer as that used for segment (B) can be used.

[0053] The vinyl resin (C) has a weight percentage of styrene monomer in its constituent monomers that is preferably 50 to 95% by weight, more preferably 60 to 90% by weight, and even more preferably 65 to 85% by weight, based on the total weight of the monomers constituting the vinyl resin (C). If the weight percentage is 95% by weight or less, the low-temperature fixability is good, and if it is 50% by weight or more, the heat-resistant storage is good.

[0054] The flow softening point of the vinyl resin (C), as measured by a flow tester, is preferably 90°C to 170°C, and more preferably 100°C to 160°C, from the viewpoint of heat-resistant storage. The following describes the method for measuring the flow softening point [T1 / 2] of vinyl resin (C) and polyester resin (D) described below. 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].

[0055] The flow softening point of vinyl resin (C) can be adjusted by controlling its weight-average molecular weight. Increasing the weight-average molecular weight of vinyl resin (C) raises its flow softening point, while decreasing it lowers it.

[0056] The vinyl resin (C) can be obtained by known polymerization methods such as solution polymerization, bulk polymerization, suspension polymerization, and emulsion polymerization using the styrene monomer and optionally (meth)acrylic acid ester monomer, carboxyl group-containing vinyl monomer, sulfonic acid group-containing vinyl monomer, nitrile monomer, and vinyl ester monomer and 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.

[0057] For the polymerization of vinyl resin (C), the same radical polymerization initiator used for the polymerization of copolymer (W) can be used. The amount of radical polymerization initiator used in the polymerization of vinyl resin (C) can be the same as the amount of radical polymerization initiator used in the polymerization of copolymer (W).

[0058] When obtaining vinyl resin (C) by solution polymerization, the same solvent as when obtaining copolymer (W) by solution polymerization can be used. The preferred solvent for obtaining vinyl resin (C) by solution polymerization is the same as that for obtaining copolymer (W) by solution polymerization.

[0059] Furthermore, when vinyl resin (C) is obtained by 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.

[0060] The vinyl resin (C) 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.

[0061] The acid value of vinyl resin (C) is preferably 0.0 to 30.0 mg KOH / g, and more preferably 1.0 to 20.0 mg KOH / g, from the viewpoint of heat resistance and storage properties.

[0062] The acid value and hydroxyl value can be measured by the method specified in JIS K0070.

[0063] The glass transition temperature of vinyl resin (C) is preferably 50°C to 70°C, more preferably 55°C to 65°C, from the viewpoint of heat resistance and low-temperature fixation.

[0064] The glass transition temperature (Tg) of vinyl resin (C) and polyester resin (D) 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.

[0065] The number-average molecular weight (Mn) of the vinyl resin (C) is preferably 2,000 to 60,000, more preferably 3,000 to 55,000, and even more preferably 4,000 to 50,000.

[0066] The weight-average molecular weight (Mw) of the vinyl resin (C) is preferably 5,000 to 900,000, more preferably 10,000 to 800,000, and even more preferably 50,000 to 700,000.

[0067] The peak-top molecular weight (Mp) of the vinyl resin (C) is preferably 3,000 to 900,000 from the viewpoint of resistance to hot offset.

[0068] Polyester resin (D) is a polyester resin obtained by polycondensation of a component containing an alcohol component (x) and a carboxylic acid component (y). The presence or absence of crystalline properties of polyester resin (D) is not particularly limited, but amorphous polyester resin is preferred.

[0069] 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 properties. These may be a single type or a combination of two or more types.

[0070] 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, 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.

[0071] 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, 2-30 carbon-12 AO adducts of bisphenols (such as bisphenol A, bisphenol F, and bisphenol S) are preferred, and more preferably 2-30 carbon-12 AO adducts of bisphenol A are preferred.

[0072] Examples of polyols with a valency of 3 or higher (x3) include polyhydric aliphatic alcohols with 3 to 36 carbon atoms (alkane polyols and their intramolecular or intermolecular dehydrated products [e.g., glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol, sorbitan, and polyglycerin]), alkylene oxide (AO) adducts of polyhydric aliphatic alcohols (1 to 30 moles added), AO adducts of trisphenols (trisphenol PA, etc.) (2 to 30 moles added), and AO adducts of novolac resins (including phenol novolac and cresol novolac, with an average degree of polymerization preferably 3 to 60) (2 to 30 moles added). Examples of AOs include those with 2 to 4 carbon atoms, such as ethylene oxide (EO), propylene oxide (PO), and butylene oxide. Among these trivalent or higher polyols (x3), from the viewpoint of heat resistance and friction fastness, the preferred choice is an AO adduct (number of added moles 2 to 30) of a novolac resin (which includes phenol novolac and cresol novolac, and whose average degree of polymerization is preferably 3 to 60) having 2 to 4 carbon atoms.

[0073] The content of diols (x2) and trivalent or higher polyols (x3) among the alcohol component (x) is preferably 40 to 100 mol%, more preferably 60 to 100 mol%, and even more preferably 70 to 100 mol%, based on the total number of moles of alcohol component (x) which is a component of the polyester resin (D), from the viewpoint of heat resistance and storage properties.

[0074] The content of AO adducts of bisphenol A with 2 to 4 carbon atoms (2 to 30 moles added) among the diols (x2) is preferably 80 mol% or more, and more preferably 90 mol% or more, based on the total number of moles of diols (x2) used, from the viewpoint of heat-resistant storage.

[0075] Examples of monocarboxylic acids (y1) include unsaturated monocarboxylic acids (e.g., (meth)acrylic acid, crotonic acid, isocrotonic acid, and cinnamic acid) and saturated monocarboxylic acids (e.g., behenic acid, stearic acid, and benzoic acid). Of these monocarboxylic acids, saturated monocarboxylic acids are preferred from the viewpoint of heat resistance and storage, and behenic acid and stearic acid are preferred.

[0076] Among polycarboxylic acids (y2), the following are examples of dicarboxylic acids: Examples include alkane dicarboxylic acids with 2 to 34 carbon atoms (including the carbon atoms of the carbonyl group) {linear alkane dicarboxylic acids (succinic acid, adipic acid, sebacic acid, azelaic acid, dodecanediic acid, 1,18-octadecanedicarboxylic acid, etc.) and branched alkane dicarboxylic acids (decyl succinic acid, etc.)}, alkene dicarboxylic acids with 4 to 34 carbon atoms (including the carbon atoms of the carbonyl group) (alkenyl succinic acids such as dodecenyl succinic acid, pentadecenyl succinic acid, octadecenyl succinic acid, maleic acid, fumaric acid, and citraconic acid, etc.), alicyclic dicarboxylic acids with 6 to 34 carbon atoms (including the carbon atoms of the carbonyl group), and aromatic dicarboxylic acids with 8 to 36 carbon atoms (phthalic acid, isophthalic acid, terephthalic acid, t-butylisophthalic acid, 2,6-naphthalenedicarboxylic acid, and 4,4'-biphenyldicarboxylic acid, etc.). Of these dicarboxylic acids, aromatic dicarboxylic acids having 8 to 36 carbon atoms (such as phthalic acid, isophthalic acid, terephthalic acid, t-butylisophthalic acid, 2,6-naphthalenedicarboxylic acid, and 4,4'-biphenyldicarboxylic acid) are preferred from the viewpoint of heat resistance and storage properties, more preferably phthalic acid, isophthalic acid, and terephthalic acid, and even more preferably isophthalic acid and terephthalic acid.

[0077] Among polycarboxylic acids (y2), examples of carboxylic acids with three or more valencies include aromatic polycarboxylic acids with 9 to 20 carbon atoms (such as trimellitic acid and pyromellitic acid) and aliphatic tricarboxylic acids with 6 to 33 carbon atoms (such as hexanetricarboxylic acid). Of these trivalent or greater carboxylic acids, trimellitic acid is preferred from the viewpoint of heat resistance and storage properties.

[0078] As the carboxylic acid component (y), anhydrides of these carboxylic acids, lower alkyl (1-4 carbon atoms) esters (methyl esters, ethyl esters, isopropyl esters, etc.) may be used, or the anhydride or lower alkyl ester may be used in combination with the above carboxylic acids.

[0079] The flow softening point of the polyester resin (D), as measured by a flow tester, is preferably 80°C to 160°C, and more preferably 90°C to 150°C, from the viewpoint of low-temperature fixability and heat-resistant storage.

[0080] The flow softening point of polyester resin (D) can be adjusted by controlling the peak top molecular weight of polyester resin (D). Increasing the peak top molecular weight of polyester resin (D) raises the softening point of polyester resin (D), while decreasing it lowers the softening point of polyester resin (D).

[0081] Polyester resin (D) 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 atmosphere (such as nitrogen gas) 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 at the end of the reaction is also effective in improving the reaction rate.

[0082] 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.

[0083] 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).

[0084] The hydroxyl value of the polyester resin (D) 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-resistant storage. A value of 10.0 mgKOH / g or higher results in good low-temperature fixation, while a value of 70.0 mgKOH / g or lower results in good heat-resistant storage.

[0085] From the viewpoint of heat-resistant storage, the acid value of the polyester resin (D) is preferably 0 to 30 mg KOH / g, more preferably 0 to 25 mg KOH / g, and even more preferably 0 to 22 mg KOH / g.

[0086] The glass transition temperature of the polyester resin (D) is preferably 50°C to 70°C, more preferably 55°C to 65°C, from the viewpoint of heat-resistant storage.

[0087] The number-average molecular weight (Mn) of the polyester resin (D) is preferably 1,900 to 9,000, more preferably 2,200 to 8,000, and even more preferably 2,500 to 7,000.

[0088] The peak top molecular weight of the polyester resin (D) is preferably 1,900 to 70,000, more preferably 2,500 to 70,000, and even more preferably 3,000 to 65,000.

[0089] The binder in the present invention may contain known toner binders other than vinyl resin (C) and polyester resin (D), to the extent that the effects of the present invention are not impaired. That is, the binder in the present invention may contain, for example, resins other than vinyl resin (C), such as crystalline vinyl resin, epoxy resin, polycarbonate resin, and polyurethane resin, as binders. If the above resins are included, the weight percentage of the above resins in the binder is preferably 50% by weight or less, more preferably 30% by weight or less, even more preferably 20% by weight or less, and particularly preferably 10% by weight or less, based on the weight of the binder.

[0090] There are no particular limitations on the method for producing the binder in the present invention, and vinyl resin (C) and / or polyester resin (D) can be produced by known kneading and grinding methods or powder mixing methods.

[0091] The sublimation transfer toner of the present invention preferably contains a release agent as a release agent for the fixing portion in order to obtain a good fixed image in the electrophotographic process.

[0092] 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).

[0093] The release agents usable in the sublimation transfer toner of the present invention include all known release agents for toners, and are not particularly limited. Examples include natural waxes such as carnauba wax, rice wax, and candelilla wax; hydrocarbon waxes such as paraffin wax, polyolefin wax, microcrystalline wax, Fischer-Tropsch wax, polyethylene wax, polypropylene wax, and ethylene-propylene copolymer; aliphatic polyesters; synthetic ester waxes synthesized from long-chain fatty acids and long-chain alcohols; amide waxes; higher fatty acids; long-chain alcohols; ketones; ethers; and derivatives such as graft compounds and block compounds thereof. These release agents may be used individually or in combination of two or more types.

[0094] The melting point of the release agent is preferably 60°C to 150°C, more preferably 60°C to 145°C, and even more preferably 65°C to 140°C. If the melting point of the release agent is 60°C or higher, the toner has good heat resistance for storage, 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.

[0095] The release agent content in the toner is preferably 0.5 to 10.0% by weight. More preferably 1.0 to 9.0% by weight. When the release agent content is within the above range, the release agent dispersibility can be improved, and good adhesion and offset performance can be achieved when printing on a copier or printer.

[0096] From the viewpoint of preventing contamination of the photoreceptor, the particle size of the release agent in the toner is preferably 30 to 300 nm, and more preferably 50 to 200 nm. The particle size of the release agent in the toner can be measured by the method described in the following examples.

[0097] The sublimation transfer toner of the present invention contains a sublimable dye.

[0098] Sublimation dyes are not particularly limited as long as they are disperse dyes with 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 yellow toner, magenta toner, and cyan toner, the color tone can be adjusted by combining two or more dyes, and dyes such as blue, yellow, orange, red, and violet can be added to the primary color toner as appropriate. In the case of black toner, a black dye formulated by mixing yellow, magenta, and cyan dyes can be used. Other dyes such as blue, orange, red, and violet can also be added to the black dye in combination. The sublimable dye content is preferably 1 to 40 parts by weight, more preferably 2 to 15 parts by weight, based on 100 parts by weight of the total amount of copolymer (W) and binder.

[0099] The sublimation transfer toner of the present invention is used as a toner by mixing it with various additives such as charge control agents and fluidizers as needed. The total content of copolymer (W) and binder is preferably 60 to 98% by weight, based on the weight of the sublimation transfer toner of the present invention.

[0100] 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 total weight of the copolymer (W) and the binder.

[0101] 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.

[0102] Furthermore, the total weight of the additives may be 0.5 to 10% by weight, preferably 1.0 to 5.0% by weight, and more preferably 1.5 to 3.5% by weight, based on the weight of the sublimation transfer toner of the present invention. By having the toner composition ratio within the above range, a toner with good electrostatic properties can be easily obtained.

[0103] The sublimation transfer toner of the present invention preferably has no sublimation dye exposed on its surface, that is, it contains the sublimation 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.)].

[0104] 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.

[0105] In the sublimation transfer toner of the present invention, the addition of a photocuring agent is unnecessary.

[0106] 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.

[0107] 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.

[0108] For example, when obtaining toner by an association polymerization method in which at least one type of fine particles are aggregated 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 dispersions (resin particulate dispersion of copolymer (W) (W0), resin particulate dispersion of vinyl resin (C) (C0), and / or resin particulate dispersion of polyester resin (D) (D0)) and additive dispersions (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.

[0109] 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.

[0110] 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.

[0111] To improve the dispersibility of the resin in an aqueous solvent, a neutralizing agent may be used to neutralize the copolymer (W) and the carboxyl groups of the vinyl resin (C) and / or polyester resin (D). Examples of neutralizing agents include organic compounds such as ammonia and triethylamine, and inorganic compounds such as sodium hydroxide.

[0112] 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 the copolymer (W) and the vinyl resin (C) and / or polyester resin (D), from the viewpoint of dispersibility.

[0113] When dispersing the copolymer (W) and the vinyl resin (C) and / or polyester resin (D) 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.

[0114] 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.

[0115] 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.

[0116] 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.

[0117] 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.).

[0118] 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.

[0119] The following describes step (1). For example, an organic solvent solution containing a copolymer (W) 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. To make the particle size of the fine particles in the dispersion 0.05 to 1 μm, it is preferable to use a high-speed shear disperser. 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).

[0120] 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).

[0121] 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.

[0122] 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.

[0123] 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.

[0124] 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.

[0125] This specification discloses the following:

[0126] (1) This disclosure relates to a sublimation transfer toner containing a copolymer (W) having a segment (A) derived from a polyolefin and a segment (B) derived from a vinyl monomer, and a sublimable dye, wherein the SP value difference (SP(B)-SP(A)) between the segment (A) derived from the polyolefin and the segment (B) derived from the vinyl monomer is 1.5 to 5.0.

[0127] Disclosure (2) is a sublimation transfer toner according to Disclosure (1), wherein in the segment (A) derived from the polyolefin, the polyolefin is polyethylene and / or polypropylene.

[0128] Disclosure (3) is a sublimation transfer toner according to Disclosure (1) or (2), wherein the vinyl monomer comprises a styrene monomer as an essential constituent monomer.

[0129] Disclosure (4) is a sublimation transfer toner according to any one of Disclosures (1) to (3), wherein the weight percentage of the segment (A) derived from the polyolefin in the copolymer (W) is 5 to 30% by weight based on the weight of the copolymer (W). [Examples]

[0130] The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples.

[0131] <Manufacturing Example 1> [Manufacturing of copolymer (W-1)] 272 parts by weight of xylene, 120 parts by weight of polyethylene [LicowaxPE130, manufactured by Clariant Co., Ltd.], and 80 parts by weight of modified polypropylene with terminal double bonds [Viscol 550-P, manufactured by Sanyo Chemical Industries, Ltd.] were charged into an autoclave. After purging with nitrogen, the temperature was raised to 175°C under stirring and in a sealed state. A mixed solution of 658 parts by weight of styrene, 64 parts by weight of butyl acrylate, 6 parts by weight of acrylic acid, 73 parts by weight of acrylonitrile, 26 parts by weight of di-t-butyl peroxide, and 118 parts by weight of xylene was added dropwise over 3 hours while controlling the autoclave temperature to 175°C to allow polymerization. After polymerization, the dropping line was washed with 50 parts by weight of xylene, and the polymerization was completed by maintaining the temperature at 175°C for another 30 minutes. Copolymer (W-1) was obtained by desolvation under reduced pressure at the same temperature and a pressure of 4 kPa or less for 3 hours.

[0132] <Manufacturing Example 2> [Manufacturing of Copolymer (W-2)] 294 parts by weight of xylene and 61 parts by weight of modified polyethylene with terminal double bonds [Sanwax 151-P, manufactured by Sanyo Chemical Industries, Ltd.] were charged into an autoclave. After purging with nitrogen, the temperature was raised to 172°C under stirring and in a sealed state. A mixed solution of 467 parts by weight of styrene, 28 parts by weight of butyl acrylate, 55 parts by weight of acrylonitrile, 22 parts by weight of di-t-butyl peroxide, and 65 parts by weight of xylene was added dropwise over 160 minutes while controlling the autoclave temperature to 172°C to allow polymerization. After polymerization, the dropping line was washed with 9 parts by weight of xylene, and the polymerization was completed by maintaining the temperature at 172°C for another 30 minutes. Copolymer (W-2) was obtained by desolvation under reduced pressure at the same temperature and a pressure of 4 kPa or less for 3 hours.

[0133] <Manufacturing Example 3> [Manufacturing of Copolymer (W-3)] 481 parts by weight of xylene and 100 parts by weight of modified polyethylene with terminal double bonds [Sanwax 151-P, manufactured by Sanyo Chemical Industries, Ltd.] were charged into an autoclave. After purging with nitrogen, the temperature was raised to 172°C under stirring and in a sealed state. A mixed solution of 534 parts by weight of styrene, 58 parts by weight of butyl acrylate, 308 parts by weight of acrylonitrile, 30 parts by weight of di-t-butyl peroxide, and 106 parts by weight of xylene was added dropwise over 160 minutes while controlling the autoclave temperature to 172°C to allow polymerization. After polymerization, the dropping line was washed with 10 parts by weight of xylene, and the polymerization was completed by maintaining the temperature at 172°C for another 30 minutes. Copolymer (W-3) was obtained by desolvation under reduced pressure at the same temperature and a pressure of 4 kPa or less for 3 hours.

[0134] <Manufacturing Example 4> [Manufacturing of copolymer (W-4)] 272 parts by weight of xylene, 40 parts by weight of modified polyethylene with terminal double bonds [Sanyo Chemical Industries, Ltd., Sanwax 171-P], and 160 parts by weight of modified polypropylene with terminal double bonds [Sanyo Chemical Industries, Ltd., Viscol 440-P] were charged into an autoclave. After purging with nitrogen, the autoclave was heated to 176°C under stirring and in a sealed state. A mixed solution of 636 parts by weight of styrene, 88 parts by weight of butyl acrylate, 70 parts by weight of acrylonitrile, 6 parts by weight of acrylic acid, 25 parts by weight of di-t-butyl peroxide, and 134 parts by weight of xylene was added dropwise over 160 minutes while controlling the autoclave temperature to 172°C to allow polymerization. After polymerization, the dropping line was washed with 34 parts by weight of xylene, and the polymerization was completed by maintaining the temperature at 176°C for another 30 minutes. Copolymer (W-4) was obtained by desolvent removal under reduced pressure at the same temperature and a pressure of 4 kPa or less for 3 hours.

[0135] <Manufacturing Example 5> [Manufacturing of Copolymer (W-5)] Copolymer (W-5) was obtained by manufacturing in the same manner as in Manufacturing Example 2, except that the parts by weight were as shown in Table 2.

[0136] <Manufacturing Example 6> [Manufacturing of Copolymer (W-6)] Copolymer (W-6) was obtained by manufacturing in the same manner as in Manufacturing Example 3, except that the parts by weight were as shown in Table 2.

[0137] <Comparative Manufacturing Example 1> [Manufacturing of Copolymer (W'-1)] 272 parts by weight of xylene was placed in an autoclave, purged with nitrogen, and then heated to 175°C under stirring and in a sealed state. A mixed solution of 658 parts by weight of styrene, 64 parts by weight of butyl acrylate, 6 parts by weight of acrylic acid, 73 parts by weight of acrylonitrile, 26 parts by weight of di-t-butyl peroxide, and 118 parts by weight of xylene was added dropwise over 3 hours while controlling the autoclave temperature to 175°C, and polymerization was carried out. After polymerization, the dropping line was washed with 50 parts by weight of xylene, and the polymerization was completed by maintaining the temperature at 175°C for another 30 minutes. Copolymer (W'-1) was obtained by desolvation under reduced pressure at the same temperature and a pressure of 4 kPa or less for 3 hours.

[0138] The physical properties of the obtained copolymers (W-1) to (W-6) and (W'-1) are shown in Table 2.

[0139] [Table 2]

[0140] <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.

[0141] <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.

[0142] <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 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 a post-treatment, the product was filtered, washed with water, and dried to obtain polymer-3.

[0143] <Manufacturing Example 10> [Manufacturing of Vinyl Resin (C-1)] 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 0.375 parts by weight of 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, and 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 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 polymers 1, 2, and 3 were added according to the mixing ratios listed in Table 3. 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 (C-1), which is an amorphous vinyl resin. The physical properties of vinyl resin (C-1) are shown in Table 3.

[0144] [Table 3]

[0145] <Manufacturing Example 11> [Manufacturing of Polyester Resin (D-1)] In a reaction vessel equipped with a condenser, thermometer, stirrer, and nitrogen inlet, 169.7 parts by weight of 2 molar EO adduct of bisphenol A, 122.5 parts by weight of 2 molar PO adduct of bisphenol A, 459.9 parts by weight of 3 molar PO adduct of bisphenol A, 4.7 parts by weight of 5.5 molar EO adduct of phenol novolac, 187.5 parts by weight of terephthalic acid, and 2.5 parts by weight of titanium diisopropoxybis(triethanolamine) as a condensation catalyst were added. At 230°C, a vacuum esterification reaction was carried out under reduced pressure of 0.5 to 2.5 kPa while removing the generated water, and an acid value of less than 2 was confirmed. Next, 53.8 parts by weight of trimellitic anhydride was added at 220°C, and atmospheric pressure esterification was carried out at 220°C for 1 hour, followed by vacuum esterification at the same temperature, and an acid value of less than 3 was confirmed. Furthermore, 53.2 parts by weight of trimellitic anhydride were added at 220°C, and a reduced-pressure esterification reaction was carried out for 2 hours under a reduced pressure of 75 kPa. After that, the esterification reaction was carried out again at atmospheric pressure, and after confirming the flow softening point of 130°C, the material was removed into a filled container and the removed material was gradually cooled to obtain polyester resin (D-1). The physical properties of polyester resin (D-1) are shown in Table 4.

[0146] [Table 4]

[0147] <Example 1> [Manufacturing of Toner (T1)] Using a Henschel mixer [FM10B, manufactured by Mitsui Miike Chemical Machinery Co., Ltd.], the binder, dye [CI Disperse Blue 56, manufactured by Huntsman Japan Co., Ltd.], polymer, release agent, and charge control agent [TN-105, manufactured by Hodogaya Chemical Co., Ltd.] were pre-mixed according to the mixing ratio (parts by weight) in Table 5, 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. Then, 1.5 parts by weight of colloidal silica [Aerosil R972, manufactured by Nippon Aerosil Co., Ltd.] was mixed with 100 parts by weight of the toner particles in a sample mill to obtain sublimation transfer toner (T1).

[0148] <Examples 2-8> [Manufacturing of toner (T2)-(T8)] Sublimation transfer toners (T2) to (T8) were obtained in the same manner as in Example 1, except that the mixing ratio (parts by weight) was followed in Table 5.

[0149] <Comparative Example 1-2> [Manufacturing of Toner (T'1)-(T'2)] Sublimation transfer toners (T'1) to (T'2) were obtained in the same manner as in Example 1, except that the mixing ratio (parts by weight) was followed in Table 5.

[0150] <Particle size of release agent in toner> The toners obtained in the examples and comparative examples were ultrathinly sectioned to approximately 100 μm. Each component dispersed in the toner, except for the release agent, was stained with ruthenium tetroxide at a concentration of 1 for 3 minutes using a vacuum electron staining device (VSC1R1H, manufactured by Philgen Co., Ltd.). The dispersion state of the release agent, which appeared white or gray due to the ruthenium tetroxide staining, was then observed in the cross-section of the toner using a transmission electron microscope (TEM) at a magnification of 10,000x. The particle size of the release agent in the toner was calculated by image analysis using an image processing device (digital microscope VHX-700F, manufactured by Keyence Corporation). Measurements were taken at the distance between two points. If the release agent was perfectly circular, the diameter was measured; if it was elliptical, the major axis was measured. The particle size of the release agent in the toner was calculated by averaging the results of 30 randomly measured points.

[0151] <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)

[0152] <Photoreceptor contamination> Sublimation transfer toner was used as a two-component developer, and continuous printing was performed using a commercially available monochrome copier. The condition of the photoreceptor was checked, and the photoreceptor contamination was evaluated according to the following criteria. Under these evaluation conditions, it is preferable that the evaluation criterion is 0 or higher. (Evaluation Criteria) ◎(Excellent): No deposits were observed on the photoreceptor surface after printing 8,000 copies. ○ (Good): After printing 8,000 sheets, some residue was observed on the surface of the photoreceptor. △ (Acceptable): After printing 4,000 copies, some residue was observed on the surface of the photoreceptor. × (Defective): After printing 2,000 copies, residue was observed on the surface of the photoreceptor.

[0153] (Printing onto transfer paper using toner) Toner is applied to the surface of plain paper at a rate of 5.0 g / m². 2 The powder was spread evenly to achieve this. The method used to apply the powder to the paper involved using a printer with the heat fuser removed. By passing this paper through a soft roller at a fixing speed (heating roller peripheral speed) of 213 mm / second and a heating roller temperature of 150°C, transfer paper with toner fixed to it was obtained. The standard paper used for sublimation transfer had a basis weight of 84 g / m². 2 I used commercially available plain paper.

[0154] (Sublimation transfer onto polyester fabric) Jersey fabric and tropical fabric were used as polyester fabrics 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 a time of 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.

[0155] <Friction fastness test> The abrasion fastness (dry friction) and (wet friction) of dyed polyester fabrics were tested and determined according to the Type II test method of JIS L 0849. The abrasion tester had a table, and the fabric to be tested was attached to this table. A cotton cloth was 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 cotton cloth was made approximately 100% wet according to JIS standards. In the wet test, after friction was completed, the cotton cloth was removed from the arm and dried. Once dry, "staining" was determined using a grayscale for staining. Under these evaluation conditions, a rating of 4 or higher is preferable.

[0156] Table 5 shows the evaluation results of the toners used in the examples and comparative examples.

[0157] [Table 5]

[0158] The toners in the examples all exhibited excellent heat resistance and storage properties, prevented photoreceptor contamination, and showed high friction fastness on the sublimation-transferred fabric. On the other hand, the toners in the comparative examples performed worse than the toners in the examples in terms of heat resistance, photoreceptor contamination, and friction fastness. [Industrial applicability]

[0159] The sublimation transfer toner of the present invention has excellent heat resistance and friction fastness, can prevent contamination of the photoreceptor, and can be suitably used for sublimation transfer applications.

Claims

1. A sublimation transfer toner comprising a copolymer (W) having a segment (A) derived from a polyolefin and a segment (B) derived from a vinyl monomer, and a sublimable dye, wherein the SP value difference (SP(B) - SP(A)) between the segment (A) derived from the polyolefin and the segment (B) derived from the vinyl monomer is 1.5 to 5.

0.

2. The sublimation transfer toner according to claim 1, wherein in the segment (A) derived from the polyolefin, the polyolefin is polyethylene and / or polypropylene.

3. The vinyl monomer comprises styrene monomer as an essential constituent monomer, as described in claim 1 or 2, for sublimation transfer toner.

4. The sublimation transfer toner according to claim 1 or 2, wherein the weight percentage of the segment (A) derived from the polyolefin in the copolymer (W) is 5 to 30% by weight based on the weight of the copolymer (W).

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