JP2021140116A - Toner for electrostatic latent image development, toner storage container, developer, developing device, process cartridge, image forming apparatus, and image forming method - Google Patents

Abstract

To provide a toner for electrostatic latent image development that prevents so-called toner drop in which toner is aggregated in a developing device to form an abnormal image such that the toner drops on a recording medium even in a low temperature fixing toner using crystalline polyester, can prevent the occurrence of a fogging image, and has excellent fixability and image density.SOLUTION: A toner for electrostatic latent image development contains a toner base including a binder resin, a colorant, and a mold release agent. The binder resin includes a crystalline polyester resin and an amorphous resin. The toner for electrostatic latent image further contains silica that is surface-treated with aluminum hydroxide. In the toner, when the peak height of the characteristic spectrum of the crystalline polyester resin is C, and the peak height of the characteristic spectrum of the amorphous resin is R, which are measured by the ATR method using an FT-IR, the peak ratio C/R is 0.01 to 0.10.SELECTED DRAWING: Figure 1

Description

The present invention relates to a toner for electrostatic latent image development, a toner container, a developer, a developing device, a process cartridge, an image forming device, and an image forming method.

The electrophotographic image forming method includes a charging step of applying an electric charge to the surface of a photoconductor which is a latent image carrier, an exposure step of exposing the surface of the charged photoconductor to form an electrostatic latent image, and a photosensitivity process. A developing step of supplying toner to an electrostatic latent image formed on the body surface to develop it, a transfer step of transferring the toner image of the photoconductor surface onto a recording medium, and a fixing step of fixing the toner image on the recording medium. And include.

Recently, an invention has been disclosed that improves fixability by using a crystalline polyester having sharp melt property as a specific non-olefin crystalline polymer for low temperature fixing from the viewpoint of energy saving as a toner (Patent Document). 1, 2). Further, a toner to which a large particle size silica and a small particle size silica are added in a specific amount is disclosed for the purpose of preventing a decrease in carrier chargeability due to adhesion of a crystalline polyester resin and an external additive to a carrier. (Patent Document 3).

However, with the conventional low-temperature fixing toner using crystalline polyester, it is difficult to prevent the toner from falling off, maintain the image density, and simultaneously suppress the generation of the fog image.

Therefore, an object of the present invention is to suppress so-called toner drop, which forms an abnormal image as if the toner had fallen on a recording medium due to the aggregation of the toner in a developing apparatus even in a low temperature fixing toner using crystalline polyester. It is an object of the present invention to provide a toner for electrostatic latent image development, which can suppress the generation of a fog image and has excellent fixability and image density.

The above problem is solved by the following configuration 1).
1) In an electrostatic latent image developing toner containing a toner base containing a binder resin, a colorant and a mold release agent.
The binding resin contains a crystalline polyester resin and an amorphous resin, and contains
The electrostatic latent image developing toner further contains silica surface-treated with at least one selected from aluminum hydroxide, boehmite and pseudo-boehmite as an external additive.
The toner for electrostatic latent image development has a peak height of a characteristic spectrum of the crystalline polyester resin measured by the ATR method (total reflection method) using FT-IR (Fourier transform infrared spectroscopic analysis measuring device). For electrostatic latent image development, the peak ratio C / R satisfies the following formula (1), where C is C and the peak height of the characteristic spectrum of the amorphous resin is R. toner.
0.01 ≤ C / R ≤ 0.10. Equation (1)

According to the present invention, even in a low-temperature fixing toner using crystalline polyester, so-called toner drop-off, which forms an abnormal image as if the toner had fallen on a recording medium due to the aggregation of the toner in a developing device, is suppressed. It is possible to provide a toner for electrostatic latent image development which can suppress the generation of a fog image and has excellent fixability and image density.

FIG. 1 is a schematic view showing an example of an image forming apparatus having the process cartridge of the present invention. FIG. 2 is a diagram showing a characteristic spectrum of the toner resin obtained by the FTIR-ATR method. FIG. 3 is a schematic view showing an example of an image forming apparatus having a charging apparatus that performs roller charging. FIG. 4 is a schematic view showing an example of an image forming apparatus having a charging apparatus that performs brush charging.

Hereinafter, embodiments of the present invention will be described in more detail.
The toner for electrostatic latent image development of the present invention (hereinafter, may be simply referred to as toner) contains a toner base containing a binder resin, a colorant and a mold release agent, and the binder resin is a crystalline polyester. The electrostatic latent image developing toner further contains silica which has been surface-treated with at least one selected from aluminum hydroxide, boehmite and pseudo-boehmite as an external additive, which comprises a resin and an amorphous resin. The toner for electrostatic latent image development has a peak height of a characteristic spectrum of the crystalline polyester resin measured by an ATR method (total reflection method) using an FT-IR (Fourier conversion infrared spectroscopic analysis measuring device). The peak ratio C / R satisfies the following formula (1), where C is C and the peak height of the characteristic spectrum of the amorphous resin is R.
0.01 ≤ C / R ≤ 0.10. Equation (1)

Conventionally, external additive particles in which silica is treated with aluminum hydroxide, boehmite or pseudo-boehmite are known, but a technique used at the same time as crystalline polyester having low temperature fixability is not disclosed.

On the other hand, in the present invention, silica having been surface-treated with at least one selected from aluminum hydroxide, boehmite and pseudo-boehmite is used, and FT-IR (Fourier transform infrared spectroscopic analysis measuring device) is used. Peak ratio C / R of the characteristic spectrum peak height C of the crystalline polyester resin in the toner and the characteristic spectrum peak height R of the amorphous resin measured by the ATR method (total reflection method). By setting to a specific range, even in low-temperature fixing toner using crystalline polyester, so-called toner drop, which forms an abnormal image as if the toner had fallen on the recording medium due to the aggregation of the toner in the developing device, can be achieved. It is possible to provide a toner for electrostatic latent image development which can suppress, suppress the generation of a fog image, and have excellent fixability and image density.

<Silica>
The silica used in the present invention is surface-treated with at least one selected from aluminum hydroxide, boehmite and pseudo-boehmite (hereinafter, may be referred to as surface-treated silica). The surface-treated silica is included in the category of an external additive in toner, and the external additive may use other particles in addition to the surface-treated silica, if necessary.

Examples of aluminum hydroxide include amorphous aluminum hydroxide and biasite.
Boehmite and pseudo-boehmite are known and can also be synthesized by a conventional method.

Examples of the method for surface-treating silica with at least one selected from aluminum hydroxide, boehmite and pseudo-boehmite include the following methods. A case where silica is surface-treated with aluminum hydroxide will be described as an example.
First, silica particles produced by the liquid phase method are dispersed in water and heated.
Next, an aqueous solution of aluminum chloride is added to the silica particles, the pH is adjusted with an aqueous solution of sodium hydroxide, and then the aluminum chloride is hydrolyzed by holding the particles, so that the surface of the silica particles is coated with aluminum hydroxide. It can be exemplified.
Further, at least one selected from aluminum hydroxide, boehmite and pseudo-boehmite is used in the range of, for example, 5 to 20% by mass, preferably 7 to 15% by mass, based on silica.

-Other particles-
The other particles can be appropriately selected depending on the intended purpose. For example, silica, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, iron oxide, copper oxide, and oxidation other than the above can be appropriately selected. Zinc, tin oxide, silica sand, clay, mica, silica ash, silica soil, chromium oxide, cerium oxide, red iron oxide, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, silicon carbide, nitride Examples include silicon. These may be used alone or in combination of two or more.
The other particles may be surface-treated in order to increase the hydrophobicity of the surface and prevent deterioration of flow characteristics and charging characteristics even under high humidity.
Examples of the surface treatment agent include a fluorine-containing silane coupling agent, a silylating agent, a silane coupling agent having an alkyl fluoride group, an organic titanate-based coupling agent, an aluminum-based coupling agent, a silicone oil, and a modified silicone oil. And so on.

The content of the surface-treated silica preferably satisfies the following formulas (2) and (3) when the blending amount with respect to 100 parts by mass of the toner base is X parts by mass.
0.36 ≦ (2.77 × C / R + 1.97 × W / R) / X ≦ 1.85 Equation (2)
0.4 ≤ X ≤ 1.0 Equation (3)
(However, the W represents the peak height of the characteristic spectrum of the release agent measured by the ATR method (total reflection method) using FT-IR (Fourier transform infrared spectroscopic analysis measuring device)).
By satisfying the above formulas (2) and (3) at the same time, the low temperature fixability is enhanced as a characteristic because the abundance of the low melting point component present on the toner surface and the amount of the external additive are defined.

The volume average particle size (D50) of the surface-treated silica in the present invention is preferably 8 nm to 120 nm.
As a result, there is little change in characteristics such as the amount of charge, fluidity, and cohesion, and deterioration of image quality (for example, transfer failure, generation of background stain image, etc.) can be suppressed. When the average particle size is 120 nm or less, wear of the photoconductor can be suppressed.
The volume average particle size (D50) of the surface-treated silica is more preferably 12 nm to 60 nm.
The volume average particle size (D50) of the surface-treated silica can be measured by a laser diffraction / scattering particle size distribution measuring device LA-750 manufactured by HORIBA, Ltd.

The toner of the present invention has a peak height of a characteristic spectrum of the crystalline polyester resin measured by the ATR method (total reflection method) using FT-IR (Fourier transform infrared spectroscopic analysis measuring device). When the peak height of the characteristic spectrum of the amorphous resin is R, the peak ratio C / R satisfies the following formula (1).
0.01 ≤ C / R ≤ 0.10. Equation (1)

The control of C / R is greatly affected by the compatibility state between the crystalline polyester resin and the amorphous resin, the degree of recrystallization, etc., and in order to satisfy the relationship described in the above formula (1), Special manufacturing conditions are required.
Specifically, for example, by using a quality engineering method, not only the material thermal properties and toner formulation, but also the manufacturing conditions such as the emulsification and granulation step, the solvent removal step, the aging and extension reaction step, and the additive mixing step are optimized. It can be controlled with.
More specifically, for example, when the prescription amount of the crystalline polyester resin is increased or the thermal characteristics of the crystalline polyester are lowered, the toner C / R becomes large. C / R becomes smaller when the amount of charge is reduced or the thermal characteristics are increased. Further, as an example of the process conditions, when the amount of the external additive charged is increased, the crystalline polyester is less likely to be exposed on the surface layer of the toner base, so that the C / R becomes smaller. C / R increases when the amount of external additive charged is reduced.

If the C / R is less than 0.01, low temperature fixability cannot be ensured, which is not preferable.
On the contrary, if the C / R exceeds 0.10, image defects derived from crystalline polyester occur, which is not preferable.
A more preferable C / R is 0.04 or more and 0.08 or less.

(C / R measurement method)
In the present invention, the peak ratio C / R and the following peak ratio W / R are measured by the ATR method (total reflection method) with FT-IR (Fourier transform infrared spectroscopic analysis measuring device; Avatar370 / ThermoElectron). It is calculated based on the obtained absorbance spectrum.

Since the ATR method requires a smooth surface, the toner is pressure-molded to form a smooth surface. In the pressure molding at this time, 2.0 g of toner is loaded with 1 ton for 60 seconds to obtain pellets having a diameter of 20 mm.

In the present invention, characteristic spectrum when the crystalline polyester resin is a crystalline state (1165 cm ^-1) (baseline height 1137-1199cm ^-1) peak heights and C, as shown in FIG. 2 amorphous The peak height of the characteristic spectrum of the quality resin (for example, in the case of polyester resin, 829 cm ^-1 (height baseline is 784-889 cm ^-1 )) was calculated as R, and C / R was calculated as the peak intensity ratio. The peak height W of the mold is defined as the peak height of the characteristic spectrum (2850 cm ^-1 ) derived from the CH expansion and contraction of the alkyl chain (height baseline is 2834-2862 cm ^-1 ).

The peak ratio in the present invention is obtained by converting the spectrum into absorbance and using the peak height.

The toner of the present invention preferably has a peak ratio W / R of 0.05 or more and 0.14 or less.
When the peak ratio W / R is 0.05 or more, the region of the release agent (wax) existing on the outermost layer of the toner is appropriate, so that the external additive particles are agitated stress in the image forming apparatus. Therefore, it is possible to suppress desorption (release) from the toner base, and it is possible to prevent the generation of a fog image due to insufficient charge rising property due to friction between the toner and the carrier over time. Further, when the peak ratio W / R is 0.14 or less, the region of the release agent (wax) existing on the outermost layer of the toner is appropriate, so that the colorant is generated by the stirring stress in the image forming apparatus. It is possible to prevent the problem that the image density becomes thin with time due to being buried in the toner base and the occurrence of a fog image.

<Toner base>
The toner base contains at least a binder resin, a colorant and a mold release agent, and further contains other components as needed.

<< Release agent >>
The release agent is not particularly limited and may be appropriately selected depending on the intended purpose, and examples thereof include waxes and waxes.
Examples of waxes and waxes include vegetable waxes such as carnauba wax, cotton wax, and wood wax and rice wax; animal waxes such as honey wax and lanolin; mineral waxes such as ozokelite and cercin; paraffin, microcrystallin, and the like. Examples include petrolatum and other petroleum waxes.
In addition to these natural waxes, synthetic hydrocarbon waxes such as Fisher Tropsch wax, polyethylene and polypropylene; synthetic waxes such as esters, ketones and ethers can be mentioned.
Further, fatty acid amide compounds such as 12-hydroxystearic amide, stearic acid amide, phthalic anhydride, and chlorinated hydrocarbons; poly-n-stearyl methacrylate and poly-n, which are low molecular weight crystalline polymer resins. Examples thereof include homopolymers or copolymers of polyacrylates such as lauryl methacrylate (for example, copolymers of n-stearyl acrylate-ethyl methacrylate); crystalline polymers having a long alkyl group in the side chain.
These release agents may be used alone or in combination of two or more.
Among these, carnauba wax, rice wax, ester wax and polypropylene are preferable.
Carnauba wax is a natural wax obtained from the leaves of carnauba palm, but a low acid value type desorbed from free fatty acids is particularly preferable because it can be uniformly dispersed in the resin.
Rice bran is a natural wax obtained by refining crude wax produced in a dewaxing or wintering step when refining rice bran oil extracted from rice bran.
The ester wax is a wax synthesized by a transesterification reaction from a monofunctional linear fatty acid and a monofunctional linear alcohol.

The content of the release agent is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 0.5 parts by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the toner. More preferably, it is 10 parts by mass or more and 10 parts by mass or less.
When the content is 0.5 parts by mass or more, the high temperature offset resistance at the time of fixing and the low temperature fixing property are good. Further, when the content is 20 parts by mass or less, the heat-resistant storage property becomes good and a high-quality image can be obtained. When the content is within the more preferable range, it is advantageous in terms of improving the image quality and the fixing stability.

<< Bundling resin >>
The binder resin includes a crystalline polyester resin and an amorphous resin, and if necessary, a polyamide, a polyester / polyamide resin, a styrene-acrylic resin, a styrene-butadiene resin, or the like can be used in combination.

(Amorphous resin)
As the amorphous resin, an amorphous polyester resin is preferable. Hereinafter, an amorphous polyester resin will be described as an example.
Examples of the amorphous polyester resin include polyester resins (AX), which are polycondensates of polyols and polycarboxylic acids, and modified polyester resins (AY) obtained by further reacting (AX) with polyepoxides (c) and the like. Can be mentioned.

(AX), (AY) and the like may be used alone, or two or more kinds may be used in combination as a mixture.

Examples of the polyol include a diol (g) and a trivalent or higher valent polyol (h), and examples of the polycarboxylic acid include a dicarboxylic acid (i) and a trivalent or higher valent polycarboxylic acid (j). It may be used together.
Examples of the polyester resin (AX) and (AY) include the following, and these can also be used in combination.
(AX1): Linear polyester resin using (g) and (i): Non-linear polyester resin using (h) and / or (j) together with (g) and (i) AY1): A modified polyester resin obtained by reacting (AX2) with (c).

The diol (g) preferably has a hydroxyl value of 180 to 1900 (mgKOH / g, the same applies hereinafter).
Specifically, alkylene glycols having 2-36 carbon atoms (ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butylene glycol, 1,6-hexanediol, etc.); 4 carbon atoms. ~ 36 alkylene ether glycols (diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol and polybutylene glycol, etc.); 6-36 carbon alicyclic diols (1,4-cyclohexanedimethanol and hydrogenation) Bisphenol A, etc.); alkylene oxide having 2 to 4 carbon atoms of the alicyclic diol [ethylene oxide (hereinafter abbreviated as EO), propylene oxide (hereinafter abbreviated as PO), butylene oxide (hereinafter abbreviated as BO), etc.] Additives (additional moles 1 to 30); alkylene oxides (EO, PO, BO, etc.) with 2 to 4 carbon atoms of bisphenols (bisphenol A, bisphenol F, bisphenol S, etc.) Additives (additional moles 2 to 30) ) And so on.

Of these, alkylene glycols having 2 to 12 carbon atoms, alkylene oxide adducts of bisphenols and their combined use are preferable, and alkylene oxide adducts of bisphenols and alkylene glycols having 2 to 4 carbon atoms are particularly preferable. And a combination of two or more of these.

In the above and below, the hydroxyl value and the acid value are measured by the method specified in JIS K 0070.

As the trivalent or higher (3 to 8 or higher) polyol (h), those having a hydroxyl value of 150 to 1900 are preferable.
Specifically, 3- to 8-valent or higher aliphatic polyhydric alcohols having 3 to 36 carbon atoms (alkane polyols and their intramolecular or intermolecular dehydrations, such as glycerin, triethylolethane, trimethylolpropane, penta). Ellisritol, sorbitol, sorbitan, polyglycerin, and dipentaerythritol; saccharides and derivatives thereof, such as glycosyl and methylglucoside; etc.); alkylene oxides having 2 to 4 carbon atoms (EO, PO, BO, etc.) of the above aliphatic polyhydric alcohols. ) Additives (additional moles 1 to 30); alkylene oxides (EO, PO and BO, etc.) having 2 to 4 carbon atoms of trisphenols (trisphenol PA, etc.) Additives (additional moles 2 to 30); novolak Examples thereof include alkylene oxides (EO, PO, BO, etc.) adducts (additional moles 2 to 30) having 2 to 4 carbon atoms of resins (phenol novolac, cresol novolac, etc .: average degree of polymerization 3 to 60).
Of these, preferred are 3- to 8-valent or higher aliphatic polyhydric alcohols and novolak resin alkylene oxide adducts (additional moles 2 to 30), and particularly preferred are novolak resin alkylene oxide adducts. Is.

The dicarboxylic acid (i) preferably has an acid value of 180 to 1250 (mgKOH / g, the same applies hereinafter).
Specifically, alcandicarboxylic acids having 4 to 36 carbon atoms (such as succinic acid, adipic acid, and sebacic acid) and alkenyl succinic acids (such as dodecenyl succinic acid); alicyclic dicarboxylic acids having 4 to 36 carbon atoms [dimeric acid]. (Dimerized linoleic acid), etc.]; Arkendicarboxylic acid having 4 to 36 carbon atoms (maleic acid, fumaric acid, citraconic acid, and mesaconic acid, etc.); Aromatic dicarboxylic acid having 8 to 36 carbon atoms (phthalic acid, isophthalic acid, etc.) , Telephthalic acid, and naphthalenedicarboxylic acid, etc.).
Of these, preferred are alkenedicarboxylic acids having 4 to 20 carbon atoms and aromatic dicarboxylic acids having 8 to 20 carbon atoms.
As the dicarboxylic acid (i), the above-mentioned acid anhydride or lower alkyl (carbon number 1 to 4) ester (methyl ester, ethyl ester, isopropyl ester, etc.) may be used.

As the trivalent or higher (3 to 6 or higher) polycarboxylic acid (j), those having an acid value of 150 to 1250 are preferable.
Specifically, aromatic polycarboxylic acids having 9 to 20 carbon atoms (trimeric acid, pyromellitic acid, etc.); vinyl polymers of unsaturated carboxylic acids [number average molecular weight (hereinafter referred to as Mn, hereinafter referred to as Mn, gel permeation chromatography). (According to (GPC)): 450 to 10000] (styrene / maleic acid copolymer, styrene / acrylic acid copolymer, α-olefin / maleic acid copolymer, styrene / fumaric acid copolymer, etc.) and the like. ..
Of these, aromatic polycarboxylic acids having 9 to 20 carbon atoms are preferable, and trimellitic acid and pyromellitic acid are particularly preferable.
As the trivalent or higher valent polycarboxylic acid (j), the above-mentioned acid anhydride or lower alkyl (carbon number 1 to 4) ester (methyl ester, ethyl ester, isopropyl ester, etc.) may be used.

Further, along with a diol (g), a polyol (h), a dicarboxylic acid (i) or a polycarboxylic acid (j), an aliphatic or aromatic hydroxycarboxylic acid (k) having 4 to 20 carbon atoms and 6 to 12 carbon atoms The lactone (l) can also be copolymerized.
Examples of the hydroxycarboxylic acid (k) include hydroxystearic acid and hardened castor oil fatty acid.
Examples of the lactone (l) include caprolactone.

Examples of the polyepoxide (c) include polyglycidyl ether [ethylene glycol diglycidyl ether, tetramethylene glycol diglycidyl ether, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, glycerin triglycidyl ether, pentaerythritol tetraglycidyl ether, and phenol novolac (phenol novolac). Average degree of polymerization 3 to 60) Diglycidyl etherified product, etc.]; Diene oxide (pentadiendioxide, hexadiendioxide, etc.) and the like can be mentioned.
Of 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 polyepoxyd (c) is preferably 2 to 8, more preferably 2 to 6, and particularly preferably 2 to 4.
The epoxy equivalent of the polyepoxyd (c) is preferably 50-500.
The lower limit is more preferably 70, particularly preferably 80, and the upper limit is even more preferably 300, particularly preferably 200.
When the number of epoxy groups and the epoxy equivalent are within the above ranges, both developability and fixability are good.
It is more preferable that the above-mentioned ranges of the number of epoxy groups per molecule and the epoxy equivalent are satisfied at the same time.

The reaction ratio of the polyol to the polycarboxylic acid is preferably 2/1 to 1/2, more preferably 1.5 / 1, as the equivalent ratio [OH] / [COOH] of the hydroxyl group [OH] and the carboxyl group [COOH]. ~ 1 / 1.3, particularly preferably 1.3 / 1-1 / 1.2.
The type of polyol and polycarboxylic acid to be used is selected in consideration of molecular weight adjustment so that the glass transition point of the finally prepared amorphous resin is 45 to 85 ° C.

In the present invention, the amorphous polyester resin can be produced in the same manner as a normal polyester production method.
For example, in the atmosphere of an inert gas (nitrogen gas or the like), the reaction temperature is preferably 150 to 280 ° C., more preferably 160 to 250, in the presence of titanium carboxylate (hereinafter referred to as titanium-containing catalyst (a)). This can be done by reacting at ° C., particularly preferably 170-240 ° C.
The reaction time is preferably 30 minutes or more, particularly preferably 2 to 40 hours, from the viewpoint of reliably performing the polycondensation reaction.
Further, it is also effective to reduce the pressure (for example, 1 to 50 mmHg) in order to improve the reaction rate at the end of the reaction.

The amount of the titanium-containing catalyst (a) added is preferably 0.0001 to 0.8%, more preferably 0.0002 to 0.6, based on the weight of the obtained polymer from the viewpoint of polymerization activity and the like. %, Especially preferably 0.0015 to 0.55%.
Further, another esterification catalyst can be used in combination as long as the catalytic effect of the titanium-containing catalyst (a) is not impaired.
Examples of other esterification catalysts include tin-containing catalysts (eg dibutyltin oxide), antimony trioxide, titanium-containing catalysts other than the titanium-containing catalyst (a) (eg titanium halide, titanium diketone enolate, titanyl carboxylate, and (Titanyl carboxylic acid salt), zirconium-containing catalyst (eg, zirconyl acetate), germanium-containing catalyst, alkali (earth) metal catalyst (eg, alkali metal or alkaline earth metal carboxylate: lithium acetate, sodium acetate, potassium acetate, acetic acid Calcium, sodium benzoate, potassium benzoate, etc.), zinc acetate and the like.
The amount of these other tactile butterflies added is preferably 0 to 0.6% with respect to the weight of the obtained polymer.
When it is within 0.6%, the coloring of the polyester resin is reduced, which is preferable for use as a color toner.
The content of the titanium-containing catalyst (a) in all the added catalysts is preferably 50 to 100% by mass.

As a method for producing the linear polyester resin (AX1), for example, the presence of a titanium-containing tactile butterfly (a) of 0.0001 to 0.8% with respect to the weight of the obtained polymer and, if necessary, another catalyst. Below, a method of heating the diol (g) and the dicarboxylic acid (i) to 180 ° C. to 260 ° C. and dehydrating and condensing them under normal pressure and / or reduced pressure conditions to obtain (AX1) can be mentioned.

As a method for producing the non-linear polyester resin (AX2), for example, the presence of a titanium-containing catalyst (a) of 0.0001 to 0.8% based on the weight of the obtained polymer and, if necessary, another catalyst. Below, the diol (g), the dicarboxylic acid (i), and the trivalent or higher valent polyol (h) are heated to 180 ° C. to 260 ° C., dehydrated and condensed under normal pressure and / or reduced pressure conditions, and then further trivalent. A method of reacting the above polycarboxylic acid (j) to obtain (AX2) can be mentioned.
The polycarboxylic acid (j) can also be reacted at the same time as the diol (g), the dicarboxylic acid (i) and the polyol (h).

As a method for producing the modified polyester resin (AY1), a modified polyester resin (AY1) is obtained by adding a polyepoxide (c) to the polyester resin (AX2) and carrying out a molecular elongation reaction of the polyester at 180 ° C. to 260 ° C. Can be mentioned.
The acid value of the non-linear polyester resin (AX2) to be reacted with the polyepoxide (c) is preferably 1 to 60, more preferably 5 to 50.
When the acid value is 1 or more, the polyepoxide (c) does not remain unreacted and may adversely affect the performance of the resin, and when it is 60 or less, the thermal stability of the resin is good.
The amount of the polyepoxide (c) used to obtain the modified polyester resin (AY1) is preferably 0.01 to 10% by mass with respect to (AX2) from the viewpoint of low temperature fixability and hot offset resistance. More preferably, it is 0.05 to 5% by mass.

Further, the toner of the present invention may contain other resins, if necessary, in addition to the polycondensation polyester resin which is an amorphous resin.
Other resins include styrene resins [copolymers of styrene and alkyl (meth) acrylates, copolymers of styrene and diene monomers, etc.], epoxy resins (bisphenol A diglycidyl ether ring-opening polymers, etc.), Examples thereof include urethane resins (diols and / or heavy adducts of trivalent or higher valent polyols and diisocyanates).
The content of the other resin in the amorphous resin is preferably 0 to 40% by mass, more preferably 0 to 30% by mass, and particularly preferably 0 to 20% by mass.

(Crystalline polyester resin)
The crystalline polyester resin used in the present invention can be a crystalline aliphatic polyester resin containing at least 60 mol% of an ester bond represented by the following general formula (1) in its molecular main chain.

(In the general formula (1), R represents a linear unsaturated aliphatic divalent carboxylic acid residue, and is a linear unsaturated aliphatic group having 2 to 20 carbon atoms, preferably 2 to 4 carbon atoms. n is an integer of 2 to 20, preferably 2 to 6).

The existence of the structure of the general formula (1) can be confirmed by ^{solid C 13 NMR.}
Specific examples of the linear unsaturated aliphatic group include linear unsaturated divalent carboxylic acids such as maleic acid, fumaric acid, 1,3-n-propendicarboxylic acid, and 1,4-n-butendicarboxylic acid. A linear unsaturated aliphatic group derived from an acid can be mentioned.

In the general formula (1), R represents a linear aliphatic dihydric alcohol residue or a bisphenol A ethylene oxide adduct.
Specific examples of the linear aliphatic dihydric alcohol residue in this case include linear aliphatic 2 such as ethylene glycol, 1,3-propylene glycol, 1,4-butanediol, and 1,6-hexanediol. It can be shown that it is derived from valence alcohol.
Since the crystalline polyester resin uses a linear unsaturated aliphatic dicarboxylic acid as its acid component, it exhibits an action effect that it is easier to form a crystal structure than when an aromatic dicarboxylic acid is used.

The crystalline polyester resin is, for example, a polyvalent composition consisting of (i) a linear unsaturated aliphatic divalent carboxylic acid or a reactive derivative thereof (acid anhydride, lower alkyl ester having 1 to 4 carbon atoms, acid halide, etc.). It can be produced by subjecting a carboxylic acid component and (ii) a polyhydric alcohol component composed of a linear aliphatic diol to a polycondensation reaction by a conventional method.
In this case, a small amount of other polyvalent carboxylic acid can be added to the polyvalent carboxylic acid component, if necessary.

The polyvalent carboxylic acid in this case includes saturated aliphatic carboxylic acids such as (i) unsaturated aliphatic divalent carboxylic acid having a branched chain, (ii) saturated aliphatic divalent carboxylic acid, and saturated aliphatic trivalent carboxylic acid. In addition to polyvalent carboxylic acids, (iii) aromatic polyvalent carboxylic acids such as aromatic divalent carboxylic acids and aromatic trivalent carboxylic acids are included.
The amount of these polyvalent carboxylic acids added is usually 30 mol% or less, preferably 10 mol% or less, based on the total carboxylic acids, and is appropriately added within the range in which the obtained polyester has crystallinity.

Specific examples of the polyvalent carboxylic acid that can be added as needed include malonic acid, succinic acid, glutaric acid, adipic acid, suberic acid, sebacic acid, citraconic acid, phthalic acid, isophthalic acid, terephthalic acid and the like. Divalent carboxylic acid; trimetic anhydride, 1,2,4-benzenetricarboxylic acid, 1,2,5-benzenetricarboxylic acid, 1,2,4-cyclohexanetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, Examples of trivalent or higher polyvalent carboxylic acids such as 1,2,5-hexanetricarboxylic acid, 1,3-dicarboxy-2-methylenecarboxypropane, 1,2,7,8-octanetetracarboxylic acid can be mentioned. can.

If necessary, a small amount of an aliphatic branched-chain dihydric alcohol, a cyclic dihydric alcohol, or a trihydric or higher polyhydric alcohol can be added to the polyhydric alcohol component.
The amount added is 30 mol% or less, preferably 10 mol% or less, based on the total alcohol, and is appropriately added within the range in which the obtained polyester has crystallinity.
Examples of polyhydric alcohols added as needed include 1,4-bis (hydroxymethyl) cyclohexane, polyethylene glycol, bisphenol A ethylene oxide adduct, bisphenol A propylene oxide adduct, glycerin and the like.

In the crystalline polyester resin, the molecular weight distribution is preferably sharp from the viewpoint of low temperature fixability, and the molecular weight is preferably relatively low.
The molecular weight of the crystalline polyester resin is such that the weight average molecular weight (Mw) is 5500 to 6500, the number average molecular weight (Mn) is 1300 to 1500 and its Mw in the molecular weight distribution of the o-dichlorobenzene-soluble component by GPC. The / Mn ratio is preferably 2-5.
The molecular weight distribution of the polyester resin is based on a molecular weight distribution diagram in which the horizontal axis is log (M: molecular weight) and the vertical axis is mass%.
In the case of the crystalline polyester resin used in the present invention, it is preferable that the crystalline polyester resin has a molecular weight peak in the range of 3.5 to 4.0 (mass%) in this molecular weight distribution diagram, and the half width of the peak is 1.5. The following is preferable.

In a crystalline polyester resin, the glass transition temperature (Tg) and the softening temperature [T (F1 / 2)] are preferably low as long as the heat-resistant storage stability of the toner is not deteriorated, but in general, the Tg is high. It is 100 to 150 ° C., preferably 110 to 140 ° C., and its T (F1 / 2) is 100 to 150 ° C., preferably 110 to 140 ° C.
When Tg and T (F1 / 2) are higher than the above range, the lower limit temperature for fixing the toner becomes higher, so that the low temperature fixability of the toner deteriorates.

Whether or not the polyester resin in the present invention has crystallinity can be confirmed by whether or not there is a peak in the X-ray diffraction pattern by the powder X-ray diffractometer. The powder X-ray diffraction measurement is performed by using a Rigaku Denki RINT1100 with a tube under the conditions of Cu and a tube voltage-current of 50 kV-30 mA using a wide-angle goniometer.

Further, the acid value of the crystalline polyester resin is preferably 10 mgKOH / g or more in order to achieve the desired low-temperature fixability from the viewpoint of affinity between the paper and the resin, while improving the hot offset property. It is preferably 45 mgKOH / g or less.

Further, the hydroxyl value of the crystalline polyester resin is preferably 5 to 60 mgKOH / g in order to achieve a predetermined low temperature fixability and good charging characteristics.

As the binder resin, a resin other than the resin described above can be used in combination as long as the performance of the toner is not impaired. Such a resin is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include polyurethane resin, silicone resin, ketone resin, petroleum resin, and hydrogenated petroleum resin. These may be used alone or in combination of two or more.

The content of the binder resin is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 50 parts by mass or more and 95 parts by mass or less, and 75 parts by mass with respect to 100 parts by mass of the toner. More than 90 parts by mass is more preferable.

<< Colorant >>
The colorant is not particularly limited and may be appropriately selected depending on the intended purpose. For example, carbon black, niglosin dye, iron black, naphthol yellow S, Hansa yellow (10G, 5G, G), cadmium yellow, etc. Yellow Iron Oxide, Yellow Clay, Yellow Lead, Titanium Yellow, Polyazo Yellow, Oil Yellow, Hansa Yellow (GR, A, RN, R), Pigment Yellow L, Benzidine Yellow (G, GR), Permanent Yellow (NCG), Vulcan Fast Yellow (5G, R), Tartrajin Lake, Kinolin Yellow Lake, Anthracan Yellow BGL, Isoindrinon Yellow, Bengala, Lead Tan, Lead Zhu, Cadmium Red, Cadmium Mercuri Red, Antimon Zhu, Permanent Red 4R, Para Red, Faise Red, Parachlor Ortho Nitroaniline Red, Resole Fast Scarlet G, Brilliant Fast Scarlet, Brilliant Carmine BS, Permanent Red (F2R, F4R, FRL, FRLL, F4RH), Fast Scarlet VD, Belkan Fast Rubin B, Brilliant Scarlet G , Risor Rubin GX, Permanent Red F5R, Brilliant Carmin 6B, Pigment Scarlet 3B, Bordeaux 5B, Truisin Maroon, Permanent Bordeaux F2K, Helio Bordeaux BL, Bordeaux 10B, Bonmaroon Light, Bonmaroon Medium, Eosin Lake, Rhodamin Lake B, Rhodamin Lake Y, Alizarin Lake, Thio Indigo Red B, Thio Indigo Maroon, Oil Red, Kinakridon Red, Pyrazolon Red, Polyazo Red, Chrome Vermilion, Benzidine Orange, Perinon Orange, Oil Orange, Cobalt Blue, Cerulean Blue, Alkaline Blue Lake, Peacock Blue Lake, Victoria Blue Lake, Metalless Phthalusin Blue, Phtalussin Blue, Fast Sky Blue, Indance Ren Blue (RS, BC), Indigo, Ultramarine, Navy Blue, Anthracinone Blue, Fast Violet B, Methyl Violet Lake, Cobalt Purple, Manganese Purple, Dioxane Violet, Anthraquinone Violet, Chrome Green, Zink Green, Chromium Oxide, Pyridian, Emerald Green, Pigment Green B, Naftor Green B, Green Gold, Acid Green Lake, Malakite Green Examples include Nrake, Phthalocyanine Green, Anthraquinone Green, Titanium Oxide, Zinc Oxide, and Litobon.

The content of the colorant is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 1 part by mass or more and 15 parts by mass or less with respect to 100 parts by mass of the toner, and 3 parts by mass or more. More preferably, it is 10 parts by mass or less.

The colorant can also be used as a masterbatch compounded with a resin. Examples of the resin to be kneaded together with the production of the master batch or the master batch include, for example, a polymer of styrene such as polystyrene, polyp-chlorostyrene, polyvinyltoluene, or a substitute thereof; in addition to the polyester resin; styrene-p-chlorostyrene. Copolymer, styrene-propylene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalin copolymer, styrene-methyl acrylate copolymer, styrene-ethyl acrylate copolymer, butyl styrene-butyl acrylate Copolymer, octyl styrene-octyl acrylate copolymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer, styrene-α-chloromethyl methacrylate copolymer Combined, styrene-acrylonitrile copolymer, styrene-vinylmethylketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-acrylonitrile-inden copolymer, styrene-maleic acid copolymer, styrene -Sterite-based copolymers such as maleic acid ester copolymers; polymethylmethacrylate, polybutylmethacrylate, polyvinyl chloride, polyvinylacetate, polyethylene, polypropylene, polyester, epoxy resin, epoxy polyol resin, polyurethane, polyamide, polyvinyl butyral , Polyacrylic acid resin, rosin, modified rosin, terpene resin, aliphatic or alicyclic hydrocarbon resin, aromatic petroleum resin, chlorinated paraffin, paraffin wax and the like. These may be used alone or in combination of two or more.

The masterbatch can be obtained by mixing the resin for the masterbatch and the colorant with a high shearing force and kneading them. At this time, an organic solvent can be used in order to enhance the interaction between the colorant and the resin. In addition, the so-called flushing method, in which an aqueous paste containing water of a colorant is mixed and kneaded together with a resin and an organic solvent, the colorant is transferred to the resin side, and water and an organic solvent component are removed is also a wet colorant. Since the cake can be used as it is, it does not need to be dried and is preferably used. A high shear dispersion device such as a three-roll mill is preferably used for mixing and kneading.

<< Other ingredients >>
The other components are not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include a charge control agent, a fluidity improver, a cleanability improver, and a magnetic material.

-Charge control agent-
The charge control agent is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a niglosin dye, a triphenylmethane dye, a chromium-containing metal complex dye, a molybdic chelate pigment, a rhodamine dye, etc. Alkoxy-based amines, quaternary ammonium salts (including fluorine-modified quaternary ammonium salts), alkylamides, phosphorus alone or compounds, tungsten alone or compounds, fluorine-based activators, salicylate metal salts, salicylic acid derivative metal salts, etc. Can be mentioned.

Specifically, bontron 03 of niglosin-based dye, bontron P-51 of quaternary ammonium salt, bontron S-34 of metal-containing azo dye, E-82 of oxynaphthoic acid-based metal complex, E of salicylic acid-based metal complex. -84, phenolic condensate E-89 (above, manufactured by Orient Chemical Industry Co., Ltd.), quaternary ammonium salt molybdenum complex TP-302, TP-415 (above, manufactured by Hodoya Chemical Industry Co., Ltd.), LRA -901, a boron complex LR-147 (manufactured by Nippon Carlit Co., Ltd.), copper phthalocyanine, perylene, quinacridone, azo pigments, and other polymer systems having functional groups such as sulfonic acid groups, carboxyl groups, and quaternary ammonium salts. Compounds and the like.

The content of the charge control agent is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 0.1 part by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the toner, and is 0. .2 parts by mass or more and 5 parts by mass or less are more preferable. When the content is 10 parts by mass or less, the chargeability of the toner is appropriate, the effect of the main charge control agent is good, the electrostatic attraction with the developing roller is appropriate, and the developer The fluidity becomes good and a high image density can be obtained. These charge control agents can be melt-kneaded together with the masterbatch and resin and then dissolved and dispersed, may be added when directly dissolved and dispersed in an organic solvent, and are immobilized on the toner surface after forming toner particles. You may.

-Liquidity improver-
The fluidity improver is not particularly limited as long as it can be surface-treated to increase hydrophobicity and prevent deterioration of fluidity characteristics and charging characteristics even under high humidity, and is appropriately selected according to the purpose. Examples thereof include silane coupling agents, silylating agents, silane coupling agents having an alkyl fluoride group, organic titanate-based coupling agents, aluminum-based coupling agents, silicone oils, modified silicone oils, and the like. Be done. It is particularly preferable that the silica and the titanium oxide are surface-treated with such a fluidity improver and used as the hydrophobic silica and the hydrophobic titanium oxide.

-Cleaning agent-
The cleaning property improving agent is not particularly limited as long as it is added to the toner in order to remove the developer after transfer remaining on the photoconductor or the primary transfer medium, and may be appropriately selected depending on the intended purpose. Examples thereof include fatty acid metal salts such as zinc stearate, calcium stearate and stearic acid, and polymer particles produced by soap-free emulsion polymerization such as polymethylmethacrylate particles and polystyrene particles. The polymer particles preferably have a relatively narrow particle size distribution, and preferably have a volume average particle size of 0.01 μm or more and 1 μm or less.

-Magnetic material-
The magnetic material is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include iron powder, magnetite and ferrite. Among these, white ones are preferable in terms of color tone.

The method for producing the toner of the present invention is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a binder resin, a colorant, a mold release agent, and other components as necessary can be mixed with a mixer or the like. After kneading with a kneader such as a hot roll or an extruder, the mixture is cooled and solidified, pulverized with a pulverizer such as a jet mill, and then classified to obtain a toner base. Toner is produced by mixing the obtained toner base and the external additive particles.
The method for producing the toner is not particularly limited, and any of bulk polymerization, solution polymerization, emulsion polymerization, and suspension polymerization can be used, for example.

(Toner container)
The toner container of the present invention means a container containing the toner of the present invention.
By mounting the toner container of the present invention on an image forming apparatus to form an image, so-called toner dropping, which forms an abnormal image in which toner is agglomerated in a developing device and the toner is dropped on a recording medium, is formed. It is possible to perform image formation utilizing the characteristics of the toner, that is, it can be suppressed, the generation of a fog image can be suppressed, and it has excellent fixability and image density.

(Developer)
The developer of the present invention includes the toner of the present invention and a carrier.
The carrier is not particularly limited and may be appropriately selected depending on the intended purpose, but a carrier having a core material and a resin layer covering the core material is preferable.

The material of the core material is not particularly limited and may be appropriately selected from known materials. For example, a manganese-strontium (Mn-Sr) -based material of 50 emu / g to 90 emu / g, manganese-magnesium ( Mn-Mg) -based materials are preferable, and highly magnetized materials such as iron powder (100 emu / g or more) and magnetite (75 emu / g to 120 emu / g) are preferable from the viewpoint of ensuring image density. Further, it is weak such as copper-zinc (Cu-Zn) type (30 emu / g to 80 emu / g) in that the contact of the toner with the photoconductor in the spiked state can be weakened, which is advantageous for improving the image quality. Magnetizing materials are preferred. These may be used alone or in combination of two or more.

The average particle size (volume average particle size (D ₅₀ )) of the core material is preferably 10 μm or more and 200 μm or less, and more preferably 40 μm or more and 100 μm or less.

The material of the resin layer is not particularly limited and may be appropriately selected from known resins depending on the intended purpose. For example, amino resins, polyvinyl resins, polystyrene resins, halogenated olefin resins, etc. Polyester resin, polycarbonate resin, polyethylene resin, polyvinyl fluoride resin, polyfluorinated vinylidene resin, polytrifluoroethylene resin, polyhexafluoropropylene resin, copolymer of vinylidene fluoride and acrylic monomer, fluoride Examples thereof include a copolymer of vinylidene compound and vinyl fluoride, a fluoroterpolymer such as a tarpolymer of tetrafluoroethylene, vinylidene fluoride and a non-fluorinated monomer, and a silicone resin. These may be used alone or in combination of two or more.

Examples of the amino resin include urea-formaldehyde resin, melamine resin, benzoguanamine resin, urea resin, polyamide resin, epoxy resin and the like. Examples of the polyvinyl-based resin include acrylic resin, polymethylmethacrylate resin, polyacrylonitrile resin, polyvinyl acetate resin, polyvinyl alcohol resin, polyvinyl butyral resin and the like. Examples of the polystyrene-based resin include polystyrene resin and styrene-acrylic copolymer resin. Examples of the halogenated olefin resin include polyvinyl chloride and the like. Examples of the polyester-based resin include polyethylene terephthalate resin and polybutylene terephthalate resin.

The resin layer may contain conductive powder or the like, if necessary. Examples of the conductive powder include metal powder, carbon black, titanium oxide, tin oxide, zinc oxide and the like. The average particle size of these conductive powders is preferably 1 μm or less. When the average particle size is 1 μm or less, there is an advantage that the electric resistance can be easily controlled.

For the resin layer, for example, the silicone resin or the like is dissolved in a solvent to prepare a coating solution, the coating solution is uniformly applied to the surface of the core material by a known coating method, dried, and then baked. It can be formed by doing. Examples of the coating method include a dipping method, a spraying method, and a brush coating method.
The solvent is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone and celsol butyl acetate.
The baking is not particularly limited, and may be an external heating method or an internal heating method. For example, a fixed electric furnace, a fluidized electric furnace, a rotary electric furnace, a burner furnace, or the like may be used. Examples thereof include a method using a method and a method using a microwave.

The amount of the resin layer in the carrier is preferably 0.01% by mass or more and 5.0% by mass or less.
When the amount is 0.01% by mass or more, the uniform resin layer can be formed on the surface of the core material. When the amount is 5.0% by mass or less, the thickness of the resin layer is appropriate and uniform carrier particles can be obtained.

The content of the carrier in the two-component developer is not particularly limited and may be appropriately selected depending on the intended purpose. For example, 90% by mass or more and 98% by mass or less is preferable, and 93% by mass or more and 97% by mass or less. Is more preferable.
The mixing ratio of the toner and the carrier of the two-component developer is preferably 1 part by mass or more and 10.0 parts by mass or less of the toner with respect to 100 parts by mass of the carrier.

Since the developer of the present invention contains the toner of the present invention, it suppresses so-called toner drop, which forms an abnormal image as if the toner had fallen on a recording medium due to the aggregation of the toner in the developing apparatus. , Occurrence of fog image can be suppressed, and excellent fixability and image density can be provided.
The developer of the present invention can be suitably used for image formation by various electrophotographic methods, and can be particularly preferably used for the following developing apparatus, process cartridge, image forming apparatus, and image forming method of the present invention.

(Developer)
In the developing apparatus of the present invention, the developer is carried while being supported by the developer carrier, an electric field is formed at a position facing the electrostatic latent image carrier, and the electrostatic is formed on the electrostatic latent image carrier. It is a device that develops a latent image with a developer to form a visible image.
The developer is the developer of the present invention.

(Process cartridge)
In the process cartridge of the present invention, an electrostatic latent image carrier that carries an electrostatic latent image and an electrostatic latent image that is supported on the electrostatic latent image carrier are developed with a developing agent and a visible image. It has at least a developing means for forming the above, and further has other means appropriately selected as needed.
As the developing means, a developer accommodating container for accommodating the toner or the developing agent of the present invention and a developing agent carrier for supporting and transporting the toner or the developing agent contained in the developing agent accommodating device are used. , At least, and may further have a layer thickness regulating member or the like for regulating the thickness of the toner layer to be supported.
The process cartridge of the present invention can be detachably provided in various image forming devices, and it is preferable that the process cartridge of the present invention is detachably provided in the image forming apparatus of the present invention described later.

The toner of the present invention also exerts an excellent effect when it is loaded into an image forming apparatus having a process cartridge to form an image. That is, by using the toner of the present invention, it is possible to provide a process cartridge having excellent image quality.

The image forming apparatus of the present invention exposes an electrostatic latent image carrier, a charging means for charging the surface of the electrostatic latent image carrier, and the surface of the charged electrostatic latent image carrier to produce an electrostatic latent image. An exposure means to be formed, a developing means for developing the electrostatic latent image with a developer to form a visible image, a transfer means for transferring the visible image to a recording medium, and a transfer means to be transferred to the recording medium. It has a fixing means for fixing a transferred image, and the developing means comprises the developing apparatus of the present invention.
Further, the image forming method of the present invention includes a charging step of charging the surface of the electrostatic latent image carrier, an exposure step of exposing the surface of the charged electrostatic latent image carrier to form an electrostatic latent image, and the static image processing. A developing step of developing a latent image with a developer to form a visible image, a transfer step of transferring the visible image to a recording medium, and a fixing step of fixing the transferred image transferred to the recording medium. The development step is performed using the development apparatus of the present invention.

FIG. 1 is a schematic view showing an example of the process cartridge of the present invention. The process cartridge 1 of FIG. 1 has a photoconductor 2, a charging means 3, a developing means 4, and a cleaning means 5.

In an image forming apparatus having a process cartridge, the photoconductor 2 is rotationally driven at a predetermined peripheral speed.
In the rotation process, the photoconductor 2 is uniformly charged with a positive or negative predetermined potential on its peripheral surface by the charging means 3, and then receives image exposure light from an image exposure means such as slit exposure or laser beam scanning exposure. Electrostatic latent images are sequentially formed on the peripheral surface of the photoconductor 2 in this way, the formed electrostatic latent image is then developed with toner by the developing means 4, and the developed toner image is the photoconductor from the paper feed unit. The transfer means sequentially transfers the images to the recording medium fed between the and the transfer means in synchronization with the rotation of the photoconductor.
The recording medium that has undergone image transfer is separated from the surface of the photoconductor, introduced into the fixing means, image-fixed, and printed out as a copy to the outside of the apparatus.
The surface of the photoconductor after transfer is cleaned by removing the transfer residual toner by the cleaning means 5, and after further static elimination, it is repeatedly used for image formation.

An excellent effect is also obtained when the toner of the present invention is used in an image forming apparatus having a contact type charging apparatus to form an image. That is, by using the toner of the present invention, it is possible to suppress the so-called toner drop, which forms an abnormal image in which the toner aggregates in the developing apparatus and the toner falls on the recording medium, and suppresses the generation of a fog image. Can provide excellent fixability and image density.

Here, FIG. 3 is a schematic view showing an example of an image forming apparatus having a charging apparatus that performs roller charging.
The drum-shaped photoconductor 10 as the charged body and the image carrier is rotationally driven at a predetermined speed (process speed) in the direction of the arrow in FIG.
The charging roller 11, which is a charging member in contact with the photoconductor 10, has a basic configuration of a core metal 12 and a conductive rubber layer 13 concentrically formed on the roller on the outer periphery of the core metal 12, and both ends of the core metal 12 are not formed. The photosensitive drum is pressed by a pressurizing means (not shown) with a predetermined pressing force while being held freely by a bearing member or the like shown in the drawing. In the case of FIG. 3, the charging roller 11 rotates the photoconductor 10. It rotates according to the drive.
The charging roller 11 is formed to have a diameter of 16 mm by coating a medium resistance rubber layer of about 100,000 Ω · cm on a core metal having a diameter of 9 mm.
As shown in FIG. 3, the core metal 12 of the charging roller 11 and the power supply 14 are electrically connected, and the power supply 14 applies a predetermined bias to the charging roller 11. As a result, the peripheral surface of the photoconductor 10 is uniformly charged to a predetermined polarity and potential.

Further, FIG. 4 is a schematic view showing an example of an image forming apparatus having a charging apparatus that performs brush charging.
The charged body and the drum-shaped photoconductor 20 as the image carrier are rotationally driven at a predetermined speed (process speed) in the direction of the arrow in FIG.
The fur brush roller 21 is in contact with the photoconductor 20 with a predetermined nip width with a predetermined pressing force against the elasticity of the brush portion 23.

The fur brush roller 21 as a contact charging member spirals a metal core metal 22 having a diameter of 6 mm that also serves as an electrode, and a tape made of a pile of conductive rayon fiber REC-B manufactured by Unitika Ltd. as a brush portion 23. It is a roll brush having an outer diameter of 14 mm and a longitudinal length of 250 mm by being wound in a shape.
The brush of the brush portion 23 has a density of 300 denier / 50 filaments and 155 brushes per square millimeter.
This roll brush was inserted into a pipe having an inner diameter of 12 mm while rotating in one direction, and the brush and the pipe were set to be concentric with each other, and left in a hot and humid atmosphere to be habitually slanted.
The resistance value of the fur brush roller 21 is 1 × 10 ⁵ Ω at an applied voltage of 100 V.
This resistance value was converted from the current flowing when a fur brush roller 21 was brought into contact with a metal drum having a diameter (φ) of 30 mm with a nip width of 3 mm and a voltage of 100 V was applied.

As for the resistance value of the fur brush charger, even if a low withstand voltage defect such as a pin hole occurs on the photoconductor 20 which is the object to be charged, an excessive leakage current flows into this part and the charging nip part becomes poorly charged. above 10 ⁴ Omega to prevent becomes defective image Konomashikuri, more preferably not more than 10 ⁷ Omega in order to inject sufficient charge on the photoreceptor surface.
In addition to REC-B manufactured by Unitika Co., Ltd., brush materials include REC-C, REC-M1, REC-M10, SA-7 manufactured by Toray Industries, Inc., and Thunderlon manufactured by Nihon Sanmo Dye Co., Ltd. , Bertron manufactured by Kanebo Co., Ltd., Cracabo manufactured by Kuraray Co., Ltd., carbon dispersed in rayon, Roval manufactured by Mitsubishi Rayon Co., Ltd., etc.
One brush has 3 denier to 10 denier, and a density of 10 filaments / bundle to 100 filaments / bundle and 80 brushes / mm to 600 brushes / mm is preferable. The fluff is preferably 1 mm to 10 mm.

The fur brush roller 21 is rotationally driven at a predetermined peripheral speed (surface speed) in the direction opposite to the rotation direction (counter) of the photoconductor 20 and comes into contact with the photoconductor surface with a speed difference. Then, by applying a predetermined charging voltage from the power supply 24 to the fur brush roller 21, the surface of the photoconductor is uniformly contact-charged to a predetermined polarity and potential.
The contact charging of the photoconductor 20 by the fur brush roller 21 is dominated by direct injection charging, and the surface of the photoconductor is charged to a potential substantially equal to the charging voltage applied to the fur brush roller 21.

In the case of magnetic brush charging as in the case of fur brush charging, the fur brush roller 21 formed of the magnetic brush with respect to the photoconductor 20 has a predetermined pressing force against the elasticity of the brush portion 23. Make contact with the nip width of.
As a magnetic brush as a contact charging member, Zn-Cu ferrite particles having an average particle size of 25 μm and Zn-Cu ferrite particles having an average particle size of 10 μm are mixed at a mass ratio of 1: 0.05, and the average particles of each are mixed. Magnetic particles obtained by coating ferrite particles having an average particle size of 25 μm having a peak at the diameter position with a medium resistance resin layer were used.
The contact charging member is composed of the coated magnetic particles produced above, a non-magnetic conductive sleeve for supporting the coated magnetic particles, and a magnet roll contained therein, and the coated magnetic particles are placed on the conductive sleeve in thickness. By coating with 1 mm, a charged nip having a width of about 5 mm was formed between the photoconductor 20 and the photoconductor 20.
The gap between the conductive sleeve holding the coated magnetic particles and the photoconductor was set to about 500 μm.
Further, the magnet roll is rotated so that the sleeve surface is rubbed in the opposite direction at twice the peripheral speed of the photoconductor surface so that the photoconductor and the magnetic brush are in uniform contact with each other. I made it.

Hereinafter, examples of the present invention will be described, but the present invention is not limited to these examples. The term "part" means a mass part.

In the following examples, the softening temperature of the resin, the glass transition point, and the weight average molecular weight were measured as follows.

<Measurement of resin softening temperature (Tm) and glass transition point (Tg)>
The softening temperature (Tm) was set according to the method described in JIS K72101 using a high-grade flow tester (manufactured by Shimadzu Corporation). While heating a 1 cm ³ sample at a heating rate of 6 ° C./min, ^{a load of 20 kg / cm 2} was applied by a plunger to extrude a nozzle having a diameter of 1 mm and a length of 1 mm. As a result, when a plunger drop-temperature curve is drawn and the height of the S-shaped curve is h, the temperature corresponding to h / 2 (the temperature at which half of the resin flows out) is set as the softening point (Tm). ..
The glass transition point (Tg) is heated from room temperature (25 ° C.) to 200 ° C. at 10 ° C./min using a differential scanning calorimeter (DSC-60, manufactured by Shimadzu Corporation), and then the temperature is lowered to 10 ° C. After cooling to room temperature at / min, when measured at a heating rate of 10 ° C / min, a curve corresponding to 1/2 the height h of the baseline below the glass transition point and the baseline above the glass transition point is formed. It was defined as the glass transition point (Tg).

<Weight average molecular weight of resin (Mw)>
The weight average molecular weight was measured using a GPC measuring device (HLC-8220 GPC, manufactured by Tosoh Corporation) and a column (TSKgel SuperHZM-H 15 cm triplet, manufactured by Tosoh Corporation). Specifically, the column was stabilized in a heat chamber at 40 ° C. Next, tetrahydrofuran (THF) was flowed through the column at a flow rate of 1 mL / min, and 50 μL to 200 μL of a THF solution of the sample of 0.05% by mass to 0.6% by mass was injected, and the weight average molecular weight of the sample was measured. .. At this time, the number average molecular weight of the sample was calculated from the relationship between the logarithmic value of the calibration curve prepared using several types of monodisperse polystyrene standard samples and the number of counts.
As standard polystyrene samples, the weight average molecular weights are 6 × 10 ² , 2.1 × 10 ³ , 4 × 10 ³ , 1.75 × 10 ⁴ , 5.1 × 10 ⁴ , 1.1 × 10 ⁵ , and so on. Samples of 3.9 × 10 ⁵ , 8.6 × 10 ⁵ , 2 × 10 ⁶ , and 4.48 × 10 ⁶ (manufactured by Pressure Chemical Co., Ltd. or Tosoh Co., Ltd.) were used.
Moreover, as a detector, an RI (refractive index) detector was used.

(Production Example 1 of Non-Linear Polyester Resin)
-Manufacture of non-linear polyester resin A-
9.0 mol of fumaric acid, 3.5 mol of trimellitic anhydride, 5.5 mol of bisphenol A (2,2) propylene oxide, 3.5 mol of bisphenol A (2,2) ethylene oxide with stainless stir bar, flow-down condenser, nitrogen gas The non-linear polyester resin A was obtained by placing it in a flask equipped with an introduction tube and a thermometer and carrying out a depolymerization reaction while stirring at a temperature of 230 ° C. in a nitrogen atmosphere.
The obtained non-linear polyester resin A had a softening point (Tm) of 145.1 ° C., a glass transition point (Tg) of 61.5 ° C., and a weight average molecular weight (Mw) of 82,000.

(Production Example 2 of Linear Polyester Resin)
-Manufacture of linear polyester resin B-
7 mol of terephthalic acid, 2.5 mol of trimellitic anhydride, 5.5 mol of bisphenol A (2,2) propylene oxide, and 3.5 mol of bisphenol A (2,2) ethylene oxide were introduced into a stainless stirring rod, a flow-down condenser, and nitrogen gas. It was placed in a flask equipped with a tube and a thermometer, and a shrink polymerization reaction was carried out while stirring at a temperature of 230 ° C. in a nitrogen atmosphere to obtain a linear polyester resin B.
The obtained linear polyester resin B had a softening point (Tm) of 102.8 ° C., a glass transition point (Tg) of 61.2 ° C., and a weight average molecular weight (Mw) of 8,000.

(Production Example 1 of Hybrid Resin)
-Manufacturing of hybrid resin C-
18 mol of styrene and 4.5 mol of butyl methacrylate as the addition polymerization reaction monomer and 0.35 mol of t-butyl hydroperoxide as the polymerization initiator were added to the dropping funnel, and 9.0 mol of fumaric acid as the addition polymerization and depolymerization reactive monomer was added. Stirring 3.5 mol of trimellitic anhydride, 5.5 mol of bisphenol A (2,2) propylene oxide, 3.8 mol of bisphenol A (2,2) ethylene oxide as a polymerization reaction monomer, and 58 mol of dibutyltin oxide as an esterification catalyst. Place in a flask equipped with a rod, a flow-down condenser, a nitrogen gas introduction tube, and a thermometer, and while stirring at 138 ° C. under a nitrogen atmosphere, premix the addition polymerization-based raw material from the dropping funnel and drop it over 4 hours. bottom.
After completion, the mixture was aged for 6 hours while being maintained at 138 ° C., then heated to 230 ° C. and reacted to obtain a hybrid resin C.
The obtained hybrid resin C had a softening point (Tm) of 151.5 ° C. and a glass transition point (Tg) of 62.1.
The obtained hybrid resin C is a polyester resin (weight average molecular weight (Mw) = 48,000) / styrene-acrylic copolymer resin (weight average molecular weight (Mw) = 190,000) = 78/22 (mass ratio). It was a composition.

(Creation of toner matrix particles A)
Crystalline polyester resin a: 2 parts by mass amorphous resin b1 (non-linear polyester resin A): 35 parts by mass amorphous resin b2 (linear polyester resin B): 55 parts by mass composite resin c (hybrid resin C) : 10 parts by mass Colorant p (Mitsubishi Carbon Black # 44, manufactured by Mitsubishi Chemical Co., Ltd.): 14 parts by mass Release agent: Carnauba wax (melting point: 81 ° C) 6 parts by mass Charge control agent: Monoazo metal complex 2 parts by mass ( Chromium-based complex salt dye (Bontron S-34 manufactured by Orient Chemical Industry Co., Ltd.)

The above raw materials are premixed using a Henshell mixer (FM20B, manufactured by Mitsui Miike Machinery Co., Ltd.), and then melted at a temperature of 100 to 130 ° C. by a twin-screw kneader (PCM-30, manufactured by Ikekai Co., Ltd.). Kneaded. The obtained kneaded product was rolled to a thickness of 2.7 mm with a roller, cooled to room temperature with a belt cooler, and roughly pulverized to 200 to 300 μm with a hammer mill. Next, after fine pulverization using a supersonic jet crusher Lab Jet (manufactured by Nippon Pneumatic Industries Co., Ltd.), the weight average particle size is 6. Classification was performed while appropriately adjusting the louver opening degree so as to be 9 ± 0.2 μm to obtain toner matrix particles. Next, 1.0 part by mass of the additive (HDK-2000, manufactured by Clariant Co., Ltd.) was stirred and mixed with 100 parts by mass of the toner base particles with a Henschel mixer to prepare toner base particles A.

(Creation of crystalline polyester resin)
The crystalline polyester resin a is a resin obtained by using 1,4-butanediol as an alcohol component and fumaric acid as a carboxylic acid component. Specifically, after the monomer of the alcohol component and the carboxylic acid component is subjected to an esterification reaction under normal pressure at 170 to 260 ° C. under the condition of no catalyst, the reaction system is trioxidized at 400 ppm with respect to the total carboxylic acid component. Antimon was added and polycondensation was carried out at 250 ° C. while removing glycol from the system under a vacuum of 3 Torr to obtain a crystalline resin. The cross-linking reaction was carried out until the stirring torque reached 10 kg · cm (100 ppm), and the reaction was stopped by releasing the reduced pressure state of the reaction system. Further, it was confirmed that the crystalline polyester resin a is a crystalline polyester by having at least one diffraction peak at a position of 2θ = 19 ° to 25 ° in the X-ray diffraction pattern by the powder X-ray diffractometer. ..

(Creation of toner matrix particles B, C, D, E)
Toner matrix particles B, C, D, and E were prepared except that the amount of the crystalline polyester resin a added was changed as follows in the preparation of the toner matrix particles A.
Toner matrix particles B: 1 part by mass of crystalline polyester a was used.
Toner matrix particles C: 4 parts by mass of crystalline polyester a was used.
Toner matrix particles D: 6 parts by mass of crystalline polyester a was used.
Toner matrix particles E: 0.5 parts by mass of crystalline polyester a was used.

The pseudo-boehmite fine particles used in the examples can be obtained by the following procedure.
First, alumina hydrate is obtained. Alumina hydrate can be obtained by known production methods such as hydrolysis of aluminum alkoxides such as aluminum isoprovoxide, neutralization of aluminum salts with alkali, and hydrolysis of aluminate. Alumina hydrate is _{represented by the constitutional formula of Al 2} O ₃ , nH ₂ O (n = 1 to 3), and when n is 1, it represents an alumina hydrate having a boehmite structure, and n is larger than 1. A case of less than 3 represents an alumina hydrate having a pseudo-boehmite structure.

(Preparation of surface-treated silica A)
First, 100 g of silica particles (Nipseal SP-200 BET specific surface area 200 m ² / g manufactured by Tosoh Silica) produced by the liquid phase method are dispersed in 2 L of water and heated to 85 ° C.
_{Next, by adding an aluminum chloride aqueous solution in an amount of 10% by mass in terms of Al 2} O ₃ to the silica particles, adjusting the pH to 5.5 with an aqueous sodium hydroxide solution, and holding the mixture for 30 minutes with stirring. Aluminum chloride was hydrolyzed, and the surface of the silica particles was coated with aluminum hydroxide to obtain surface-treated silica A. The volume average particle size (D50) of the surface-treated silica was 20 nm.

(Preparation of surface-treated silicas B, C, D)
Surface-treated silica B: In the preparation of the surface-treated silica A, the amount of the aluminum chloride aqueous solution added was changed to 5% by weight to obtain the surface-treated silica B.
Surface-treated silica C: In the preparation of the surface-treated silica A, the amount of the aluminum chloride aqueous solution added was changed to 20% by weight to obtain the surface-treated silica C.
Surface-treated silica D: In the preparation of the surface-treated silica A, the aqueous aluminum chloride solution was replaced with a pseudo-bemite aqueous solution, and the amount added was 10% by weight to obtain the surface-treated silica D.

(Examples 1 to 10, Comparative Examples 1 to 2)
Various surface-treated silicas were added and mixed with respect to 100 parts by mass of the toner matrix particles according to the formulation shown in Table 1. A Henschel mixer (FM20C / I manufactured by Nippon Coke Industries Co., Ltd.) was used for the mixing treatment, and various toners were obtained by repeating rotation 1 min and stop 1 min 15 times at a rotation speed of 3176 rpm (total mixing time 15 min). The surface-treated silica and the additive (HDK-2000, manufactured by Clariant AG) were added at the same time.

With respect to the obtained various toners, the peak ratio C / R was measured according to the method described above. The results are shown in Table 2.

<Preparation of developer>
5% by mass of each toner produced and 95% by mass of a copper-zinc ferrite carrier coated with a silicone resin and having an average particle diameter of 40 μm were mixed to prepare each two-component developer.

<Image evaluation>
Using each of the obtained two-component developing agents, development was performed with a remodeling machine (imageoMF7070, manufactured by Ricoh Co., Ltd.), and 5,000 sheets were developed in a low-temperature and low-humidity environment (temperature 10 ° C., humidity 15% RH). At / day, after initial and 100K (100,000) sheets are output, 3 sheets each of white solid and black solid images are printed on A3 size paper (brand: RICOH MyPaper), and the fog on the obtained solid image is visually observed. It was observed and evaluated based on the following evaluation criteria for fog. In addition, the toner drop was evaluated by visually measuring the score of the toner drop formed on the paper. Further, the image density (ID) of the solid image was measured with X-Rite938 (manufactured by X-RITE) and evaluated based on the following image density evaluation criteria. For low temperature fixability, a solid image with an adhesion amount of 0.4 mg / cm ² was output on paper (Type 6200 manufactured by Ricoh) through exposure, development, and transfer steps. The fixing line speed was 180 mm / sec. The fixing temperature was sequentially output in increments of 5 ° C., and the lower limit temperature at which cold offset did not occur (fixing lower limit temperature: low temperature fixability) was measured. The NIP width of the fixing device was 11 mm. It was evaluated according to the following evaluation criteria. The results are shown in Table 2.

[Evaluation criteria for fog (dirt)]
◎: Very good with no fog ○: Almost no fog, good △: Slight fog occurs, but within the standard ×: Fogging, defective

[Evaluation criteria for toner drop]
⊚: The number of toner drops is 0 to 1. ○: The number of toner drops is 2-3. Δ: The number of toner drops is 4 to 5 ×: The number of toner drops is 6 or more.

[Evaluation criteria for image density]
⊚: Image density (ID) is 1.40 or more ○: Image density (ID) is 1.20 or more and less than 1.40 Δ: Image density (ID) is 1.00 or more and less than 1.20 ×: Image density (ID) ) Is less than 1.00

[Evaluation criteria for low temperature fixability]
⊚: less than 130 ° C 〇: 130 ° C or more and less than 145 ° C Δ: 145 ° C or more and less than 160 ° C ×: 160 ° C or more

[comprehensive evaluation]
◎: Satisfies significantly above the standard 〇: Satisfies above the standard △: Meets the standard ×: Does not meet the standard at all

From the results in Table 2, excellent results were shown in each of the above evaluation items in each example.

1 Process cartridge 2 Photoreceptor 3 Charging means 4 Developing means 5 Cleaning means 10 Photoreceptor 11 Charging roller 12 Core metal 13 Conductive rubber layer 14 Power supply 20 Photoreceptor 21 Fur brush roller 22 Core metal 23 Brush part 24 Power supply

Japanese Patent No. 2931899 Japanese Unexamined Patent Publication No. 2001-222138 Japanese Patent No. 6260207

Claims (8)

In an electrostatic latent image developing toner containing a toner base containing a binder resin, a colorant, and a mold release agent.
The binding resin contains a crystalline polyester resin and an amorphous resin, and contains
The electrostatic latent image developing toner further contains silica surface-treated with at least one selected from aluminum hydroxide, boehmite and pseudo-boehmite as an external additive.
The toner for electrostatic latent image development has a peak height of a characteristic spectrum of the crystalline polyester resin measured by the ATR method (total reflection method) using FT-IR (Fourier transform infrared spectroscopic analysis measuring device). For electrostatic latent image development, the peak ratio C / R satisfies the following formula (1), where C is C and the peak height of the characteristic spectrum of the amorphous resin is R. toner.
0.01 ≤ C / R ≤ 0.10. Equation (1) The toner for electrostatic latent image development according to claim 1, wherein the ratio (W / R) is 0.05 or more and 0.14 or less.
(However, the W represents the peak height of the characteristic spectrum of the release agent measured by the ATR method (total reflection method) using FT-IR (Fourier transform infrared spectroscopic analysis measuring device)). A toner container containing the toner for electrostatic latent image development according to claim 1 or 2. A developer comprising the toner according to claim 1 or 2 and a carrier. The developer is carried while being supported by the developer carrier, an electric field is formed at a position facing the electrostatic latent image carrier, and the electrostatic latent image formed on the electrostatic latent image carrier is developed with the developer. It is a developing device that forms a visible image.
A developing apparatus according to claim 4, wherein the developing agent is the developing agent. It has an electrostatic latent image carrier and a developing means for developing a electrostatic latent image formed on the electrostatic latent image carrier by using a developing agent to form a visible image, and forms an image. A process cartridge that can be attached to and detached from the device body.
A process cartridge according to claim 5, wherein the developing means comprises the developing apparatus according to claim 5. An electrostatic latent image carrier, a charging means for charging the surface of the electrostatic latent image carrier, and
An exposure means that exposes the surface of a charged electrostatic latent image carrier to form an electrostatic latent image,
A developing means that develops the electrostatic latent image with a developer to form a visible image,
A transfer means for transferring the visible image to a recording medium,
A fixing means for fixing the transferred image transferred to the recording medium, and
It is an image forming apparatus having
An image forming apparatus according to claim 5, wherein the developing means comprises the developing apparatus according to claim 5. A charging process that charges the surface of the electrostatic latent image carrier,
An exposure process that exposes the surface of a charged electrostatic latent image carrier to form an electrostatic latent image,
A developing step of developing the electrostatic latent image with a developer to form a visible image,
A transfer step of transferring the visible image to a recording medium,
A fixing step of fixing the transferred image transferred to the recording medium, and
It is an image forming method including
An image forming method, characterized in that the developing step is performed using the developing apparatus according to claim 5.

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