JP6758917B2 - toner - Google Patents

Description

The present invention relates to toners used in image forming methods such as electrophotographic, electrostatic recording and toner jet methods.

In recent years, while there is a demand for a means for outputting a higher-definition full-color image, there is an increasing demand for energy saving, and energy saving is also required for toner. As one means for achieving energy saving of toner, there is a means for containing a crystalline resin in the toner. As a result, it is possible to set the softening temperature of the toner lower by utilizing the sharp melt property of the crystalline resin, and it is possible to improve the low temperature fixability.
However, in the toner containing a crystalline resin, an offset phenomenon occurs in which the crystalline resin in the toner adheres to the surface of the fixing member and the toner attached to the fixing member is retransferred to the next transfer material. was there. Therefore, Patent Document 1 discloses that a toner containing a block resin of a crystalline polyester and a styrene polymer as a binder resin reduces the offset to the fixing member.

Japanese Unexamined Patent Publication No. 4-250462

However, when a toner in which a block resin of styrene-modified polyester was added to a binder resin made of styrene acrylic resin or polyester resin was examined, the charge stability of the toner whose durability was deteriorated in a high temperature and high humidity environment was lowered, and fog was formed. Was found to occur.
An object of the present invention is to provide a toner having excellent heat resistance, low temperature fixability and charge stability.

The present invention is a toner having toner particles containing a binder resin, a colorant, a styrene-modified polyester and a diester compound.
The melting point (Tm) of the styrene-modified polyester is 55 ° C. or higher and 90 ° C. or lower.
The content of the styrene-modified polyester is 1.0 part by mass or more and 30.0 parts by mass or less with respect to 100.0 parts by mass of the binder resin.
The styrene-modified polyester is a block polymer and
The diester compound has a structure represented by the following formula (1) and has a structure represented by the following formula (1).
The content of the toner of the diester compound, a toner, characterized in that at 0.1ppm least 10.0ppm less.

（式（１）中、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴は、それぞれ独立して、ＨまたはＣＨ₃を示す。）

(In equation (1), R ¹ , R ² , R ³ , and R ⁴ independently represent H or CH _3. )

According to the present invention, it is possible to provide a toner having excellent heat resistance, low temperature fixability and charge stability.

Hereinafter, the present invention will be described in detail.

The toner of the present invention has toner particles containing a binder resin, a colorant, a styrene-modified polyester and a diester compound. Each material in the toner particles has the following characteristics. The melting point (Tm) of the styrene-modified polyester is 55 ° C. or higher and 90 ° C. or lower. The diester compound has a structure represented by the following formula (1), and the content in the toner is 0.1 ppm or more and 10.0 ppm or less.

（式（１）中、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴は、それぞれ独立して、ＨまたはＣＨ₃を示す。）

(In equation (1), R ¹ , R ² , R ³ , and R ⁴ independently represent H or CH _3. )

The present inventors have obtained a toner having excellent low-temperature fixability and charge stability by further using a specific styrene-modified polyester and a specific diester compound for the toner particles having a binder resin and a colorant. I found that it was possible.

Since the styrene-modified polyester of the present invention is a crystalline resin, it is sharp melt and has excellent low-temperature fixability, but has low elasticity and inferior mechanical strength. Therefore, when this styrene-modified polyester is used alone as the binder resin, it is difficult to obtain sufficient durability, and image harmful effects such as development streaks are likely to occur. Therefore, when the styrene-modified polyester and other binder resin are used in combination, the polyester moiety (also referred to as the crystalline polyester moiety) of the styrene-modified polyester tends to act as a leak site for charging. Therefore, if the dispersed state of the polyester portion is biased, the charge stability is significantly lowered. In particular, in toner whose durability has deteriorated, when the exposure of toner particles increases due to the burial of an external additive or the like, image harmful effects such as fog are likely to occur. In the present invention, by adding a diester compound having a high affinity with the polyester moiety of the styrene-modified polyester, the polyester moiety that can be a leak site of charging can be uniformly dispersed in the toner, and the charging stability is improved. To do.

In the present invention, the diester compound has a structure represented by the above formula (1). Since the diester compound having the above structure has a high affinity with the polyester moiety of the styrene-modified polyester of the present invention, it is effective in uniformly dispersing the polyester moiety. Specific examples of the diester compound include dimethyl succinate and dimethyl tetramethylsuccinate.

Further, in the present invention, the content of the diester compound in the toner is 0.1 ppm or more and 10.0 ppm or less. If it is less than 0.1 ppm, the effect of dispersing the polyester portion of the styrene-modified polyester cannot be obtained, so that fog occurs. On the other hand, if it exceeds 10.0 ppm, the amount of the diester compound is too large, and the heat resistance of the toner is lowered. More preferably, it is 0.2 ppm or more and 8.0 ppm or less.

The melting point (Tm) of the styrene-modified polyester is 55 ° C. or higher and 90 ° C. or lower. When the melting point (Tm) is lower than 55 ° C., blocking is likely to occur and it is difficult to use from the viewpoint of heat resistance. When the melting point (Tm) is higher than 90 ° C., the temperature required for melting the styrene-modified polyester becomes high, so that it is difficult to use from the viewpoint of low-temperature fixability. More preferably, it is 60 ° C. or higher and 85 ° C. or lower. The melting point of the styrene-modified polyester can be controlled by the monomer that produces the polyester moiety and the ratio of the polyester moiety to the styrene-modified moiety (vinyl polymer moiety).

The styrene-modified polyester preferably has a vinyl polymer moiety and a polyester moiety having a structural unit represented by the following formula (2). By having the structural unit represented by the following formula (2), the affinity between the polyester moiety and the diester compound becomes good.

（式（２）中、ｍは６以上１４以下の整数、ｎは６以上１６以下の整数を示す。）

(In equation (2), m is an integer of 6 or more and 14 or less, and n is an integer of 6 or more and 16 or less.)

The polyester moiety of the styrene-modified polyester can be obtained, for example, by condensation polymerization of the dicarboxylic acid represented by the following formula (A) and the diol represented by the following formula (B).
HOOC- (CH ₂ ) _m- COOH formula (A)
(In formula (A), m represents an integer of 6 or more and 14 or less.)
HO- (CH ₂ ) _n- OH formula (B)
(In equation (B), n represents an integer of 6 or more and 16 or less.)

As the dicarboxylic acid, a compound having an alkyl esterified carboxy group, a compound having an acid anhydride, or the like may be used as long as it produces the same partial skeleton at the polyester moiety. As the dicarboxylic acid represented by the formula (A), suberic acid, sebacic acid, dodecanedioic acid, tetradecanedioic acid and the like are preferable.

Examples of the diol represented by the formula (B) include 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, and 1,12-. Dodecanediol, 1,14-tetradecanediol and the like are preferable.

For the composition of the vinyl polymer moiety of the styrene-modified polyester, a known vinyl monomer such as methyl methacrylate or n-butyl acrylate can be used in addition to styrene.

In the present invention, the styrene-modified polyester is preferably a block polymer. When a block polymer is used, the binder resin and the block polymer have a phase-separated structure in the toner. As a result, the toughness of the binder resin is maintained, the durability is improved, and image harmful effects such as development streaks are less likely to occur. In addition, heat resistance is also improved.

The definition of block polymer is a polymer composed of multiple blocks connected in a linear shape (a glossary of basic terminology of polymer science by the International Union of Pure and Applied Chemistry Polymer Naming Law Committee). Yes, the present invention also follows that definition.

The content of the styrene-modified polyester is preferably 1.0 part by mass or more and 30.0 parts by mass or less with respect to 100.0 parts by mass of the binder resin. If it is 1.0 part by mass or more, the low temperature fixability is improved. If it is 30.0 parts by mass or less, the stress resistance is less likely to be lowered, so that the durability is less likely to be lowered, and image harmful effects such as development streaks are less likely to occur. The content of the styrene-modified polyester is more preferably 2.0 parts by mass or more and 30.0 parts by mass or less.

The mass ratio (C: A ratio) of the polyester moiety (C) and the vinyl polymer moiety (A) of the styrene-modified polyester is preferably in the range of 40:60 to 80:20, preferably 40:60 to 70:30. More preferably, it is in the range. In the range of 40:60 to 80:20, the balance between the sharp melt property and the compatibility with the binder resin at the time of dissolution is improved, and the low temperature fixability is improved.

The weight average molecular weight (Mw) of the styrene-modified polyester is preferably 15,000 or more and 45,000 or less, and more preferably 20,000 or more and 40,000 or less. When the weight average molecular weight of the styrene-modified polyester is 15,000 or more, the mechanical strength of the styrene-modified polyester is excellent, the durability is improved, and image harmful effects such as development streaks are less likely to occur. Further, when the weight average molecular weight of the styrene-modified polyester is 45,000 or less, the movement of the molecules is unlikely to be slow, the plasticizing effect at the time of melting is easily obtained, and the low-temperature fixability is improved.

The method for producing the toner particles according to the present invention may be any production method, but the composition for toner in an aqueous medium such as a suspension polymerization method, an emulsion polymerization method and a suspension granulation method. It is preferably obtained by a method for producing toner particles for granulating (for example, a polymerizable monomer composition).

Hereinafter, a method for producing toner particles will be described using a suspension polymerization method, which is one of the preferred production methods among the methods for producing toner particles used in the present invention.

Polymerizable monomers, colorants, styrene-modified polyesters, diester compounds, and optionally mold release agents and other additives that produce the binder resin, such as homogenizers, ball mills, ultrasonic dispersers, etc. Dissolve or disperse uniformly depending on the disperser. A polymerization initiator is dissolved therein to prepare a polymerizable monomer composition. Next, the toner particles are produced by suspending the polymerizable monomer composition in an aqueous medium containing a dispersion stabilizer and performing polymerization.

The binder resin of the present invention can be obtained by polymerizing a polymerizable monomer. As the polymerizable monomer, a vinyl-based polymerizable monomer capable of radical polymerization can be used. As the vinyl-based polymerizable monomer, a monofunctional polymerizable monomer (a monomer having one polymerizable functional group) or a polyfunctional polymerizable monomer (a single amount having a plurality of polymerizable functional groups). Body) can be used.

Examples of the monofunctional polymerizable monomer include styrene-based monomers such as styrene, o- (m-, p-) methyl styrene, and m- (p-) ethyl styrene; methyl acrylate, ethyl acrylate, and n-propyl. Acrylic-based polymerizable monomers such as acrylate, iso-propyl acrylate, n-butyl acrylate, iso-butyl acrylate, tert-butyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, and cyclohexyl acrylate; Methacrylate-based polymerizations such as methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, iso-propyl methacrylate, n-butyl methacrylate, iso-butyl methacrylate, tert-butyl methacrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate, and n-octyl methacrylate. Examples include sex monomers.

Examples of the polyfunctional polymerizable monomer include diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, 1,6-hexanediol diacrylate, ethylene glycol dimethacrylate, and diethylene glycol dimethacrylate. Examples thereof include triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, divinylbenzene, divinylnaphthalin, and divinyl ether.

The monofunctional polymerizable monomer alone or in combination of two or more, or the monofunctional polymerizable monomer and the polyfunctional polymerizable monomer in combination, or the polyfunctional polymerizable monomer. The monomer can be used alone or in combination of two or more.

The polymerization initiator may be added at the same time as the other additives are added to the polymerizable monomer, or may be mixed immediately before suspension in the aqueous medium. Further, immediately after granulation and before starting the polymerization reaction, a polymerizable monomer or a polymerization initiator dissolved in a solvent may be added.

Specific examples of the polymerization initiator include the following.

2,2'-azobis- (2,4-dimethylvaleronitrile), 2,2'-azobisisobutyronitrile, 1,1'-azobis (cyclohexane-1-carbonitrile), 2,2'-azobis Azo or diazo polymerization initiators such as -4-methoxy-2,4-dimethylvaleronitrile, azobisisobutyronitrile; benzoyl peroxide, t-butylperoxy2-ethylhexanoate, t-butylper Oxypivalate, t-butylperoxyisobutyrate, t-butylperoxyneodecanoate, methylethylketone peroxide, diisopropylperoxycarbonate, cumenehydroperoxide, 2,4-dichlorobenzoyl peroxide, lauroyl peroxide, etc. Peroxide-based polymerization initiator.

In the toner of the present invention, a polar resin such as an amorphous polyester resin can be used together with the above-mentioned binder resin. In particular, when toner particles are produced by the suspension polymerization method, if a polar resin is added to the polymerizable monomer composition, a thin layer can be formed on the surface of the toner particles by the polar resin. That is, the addition of the polar resin can strengthen the shell portion of the core-shell structure.

The content of the polar resin is preferably 1.0 part by mass or more and 20.0 parts by mass or less, and more preferably 2.0 parts by mass or more and 10.0 parts by mass or less with respect to 100.0 parts by mass of the binder resin.

The following organic pigments, organic dyes, and inorganic pigments can be used as colorants in the toner of the present invention.

Examples of the cyan-based colorant include a copper phthalocyanine compound and its derivative, an anthraquinone compound, and a basic dye lake compound. Specifically, the following can be mentioned. C. I. Pigment Blue 1, 7, 15, 15: 1, 15: 2, 15: 3, 15: 4, 60, 62, 66.

Examples of the magenta colorant include the following. Condensed azo compound, diketopyrrolopyrrole compound, anthraquinone, quinacridone compound, basic dye lake compound, naphthol compound, benzimidazolone compound, thioindigo compound, and perylene compound. Specifically, the following can be mentioned. C. I. Pigment Red 2, 3, 5, 6, 7, 23, 48: 2, 48: 3, 48: 4, 57: 1, 81: 1, 122, 144, 146, 150, 166, 169, 177, 184, 185, 202, 206, 220, 221, 254, 282, C.I. I. Pigment Violet 19.

Examples of the yellow colorant include condensed azo compounds, isoindolinone compounds, anthraquinone compounds, azo metal complexes, methine compounds, and allylamide compounds. Specifically, the following can be mentioned. C. I. Pigment Yellow 12, 13, 14, 15, 17, 62, 74, 83, 93, 94, 95, 97, 109, 110, 111, 120, 127, 128, 129, 147, 151, 154, 155, 168, 174, 175, 176, 180, 181, 185, 191 and 194, C.I. I. Solvent Yellow 98, C.I. I. Solvent Yellow 162.

Examples of the black colorant include carbon black and those colored black by using the above-mentioned yellow colorant, magenta colorant, and cyan colorant.

When the toner particles are obtained by the suspension polymerization method, it is preferable to use a colorant that has been hydrophobized with a substance that does not inhibit polymerization in consideration of the polymerization inhibitory property and the aqueous phase transfer property of the colorant. .. A preferred method for hydrophobizing the dye is a method in which a polymerizable monomer is polymerized in advance in the presence of these dyes to obtain a colored polymer, and the obtained colored polymer is used as a polymerizable monomer. Add to the composition. Further, the carbon black may be treated with a substance (polyorganosiloxane) that reacts with the surface functional group of the carbon black, in addition to the hydrophobizing treatment similar to the above dye.

These colorants can be used alone or in the form of a solid solution. The colorant used in the present invention is selected from the viewpoints of hue angle, saturation, lightness, light resistance, OHP transparency, and dispersibility in toner particles.

The amount of the colorant added is preferably 1.0 part by mass or more and 20.0 parts by mass or less with respect to 100.0 parts by mass of the binder resin.

The toner of the present invention may contain a mold release agent. Specifically, the following; monofunctional ester waxes typified by behenyl behenate, stearyl stearate, palmityl palmitate, etc .; bifunctional ester waxes typified by dibehenyl sebacate, hexanediol dibehenate, etc.; Trifunctional ester waxes represented by glycerin tribehenate; tetrafunctional ester waxes represented by pentaerythritol tetrastearate, pentaerythritol tetrapalmitate, etc .; dipentaerythritol hexastearate, dipentaerythritol hexapalmi Hexofunctional ester waxes such as tate; Polyfunctional ester waxes such as polyglycerin behenate; Natural ester waxes such as carnauba wax and rice wax; Paraffin wax, microcrystallin wax, Petrolatum and other petroleum waxes and derivatives thereof; Hydrocarbon waxes and derivatives thereof according to the Fisher Tropsch method; Polyethylene wax, Polypropylene wax and other polyolefin waxes and their derivatives; Higher aliphatic alcohols; Stearic acid, palmitic acid and other fatty acids; Acid amides Examples include wax.

The amount of the release agent added is preferably 1.0 part by mass or more and 30.0 parts by mass or less with respect to 100.0 parts by mass of the binder resin.

In the toner of the present invention, a charge control agent can be added as needed. As the charge control agent, a known charge control agent can be used. Further, when the toner particles are produced by the suspension polymerization method, a charge control agent having low polymerization inhibitory property and substantially no solubilized product in an aqueous medium is particularly preferable. As the charge control agent, there are one that controls the toner to be load-electric and one that controls the toner to be positively charged.

Examples of the toner that is controlled to be load-electric are as follows. Monoazo metal compounds, acetylacetone metal compounds, aromatic oxycarboxylic acids, aromatic dicarboxylic acids, oxycarboxylic acids and dicarboxylic acid-based metal compounds, aromatic oxycarboxylic acids, aromatic mono and polycarboxylic acids and their metal salts, Examples thereof include anhydrides, esters, phenol derivatives such as bisphenol, urea derivatives, metal-containing salicylic acid-based compounds, metal-containing naphthoic acid-based compounds, boron compounds, quaternary ammonium salts, calix arene, and charge control resins.

On the other hand, examples of the charge control agent for controlling the toner to be positively charged include the following. Guanidin compounds; imidazole compounds; quaternary ammonium salts such as tributylbenzylammonium-1-hydroxy-4-naphthosulfonate, tetrabutylammonium tetrafluoroborate, and onium salts such as phosphonium salts which are analogs thereof. And these lake pigments; triphenylmethane dyes and their lake pigments (as lake agents, phosphotung acid, phosphomolybdic acid, phosphotungene molybdic acid, tannic acid, lauric acid, gallic acid, ferricianide, and Ferocyanide); Metal salt of higher fatty acid; Charge control resin.

These charge control agents may be added alone or in combination of two or more. The amount of the charge control agent added is preferably 0.1 part by mass or more and 20.0 parts by mass or less, more preferably 0.5 parts by mass or more and 10.0 parts by mass with respect to 100.0 parts by mass of the binder resin. It is less than a part.

When the toner particles are granulated in an aqueous medium by the suspension method, the aqueous medium may contain a dispersion stabilizer. As the dispersion stabilizer, known dispersion stabilizers of inorganic compounds and dispersion stabilizers of organic compounds can be used. As dispersion stabilizers for inorganic compounds, calcium phosphate, magnesium phosphate, aluminum phosphate, zinc phosphate, calcium carbonate, magnesium carbonate, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, calcium metasilicate, calcium sulfate, barium sulfate , Bentonite, silica, and alumina.

On the other hand, examples of the dispersion stabilizer of the organic compound include polyvinyl alcohol, gelatin, methyl cellulose, methyl hydroxypropyl cellulose, ethyl cellulose, sodium salt of carboxymethyl cellulose, polyacrylic acid and its salt, and starch. The amount of these dispersion stabilizers used is preferably 0.2 parts by mass or more and 20.0 parts by mass or less with respect to 100.0 parts by mass of the polymerizable monomer.

When a dispersion stabilizer of an inorganic compound is used as the dispersion stabilizer, a commercially available one may be used as it is, but in order to obtain a dispersion stabilizer having a finer particle size, the inorganic compound is produced in an aqueous medium. May be good. For example, in the case of calcium phosphate, it can be obtained by mixing an aqueous solution of sodium phosphate and an aqueous solution of calcium chloride under high stirring.

An external additive may be added to the toner particles in order to impart various properties to the toner. Examples of the external additive for improving the fluidity of the toner include silica fine particles, titanium oxide fine particles, and inorganic fine particles such as their double oxide fine particles.

Examples of the silica fine particles include dry silica or fumed silica produced by vapor phase oxidation of a silicon halide, wet silica produced from water glass, and sol-gel silica produced by a sol-gel method. Further, the dry silica may be a composite fine particle of silica and another metal oxide by using a metal halogen compound such as aluminum chloride, titanium chloride or the like together with a silicon halogen compound in the manufacturing process.

By hydrophobizing the surface of the inorganic fine particles with a treatment agent, it is possible to adjust the triboelectric charge of the toner, improve the environmental stability, and improve the fluidity under high temperature and high humidity. , It is preferable to use inorganic fine particles that have been hydrophobized.

Treatment agents for hydrophobizing inorganic fine particles include unmodified silicone varnish, various modified silicone varnishes, unmodified silicone oil, various modified silicone oils, silane compounds, silane coupling agents, and other organosilicon compounds. , Organosilicon compounds. Among them, silicone oil is preferable. These treatment agents may be used alone or in combination.

The amount of the external additive added is preferably 0.5 parts by mass or more and 5.0 parts by mass or less, more preferably 1.0 part by mass, based on 100.0 parts by mass of the toner particles before the treatment of the external additive. It is 5 parts by mass or more and 2.5 parts by mass or less.

Hereinafter, methods for measuring various physical properties according to the present invention will be described.

<Measuring method of melting point of styrene-modified polyester>
The melting point (Tm) of the styrene-modified polyester is measured according to ASTM D3418-82 using a differential scanning calorimetry device "Q1000" (manufactured by TA Instruments).

The melting points of indium and zinc are used for temperature correction of the device detector, and the heat of fusion of indium is used for the correction of calorific value. Specifically, 5 mg of a sample (styrene-modified polyester) is precisely weighed, placed in an aluminum pan, and an empty aluminum pan is used as a reference in a measurement temperature range of 30 to 200 ° C. The measurement is performed at a heating rate of 10 ° C./min. In the measurement, the temperature is raised to 200 ° C., then lowered to 30 ° C., and then raised again. The maximum endothermic peak of the DSC curve in the temperature range of 30 to 200 ° C. in the second temperature raising process is defined as the melting point (Tm) of the styrene-modified polyester.

<Method of measuring the content of diester compound>
The quantification of the diester compound in the toner is measured by gas chromatography (GC) as follows.

Weigh 500 mg of toner and place it in a sample bottle. To this, add 10.0 g of carefully weighed acetone, cover it, mix well, and mix well. A desktop ultrasonic cleaner with an oscillation frequency of 42 kHz and an electrical output of 125 W (for example, trade name "B2510J-MTH", Branson). Is irradiated with ultrasonic waves for 30 minutes. Then, filtration is performed using a solvent-resistant membrane filter "Maeshori Disc" (manufactured by Tosoh Corporation) having a pore diameter of 0.2 μm, and 2 μl of the filtrate is analyzed by gas chromatography. Then, the content of the diester compound is calculated from a calibration curve prepared in advance using the diester compound.

The measuring device and measuring conditions are as follows.
GC: HP 6890GC
Column: HP INNOWax (200 μm x 0.40 μm x 25 m)
Carrier gas: He (constant pressure mode: 20 psi)
Oven: (1) Hold at 50 ° C for 10 minutes, (2) Raise to 300 ° C at 10 ° C / min, (3) Hold at 300 ° C for 5 minutes Injection port: 300 ° C, pulsed splitless mode (20 → 40psi, hold 0.5 minutes)
Split ratio: 5.0: 1.0
Detector: 320 ° C (FID)

The present invention will be specifically described with reference to the following examples. However, this does not limit the present invention in any way. Examples 12 to 14 are reference examples. Unless otherwise specified, all parts and% in Examples and Comparative Examples are based on mass.

<Manufacturing of vinyl polymer>
A reaction vessel equipped with a stirrer, a thermometer, a nitrogen introduction tube, and a decompression device was heated with 50.0 parts of xylene substituted with nitrogen, and refluxed at a liquid temperature of 140 ° C. A mixture of 100.0 parts of styrene and 8.0 parts of Dimethyl 2,2'-azobis (2-methylpropionate) as a polymerization initiator was added dropwise to the reaction vessel over 3 hours, and the solution was added dropwise for 3 hours after completion of the addition. Stirred. Then, xylene and residual styrene were distilled off at 160 ° C. and 1 hPa to obtain a vinyl polymer. The weight average molecular weight (Mw) of the obtained vinyl polymer was measured by gel permeation chromatography (GPC) and found to be 8000.

<Manufacturing of styrene-modified polyester 1>
100.0 parts of vinyl polymer 1 in a reaction vessel equipped with a stirrer, thermometer, nitrogen introduction pipe, dehydration pipe, and decompression device, 128.0 parts of xylene as an organic solvent, 82 parts of 1,12-dodecanediol .7 parts were added. Further, 0.6 part of titanium (IV) isopropoxide was added as an esterification catalyst, and the mixture was reacted at 150 ° C. for 4 hours under a nitrogen atmosphere. Then, 78.8 parts of sebacic acid was added and reacted at 150 ° C. for 3 hours and at 180 ° C. for 4 hours. Then, the reaction was further carried out at 180 ° C. and 1 hPa until a desired weight average molecular weight (Mw) was obtained to obtain a styrene-modified polyester 1. Table 1 shows the physical properties of the obtained styrene-modified polyester 1. As shown in Table 1, by using sebacic acid and 1,12-dodecanediol as the monomer for polyester, the polyester moiety having the structural unit (m = 8, n = 12) represented by the formula (2). It is shown that the styrene-modified polyester 1 having the above is obtained.

<Manufacturing of styrene-modified polyester 2-5>
Styrene-modified polyesters 2 to 5 were obtained in the same manner as in the production of styrene-modified polyester 1 except that the raw materials and the addition amounts shown in Table 1 were changed. Table 1 shows the physical properties of the obtained styrene-modified polyesters 2 to 5. Similar to the styrene-modified polyester 1, by using the polyester monomer shown in Table 1, the styrene-modified polyester 2 has a polyester moiety having a structural unit (values of m and n in Table 1) represented by the formula (2). It is shown that ~ 5 is obtained.

<Manufacturing of styrene-modified polyester 6>
A reaction vessel equipped with a stirrer, a thermometer, a nitrogen introduction tube, and a decompression device was heated with 40.0 parts of xylene substituted with nitrogen, and refluxed at a liquid temperature of 140 ° C. A mixed solution of 36.3 parts of styrene, 2.9 parts of dicumyl peroxide, and 2.3 parts of acrylic acid was added dropwise over 3 hours, and after completion of the addition, the solution was stirred for 3 hours. Subsequently, 0.6 part of titanium (IV) isopropoxide was added as an esterification catalyst to 91.5 parts of 1,12-dodecanediol, and the mixture was reacted at 150 ° C. for 4 hours. Then, 85.0 parts of sebacic acid was added, and the mixture was reacted at 150 ° C. for 3 hours and at 180 ° C. for 4 hours. Then, the reaction was further carried out at 180 ° C. and 1 hPa until a desired weight average molecular weight (Mw) was obtained to obtain a styrene-modified polyester 6. Table 1 shows the physical properties of the obtained styrene-modified polyester 6.

In Table 1, the ratio shows the mass ratio (C: A ratio) of the polyester moiety (C) and the vinyl polymer moiety (A).

<Manufacturing of diester mixed solution 1>
1000.0 parts of styrene and 0.1 part of dimethyl succinate were put into a container equipped with a stirrer, and the mixture was stirred and mixed to obtain a diester mixed solution 1.

<Manufacturing of diester mixed solution 2>
999.9 parts of styrene and 0.1 part of dimethyl tetramethylsuccinate were put into a container equipped with a stirrer, and the mixture was stirred and mixed to obtain a diester mixed solution 2.

<Manufacturing of toner 1>
For 30.0 parts of styrene, C.I. I. 5.0 parts of Pigment Blue 15: 3 and 0.5 part of charge control agent (Bontron E84; manufactured by Orient Chemical Industry Co., Ltd.) were prepared. These were introduced into an attritor (manufactured by Nippon Coke Industries, Ltd.) and stirred at 200 rpm at 25 ° C. for 180 minutes using zirconia beads having a radius of 1.25 mm to prepare a pigment dispersion composition.

On the other hand, 900 parts of ion-exchanged water heated to 60 ° C. and 2.5 parts of calcium phosphate were added to a separate container, and T.I. K. An aqueous medium was obtained by stirring at 10000 rpm using a homomixer (manufactured by Tokushu Kagaku Kogyo).

In addition, the following materials are used in T.I. K. Using a homomixer, the mixture was mixed and dispersed at 5000 rpm.
・ Pigment dispersion composition 35.5 parts ・ Styrene 44.7 parts ・ n-Butyl acrylate 24.0 parts ・ Styrene-modified polyester 1 6.0 parts ・ Diester mixture 2 1.3 parts ・ Acrystalline polyester resin (weight) Average molecular weight 9500, glass transition temperature 73 ° C) 4.5 parts After heating to 60 ° C, 6.0 parts of hydrocarbon wax (HNP-9; manufactured by Nippon Seiko Co., Ltd.) was added and dispersed for 30 minutes. Mixing was carried out to dissolve 7.0 parts of the polymerization initiator perbutyl PV (manufactured by Nichiyu Co., Ltd.) to prepare a polymerizable monomer composition.

The above-mentioned polymerizable monomer composition was put into the above-mentioned aqueous medium, and in a temperature of 60 ° C. and a nitrogen atmosphere, T.I. K. The polymerizable monomer composition was granulated by stirring with a homomixer at 12000 rpm for 10 minutes. Then, the temperature was raised to 70 ° C. while stirring with a paddle stirring blade. After reacting for 4 hours, the temperature was further raised to 85 ° C. and the reaction was carried out for 1 hour. After cooling, hydrochloric acid was added to adjust the pH to 1.4, and the mixture was stirred for 2 hours. After filtering and washing with water, the mixture was dried at a temperature of 40 ° C. for 48 hours to obtain toner particles.

The weight average particle size (D4) of the obtained toner particles was measured with a Coulter counter Multisizer 3 (manufactured by Beckman Coulter) and found to be 6.2 μm.

With respect to 129.0 parts of the toner particles, 1.0 part of hydrophobic silica fine particles (average number of primary particles: 7 nm) treated with dimethyl silicone oil as an external additive was added to FM mixer (manufactured by Nippon Coke Industries, Ltd.). ) For 10 minutes to obtain toner 1. Table 2 shows the physical properties of the obtained toner 1.

<Manufacturing of toner 2>
(Preparation of binder resin particle dispersion)
・ 74.8 parts of styrene ・ 24.0 parts of n-butyl acrylate ・ 21.2 parts of diester mixture or more mixed and dissolved, and the nonionic surfactant (Nonipol 400; manufactured by Sanyo Kasei Co., Ltd.) 1 .5 parts and 2.2 parts of anionic surfactant (Neogen SC; manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) were dissolved in 120.0 parts of ion-exchanged water and dispersed and emulsified. While slowly mixing for 10 minutes, 10.0 parts of ion-exchanged water in which 1.5 parts of ammonium persulfate was dissolved was added as a polymerization initiator, and nitrogen substitution was performed. The contents were heated to a temperature of 70 ° C. with stirring, and emulsion polymerization was continued as it was for 4 hours to prepare a binder resin particle dispersion liquid in which resin particles having an average particle size of 0.29 μm were dispersed.

(Preparation of styrene-modified polyester resin particle dispersion)
・ Styrene-modified polyester 1 50.0 parts ・ Anionic surfactant (Neogen SC; manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 7.0 parts ・ Ion exchanged water 200.0 parts or more is heated to 95 ° C and homogenizer (IKA) After dispersion using (manufactured by Gorin), dispersion treatment is performed with a pressure discharge homogenizer (manufactured by Gorin) to prepare a dispersion of styrene-modified polyester resin particles obtained by dispersing resin particles having an average particle size of 0.42 μm. did.

(Preparation of colorant particle dispersion)
・ C. I. Pigment Blue 15: 3 20.0 parts ・ Anionic surfactant (Neogen SC; manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) 3.0 parts ・ Ion-exchanged water 78.0 parts or more is mixed and sand grinder mill (manufactured by Imex) ) Was used for dispersion. When the particle size distribution in this colorant particle dispersion was measured using a particle size measuring device (LA-700, manufactured by HORIBA, Ltd.), the average particle size of the contained colorant particles was 0.20 μm, and 1 μm. No oversized particles were observed.

(Preparation of release agent particle dispersion)
・ Hydrocarbon wax (HNP-9; manufactured by Nippon Seiki Co., Ltd.) 50.0 parts ・ Anionic surfactant (Neogen SC; manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 7.0 parts ・ Ion-exchanged water 200.0 parts or more After heating to a temperature of 95 ° C. and dispersing using a homogenizer (manufactured by IKA), dispersion treatment is performed with a pressure discharge type homogenizer (manufactured by Gorin) to disperse a release agent having an average particle size of 0.50 μm. A release agent particle dispersion was prepared.

(Preparation of charge control agent particle dispersion)
・ Charge control agent (Bontron E84; manufactured by Orient Chemical Industry Co., Ltd.) 5.0 parts ・ Anionic surfactant (Neogen SC; manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 3.0 parts ・ Ion-exchanged water 78.0 parts or more mixed Then, it was dispersed using a sand grinder mill (manufactured by Imex). When the particle size distribution in this charge control agent particle dispersion was measured using a particle size measuring device (LA-700, manufactured by HORIBA, Ltd.), the average particle size of the contained particles was 0.22 μm and exceeded 1 μm. No coarse particles were observed.

(Preparation of amorphous polyester resin particle dispersion)
-Atypical polyester (weight average molecular weight 9500, glass transition temperature 73 ° C) 50.0 parts-Anionic surfactant (Neogen SC; manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 7.0 parts-Ion-exchanged water 200.0 parts The above was heated to 95 ° C. and dispersed using a homogenizer (manufactured by IKA), and then dispersed by a pressure discharge type homogenizer (manufactured by Gorin) to disperse resin particles having an average particle size of 0.50 μm. A dispersion of amorphous polyester resin particles was prepared.

(Making toner)
・ 100.0 parts of binder resin particle dispersion (solid content)
-Styrene-modified polyester resin particle dispersion 5.0 parts (solid content)
-Colorant particle dispersion 4.5 parts (solid content)
・ 5.0 parts of mold release agent particle dispersion (solid content)
The above materials were put into a separable flask equipped with a stirrer, a cooling tube, and a thermometer and stirred. This mixed solution was adjusted to pH = 5.2 with a 1N aqueous potassium hydroxide solution.

50.0 parts of a 20% sodium chloride aqueous solution was added dropwise to the above mixed solution, heated to 50 ° C. while stirring the inside of the flask in a heating oil bath, and held at 50 ° C. for 1 hour to hold core agglomerated particles. Was produced.

Further, slowly add 4.0 parts (solid content) of the amorphous polyester resin particle dispersion and 0.5 part (solid content) of the charge control agent particle dispersion, and hold at 50 ° C. for 30 minutes to hold the core / shell. An agglomerated particle dispersion was prepared.

After adding 3.0 parts of an anionic surfactant (Neogen SC; manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) to the core / shell agglomerated particle dispersion, the flask was sealed, heated to 95 ° C., and held for 4 hours. After cooling, the product was filtered, thoroughly washed with ion-exchanged water, and dried to obtain toner particles.

The weight average particle size (D4) of the obtained toner particles was measured with a Coulter counter Multisizer 3 (manufactured by Beckman Coulter) and found to be 6.3 μm.

For 119.0 parts of the toner particles, 1.0 part of hydrophobic silica fine particles (average number of primary particles: 7 nm) treated with dimethyl silicone oil as an external additive was added to FM mixer (manufactured by Nippon Coke Industries, Ltd.). ) For 10 minutes to obtain toner 2. Table 2 shows the physical properties of the obtained toner 2.

<Manufacturing of toners 3 to 16>
Toners 3 to 16 were obtained by the same manufacturing method as that of toner 1 except that the materials and the addition amounts shown in Table 2 were changed. Table 2 shows the physical properties of the obtained toners 3 to 16.

[Example 1]
LBP9660Ci (manufactured by Canon Inc.) was used as the evaluation machine. The toner contained therein was extracted from the cyan cartridge, then toner 1 was introduced to refill the toner, and the following items were evaluated. A LETTER size XEROX 4200 (manufactured by XEROX, with a basis weight of 75 g / m ² ) was used as the evaluation paper. Unless otherwise specified, the evaluation was performed in a normal temperature and humidity environment (25 ° C., 50% RH). Moreover, the heat resistance (blocking) was evaluated by the toner alone. The evaluation results are shown in Table 3.

<Low temperature fixability>
An image having an area of 2 cm × 2 cm was output on the evaluation paper with a toner loading amount of 0.9 mg / cm ² . While changing the fixing temperature control, the fixing temperature at the time when the offset occurred at the rear end of the evaluation paper when passing through the fixing device was confirmed, and the evaluation was performed based on the following evaluation criteria.
A: No offset at 120 ° C B: Offset occurs at 120 ° C C: Offset occurs at 130 ° C D: Offset occurs at 140 ° C

<Development streaks>
12,000 images with a print ratio of 5% were output. After outputting 12,000 sheets, a halftone image having a toner loading amount of 0.20 mg / cm ² was prepared, and the image and the developing roller were visually confirmed and evaluated based on the following evaluation criteria.
A: No vertical streaks can be seen on the developing roller or the image.
B: Although there are fine streaks on the developing roller, no vertical streaks can be seen on the image.
C: Although there are some streaks on the developing roller, no vertical streaks can be seen on the image.
D: Streaks are seen on the developing roller and the halftone image.

<Fog>
After the evaluation of the development streaks, the developing streaks were left to stand in a high temperature and high humidity environment (32 ° C./80% RH) for 3 days. After being left unattended, an image having a white background is output, and the fog density (fog density) is determined from the difference between the whiteness of the white background of the output image and the whiteness of the evaluation paper measured by "REFLECTMER MODEL TC-6DS" (manufactured by Tokyo Denshoku Co., Ltd.). %) Was calculated and image fog was evaluated. An amber light filter was used as the filter.
A: 0.5% or less B: 0.6% or more and 1.5% or less C: 1.6% or more and 2.5% or less D: 2.6% or more

<Heat resistance (blocking)>
5 g of the toner was placed in a 50 cc polycup and left at a temperature of 55 ° C. and a humidity of 10% RH for 3 days to check for agglomerates and evaluated according to the following criteria.
A: No agglomerates B: Minor agglomerates occur, collapse when touched with a finger C: Aggregates occur, collapse when lightly pressed with a finger D: Completely aggregate, do not collapse when pressed with a finger

[Examples 2 to 14, Comparative Examples 1 and 2]
The same evaluation as in Example 1 was performed using the toners shown in Table 3. The evaluation results are shown in Table 3.

Claims (2)

A toner having toner particles containing a binder resin, a colorant, a styrene-modified polyester, and a diester compound.
The melting point (Tm) of the styrene-modified polyester is 55 ° C. or higher and 90 ° C. or lower.
The content of the styrene-modified polyester is 1.0 part by mass or more and 30.0 parts by mass or less with respect to 100.0 parts by mass of the binder resin.
The styrene-modified polyester is a block polymer and
The diester compound has a structure represented by the following formula (1) and has a structure represented by the following formula (1).
Toner, wherein the content of the toner of the diester compound is 0.1ppm or more 10.0ppm less.

(In equation (1), R ¹ , R ² , R ³ , and R ⁴ independently represent H or CH _3. ) The toner according to claim 1, wherein the polyester portion of the styrene-modified polyester has a structure represented by the following formula (2).

(In equation (2), m is an integer of 6 or more and 14 or less, and n is an integer of 6 or more and 16 or less.)