JP4817386B2 - Image forming apparatus and toner and developer used therefor - Google Patents

Description

  The present invention provides an image forming apparatus capable of simultaneously achieving excellent low-temperature fixability and filming property of toner even in an ultra-high-speed image forming apparatus, and a toner, developer, toner or developer container, and process used therefor It relates to the cartridge.

  In recent years, there has been a general demand for higher speed and higher image quality in the electrophotographic imaging industry. In particular, toner fixability, which is one of the factors that have an important influence on image quality, deteriorates as the image forming speed, that is, the so-called system speed of the image forming apparatus, increases. It is a problem to make it.

The unfixed toner image on the paper is fixed by heat and pressure in the fixing device, and the toner image is fixed to the paper. However, when the system speed increases, the unfixed toner image on the paper cannot receive a sufficient amount of heat in the fixing device. In other words, the toner with poor fixing is peeled off from the paper.
It is conceivable to raise the fixing temperature in order to increase the system speed and not to drop the fixing.However, there are limitations in terms of side effects due to an increase in the in-machine temperature, the life of the fixing member, and energy saving. It is enough. Therefore, particularly in an ultra-high speed machine, improvement in the fixing performance of the toner itself is required, and there is a need for a toner design that has high-speed image formation with a fixing device and good fixability even with a low heat quantity.

Various studies have been made to improve the fixing property of the toner.
For example, in order to improve the fixing performance of the toner itself, a method of controlling the thermal characteristics of the resin itself is known. However, lowering the Tg (glass transition temperature) of the resin will cause deterioration in heat-resistant storage stability and fixing strength, and if the F _1/2 temperature is lowered due to the lower molecular weight of the resin, the occurrence of hot offset and gloss are too high. Problems such as (gloss controllability) occur. For this reason, by controlling the thermal characteristics of the resin itself, it has not yet been possible to obtain a toner having excellent low-temperature fixability and excellent heat-resistant storage stability and offset resistance.

  In order to cope with such low-temperature fixing, attempts have been made to use polyester resins that are excellent in low-temperature fixing properties and relatively good in heat-resistant storage, in place of styrene-acrylic resins that have been widely used in the past (Patent Documents 1 to 3). 6: JP-A-60-90344, JP-A-64-15755, JP-A-2-82267, JP-A-3-229264, JP-A-3-41470, JP-A-11-305486 Publication). In addition, there is an attempt to add a specific non-olefinic crystalline polymer having a sharp melt property at a glass transition temperature to a binder for the purpose of improving low-temperature fixability (Patent Document 7: JP-A-62-63940). However, it cannot be said that the molecular structure and molecular weight are optimized.

  There are also attempts to use crystalline polyester having sharp melt properties (Patent Document 8: Japanese Patent No. 2931899, Patent Document 9: Japanese Patent Laid-Open No. 2001-222138). The acid value and the hydroxyl value of the resin are as low as 5 or less and 20 or less, respectively, and since the affinity between paper and crystalline polyester is low, sufficient low-temperature fixability cannot be obtained. Also, in Patent Document 9, the molecular structure and molecular weight of the crystalline polyester are not optimized, and the release roller is not applied to the fixing roller while having an appropriate gloss, or the amount of oil applied is very small. Even with the fixing method, the toner has sufficient low-temperature fixing property and sufficient offset prevention property, and at the same time, it is not a toner excellent in toner storage stability, transferability, durability, charging stability against humidity, and pulverization property.

Further, in the technique described in Patent Document 10 (Japanese Patent Application Laid-Open No. 2002-214833), an incompatible and island-like phase separation structure between a crystalline polyester resin and an amorphous polyester resin, or a difference in THF insolubles in the resin. By specifying the maximum peak temperature that appears on the endothermic side in the DSC curve measured by a scanning calorimeter, both the lower limit of fixability and storage stability are achieved, but it cannot be said that sufficient quality has been obtained. There was found.
In addition, as described above, it is effective to use a crystalline polyester resin in order to provide a sufficient fixability in a high-speed machine, particularly an ultra-high-speed image forming engine. When the phenomenon of filming occurs and the filming progresses, a white-out abnormal image occurs in the solid image.

In improving the filming, Japanese Patent Application Laid-Open No. 2005-189594 discloses that a bias having the same polarity as the toner is applied to the brush roller, and the toner collected by the brush roll is discharged onto the photoreceptor. It has been proposed that when the toner discharged from the brush roll passes through the cleaning blade, the cleaning blade scrapes off the filming material adhering to the photosensitive member, but means for forcibly scraping off the filmed material. It is not a means for preventing filming and is not a fundamental solution.
JP 60-90344 A JP-A 64-15755 Japanese Patent Laid-Open No. 2-82267 JP-A-3-229264 JP-A-3-41470 JP-A-11-305486 JP 62-63940 A Japanese Patent No. 2931899 JP 2001-222138 A JP 2002-214833 A JP 2005-189594 A

  The present invention has been made to solve the problems in the above-mentioned image forming apparatus having an ultra-high system speed, and an image forming apparatus capable of simultaneously achieving a filming property of toner as well as an excellent low-temperature fixing property. It is an object to provide a toner, a developer, a toner or developer container, and a process cartridge to be used.

As a result of intensive studies, the present inventors have found that in an image forming apparatus having a system speed of 500 to 1700 mm / sec, the visible image on the recording medium contains at least a binder resin and a colorant. ATR using at least one polyester resin having crystallinity and one kind being an amorphous resin and using an FT-IR (Fourier Transform Infrared Spectrometer) of the toner. In the method (total reflection method), when the peak height of the characteristic spectrum of the crystalline polyester resin is W and the peak height of the characteristic spectrum of the amorphous resin is R, it is expressed as W / R. After the transfer is performed, the peak ratio is 0.050 to 0.555, and the amount of toner in the visible image portion on the surface of the image carrier is W (mg / cm ² ) when the image forming apparatus forms an image. On the surface of the image carrier The amount of residual toner in the case of the A (mg / cm ²⁾ that the following formula - by T (1) is 75% to 100%, turned out to be possible to solve the above problems did.
Toner transfer rate T (%) = (W−A) × 100 / W Formula− (1)
That is, the said subject is solved by (1)-(11) of this invention.

(1) an image carrier that carries a latent image;
A charging device for charging the surface of the image carrier;
An exposure device for writing an electrostatic latent image on the surface of the charged image carrier;
A developing device that visualizes the electrostatic latent image formed on the surface of the image carrier using a developer containing toner;
A transfer device for transferring a visible image on the surface of the image carrier onto a transfer medium and / or a recording medium;
A cleaning device for cleaning the transfer residual toner remaining on the surface of the image carrier;
In an image forming apparatus comprising a fixing device for fixing a visible image on a recording medium,
The system speed is 500-1700 mm / sec,
The toner contains at least a binder resin, a fatty acid amide compound, and a colorant. The fatty acid amide compound is internally added in the toner, and the binder resin has at least a crystalline polyester resin and a non-crystalline resin. A characteristic spectral peak height of the crystalline polyester resin in the ATR method (total reflection method) using the FT-IR (Fourier transform infrared spectroscopic analyzer) of the toner. W, where R is the peak height of the characteristic spectrum of the amorphous resin, the peak ratio indicated by W / R is 0.450 to 0.553 , and when the image forming apparatus forms an image, The amount of toner in the visible image portion on the surface of the image carrier is W (mg / cm ² ), and the amount of transfer residual toner remaining on the surface of the image carrier after transfer is A (mg / cm ² ). The following formula-( ) Toner transfer ratio T which is expressed by the image forming apparatus, characterized in that 75 to 100%.
Toner transfer rate T (%) = (W−A) × 100 / W Formula− (1)

(2) The developer is a developer for developing a two-component electrostatic image containing a carrier made of magnetic particles, and the toner concentration (toner weight / (toner weight + carrier weight)) is 4 wt%, and the mixture is stirred and mixed. In the charge amount of the toner measured by the V blow-off device single mode as the initial agent, the toner charge fluctuation rate (%) P represented by the following formula-(2) is 0 to 40% (1) ).
Toner charge fluctuation rate (%) P
= (M−H) × 100 / ((H + M) ÷ 2) Formula− (2)
(However, M is the toner charge amount at 23 ° C. and 55% relative humidity in the environment.
The toner charge amount in the environment of 42 ° C. and relative humidity 40% is H. )

(3) The (1) or (1) above, wherein the amorphous resin is a polyester resin formed in the presence of titanium dihydroxybis (triethanolaminate ) which is a titanium-containing catalyst (a). The image forming apparatus according to 2).

(4) The image forming apparatus according to any one of (1) to (3), wherein the crystalline polyester resin has an acid value of 20 to 45 mgKOH / g.
(5) The image forming apparatus according to any one of (1) to (4), wherein the crystalline polyester resin has a hydroxyl value of 5 to 50 mgKOH / g.

(6) The image forming apparatus according to any one of (1) to (5), wherein the toner contains a wax as a release agent, and the melting point of the wax is 70 to 150 ° C.

According to the present invention, it is possible to provide an image forming apparatus and a toner excellent in filming property and low-temperature fixing property even in an ultrahigh-speed image forming apparatus.
Further, according to the present invention, it is possible to provide the image forming apparatus, and the toner, developer, toner and developer container, and process cartridge used therefor.

As a result of intensive studies, the present inventors have found a mechanism analysis and a countermeasure for the toner filming problem on the photoreceptor that occurs when a toner containing a crystalline polyester resin is used in an ultra-high speed machine.
The present invention is described in further detail below.
In an ultra-high-speed image forming apparatus having a high system speed, particularly a linear speed of 500 to 1700 mm / s, it is effective to use a crystalline polyester resin as a toner in order to provide a sufficient fixability. In the present invention, the system speed refers to the moving speed of the fixing medium.
However, it has been found that if the amount of crystalline polyester resin on the toner surface by FT-ATR is large, the charging ability of the toner is lowered. In particular, the ultra-high-speed image forming device is a high-speed engine, so that the time from when the toner is charged into the developing unit through the replenishing port until it is consumed by the developing sleeve to the image carrier is extremely short, and it is not sufficiently charged with stirring. Development is also a problem of the fate of toner for high-speed machines.

A toner with a low charge amount has a greater amount of toner adhering to the image carrier under the same development conditions than a toner with a high charge amount. When transferred, the toner in the layer close to the image carrier is not easily transferred, resulting in a deterioration in transfer rate.
The transfer residual toner on the image carrier due to the deterioration of the transfer rate is pressed against the blade or brush by the cleaning device, so that the toner is gradually fixed to the photoconductor and filmed.
The point to solve the filming problem is the toner transfer rate T, and the filming problem can be prevented by controlling the transfer rate T to 75 to 100%.
When the transfer rate is lower than 75%, the transfer residual toner is pressed against the blade or brush by the cleaning device, and gradually adheres to the photoconductor and forms a film. End up.
In the case of 75% or more, the degree of filming is small, and an abnormal image does not appear in the solid image.

  When a crystalline polyester resin that is indispensable for securing fixing properties is used for the toner, as a means for achieving a transfer rate of 75% or more, the amount of the crystalline polyester resin localized on the toner surface can be optimized. It is an important and effective means. If a large amount of crystalline polyester resin is localized on the toner surface, the toner charge amount is likely to fluctuate, resulting in deterioration of the transfer rate and filming. However, if the amount of crystalline polyester resin is reduced, ultra-high speed Therefore, it is important not to reduce the total amount of the crystalline polyester resin but to reduce the total amount of the crystalline polyester resin and to prevent the crystalline polyester resin from precipitating on the toner surface. In the present invention, by using an amorphous resin together with the crystalline polyester resin, the amount of the crystalline polyester resin localized on the toner surface can be optimized. Further, it is preferable to provide a margin for the transfer rate in combination with other means described below.

  The localized amount of the crystalline polyester resin on the toner surface of the present invention is determined from an absorbance spectrum obtained by ATR method (total reflection method) measurement by “Avatar 370 / Thermo Electron Co., Ltd.” with FT-IR (Fourier transform infrared spectroscopic measurement device). The characteristic peak height of the crystalline polyester resin is W, the characteristic peak height of the amorphous resin is R, and the crystalline polyester resin peak ratio represented by W / R is 0.050. It is preferable that it is -0.555. 0.080 to 0.450 is more preferable.

It is extremely important that the crystalline polyester resin peak ratio represented by W / R is 0.050 to 0.555. The crystalline polyester resin and amorphous resin peak ratio on the toner surface represents the localized state of the crystalline polyester resin on the toner surface.
When the resin peak ratio indicated by W / R is smaller than 0.050, the filming property of the toner is good, but the fixing property is inferior.
When the resin peak ratio indicated by W / R is larger than 0.555, the toner fixing property is good, but the filming property is inferior.

  It is considered that such control of the resin peak ratio indicated by W / R is determined by the compatibility state of the crystalline polyester resin with the amorphous resin. However, since there are places where crystallinity is difficult to measure, in the present invention, by using quality engineering techniques, the manufacturing conditions such as the ratio of toner prescription raw materials, the kneading step, the pulverizing step, and the additive mixing step are optimized. By making the formulation and the production conditions such that the crystalline polyester resin peak ratio represented by W / R falls within 0.050 to 0.555 as optimum conditions, it is achieved intentionally and reliably. In other words, the technical key point of the present invention is that the optimum conditions for formulation and production are found in consideration of the balance of filming property, fixing property, and productivity.

  For example, when the amount of the raw material for the crystalline polyester resin is too large, the amount of the crystalline polyester resin localized on the toner surface increases. Crystalline polyester resin localized on the toner surface by reducing the compatibility of crystalline polyester resin and amorphous resin by adding an auxiliary agent that can recrystallize more crystalline polyester resin as raw material of toner Will increase. This is a balance problem, and it is preferable to determine an appropriate reference line in consideration of the recrystallization state.

Measurement method of crystalline polyester resin peak ratio indicated by W / R The crystalline polyester resin peak ratio on the toner surface is measured by ATR method (total reflection method) using FT-IR (Fourier transform infrared spectroscopic analyzer). It is obtained from the peak intensity ratio known from the ATR spectrum. Since the ATR method requires a smooth surface, the toner is pressure-molded to create a smooth surface. At this time, pressure molding was performed by applying 1 t to 0.6 g of toner for 30 sec to obtain a pellet having a diameter of 20 mm.

In the present invention, the peak height of the characteristic spectrum (1165 cm ⁻¹ ) in the crystalline state of the crystalline polyester resin is W (FIG. 2, the height base line is 1199 to 1137 cm ⁻¹ ). Characteristic spectrum (for example, 829 cm ^-1 for polyester resin, "Figure 3, height baseline is 784-889 cm ^-1 ", for styrene-acrylic resin, 699 cm ^-1 "Figure 4, height base. The line was calculated with the peak height of 714-670 cm ^-1 ") as R and W / R as the peak intensity ratio. In the present invention, the peak intensity ratio is obtained by converting the spectrum to absorbance and using the peak height.

Further, as a means for giving a margin to the transfer rate, the following method may be mentioned.
For example, using quality engineering, transfer conditions such as transfer current, voltage, pressure, transfer material type, etc. are factors, and engine temperature is an error factor, which affects the transfer rate according to the characteristics of each image forming device. By optimizing the factor level, controlling the transfer rate to 75% or more is the most effective means for preventing filming without degrading quality such as toner fixability.

Transfer rate measurement method:
The toner density of the developer and the developing bias of the corresponding developing device are adjusted, and a toner having a toner amount of 1.0 to 1.4 mg / cm ² is adhered to the photoreceptor.
A 5 × 2 cm cello tape (registered trademark) is applied to the image on the photoreceptor, and the entire surface is pressed with a finger, and the toner on the photoreceptor is transferred to the tape without leaving any residue. The weight of the toner transferred to the tape is obtained by subtracting the weight of the single tape before transfer from the total weight of the tape after transfer and the toner transferred on the tape, and is defined as W.
After the image is transferred by the transfer device, the weight of the transfer residual toner on the photoconductor is measured by the same procedure as the tape method, and is set as A.
The toner transfer rate is calculated according to Formula (1).
Toner transfer rate T (%) = (W−A) × 100 / W Formula− (1)

Furthermore, as a means for controlling the transfer rate, by optimizing the prescription and manufacturing method on the toner side, the toner charge amount environment fluctuation rate is reduced, and the chargeability of the toner is stabilized, so that the toner layer adhering to the image carrier does not increase. It was found that the transfer rate can be secured by controlling in this way.
The toner charge amount environmental fluctuation rate obtained by the following measurement method is preferably 40% or less. 30% or less is more preferable. When the environmental fluctuation rate of toner charging exceeds 40%, the charge amount becomes lower in the in-machine engine section where the temperature is higher than normal temperature and humidity. Under the same development conditions, the amount of toner adhering to the image carrier increases, and when transferred, toner in a layer near the image carrier is difficult to transfer, resulting in a deterioration in transfer rate. When the transfer rate deteriorates to less than 75%, the transfer residual toner is pressed against the blade or the brush by the cleaning device, and gradually adheres to the photoconductor and forms a film, resulting in an abnormal white image on the solid image. End up.

In order to control the environmental fluctuation of the toner chargeability as described above, the quality engineering is also used. The toner raw material type, the charge amount, the external additive mixing conditions, etc. are used as factors, and the engine temperature is used as an error factor. In accordance with the characteristics of the forming apparatus, it is effective to find the optimum level of each factor that stabilizes the toner chargeability most.
For example, when the amount of crystalline polyester resin charged in the toner formulation is reduced, the toner charge fluctuation rate is improved. When the amount of crystalline polyester resin charged is increased, the toner charge fluctuation rate is deteriorated. In addition, there are means such as prevention of burying of the external additive by the hydrophobized large particle size silica, improvement of the toner charge rise margin by examining the type of titanium, and optimization of the external addition state to the toner by examining the mixing condition of the external additive.

Details of the measurement of the toner charge amount by the V blow-off device single mode method will be described.
The toner and the carrier were allowed to stand in a predetermined environment (temperature, humidity) for 2 hours at a toner concentration (toner weight / (toner weight + carrier weight)) of 4 wt%, and 6 g of the mixture was stirred and mixed for 780 seconds with a mag roll with a rotation speed of 285 rpm. 1 g of developer is weighed from the initial agent, and the toner charge amount distribution is measured by a single mode method using a V blow-off device (manufactured by Ricoh Creative Development Co., Ltd.).
When blowing, a mesh of 795 mesh is used.
The measurement conditions of the single mode method are height 5 mm, suction 100, and double blow.
When the toner charge amount at 23 ° C. and 55% relative humidity is M, and the toner charge amount at 42 ° C. and 40% relative humidity is H, the toner charge fluctuation rate (%) P is expressed by the following formula − ( 2).
Toner charge fluctuation rate (%) P
= (M−H) × 100 / ((H + M) ÷ 2) Formula− (2)
The details of other measurement conditions conform to the conditions described in Japanese Patent No. 3487464.

The amorphous resin used in the present invention is preferably an amorphous polyester resin, and the catalyst used for preparing the amorphous polyester resin is a specific titanium represented by the following formula (I) or (II): It is important to use the contained catalyst (a). By using the catalyst, the toner charge amount environmental fluctuation rate is improved. The reason is unknown, but the charge control agent can be uniformly dispersed in the amorphous polyester resin by a specific catalyst, and the amorphous polyester resin and the crystalline polyester resin are more easily melted. It is conceivable that the precipitated crystalline polyester resin is reduced.
Ti (-X) m (-OH) n (I)
O = Ti (-X) p (-OR) q (II)
[Wherein X is a residue obtained by removing H of one OH group from mono- or polyalkanolamine having 2 to 12 carbon atoms, and other OH groups of polyalkanolamine are directly bonded to the same Ti atom. An OH group may be polycondensed in the molecule to form a ring structure, or an OH group directly bonded to another Ti atom may be polycondensed between molecules to form a repeating structure. The degree of polymerization in the case of forming a repeating structure is 2-5. R is H or an alkyl group having 1 to 8 carbon atoms which may contain 1 to 3 ether bonds. m is an integer of 1 to 4, n is an integer of 0 to 3, and the sum of m and n is 4. p is an integer of 1 to 2, q is an integer of 0 to 1, and the sum of p and q is 2. When m or p is 2 or more, each X may be the same or different. ]

Two or more of the titanium-containing catalysts represented by the formula (I) or (II) may be used in combination. In the general formulas (I) and (II), X is a residue obtained by removing the H atom of one OH group from a mono- or polyalkanolamine having 2 to 12 carbon atoms, and the number of nitrogen atoms, ie, primary, The total number of secondary and tertiary amino groups is usually 1 to 2, preferably 1.
Examples of the monoalkanolamine include ethanolamine and propanolamine. Polyalkanolamines include dialkanolamines (such as diethanolamine, N-methyldiethanolamine, and N-butyldiethanolamine), trialkanolamines (such as triethanolamine, and tripropanolamine), and tetraalkanolamines (N, N, N). ', N'-tetrahydroxyethylethylenediamine and the like).

  In the case of polyalkanolamine, at least one OH group is present in addition to the OH group that is a residue other than H used to form a Ti—O—C bond with a Ti atom, and this is the same Ti atom. A ring structure may be formed by polycondensation with a directly bonded OH group in the molecule, or a repeating structure may be formed by polycondensation between molecules with an OH group directly bonded to another Ti atom. The degree of polymerization in the case of forming a repeating structure is 2-5. When the degree of polymerization is 6 or more, the catalytic activity is lowered, so that one oligomer component is increased, which causes deterioration of toner blocking properties.

Preferred as X are residues of dialkanolamine (particularly diethanolamine) and residues of trialkanolamine (particularly triethanolamine), and particularly preferred are residues of triethanolamine.
R is H or an alkyl group having 1 to 8 carbon atoms which may contain 1 to 3 ether bonds. Specific examples of the alkyl group having 1 to 8 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, n-hexyl group, n-octyl group, β-methoxyethyl group, And β-ethoxyethyl group. Among these Rs, H and an alkyl group having 1 to 4 carbon atoms not containing an ether bond are preferable, and H, an ethyl group, and an isopropyl group are more preferable.

In Formula (I), m is an integer of 1-4, Preferably it is an integer of 1-3. n is an integer of 0 to 3, preferably an integer of 1 to 3. The sum of m and n is 4.
In formula (II), p is an integer of 1 to 2, q is an integer of 0 to 1, and the sum of p and q is 2. When m or p is 2 or more, a plurality of Xs may be the same or different, but are preferably the same.

  Specific examples of the titanium-containing catalyst (a) represented by the general formula (I) in the present invention include titanium dihydroxybis (triethanolaminate), titanium trihydroxytriethanolamate, titanium dihydroxybis. (Diethanolaminate), titanium dihydroxybis (monoethanolamate), titanium dihydroxybis (monopropanolamate), titanium dihydroxybis (N-methyldiethanolamate), titanium dihydroxybis (N-butyldiethanolamate), tetrahydroxytitanium And the reaction product of N, N, N ′, N′-tetrahydroxyethylethylenediamine and intramolecular or intermolecular polycondensates thereof.

  Specific examples of those represented by the general formula (II) include titanyl bis (triethanolaminate), titanyl bis (diethanolamate), titanyl bis (monoethanolamate), titanyl hydroxyethanolamate, titanylhydroxytriethanolamate, Examples include titanyl ethoxytriethanolamate, titanyl isopropoxytriethanolamate, and intramolecular or intermolecular polycondensates thereof. Such as a polycondensate.

Among these, preferred are titanium dihydroxybis (triethanolamate), titanium dihydroxybis (diethanolamate), titanylbis (triethanolamate), polycondensates thereof, and combinations thereof, more preferably Titanium dihydroxybis (triethanolamate), its polycondensate, in particular titanium dihydroxybis (triethanolamate).
These titanium-containing catalysts (a) can be stably obtained, for example, by reacting commercially available titanium dialkoxybis (alcohol aminate; manufactured by Dupont, etc.) at 70 to 90 ° C. in the presence of water. it can.

The polycondensation polyester resin constituting the toner binder of the present invention is a polyester resin (AX), which is a polycondensate of a polyol and a polycarboxylic acid, and a modification obtained by further reacting polyepoxide (C) with (AX). A polyester resin (AY) etc. are mentioned. (AX), (AY) and the like may be used alone or in combination of two or more.
Examples of the polyol include a diol (g) and a trivalent or higher polyol (h), and examples of the polycarboxylic acid include a dicarboxylic acid (i) and a trivalent or higher polycarboxylic acid (j). You may use together.
Examples of the polyester resins (AX) and (AY) include the following, and these can also be used in combination.
(AX1): Linear polyester resin using (g) and (i) (AX2): Non-linear polyester resin using (h) and / or (j) together with (g) and (i) ( AY1): Modified polyester resin obtained by reacting (AX2) with (c)

  As the diol (g), those having a hydroxyl value of 180 to 1900 (mg KOH / g, the same applies hereinafter) are preferable. Specifically, alkylene glycol having 2 to 36 carbon atoms (ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butylene glycol, 1,6-hexanediol, etc.); carbon number 4 -36 alkylene ether glycols (such as diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol and polypropylene glycol); alicyclic diols having 6 to 36 carbon atoms (1,4-cyclohexanedimethanol and hydrogenation) Bisphenol A and the like; an alkylene oxide having 2 to 4 carbon atoms of the above alicyclic diol [ethylene oxide (hereinafter abbreviated as EO), propylene oxide (hereinafter abbreviated as PO) and putylene oxide (hereinafter referred to as BO) Adducts (addition mole number 1-30); adducts (additions) of bisphenols (bisphenol A, bisphenol F, bisphenol S, etc.) having 2 to 4 carbon atoms alkylene oxides (EO, PO, BO, etc.) Mole number 2-30) etc. are mentioned.

Among these, preferred are alkylene glycols having 2 to 12 carbon atoms, alkylene oxide adducts of bisphenols, and combinations thereof. Particularly preferred are alkylene oxide adducts of bisphenols, alkylene glycols having 2 to 4 carbon atoms. 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 defined 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, an aliphatic polyhydric alcohol having 3 to 36 or more carbon atoms having 3 to 8 carbon atoms (an alkane polyol and an intramolecular or intermolecular dehydrate thereof such as glycerin, triethylolethane, pentaerythritol, sorbitol, Sorbitan, polyglycerin, and dipentaerythritol; sugars and derivatives thereof such as sucrose and methyl glucoside; and the like; adducts of the above aliphatic polyhydric alcohols having 2 to 4 carbon atoms (such as EO, PO, and BO) Addition mole number 1-30); Trisphenol (trisphenol PA, etc.) adduct of C2-C4 alkylene oxide (EO, PO, BO, etc.) (addition mole number 2-30); Novolac resin (phenol novolac) And cresol novolak, etc .: average degree of polymerization of 3 Alkylene oxides having 2 to 4 carbon atoms 0) (EO, PO, BO, etc.) adducts (added mole number 2 to 30), and the like.
Among these, preferred are 3 to 8 or higher aliphatic polyhydric alcohols and alkylene oxide adducts of novolac resins (addition mole number: 2 to 30), and particularly preferred are alkylene oxide adducts of novolak resins. It is.

As the dicarboxylic acid (i), those having an acid value of 180 to 1250 (mg KOH / g, the same applies hereinafter) are preferable. Specifically, alkane dicarboxylic 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 [dimer acid] (Dimerized linoleic acid) etc.]; C4-C36 alkene dicarboxylic acid (maleic acid, fumaric acid, citraconic acid, mesaconic acid, etc.); C8-36 aromatic dicarboxylic acid (phthalic acid, isophthalic acid) , Terephthalic acid, and naphthalenedicarboxylic acid). Of these, preferred are alkene dicarboxylic acids having 4 to 20 carbon atoms and aromatic dicarboxylic acids having 8 to 20 carbon atoms. As (i), acid anhydrides or lower alkyl (carbon number 1 to 4) esters (methyl ester, ethyl ester, isopropyl ester, etc.) described above may be used.

  The trivalent or higher (3 to 6 or higher) polycarboxylic acid (j) preferably has an acid value of 150 to 1250 mg. Specifically, an aromatic polycarboxylic acid having 9 to 20 carbon atoms (trimellitic acid, pyromellitic acid, etc.); vinyl polymer of unsaturated carboxylic acid [number average molecular weight (hereinafter referred to as Mn, gel permeation chromatography) (By GPC): 450-10000] (styrene / maleic acid copolymer, styrene / acrylic acid copolymer, α-olefin / maleic acid copolymer, styrene / fumaric acid copolymer, etc.), and the like. . Among these, preferred are aromatic polycarboxylic acids having 9 to 20 carbon atoms, and particularly preferred are trimellitic acid and pyromellitic acid. As the trivalent or higher polycarboxylic acid (j), acid anhydrides or lower alkyl (1 to 4 carbon atoms) esters (methyl ester, ethyl ester, isopropyl ester, etc.) described above may be used.

Further, together with (g), (h), (i) and (j), an aliphatic or aromatic hydroxycarboxylic acid (k) having 4 to 20 carbon atoms and a lactone (l) having 6 to 12 carbon atoms are copolymerized. You can also
Examples of the hydroxycarboxylic acid (k) include hydroxystearic acid and hydrogenated 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, phenol novolac ( Average polymerization degree 3 to 60) glycidyl etherified compound, 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 (c) is preferably 2-8, more preferably 2-6, and particularly preferably 2-4.
The epoxy equivalent of (c) is preferably 50 to 500. The lower limit is more preferably 70, particularly preferably 80, and the upper limit is further 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 if 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 and the polycarboxylic acid is preferably 2/1 to 1/2, more preferably 1.5 / 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 selected in consideration of molecular weight adjustment so that the glass transition point of the polyester toner binder to be finally adjusted is 45 to 85 ° C.

  In the present invention, the amorphous polyester resin used as the toner binder can be produced in the same manner as in the usual polyester production method. For example, the reaction temperature is preferably 150 to 280 ° C, more preferably 160 to 250 ° C, particularly preferably 170 to 240 ° C in the presence of a titanium-containing catalyst (a) in an inert gas (nitrogen gas or the like) atmosphere. It can be performed by reacting. The reaction time is preferably 30 minutes or longer, particularly 2 to 40 hours from the viewpoint of reliably performing the polycondensation reaction. 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 addition amount of (a) is preferably 0.0001 to 0.8%, more preferably 0.0002 to 0.6%, particularly preferably 0.0002 to 0.6%, based on the weight of the polymer obtained from the viewpoint of polymerization activity and the like. Preferably it is 0.0015 to 0.55%.
In addition, other esterification catalysts can be used in combination as long as the catalytic effect of (a) is not impaired. Examples of other esterification catalysts include tin-containing catalysts (eg, dibutyltin oxide), antimony trioxide, titanium-containing catalysts other than (a) (eg, titanium alkoxide, potassium titanyl oxalate, and titanium terephthalate), zirconium-containing catalysts (Eg zirconyl acetate), germanium-containing catalysts, alkali (earth) metal catalysts (eg alkali metal or alkaline earth metal carboxylates: lithium acetate, sodium acetate, potassium acetate, calcium acetate, sodium benzoate, and benzoic acid Potassium), and zinc acetate. The addition amount of these other butterflies is preferably 0 to 0.6% based on the weight of the polymer obtained. By making it within 0.6%, the coloration of the polyester resin is reduced, which is preferable for use in color toners. The content of (a) in all the added catalysts is preferably 50 to 100%.

  As a method for producing the linear polyester resin (AX1), for example, 0.0001 to 0.8% of butterfly (a) with respect to the weight of the obtained polymer, and optionally in the presence of another catalyst, Examples include a method in which the diol (g) and the dicarboxylic acid (i) are heated to 180 ° C. to 260 ° C. and subjected to dehydration condensation under normal pressure and / or reduced pressure conditions to obtain (AX1).

  As a method for producing the non-linear polyester resin (AX2), for example, 0.0001 to 0.8% of the catalyst (a) with respect to the weight of the obtained polymer, and if necessary, in the presence of another catalyst, Diol (g), dicarboxylic acid (i), and trihydric or higher polyol (h) are heated to 180 ° C. to 260 ° C. and subjected to dehydration condensation under normal pressure and / or reduced pressure conditions. The method of reacting polycarboxylic acid (j) and obtaining (AX2) is mentioned. (J) can also be reacted simultaneously with (g), (i) and (h).

Examples of the method for producing the modified polyester resin (AY1) include a method of obtaining (AY1) by adding a polyepoxide (c) to the polyester resin (AX2) and performing a molecular extension reaction of the polyester at 180 ° C. to 260 ° C. .
The acid value of (AX2) to be reacted with (c) is preferably 1 to 60, more preferably 5 to 50. When the acid value is 1 or more, (c) remains unreacted and does not adversely affect the performance of the resin, and when it is 60 or less, the thermal stability of the resin is good.
In addition, the amount of (c) used to obtain (AY1) is preferably 0.01 to 10%, more preferably 0.8% with respect to (AX2), from the viewpoints of low-temperature fixability and hot offset resistance. 05 to 5%.

In addition to the above polycondensed polyester resin, the resin binder of the present invention may contain other resins as required.
Other resins include styrene resins (such as copolymers of styrene and alkyl (meth) acrylate, copolymers of styrene and diene monomers), epoxy resins (such as bisphenol A diglycidyl ether ring-opening polymer), Examples thereof include urethane resins (diols and / or polyaddition products of trivalent or higher polyols and diisocyanates, etc.).
The content of the other resin in the toner binder is preferably 0 to 40% by weight, more preferably 0 to 30% by weight, and particularly preferably 0 to 20% by weight.

（前記一般式（１）中、Ｒは直鎖状不飽和脂肪族２価カルボン酸残基を示し、炭素数２〜２０、好ましくは２〜４の直鎖状不飽和脂肪族基である。ｎは２〜２０、好ましくは２〜６の整数である。）
一般式（１）の構造の存在は固体Ｃ¹³ＮＭＲにより確認することができる。
前記直鎖状不飽和脂肪族基の具体例としては、マレイン酸、フマル酸、１，３−ｎ−プロペンジカルボン酸、１，４−ｎ−ブテンジカルボン酸等の直鎖状不飽和２価カルボン酸由来の直鎖状不飽和脂肪族基を挙げることができる。 (Crystalline polyester A)
The crystalline polyester resin (A) used in the present invention comprises 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. And

(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 presence 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-propene dicarboxylic acid, and 1,4-n-butene dicarboxylic acid. Mention may be made of linear unsaturated aliphatic groups derived from acids.

In the general formula (1), (CH ₂ ) n represents a linear aliphatic dihydric alcohol residue.
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. Those derived from dihydric alcohols can be indicated. Since the polyester resin (A) uses a linear unsaturated aliphatic dicarboxylic acid as the acid component, the polyester resin (A) exhibits an effect that a crystal structure is easily formed as compared with the case where an aromatic dicarboxylic acid is used.

The polyester resin (A) is a polyvalent carboxylic acid comprising (i) a linear unsaturated aliphatic divalent carboxylic acid or a reactive derivative thereof (an acid anhydride, a lower alkyl ester having 1 to 4 carbon atoms, an acid halide, etc.). It can be produced by subjecting an 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 as necessary. The polyvalent carboxylic acid in this case includes (i) a saturated aliphatic divalent carboxylic acid having a branched chain, (ii) a saturated aliphatic divalent carboxylic acid, a saturated aliphatic trivalent carboxylic acid, and the like. 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 addition amount of these polyvalent carboxylic acids is usually 30 mol% or less, preferably 10 mol% or less, based on the total carboxylic acid, and is appropriately added within the range where the resulting polyester has crystallinity.

  Specific examples of polyvalent carboxylic acids 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, etc. A divalent carboxylic acid of: trimethic anhydride, 1,2,4-benzenetricarboxylic acid, 1,2,5-benzenetricarboxylic acid, 1,2,4-cyclohexanetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, And trivalent or higher polyvalent carboxylic acids such as 1,2,5-hexanetricarboxylic acid, 1,3-dicarboxyl-2-methylenecarboxypropane, 1,2,7,8-octanetetracarboxylic acid, etc. it can.

A trivalent or higher polyhydric alcohol can be added to the polyhydric alcohol component, if necessary, in addition to a small amount of an aliphatic branched dihydric alcohol or cyclic dihydric alcohol. The addition amount 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 resulting polyester has crystallinity.
Examples of polyhydric alcohol 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 polyester resin (A), the molecular weight distribution is preferably sharp from the viewpoint of low-temperature fixability, and the molecular weight is preferably a relatively low molecular weight. As for the molecular weight of the polyester resin (A), the weight average molecular weight (Mw) is 5500-6500, the number average molecular weight (Mn) is 1300-1500 and The Mw / Mn ratio is preferably 2-5.
The molecular weight distribution of the polyester resin (A) is based on a molecular weight distribution diagram in which the horizontal axis is log (M: molecular weight) and the vertical axis is weight%. In the case of the polyester resin (A) used in the present invention, in this molecular weight distribution diagram, it is preferable to have a molecular weight peak in the range of 3.5 to 4.0 (wt%), and the half width of the peak is 1. 5 or less is preferable.

In the polyester resin (A), the glass transition temperature (Tg) and the softening temperature [T (F _1/2 )] are desirably low so long as the heat resistant storage stability of the toner is not deteriorated. Tg is 80 to 130 ° C., preferably 80 to 125 ° C., and T (F _1/2 ) is 80 to 130 ° C., preferably 80 to 125 ° C. When Tg and T (F _1/2 ) are higher than the above ranges, the lower limit fixing temperature of the toner is increased, so that the low temperature fixing property of the toner is deteriorated.

Whether or not the polyester resin fine particles in the present invention have crystallinity can be confirmed by whether or not a peak exists in the X-ray diffraction pattern by the powder X-ray diffractometer. The polyester resin (A) having crystallinity used in the present invention has a diffraction pattern in which at least one diffraction peak exists at a position where 2θ is 20 ° to 25 °, and preferably 2θ is at least (i It is characterized in that diffraction peaks are present at positions of 19 ° to 20 °, (ii) 21 ° to 22 °, (iii) 23 ° to 25 °, and (iv) 29 ° to 31 °.
The powder X-ray diffraction measurement was performed using a Rigaku Electric RINT1100, using a wide-angle goniometer under the conditions of a tube bulb with Cu and a tube voltage-current of 50 kV-30 mA. (FIG. 5: X-ray diffraction result of crystalline polyester resin, FIG. 6: Example of X-ray diffraction result of toner of the present invention)

When two or more kinds of polyester resins are used in combination, and when at least one kind of polyester resin and another resin are mixed, powder mixing or melt mixing may be performed in advance, or they may be mixed at the time of toner formation. The temperature at the time of melt mixing is preferably 80 to 180 ° C, more preferably 100 to 170 ° C, and particularly preferably 120 to 160 ° C.
If the mixing temperature is too low, sufficient mixing cannot be achieved, which may result in non-uniformity. When two or more kinds of polyester resins are mixed, if the mixing temperature is too high, averaging due to transesterification occurs, so that the resin physical properties necessary as a toner binder may not be maintained.

The mixing time in the case of melt mixing is preferably 10 seconds to 30 minutes, more preferably 20 seconds to 10 minutes, and particularly preferably 30 seconds to 5 minutes. When two or more kinds of polyester resins are mixed, if the mixing time is too long, averaging due to transesterification occurs, so that the resin physical properties necessary as a toner binder may not be maintained.
Examples of the mixing device in the case of melt mixing include a batch type mixing device such as a reaction tank and a continuous mixing device. In order to uniformly mix at an appropriate temperature in a short time, a continuous mixing device is preferable. Examples of the continuous mixing device include an extruder, a continuous kneader, and a three roll. Of these, extruders and container kneaders are preferred.
In the case of powder mixing, it can be mixed with normal mixing conditions and mixing equipment.
As mixing conditions in the case of powder mixing, the mixing temperature is preferably 0 to 80 ° C, more preferably 10 to 60 ° C. The mixing time is preferably 3 minutes or more, more preferably 5 to 60 minutes. Examples of the mixing device include a Henschel mixer, a Nauter mixer, and a bumper mixer. A Henschel mixer is preferred.

  The acid value of the crystalline polyester resin (A) is preferably 20 mgKOH / g or more in order to achieve the desired low-temperature fixability from the viewpoint of the affinity between paper and resin. On the other hand, in order to improve hot offset property, it is preferable that it is 45 mgKOH / g or less.

  Further, the hydroxyl value of the crystalline polyester resin (A) is preferably 5 to 50 mgKOH / g in order to achieve a predetermined low-temperature fixability and good charging characteristics.

It was confirmed that the fixing is remarkably improved by the inclusion of the fatty acid amide compound in the present invention. Although the principle is not clear, the silicone oil applied to the fixing roll during fixing is transferred to the image surface, and the nucleating agent prevents the oil from penetrating the image, resulting in the oil remaining on the image surface for a long time. Is presumed to have. If the oil is on the surface of the fixed image for a long time, it will be resistant to rubbing and the like, and the image fixing property immediately after fixing is at the best level.
Since there is a need for an improvement in fixability immediately after fixing for a business environment in which a system with a linear speed of 500 to 1700 mm / sec, which is an object of the present invention, is used frequently, especially for users such as roll paper, fatty acid amide There is a need for combined effects of compounds.

As the fatty acid amide compound, a compound represented by R ₁ —CO—NR ₂ R ₃ is used. In the formula, R ₁ is an aliphatic hydrocarbon group having 10 to 30 carbon atoms, and R ₂ and R ₃ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms. Or an aralkyl group having 7 to 10 carbon atoms. Here, the alkyl group, aryl group, and aralkyl group of R ₂ and R ₃ may be substituted with a generally inactive substituent such as a fluorine atom, a chlorine atom, a cyano group, an alkoxy group, or an alkylthio group. However, it is more preferably unsubstituted.
Examples of preferable compounds include stearic acid amide, stearic acid methylamide, stearic acid diethylamide, stearic acid benzylamide, stearic acid phenylamide, behenic acid amide, behenic acid dimethylamide, myristic acid amide, palmitic acid amide and the like.

（式中Ｒ₁、Ｒ₃は炭素数５〜２１のアルキル基またはアルケニル基、Ｒ₂は炭素数１〜２０のアルキレン基を示す。） In the present invention, among the fatty acid amide compounds, alkylene bis fatty acid amides are particularly preferably used. The alkylene bis fatty acid amide is a compound represented by the following general formula (II).

(Wherein R ₁ and R ₃ represent an alkyl group or alkenyl group having 5 to 21 carbon atoms, and R ₂ represents an alkylene group having 1 to 20 carbon atoms.)

Examples of the alkylene bis saturated fatty acid amide represented by the general formula (II) include methylene bis stearic acid amide, ethylene bis stearic acid amide, methylene bis palmitic acid amide, ethylene bis palmitic acid amide, methylene bis behenic acid amide, ethylene bis Examples thereof include behenic acid amide, hexamethylene bisstearic acid amide, hexaethylene bispalmitic acid amide, and hexamethylene bisbehenic acid amide. Of these, ethylene bis stearamide is most preferred.
These fatty acid amide compound, a softening point Tm (Tsp) is at lower than the surface temperature T _H during use of the fixing member, a fixing member surface, can serve effectively as a release agent.

Specific examples of alkylene bis fatty acid amide compounds that can be used in addition to the above include propylene bis stearic acid amide, butylene bis stearic acid amide, methylene bis oleic acid amide, ethylene bis oleic acid amide, propylene bis oleic acid amide, Butylene bis oleic acid amide, methylene bis lauric acid amide, ethylene bis lauric acid amide, propylene bis lauric acid amide, butylene bis lauric acid amide, methylene bis myristic acid amide, ethylene bis myristic acid amide, propylene bis myristic acid amide, butylene bis Myristic acid amide, Propylene bispalmitic acid amide, Butylene bispalmitic acid amide, Methylene bispalmitoleic acid amide, Ethylene bispalmitoleic acid amide, Propylene vinyl Palmitoleic acid amide, butylene bispalmitoleic acid amide, methylene bisarachidic acid amide, ethylene bisarachidic acid amide, propylene bisarachidic acid amide, butylene bisarachidic acid amide, methylene biseicosenoic acid amide, ethylene biseicosenoic acid Amide, Propylene biseicosenoic acid amide, Butylene biseicosenoic acid amide, Methylene bis behenic acid amide, Ethylene bis behenic acid amide, Propylene bis behenic acid amide, Butylene bis behenic acid amide, Methylene bis Mention may be made of alkylene bis fatty acid amide compounds of saturated or monovalent unsaturated fatty acids such as erucic acid amide, ethylene biserucic acid amide, propylene biserucic acid amide, butylene biserucic acid amide.

  Moreover, you may use the wax as a mold release agent, and it is preferable that melting | fusing point of a wax is 70-150 degreeC. When the temperature is lower than 70 ° C., the heat resistant storage stability of the toner is poor. When it is higher than 150 ° C., there is a possibility that the releasability cannot be sufficiently achieved.

  As the wax, conventionally known waxes can be used. For example, low molecular weight polyethylene wax, low molecular weight polyolefin wax such as polypropylene, synthetic hydrocarbon wax such as Fischer-Tropsch wax, natural wax such as beeswax, carnauba wax, candelilla wax, rice wax, montan wax, Examples include petroleum waxes such as paraffin wax and microcrystalline wax, higher fatty acids such as stearic acid, palmitic acid, and myristic acid, metal salts of higher fatty acids, higher fatty acid amides, synthetic ester waxes, and various modified waxes thereof.

Of these, carnauba wax and its modified wax, polyethylene wax, and synthetic ester wax are preferably used. In particular, the synthetic ester wax pentaerythritol tetrabehenate is most preferred. The reason for this is that carnauba wax and its modified wax and synthetic ester wax are appropriately finely dispersed with respect to the polyester resin and polyol resin, so that the toner has excellent offset prevention, transferability and durability as described later. This is because it is easy.
These waxes can be used alone or in combination of two or more.
The amount of these release agents used is preferably 2 to 15% by weight based on the toner. If it is less than 2% by weight, the effect of preventing offset is insufficient, and if it exceeds 15% by weight, transferability and durability are deteriorated.

As the colorant, known pigments and dyes capable of obtaining yellow, magenta, cyan, and black toners can be used.
For example, the yellow pigments include cadmium yellow, pigment yellow 155, benzimidazolone, mineral fast yellow, nickel titanium yellow, navel yellow, naphthol yellow S, Hansa yellow G, Hansa yellow 10G, benzidine yellow GR, quinoline yellow lake, Permanent yellow NCG, tartrazine lake and the like can be mentioned.

  Examples of the orange pigment include molybdenum orange, permanent orange GTR, pyrazolone orange, Vulcan orange, indanthrene brilliant orange RK, benzidine orange G, indanthrene brilliant orange GK and the like.

  Examples of red pigments include Bengala, Quinacridone Red, Cadmium Red, Permanent Red 4R, Risor Red, Pyrazolone Red, Watching Red Calcium Salt, Lake Red D, Brilliant Carmine 6B, Eosin Lake, Rhodamine Lake B, Alizarin Lake, Brilliant Carmine 3B, etc. Is mentioned.

Examples of purple pigments include fast violet B and methyl violet lake.
Examples of blue pigments include cobalt blue, alkali blue, Victoria blue lake, phthalocyanine blue, metal-free phthalocyanine blue, phthalocyanine blue partially chlorinated, first sky blue, and indanthrene blue BC.

Examples of the green pigment include chrome green, chromium oxide, pigment green B, and malachite green lake.
Examples of black pigments include azine dyes such as carbon black, oil furnace black, channel black, lamp black, acetylene black, and aniline black, metal salt azo dyes, metal oxides, and composite metal oxides.
These can use 1 type (s) or 2 or more types.

The toner for image formation according to the present invention may contain a charge control agent in the toner, if necessary.
For example, nigrosine, azine dyes containing an alkyl group having 2 to 16 carbon atoms (Japanese Patent Publication No. 42-1627), basic dyes such as C.I. I. Basic Yellow 2 (C.I. 41000), C.I. I. Basic Yellow 3, C.I. I. Basic Red 1 (C.I. 45160), C.I. I. Basic Red 9 (C.I. 42500), C.I. I. Basic Violet 1 (C.I. 42535), C.I. I. Basic Violet 3 (C.I. 42555), C.I. I. Basic Violet 10 (C.I. 45170), C.I. I. Basic Violet 14 (C.I. 42510), C.I. I. Basic Blue 1 (C.I. 42025), C.I. I. Basic Blue 3 (C.I. 51005), C.I. I. Basic Blue 5 (C.I. 42140), C.I. I. Basic Blue 7 (C.I. 42595), C.I. I. Basic Blue 9 (C.I. 52015), C.I. I. Basic Blue 24 (C.I. 52030), C.I. I. Basic Blue 25 (C.I. 52025), C.I. I. Basic Blue 26 (C.I. 44045), C.I. I. Basic Green 1 (C.I. 42040), C.I. I. Lake pigments of these basic dyes, such as Basic Green 4 (C.I. 42000), C.I. I. Solvent Black 8 (C.I. 26150), quaternary ammonium salts such as benzoylmethyl hexadecyl ammonium chloride, decyl trimethyl chloride, or dialkyl tin compounds such as dibutyl or dioctyl, dialkyl tin borate compounds, guanidine derivatives, containing amino groups Polyamine resins such as vinyl polymers, condensation polymers containing amino groups, Japanese Patent Publication No. 41-20153, Japanese Patent Publication No. 43-27596, Japanese Patent Publication No. 44-6397, Japanese Patent Publication No. 45-26478 Metal complex salts of monoazo dyes described, Japanese Patent Publication No. 55-42752, Japanese Patent Publication No. 59-7385, salicylic acid, dialkylsalicylic acid, naphthoic acid, dicarboxylic acid Zn, Al, Co, Cr , Fe, etc. Metal complex, a copper phthalocyanine pigment obtained by sulfonation, organic boron salts, fluorine-containing quaternary ammonium salts, calixarene compounds, and the like. Naturally, color toners other than black should avoid the use of charge control agents that impair the desired color, and white metal salts of salicylic acid derivatives are preferably used.

  In the image forming toner of the present invention, the transferability and durability are further improved by externally adding inorganic fine particles such as silica, titanium oxide, alumina, silicon carbide, silicon nitride, boron nitride and resin fine particles to the base toner particles. I am letting.

This effect can be obtained by covering the wax that lowers transferability and durability with these external additives and reducing the contact area due to the toner surface being covered with fine particles. The surface of these inorganic fine particles is preferably subjected to a hydrophobic treatment, and metal oxide fine particles such as silica and titanium oxide subjected to the hydrophobic treatment are preferably used. As the resin fine particles, polymethyl methacrylate or polystyrene fine particles having an average particle size of about 0.05 to 1 μm obtained by a soap-free emulsion polymerization method are suitably used. In addition, the combination of hydrophobized silica and hydrophobized titanium oxide increases the amount of hydrophobized titanium oxide externally added compared to the amount of hydrophobized silica externally charged. The toner can be excellent in stability of the toner, and can be improved in the toner transfer rate and the main problem of the present invention.

In combination with the above-mentioned inorganic fine particles, silica having a specific surface area of 20 to 50 m ² / g or resin fine particles having an average particle diameter of 1/100 to 1/8 of the average particle diameter of the toner can be used. The durability can be improved by externally adding an external additive having a particle size larger than that of the additive to the toner. This is because the metal oxide particles externally added to the toner tend to be embedded in the base toner particles in the process where the toner is mixed and stirred with the carrier in the developing device, charged, and used for development. This is because it is possible to prevent the metal oxide fine particles from being embedded by externally adding an external additive having a particle size larger than that of the oxide fine particles to the toner.

  The above-mentioned inorganic fine particles and resin fine particles are contained (internally added) in the toner, but the effect is reduced as compared with the case of external addition, but the effect of improving transferability and durability can be obtained and the pulverization property of the toner can be improved. Can do. In addition, since external addition and internal addition can be used together to suppress embedding of externally added fine particles, excellent transferability can be stably obtained and durability can be improved.

  In addition, the following are mentioned as a typical example of the hydrophobization processing agent used here. Dimethyldichlorosilane, trimethylchlorosilane, methyltrichlorosilane, allyldimethyldichlorosilane, allylphenyldichlorosilane, benzyldimethylchlorosilane, bromomethyldimethylchlorosilane, α-chloroethyltrichlorosilane, p-chloroethyltrichlorosilane, Chloromethyldimethylchlorosilane, chloromethyltrichlorosilane, p-chlorophenyltrichlorosilane, 3-chloropropyltrichlorosilane, 3-chloropropyltrimethoxysilane, vinyltriethoxysilane, vinylmethoxysilane, vinyl-tris (β-methoxyethoxy) ) Silane, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, divinyldichlorosilane, dimethylvinylchlorosilane, octyl Trichlorosilane, decyl-trichlorosilane, nonyl-trichlorosilane, (4-t-propylphenyl) -trichlorosilane, (4-t-butylphenyl) -trichlorosilane, dipentyl-dichlorosilane, dihexyl-dichlorosilane, dioctyl-dichlorosilane, dinonyl -Dichlorosilane, didecyl-dichlorosilane, didodecyl-dichlorosilane, dihexadecyl-dichlorosilane, (4-t-butylphenyl) -octyl-dichlorosilane, dioctyl-dichlorosilane, didecenyl-dichlorosilane, dinonenyl-dichlorosilane, di-2-ethylhexyl-dichlorosilane, di- 3,3-dimethylpentyl-dichlorosilane, trihexyl-chlorosilane, trioctyl-chlorosilane, tridecyl-chlorosilane Dioctyl-methyl-chlorosilane, octyl-dimethyl-chlorosilane, (4-t-propylphenyl) -diethyl-chlorosilane, octyltrimethoxysilane, hexamethyldisilazane, hexaethyldisilazane, diethyltetramethyldisilazane, hexaphenyldisilazane , Hexatolyl disilazane and the like. In addition, titanate coupling agents and aluminum coupling agents can also be used.

  In addition, as an external additive for the purpose of improving the cleaning property, a lubricant such as an aliphatic metal salt or a fine particle of polyvinylidene fluoride can be used in combination.

  When the toner of the present invention is used for a two-component developer, it is used by mixing with carrier powder. As the carrier in this case, a known carrier can be used, and examples thereof include iron powder, ferrite powder, magnetite powder, nickel powder, glass beads, and the like whose surface is coated with a resin, etc. The diameter is preferably a volume average particle diameter of 25 to 200 μm.

  As the toner container of the present invention, a developer containing the image forming toner of the present invention is filled, and a conventionally known shape can be used.

  The method for producing the toner of the present invention is not particularly limited, and includes a melt-kneading pulverization method and a polymerization method, a polyaddition reaction method using an isocyanate group-containing prepolymer, a solvent dissolution method, a solvent removal method, and a pulverization method. In addition, it can be produced by a melt spray method. Among these production methods, a melt kneading method, a polymerization method in which a monomer composition containing a specific crystalline polymer and a polymerizable monomer is directly polymerized in an aqueous phase (suspension polymerization method / emulsification method). Polymerization method), a polyaddition reaction method in which a composition containing a specific crystalline polymer and an isocyanate group-containing prepolymer is directly extended / crosslinked with amines in an aqueous phase, dissolved in a solvent, desolvated and pulverized. It is preferable to employ a method, and a conventionally known production method can be used.

  As an apparatus for melt-kneading the toner, a batch type twin roll, a Banbury mixer and a continuous type twin screw extruder, for example, KTK type twin screw extruder manufactured by Kobe Steel, TEM type twin screw extruder manufactured by Toshiba Machine Co., Ltd. , KCK's twin screw extruder, Ikegai Iron Works 'PCM type twin screw extruder, Kurimoto Iron Works' KEX type twin screw extruder, continuous single screw kneader, such as Bush's co-kneader Preferably used.

  In the polymerization method and the polyaddition reaction method using an isocyanate group-containing prepolymer, the emulsification (formation of droplets) treatment is mandatory by applying mechanical energy in the aqueous phase. Examples of the mechanical energy applying means include strong stirring such as homomixer, ultrasonic wave, and manton gorin, or ultrasonic vibration energy applying means.

  For pulverization, coarse pulverization can be performed using a hammer mill, a rotoplex, or the like, and a fine pulverizer using a jet stream or a mechanical pulverizer can be used. The average particle size is 3 to 15 μm. It is desirable to do so. Further, the pulverized product is adjusted in particle size to 5 to 20 μm by a wind classifier or the like.

  In the external addition of the external additive to the base toner, the base toner and the external additive are mixed and stirred using a mixer to coat the toner surface while the external additive is being crushed. At this time, it is important in terms of durability that external additives such as inorganic fine particles and resin fine particles are uniformly and firmly attached to the base toner.

An example of an image forming apparatus using the toner of the present invention as a developer will be described.
FIG. 1 is a schematic configuration diagram illustrating an example of an image forming apparatus according to the present invention. In the figure, reference numeral (100) is a copying apparatus main body, (200) is a paper feed table on which the copying apparatus is placed, (300) is a scanner mounted on the copying apparatus main body (100), and (400) is an automatic document feeder mounted thereon. (ADF).
The copying apparatus main body (100) includes four image forming means (18) including various means for performing an electrophotographic process such as charging, developing, and cleaning around a photosensitive member (40) as a latent image carrier. Two parallel tandem image forming apparatuses (20) are provided. Above the tandem image forming apparatus (20), there is provided an exposure apparatus (21) that exposes the photoreceptor (40) with laser light based on image information to form a latent image. An intermediate transfer belt (10) made of an endless belt member is provided at a position facing each photoconductor (40) of the tandem type image forming apparatus (20). Primary transfer means (62) for transferring the toner images of the respective colors formed on the photoconductor (40) to the intermediate transfer belt (10) at positions facing the photoconductor (40) via the intermediate transfer belt (10). ) Is arranged.

  Further, below the intermediate transfer belt (10), a secondary transfer device (for transferring the toner images superimposed on the intermediate transfer belt (10) onto transfer paper conveyed from the paper feed table (200) in a batch. 22) is arranged. The secondary transfer device (22) is configured by spanning a secondary transfer belt (24), which is an endless belt, between two rollers (23), and a support roller (16) via an intermediate transfer belt (10). The toner image on the intermediate transfer belt (10) is transferred to the transfer paper. Next to the secondary transfer device (22), a fixing device (25) for fixing the image on the transfer paper is provided. The fixing device (25) is configured by pressing a pressure roller (27) against a fixing belt (26) which is an endless belt.

The secondary transfer device (22) described above also has a sheet transport function for transporting the transfer paper after image transfer to the fixing device (25). Of course, as the secondary transfer device (22), a transfer roller or a non-contact charger may be arranged. In such a case, it is difficult to provide this sheet conveying function together.
In the illustrated example, the transfer paper is inverted under the secondary transfer device (22) and the fixing device (25) so as to record images on both sides of the transfer paper in parallel with the tandem image forming device (20). An inverting device (28) is provided.

The developer containing the toner is used for the developing device (4) of the image forming means (18).
In the developing device (4), the developer carrying member carries and conveys the developer, and an alternating electric field is applied at a position facing the photoconductor (40) to develop the latent image on the photoconductor (40). By applying the alternating electric field, the developer is activated, the charge amount distribution of the toner can be narrowed, and the developability can be improved.

  Further, the developing device (4) can be a process cartridge that is integrally supported together with the photoreceptor (40) and is detachably formed on the image forming apparatus main body. In addition, the process cartridge may include a charging unit and a cleaning unit.

The operation of the image forming apparatus is as follows.
First, the document is set on the document table (30) of the automatic document feeder (400), or the document is opened on the contact glass (32) of the scanner (300) by opening the automatic document feeder (400). Then, the automatic document feeder (400) is closed and pressed by it.
When a start switch (not shown) is pressed, when the document is set on the automatic document feeder (400), the document is transported and moved onto the contact glass (32), and then the other contact glass (32). When the document is set on the scanner, the scanner (300) is immediately driven to travel on the first traveling body (33) and the second traveling body (34). Then, the first traveling body (33) emits light from the light source, and the reflected light from the document surface is further reflected toward the second traveling body (34) and reflected by the mirror of the second traveling body (34). Then, the image is placed in the reading sensor (36) through the imaging lens (35), and the content of the original is read.

  When a start switch (not shown) is pressed, one of the support rollers (14), (15), and (16) is driven to rotate by the drive motor (not shown), and the other two support rollers are driven to rotate. The transfer belt (10) is rotated and conveyed. At the same time, the individual image forming means (18) rotates the photoreceptor (40) to form monochrome images of black, yellow, magenta, and cyan on each photoreceptor (40). Then, along with the conveyance of the intermediate transfer belt (10), these monochrome images are sequentially transferred to form a composite color image on the intermediate transfer belt (10).

On the other hand, when a start switch (not shown) is pressed, one of the paper feed rolls (42) of the paper feed table (200) is selectively rotated, and one of paper feed cassettes (44) provided in multiple stages in the paper bank (43). The sheet is fed out from the sheet, separated one by one by a separating roll (45), put into a sheet feeding path (46), conveyed by a conveying roll (47), and fed to a sheet feeding path (48) in the copying machine main body (100). Guide and stop against the resist roll (49).
Alternatively, the sheet feed roll (50) is rotated to feed out the sheets on the manual feed tray (51), separated one by one by the separation roll (52), put into the manual feed path (53), and the registration roll (49). ) And stop.
Then, the registration roll (49) is rotated in time with the composite color image on the intermediate transfer belt (10), and the sheet is fed between the intermediate transfer belt (10) and the secondary transfer device (22). The image is transferred by the next transfer device (22) and a color image is recorded on the sheet.

The sheet after the image transfer is conveyed by the secondary transfer device (22) and sent to the fixing device (25). The fixing device (25) applies heat and pressure to fix the transferred image, and then the switching claw. It is switched at (55), discharged by the discharge roll (56), and stacked on the discharge tray (57). Alternatively, it is switched by the switching claw (55) and put into the sheet reversing device (28), where it is reversed and guided again to the transfer position, and after the image is recorded also on the back surface, the discharge tray (56) discharges the discharge tray (56). 57) Drain up.
On the other hand, the intermediate transfer belt (10) after the image transfer is removed by the intermediate transfer belt cleaning device (17) to remove residual toner remaining on the intermediate transfer belt (10) after the image transfer, and the tandem image forming device (20). To prepare for image formation again.

  EXAMPLES The present invention will be further described below with reference to examples, but the present invention is not limited thereto. In the following, “part” means part by weight, and “%” means weight%.

<Synthesis example of crystalline polyester resin>
Synthesis Example 1 <Crystalline Polyester Resin No. Synthesis of 1>
A 5-liter four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer and a thermocouple was added to 25 mol of 1,4-butanediol, 23.75 mol of fumaric acid, 1.65 mol of trimellitic anhydride, hydroquinone After adding 5.3 g and reacting at 160 ° C. for 5 hours, the temperature was raised to 200 ° C. and reacted for 1 hour, and further reacted at 8.3 KPa for 1 hour, so that crystalline polyester resin No. 1 was reacted. 1 was obtained.

Synthesis Example 2 <Crystalline Polyester Resin No. Synthesis of 2>
A crystalline polyester resin No. 1 was prepared in the same manner as in Synthesis Example 1 except that the raw materials were changed to the following. 2 was obtained.
(No. 2)
1,4-butanediol: 23.75 mol Ethylene glycol: 1.25 mol Fumaric acid: 22.75 mol Trimellitic anhydride: 1.65 mol Hydroquinone: 4.8 g

<Synthesis Example of Amorphous Polyester Resin>
[Synthesis of Titanium-Containing Catalyst (a)]
An 80% aqueous solution of titanium dihydroxybis (triethanolamate) is placed in a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introduction tube capable of bubbling in the liquid, and gradually heated to 90 ° C. under bubbling in the liquid with nitrogen. The mixture was heated to 90 ° C. and reacted (hydrolyzed) at 90 ° C. for 4 hours to obtain titanium dihydroxybis (triethanolaminate).
In the following examples, the titanium-containing catalyst (a) used in the present invention can be obtained by the same synthesis method.

[Synthesis of Linear Polyester Resin (AX1-1)]
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 430 parts of PO2 molar adduct of bisphenol A, 300 parts of PO3 molar adduct of bisphenol A, 257 parts of terephthalic acid, 65 parts of isophthalic acid, maleic anhydride 10 parts and 2 parts of titanium dihydroxybis (triethanolaminate) as a condensation catalyst were added and reacted at 220 ° C. for 10 hours while distilling off the water produced under a nitrogen stream. Subsequently, it was made to react under the reduced pressure of 5-20 mmHg, and when the acid value became 5, it took out, cooled to room temperature, and grind | pulverized, and the linear polyester resin (AX1-1) was obtained.
(AX1-1) contained no THF-insoluble matter, and had an acid value of 7, a hydroxyl value of 12, Tg of 60 ° C., Mn of 6940, and Mp of 19100. The ratio of components having a molecular weight of 1500 or less was 1.2%.

[Synthesis of Non-Linear Polyester Resin (AX2-1)]
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 350 parts of EO2 molar adduct of bisphenol A, 326 parts of PO3 molar adduct of bisphenol A, 278 parts of terephthalic acid, 40 parts of phthalic anhydride and a condensation catalyst 2 parts of titanium dihydroxybis (triethanolaminate) 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 reduced pressure of 5 to 20 mmHg. When the acid value becomes 2 or less, the mixture is cooled to 180 ° C., added with 62 parts of trimellitic anhydride, taken out after reaction for 2 hours under sealed at normal pressure, and cooled to room temperature. To obtain a non-linear polyester resin (AX2-1). (AX2-1) contained no THF-insoluble matter, and its acid value was 35, the hydroxyl value was 17, Tg was 69 ° C., Mn was 3920, and Mp was 11200. The ratio of components having a molecular weight of 1500 or less was 0.9%.

[Synthesis of Amorphous Polyester Resin A]
400 parts of (AX1-1) and 600 parts of (AX2-1) were melt-mixed with a continuous kneader at a jacket temperature of 150 ° C. and a residence time of 3 minutes. The molten resin was cooled to 30 ° C. for 4 minutes using a steel belt cooler and pulverized to obtain the amorphous polyester resin A of the present invention.

[Synthesis of linear polyester resin (CAX1-1)]
The reaction was performed in the same manner as the linear polyester resin (AX1-1) except that the polycondensation catalyst was replaced with titanium tetraisopropoxide. Since the reaction was stopped in the middle due to catalyst deactivation and the problem that the generated water could not be distilled occurred, 2 parts of titanium tetraisopropoxide was added four times during the reaction, and a comparative linear polyester resin (CAX1) was added. -1) was obtained.
(CAX1-1) contained no THF-insoluble matter, and had an acid value of 7, a hydroxyl value of 12, Tg of 58 ° C., Mn of 6220, and Mp of 18900. The ratio of components having a molecular weight of 1500 or less was 2.2%.

[Synthesis of Non-Linear Polyester Resin (CAX2-1)]
The reaction was conducted in the same manner as the non-linear polyester resin (AX2-1) except that the polycondensation catalyst was replaced with titanium tetraisopropoxide. The reaction was allowed to proceed for 16 hours under normal pressure and for 8 hours under reduced pressure. Since the reaction rate was slow, 2 parts of titanium tetrapropoxide were added three times during the reaction to obtain a comparative non-linear polyester resin (CAX2-1).
(CAX2-1) contained no THF-insoluble matter, and its acid value was 34, the hydroxyl value was 16, Tg was 68 ° C., Mn was 3420, and Mp was 12100. The ratio of components having a molecular weight of 1500 or less was 2.1%.

[Synthesis of Amorphous Polyester Resin B]
400 parts of (CAX1-1) and 600 parts of (CAX2-1) were melt-mixed with a continuous kneader at a jacket temperature of 150 ° C. and a residence time of 3 minutes. The molten resin was cooled to 30 ° C. for 4 minutes using a steel belt cooler and pulverized to obtain amorphous polyester resin B.

<Example of toner production>
Example 1
Formula:
<Production of toner by kneading and grinding>
The following toner composition was sufficiently mixed with a blender and then melt-kneaded (kneading temperature: 140 ° C., extrusion speed: 10 kg / hour, rolling gap: 2 mm, standing time until pulverization: 48 hours) with a twin screw extruder. Thereafter, this was pulverized and classified to obtain a base toner having a volume average particle diameter of about 7.6 μm. To 100 parts of the base toner, 0.4 part of hydrophobic silica (surface-treated product with hexamethyldisilazane, average particle size of primary particles is 0.02 μm) as an external additive is mixed with a Henschel mixer. And a cyan toner was obtained. The mixing conditions were 1500 rpm and 8 cycles. In 1 cycle, the mixture was stirred for 60 seconds and then stopped for 60 seconds. The transfer current value for filming evaluation is 30 μA.
-Crystalline polyester resin No. 1 35 parts amorphous polyester resin B 65 parts polypropylene wax (melting point: 151 ° C.) 5 parts Charge control agent (metal salt of a salicylic acid derivative) 2 parts Colorant (copper phthalocyanine blue pigment) 6 parts Stearic Acid amide compound (melting point: 115 ° C.) 5 parts The crystalline polyester resin and the toner obtained were evaluated according to the following measurement method and evaluation method. The results are shown in Tables 1 and 2.

<Measurement method>
(1) Measuring method of crystalline polyester resin peak ratio represented by W / R The crystalline polyester resin peak ratio on the toner surface is measured by ATR method (total reflection) using FT-IR (Fourier transform infrared spectroscopic analyzer). The peak intensity ratio obtained from the ATR spectrum in (Method). Since the ATR method requires a smooth surface, the toner is pressure-molded to create a smooth surface. At this time, pressure molding was performed by applying 1 t to 0.6 g of toner for 30 sec to obtain a pellet having a diameter of 20 mm.
In the present invention, the peak height of the characteristic spectrum (1165 cm ⁻¹ ) in the crystalline state of the crystalline polyester resin is W (FIG. 2, the height base line is 1199 to 1137 cm ⁻¹ ). Characteristic spectrum (for example, 829 cm ^-1 for polyester resin, "Figure 3, height baseline is 784-889 cm ^-1 ", for styrene-acrylic resin, 699 cm ^-1 "Figure 4, height base. The line was calculated with the peak height of 714-670 cm ^-1 ") as R and W / R as the peak intensity ratio. In the present invention, the peak intensity ratio is obtained by converting the spectrum to absorbance and using the peak height. (See FIGS. 2, 3, and 4 for examples).

(2) Transfer rate measurement method The toner density of the developer and the developing bias of the developing device are adjusted, and a toner having a toner amount of 1.0 to 1.4 mg / cm ² is adhered to the photoreceptor.
A 5 × 2 cm cello tape (registered trademark) is applied to the image on the photoreceptor, and the entire surface is pressed with a finger, and the toner on the photoreceptor is transferred to the tape without leaving any residue. The weight of the toner transferred to the tape is obtained by subtracting the weight of the single tape before transfer from the total weight of the tape after transfer and the toner transferred on the tape, and is defined as W.
After the image is transferred by the transfer device, the weight of the transfer residual toner on the photoconductor is measured by the same procedure as the tape method, and is set as A.
The toner transfer rate is calculated according to Formula (1).
Toner transfer rate (%) = (W−A) × 100 / W Formula− (1)

(3) The measurement details of the toner charge amount by the single mode method in the V blow-off device are described.
The toner and carrier were left as a developer having a toner concentration of 4 wt% in a predetermined environment (temperature, humidity) for 2 hours, and then the developer was placed in a metal gauge and stirred and mixed for 780 seconds with a stirrer at 285 rpm. 1 g of developer is weighed from 6 g of the initial agent, and the charge amount distribution of the toner is measured by a single mode method using a V blow-off device (manufactured by Ricoh Creative Development Co., Ltd.). When blowing, a mesh of 795 mesh is used.
Here, the single mode method is the above-described V blow-off device (manufactured by Ricoh Creative Development Co., Ltd.), and the single mode is selected according to the device manual. The measurement conditions are 5 mm in height, suction 100, and double blow.
When the toner charge amount at 23 ° C. and 55% relative humidity is M and the toner charge amount at 42 ° C. and 40% relative humidity is H, the toner charge fluctuation rate (%) ) Find P.
Toner charge fluctuation rate (%) P
= (M−H) × 100 / ((H + M) ÷ 2) Formula− (2)
The principle of the V blow-off device is the same as that described in Japanese Patent No. 3487464.
The details of other measurement conditions conform to the maximum values of the single mode measurement method in the instrument manual.

(4) Measurement of Resin Acid Value and Hydroxyl Value The method for measuring the acid value and hydroxyl value of the resin is according to the method specified in JIS K 0070. However, when the sample did not dissolve, a solvent such as dioxane or THF, o-dichlorobenzene was used as the solvent.

(5) Measurement of wax melting point A TG-DSC system TAS-100 manufactured by Rigaku Corporation was used. First, about 10 mg of a sample is placed in an aluminum sample container, which is placed on a holder unit and set in an electric furnace. Heat from 25 ° C. to 180 ° C. at a heating rate of 10 ° C./min. The melting point was calculated from the contact point between the tangent line of the endothermic curve near the melting point and the base line using the analysis system in the TAS-100 system.

(6) Measurement of system speed A4 paper, longitudinal direction paper (length of paper passing direction is 297 mm), continuous 100 sheets, output by the corresponding image forming apparatus, the output time from the start to the end is A second, the system When the speed was B, the system speed was determined by the following formula.
B (mm / sec) = 100 sheets × 297 mm ÷ A seconds

<Evaluation>
(1) Filming evaluation carrier production Silicone resin solution 132.2 parts [Solid content 23% by weight (SR2410: Toray Dow Corning Silicone)]
Aminosilane 0.66 part [solid content 100% by weight (SH6020: manufactured by Toray Dow Corning Silicone)]
Conductive particle 1 31 parts [Substrate: alumina, surface treatment; lower layer = tin dioxide / upper layer = tin oxide containing tin oxide, particle size: 0.35 μm, particle powder specific resistance: 3.5 Ω · cm]
-300 parts of toluene was dispersed with a homomixer for 10 minutes to obtain a silicone resin coating film forming solution. Volume average particle size: 70 μm calcined ferrite powder is used as the core material, and the temperature inside the coater is 40 ° C. by a Spira coater (Okada Seiko Co., Ltd.) so that the coating film forming solution has a film thickness of 0.15 μm on the surface of the core material. And dried. The obtained carrier was fired in an electric furnace at 300 ° C. for 1 hour. After cooling, the ferrite powder bulk was pulverized using a sieve having an opening of 125 μm to obtain [Carrier 1].

(Image evaluation)
4% by weight of the toner prepared as described above and 96% by weight of the prototype carrier are mixed, and the resulting two-component developer is used to develop with a modified Ricoh copier imagio NEO C600. To evaluate images at 50,000 sheets / day, initial and 100,000 sheets, respectively. Three sheets of solid black (A3) were output, and the degree of white-out image portions due to toner filming on the photoreceptor was visually evaluated.
The remodeled image of the imgio NEO C600 machine was such that the linear velocity was 1650 mm / sec, the development gap was 1.26 mm, the doctor blade gap was 1.6 mm, and the reflective photosensor function was OFF. . The actual temperature regions of the image carrier, the developing device, and the transfer device are controlled to be 30 to 48 ° C. (heating or cooling).
The image quality is worse as the number of white-out images due to the toner filming on the photoreceptor in a black solid image increases.
The evaluation results were visually expressed as the number of white spots on the whole solid image, and ranked as follows.
◎: Remarkably excellent with few whiteout image portions ○: Remarkably excellent with few whiteout image portions △: Normal whiteout image portion ×: Very many whiteout image portions

(2) Low-temperature fixability The Ricoh copier imagio NEO C600 remodeled machine which was remodeled using the two-component developer produced as described above so that the linear velocity was 1650 mm / sec and the oil coating apparatus was removed. The temperature of the fixing roller was changed in increments of 5 ° C., and the temperature at which low temperature fixing was possible was measured. The fixing roll was evaluated under the condition that no oil was applied, and the Ricoh full color PPC paper type 6200 was used as the transfer paper.
By changing the fixing temperature of the fixing unit alone, a copy image was obtained in which the image density by the Macbeth densitometer was 1.2. The copy image at each temperature was rubbed 10 times with a clock meter equipped with a sand eraser, the image density before and after that was measured, and the fixing rate was determined by the following formula.
Fixing rate (%) = [(image density after 10 times of sand eraser) / (previous image density)] × 100
The temperature at which a fixing rate of 70% or more was achieved was defined as the minimum fixing temperature. The criteria for determining low temperature fixability are as follows.
The evaluation results were expressed as follows.
◎: Fixing starts at a very low temperature and the lower limit fixing temperature is low, and the fixing property is very low. ○: The fixing property is very good. △: The fixing property is lower than that of a conventional toner. Inferior

Comparative Example 1
In Example 1, it evaluated similarly to Example 1 except having changed the following real machine evaluation conditions.
The transfer current value for filming evaluation is 25 μA.

Comparative Example 2
In Example 1, except that the fatty acid amide compound was changed as follows, a toner was obtained in the same manner as in Example 1 and evaluated in the same manner.
Stearamide compound (melting point: 115 ° C.) 0 part Example 2
In Example 1, it evaluated similarly to Example 1 except having changed the following real machine evaluation conditions.
The mixing condition was 1000 rpm for 5 cycles, and in 1 cycle, the mixture was stirred for 60 seconds and then stopped for 60 seconds.

Example 3
In Example 1, a toner was obtained in the same manner as in Example 1 except that the crystalline polyester resin and the amorphous polyester resin were changed as follows, and evaluated in the same manner.
-Crystalline polyester resin No. 2 30 parts Amorphous polyester resin B 70 parts

Comparative Example 3
In Example 1, a toner was obtained in the same manner as in Example 1 except that the crystalline polyester resin and the amorphous polyester resin were changed as follows, and evaluated in the same manner.
-Crystalline polyester resin No. 1 4 parts 96 parts of amorphous polyester resin B

Example 4
In Example 3, a toner was obtained and evaluated in the same manner as in Example 3 except that the amorphous polyester resin was changed as follows.
・ Amorphous polyester resin A 70 parts

Example 5
In Example 4, a toner was obtained and evaluated in the same manner as in Example 4 except that the wax was changed as follows.
- polypropylene wax (melting point: 145 ° C.) 5 parts

1 is a cross-sectional view of an example of an image forming apparatus of the present invention. It is a graph which shows the characteristic spectrum of the crystalline state of crystalline polyester resin. It is a graph which shows the characteristic spectrum of the polyester resin which is an amorphous resin. It is a graph which shows the characteristic spectrum of the styrene acrylic resin which is an amorphous resin. It is a graph which shows the X-ray-diffraction result of crystalline polyester resin. It is an example of the graph which shows the X-ray-diffraction result of this invention toner.

Explanation of symbols

4 Developing device 10 Intermediate transfer belt 14 Support roll 15 Support roll 16 Support roll 17 Intermediate transfer belt cleaning device 18 Image forming means 20 Tandem type image forming device 21 Laser exposure device 22 Secondary transfer device 23 Roll 24 Endless secondary transfer belt 25 Fixing device 26 Fixing belt 27 Pressure roll 25 Fixing device 28 Sheet reversing device 30 Document table 32 Contact glass 33 First traveling member 34 Second traveling member 35 Imaging lens 36 Reading sensor 40 Photosensitive member 42 Feeding roller 43 Paper bank 44 Paper feed cassette 45 Separation roll 46 Paper feed path 47 Transport roll 48 r Paper feed path 49 Registration roll 50 Paper feed roll 51 Manual feed tray 52 Separation roll 53 Manual feed path 54 Registration roll 55 Switching claw 56 Ejection roll 57 Ejection tray 62 Primary transfer means 100 Okimoto 200 feeder table 300 Scanner 400 automatic document feeder (ADF)

Claims (6)

An image carrier for carrying a latent image;
A charging device for charging the surface of the image carrier;
An exposure device for writing an electrostatic latent image on the surface of the charged image carrier;
A developing device that visualizes the electrostatic latent image formed on the surface of the image carrier using a developer containing toner;
A transfer device for transferring a visible image on the surface of the image carrier onto a transfer medium and / or a recording medium;
A cleaning device for cleaning the transfer residual toner remaining on the surface of the image carrier;
In an image forming apparatus comprising a fixing device for fixing a visible image on a recording medium,
The system speed is 500-1700 mm / sec,
The toner contains at least a binder resin, a fatty acid amide compound, and a colorant, and the binder resin contains at least a crystalline polyester resin and an amorphous resin, and the fatty acid amide compound is a toner. The peak height of the characteristic spectrum of the crystalline polyester resin in the ATR method (total reflection method) using FT-IR (Fourier transform infrared spectroscopic measurement device) of the toner is internally added. W, where R is the peak height of the characteristic spectrum of the amorphous resin, the peak ratio indicated by W / R is 0.450 to 0.553, and when the image forming apparatus forms an image, The amount of toner in the visible image portion on the surface of the image carrier is W (mg / cm ² ), and the amount of transfer residual toner remaining on the surface of the image carrier after transfer is A (mg / cm ² ). The following formula-( ) Toner transfer ratio T which is expressed by the image forming apparatus, characterized in that 75 to 100%.
Toner transfer rate T (%) = (W−A) × 100 / W Formula− (1) The developer is a developer for developing a two-component electrostatic image containing a carrier made of magnetic particles, and an initial agent mixed with stirring at a toner concentration (toner weight / (toner weight + carrier weight)) of 4 wt%. The toner charge fluctuation rate (%) P represented by the following formula-(2) is 0 to 40% in the charge amount of the toner measured by the single mode of the V blow-off device. Image forming apparatus.
Toner charge fluctuation rate (%) P
= (M−H) × 100 / ((H + M) ÷ 2) Formula− (2)
(However, M is the toner charge amount at 23 ° C. and 55% relative humidity in the environment.
The toner charge amount in the environment of 42 ° C. and relative humidity 40% is H. )   The image according to claim 1 or 2, wherein the amorphous resin is a polyester resin formed in the presence of titanium dihydroxybis (triethanolaminate) which is a titanium-containing catalyst (a). Forming equipment.   The image forming apparatus according to claim 1, wherein an acid value of the crystalline polyester resin is 20 to 45 mg KOH / g.   The image forming apparatus according to claim 1, wherein the crystalline polyester resin has a hydroxyl value of 5 to 50 mgKOH / g.   The image forming apparatus according to claim 1, wherein the toner contains a wax as a release agent, and the melting point of the wax is 70 to 150 ° C. 6.

Images