JP2005091881A - Electrostatic charge image developing toner, method for forming image, and toner cartridge - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide toner which can be fixed at a low temperature even when a fixing device with less fixing energy for image formation is used, which has excellent fixing property and heat-resistant storage property and preferable magnetic characteristics, and to provide a method for forming an image and a toner cartridge using the toner. <P>SOLUTION: The toner contains: a polycondensation polyester resin as a binder resin prepared in the presence of at least one kind of titanium-containing catalyst selected from a group consisting of halogenated titanium, titan diketone enolate, titanium carboxylate, carboxylic acid titanyl and titanyl carboxylate; and a black iron oxide compound as a colorant comprising a titanium component and an iron component, with 10 to 45 wt.% proportion of the titanium component is terms of Ti atoms to Fe atoms measured by a wavelength dispersion type X-ray fluorescent analyzer. The toner cartridge is charged with the above toner. An image is formed by an apparatus mounting a fixing device which is capable of low energy fixing by using the above toner. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a toner used in electrophotography and the like and an image forming method using the same, and more particularly, to a toner that is considered to be applied to an apparatus having a low fixing energy.

  Conventionally, various methods are known as electrophotography. Generally, a photoconductive substance is used to form an electric latent image on a photosensitive member (image carrier) by various means, and then the latent image is formed. The image is developed using dry toner, the toner image is transferred onto a transfer medium such as paper, and then fixed by heating, pressurizing, or the like to obtain a copy.

  There are roughly two types of methods for developing electrical latent images: a liquid development method using a developer in which various pigments and dyes are finely dispersed in an insulating organic liquid, a cascade method, a magnetic brush method, a powder cloud method, etc. There are dry development methods that use toner in which a colorant such as carbon black is dispersed in natural or synthetic resin, such as one-component development method using only toner and two-component development method using toner and carrier. There is.

  Methods for heat-fixing toner images on transfer paper can be broadly classified into contact fixing methods and non-contact fixing methods. The former includes heating roller fixing, belt fixing, the latter includes flash fixing, and oven (atmosphere) fixing. . The heating roller fixing method is a very heat efficient fixing method because the toner image and the heating roller are in direct contact with each other, and the apparatus can be downsized.

  However, due to energy saving in recent years, the heat energy that can be used at the time of fixing has become very small. For this reason, the toner used in such a fixing device is required to be further fixed at a low temperature.

As a technique for solving this problem, several proposals have conventionally been made.
For example, roll fixing toner (for example, refer to Patent Document 1) in which core particles made of polyester resin and wax having a polar group are coated with a resin, and the melt viscosity of the polyester resin and wax is defined, and a specific polyester resin and mold release Film fixing toner comprising an agent and defining the melt viscosity of the polyester resin at 80 to 120 ° C., the slope of the graph of the melt viscosity and the temperature, and the melt viscosity of a specific release agent (for example, Patent Document 2, Patent Document 3, Patent Document 4)), a film comprising a specific polyester resin and a release agent, which defines the melt viscosity, melt viscosity and temperature gradient of the polyester resin at 80 to 120 ° C., and the melt viscosity of the specific release agent A fixing capsule toner (for example, see Patent Document 5), a specific polyester resin, an organometallic compound, a release agent, Film fixing toner that defines the melt viscosity of a steal resin at 120 to 150 ° C., the gradient of the graph of melt viscosity and temperature, and the melt viscosity of a specific release agent (see, for example, Patent Document 6) at 110 to 130 ° C. A toner composed of a styrene-acrylic resin that defines the relationship between the measured melt viscosity and temperature (for example, see Patent Document 7), a toner that contains a specific charge control agent and defines an average viscosity gradient (for example, a patent) Reference 8), a novel polyester resin in which a polycondensation catalyst of a polyol component and a polycarboxylic acid component is a titanate ester of a diol (see, for example, Patent Document 9) is disclosed.

  As described above, the toner can be fixed even at a low temperature of the hot mouth roller (low temperature fixability) and the toner does not fuse to the heat roll (hot offset resistance) even at a high temperature of the heat roller. It is known to use a polyester resin as an excellent material. However, energy saving in an image forming apparatus is further advanced, and it has become difficult to obtain sufficient fixability with the conventional technology.

  In the case of a monochrome toner, it is common to use carbon black as a colorant. However, in the case of a magnetic toner, a magnetic material may also serve as a colorant. Such magnetic toners have been obtained that are fixed at a lower temperature than when carbon black is used. The reason for this is thought to be that the metal material, which is the main constituent material of the magnetic material, has a higher thermal conductivity than carbon black.

  However, the inclusion of a magnetic substance is not a problem when used as a magnetic one-component toner, but when it is contained in a non-magnetic toner, the adhesion to the magnetic sleeve and carrier is increased to lower the developability. In order to obtain a magnetization value that does not cause a problem, there is a means of reducing the content. However, when the content is small, there is a problem that the effect of fixing at low temperature is not exhibited.

In recent years, attempts have been made to use black metal compound fine powder as a colorant to replace carbon black.
As such an example, for example, a mixture of Fe ₂ TiO ₅ and Fe ₂ O ₃ —FeTiO ₃ solid solution having an average particle diameter of 0.1 to 0.5 μm (see, for example, Patent Document 10), FeO of 25 to 25 are used. 30% magnetic iron oxide (see, for example, Patent Document 11, Patent Document 12, and Patent Document 13), magnetite with a residual magnetization of 6 emu / g or less (see, for example, Patent Document 14 and Patent Document 15), and Ti inside. , Iron oxide particles made of Ti and Fe on the surface (for example, see Patent Document 16), saturation magnetization 0.5 to 10 emu / g, particle size 0.1 to 0.4 μm, rutile coated with Fe ₂ TiO ₄ Type TiO ₂ mixed phase crystal (see, for example, Patent Document 17), saturation magnetization of 30 emu / g or less, metal compound having a dielectric loss factor of 50 or less (see, for example, Patent Document 18), saturation magnetization of 40 emu / g or less, content 2 Parts by weight or less of the metal compound (e.g., see Patent Document 19.) Have been disclosed.

However, since the black metal compound fine powder as described above has a larger particle size than carbon black, the dispersion becomes non-uniform when used as a toner component, and the desired black unless used in a larger amount than carbon black. The degree of low-temperature fixing is low. On the other hand, however, if it is used in an excessive amount, there arises a problem that the developability is lowered due to the magnetism of the black metal compound fine powder.
Japanese Patent No. 2743476 Japanese Patent Laid-Open No. 3-122661 Japanese Patent Laid-Open No. 4-85550 Japanese Patent Publication No. 8-16804 Japanese Patent Publication No. 8-12459 Japanese Patent Publication No. 7-82250 Japanese Examined Patent Publication No. 7-72809 Japanese Patent Laid-Open No. 10-246989 JP 2002-148867 A Patent No. 2736680 Japanese Patent No. 3101782 Japanese Patent No. 3108823 Japanese Patent No. 3174960 Japanese Patent No. 3224774 Japanese Patent No. 3261888 JP 2000-319021 A JP 2002-129063 A JP 2002-189313 A JP 2002-196528 A

  The present invention has been made in view of the problems as described above, and can be fixed at low temperature even when using a fixing device with low fixing energy in image formation, and has excellent fixability and heat-resistant storage stability. A toner having suitable magnetic properties, an image forming method using the toner, and a toner cartridge are provided.

  The present invention uses a polyester resin formed in the presence of a specific catalyst as a binder resin, which is a component contained in the toner, and a new black colorant (black iron oxide compound) instead of carbon black as a colorant. It has been found that the above-mentioned problems can be solved by using it, and the present invention has been completed. Hereinafter, the present invention will be specifically described.

  The invention according to claim 1 is an electrostatic image developing toner comprising a binder resin and a colorant, wherein the binder resin is titanium halide, titanium diketone enolate, titanium carboxylate, titanyl carboxylate, and titanyl carboxylate. A polycondensation polyester resin formed in the presence of at least one titanium-containing catalyst selected from the group consisting of salts, wherein the colorant is a black iron oxide compound containing a titanium component and an iron component, and The electrostatic charge image developing toner is characterized in that the content of the titanium component is 10 to 45% by weight with respect to Fe atoms in terms of Ti atoms, as measured by a wavelength dispersion type fluorescent X-ray apparatus.

  The invention according to claim 2 is the electrostatic image developing toner according to claim 1, wherein the titanium diketone enolate is titanium acetylacetonate.

  The invention according to claim 3 is the electrostatic image developing toner according to claim 1, wherein the titanium carboxylate is an aromatic titanium titanium carboxylate.

  A fourth aspect of the present invention is the electrostatic image developing toner according to the first aspect, wherein the carboxylic acid titanyl salt is a titanyl maleate salt or a titanyl oxalate salt.

  The invention according to claim 5 is the electrostatic image developing toner according to claim 1, wherein a part of the molecular skeleton of the polyester resin is modified with polyepoxide.

  6. The electrostatic image developing toner according to claim 1, wherein the content of the black iron oxide compound is 15 to 40% by weight based on the total amount of the toner. It is.

  The invention of claim 7 is characterized in that the toner contains at least one wax component selected from carnauba wax, rice wax, and ester wax in an amount of 0.5 to 10% by weight based on the total amount of the toner. Item 7. The electrostatic image developing toner according to any one of Items 1 to 6.

The invention according to claim 8 is the electrostatic charge according to any one of claims 1 to 7, wherein the saturation magnetization σs of the toner is 0.1 to 5.0 emu / g in a magnetic field of 398 Am ² / Kg. This is an image developing toner.

  The invention of claim 9 is the toner for developing an electrostatic image according to claim 1, wherein the toner for developing an electrostatic image is used as a two-component toner material.

  A tenth aspect of the present invention is a toner cartridge filled with the toner that is detachable from an image forming apparatus that forms an image using the toner, and the toner is the toner according to any one of the first to ninth aspects. There is a toner cartridge characterized by being.

  According to an eleventh aspect of the present invention, an electrostatic latent image developing toner containing a binder resin and a colorant is formed on an electrostatic latent image formed on an image carrier of an image forming apparatus, and the image is formed. An image forming method for transferring and fixing on a transfer material, wherein the binder resin of the toner for developing an electrostatic charge image is titanium halide, titanium diketone enolate, titanium carboxylate, titanyl carboxylate, and titanyl carboxylate A polycondensation polyester resin formed in the presence of at least one titanium-containing catalyst selected from the group consisting of salts, wherein the colorant is a black iron oxide compound containing a titanium component and an iron component, and The content of the titanium component is an image forming method characterized in that a value measured by a wavelength dispersion type fluorescent X-ray apparatus is 10 to 45% by weight with respect to Fe atoms in terms of Ti atoms.

Each of the binder resin and the colorant used as main components in the toner of claims 1 to 9 is a polyester resin formed in the presence of a titanium-containing catalyst in the binder resin, and the content of the titanium component in the colorant is further increased. By using the specified black iron oxide compound, low-temperature fixing is possible even when using a fixing device with low fixing energy in image formation, and it has excellent fixing properties and heat-resistant storage properties, and has suitable magnetic properties. Toner can be provided.
Further, by selecting a titanium-containing catalyst, the condensation reaction proceeds well, and a polyester resin adjusted to a suitable molecular weight is obtained. With such a catalyst, the viscosity and elasticity of the polyester resin can be suitably controlled, and the glossiness and hot offset resistance can be adjusted. Alternatively, the hot offset property can be further improved by modifying the polyester resin with polyepoxide. Further, by adjusting the content of the black iron oxide compound, the fixing temperature can be lowered while maintaining the coloring power. Alternatively, the inclusion of the wax component can further improve the low-temperature fixability. Furthermore, by defining the saturation magnetization σs of the toner, the coercive force with the toner carrier incorporating the magnet is made favorable, the developability is good, and problems such as toner scattering and background contamination can be avoided. .

  According to the toner cartridge of the tenth aspect, it is possible to make the image forming apparatus compact and to perform simple and steady maintenance work. That is, only by replacing the toner cartridge filled with the toner of the present invention, low-temperature fixing is possible, and stable image quality with excellent fixability and heat-resistant storage stability can be realized.

  According to the image forming method of the present invention, since the toner of the present invention capable of low-temperature fixing and having suitable magnetic properties is used for developing an electrostatic image, excellent fixing can be performed even when a fixing device having a low fixing energy is used. Stability and heat-resistant storage stability, and stable image formation is possible.

  As described above, the toner used in the present invention includes at least a binder resin and a colorant, and the binder resin includes titanium halide, titanium diketone enolate, titanium carboxylate, titanyl carboxylate, and titanyl carboxylate. A polycondensation polyester resin formed in the presence of at least one titanium-containing catalyst selected from the group consisting of: a titanium component measured by a wavelength dispersive X-ray fluorescence apparatus as a colorant; A toner for developing an electrostatic image, wherein a black iron oxide compound containing 10 to 45% by weight with respect to atoms is used. Hereinafter, at least the binder resin and the colorant contained in the toner of the present invention will be sequentially described.

First, examples of the catalyst containing titanium used in the synthesis of the polyester resin in the present invention include titanium halide, titanium diketone enolate, titanium carboxylate, titanyl carboxylate, and titanyl carboxylate. Specific examples of these are exemplified below.
Among the titanium-containing catalysts, the titanium halide is not particularly limited, and examples thereof include dichlorotitanium, trichlorotitanium, tetrachlorotitanium, trifluorotitanium, tetrafluorotitanium, and tetrabromotitanium.

  The titanium diketone enolate is not particularly limited, and examples thereof include titanium acetylacetonate, titanium diisopropoxide bisacetylacetonate, and titanyl acetylacetonate. Of these titanium diketone enolates, titanium acetylacetonate is preferred.

  Although it does not specifically limit as carboxylate titanium, For example, C1-C32 aliphatic carboxylate titanium, C7-38 aromatic carboxylate titanium, etc. are mentioned. In the case of titanium polycarboxylate having a valence of 2 or more, the number of carboxyl groups coordinated to titanium may be one or more, and a free carboxyl group may exist without being coordinated to titanium.

  Although it does not specifically limit as C1-C32 aliphatic carboxylate titanium, For example, aliphatic monocarboxylic acid titanium, aliphatic dicarboxylic acid titanium, aliphatic tricarboxylic acid titanium, and 4-8 valent or more aliphatic polycarboxylic acid. Examples thereof include titanium carboxylate.

  The aliphatic monocarboxylic acid titanium is not particularly limited, and examples thereof include titanium formate, titanium acetate, titanium propionate, and titanium octoate. The aliphatic dicarboxylic acid titanium is not particularly limited, and examples thereof include titanium oxalate, titanium succinate, titanium maleate, titanium adipate, and titanium sebacate. Although it does not specifically limit as aliphatic tricarboxylic acid titanium, For example, hexane tricarboxylic acid titanium, isooctane tricarboxylic acid titanium, etc. are mentioned. Although it does not specifically limit as aliphatic tricarboxylic acid titanium, For example, octane tetracarboxylic acid titanium, decane tetracarboxylic acid titanium, etc. are mentioned.

  The aromatic carbonic acid titanium having 7 to 38 carbon atoms is not particularly limited. For example, aromatic monocarboxylic acid titanium, aromatic dicarboxylic acid titanium, aromatic tricarboxylic acid titanium, and tetravalent to octavalent or higher aromatic polycarboxylic acid. Examples include titanium carboxylate.

The aromatic monocarboxylic acid titanium is not particularly limited, and examples thereof include titanium benzoate. The aromatic titanium dicarboxylate is not particularly limited. For example, titanium phthalate, titanium terephthalate, titanium isophthalate, titanium 1,3-naphthalenedicarboxylate, titanium 4,4-biphenyldicarboxylate, 2,5-toluenedicarboxylic acid Examples thereof include titanium oxide and titanium anthracene dicarboxylate. Although it does not specifically limit as aromatic tricarboxylic acid titanium, For example, trimellitic acid titanium, 2,4,6 mononaphthalene tricarboxylic acid titanium etc. are mentioned. Although it does not specifically limit as aromatic polycarboxylic acid titanium, For example, pyromellitic acid titanium, 2,3,4,6- naphthalene tetracarboxylic acid titanium etc. are mentioned.
Among these titanium carboxylates, an aromatic titanium carboxylate having 7 to 38 carbon atoms is preferable, and an aromatic titanium dicarboxylate is more preferable.

  Although it does not specifically limit as carboxylate titanyl, For example, C1-C32 aliphatic carboxylate titanyl, C7-38 aromatic carboxylate titanyl, etc. are mentioned. In the case of divalent or higher polycarboxylic acid titanyl, the number of carboxy groups coordinated to titanium may be one or more, and a free carboxyl group may be present without coordination to titanium.

  Although it does not specifically limit as a C1-C32 aliphatic carboxylate titanyl, For example, an aliphatic monocarboxylic acid titanyl, an aliphatic dicarboxylic acid titanyl, an aliphatic tricarboxylic acid titanyl, and a 4- to 8-valent or more aliphatic polycarboxylic acid. And titanyl carboxylate.

  The aliphatic monocarboxylic acid titanyl is not particularly limited, and examples thereof include titanyl formate, titanyl acetate, titanyl propionate, and titanyl octoate. Although it does not specifically limit as aliphatic dicarboxylate titanyl, For example, titanyl oxalate, titanyl succinate, titanyl maleate, titanyl adipate, titanyl sebacate, etc. are mentioned. Although it does not specifically limit as aliphatic tricarboxylic acid titanyl, For example, hexane tricarboxylic acid titanyl, isooctane tricarboxylic acid titanyl, etc. are mentioned. Although it does not specifically limit as a 4-8 valent or more aliphatic polycarboxylic acid titanyl, For example, an octane tetracarboxylic-acid titanyl, a decane tetracarboxylic-acid titanyl, etc. are mentioned.

  Although it does not specifically limit as C7-38 aromatic carboxylic acid titanyl, For example, aromatic monocarboxylic acid titanyl, aromatic dicarboxylic acid titanyl, aromatic tricarboxylic acid titanyl, and 4-8 valent or more aromatic polycarboxylic acid. And titanyl carboxylate.

  The titanyl aromatic monocarboxylate is not particularly limited, and examples thereof include titanyl benzoate. Although it does not specifically limit as aromatic dicarboxylate titanyl, For example, titanyl phthalate, titanyl terephthalate, titanyl isophthalate, titanyl 1,3-naphthalenedicarboxylate, titanyl 4,4-biphenyl dicarboxylate, 2,5-toluene dicarboxylic Examples thereof include titanyl acid and titanyl anthracene dicarboxylate. The aromatic tricarboxylic acid titanyl is not particularly limited, and examples thereof include titanyl trimellitic acid and titanyl 2,4,6-naphthalene tricarboxylic acid. Although it does not specifically limit as 4- to 8-valent or more aromatic polycarboxylic acid titanyl, For example, titanyl pyromellitic acid, titanyl 2,3,4,6-naphthalene tetracarboxylic acid, etc. are mentioned.

  Although it does not specifically limit as carboxylic acid titanyl salt, For example, an aliphatic dicarboxylic acid titanyl, an aliphatic tricarboxylic acid titanyl, 4-8 or more aliphatic polycarboxylic acid titanyl, aromatic dicarboxylic acid titanyl, aromatic tricarboxylic acid Alkali metal (lithium, sodium, potassium, etc.) or alkaline earth metal (magnesium, calcium, barium, etc.) salt of titanyl, or titanyl carboxylate listed in titanyl of 4-8 or higher aromatic polycarboxylic acid Etc. Of these carboxylic acid titanyl salts, maleic acid titanyl salt and oxalic acid titanyl salt are preferred.

The amount of the titanium-containing catalyst used is not particularly limited, but the lower limit is preferably 0.01% and 0.02% is further based on the total weight of the polyol and polycarboxylic acid used to obtain the polyester resin shown below. Preferably, 0.03% is particularly preferable, and 0.05% is most preferable. The upper limit is preferably 5%, more preferably 2%, particularly preferably 1.5%, and most preferably 0.8%. When it is 0.01% or more, the effect as a polycondensation catalyst is sufficiently obtained, and when it is 5% or less, high catalytic action is obtained according to the amount of catalyst. In addition, when the amount is within the above-mentioned range of the catalyst amount, the necessary properties of the toner using the toner binder made of the polyester resin to be obtained become better.
In the above and below, “%” means “% by weight” unless otherwise specified.

  Among these titanium-containing catalysts, preferred are titanium diketone enolate, titanium carboxylate, titanyl carboxylate and combinations thereof, more preferably titanium diketone enolate, aromatic carboxylic acid titanium, aliphatic carboxylic acid. Acid titanyl salts, aromatic carboxylic acid titanyl salts and combinations thereof, more preferably, among titanium acetylacetonate, aromatic dicarboxylic acid titanium, and carboxylic acid titanyl salts, alkali metal salts and combinations thereof, particularly preferable. Is titanium terephthalate, titanium isophthalate, titanium orthophthalate, titanyl oxalate, titanyl maleate and combinations thereof, most preferably titanium terephthalate, potassium titanyl oxalate and combinations thereof.

Next, the polyester resin constituting the toner binder of the present invention is not particularly limited, but specific examples include the following, and these can also be used in combination.
Linear polyester (Y): Linear polyester resin using diol and dicarboxylic acid Non-linear polyester (X): Non-linear polyester resin using polyol and / or polycarboxylic acid together with diol and dicarboxylic acid Modified polyester : Modified polyester resin obtained by reacting (Y) and (X) with polyepoxide.

The diol is not particularly limited. For example, a diol having a hydroxyl value of 180 to 1900 mg KOH / g, specifically, an alkylene glycol having 2 to 12 carbon atoms (ethylene glycol, 1,2-propylene glycol, 1,3-propylene). Glycol, 1,4-butylene glycol and 1,6-hexanediol); alkylene ether glycol (diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol and polybutylene glycol); alicyclic diol (1 , 4-cyclohexanedimethanol and hydrogenated bisphenol A); bisphenols (such as bisphenol A, bisphenol F and bisphenol S); Adducts of ethylene oxide (hereinafter abbreviated as FO, propylene oxide (hereinafter abbreviated as PO), butylene oxide (hereinafter abbreviated as BO), etc.); alkylene oxides of 2 to 4 carbon atoms of the above bisphenols ( EO, PO, and BO)) and the like.
Among these, preferred are alkylene glycols having 2 to 12 carbon atoms, alkylene oxide adducts of bisphenols, and combinations thereof, and particularly preferred are alkylene oxide adducts of bisphenols, and those having 2 carbon atoms. Use in combination with ˜12 alkylene glycols.
In the above and below, the hydroxyl value and the acid value are measured by the method defined in JIS K 0070.

Although it does not specifically limit as polyol more than trivalence, For example, polyols with a hydroxyl value of 150-1900 mgKOH / g, specifically, 3-8 or more aliphatic polyhydric alcohol (glycerin, triethylolethane, Trimethylolpropane, pentaerythritol, and sorbitol); adducts of the above-mentioned aliphatic polyhydric alcohols with 2 to 4 carbon oxides (such as EO, PO, and BO); trisphenols (such as trisphenol PA); novolac resins (Phenol novolac and cresol novolak); Trisphenols adducts having 2 to 4 carbon atoms such as EO, PO and BO; C2-4 alkylene oxides of the novolac resin (EO, PO and BO) etc.)
Among these, preferred are aliphatic polyhydric alcohols having 3 to 8 valences or higher and alkylene oxide adducts of novolak resins, and particularly preferred are alkylene oxide adducts of novolak resins.

  On the other hand, the dicarboxylic acid is not particularly limited. For example, dicarboxylic acid having an acid value of 180 to 1250 mg KOH / g, specifically, alkylene dicarboxylic acid having 4 to 36 carbon atoms (succinic acid, adipic acid, sebacic acid and dodecenyl succinic acid). Acid etc.): C4-C36 alkenylene dicarboxylic acid (maleic acid, fumaric acid, etc.); C8-36 aromatic dicarboxylic acid (phthalic acid, isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid, etc.), etc. It is done. Of these, preferred are alkenylene dicarboxylic acids having 4 to 20 carbon atoms and aromatic dicarboxylic acids having 8 to 20 carbon atoms. Moreover, even if these use together 2 or more types, there is no problem. In addition, as the dicarboxylic acid, acid anhydrides as described above or lower (1 to 4 carbon atoms) alkyl esters (methyl ester, ethyl ester, isopropyl ester, etc.) may be used.

  Although it does not specifically limit as polycarboxylic acid more than trivalence, For example, polycarboxylic acid of acid value 150-1250 mgKOH / g, specifically, C9-C20 aromatic polycarboxylic acid (trimellitic acid, pyromellitic acid) Merit acid, etc.); vinyl polymer of unsaturated carboxylic acid (styrene / maleic acid copolymer, styrene / acrylic acid copolymer, α-olefin / maleic acid copolymer, styrene / fumaric acid copolymer, etc.), etc. Is mentioned. Among these, preferred are aromatic polycarboxylic acids having 9 to 20 carbon atoms, and particularly preferred are trimellitic acid and pyromellitic acid. In addition, as a polycarboxylic acid more than trivalence, you may use the acid anhydride of the above-mentioned thing, or a lower (C1-C4) alkylester (Methyl ester, ethyl ester, isopropyl ester, etc.).

  Moreover, hydroxycarboxylic acid can also be copolymerized with a diol, a polyol, dicarboxylic acid, and polycarboxylic acid. Although it does not specifically limit as hydroxycarboxylic acid, For example, a hydroxy stearic acid, hydrogenated castor oil fatty acid, etc. are mentioned.

In the present invention, it is preferable that at least a part of the polyester resin is modified with polyepoxide. Examples thereof include a polyester resin that is a polycondensate of polyol and polycarboxylic acid, and a modified polyester resin that is obtained by further reacting a polyepoxide or the like with a polyester resin that is a polycondensate of polyol and polycarboxylic acid. The polyester resin and modified polyester resin may be used alone or in combination of two or more.
Although it does not specifically limit as a polyol, For example, diol, a trihydric or more polyol, etc. are mentioned. Although it does not specifically limit as polycarboxylic acid, For example, dicarboxylic acid, trivalent or more polycarboxylic acid, etc. are mentioned.

  The polyepoxide is not particularly limited. For example, polyglycidyl ether [ethylene glycol diglycidyl ether, tetramethylene glycol diglycidyl ether, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, glycerin triglycidyl ether, bentaerythritol tetraglycidyl ether, Phenol novolac (average polymerization degree 3 to 60) glycidyl etherified product, etc.]; diene oxide (pentadiene dioxide, hexadiene dioxide, etc.) and the like. Among these, polyglycidyl ether is preferable, and ethylene glycol diglycidyl ether and bisphenol A diglycidyl ether are more preferable.

  The number of epoxy groups per molecule of the polyepoxide is preferably 2 to 8, more preferably 2 to 6, and particularly preferably 2 to 4. Although it does not specifically limit as an epoxy equivalent of polyepoxide, Preferably it is 50-500. The lower limit is more preferably 70, particularly preferably 80, and the upper limit is more preferably 300, particularly preferably 200. When the number of epoxy groups and / or the epoxy equivalent is within the above range, both developability and fixability are improved. More preferably, the above-mentioned ranges of the number of epoxy groups per molecule and the range of epoxy equivalents are satisfied at the same time.

  The ratio of the polyol and the polycarboxylic acid is preferably 2/1 to 1/2, more preferably 1.5 / 1 to 1 as an equivalent ratio [OH] / [COOH] of the hydroxyl group [OH] and the carboxyl group [COOH]. 1 / 1.3, particularly preferably 1.3 / 1 to 1 / 1.2. The types of polyol and polycarboxylic acid to be used are preferably selected in consideration of molecular weight adjustment so that the glass transition point of the polyester toner binder to be finally adjusted is 40 to 90 ° C.

Although it does not specifically limit as a specific example of linear polyester resin (Y) using the said diol and dicarboxylic acid, For example, the following (1)-(3) etc. are mentioned.
(1) Bisphenol A · PO2 molar adduct / terephthalic acid polycondensate.
(2) Bisphenol A · EO 4 mol adduct / bisphenol A · PO 2 mol adduct / terephthalic acid polycondensate.
(3) Bisphenol A · PO2 mol adduct / bisphenol A · PO3 mol adduct / terephthalic acid / isophthalic acid / maleic anhydride polycondensate.

Although it does not specifically limit as a specific example of the said non-linear polyester resin (X), For example, the following (4)-(10) etc. are mentioned.
(4) Bisphenol A · EO 2 mol adduct / bisphenol A · PO 3 mol adduct / terephthalic acid / phthalic anhydride / trimellitic anhydride polycondensate.
(5) Bisphenol A · PO2 mol adduct / bisphenol A · PO3 mol adduct / bisphenol A · EO2 mol adduct / phenol novolac PO5 mol adduct / terephthalic acid / maleic anhydride / dimethyl terephthalic acid ester / trimellitic anhydride Acid polycondensate.
(6) Bisphenol A · EO 2 mol adduct / bisphenol A · PO 2 mol adduct / terephthalic acid / trimellitic anhydride polycondensate.
(7) Bisphenol A · EO 2 mol adduct / bisphenol A · PO 2 mol adduct / terephthalic acid / maleic anhydride / trimellitic anhydride polycondensate.
(8) Bisphenol A · PO 2 mol adduct / bisphenol A · PO 3 mol adduct / terephthalic acid / isophthalic acid / maleic anhydride / trimellitic anhydride polycondensate.
(9) Bisphenol A · PO 2 mol adduct / bisphenol A · PO 3 mol adduct / phenol novolak EO adduct / isophthalic acid / trimellitic anhydride polycondensate.
(10)) Bisphenol A · EO 2 mol adduct / bisphenol A · PO 2 mol adduct / PO5 mol adduct of phenol novolac / terephthalic acid / fumaric acid / trimellitic anhydride polycondensate.

  Although it does not specifically limit as a specific example of the modified polyester resin which made the polyepoxide react with the non-linear polyester resin using polyol and / or polycarboxylic acid with diol and dicarboxylic acid, For example, the following (11)- (20).

(11) Modification obtained by reacting tetramethylene glycol diglycidyl ether with a polycondensate of bisphenol A · PO 2 mol adduct / bisphenol A · EO 2 mol adduct / phenol novolak PO5 mol adduct / terephthalic acid / dodecenyl succinic anhydride polyester.
(12) Bisphenol A · PO2 mol adduct / bisphenol A · PO3 mol adduct / bisphenol A · EO2 mol adduct / PO5 mol adduct of phenol novolac / terephthalic acid / dodecenyl succinic anhydride heavy bond ethylene glycol diglycidyl ether Modified polyester obtained by reacting
(13) Reaction of bisphenol A diglycidyl ether with bisphenol A · PO 2 mol adduct / bisphenol A · PO 3 mol adduct / phenol novolak EO adduct / isophthalic acid / maleic anhydride / trimellitic anhydride polycondensate The resulting modified polyester.
(14) Bisphenol A / PO 2 mol adduct / Bisphenol A / PO 3 mol adduct / Bisphenol A / EO 2 mol adduct / EO adduct of phenol novolac / Terephthalic acid / Isophthalic acid / Trimellitic anhydride polycondensate A modified polyester obtained by reacting diglycidyl ether.
(15) Bisphenol A / PO 2 mol adduct / bisphenol A / PO 3 mol adduct / bisphenol A / EO 2 mol adduct / phenol novolak PO5 mol adduct / terephthalic acid / isophthalic acid / maleic anhydride / trimellitic anhydride heavy A modified polyester obtained by reacting a condensate with bisphenol A diglycidyl ether.
(16) A modified polyester obtained by reacting ethylene glycol diglycidyl ether with bisphenol A · PO 3 mol adduct / phenol novolac PO 5 mol adduct / terephthalic acid / fumaric acid / trimellitic anhydride polycondensate.
(17) A modified polyester obtained by reacting tetramethylene glycol diglycidyl ether with a polycondensate of bisphenol A · PO 2 mol adduct / phenol novolac PO 5 mol adduct / terephthalic acid / dodecenyl succinic anhydride / trimellitic anhydride.
(18) Modified polyester obtained by reacting bisphenol A · PO2 molar adduct / bisphenol A · EO2 molar adduct / phenol novolak EO adduct / terephthalic acid / trimellitic anhydride polycondensate with ethylene glycol diglycidyl ether .
(19) Modification obtained by reacting bisphenol A diglycidyl ether with bisphenol A · PO2 mol adduct / bisphenol A · PO3 mol adduct / PO5 mol adduct of phenol novolac / terephthalic acid / trimellitic anhydride polycondensate polyester.
(20) A modified polyester obtained by reacting a phenol novolac glycidyl etherified product with a bisphenol A · PO 2 mol adduct / bisphenol A · EO 2 mol adduct / terephthalic acid / trimellitic anhydride polycondensate.

Binders (toner binders) for toners are required to have different physical properties for full color and monochrome use, and therefore the design of polyester resin differs depending on the application.
That is, since a high-gloss image is required for full color use, it is necessary to use a low-viscosity binder. However, for monochrome use, gloss is not particularly necessary, and hot offset properties are important, so it is necessary to use a highly elastic binder. .

  Non-linear polyesters, modified polyesters, and mixtures thereof are preferred for obtaining high hot offset resistance useful for monochrome copying machines and the like. In this case, since it is preferable that it is highly elastic, as this polyester resin, what uses both polyol and polycarboxylic acid is especially preferable. The ratio of the polyol and the polycarboxylic acid is such that the sum of the number of moles of the polyol and the polycarboxylic acid is preferably 0.1 to 40 mol% with respect to the total number of moles of the diol, polyol, dicarboxylic acid, and polycarboxylic acid. Preferably it is 0.5-25 mol%, especially 1-20 mol%.

  In the case of monochrome polyester resin, from the viewpoint of hot offset resistance, the temperature (TE) at which the storage elastic modulus (G ′) of the polyester resin is 6000 Pa is preferably 130 to 230 ° C., more preferably 140 to 230 ° C., It is 150-230 degreeC especially.

  TE is, for example, a block after melt-kneading a resin for 30 minutes at 130 ° C. and 70 rpm using a lab plast mill, using a commercially available dynamic viscoelasticity measuring device while changing the resin temperature (G It is calculated by measuring ').

  From the viewpoint of low-temperature fixability and heat-resistant storage stability, the temperature (TE) at which the complex viscosity (η *) of the monochrome polyester resin becomes 1000 Pa · s is preferably 80 to 140 ° C., more preferably 90 to 135 ° C. In particular, it is 105 to 130 ° C.

  The monochrome polyester resin preferably contains 5 to 70% of tetrahydrofuran (THF) insoluble matter, more preferably 10 to 60%, particularly 15 to 50%. When the THF-insoluble content is 5% or more, the hot offset resistance is good, and when it is 70% or less, good low-temperature fixability is obtained.

The above-mentioned THF-insoluble matter and THF-soluble matter can be obtained by the following method.
About 0.5 g of a sample is precisely weighed into a 200 ml stoppered Meyer flask, 50 ml of THF is added, and the mixture is stirred and refluxed for 3 hours. After cooling, the insoluble matter is filtered off with a glass filter. The value (%) of THF-insoluble matter is calculated from the weight ratio of the resin content on the glass filter after vacuum drying at 80 ° C. for 3 hours and the weight of the sample.
Note that this filtrate is used as a THF soluble component for the molecular weight measurement described later.

  The peak top molecular weight of the polyester resin is preferably 1000 to 30000, more preferably 1500 to 25000, and particularly 1800 to 20000 for both monochrome and full color applications. When the peak top molecular weight is 1000 or more, the heat-resistant storage stability and the powder flowability are good, and when it is 30000 or less, the pulverization property of the toner is improved and the productivity is good.

In the above and the following, the peak top molecular weight and number average molecular weight of the polyester resin are measured under the following conditions using GPC for the THF-soluble matter.
Apparatus: Tosoh HLC-8120
Column: TSKgelGMHXL (2)
TSKgelMultiporeHXL-M (1 pc.)
Measurement temperature: 40 ° C
Sample solution: 0.25% THF solution Injection volume: 100 μl
Detector: Refractive index detector Reference material: Polystyrene The molecular weight showing the maximum peak height on the chromatogram obtained under the above conditions is called the peak top molecular weight.

The Tg of the polyester resin is preferably 40 to 90 ° C., more preferably 50 to 80 ° C., particularly 55 to 75 ° C. for both monochrome and full color applications. When the Tg is in the range of 40 ° C. to 90 ° C., the heat resistant storage stability and the low temperature fixability become better.
In the above and below, the Tg of the polyester resin is measured by a method (DSC method) defined in ASTM D3418-82 using DSC20 and SSC / 580 manufactured by Seiko Denshi Kogyo Co., Ltd.

  The production method of the linear polyester resin is not particularly limited. For example, the polyester resin is prepared by heating diol, dicarboxylic acid and polycondensation catalyst to 180 ° C. to 260 ° C. and dehydrating and condensing under normal pressure and / or reduced pressure conditions. And the like.

  Although it does not specifically limit as a manufacturing method of a non-linear polyester resin, For example, diol, dicarboxylic acid, a trihydric or more polyol, and a polycondensation catalyst are heated at 180 to 260 degreeC, and it spin-dry | dehydrates on normal pressure and / or pressure reduction conditions. Examples thereof include a method in which after condensation, a tricarboxylic or higher polycarboxylic acid is further reacted to obtain a polyester resin. A tricarboxylic or higher polycarboxylic acid can be reacted simultaneously with a diol, a dicarboxylic acid and a trivalent or higher polyol.

Although it does not specifically limit as a manufacturing method of modified polyester resin, For example, the method etc. which obtain modified polyester resin by adding polyepoxide to non-linear polyester resin, and performing molecular extension reaction of polyester at 180 to 260 degreeC are mentioned. .
In the toner binder (binder resin) used in the present invention, two or more polyester resins can be used in combination.

  Next, the black iron oxide compound according to the present invention includes, for example, a magnetite particle powder whose particle surface is coated with a titanium compound, a mixed powder of magnetite particle powder and a titanium compound, or a hematite particle powder whose particle surface is coated with a titanium compound. Each of the reduced powders obtained by reduction is obtained by a method of heating and firing at a temperature of 700 ° C. or higher in a non-oxidizing atmosphere and then pulverizing. When magnetite particle powder whose particle surface is coated with a titanium compound is used as a raw material, it is a preferable method from the viewpoint of easily obtaining particles having a small magnetization value and non-magnetism.

The magnetite particle powder and the hematite particle powder may be particles in any form such as granular, spherical, and needle-like, and particles having a size of about 0.03 to 1.5 μm can be used. There is a correlation between the size of the raw material particles and the size of the product particles. When small raw material particles are used, small product particles tend to be obtained. When large raw material particles are used, large product particles tend to be obtained. It is in.
As the structure of the black oxide compound, a polycrystalline particle powder containing a Fe ₂ O ₃ —FeTiO ₃ solid solution is preferable because it is black and weak in magnetism.

As the titanium compound, any of hydrated oxide, hydroxide and oxide of titanium can be used. When mixing with magnetite particle powder, it is preferable to use a water-soluble titanium compound. The amount of the titanium compound is preferably in the range of 10 to 45 wt. When the amount is less than 10% by weight, the magnetization value of the obtained black pigment particle powder is increased, the developing ability of the toner is lowered, and the image density is lowered. If it exceeds 45% by weight, non-magnetic black pigment particle powder can be obtained, but since the amount of TiO ₂ produced increases, the L value (brightness) increases and the toner coloring power decreases.
The ratio with respect to Fe atoms in terms of Ti atoms can be determined from the ratio of the obtained main peak using a fluorescent X-ray analyzer.

  That is, in the black iron oxide compound composed of a titanium component and an iron component used as the colorant of the present invention, the content of the titanium component is a value measured with a wavelength dispersive X-ray fluorescence apparatus with respect to Fe atoms in terms of Ti atoms. As mentioned above, 10 to 45% by weight is preferable from the viewpoint of dispersibility.

  The present invention relates to a polycondensation polyester resin formed in the presence of a titanium-containing catalyst as a binder resin, and as a colorant, a titanium component measured with a wavelength dispersive fluorescent X-ray apparatus with respect to Fe atoms in terms of Ti atoms. By using a black iron oxide compound containing 10 to 45% by weight, the disadvantages of the prior art are improved. That is, in the present invention, even when a black iron oxide compound having a particle size larger than that of carbon black is used, the dispersibility of the black iron oxide compound is good. And does not adversely affect heat storage stability.

  The mechanism by which the dispersibility of the black iron oxide compound is improved in the present invention is not clear, but the polycondensation polyester resin formed in the presence of the titanium-containing catalyst and the titanium component are converted into Fe atoms in terms of Ti atoms. By using the black iron oxide compound contained in an amount of 10 to 45% by weight, it is considered that the affinity of the black iron oxide compound for the resin is increased and the dispersibility is improved.

  The content of the black iron oxide compound contained in the toner is 15 to 40 parts by weight, preferably 20 to 30 parts by weight. When the amount is less than 15 parts by weight, the coloring power of the toner is insufficient, and the toner has a reddish color. Further, the fixing temperature is not sufficiently lowered. In the case of 40 parts by weight or more, the specific gravity of the toner becomes too large and the developing ability is lowered.

In the present invention, the saturation magnetization σs of the toner measured with a magnetic field of 398 Am ² / Kg is preferably 0.08 to 5.5 emu / g, more preferably 0.1 to 5.0 emu / g. . When the saturation magnetization of the toner is 5.5 emu / g or more, the holding force with the toner carrier having a built-in magnet such as a magnetic sleeve or a magnetic brush becomes strong, and the developability to the photoreceptor deteriorates. When it is less than 0.08 emu / g, the holding force with the toner carrier is weakened, and the toner scattering and the soiling are worsened.

  The saturation magnetization of the toner was measured by using a magnetometer BHU-60 manufactured by Riken Denshi Co., Ltd., and sweeping the magnetic field to 5 KOe in a toner filled in a cell having an inner diameter of 7 mmφ and a height of 10 mm. It is obtained from a history curve.

In the present invention, the wax component preferably contains at least one selected from carnauba wax, rice wax, and ester wax.
Carnauba wax is a natural wax obtained from the leaves of carnauba palm, but a low acid value type from which free fatty acids are eliminated is particularly preferable because it can be uniformly dispersed in the binder resin. Rice wax is a natural wax obtained by refining crude wax produced in a dewaxing or wintering process when refining rice bran oil extracted from rice bran. Ester wax is synthesized by ester reaction from monofunctional linear fatty acid and monofunctional linear alcohol.

  These wax components are used alone or in combination as described above. The added amount of the wax component is 0.5 to 10 parts by weight, more preferably 2 to 8 parts by weight. In the present invention, other wax components of carnauba wax, rice wax, and synthetic ester wax can be used. For example, polyolefin wax such as polypropylene wax and polyethylene wax.

Further, the toner of the present invention can use other resins than the polyester resin.
As other resins used in the present invention, conventionally known resins are used. For example, styrene, poly-α-still styrene, styrene-chlorostyrene copolymer, styrene-propylene copolymer, styrene-butadiene copolymer, styrene-vinyl chloride copolymer, styrene-vinyl acetate copolymer, styrene -Styrene such as maleic acid copolymer, styrene-acrylic acid ester copolymer, styrene-methacrylic acid ester copolymer, styrene-α-chloroacrylic acid methyl copolymer, styrene-acrylonitrile-acrylic acid ester copolymer Resin (monopolymer or copolymer containing styrene or styrene-substituted product), epoxy resin, vinyl chloride resin, rosin-modified maleic acid resin, phenol resin, polyethylene resin, polypropylene resin, petroleum resin, polyurethane resin, ketone resin, Ethylene-ethyl acrylate copolymer Examples thereof include coalescence, xylene resin, and polyvinyl butyrate resin. Moreover, the manufacturing method of these resin is not specifically limited, either bulk polymerization, solution polymerization, emulsion polymerization, and suspension polymerization can be used.

  In the toner of the present invention, polarity control can be blended in order to control polarity. Examples of the polarity control agent in this case include nigrosine dyes, quaternary ammonium salts, amino group-containing polymers, metal-containing azo dyes, salicylic acid complex compounds, and phenol compounds.

  The toner production method of the present invention may be a conventionally known method, in which a resin component, a colorant, a wax component, and other cases, a charge control agent or the like are mixed using a mixer or the like, and kneaded such as a heat roll or an extruder. After kneading using a machine, the mixture is cooled and solidified, pulverized by pulverization such as a jet mill, and then classified.

  Other additives may be added to the toner as necessary. Examples of the additive include silica, aluminum oxides, and titanium oxides. When the main purpose is to impart high fluidity, the average primary particle diameter of the hydrophobized silica or rutile type fine particle titanium oxide is suitably 0.001 to 1 μm, preferably 0.005 to 0.1 μm. In particular, organosilane surface-treated silica or titania is preferable, and is usually used in a proportion of 0.1 to 5% by weight, preferably 0.2 to 2% by weight.

  Further, for example, when the toner of the present invention is used as a two-component dry toner (two-component toner), the carrier used by mixing is mainly composed of glass, iron, ferrite, nickel, zircon, silica or the like. , A powder having a particle size of about 30 to 1000 μm, or a powder coated with a styrene-acrylic resin, a silicon resin, a polyamide resin, a polyvinylidene fluoride resin, etc. using the powder as a core material can be used. is there.

  In addition, the toner of the present invention can be used by being filled in a toner cartridge that is detachably attached to a so-called image forming apparatus, which is mounted on various electrophotographic apparatuses. By using the toner cartridge in such a form, it is possible to perform low-temperature fixing simply by replacing the toner cartridge filled with the toner of the present invention, and to realize stable image formation with excellent fixing property and heat-resistant storage stability. . Further, if the toner cartridge is used, the image forming apparatus can be made compact, and simple and steady maintenance work can be performed.

  Further, the toner of the present invention forms an image in various electrophotography as described above, that is, forms an electrostatic latent image formed on an image carrier with toner, and transfers this development onto a transfer target. It is configured to be used in an image forming method for fixing. In particular, since it can be fixed at low temperature and has suitable magnetic properties, it can be applied to a method that requires fixing with low energy, and moreover, The fixing property and heat-resistant storage stability are excellent, and a stable image can be formed.

EXAMPLES The present invention will be further described below with reference to examples, but the present invention is not limited thereto.
Hereinafter, parts are parts by weight. In addition, the softening point described below was obtained by measurement under the following conditions (the temperature was raised at a constant speed using a flow tester under the following conditions, and the temperature at which the outflow amount was halved was defined as the softening point. .)

<Measurement method of softening point>
Apparatus: Flow tester CFT-500D (manufactured by Shimadzu Corporation)
Load: 20 kgf / cm ²
Die: 1mmφ-1mm
Temperature increase rate: 6 ° C / min
Sample amount: 1.0 g

First, various linear polyester resins, non-linear polyester resins, and modified polyester resins used in the toner formulations of Examples and Comparative Examples were synthesized.
[Synthesis of linear polyester resin]
Linear polyester (A1):
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 430 parts of bisphenol A / PO2 molar adduct, 300 parts of bisphenol A / PO3 molar adduct, 257 parts of terephthalic acid, 65 parts of isophthalic acid, maleic anhydride 10 2 parts of titanyl potassium oxalate as a polycondensation catalyst and a polycondensation catalyst were added and reacted at 220 ° C. for 10 hours while distilling off the water produced in a nitrogen stream. Subsequently, it was made to react under reduced pressure of 5-20 mmHg, and when the acid value became 5, it took out, cooled to room temperature, and pulverized, and linear polyester resin (A1) was obtained. A1 did not contain THF-insoluble matter, and had an acid value of 8, a hydroxyl value of 12, a Tg of 59 ° C., a number average molecular weight of 6890, and a peak top molecular weight of 19,800.

Linear polyester (A2):
Except that the polycondensation catalyst was replaced with 2 parts of titanium terephthalate, the reaction was carried out in the same manner as in A1, cooled to room temperature, and then pulverized to obtain a linear polyester resin (A2).

[Synthesis of linear polyester tree for comparison]
Comparative linear polyester (Ac1):
The reaction was carried out in the same manner as in A1 except that the polycondensation catalyst was replaced with 2 parts of titanium tetraglycoxide. Since the reaction rate was slow, a linear polyester resin for comparison (Ac1) was obtained by reacting under normal pressure for 16 hours and under reduced pressure for 8 hours. Ac1 is a purple-brown resin that does not contain THF insolubles, has an acid value of 5, a hydroxyl value of 11, a Tg of 58 ° C., a number average molecular weight of 6500, and a peak top molecular weight of 20200. .

Linear polyester for comparison: (No polycondensate can be obtained)
The reaction was carried out in the same manner as in A1 except that the polycondensation catalyst was replaced with 2 parts of titanium tetrabutoxide. Since the reaction stopped due to catalyst deactivation and the generated water could not be distilled off, 1.5 parts of titanium tetrabutoxide was added five times during the reaction. The desired polycondensate could not be obtained. Further, the reaction product was strongly colored purple-brown.

[Synthesis of non-linear polyester resin]
Non-linear polyester (B1):
In a reaction vessel equipped with a condenser, a stirrer, and a nitrogen introduction tank, 350 parts of bisphenol A / EO 2 mol adduct, 326 parts of bisphenol A / PO 3 mol adduct, 278 parts of terephthalic acid, 40 parts of phthalic anhydride and polycondensation catalyst Then, 1.5 parts of potassium titanyl oxalate was added and reacted at 230 ° C. for 10 hours while distilling off the water produced in a nitrogen stream. Next, the reaction is carried out under a reduced pressure of 5 to 20 mmHg, and when the acid value becomes 2 or less, it is cooled to 180 ° C., 62 parts of trimellitic anhydride is added, taken out after reaction for 2 hours under normal pressure sealing, and cooled to room temperature. Thereafter, the mixture was pulverized to obtain a non-linear polyester resin (B1). B1 did not contain THF-insoluble matter, and its acid value was 36, hydroxyl value was 17, Tg was 69 ° C., number average molecular weight was 3810, and peak top molecular weight was 11400.

Non-linear polyester (B2):
A linear polyester resin (B2) was obtained by reacting in the same manner as in B1 except that the polycondensation catalyst was replaced with 1.5 parts of titanium terephthalate, cooling to room temperature, and pulverizing. B2 contained no THF-insoluble matter, and had an acid value of 33, a hydroxyl value of 15, a Tg of 69 ° C., a number average molecular weight of 4130, and a peak top molecular weight of 11830.

Non-linear polyester (B3):
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 132 parts of bisphenol A / PO 2 mol adduct, 371 parts of bisphenol A / PO 3 mol adduct, 20 parts of bisphenol A / EO 2 mol adduct, phenol novolac (average) PO5 mol adduct with a polymerization degree of about 5) 125 parts, 201 parts of terephthalic acid, 25 parts of maleic anhydride, 35 parts of dimethyl terephthalic acid ester and 1.5 parts of potassium titanyl oxalate as a polycondensation catalyst It was made to react for 10 hours, distilling off the water produced | generated under air flow. Next, the reaction is carried out under a reduced pressure of 5 to 20 mmHg. When the acid value becomes 2 or less, the mixture is cooled to 180 ° C., added with 65 parts of trimellitic anhydride, taken out after reaction for 2 hours under normal pressure sealing, and cooled to room temperature. Thereafter, it was pulverized to obtain a non-linear polyester resin (B3). B3 had a softening point of 142 ° C., an acid value of 30, a hydroxyl value of 17, a Tg of 57 ° C., a number average molecular weight of 1380, a peak top molecular weight of 4150, and a THF insoluble content of 26%.

Non-linear polyester (B4):
In a reaction vessel equipped with a cooling tube, a pulverizer and a nitrogen introduction tube, 410 parts of bisphenol A / PO2 molar adduct, 270 parts of bisphenol A / PO3 molar adduct, 110 parts of terephthalic acid, 125 parts of isophthalic acid, maleic anhydride 15 parts and 2 parts of potassium titanyl oxalate as a polycondensation catalyst were added and reacted at 220 ° C. for 10 hours while distilling off the water produced in a nitrogen stream. Next, the reaction is carried out under a reduced pressure of 5 to 20 mmHg, and when the acid value becomes 2 or less, it is cooled to 180 ° C., 25 parts of trimellitic anhydride is added, taken out after reaction for 2 hours under normal pressure sealing, and cooled to room temperature. After pulverization, a non-linear polyester resin (B4) was obtained. B4 contained no THF-insoluble matter, and had an acid value of 18, a hydroxyl value of 35, a Tg of 61 ° C., a number average molecular weight of 1990, and a peak top molecular weight of 5310.

Non-linear polyester (B5):
A non-linear polyester resin (B5) was obtained by reacting in the same manner as in B4 except that the polycondensation catalyst was replaced with 2 parts of titanium terephthalate, cooling to room temperature, and pulverizing. B5 contained no THF-insoluble matter, and had an acid value of 17, a hydroxyl value of 35, a Tg of 61 ° C., a number average molecular weight of 2110, and a peak top molecular weight of 5450.

[Synthesis of non-linear polyester resin for comparison]
Nonlinear polyester for comparison (Bc1)
The reaction was carried out in the same manner as in B1 except that the polycondensation catalyst was replaced with 2 parts of titanium tetraglycoxide. Since the reaction was stopped in the middle due to catalyst deactivation, there was a problem that the produced water could not be distilled. Therefore, 1.5 parts of titanium tetraglycoxide was added four times during the reaction, and a non-linear polyester resin for comparison was used. (Bc1) was obtained. Bc1 is a purple-brown resin that does not contain THF insolubles, has an acid value of 33, a hydroxyl value of 16, Tg of 68 ° C., a number average molecular weight of 3680, and a peak top molecular weight of 11800. It was.

[Synthesis of modified polyester resin]
Modified polyester (C1):
In a reaction vessel equipped with a condenser, a stirrer, and a nitrogen introduction tube, 549 parts of bisphenol A / PO 2 mol adduct, 20 parts of bisphenol A / PO 3 mol adduct, 133 parts of bisphenol A ethylene oxide 2 mol adduct, phenol novolac ( 10 parts of EO 5 mol adduct with an average degree of polymerization of 5), 252 parts of terephthalic acid, 19 parts of isophthalic acid, 10 parts of trimellitic anhydride and 2 parts of titanium acetylacetonate as a polycondensation catalyst. The reaction was carried out for 10 hours while distilling off the water produced. Subsequently, it was made to react under reduced pressure of 5-20 mmHg, and it was made to react until an acid value became 2 or less. Next, 50 parts of trimellitic anhydride was added and reacted under normal pressure for 1 hour, and then reacted under reduced pressure of 20 to 40 mmHg. When the softening point reached 105 ° C., 20 parts of bisphenol A diglycidyl ether was added, After taking out at a softening point of 150 ° C., cooling to room temperature and pulverizing, a modified polyester resin (C1) was obtained. The softening point of C1 was 150 ° C., the acid value was 53, the hydroxyl value was 17, Tg was 74 ° C., the number average molecular weight was 1800, the peak top molecular weight was 6700, and the THF insoluble content was 33%.

Modified polyester (C2):
A modified polyester resin (C2) was obtained by reacting in the same manner as in C1 except that the polycondensation catalyst was replaced by 2 parts of potassium titanyl maleate, taking out at a softening point of 150 ° C., cooling to room temperature, and pulverizing. The softening point of C2 was 150 ° C., the acid value was 51, the hydroxyl value was 16, Tg was 74 ° C., the number average molecular weight was 1940, the peak top molecular weight was 6630, and the THF insoluble content was 35%.

Modified polyester (C3)
In a reaction vessel equipped with a condenser, a stirrer and a nitrogen inlet, 317 parts of bisphenol A / EO 2 mol adduct, 57 parts of bisphenol A · PO 2 mol adduct, 298 parts of bisphenol A · PO 3 mol adduct, phenol novolac (average) PO5 mol adduct with a polymerization degree of about 5) 75 parts, 30 parts of isophthalic acid, 157 parts of terephthalic acid, 27 parts of maleic anhydride and 1.5 parts of potassium titanyl oxalate as a polycondensation catalyst, at 230 ° C. under nitrogen stream The reaction was carried out for 10 hours while distilling off the water produced. Next, the reaction was carried out under reduced pressure of 5 to 20 mmHg. When the acid value became 2 or less, the mixture was cooled to 180 ° C., and then 68 parts of trimellitic anhydride was added and reacted at normal pressure for 1 hour. When the reaction was carried out under reduced pressure of 40 mmHg and the softening point reached 120 ° C., 25 parts of bisphenol A diglycidyl ether was added, taken out at a softening point of 155 ° C., cooled to room temperature, and crushed to obtain a modified polyester resin (C3). It was. C3 had a softening point of 155 ° C., an acid value of 10, a hydroxyl value of 29, a Tg of 58 ° C., a number average molecular weight of 3120, a peak top molecular weight of 6130, and a THF insoluble content of 36%.

Modified polyester (C4):
A modified polyester resin (C4) was obtained by reacting in the same manner as in C3 except that the condensation catalyst was replaced with titanium terephthalate 1.5, cooling to room temperature, and pulverizing. C4 had a softening point of 155 ° C., an acid value of 9, a hydroxyl value of 28, a Tg of 59 ° C., a number average molecular weight of 3050, a peak top molecular weight of 6010, and a THF insoluble content of 38%.

(Example 1)
Each component shown in the following toner formulation 1 is kneaded using a biaxial extruder, pulverized and classified to a weight average particle size of 7.5 μm, and then silica fine powder (R-972: client using a Henschel mixer). (Made in Japan) 0.75 part by weight was mixed to obtain the toner of Example 1.

(Toner Formula 1)
Linear polyester resin (A1) 10 parts by weight Non-linear polyester resin (B1) 40 parts by weight Ti-Fe colorant 45 parts by weight (Ti content: 40% by weight, average primary particle size 0.33 μm)
Charge control agent (Spiron Black TR-H: Hodogaya Chemical) 2 parts by weight Low molecular weight polypropylene 3 parts by weight (weight average molecular weight: 6000)

The obtained toner had a saturation magnetization σs of 5.5 emu / g. A two-component toner (developer) having a toner concentration of 3.5 parts by weight was prepared using this toner and a carrier in which spherical ferrite particles having an average particle diameter of 80 μm were coated with a silicone resin.
Using the adjusted developer, the toner fixability and heat-resistant storage stability were evaluated. The results are shown in Table 1 below.

<Fixability evaluation method>
A fixing device (surface pressure: 0.7 × 10 ⁵ Pa.s) having the configuration shown in FIG. A fixing tape (manufactured by 3M) is applied to the image after fixing (toner adhesion amount: 0.85 ± 0.05 mg / cm ² ), a constant pressure (2 Kg) is applied, and then slowly peeled off. The image density before and after that is measured with a Macbeth densitometer, and the fixing rate is calculated by the following equation.
Fixing rate (%) = (image density after tape peeling / original image density) × 100
(Original image density: Image density before tape attachment)
The temperature of the fixing roller is lowered stepwise, and the temperature at which the fixing rate shown by the above formula becomes 80% or less is defined as the fixing temperature.

<Method for evaluating heat-resistant storage stability>
A 50 cc glass container is filled with toner and left in a constant temperature bath at 55 ° C. for 24 hours. The toner is cooled to room temperature, and the penetration is measured by a penetration test (JIS K2235-1991). The larger this value, the better the heat resistant storage stability.

(Example 2)
Each component shown in the following toner formulation 2 is kneaded using a biaxial extruder, pulverized and classified to a weight average particle size of 6.5 μm, and then silica fine powder (R-972: client using a Henschel mixer). 1.00 parts by weight of Japan) was mixed to obtain the toner of Example 2.

(Toner Formula 2)
Linear polyester resin (A2) 35 parts by weight Non-linear polyester resin (B2) 55 parts by weight Ti-Fe colorant 10 parts by weight (Ti content: 45% by weight, average primary particle size 0.25 μm)
Charge control agent (Spiron Black TR-H: Hodogaya Chemical) 2 parts by weight Low molecular weight polypropylene 3 parts by weight (weight average molecular weight: 6000)

  The toner obtained had a saturation magnetization σs of 0.08 emu / g. The toner of Example 2 was prepared as a developer under the same conditions as in Example 1, and the toner fixability and heat-resistant storage stability were evaluated in the same manner as in Example 1. The results are shown in Table 1 below.

(Example 3)
Each component shown in the following toner formulation 3 is kneaded using a biaxial extruder, pulverized and classified to a weight average particle size of 5.5 μm, and then silica fine powder (R-972: client using a Henschel mixer). 1.50 parts by weight of Japan) was mixed to obtain a toner of Example 3.

(Toner Formula 3)
Linear polyester resin (B3) 49 parts by weight Ti-Fe colorant 45 parts by weight (Ti content: 35% by weight, average primary particle size 0.45 μm)
Charge control agent (Spiron Black TR-H: Hodogaya Chemical) 2 parts by weight Low molecular weight polypropylene 4 parts by weight (weight average molecular weight: 6000)

  The saturation magnetization σs of the toner was 5.3 emu / g. The toner of Example 3 was prepared as a developer under the same conditions as in Example 1, and the toner fixability and heat-resistant storage stability were evaluated in the same manner as in Example 1. The results are shown in Table 1 below.

(Comparative Example 1)
Each component shown in the toner formulation 4 below is kneaded using a biaxial extruder, pulverized and classified to a weight average particle size of 6.5 μm, and then silica fine powder (R-972: client using a Henschel mixer). (Japan) 1.00 parts by weight were mixed to obtain a toner of Comparative Example 1.

(Toner Formula 4)
Linear polyester resin (Ac1) 35 parts by weight Non-linear polyester resin (Bc1) 55 parts by weight Ti-Fe colorant 10 parts by weight (Ti content: 45% by weight, average primary particle size 0.25 μm)
Charge control agent (Spiron Black TR-H: Hodogaya Chemical) 2 parts by weight Low molecular weight polypropylene 3 parts by weight
(Weight average molecular weight: 6000)

  The saturation magnetization σs of the toner was 0.09 emu / g. The toner of Comparative Example 1 was prepared as a developer under the same conditions as in Example 1, and the toner fixability and heat resistant storage stability were evaluated in the same manner as in Example 1. The results are shown in Table 1 below.

(Comparative Example 2)
Each component shown in the following toner formulation 5 is kneaded using a biaxial extruder, pulverized and classified to a weight average particle size of 6.5 μm, and then silica fine powder (R-972: client using a Henschel mixer). (Japan) 1.00 parts by weight were mixed to obtain a toner of Comparative Example 2.

(Toner Formula 5)
Linear polyester resin (Ac2) 35 parts by weight Non-linear polyester resin (Bc2) 55 parts by weight Ti-Fe colorant 10 parts by weight (Ti content: 45% by weight, average primary particle size 0.25 μm)
Charge control agent (Spiron Black TR-H: Hodogaya Chemical) 2 parts by weight Low molecular weight polypropylene 3 parts by weight (weight average molecular weight: 6000)

  The saturation magnetization σs of the toner was 0.08 emu / g. The toner of Comparative Example 2 was prepared as a developer under the same conditions as in Example 1, and the toner fixability and heat resistant storage stability were evaluated in the same manner as in Example 1. The results are shown in Table 1 below.

Example 4
Each component shown in the toner formulation 6 below is kneaded using a biaxial extruder, pulverized and classified to a weight average particle size of 6.5 μm, and then silica fine powder (R-972: client using a Henschel mixer). The toner of Example 4 was obtained by mixing 1.25 parts by weight of Japan.

(Toner Formula 6)
Modified polyester resin (C1) 49 parts by weight Ti-Fe colorant 43 parts by weight (Ti content: 20% by weight, average primary particle size 0.25 μm)
Charge control agent (Spiron Black TR-H: Hodogaya Chemical) 2 parts by weight Low molecular weight polypropylene 4 parts by weight
(Weight average molecular weight: 6000)

  The saturation magnetization σs of the toner was 5.1 emu / g. The toner of Example 4 was prepared as a developer under the same conditions as in Example 1, and the toner fixability and heat-resistant storage stability were evaluated in the same manner as in Example 1. The results are shown in Table 1 below.

(Example 5)
Each component shown in the toner formulation 7 below is kneaded using a biaxial extruder, pulverized and classified to a weight average particle size of 7.5 μm, and then silica fine powder (R-972: client using a Henschel mixer). (Made in Japan) 0.75 part by weight was mixed to obtain a toner of Example 5.

(Toner Formula 7)
Modified polyester resin (C2) 49 parts by weight Ti-Fe colorant 13 parts by weight (Ti content: 45% by weight, average primary particle size 0.15 μm)
Charge control agent (Spiron Black TR-H: Hodogaya Chemical) 2 parts by weight Low molecular weight polypropylene 4 parts by weight
(Weight average molecular weight: 6000)

  The saturation magnetization σs of the toner was 0.09 emu / g. The toner of Example 5 was prepared as a developer under the same conditions as in Example 1, and the toner fixability and heat-resistant storage stability were evaluated in the same manner as in Example 1. The results are shown in Table 1 below.

(Example 6)
The components shown in the following toner formulation 8 are kneaded using a biaxial extruder, pulverized and classified to a weight average particle size of 5.5 μm, and then silica fine powder (R-972: client using a Henschel mixer). 1.50 parts by weight (made in Japan) was mixed to obtain a toner of Example 6.

(Toner Formula 8)
Non-linear polyester resin (B4) 35 parts by weight Modified polyester resin (C3) 55 parts by weight Ti-Fe colorant 10 parts by weight (Ti content: 45% by weight, average primary particle size 0.25 μm)
Charge control agent (Spiron Black TR-H: Hodogaya Chemical) 2 parts by weight Low molecular weight polypropylene 3 parts by weight
(Weight average molecular weight: 6000)

  The saturation magnetization σs of the toner was 0.12 emu / g. The toner of Example 6 was prepared as a developer under the same conditions as in Example 1, and the toner fixability and heat-resistant storage stability were evaluated in the same manner as in Example 1. The results are shown in Table 1 below.

(Example 7)
The components shown in the following toner formulation 9 are kneaded using a biaxial extruder, pulverized and classified to a weight average particle size of 5.5 μm, and then silica fine powder (R-972: client using a Henschel mixer). 1.50 parts by weight of Japan) were mixed to obtain a toner of Example 7.

(Toner Formula 9)
Non-linear polyester resin (B5) 25 parts by weight Modified polyester resin (C4) 25 parts by weight Ti-Fe colorant 45 parts by weight (Ti content: 20% by weight, average primary particle size 0.35 μm)
Charge control agent (Spiron Black TR-H: Hodogaya Chemical) 2 parts by weight Low molecular weight polypropylene 3 parts by weight
(Weight average molecular weight: 6000)

  The saturation magnetization σs of the toner was 4.75 emu / g. The toner of Example 7 was prepared as a developer under the same conditions as in Example 1, and the toner fixability and heat resistant storage stability were evaluated in the same manner as in Example 1. The results are shown in Table 1 below.

(Example 8)
Each component shown in the following toner formulation 10 is kneaded using a biaxial extruder, pulverized and classified to a weight average particle size of 6.0 μm, and then silica fine powder (R-972: client using a Henschel mixer). The toner of Example 8 was obtained by mixing 1.25 parts by weight of Japan.

(Toner Formula 10)
Non-linear polyester resin (B5) 38 parts by weight Modified polyester resin (C4) 38 parts by weight Ti-Fe colorant 17 parts by weight (Ti content: 30% by weight, average primary particle size 0.25 μm)
Charge control agent (Spiron Black TR-H: Hodogaya Chemical) 2 parts by weight Low molecular weight polyethylene 5 parts by weight
(Weight average molecular weight: 1000)

  The saturation magnetization σs of the toner was 1.50 emu / g. The toner of Example 8 was prepared as a developer under the same conditions as in Example 1, and the toner fixability and heat-resistant storage stability were evaluated in the same manner as in Example 1. The results are shown in Table 1 below.

Example 9
Each component shown in the following toner formulation 11 is kneaded using a biaxial extruder, pulverized and classified to a weight average particle size of 6.0 μm, and then silica fine powder (R-972: client using a Henschel mixer). The toner of Example 9 was obtained by mixing 1.25 parts by weight of Japan.

(Toner Formula 11)
Non-linear polyester resin (B5) 27.5 parts by weight Modified polyester resin (C4) 27.5 parts by weight Ti-Fe colorant 38 parts by weight (Ti content: 30% by weight, average primary particle size 0.25 μm)
Charge control agent (Spiron Black TR-H: Hodogaya Chemical) 2 parts by weight Low molecular weight polyethylene 5 parts by weight (weight average molecular weight: 1000)

  The saturation magnetization σs of the toner was 3.75 emu / g. The toner of Example 9 was prepared as a developer under the same conditions as in Example 1, and the toner fixability and heat-resistant storage stability were evaluated in the same manner as in Example 1. The results are shown in Table 1 below.

(Example 10)
Each component shown in the following toner formulation 12 is kneaded using a biaxial extruder, pulverized and classified to a weight average particle size of 6.0 μm, and then silica fine powder (R-972: client using a Henschel mixer). The toner of Example 10 was obtained by mixing 1.25 parts by weight of Japan.

(Toner Formula 12)
Non-linear polyester resin (B5) 32 parts by weight Modified polyester resin (C4) 32 parts by weight Ti-Fe colorant 30 parts by weight (Ti content: 40% by weight, average primary particle size 0.15 μm)
Charge control agent (Spiron Black TR-H: Hodogaya Chemical) 2 parts by weight Low molecular weight polyethylene 3.25 parts by weight (weight average molecular weight: 1000)
0.75 parts by weight of carnauba wax

  The saturation magnetization σs of the toner was 0.75 emu / g. The toner of Example 10 was prepared as a developer under the same conditions as in Example 1, and the toner fixability and heat-resistant storage stability were evaluated in the same manner as in Example 1. The results are shown in Table 1 below.

(Example 11)
The components shown in the following toner formulation 13 are kneaded using a biaxial extruder, pulverized and classified to a weight average particle size of 6.0 μm, and then silica fine powder (R-972: client using a Henschel mixer). (Japan) 1.25 parts by weight were mixed to obtain a toner of Example 11.

(Toner Formula 13)
Non-linear polyester resin (B4) 30 parts by weight Modified polyester resin (C3) 30 parts by weight Ti-Fe colorant 30 parts by weight (Ti content: 40% by weight, average primary particle size 0.15 μm)
Charge control agent (Spiron Black TR-H: Hodogaya Chemical) 2 parts by weight Rice wax 8 parts by weight

  The saturation magnetization σs of the toner was 0.85 emu / g. The toner of Example 11 was prepared as a developer under the same conditions as in Example 1, and the toner fixability and heat-resistant storage stability were evaluated in the same manner as in Example 1. The results are shown in Table 1 below.

(Example 12)
Each component shown in the following toner formulation 14 is kneaded using a biaxial extruder, pulverized and classified to a weight average particle size of 6.0 μm, and then silica fine powder (R-972: client using a Henschel mixer). The toner of Example 12 was obtained by mixing 1.25 parts by weight of Japan.

(Toner Formula 14)
Non-linear polyester resin (B4) 34 parts by weight Modified polyester resin (C3) 34 parts by weight Ti-Fe colorant 25 parts by weight (Ti content: 25% by weight, average primary particle size 0.15 μm)
Charge control agent (Spiron Black TR-H: Hodogaya Chemical) 2 parts by weight Synthetic ester wax 5 parts by weight

  The saturation magnetization σs of the toner was 1.45 emu / g. The toner of Example 12 was prepared as a developer under the same conditions as in Example 1, and the toner fixability and heat resistant storage stability were evaluated in the same manner as in Example 1. The results are shown in Table 1 below.

It was confirmed that all of the toners of Examples 1 to 12 of the present invention have a low fixing temperature and excellent heat-resistant storage stability. Also, the saturation magnetization σs was 0.08 to 5.5 emu / g in a magnetic field of 398 Am ² / Kg, indicating a good value.

FIG. 2 is a schematic diagram illustrating a schematic configuration of a fixing device mounted on an image forming apparatus (imagio MF6550) in order to evaluate toner fixability in an example.

Explanation of symbols

1 Fixing roller
2 Pressure roller
3 Metal cylinder
4 Offset prevention layer
5 Heating lamp
6 Metal cylinder
7 Offset prevention layer 8 Heating lamp T Toner image S Adhesive support

Claims (11)

  In the toner for developing an electrostatic charge image including a binder resin and a colorant, the binder resin is selected from the group consisting of titanium halide, titanium diketone enolate, titanium carboxylate, titanyl carboxylate, and titanyl carboxylate. A polycondensation polyester resin formed in the presence of at least one titanium-containing catalyst, wherein the colorant is a black iron oxide compound containing a titanium component and an iron component, and the content of the titanium component is a wavelength. A toner for developing an electrostatic charge image, characterized in that a value measured by a dispersive fluorescent X-ray apparatus is 10 to 45% by weight with respect to Fe atoms in terms of Ti atoms.   2. The electrostatic image developing toner according to claim 1, wherein the titanium diketone enolate is titanium acetylacetonate.   The electrostatic image developing toner according to claim 1, wherein the titanium carboxylate is an aromatic titanium titanium carboxylate.   2. The electrostatic image developing toner according to claim 1, wherein the carboxylic acid titanyl salt is a titanyl maleate salt or a titanyl oxalate salt.   2. The electrostatic image developing toner according to claim 1, wherein a part of the molecular skeleton of the polyester resin is modified with polyepoxide.   6. The electrostatic image developing toner according to claim 1, wherein the content of the black iron oxide compound is 15 to 40% by weight based on the total amount of the toner.   7. The toner according to claim 1, wherein the toner contains at least one wax component selected from carnauba wax, rice wax, and ester wax in an amount of 0.5 to 10% by weight based on the total amount of the toner. The toner for developing an electrostatic charge image according to 1. The toner for developing an electrostatic charge image according to claim 1, wherein a saturation magnetization σs of the toner is 0.1 to 5.0 emu / g in a magnetic field of 398 Am ² / Kg.   2. The electrostatic image developing toner according to claim 1, wherein the electrostatic image developing toner is used as a two-component toner material.   A toner cartridge that is removably attached to an image forming apparatus that forms an image using toner, and that is filled with the toner, wherein the toner is the toner according to claim 1. cartridge.   Forming an image on the electrostatic latent image formed on the image carrier of the image forming apparatus by using an electrostatic charge image developing toner containing a binder resin and a colorant, and transferring the image onto the transfer target; An image forming method for fixing, wherein the binder resin of the toner for developing an electrostatic charge image is selected from the group consisting of titanium halide, titanium diketone enolate, titanium carboxylate, titanyl carboxylate, and titanyl carboxylate. A polycondensation polyester resin formed in the presence of at least one titanium-containing catalyst, wherein the colorant is a black iron oxide compound containing a titanium component and an iron component, and the content of the titanium component is a wavelength. An image forming method, wherein a value measured by a dispersion type fluorescent X-ray apparatus is 10 to 45% by weight with respect to Fe atoms in terms of Ti atoms.

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