JP6375651B2 - Image forming method and image forming apparatus - Google Patents

Description

  The present invention relates to an image forming method and an image forming apparatus using the same.

In order to improve the low-temperature fixability, a method of lowering the glass transition temperature (Tg) of the amorphous polyester resin or a method of reducing the molecular weight can be considered so as to eutectic with the crystalline polyester resin. However, it is easy to imagine that if the melt viscosity is lowered by simply lowering the Tg of the amorphous polyester resin or reducing the molecular weight, the heat-resistant storage stability of the toner and the high-temperature offset property during fixing will deteriorate. Is done. Therefore, this method has a limit due to a trade-off with heat-resistant storage stability even if low-temperature fixing is aimed.
In addition, if the ratio of the crystalline polyester resin is increased in pursuit of further sharp melt properties, there is a problem that the electric resistance is lowered, and there are many problems in charging performance and transfer performance, and low temperature fixability and There was a limit due to a trade-off with the margin of the image forming process.

  On the other hand, a toner containing a non-linear amorphous polyester resin A, an amorphous polyester resin B, and a crystalline polyester resin C is known. This toner can ensure low-temperature fixability by the non-linear amorphous polyester resin A having a low Tg. In addition, the non-linear amorphous polyester resin A has a branched structure in the molecular skeleton, and the molecular chain has a three-dimensional network structure. it can. Further, the melting temperature of the toner that affects the heat resistance and storage stability can be adjusted by the amorphous polyester resin B, and the sharp melt property can be imparted by the crystalline polyester C. As a result, the heat resistant storage stability and high temperature offset resistance of the toner can be maintained.

However, toners with rubber properties up to now have the property of being deformed but not flowing, so the storage stability associated with melting and fusing such as solidification and unit lock due to heat generation of the drive shaft is not possible. Although there was no problem, it was found that there are problems related to toner aggregation accompanying deformation, and various problems occur in an actual image forming apparatus.
Specifically, with ease of deformation, the toner deforms when pressure is applied to the toner, thereby increasing the adhesion between the toners and causing the toner to easily aggregate. Due to this characteristic, when a transfer pressure is applied at the transfer portion, the toners are brought into close contact with each other, and the toner remains on the photosensitive member side, so that white spots are likely to occur. Particularly in fine line images such as letters and lines, the development electric field tends to concentrate, and the amount of toner adhesion tends to increase. As a result, the density of the toner increases when subjected to transfer pressure, and the central part of the fine line is exposed to light. Phenomenon such as transfer dropout remaining on the body side is likely to occur.

Known techniques for the purpose of preventing omission in transfer include those for controlling the surface property on the photoconductor side (Patent Documents 1 and 2), those for imparting elasticity to the transfer member (Patent Document 3), transfer member and photoconductor A device that provides a difference in linear velocity other than during printing and the application of lubricant to the toner (Patent Document 4), one that regulates the linear velocity ratio between the transfer member and the photosensitive member (Patent Document 5), and controls the shape of the toner side (Patent Documents 6 and 7) and the like, but none of the documents describes or suggests prevention of transfer dropout in the low-temperature fixing toner having elasticity as used in the present invention.
In addition, since the toner used in the present invention is easily deformed, aggregation at the transfer portion cannot be prevented even if the shape conditions of the known technique are maintained.

  SUMMARY OF THE INVENTION An object of the present invention is to provide an image forming method that does not cause transfer loss even when a toner having both low heat resistance and low temperature fixability using a resin having extremely low Tg and rubber elasticity due to a branched structure. .

In the present invention, a toner satisfying specific requirements for storage elastic moduli X and Y described later is used. The inventors of the present invention have studied the prevention of transfer dropout when such a toner is used. As a result, it is difficult for an electrical problem in transfer to occur, and if the charge corresponding to the charge amount of the toner is applied properly to the transfer portion. As a result, the present invention was found.
That is, the above problem is solved by the following invention 1).
1) When at least a polyester resin is contained, and the storage elastic modulus G ′ (40) at 40 ° C. of the THF-insoluble matter is X and the storage elastic modulus G ′ (100) at 100 ° C. is Y, Y is 1.0 × An electrophotographic image forming method using a toner having 10 ^{5 to} 1.0 × 10 ⁷ Pa and X / Y ≦ 3.5 × 10, and a coefficient of friction (μpc) of the photosensitive member, The friction coefficient (μtrans) of the toner image transfer medium in contact with the body satisfies the relationship of “μpc <μtrans”, and the linear velocity difference between the linear velocity (Vopc) of the photoreceptor and the linear velocity (Vtrans) of the toner image transfer medium. Satisfies the relationship | {(Vopc−Vtrans) / Vtrans} × 100 | ≦ 0.5.

  According to the present invention, it is possible to provide an image forming method that does not cause transfer loss even when a toner having both heat resistant storage stability and low-temperature fixability using a resin having rubber elasticity due to a branched structure having a very low Tg.

1 is a diagram illustrating an example of an image forming apparatus of the present invention. FIG. 3 is an enlarged view of the image forming unit 6Y of FIG. FIG. 3 is a cross-sectional view of an example of an image forming unit in a case where a mechanism for applying a lubricant is provided in one of the processes around the photosensitive member in order to apply a lubricant to the photosensitive member to reduce the friction coefficient of the photosensitive member. Explanatory drawing of the measuring method of the surface friction coefficient of the photoreceptor by the Euler belt method. FIG. 6 is an explanatory view of a method for measuring the surface friction coefficient of the intermediate transfer belt.

Hereinafter, the present invention 1) will be described in detail, but the following 2) to 5) are also included in the embodiment of the present invention, and these will also be described together.
2) The image forming method according to 1), wherein a lubricant is applied to the photoreceptor.
3) The image forming method according to 1) or 2), wherein the toner to which the lubricant is added is supplied to the surface of the photoreceptor through a development process, and the lubricant is supplied to a cleaning portion of the photoreceptor.
4) The image forming method according to any one of 1) to 3), wherein a layer containing a fluororesin is provided as a surface layer of the charge transport layer of the photoreceptor.
5) An image forming apparatus used for carrying out the image forming method according to any one of 1) to 4), wherein the toner image transfer means, a mechanism for controlling a coefficient of friction of a photoconductor, and a photoconductor motor are adjusted to adjust the photosensitivity. It has a mechanism that can finely adjust the linear velocity of the body with respect to the linear velocity of the toner image transfer medium, and the friction coefficient (μpc) of the photoconductor and the friction coefficient (μtrans) of the toner image transfer medium in contact with the photoconductor , And satisfies the relationship of “μpc <μtrans” and the linear velocity difference between the linear velocity (Vopc) of the photoreceptor and the linear velocity (Vtrans) of the toner image transfer medium is | {(Vopc−Vtrans) / Vtrans} × 100 | An image forming apparatus that can be controlled so as to satisfy a relationship of ≦ 0.5.

The toner used in the present invention contains at least a polyester resin and satisfies specific requirements regarding storage elastic modulus X and Y. Such a toner is obtained by containing a non-linear amorphous polyester resin A, an amorphous polyester resin B, and a crystalline polyester resin C.
The non-linear amorphous polyester resin A can be obtained by a reaction between a non-linear reactive precursor and a curing agent, and its Tg is −60 ° C. to 0 ° C. The amorphous polyester resin B has a Tg of 40 ° C to 80 ° C.
The glass transition temperature (Tg1st) of the toner at the first temperature increase in differential scanning calorimetry (DSC) is 20 ° C. to 50 ° C.

The storage modulus [G ′ (100) (THF insoluble content)] at 100 ° C. of the THF insoluble content of the toner used in the present invention is 1.0 × 10 ^{5 to} 1.0 × 10 ⁷ Pa. 0 × 10 ^{5 to} 5.0 × 10 ⁶ Pa is preferable.
Further, the storage elastic modulus [G ′ (40) (THF insoluble content)] at 40 ° C. of the THF insoluble content of the toner used in the present invention is X, and the [G ′ (100) (THF insoluble content)] is Y. , X / Y is 3.5 × 10 or less, preferably 3.3 × 10 or less. The lower limit of X / Y is not particularly limited and can be appropriately selected according to the purpose, but is preferably 2.0 × 10 or more.
When the toner used in the present invention satisfies the above requirements, the compatibilization between the crystalline polyester resin and the amorphous polyester resin B, which is a high Tg component, is promoted, and the heat flow evaluation apparatus (flow tester) ½ Outflow temperature is lowered and image gloss is improved.

  Further, the glass transition temperature [Tg2nd (THF insoluble matter)] at the second temperature increase in the differential scanning calorimetry (DSC) of the THF insoluble matter of the toner is preferably −40 ° C. to 30 ° C. Thereby, the compatibilization of the amorphous polyester resin B and the crystalline polyester resin C, which are high Tg components, is promoted, and the low-temperature fixability is improved. When the Tg2nd (THF insoluble content) is less than −40 ° C., the heat resistant storage stability may be deteriorated, and when it exceeds 30 ° C., the low temperature fixability may be deteriorated. The Tg2nd (THF insoluble matter) corresponds to the Tg2nd of the non-linear amorphous polyester resin A, and lowers the Tg2nd than other amorphous polyester resins, so that it works favorably at low temperature fixability. Moreover, when the non-linear amorphous polyester resin A has a urethane bond or a urea bond having a high cohesive force, the effect of maintaining heat-resistant storage stability becomes more remarkable.

Since the toner has a low Tg but a three-dimensional network structure, it exhibits rubber elasticity at room temperature. Therefore, the storage elastic modulus G ′ (50) at 50 ° C. is considerably low, being 5.0 × 10 ^{7 to} 1.0 × 10 ⁸ Pa. G ′ (50) will be described later.
This toner has the following characteristics (a) to (c) because of its low elasticity when the in-machine temperature rises. For this reason, when this toner is used in an electrophotographic image forming apparatus, an abnormal image such as transfer dropout (also referred to as worm-eaten) tends to occur at the transfer portion.
(A) Since it has elasticity, it does not melt or solidify to the melting point.
(B) Since it has elasticity, it deforms when pressure is applied.
(C) When the compression is performed in a narrow portion with the above deformation, the contact area between the toner and the toner sandwiched by the deformation of the toner increases, and the adhesion force tends to increase.

The mechanism of transfer loss is generated by the following (d) and (e).
(D) When a toner having a low circularity or a toner having a low aspect ratio is used, the contact point and the contact surface increase more than the sphere when the toner in the toner layer is pressed against each other when pressure is applied at the transfer nip. The cohesion between toners increases.
(E) When the toner passes through the transfer nip, the pressed toner becomes a lump and remains on the photoconductor side, not on the transfer material side.

Therefore, it is advantageous for the toner to be closer to a sphere to prevent the transfer from being lost. However, since the spherical toner is difficult to clean, it is necessary to balance it so that the toner has a certain degree of circularity and aspect ratio. In order to facilitate separation, measures are often taken to reduce the coefficient of friction on the photoreceptor side.
However, if the toner has elasticity, even if the original shape is a spherical shape, the contact area between the toners increases due to being pushed and deformed, which is disadvantageous with respect to the lack of transfer. This abnormal image is more likely to occur when the toner is deformed to cope with blade cleaning. For this reason, in order to perform image formation using elastic toner, it is necessary to cope with transfer loss.

On the other hand, many conventional low-temperature fixing toners use a crystalline resin to develop a low-temperature fixing property. In such toners, the crystalline resin is used only for sharp melt, and the low-temperature fixing property is Mainly secured by amorphous rubber-like resin. Therefore, such a transfer problem due to a decrease in electrical resistance in the toner has an advantage that it is less likely to occur than a toner in which equivalent low-temperature fixability is expressed only by a crystalline resin.
Therefore, in many cases, it is necessary to select the transfer bias and the mechanical conditions of the transfer area in order to control the transfer. However, since the electrical behavior is stable in this system, the generation of reversely charged toner occurs. The transfer electrical problems such as are unlikely to occur.
As a result of the study by the present inventors, operations such as pre-transfer charging, post-transfer charging, and static elimination are unnecessary, and if the charge corresponding to the toner charge amount is applied to the transfer portion properly, the mechanical conditions are controlled. It was found that transcription was possible.

  As a result of further investigation, a relationship of μpc <μtrans is established between the friction coefficient μpc of the photoconductor used for image formation and the friction coefficient μtrans of the toner image transfer medium in contact with the photoconductor, and the line of the photoconductor When combined with a transfer unit in which the linear velocity difference between the linear velocity (Vopc) and the linear velocity (Vtrans) of the toner image transfer medium satisfies | {(Vopc−Vtrans) / Vtrans} × 100 | ≦ 0.5, it has elasticity. It has been found that both low-temperature fixability and suppression of transfer loss can be achieved when toner is used.

<Nonlinear Amorphous Polyester Resin A>
Since the non-linear amorphous polyester resin A has a very low Tg, it has a property of being deformed at a low temperature, deformed by heating and pressurizing at the time of fixing, and adheres to a recording medium such as paper at a lower temperature. The non-linear amorphous polyester resin A has a branched structure in the molecular skeleton because the reactive precursor is non-linear, and the molecular chain has a three-dimensional network structure. It has a rubbery property of deforming but not flowing. As a result, the heat resistant storage stability and high temperature offset resistance of the toner can be maintained. In addition, when the non-linear amorphous polyester resin A has a urethane bond and / or a urea bond having high cohesive energy, adhesion to a recording medium such as paper is further improved. In addition, since the urethane bond and / or the urea bond behave like a pseudo-crosslinking point, the rubber property becomes stronger, and as a result, the heat resistant storage resistance and the high temperature offset resistance of the toner are more excellent. The non-linear amorphous polyester resin A is obtained by a reaction between a non-linear reactive precursor and a curing agent.
Here, non-linear means having a branched structure imparted by a trivalent or higher alcohol and / or a trivalent or higher carboxylic acid.

-Non-linear reactive precursor-
The non-linear reactive precursor is not particularly limited as long as it is a polyester resin having a group capable of reacting with a curing agent (hereinafter sometimes referred to as “prepolymer”). You can choose.
Examples of the group capable of reacting with the curing agent in the prepolymer include a group capable of reacting with an active hydrogen group. Examples thereof include an isocyanate group, an epoxy group, a carboxylic acid group, and an acid chloride group. Among these, an isocyanate group is preferable because a urethane bond and / or a urea bond can be introduced into the non-linear amorphous polyester resin A. Moreover, as said prepolymer, the polyester resin which has an isocyanate group is preferable.

--Polyester resin having isocyanate group--
There is no restriction | limiting in particular as the polyester resin which has the said isocyanate group, According to the objective, it can select suitably, For example, the reaction product etc. of the polyester resin and polyisocyanate which have an active hydrogen group are mentioned.
The polyester resin having an active hydrogen group can be obtained, for example, by polycondensing a diol, a dicarboxylic acid, a trivalent or higher alcohol and / or a trivalent or higher carboxylic acid. The trivalent or higher alcohol and the trivalent or higher carboxylic acid impart a branched structure to the polyester resin having the isocyanate group.

--- Diol ---
There is no restriction | limiting in particular as said diol, According to the objective, it can select suitably. Examples thereof include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, 1,8 -Aliphatic diols such as octanediol, 1,10-decanediol, 1,12-dodecanediol; having an oxyalkylene group such as diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol Diols: 1,4-cyclohexanedimethanol, alicyclic diols such as hydrogenated bisphenol A; alicyclic diols added with alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide; Nord A, bisphenol F, bisphenol such as bisphenol S; the bisphenols include ethylene oxide, propylene oxide, and alkylene oxide adducts of bisphenols such as those obtained by adding alkylene oxides such as butylene oxide. Among these, an aliphatic diol having 4 to 12 carbon atoms is preferable.
These diols may be used alone or in combination of two or more.

--- Dicarboxylic acid ---
There is no restriction | limiting in particular as said dicarboxylic acid, According to the objective, it can select suitably. Examples thereof include aliphatic dicarboxylic acids and aromatic dicarboxylic acids. Moreover, you may use these anhydrides, a lower (C1-C3) alkylesterification thing, a halide, etc.
Examples of the aliphatic dicarboxylic acid include succinic acid, adipic acid, sebacic acid, dodecanedioic acid, maleic acid, and fumaric acid.
The aromatic dicarboxylic acid is preferably an aromatic dicarboxylic acid having 8 to 20 carbon atoms. Examples thereof include phthalic acid, isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid and the like.
Of these, aliphatic dicarboxylic acids having 4 to 12 carbon atoms are preferred.
These dicarboxylic acids may be used individually by 1 type, and may use 2 or more types together.

--Alcohol having a valence of 3 or more ---
There is no restriction | limiting in particular as said trihydric or more alcohol, According to the objective, it can select suitably, For example, alkylene oxide of trihydric or more aliphatic alcohol, trihydric or more polyphenols, trihydric or more polyphenols Examples include adducts.
Examples of the trihydric or higher aliphatic alcohol include glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol and the like.
Examples of the trihydric or higher polyphenols include trisphenol PA, phenol novolak, cresol novolak, and the like.
Examples of the alkylene oxide adducts of trihydric or higher polyphenols include those obtained by adding alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide to trihydric or higher polyphenols.

--Carboxylic acid having a valence of 3 or more ---
There is no restriction | limiting in particular as said trivalent or more carboxylic acid, According to the objective, it can select suitably, For example, trivalent or more aromatic carboxylic acid etc. are mentioned. Moreover, you may use these anhydrides, a lower (C1-C3) alkylesterification thing, a halide, etc.
The trivalent or higher aromatic carboxylic acid is preferably a trivalent or higher aromatic carboxylic acid having 9 to 20 carbon atoms. Examples thereof include trimellitic acid and pyromellitic acid.

--- Polyisocyanate ---
There is no restriction | limiting in particular as said polyisocyanate, According to the objective, it can select suitably, For example, diisocyanate, trivalent or more isocyanate etc. are mentioned.
Examples of the diisocyanate include aliphatic diisocyanates, alicyclic diisocyanates, aromatic diisocyanates, araliphatic diisocyanates, isocyanurates, and those blocked with phenol derivatives, oximes, caprolactams, and the like.
Examples of the aliphatic diisocyanate include tetramethylene diisocyanate, hexamethylene diisocyanate, methyl 2,6-diisocyanatocaproate, octamethylene diisocyanate, decamethylene diisocyanate, dodecamethylene diisocyanate, tetradecamethylene diisocyanate, trimethylhexane diisocyanate, tetra And methyl hexane diisocyanate.
Examples of the alicyclic diisocyanate include isophorone diisocyanate and cyclohexylmethane diisocyanate.

Examples of the aromatic diisocyanate include tolylene diisocyanate, diisocyanatodiphenylmethane, 1,5-naphthylene diisocyanate, 4,4′-diisocyanatodiphenyl, 4,4′-diisocyanato-3,3′-dimethyldiphenyl. 4,4'-diisocyanato-3-methyldiphenylmethane, 4,4'-diisocyanato-diphenyl ether, and the like.
Examples of the araliphatic diisocyanate include α, α, α ′, α′-tetramethylxylylene diisocyanate.
Examples of the isocyanurates include tris (isocyanatoalkyl) isocyanurate and tris (isocyanatocycloalkyl) isocyanurate.
These polyisocyanates may be used alone or in combination of two or more.

-Curing agent-
The curing agent is not particularly limited as long as it is a curing agent that reacts with the non-linear reactive precursor and generates the non-linear amorphous polyester resin A, and is appropriately selected according to the purpose. Examples thereof include active hydrogen group-containing compounds.

-Active hydrogen group-containing compound-
There is no restriction | limiting in particular as an active hydrogen group in the said active hydrogen group containing compound, According to the objective, it can select suitably, For example, a hydroxyl group (alcoholic hydroxyl group and phenolic hydroxyl group), an amino group, a carboxyl group, a mercapto group etc. Can be mentioned. These may be used individually by 1 type and may use 2 or more types together.
There is no restriction | limiting in particular as said active hydrogen group containing compound, Although it can select suitably according to the objective, Amines are preferable at the point which can form a urea bond.
Examples of the amines include diamines, trivalent or higher amines, amino alcohols, amino mercaptans, amino acids, and those obtained by blocking these amino groups. These may be used individually by 1 type and may use 2 or more types together.
Among these, diamine and a mixture of diamine and a small amount of trivalent or higher amine are preferable.

Examples of the diamine include aromatic diamine, alicyclic diamine, and aliphatic diamine.
Examples of the aromatic diamine include phenylene diamine, diethyl toluene diamine, and 4,4′-diaminodiphenyl methane.
Examples of the alicyclic diamine include 4,4′-diamino-3,3′-dimethyldicyclohexylmethane, diaminocyclohexane, and isophorone diamine.
Examples of the aliphatic diamine include ethylene diamine, tetramethylene diamine, and hexamethylene diamine.

Examples of the trivalent or higher amine include diethylenetriamine and triethylenetetramine.
Examples of the amino alcohol include ethanolamine and hydroxyethylaniline.
Examples of the amino mercaptan include aminoethyl mercaptan and aminopropyl mercaptan.
Examples of the amino acid include aminopropionic acid and aminocaproic acid.
Examples of the blocked amino group include ketimine compounds and oxazoline compounds obtained by blocking amino groups with ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone.

The non-linear amorphous polyester resin A preferably satisfies any of the following (a) to (c) in order to lower the Tg and to easily impart the property of being deformed at a low temperature.
(A) A diol component is included as a constituent component, and the diol component contains 50% by mass or more of an aliphatic diol having 4 to 12 carbon atoms.
(B) 50% by mass or more of an aliphatic diol having 4 to 12 carbon atoms is contained in all alcohol components.
(C) A dicarboxylic acid component is included as a constituent component, and the dicarboxylic acid component contains 50% by mass or more of an aliphatic dicarboxylic acid having 4 to 12 carbon atoms.

The non-linear amorphous polyester resin A has a Tg of -60 ° C to 0 ° C, more preferably -40 ° C to -20 ° C. When the Tg is less than −60 ° C., the flow of toner at a low temperature cannot be suppressed, heat resistance storage stability is deteriorated, and filming resistance is deteriorated. If the Tg exceeds 0 ° C., the toner is not sufficiently deformed by heating and pressing during fixing, and the low-temperature fixability becomes insufficient.
The weight average molecular weight of the non-linear amorphous polyester resin A is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 20,000 to 100,000 in GPC (gel permeation chromatography) measurement. When the weight average molecular weight is less than 20,000, the toner tends to flow at a low temperature and may have poor heat-resistant storage stability, and the viscosity at the time of melting may be low, and the high temperature offset property may be reduced. On the other hand, if it exceeds 100,000, the low-temperature fixability deteriorates.

The molecular structure of the non-linear amorphous polyester resin A can be confirmed by X-ray diffraction, GC / MS, LC / MS, IR measurement, etc. in addition to NMR measurement by solution or solid. At a convenient infrared absorption spectrum, and a method of detecting the 965 ± 10 cm ^-1 and 990 ± 10 cm ^-1 and having no absorption based on olefin? Ch (out-of-plane deformation vibration) as an amorphous polyester resin .
The content of the non-linear amorphous polyester resin A is not particularly limited and may be appropriately selected depending on the intended purpose, but it is preferably 5 to 25 parts by mass with respect to 100 parts by mass of the toner, and 10 to 20 Part by mass is more preferable. When the content is less than 5 parts by mass, the low-temperature fixability and the high-temperature offset resistance may be deteriorated. When the content exceeds 25 parts by mass, the heat-resistant storage stability is deteriorated and the glossiness of an image obtained after fixing may be reduced. . When the content is in the more preferable range, it is advantageous in that it is excellent in all of low-temperature fixability, high-temperature offset resistance, and heat-resistant storage stability.

<Amorphous polyester resin B>
The amorphous polyester resin B is not particularly limited as long as Tg is 40 ° C. to 80 ° C., and can be appropriately selected according to the purpose, but a linear polyester resin is preferable.
Further, as the amorphous polyester resin B, an unmodified polyester resin is preferable. The unmodified polyester resin here is a polyester resin obtained by using a polyhydric alcohol and a polyvalent carboxylic acid such as a polyvalent carboxylic acid, a polyvalent carboxylic acid anhydride, a polyvalent carboxylic acid ester, or a derivative thereof. It is a polyester resin that is not modified with an isocyanate compound or the like.

Examples of the polyhydric alcohol include diols.
Examples of the diol include polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane and polyoxyethylene (2.2) -2,2-bis (4-hydroxyphenyl) propane. Bisphenol A alkylene (2 to 3 carbon atoms) oxide (average addition mole number 1 to 10) adduct; ethylene glycol, propylene glycol; hydrogenated bisphenol A, hydrogenated bisphenol A alkylene (2 to 3 carbon atoms) Examples include oxide (average added mole number 1 to 10) adducts.
These may be used individually by 1 type and may use 2 or more types together.

Examples of the polyvalent carboxylic acid include dicarboxylic acid.
Examples of the dicarboxylic acid include adipic acid, phthalic acid, isophthalic acid, terephthalic acid, fumaric acid, maleic acid, dodecenyl succinic acid, octyl succinic acid and the like, or an alkyl group having 1 to 20 carbon atoms or 2 to 20 carbon atoms. And succinic acid substituted with an alkenyl group.
These may be used individually by 1 type and may use 2 or more types together.

Further, the amorphous polyester resin B may contain a trivalent or higher carboxylic acid and / or a trivalent or higher alcohol at the end of the resin chain in order to adjust the acid value or the hydroxyl value.
Examples of the trivalent or higher carboxylic acid include trimellitic acid, pyromellitic acid, or acid anhydrides thereof.
Examples of the trivalent or higher alcohol include glycerin, pentaerythritol, and trimethylolpropane.

  The molecular weight of the amorphous polyester resin B is not particularly limited and may be appropriately selected depending on the purpose. However, if the molecular weight is too low, the toner may be inferior in heat-resistant storage and durability against stress such as stirring in the developing machine. If the molecular weight is too high, the viscoelasticity at the time of melting of the toner will increase and low-temperature fixability. May be inferior. Therefore, the weight average molecular weight (Mw) in GPC measurement is preferably 3000 to 10,000, and more preferably 4000 to 7000. Moreover, 1000-4000 are preferable and, as for a number average molecular weight (Mn), 1500-3000 are more preferable. Further, Mw / Mn is preferably 1.0 to 4.0, and more preferably 1.0 to 3.5.

There is no restriction | limiting in particular in the acid value of the said amorphous polyester resin B, Although it can select suitably according to the objective, 1-50 mgKOH / g is preferable and 5-30 mgKOH / g is more preferable. When the acid value is 1 mgKOH / g or more, the toner is likely to be negatively charged, and further, the affinity between the paper and the toner is improved during fixing on the paper, and the low-temperature fixability can be improved. On the other hand, when the acid value exceeds 50 mgKOH / g, the charging stability, particularly the charging stability against environmental fluctuations may be lowered.
There is no restriction | limiting in particular in the hydroxyl value of the said amorphous polyester resin B, Although it can select suitably according to the objective, It is preferable that it is 5 mgKOH / g or more.

The amorphous polyester resin B has a Tg of preferably 40 ° C to 80 ° C, more preferably 50 ° C to 70 ° C. When the Tg is less than 40 ° C., the heat resistant storage stability of the toner and the durability against stress such as stirring in the developing machine are inferior, and the filming resistance deteriorates. On the other hand, if Tg exceeds 80 ° C., the deformation due to heating and pressurization at the time of fixing the toner is not sufficient, and the low-temperature fixability becomes insufficient.
The molecular structure of the amorphous polyester resin B can be confirmed by X-ray diffraction, GC / MS, LC / MS, IR measurement, etc., in addition to NMR measurement by solution or solid. At a convenient infrared absorption spectrum, and a method of detecting the 965 ± 10 cm ^-1 and 990 ± 10 cm ^-1 and having no absorption based on olefin? Ch (out-of-plane deformation vibration) as an amorphous polyester resin .

  The content of the amorphous polyester resin B is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 50 to 90 parts by weight, more preferably 60 to 80 parts by weight with respect to 100 parts by weight of the toner. preferable. When the content is less than 50 parts by mass, the dispersibility of the pigment and the release agent in the toner is deteriorated and the image may be easily fogged or disturbed. On the other hand, when the amount exceeds 90 parts by mass, the content of the crystalline polyester resin C and the non-linear amorphous polyester resin A is decreased, so that the low-temperature fixability may be inferior. When the content is in the more preferable range, it is advantageous in that it is excellent in all of high image quality and low temperature fixability.

<Crystalline polyester resin C>
Since the crystalline polyester resin C has high crystallinity, the viscosity is rapidly lowered near the fixing start temperature. When the crystalline polyester resin C having such characteristics is used together with the amorphous polyester resin B, the heat resistant storage stability is good due to the crystallinity until immediately before the melting start temperature, and the melting of the crystalline polyester resin C at the melting start temperature. Causes a sharp drop in viscosity (sharp melt property), which is compatible with amorphous polyester resin B, and causes a sudden drop in viscosity to fix. Toner is obtained. Also, good results are shown for the release width (difference between the fixing lower limit temperature and the high temperature resistant offset occurrence temperature).
The crystalline polyester resin C in the present invention refers to one obtained from a polyhydric alcohol and a polyvalent carboxylic acid such as a polyvalent carboxylic acid, a polyvalent carboxylic acid anhydride, a polyvalent carboxylic acid ester, or a derivative thereof. Accordingly, the crystalline polyester resin C does not include a modified polyester resin, for example, the prepolymer and a resin obtained by crosslinking and / or elongation reaction of the prepolymer.

-Polyhydric alcohol-
There is no restriction | limiting in particular as said polyhydric alcohol, According to the objective, it can select suitably, For example, diol and trihydric or more alcohol are mentioned.
Examples of the diol include saturated aliphatic diol. Examples thereof include linear saturated aliphatic diols and branched saturated aliphatic diols. Among these, linear saturated aliphatic diols are preferable, and linear saturated aliphatic diols having 2 to 12 carbon atoms are more preferable. . When the saturated aliphatic diol is branched, the crystallinity of the crystalline polyester resin C may be lowered, and the melting point may be lowered. Further, when the saturated aliphatic diol has more than 12 carbon atoms, it is difficult to obtain a practical material.

Examples of the saturated aliphatic diol include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1, 8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,13-tridecanediol, 1,14-tetradecanediol, 1, Examples thereof include 18-octadecanediol and 1,14-eicosandecanediol. Among these, the crystalline polyester resin C has high crystallinity and is excellent in sharp melt properties, so that ethylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, 1, 10-decanediol and 1,12-dodecanediol are preferred.
Examples of the trihydric or higher alcohol include glycerin, trimethylolethane, trimethylolpropane, and pentaerythritol.
These may be used individually by 1 type and may use 2 or more types together.

-Multivalent carboxylic acid-
There is no restriction | limiting in particular as said polyvalent carboxylic acid, According to the objective, it can select suitably, For example, bivalent carboxylic acid and trivalent or more carboxylic acid are mentioned.
Examples of the divalent carboxylic acid include oxalic acid, succinic acid, glutaric acid, adipic acid, peric acid, azelaic acid, sebacic acid, 1,9-nonanedicarboxylic acid, 1,10-decanedicarboxylic acid, 1, Saturated aliphatic dicarboxylic acids such as 12-dodecanedicarboxylic acid, 1,14-tetradecanedicarboxylic acid, 1,18-octadecanedicarboxylic acid; phthalic acid, isophthalic acid, terephthalic acid, naphthalene-2,6-dicarboxylic acid, malonic acid, Aromatic dicarboxylic acids such as dibasic acids such as mesaconic acid; and the like, and anhydrides and lower (C1 to C3) alkyl esters thereof.
Examples of the trivalent or higher carboxylic acid include 1,2,4-benzenetricarboxylic acid, 1,2,5-benzenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, and the like, and anhydrides thereof. Lower (carbon number 1 to 3) alkyl ester and the like.
In addition to the saturated aliphatic dicarboxylic acid and aromatic dicarboxylic acid, the polyvalent carboxylic acid may include a dicarboxylic acid having a sulfonic acid group. Furthermore, in addition to the saturated aliphatic dicarboxylic acid and aromatic dicarboxylic acid, a dicarboxylic acid having a double bond may be contained. These may be used individually by 1 type and may use 2 or more types together.

The crystalline polyester resin C is preferably composed of a linear saturated aliphatic dicarboxylic acid having 4 to 12 carbon atoms and a linear saturated aliphatic diol having 2 to 12 carbon atoms. That is, it is preferable to have a structural unit derived from a saturated aliphatic dicarboxylic acid having 4 to 12 carbon atoms and a structural unit derived from a saturated aliphatic diol having 2 to 12 carbon atoms. As a result, the crystallinity becomes high and the sharp melt property is excellent, so that excellent low-temperature fixability can be exhibited.
There is no restriction | limiting in particular in the melting | fusing point of the said crystalline polyester resin C, Although it can select suitably according to the objective, 60 to 80 degreeC is preferable. If the melting point is less than 60 ° C., the crystalline polyester resin C is likely to melt at low temperatures and the heat-resistant storage stability of the toner may be reduced. Insufficient, low-temperature fixability may decrease.

  The molecular weight of the crystalline polyester resin C is not particularly limited and may be appropriately selected depending on the purpose. However, those with sharp molecular weight distribution and low molecular weight are excellent in low-temperature fixability, and when there are many components with low molecular weight, the heat-resistant storage stability is lowered. Therefore, the soluble content of orthodichlorobenzene in crystalline polyester resin C is GPC. In measurement, it is preferable that they are weight average molecular weight (Mw) 3000-30000, number average molecular weight (Mn) 1000-10000, and Mw / Mn = 1.0-10. More preferably, it is weight average molecular weight (Mw) 5000-15000, number average molecular weight (Mn) 2000-10000, Mw / Mn = 1.0-5.0.

The acid value of the crystalline polyester resin C is not particularly limited and can be appropriately selected according to the purpose. From the viewpoint of affinity between paper and resin, in order to achieve desired low-temperature fixability, 5 mgKOH / g or more is preferable, and 10 mgKOH / g or more is more preferable. On the other hand, in order to improve the high temperature offset resistance, 45 mgKOH / g or less is preferable.
The hydroxyl value of the crystalline polyester resin C is not particularly limited and may be appropriately selected according to the purpose. However, in order to achieve a desired temperature fixability and to achieve good charging characteristics, 0 to 50 mgKOH / g is preferable, and 5-50 mgKOH / g is more preferable.
The molecular structure of the crystalline polyester resin C can be confirmed by X-ray diffraction, GC / MS, LC / MS, IR measurement, etc., in addition to NMR measurement by solution or solid. For example, in the infrared absorption spectrum, a method of detecting, as crystalline polyester resin C, those having absorption at 965 ± 10 cm ⁻¹ and 990 ± 10 cm ⁻¹ based on δCH (out-of-plane variable angular vibration) of olefins can be mentioned.

  There is no restriction | limiting in particular in content of the said crystalline polyester resin C, Although it can select suitably according to the objective, 3-20 mass parts is preferable with respect to 100 mass parts of toner, and 5-15 mass parts is more preferable. . If the content is less than 3 parts by mass, the low-temperature fixability may be inferior due to insufficient sharp-melting with the crystalline polyester resin C. May occur easily. When the content is within the more preferable range, it is advantageous in that it is excellent in all of high image quality and low temperature fixability.

<Other ingredients>
In addition to the components described above, the toner of the present invention may contain additives such as a release agent, a colorant, a charge control agent, an external additive, a fluidity improver, a cleaning property improver, and a magnetic material as necessary. It can be included.

-Release agent-
There is no restriction | limiting in particular as said mold release agent, It can select suitably from well-known things, For example, the following are mentioned.
Examples of waxes and waxes include plant waxes such as carnauba wax, cotton wax, wood wax, and rice wax; animal waxes such as beeswax and lanolin; mineral waxes such as ozokerite and cercin; paraffin and microcrystalline And natural waxes such as petroleum waxes such as Petrolatum;
In addition to these natural waxes, synthetic hydrocarbon waxes such as Fischer-Tropsch wax, polyethylene, and polypropylene; synthetic waxes such as esters, ketones, and ethers;
Furthermore, fatty acid amide compounds such as 12-hydroxystearic acid amide, stearic acid amide, phthalic anhydride imide, chlorinated hydrocarbon; low molecular weight crystalline polymer resin, poly-n-stearyl methacrylate, poly-n -Polyacrylate homopolymer or copolymer such as lauryl methacrylate (eg, n-stearyl acrylate-ethyl methacrylate copolymer); crystalline polymer having a long alkyl group in the side chain, etc. Good.
Among these, hydrocarbon waxes such as paraffin wax, microcrystalline wax, Fischer-Tropsch wax, polyethylene wax, and polypropylene wax are preferable.

The melting point of the release agent is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 60 ° C to 80 ° C. When the melting point is less than 60 ° C., the release agent tends to melt at low temperatures, and the heat resistant storage stability may be inferior. When the melting point exceeds 80 ° C., even when the resin is melted and is in the fixing temperature region, the release agent may not be sufficiently melted to cause a fixing offset and cause an image defect.
There is no restriction | limiting in particular in content of a mold release agent, Although it can select suitably according to the objective, 2-10 mass parts is preferable with respect to 100 mass parts of toner, and 3-8 mass parts is more preferable. If the content is less than 2 parts by mass, the high temperature offset resistance and the low temperature fixability at the time of fixing may be inferior. If the content exceeds 10 parts by mass, heat resistant storage stability may be deteriorated or image fogging may occur. is there. When the content is in the more preferable range, it is advantageous in terms of improving the image quality and improving the fixing stability.

-Colorant-
There is no restriction | limiting in particular as said coloring agent, According to the objective, it can select suitably.
There is no restriction | limiting in particular in content of a coloring agent, Although it can select suitably according to the objective, 1-15 mass parts is preferable with respect to 100 mass parts of toner, and 3-10 mass parts is more preferable.

  Examples of colorants include carbon black, nigrosine dye, iron black, naphthol yellow S, Hansa yellow (10G, 5G, G), cadmium yellow, yellow iron oxide, ocher, yellow lead, titanium yellow, polyazo yellow, oil Yellow, Hansa Yellow (GR, A, RN, R), Pigment Yellow L, Benzidine Yellow (G, GR), Permanent Yellow (NCG), Vulcan Fast Yellow (5G, R), Tartrazine Lake, Quinoline Yellow Lake, Anthra Zan Yellow BGL, Isoindolinone Yellow, Bengala, Red Plum, Lead Zhu, Cadmium Red, Cadmium Mercury Red, Antimon Zhu, Permanent Red 4R, Para Red, Faise Red, Parachlor Ortho Nitroaniline Red, Resol Fast Scarlet G, Brilliant Fast Scarlet, Brilliant Carmin Min BS, Permanent Red (F2R, F4R, FRL, FRLL, F4RH), Fast Scarlet VD, Belkan Fast Rubin B, Brilliant Scarlet G, Resol Rubin GX, Permanent Red F5R, Brilliant Carmine 6B, Pigment Scarlet 3B, Bordeaux 5B, Toluidine Maroon, Permanent Bordeaux F2K, Helio Bordeaux BL, Bordeaux 10B, Bon Maroon Light, Bon Maroon Medium, Eosin Lake, Rhodamine Lake B, Rhodamine Lake Y, Alizarin Lake, Thioindigo Red B, Thioindigo Maroon, oil red, quinacridone red, pyrazolone red, polyazo red, chrome vermilion, ben Gin orange, Perinone orange, Oil orange, Cobalt blue, Cerulean blue, Alkaline blue rake, Peacock blue rake, Victoria blue rake, Metal-free phthalocyanine blue, phthalocyanine blue, Fast sky blue, Indanthrene blue (RS, BC), Indigo, ultramarine blue, bitumen, anthraquinone blue, fast violet B, methyl violet lake, cobalt purple, manganese purple, dioxane violet, anthraquinone violet, chrome green, zinc green, chromium oxide, pyridian, emerald green, pigment green B, naphthol green B , Green Gold, Acid Green Lake, Malachite Green Lake, Phthalocyanine Green, Anthraquinone Green, Titanium oxide, zinc white, ritbon, etc. are mentioned.

  The colorant can also be used as a master batch combined with a resin. Examples of the resin to be kneaded together with the production of the master batch or the master batch include, in addition to the amorphous polyester resin B, styrene such as polystyrene, poly-p-chlorostyrene, and polyvinyltoluene, or a polymer of a substituted product thereof; styrene -P-chlorostyrene copolymer, styrene-propylene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene-methyl acrylate copolymer, styrene-ethyl acrylate copolymer, Styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer, styrene-α-chloro Methyl methacrylate copolymer, styrene-acrylic Nitrile copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-acrylonitrile-indene copolymer, styrene-maleic acid copolymer, styrene-maleic acid ester Styrene copolymers such as copolymers; polymethyl methacrylate, polybutyl methacrylate, polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, polyester, epoxy resin, epoxy polyol resin, polyurethane, polyamide, polyvinyl butyral, polyacrylic acid Examples thereof include resins, rosins, modified rosins, terpene resins, aliphatic or alicyclic hydrocarbon resins, aromatic petroleum resins, chlorinated paraffins, and paraffin waxes. These may be used individually by 1 type and may use 2 or more types together.

  The masterbatch can be obtained by mixing and kneading the masterbatch resin and the colorant under high shearing force. At this time, an organic solvent can be used in order to enhance the interaction between the colorant and the resin. Also, a so-called flushing method called an aqueous paste of a colorant is mixed and kneaded together with a resin and an organic solvent, the colorant is transferred to the resin side, and moisture and organic solvent components are removed. This is preferable because it can be dried. For mixing and kneading, a high shear dispersion device such as a three-roll mill is preferably used.

-Charge control agent-
There is no restriction | limiting in particular in the said charge control agent, According to the objective, it can select suitably. Examples include nigrosine dyes, triphenylmethane dyes, chromium-containing metal complex dyes, molybdate chelate pigments, rhodamine dyes, alkoxy amines, quaternary ammonium salts (including fluorine-modified quaternary ammonium salts), alkyls. Examples include amide, phosphorus simple substance or compound, tungsten simple substance or compound, fluorine-based activator, salicylic acid metal salt, and metal salt of salicylic acid derivative. Specifically, Nitronine-based dye Bontron 03, quaternary ammonium salt Bontron P-51, metal-containing azo dye Bontron S-34, oxynaphthoic acid metal complex E-82, salicylic acid metal complex E- 84, E-89 of a phenol-based condensate (above, manufactured by Orient Chemical Co., Ltd.), TP-302 of a quaternary ammonium salt molybdenum complex, TP-415 (above, manufactured by Hodogaya Chemical Co., Ltd.), LRA-901, LR-147 (manufactured by Nippon Carlit) which is a boron complex, copper phthalocyanine, perylene, quinacridone, azo pigments, and other polymer compounds having functional groups such as sulfonic acid groups, carboxyl groups, and quaternary ammonium salts. It is done.

  The content of the charge control agent is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 0.1 to 10 parts by weight, and preferably 0.2 to 5 parts by weight with respect to 100 parts by weight of the toner. Is more preferable. When the content exceeds 10 parts by mass, the chargeability of the toner is too high, the effect of the main charge control agent is reduced, the electrostatic attraction force with the developing roller is increased, the flowability of the developer is reduced, and the image The concentration may decrease. These charge control agents can be dissolved and dispersed after being melt-kneaded with a masterbatch and resin, or may be added when directly dissolving and dispersing in an organic solvent, or after toner particles are produced on the toner surface. It may be fixed.

-External additive-
As the external additive, in addition to oxide fine particles, inorganic fine particles or hydrophobic treated inorganic fine particles can be used in combination. The average particle size of the hydrophobized primary particles is preferably 1 to 100 nm, preferably 5 to 70 nm. The inorganic fine particles are more preferable.
Further, it is preferable that at least one kind of inorganic fine particles having an average particle diameter of 20 nm or less of the hydrophobized primary particles and at least one kind of inorganic fine particles having an average particle diameter of the primary particles of 30 nm or more. Moreover, it is preferable that the specific surface area by BET method is 20-500 m < ² > / g.

The external additive is not particularly limited and may be appropriately selected depending on the purpose. For example, silica fine particles, hydrophobic silica, fatty acid metal salts (for example, zinc stearate, aluminum stearate), metal oxides (for example, Titania, alumina, tin oxide, antimony oxide, etc.) and fluoropolymers.
Suitable additives include hydrophobized silica, titania, titanium oxide, and alumina fine particles. Examples of the silica fine particles include R972, R974, RX200, RY200, R202, R805, and R812 (all manufactured by Nippon Aerosil Co., Ltd.). Further, as titania fine particles, for example, P-25 (manufactured by Nippon Aerosil Co., Ltd.), STT-30, STT-65C-S (all manufactured by Titanium Industry Co., Ltd.), TAF-140 (manufactured by Titanium Industry Co., Ltd.), MT- 150W, MT-500B, MT-600B, MT-150A (all of which are manufactured by Teica), and the like.
Examples of the hydrophobized titanium oxide fine particles include T-805 (manufactured by Nippon Aerosil Co., Ltd.), STT-30A, STT-65S-S (all manufactured by Titanium Industry Co., Ltd.), TAF-500T, TAF-1500T ( All of them are manufactured by Fuji Titanium Industry Co., Ltd.), MT-100S, MT-100T (all manufactured by Teika), IT-S (made by Ishihara Sangyo Co., Ltd.), and the like.

Hydrophobized oxide fine particles, hydrophobized silica fine particles, hydrophobized titania fine particles, and hydrophobized alumina fine particles include, for example, methyltrimethoxysilane and methyltriethoxysilane as hydrophilic fine particles. It can be obtained by treating with a silane coupling agent such as octyltrimethoxysilane. In addition, silicone oil-treated oxide fine particles and inorganic fine particles obtained by treating silicone oil with heat if necessary to treat it with inorganic fine particles are also suitable.
Examples of the silicone oil include dimethyl silicone oil, methylphenyl silicone oil, chlorophenyl silicone oil, methyl hydrogen silicone oil, alkyl-modified silicone oil, fluorine-modified silicone oil, polyether-modified silicone oil, alcohol-modified silicone oil, amino acid. Modified silicone oil, epoxy-modified silicone oil, epoxy / polyether-modified silicone oil, phenol-modified silicone oil, carboxyl-modified silicone oil, mercapto-modified silicone oil, methacryl-modified silicone oil, α-methylstyrene-modified silicone oil, and the like.

Examples of the inorganic fine particles include silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, iron oxide, copper oxide, zinc oxide, tin oxide, silica sand, clay, mica, silica Examples include apatite, diatomaceous earth, chromium oxide, cerium oxide, pengala, antimony trioxide, magnesium oxide, zirconium oxide, parium sulfate, barium carbonate, calcium carbonate, silicon carbide, and silicon nitride. Among these, silica and titanium dioxide are particularly preferable.
The content of the external additive is not particularly limited and may be appropriately selected depending on the intended purpose. It is preferably 0.1 to 5 parts by weight, more preferably 0.3 to 3 parts by weight with respect to 100 parts by weight of the toner. preferable.
There is no restriction | limiting in particular in the average particle diameter of the primary particle of the said inorganic fine particle, Although it can select suitably according to the objective, 100 nm or less is preferable and 3-70 nm is more preferable. If it is smaller than 3 nm, the inorganic fine particles are buried in the toner, and its function is hardly exhibited effectively. On the other hand, if it is larger than 70 nm, the surface of the photoreceptor is not uniformly damaged, which is not preferable.

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

-Cleaning improver-
The cleaning property improving agent is not particularly limited as long as it is added to the toner in order to remove the developer after transfer remaining on the photoreceptor or the primary transfer medium, and can be appropriately selected according to the purpose. it can. Examples thereof include fatty acid metal salts such as zinc stearate, calcium stearate and stearic acid, polymer fine particles produced by soap-free emulsion polymerization such as polymethyl methacrylate fine particles and polystyrene fine particles.
The polymer fine particles preferably have a relatively narrow particle size distribution, and those having a volume average particle size of 0.01 to 1 μm are suitable.

-Magnetic material-
There is no restriction | limiting in particular as said magnetic material, According to the objective, it can select suitably, For example, iron powder, a magnetite, a ferrite etc. are mentioned. Among these, white is preferable in terms of color tone.

<Toner characteristics>
The toner used in the present invention preferably has a glass transition temperature (Tg1st) of 20 ° C. to 50 ° C. at the first temperature increase in differential scanning calorimetry (DSC).
In the conventional toner, when the Tg is about 50 ° C. or less, toner aggregation is likely to occur due to a temperature change in the storage environment and the toner transportation in the summer or the tropical region. As a result, solidification in the toner bottle and fixation of the toner in the developing machine occur. Further, replenishment failure due to toner clogging in the toner bottle and image abnormality due to toner fixation in the developing machine are likely to occur.
The toner used in the present invention has a Tg lower than that of a conventional toner. However, since the amorphous polyester resin A, which is a low Tg component in the toner, is non-linear, the heat-resistant storage stability can be maintained. In particular, when the non-linear amorphous polyester resin A has a urethane bond or a urea bond having a high cohesive force, the effect of maintaining heat resistant storage stability becomes more remarkable.
If the Tg1st is less than 20 ° C., the heat resistant storage stability is reduced, blocking in the developing machine and filming on the photoreceptor occur, and if it exceeds 50 ° C., the low temperature fixability of the toner is lowered.

  Further, the difference between the glass transition temperature Tg2nd of the first DSC temperature rise and the glass transition temperature Tg2nd of the DSC second temperature increase (Tg1st-Tg2nd) of the toner used in the present invention is not particularly limited, but the low temperature fixability is improved. It is preferable that it is 10 degreeC or more at the point which is excellent. That the difference is 10 ° C. or higher is that the crystalline polyester resin C that existed in an incompatible state before heating (before the first temperature increase), the non-linear amorphous polyester resin A, and It means that the amorphous polyester resin B is in a compatible state after heating (after the first temperature increase). In addition, the compatible state after a heating does not need to be a complete compatible state. The upper limit of the difference is not particularly limited and can be appropriately selected according to the purpose, but is preferably 50 ° C. or lower.

The melting point of the toner used in the present invention is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 60 ° C. to 80 ° C.
The volume average particle diameter of the toner used in the present invention is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 3 to 7 μm. The ratio of the volume average particle diameter to the number average particle diameter is preferably 1.2 or less. Moreover, it is preferable to contain 1-10 number% of components with a volume average particle diameter of 2 micrometers or less.

The toner used in the present invention has the following viscoelastic properties.
When continuous image formation is performed by the image forming apparatus, the surface temperature of the toner carrier, the photoreceptor, and their peripheral members reaches 50 ° C. Since the toner is subjected to a developing process in this temperature range, if the toner is extremely easily deformed at 50 ° C., the toner may aggregate in the developing portion or may adhere to the toner carrier before reaching the transfer portion. As a result, spot-like stains derived from toner aggregates and white spots due to abnormal supply of toner to the photoreceptor occur. Moreover, heat-resistant storage stability also falls. Therefore, the storage elastic modulus G ′ (50) at 50 ° C. is preferably 5.0 × 10 ⁷ Pa or more. In order to satisfy this requirement, for example, a resin having a large molecular weight may be used, or the ratio of the aromatic resin to the aliphatic may be increased.

Further, in the toner of the present invention, as the amorphous polyester resin A, a resin having a small change in viscoelasticity at 40 ° C. and 100 ° C. is used to suppress the amount of change in the storage elastic modulus of the toner in the fixing region. Thus, both the low-temperature fixability in which a cold offset hardly occurs and the high-temperature fixability in which a hot offset hardly occurs are satisfied. However, since such a resin is used, if the viscoelasticity of the toner at 50 ° C. is too high, the viscoelasticity of the toner is hardly lowered even when heated, and it is difficult to ensure low-temperature fixability. Therefore, there is an upper limit to the storage elastic modulus G ′ (50) at 50 ° C., and in the present invention, 1.0 × 10 ⁸ Pa or less is desirable.

<Calculation method and analysis method of various characteristics of toner and toner component>
Various physical properties of the non-linear amorphous polyester resin A, the amorphous polyester resin B, the crystalline polyester resin C, and the release agent may be measured on their own. Each component may be separated by GPC or the like, and for these, physical properties such as Tg, molecular weight, melting point, etc. may be measured or the mass ratio of the constituent components may be obtained by an analysis method described later.

Separation of each component by GPC can be performed, for example, by the following method.
In GPC measurement using THF as a mobile phase, the eluate is fractionated by a fraction collector or the like, and fractions corresponding to a desired molecular weight portion of the entire integral of the elution curve are collected. After concentrating and drying this collected eluate with an evaporator or the like, the solid content is dissolved in a heavy solvent such as deuterated chloroform or deuterated THF, and 1H-NMR measurement is performed. From the integration ratio of each element, the resin in the eluted component is dissolved. The constituent monomer ratio is calculated.
As another method, after concentrating the eluate, it is hydrolyzed with sodium hydroxide or the like, and the decomposition product is subjected to qualitative quantitative analysis by high performance liquid chromatography (HPLC) to calculate the constituent monomer ratio.

  The toner manufacturing method forms toner base particles while generating a non-linear amorphous polyester resin A by an extension reaction and / or a cross-linking reaction between the non-linear reactive precursor and the curing agent. In this case, the non-linear amorphous polyester resin A may be separated from the actual toner by GPC or the like, and the Tg thereof may be obtained separately. A non-linear amorphous polyester resin A may be synthesized by an extension reaction and / or a cross-linking reaction with a curing agent, and Tg and the like may be measured from the synthesized non-linear amorphous polyester resin A.

<< Toner component separation means >>
An example of a separation unit for each component when analyzing toner will be described.
First, 1 g of toner is put into 100 mL of THF and stirred at 25 ° C. for 30 minutes to obtain a solution in which soluble components are dissolved. This is filtered through a membrane filter having an opening of 0.2 μm to obtain a THF soluble component in the toner. Subsequently, this is melt | dissolved in THF, it is set as the sample for GPC measurement, and it inject | pours into GPC used for the molecular weight measurement of each above-mentioned resin.
On the other hand, a fraction collector is placed at the eluate outlet of GPC, and the eluate is collected every predetermined count, and the eluate is eluted every 5% in area ratio from the elution curve elution start (curve rise). Get. Next, for each elution, 30 mg of sample is dissolved in 1 mL of deuterated chloroform, and 0.05% by volume of tetramethylsilane (TMS) is added as a reference substance. The solution is filled in a glass tube for NMR measurement having a diameter of 5 mm, and a spectrum is obtained by performing integration 128 times at a temperature of 23 ° C. to 25 ° C. using a nuclear magnetic resonance apparatus (JNM-AL400 manufactured by JEOL Ltd.). The monomer composition and composition ratio of the non-linear amorphous polyester resin A, the amorphous polyester resin B, and the crystalline polyester resin C contained in the toner are determined from the peak integration ratio of the obtained spectrum. be able to.

For example, peak assignment is performed as follows, and the component ratio of the constituent monomer is determined from each integral ratio.
The assignment of the peak can be performed, for example, as follows.
-Near 8.25 ppm: derived from benzene ring of trimellitic acid (for one hydrogen)
-8.07-8.10 ppm vicinity: Derived from the benzene ring of terephthalic acid (for 4 hydrogen)
・ 7.1 to 7.25 ppm vicinity: derived from benzene ring of bisphenol A (for 4 hydrogens)
・ Approximately 6.8 ppm: Derived from the benzene ring of bisphenol A (for 4 hydrogens) and from the double bond of fumaric acid (for 2 hydrogens)
・ 5.2 to 5.4 ppm vicinity: bisphenol A propylene oxide adduct derived from methine (one hydrogen)
3.7-4.7 ppm vicinity: derived from methylene of bisphenol A propylene oxide adduct (for 2 hydrogens) and derived from methylene of bisphenol A ethylene oxide adduct (for 4 hydrogens)
-Around 1.6 ppm: derived from methyl group of bisphenol A (for 6 hydrogens)

From these results, for example, the extract recovered in the fraction in which the non-linear amorphous polyester resin A accounts for 90% by mass or more can be treated as the non-linear amorphous polyester resin A. . Similarly, the extract recovered in the fraction in which the amorphous polyester resin B occupies 90% by mass or more is regarded as the amorphous polyester resin B, and the crystalline polyester resin C is recovered in the fraction in which 90% by mass or more. The extracted products can be handled as the crystalline polyester resin C, respectively.

<< Measurement Method of Melting Point and Glass Transition Temperature (Tg) >>
The melting point and Tg in the present invention can be measured using, for example, a DSC system. Specifically, it can be measured by the following procedure.
First, about 5.0 mg of a target sample is placed in an aluminum sample container, and the sample container is placed on a holder unit and set in an electric furnace. Next, heating is performed from −80 ° C. to 150 ° C. at a temperature rising rate of 10 ° C./min in a nitrogen atmosphere (first temperature increase). Thereafter, the temperature is lowered from 150 ° C. to −80 ° C. at a temperature drop rate of 10 ° C./min, and further heated to 150 ° C. at a temperature rise rate of 10 ° C./min (second temperature rise). At each of the first temperature increase and the second temperature increase, a DSC curve is measured using a differential scanning calorimeter (Q-200: manufactured by TA Instruments).
From the obtained DSC curve, the DSC curve at the first temperature rise can be selected using the analysis program in the Q-200 system, and the Tg at the first temperature rise of the target sample can be obtained. Similarly, the DSC curve at the second temperature increase can be selected, and the Tg of the target sample at the second temperature increase can be obtained.
Further, from the obtained DSC curve, using the analysis program in the Q-200 system, the DSC curve at the first temperature rise is selected, and the endothermic peak top temperature at the first temperature rise of the target sample is obtained as the melting point. Can do. Similarly, the DSC curve at the second temperature increase can be selected, and the endothermic peak top temperature at the second temperature increase of the target sample can be obtained as the melting point.

In the present invention, when toner is used as the target sample, the glass transition temperature at the first temperature rise is Tg1st, and the glass transition temperature at the second temperature rise is Tg2nd.
In the present invention, the non-linear amorphous polyester resin A, the amorphous polyester resin B, the crystalline polyester resin C, and the Tg and melting point of other components such as the release agent As for, unless otherwise specified, the endothermic peak top temperature and Tg at the second temperature rise are defined as the melting point and Tg of each target sample.

<< Measurement Method of Particle Size Distribution >>
The volume average particle diameter (D4) and the number average particle diameter (Dn) of the toner, and the ratio (D4 / Dn) are determined using, for example, Coulter Counter TA-II, Coulter Multisizer II (both manufactured by Coulter). Can be measured. In the present invention, Coulter Multisizer II is used. The measurement method is as follows.
First, 0.1 to 5 mL of a surfactant [preferably polyoxyethylene alkyl ether (nonionic surfactant)] as a dispersant is added to 100 to 150 mL of the electrolytic aqueous solution. Here, the electrolytic aqueous solution is a 1 mass% NaCl aqueous solution prepared using primary sodium chloride, and for example, ISOTON-II (manufactured by Coulter) can be used. Next, 2 to 20 mg of a measurement sample is added. The electrolytic aqueous solution in which the sample is suspended is dispersed for about 1 to 3 minutes with an ultrasonic disperser, and the volume and number of toner particles or toner are measured with the measuring device using a 100 μm aperture as the aperture, and the volume distribution is measured. And calculate the number distribution. From the obtained distribution, the volume average particle diameter (D4) and the number average particle diameter (Dn) of the toner can be obtained.
As a channel, it is 2.00 micrometers or more and less than 2.52 micrometers; 2.52 micrometers or more and less than 3.17 micrometers; 3.17 micrometers or more and less than 4.00 micrometers; 4.00 micrometers or more and less than 5.04 micrometers; 5.04 micrometers or more and less than 6.35 micrometers; .35 μm or more and less than 8.00 μm; 8.00 μm or more and less than 10.08 μm; 10.08 μm or more and less than 12.70 μm; 12.70 μm or more and less than 16.00 μm; 16.00 μm or more and less than 20.20 μm; Less than 40 μm; 25.40 μm or more and less than 32.00 μm; 3 channels of 32.00 μm or more and less than 40.30 μm are used, and particles having a particle size of 2.00 μm or more and less than 40.30 μm are targeted.

<< Method for measuring molecular weight >>
The molecular weight of each component of the toner can be measured, for example, by the following method.
・ Permeation chromatography (GPC) measuring device
: GPC-8220GPC (manufactured by Tosoh Corporation)
・ Column: TSKgel SuperHZM-H 15cm triple (manufactured by Tosoh Corporation)
・ Temperature: 40 ℃
・ Solvent: THF
・ Flow rate: 0.35 mL / min
Sample: 0.4 mL of 0.15% by mass sample was injected. Sample pretreatment: Toner was dissolved in THF (stabilized Wako Pure Chemical Industries, Ltd.) at a concentration of 0.15% by mass. Filter through a 2 μm filter and use the filtrate as a sample. 100 μL of the THF sample solution is injected and measured.

When measuring the molecular weight of a sample, the molecular weight distribution of the sample is calculated from the relationship between the logarithmic value of a calibration curve prepared from several types of monodisperse polystyrene standard samples and the number of counts. As a standard polystyrene sample for preparing a calibration curve, Showd STANDARD Std. No S-7300, S-210, S-390, S-875, S-1980, S-10.9, S-629, S-3.0, S-0.580 are used. An RI (refractive index) detector is used as the detector.

<< Measurement Method of Storage Elastic Modulus (G ') >>
The storage elastic modulus (G ′) under various conditions can be measured using, for example, a dynamic viscoelasticity measuring device (ARES, manufactured by TA Instruments). The frequency at the time of measurement is 1 Hz.
Specifically, the measurement sample was molded into a pellet having a diameter of 8 mm and a thickness of 1 to 2 mm, fixed to a parallel plate having a diameter of 8 mm, and then closely adhered to the parallel plate at a temperature within 10 to 15 ° C. from the Tg1st of the toner. Hold temperature for 15 minutes. Then, it cools to 30 degreeC, making the load concerning the sample of a plate constant, and hold | maintains for 48 hours in the state of 30 degreeC. At the start of measurement, the storage elastic modulus is measured by increasing the temperature to 200 ° C. at a rate of temperature increase of 2.0 ° C./min with a strain amount of 0.1% (strain amount control mode). The same applies to the constituent components of the toner.

<Toner production method>
A method for producing the toner is not particularly limited and may be appropriately selected depending on the intended purpose. The non-linear amorphous polyester resin A, the amorphous polyester resin B, and the crystalline polyester resin C may be selected. In addition, if necessary, it is preferably granulated by dispersing an oil phase containing the release agent, the colorant and the like in an aqueous medium.
Further, the toner includes the non-linear reactive precursor, the amorphous polyester resin B, and the crystalline polyester resin C. If necessary, the toner further includes the curing agent, the release agent, and the coloring agent. It is preferable to granulate by dispersing an oil phase containing an agent in an aqueous medium.
An example of such a method for producing the toner is a known dissolution suspension method.
As an example of a toner manufacturing method, toner base particles are formed while generating a non-linear amorphous polyester resin A by an extension reaction and / or a cross-linking reaction between the non-linear reactive precursor and the curing agent. The method to do is shown below. In this method, the aqueous medium is prepared, the oil phase containing the toner material is prepared, the toner material is emulsified or dispersed, and the organic solvent is removed.

-Preparation of aqueous medium (aqueous phase)-
The aqueous medium can be prepared, for example, by dispersing resin particles in an aqueous medium. There is no restriction | limiting in particular in the addition amount in the aqueous medium of the said resin particle, Although it can select suitably according to the objective, 0.5-10 mass parts is preferable with respect to 100 mass parts of said aqueous media.
There is no restriction | limiting in particular as said aqueous medium, According to the objective, it can select suitably, For example, water, the solvent miscible with water, these mixtures etc. are mentioned. These may be used individually by 1 type and may use 2 or more types together. Among these, water is preferable.
The solvent miscible with water is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include alcohol, dimethylformamide, tetrahydrofuran, cellosolves, and lower ketones. There is no restriction | limiting in particular as said alcohol, According to the objective, it can select suitably, For example, methanol, isopropanol, ethylene glycol etc. are mentioned. There is no restriction | limiting in particular as said lower ketone, According to the objective, it can select suitably, For example, acetone, methyl ethyl ketone, etc. are mentioned.

-Preparation of oil phase-
The preparation of the oil phase containing the toner material includes at least the non-linear reactive precursor, the amorphous polyester resin B, and the crystalline polyester resin C, and if necessary, the curing A toner material containing an agent, the release agent, the colorant, and the like can be dissolved or dispersed in an organic solvent.
There is no restriction | limiting in particular as said organic solvent, Although it can select suitably according to the objective, The organic solvent whose boiling point is less than 150 degreeC is preferable at the point which is easy to remove.
The organic solvent having a boiling point of less than 150 ° C. is not particularly limited and may be appropriately selected depending on the intended purpose. For example, toluene, xylene, benzene, carbon tetrachloride, methylene chloride, 1,2-dichloroethane, 1,1 , 2-trichloroethane, trichloroethylene, chloroform, monochlorobenzene, dichloroethylidene, methyl acetate, ethyl acetate, methyl ethyl ketone, methyl isobutyl ketone and the like. These may be used individually by 1 type and may use 2 or more types together.
Among these, ethyl acetate, toluene, xylene, benzene, methylene chloride, 1,2-dichloroethane, chloroform, carbon tetrachloride and the like are preferable, and ethyl acetate is more preferable.

-Emulsification or dispersion-
The emulsification or dispersion of the toner material can be performed by dispersing the oil phase containing the toner material in the aqueous medium. Then, when emulsifying or dispersing the toner material, the nonlinear amorphous polyester resin A is obtained by subjecting the curing agent and the nonlinear reactive precursor to an extension reaction and / or a crosslinking reaction. Generate.

The non-linear amorphous polyester resin A can be produced, for example, by the following methods (1) to (3).
(1) An oil phase containing the non-linear reactive precursor and the curing agent is emulsified or dispersed in an aqueous medium, and the curing agent and the non-linear reactive precursor in the aqueous medium Is produced by subjecting to elongation reaction and / or crosslinking reaction.
(2) The oil phase containing the non-linear reactive precursor is emulsified or dispersed in an aqueous medium to which the curing agent is added in advance, and the curing agent and the non-linear reactive precursor are added in the aqueous medium. A method of producing a body by an extension reaction and / or a crosslinking reaction.
(3) After emulsifying or dispersing the oil phase containing the non-linear reactive precursor in an aqueous medium, the curing agent is added to the aqueous medium, and the curing agent is added from the particle interface in the aqueous medium. And a non-linear reactive precursor by an extension reaction and / or a crosslinking reaction.
When the curing agent and the nonlinear reactive precursor are subjected to an extension reaction and / or a crosslinking reaction from the particle interface, the nonlinear amorphous polyester is preferentially formed on the surface of the toner to be produced. Since the resin A is formed, a concentration gradient of the non-linear amorphous polyester resin A can be provided in the toner.

There are no particular restrictions on the reaction conditions (reaction time, reaction temperature) for producing the non-linear amorphous polyester resin A. Depending on the situation, it can be appropriately selected.
The reaction time is preferably 10 minutes to 40 hours, more preferably 2 to 24 hours.
The reaction temperature is preferably 0 ° C to 150 ° C, more preferably 40 ° C to 98 ° C.

The method for stably forming the dispersion containing the non-linear reactive precursor in the aqueous medium is not particularly limited and can be appropriately selected depending on the purpose. Examples thereof include a method in which an oil phase prepared by dissolving or dispersing a toner material in a solvent is added to an aqueous medium phase and dispersed by shearing force.
The disperser for the dispersion is not particularly limited and can be appropriately selected depending on the purpose. For example, a low-speed shear disperser, a high-speed shear disperser, a friction disperser, a high-pressure jet disperser, Examples include an ultrasonic disperser. Among these, a high-speed shearing disperser is preferable in that the particle size of the dispersion (oil droplets) can be controlled to 2 to 20 μm.
When the high-speed shearing disperser is used, conditions such as the number of rotations, the dispersion time, and the dispersion temperature can be appropriately selected according to the purpose. The rotational speed is preferably 1000 to 30000 rpm, more preferably 5000 to 20000 rpm. In the case of a batch method, the dispersion time is preferably 0.1 to 5 minutes. The dispersion temperature is preferably 0 ° C to 150 ° C, more preferably 40 ° C to 98 ° C under pressure. In general, dispersion is easier when the dispersion temperature is higher.

  The amount of the aqueous medium used when emulsifying or dispersing the toner material is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 50 to 2000 parts by mass with respect to 100 parts by mass of the toner material. -1000 mass parts is more preferable. When the amount of the aqueous medium used is less than 50 parts by mass, the dispersion state of the toner material is deteriorated, and toner base particles having a predetermined particle diameter may not be obtained. When the amount exceeds 2000 parts by mass, the production cost is high. May be.

When emulsifying or dispersing the oil phase containing the toner material, it is preferable to use a dispersant from the viewpoint of stabilizing the dispersion such as oil droplets to obtain a desired shape and sharpening the particle size distribution. .
There is no restriction | limiting in particular in the said dispersing agent, According to the objective, it can select suitably, For example, surfactant, a sparingly water-soluble inorganic compound dispersing agent, a polymeric protective colloid, etc. are mentioned. These may be used individually by 1 type and may use 2 or more types together. Among these, surfactants are preferable.
There is no restriction | limiting in particular as said surfactant, According to the objective, it can select suitably, For example, using anionic surfactant, a cationic surfactant, a nonionic surfactant, an amphoteric surfactant etc. Can do.
Examples of the anionic surfactant include alkylbenzene sulfonates, α-olefin sulfonates, and phosphate esters. Among these, those having a fluoroalkyl group are preferable.

A catalyst can be used for the elongation reaction and / or the crosslinking reaction in producing the non-linear amorphous polyester resin A.
There is no restriction | limiting in particular as said catalyst, According to the objective, it can select suitably, For example, a dibutyltin laurate, a dioctyltin laurate, etc. are mentioned.

-Removal of organic solvent-
The method for removing the organic solvent from the dispersion such as the emulsified slurry is not particularly limited and may be appropriately selected depending on the intended purpose. For example, the temperature of the entire reaction system is gradually raised, and the organic in the oil droplets Examples include a method of evaporating the solvent, and a method of removing the organic solvent in the oil droplets by spraying the dispersion liquid in a dry atmosphere.
When the organic solvent is removed, toner base particles are formed. The toner base particles can be washed, dried, etc., and further classified. The classification may be performed by removing fine particle portions in a liquid by a cyclone, a decanter, centrifugation, or the like, or may be performed after drying.

-Washing-
The method for cleaning the toner is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a method of washing with water and washing with acid after alkali cleaning is preferable.
By performing the alkali cleaning, it is possible to remove emulsifiers, dispersants, ionic impurities, and the like present on the toner particle surfaces.
In particular, in the toner including at least the adhesive substrate, the resin fine particles are used as a dispersion (emulsification) stabilizer in order to sharpen the particle size distribution. If the resin fine particles are excessively present on the toner surface, the fixing is performed. It is preferable to remove it because it may impair the chargeability or adversely affect the chargeability.
In this respect, since the resin fine particles contain an acidic component, they can be easily removed by swelling or dissolving them by alkali washing.

The obtained toner base particles may be mixed with particles such as the external additive and the charge control agent. At this time, by applying a mechanical impact force, it is possible to prevent the particles such as the external additive from detaching from the surface of the toner base particles.
The method for applying the mechanical impact force is not particularly limited and may be appropriately selected depending on the purpose.For example, a method for applying an impact force to a mixture using a blade rotating at high speed, Examples include a method in which a mixture is charged and accelerated to cause particles or particles to collide with an appropriate collision plate.
The apparatus used in the above method is not particularly limited, and can be appropriately selected according to the purpose. For example, an ang mill (manufactured by Hosokawa Micron Co., Ltd.) and an I-type mill (manufactured by Nippon Pneumatic Co., Ltd.) are modified to lower the pulverization air pressure. Examples thereof include a device, a hybridization system (manufactured by Nara Machinery Co., Ltd.), a kryptron system (manufactured by Kawasaki Heavy Industries, Ltd.), and an automatic mortar.

(Developer)
The developer of the present invention contains at least the toner and, if necessary, other components such as a carrier as appropriate.
For this reason, it is excellent in transferability, chargeability, etc., and a high quality image can be formed stably.
The developer may be a one-component developer or a two-component developer. However, when used in a high-speed printer or the like corresponding to the recent improvement in information processing speed, the life is improved. Agents are preferred.
When the developer is used as a one-component developer, even if the balance of the toner is performed, the fluctuation of the toner particle diameter is small, the filming of the toner on the developing roller, the blade for thinning the toner, etc. The toner is less fused to the member, and good and stable developability and images can be obtained even with long-term stirring in the developing device.
When the developer is used as a two-component developer, there is little fluctuation in the particle diameter of the toner even if the toner balance for a long period of time is performed, and good and stable developability and long-term agitation in the developing device. An image is obtained.

<Career>
There is no restriction | limiting in particular in the said carrier, Although it can select suitably according to the objective, What has a core material and the resin layer which coat | covers a core material is preferable.

−Core material−
There is no restriction | limiting in particular as a material of the said core material, According to the objective, it can select suitably, For example, 50-90 emu / g manganese-strontium type material, 50-90 emu / g manganese-magnesium type material etc. Can be mentioned. In order to ensure the image density, it is preferable to use a highly magnetized material such as iron powder of 100 emu / g or more and magnetite of 75 to 120 emu / g. In addition, it is preferable to use a low-magnetization material such as 30-80 emu / g of copper-zinc system because it can reduce the impact of the developer in a spiked state on the photoconductor and is advantageous for high image quality. .
These may be used individually by 1 type and may use 2 or more types together.
There is no restriction | limiting in particular in the volume average particle diameter of the said core material, Although it can select suitably according to the objective, 10-150 micrometers is preferable and 40-100 micrometers is more preferable. If the volume average particle diameter is less than 10 μm, fine particles are increased in the carrier, and the magnetization per particle may be reduced to cause carrier scattering. On the other hand, if the thickness exceeds 150 μm, the specific surface area may be reduced and toner scattering may occur, and in the case of a full color having many solid portions, the reproduction of the solid portions may be particularly poor.

  When toner is used as a two-component developer, it is mixed with the carrier. The content of the carrier in the two-component developer is not particularly limited and can be appropriately selected according to the purpose, but is preferably 90 to 98 parts by mass with respect to 100 parts by mass of the two-component developer. 93-97 mass parts is more preferable.

The electrophotographic image forming apparatus of the present invention has a toner image transfer means, and a mechanism for controlling the friction coefficient of the photoconductor and a linear motor speed by adjusting the photoconductor motor. It is necessary to have a mechanism capable of fine adjustment with respect to the linear velocity of the sheet or intermediate transfer medium.
However, since the image transfer apparatus having a larger number of transfers is more likely to be a problem, the image forming apparatus having the intermediate transfer process is more effective.
Hereinafter, an example of the image forming apparatus of the present invention will be described with reference to FIGS.

[Whole process]
As shown in FIG. 1, a toner replenishing device 31 above the image forming apparatus main body 100 includes a toner cartridge (toner container) 32Y as a powder container corresponding to each color (yellow, magenta, cyan, black). 32M, 32C, and 32K are detachably (replaceable). A portion other than the toner cartridge in the toner replenishing device 31 is a toner conveying device that conveys toner discharged from the toner cartridge to a developing device described later. An intermediate transfer unit (intermediate transfer member) 15 is disposed below the toner supply device 31. Image forming portions 6Y, 6M, 6C, and 6K corresponding to the respective colors (yellow, magenta, cyan, and black) are arranged in parallel so as to face the intermediate transfer belt 8 of the intermediate transfer unit 15.

FIG. 2 is an enlarged view of the image forming unit 6Y. The image forming unit 6Y corresponding to yellow includes a photosensitive drum 1Y as a latent image carrier, a charging unit 4Y disposed around the photosensitive drum 1Y, a developing device 5Y (developing unit), a cleaning unit 2Y, and a charge eliminating unit (not shown). ) Etc. Then, an image forming process (charging process, exposure process, developing process, transfer process, cleaning process) is performed on the photosensitive drum 1Y, and a yellow image is formed on the photosensitive drum 1Y.
The other three image forming units 6M, 6C, and 6K have substantially the same configuration as the image forming unit 6Y except that the color of the toner used is different.

In FIG. 2, the photosensitive drum 1Y is rotationally driven in the clockwise direction in the drawing by a drive motor (not shown). Then, the surface of the photosensitive drum 1Y is uniformly charged at the charging position by the charging unit 4Y (“charging process”).
Thereafter, the surface of the photosensitive drum 1Y reaches the irradiation position of the laser light L emitted from the exposure unit 7 (see FIG. 1), and an electrostatic latent image corresponding to yellow is formed by exposure scanning at this position. ("Exposure process").
Thereafter, the surface of the photosensitive drum 1Y comes into contact with the developer 54Y magnetically pumped onto the developing sleeve 51Y at a position facing the developing device 5Y, and the toner adheres to a portion corresponding to the electrostatic latent image. ("Development process"). The developer after the development is separated from the developing sleeve at the position of the agent separation pole 53Y, returned to the stirring screw 55Y, stirred, mixed with the toner again while being conveyed to the screw, and used again for development.
The formed toner image is electrostatically transferred onto the intermediate transfer belt 8 by the current flowing from the primary transfer roller 9Y (“primary transfer process”), and the surface of the photoreceptor after transfer reaches a position facing the cleaning unit 2Y. . At this position, the untransferred toner remaining on the photosensitive drum 1Y is mechanically scraped and collected by the cleaning blade 2a (“cleaning step”).
Finally, the surface of the photosensitive drum 1Y reaches a position facing a neutralization unit (not shown), and the residual potential on the photosensitive drum 1 is removed at this position.
Thus, a series of image forming processes performed on the photosensitive drum 1 is completed.

The image forming process described above is performed in the image forming units 6M, 6C, and 6K in the same manner as the image forming unit 6Y. In other words, the laser beam L based on the image information is irradiated from the exposure unit (exposure device) 7 disposed below the image forming unit toward the photosensitive drums of the image forming units 6M, 6C, and 6K. . Specifically, the exposure unit 7 emits a laser beam L from a light source, and scans the laser beam L with a polygon mirror, which is a rotationally driven rotary polygon mirror, on a photosensitive drum via a plurality of optical elements. Irradiate.
Thereafter, the toner images of the respective colors formed on the respective photosensitive drums through the development process are transferred onto the intermediate transfer belt 8 in an overlapping manner (“primary transfer process”). In this way, a color image is formed on the intermediate transfer belt 8.

Here, as shown in FIG. 1, the intermediate transfer unit 15 includes an intermediate transfer belt 8, four primary transfer bias rollers 9Y, 9M, 9C, and 9K, a secondary transfer backup roller 12, a cleaning backup roller 13, and a tension roller. 14 and the intermediate transfer cleaning unit 10. The intermediate transfer belt 8 is stretched and supported by the three rollers 12 to 14 and is endlessly moved in the direction of the arrow in FIG.
The four primary transfer bias rollers 9Y, 9M, 9C, and 9K respectively sandwich the intermediate transfer belt 8 with the photosensitive drums 1Y, 1M, 1C, and 1K to form a primary transfer nip. The primary transfer bias rollers 9Y, 9M, 9C, and 9K are applied with a transfer bias having a polarity opposite to the polarity of the toner. The intermediate transfer belt 8 travels in the direction of the arrow, and sequentially passes through the primary transfer nips of the primary transfer bias rollers 9Y, 9M, 9C, and 9K. In this way, the toner images of the respective colors on the photosensitive drums 1Y, 1M, 1C, and 1K are primarily transferred while being superimposed on the intermediate transfer belt 8.

Thereafter, the intermediate transfer belt 8 onto which the toner images of the respective colors are transferred in a superimposed manner reaches a position facing the secondary transfer roller 19. At this position, the secondary transfer backup roller 12 sandwiches the intermediate transfer belt 8 with the secondary transfer roller 19 to form a secondary transfer nip. The four-color toner images formed on the intermediate transfer belt 8 are transferred onto a transfer material (recording material) P such as transfer paper conveyed to the position of the secondary transfer nip (“secondary” Transfer process "). At this time, untransferred toner that has not been transferred to the transfer material P remains on the intermediate transfer belt 8.
Thereafter, the intermediate transfer belt 8 reaches the position of the intermediate transfer cleaning unit 10. At this position, the untransferred toner on the intermediate transfer belt 8 is collected. Thus, a series of transfer processes performed on the intermediate transfer belt 8 is completed.

The material P to be transferred conveyed to the position of the secondary transfer nip is conveyed from the paper supply unit 26 disposed below the apparatus main body 100 via the paper supply roller 27, the registration roller pair 28, and the like. It is. Specifically, a plurality of transfer materials P such as transfer paper are stored in the paper supply unit 26 in a stacked manner. When the paper feed roller 27 is rotated in the counterclockwise direction in FIG. 1, the uppermost transfer material P is fed between the rollers of the registration roller pair 28.
The transfer material P conveyed to the registration roller pair 28 is temporarily stopped at the position of the roller nip of the registration roller pair 28 that has stopped rotating. Then, the registry roller pair 28 is rotationally driven in synchronization with the color image on the intermediate transfer belt 8, and the transfer material P is conveyed toward the secondary transfer nip. In this way, a desired color image is transferred onto the transfer material P.

Thereafter, the transfer material P on which the color image has been transferred at the position of the secondary transfer nip is conveyed to the position of the fixing unit 20. At this position, the color image transferred to the surface is fixed on the transfer material P by heat and pressure generated by the fixing roller and the pressure roller.
Thereafter, the transfer material P is discharged out of the apparatus through the rollers of the discharge roller pair 29. The transfer material P discharged from the apparatus by the discharge roller pair 29 is sequentially stacked on the stack unit 30 as an output image.
Thus, a series of image forming processes is completed.

<Adjustment of photosensitive member surface friction coefficient>
When nothing is done, the surface of the photoconductor is rubbed in each process step, and therefore tends to increase with aging. Similarly, the intermediate transfer belt also deteriorates over time. However, the intermediate transfer belt is often lower in hardness than the photoconductor (except when the photoconductor is a belt photoconductor) and has some elasticity. The intermediate transfer belt is often superior to the photoreceptor in terms of deterioration due to friction. Therefore, in order to obtain a good image while balancing the friction coefficient μ, it is preferable to reduce the surface friction coefficient of the photoreceptor.
The following two methods are conceivable as methods for adjusting the friction coefficient of the photoreceptor.

<Applying lubricant>
The first method is a method of applying a lubricant to the photoconductor to lower the coefficient of friction of the photoconductor.
There are two possible routes for applying the lubricant. The first is means for providing a mechanism for applying a lubricant to one of the processes around the photoreceptor. In this case, the friction coefficient relationship of the present invention can be easily made, and the effect can be exhibited continuously over time. A cross-sectional view of an example image forming unit is shown in FIG.
In FIG. 3, a lubricant application mechanism is provided on the downstream side of the cleaning blade 2a.
The lubricant application mechanism applies a rod-like lubricant 202Y onto the photoreceptor via the brush 201Y, and rubs it onto the photoreceptor surface with the application blade 203Y, thereby forming a low friction coefficient film on the photoreceptor surface. When the surface portion of the film is roughened and the coefficient of friction increases, the roughened surface is scraped and smoothed by the cleaning blade 2a, and a lubricant is newly supplied after the smoothing.
In this case, μ is controlled by the linear velocity of the brush or the pressing force of the lubricant to the brush. Further, since the pressing force may decrease when the lubricant decreases with time, the linear speed of the brush may be changed according to the time (number of printed sheets or number of rotations of the photoreceptor).

The second means for supplying the lubricant to the photoconductor is a method in which toner and lubricant are mixed, supplied to the developing unit through toner replenishment, and supplied to the photoconductor together with the toner during development from the developing unit. The lubricant supplied to the photosensitive member from the developing unit together with the toner is hardly charged, so it is rarely electrostatically transferred (of course, the contacted portion is mechanically rubbed and also supplied to the intermediate transfer belt). Therefore, the lubricant is not supplied at all to the intermediate transfer portion), but most of the lubricant passes through the primary transfer portion and is supplied to the cleaning portion. Also in this case, the relationship of the friction coefficient of the present invention can be easily made, and the effect can be exerted continuously over time. This method is simple in structure because it is not necessary to provide a lubricant application mechanism around the photosensitive member, but because the lubricant is present together with the toner in the developing portion, friction charging between the toner and the carrier is hindered. There is a case. Therefore, it is used when the charging ability of the toner is high.
Further, with the first means described above, when the amount of toner entering the cleaning portion is large (for example, a solid image or a vertical band image), all the toner cannot be scraped off by the cleaning blade 2a, and the photosensitive Lubricant supply to the body may be hindered. However, if this method is used in combination with a method of mixing a lubricant with toner, the lubricant supplied with the toner is supplied to the coating blade 203 even if the lubricant is not supplied by the brush 201. Useful. Therefore, a system using both of them may be used.

As the lubricant supplied to the photoreceptor, boron nitride or a fatty acid metal salt is often used. Boron nitride has a layered structure similar to graphite, is not easily oxidized, and is not easily affected by electric discharge, so it is compatible with the electrophotographic process. In addition, as the fatty acid metal salt, for example, fatty acid metal salt having a lamellar crystal structure such as zinc stearate, calcium stearate, barium stearate, aluminum stearate, magnesium stearate, lauroyl lysine, monocetyl phosphate sodium zinc salt, Examples include substances such as lauroyl taurine calcium.
In addition to these, liquid materials such as silicone oil, fluorine-based oil, and natural wax, and gaseous materials can be added as an external addition method.

<Low Friction Coefficient Layer for Photoreceptor Creation>
A second method for adjusting the friction coefficient of the photoreceptor is to provide a low friction coefficient layer on the surface layer of the charge transport layer of the photoreceptor. In this method, the coefficient of friction of the photoreceptor can be kept low even without a special lubricant application mechanism. For example, a fluororesin or wax is added to the low friction coefficient layer as a lubricant.
However, in the case of this method, when the surface layer is scraped, the fluororesin or wax exudes and the surface friction coefficient decreases. Further, if this layer is all removed, the friction coefficient cannot be lowered. Therefore, it is preferably used in combination with the method of applying the lubricant. This method is often used on low end user machines with a short life.

<Method for measuring surface friction coefficient of photoconductor>
The surface friction coefficient of the photoreceptor is measured by the Euler belt method.
An example of the operation will be described with reference to FIG. 4. A belt shape obtained by cutting a Ricoh plain paper type 6200 A4T eye P on the outer peripheral quarter portion of the cylindrical photosensitive member surface S so that the paper scribing direction is the longitudinal direction. Contact the measurement member, apply a load W (100 g) to one (lower end), connect the force gauge G to the other, move the force gauge at a constant speed, and the force gauge when the belt starts moving Is calculated by the following formula.
μs = 2 / π × ln (F / W)
In the formula, μs: surface static friction coefficient, F: force gauge reading (g), W: load (100 g)
Further, in the case of an intermediate transfer belt, the intermediate transfer belt is fixed to a cylindrical shape having a diameter of 40, and the intermediate transfer belt is wound up to about a half of its circumference, and the measurement is performed in the same manner using the quarter of the outer circumference of the cylinder. Just do it. An outline of a part of this is shown in FIG. In the figure, only a part of the long endless intermediate transfer belt is shown.

EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated further more concretely, this invention is not limited at all by these Examples. Unless otherwise specified, “parts” and “%” refer to “parts by mass” and “mass%”.
Each measured value was measured by the method described above. Moreover, Tg, melting | fusing point, molecular weight, etc. of non-linear amorphous polyester resin A, amorphous polyester resin B, crystalline polyester resin C, etc. are the measured values of each resin obtained by the manufacture example.

(Production Example 1)
<Synthesis of ketimine>
170 parts of isophorone diamine and 75 parts of methyl ethyl ketone were charged into a reaction vessel equipped with a stirrer and a thermometer, and reacted at 50 ° C. for 5 hours to obtain [ketimine compound 1]. The amine value of [ketimine compound 1] was 418.

(Production Example A1)
<Synthesis of Non-Linear Amorphous Polyester Resin A1>
-Synthesis of prepolymer A1-
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 3-methyl-1,5-pentanediol, isophthalic acid, and adipic acid were mixed at a molar ratio of hydroxyl group to carboxyl group “OH / COOH” of 1. 1 was added. The diol component was 100 mol% 3-methyl-1,5-pentanediol, and the dicarboxylic acid component was 45 mol% isophthalic acid and 55 mol% adipic acid. Further, trimethylolpropane was added together with titanium tetraisopropoxide (1000 ppm based on all resin components) so as to be 1.5 mol% of the total monomers. Thereafter, the temperature was raised to 200 ° C. in about 4 hours, then heated to 230 ° C. over 2 hours, and reacted until there was no effluent water. Then, it was made to react under reduced pressure of 10-15 mmHg for 5 hours, and intermediate polyester A1 was obtained.
Next, the intermediate polyester A1 and isophorone diisocyanate (IPDI) are mixed in a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe at a molar ratio (isocyanate group of IPDI / hydroxyl group of intermediate polyester) of 2.0. Then, after diluting with ethyl acetate to a 50% ethyl acetate solution, the mixture was reacted at 100 ° C. for 5 hours to obtain Prepolymer A1.

-Synthesis of non-linear amorphous polyester resin A1-
The obtained prepolymer A1 is stirred in a reaction vessel equipped with a heating device, a stirrer and a nitrogen introduction tube, and the amount of amine of [ketimine compound 1] is equimolar with respect to the amount of isocyanate in the prepolymer A1. An amount of [ketimine compound 1] was dropped into the reaction vessel and stirred at 45 ° C. for 10 hours, and then the prepolymer extension product was taken out. The obtained prepolymer extension product was dried under reduced pressure at 50 ° C. until the amount of residual ethyl acetate was 100 ppm or less to obtain a nonlinear amorphous polyester resin A1.

(Production Example A2)
<Synthesis of Non-Linear Amorphous Polyester Resin A2>
-Synthesis of prepolymer A2-
In a reaction vessel equipped with a condenser, a stirrer, and a nitrogen introduction pipe, 3-methyl-1,5-pentanediol and adipic acid were mixed with a molar ratio of hydroxyl group to carboxyl group “OH / COOH” of 1.1. It was thrown to become. The diol component was 100% by mole of 3-methyl-1,5-pentanediol, and the dicarboxylic acid component was 100% by mole of adipic acid. Further, trimethylolpropane was added together with titanium tetraisopropoxide (1000 ppm based on all resin components) so as to be 1.5 mol% of the total monomers. Thereafter, the temperature was raised to 200 ° C. in about 4 hours, and then the temperature was raised to 230 ° C. over 2 hours until the effluent water disappeared. Then, it was made to react under reduced pressure of 10-15 mmHg for 5 hours, and intermediate polyester A2 was obtained.
Next, the intermediate polyester A2 and isophorone diisocyanate (IPDI) were mixed at a molar ratio (isocyanate group of IPDI / hydroxyl group of intermediate polyester) 2.0 in a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube. Then, after diluting with ethyl acetate to a 50% ethyl acetate solution, the mixture was reacted at 100 ° C. for 5 hours to obtain Prepolymer A2.

-Synthesis of non-linear amorphous polyester resin A2-
The obtained prepolymer A2 is stirred in a reaction vessel equipped with a heating device, a stirrer and a nitrogen introduction tube, and the amount of amine of [ketimine compound 1] is equimolar with respect to the amount of isocyanate in the prepolymer A2. An amount of [ketimine compound 1] was dropped into the reaction vessel and stirred at 45 ° C. for 10 hours, and then the prepolymer extension product was taken out. The obtained prepolymer extension product was dried under reduced pressure at 50 ° C. until the amount of residual ethyl acetate was 100 ppm or less to obtain a non-linear amorphous polyester resin A2.

(Production Example A3)
<Synthesis of Nonlinear Amorphous Polyester Resin A3>
-Synthesis of prepolymer A3-
In a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe, bisphenol A ethylene oxide 2-mole adduct, bisphenol A propylene oxide 2-mole adduct, terephthalic acid, trimellitic anhydride, The molar ratio “OH / COOH” is 1.3, the diol component is 90 mol% of bisphenol A ethylene oxide 2 mol adduct, 10 mol% of bisphenol A propylene oxide 2 mol adduct, and the carboxylic acid component is terephthalic acid. Titanium tetraisopropoxide (1000 ppm with respect to all resin components) was added so as to be 90 mol% and trimellitic anhydride 10 mol%. Thereafter, the temperature was raised to 200 ° C. in about 4 hours, and then the temperature was raised to 230 ° C. over 2 hours until the effluent water disappeared. Then, it was made to react under reduced pressure of 10-15 mmHg for 5 hours, and intermediate body polyester A3 was obtained.
Next, the intermediate polyester A3 and isophorone diisocyanate (IPDI) were mixed at a molar ratio (IPDI isocyanate group / intermediate polyester hydroxyl group) of 2.0 in a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe. The mixture was diluted with 50% ethyl acetate solution with ethyl acetate, and reacted at 100 ° C. for 5 hours to obtain Prepolymer A3.

-Synthesis of non-linear amorphous polyester resin A3-
The obtained prepolymer A3 is stirred in a reaction vessel equipped with a heating device, a stirrer and a nitrogen introduction tube, and the amount of amine of [ketimine compound 1] is equimolar with respect to the amount of isocyanate in the prepolymer A3. An amount of [ketimine compound 1] was dropped into the reaction vessel and stirred at 45 ° C. for 10 hours, and then the prepolymer extension product was taken out. The obtained prepolymer extension product was dried under reduced pressure at 50 ° C. until the amount of residual ethyl acetate was 100 ppm or less to obtain a nonlinear amorphous polyester resin A3.

(Production Example A4)
<Synthesis of Non-Linear Amorphous Polyester Resin A4>
-Synthesis of prepolymer A4-
1,2-propylene glycol, terephthalic acid, adipic acid, and trimellitic anhydride are mixed in a reaction vessel equipped with a cooling pipe, a stirrer, and a nitrogen introduction pipe, and the molar ratio of hydroxyl group to carboxyl group is "OH / COOH". 1.3, the diol component is 100 mol% of 1,2-propylene glycol, the dicarboxylic acid component is 80 mol% of terephthalic acid, and 20 mol% of adipic acid, and the amount of trimellitic anhydride in all monomers is Titanium tetraisopropoxide (1000 ppm with respect to all resin components) was added so as to be 2.5 mol%. Thereafter, the temperature was raised to 200 ° C. in about 4 hours, and then the temperature was raised to 230 ° C. over 2 hours until the effluent water disappeared. Then, it was made to react under reduced pressure of 10-15 mmHg for 5 hours, and intermediate body polyester A4 was obtained.
Next, the intermediate polyester A4 and isophorone diisocyanate are charged at a molar ratio (IPDI isocyanate group / intermediate polyester hydroxyl group) of 2.0 in a reaction vessel equipped with a cooling pipe, a stirrer, and a nitrogen introduction pipe. After diluting with ethyl acetate to a 50% ethyl acetate solution, the mixture was reacted at 100 ° C. for 5 hours to obtain Prepolymer A4.

-Synthesis of non-linear amorphous polyester resin A4-
The obtained prepolymer A4 is stirred in a reaction vessel equipped with a heating device, a stirrer and a nitrogen introduction tube, and the amount of amine of [ketimine compound 1] is equimolar with respect to the amount of isocyanate in the prepolymer A4. An amount of [ketimine compound 1] was dropped into the reaction vessel and stirred at 45 ° C. for 10 hours, and then the prepolymer extension product was taken out. The obtained prepolymer extension product was dried under reduced pressure at 50 ° C. until the amount of residual ethyl acetate was 100 ppm or less to obtain a non-linear amorphous polyester resin A4.

(Production Example A5)
<Synthesis of Non-Linear Amorphous Polyester Resin A5>
-Synthesis of prepolymer A5-
3-Methyl-1,5-pentanediol, isophthalic acid, adipic acid, and trimellitic anhydride are mixed in a reaction vessel equipped with a condenser, a stirrer, and a nitrogen introduction pipe with a molar ratio of hydroxyl group to carboxyl group. OH / COOH ”is 1.5, the diol component is 100% by mole of 3-methyl-1,5-pentanediol, the dicarboxylic acid component is 40% by mole of isophthalic acid, and 60% by mole of adipic acid. Titanium tetraisopropoxide (1000 ppm with respect to all resin components) was added so that the amount of trimellitic anhydride in the mixture was 1 mol%. Thereafter, the temperature was raised to 200 ° C. in about 4 hours, and then the temperature was raised to 230 ° C. over 2 hours until the effluent water disappeared. Then, it was made to react under reduced pressure of 10-15 mmHg for 5 hours, and intermediate polyester A5 was obtained.
Next, the intermediate polyester A5 and isophorone diisocyanate are charged at a molar ratio (IPDI isocyanate group / intermediate polyester hydroxyl group) of 2.0 in a reaction vessel equipped with a cooling pipe, a stirrer, and a nitrogen introduction pipe. After diluting with ethyl acetate to a 50% ethyl acetate solution, the mixture was reacted at 100 ° C. for 5 hours to obtain Prepolymer A5.

-Synthesis of non-linear amorphous polyester resin A5-
The obtained prepolymer A5 is stirred in a reaction vessel equipped with a heating device, a stirrer and a nitrogen introduction tube, and the amount of amine of [ketimine compound 1] is equimolar with respect to the amount of isocyanate in the prepolymer A5. An amount of [ketimine compound 1] was dropped into the reaction vessel and stirred at 45 ° C. for 10 hours, and then the prepolymer extension product was taken out. The obtained prepolymer extension product was dried under reduced pressure at 50 ° C. until the amount of residual ethyl acetate was 100 ppm or less to obtain a non-linear amorphous polyester resin A5.

(Production Example B1)
<Synthesis of Amorphous Polyester Resin B1>
A four-necked flask equipped with a nitrogen inlet tube, dehydration tube, stirrer, and thermocouple, bisphenol A ethylene oxide 2 mol adduct, bisphenol A propylene oxide 2 mol adduct, terephthalic acid, adipic acid, hydroxyl group and carboxyl The molar ratio “OH / COOH” with the group is 1.3, the molar ratio of bisphenol A ethylene oxide 2-mole adduct and bisphenol A propylene oxide 2-mole adduct is 60/40, and the terephthalic acid and adipic acid Titanium tetraisopropoxide (500 ppm with respect to all resin components) was added so that the molar ratio was 97/3. Thereafter, the mixture is reacted at 230 ° C. under normal pressure for 8 hours, and further reacted under reduced pressure of 10 to 15 mmHg for 4 hours, and then trimellitic anhydride is added to the reaction vessel so as to be 1 mol% with respect to the total resin components. The amorphous polyester resin B1 was obtained by reacting at 180 ° C. under normal pressure for 3 hours.

(Production Example B2)
<Synthesis of Amorphous Polyester Resin B2>
A four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple. The molar ratio of OH / COOH is 1.4, the molar ratio of bisphenol A propylene oxide 2-mol adduct and 1,3-propylene glycol is 90/10, and the molar ratio of terephthalic acid to adipic acid is Titanium tetraisopropoxide (500 ppm with respect to all resin components) was added so as to be 80/20. Thereafter, the mixture is reacted for 8 hours at 230 ° C. under normal pressure, and further for 4 hours under reduced pressure of 10 to 15 mmHg. The amorphous polyester resin B2 was obtained by reacting at 180 ° C. and normal pressure for 3 hours.

(Production Example B3)
<Synthesis of Amorphous Polyester Resin B3>
A four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple is charged with hydroxyl group of bisphenol A ethylene oxide side 2 mol adduct, bisphenol A propylene oxide 2 mol adduct, isophthalic acid, and adipic acid. And the carboxyl group molar ratio “OH / COOH” is 1.2, the molar ratio of bisphenol A ethylene oxide side 2 mol adduct and bisphenol A propylene oxide 2 mol adduct is 80/20, Titanium tetraisopropoxide (500 ppm with respect to all resin components) was added so that the molar ratio of adipic acid was 80/20. Then, after reacting under normal pressure at 230 ° C. for 8 hours and further reacting under reduced pressure of 10 to 15 mmHg for 4 hours, trimellitic anhydride was added to the reaction vessel so as to be 1 mol% based on the total resin components, The mixture was reacted at 180 ° C. under normal pressure for 3 hours to obtain amorphous polyester resin B3.

(Production Example B4)
<Synthesis of Amorphous Polyester Resin B4>
A four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple is charged with bisphenol A ethylene oxide side 2 mol adduct, bisphenol A propylene oxide 3 mol adduct, isophthalic acid, and adipic acid. And the carboxyl group molar ratio “OH / COOH” is 1.3, the molar ratio of bisphenol A ethylene oxide side 2 mol adduct and bisphenol A propylene oxide 3 mol adduct is 85/15, Titanium tetraisopropoxide (500 ppm with respect to all resin components) was added so that the molar ratio of adipic acid was 80/20. Then, after reacting under normal pressure at 230 ° C. for 8 hours and further reacting under reduced pressure of 10 to 15 mmHg for 4 hours, trimellitic anhydride was added to the reaction vessel so as to be 1 mol% based on the total resin components, The mixture was reacted at 180 ° C. under normal pressure for 3 hours to obtain amorphous polyester resin B4.

(Production Example B5)
<Synthesis of Amorphous Polyester Resin B5>
A four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple is combined with bisphenol A ethylene oxide side 2 mol adduct, bisphenol A propylene oxide 3 mol adduct, terephthalic acid, and adipic acid. And the carboxyl group molar ratio “OH / COOH” is 1.3, the molar ratio of bisphenol A ethylene oxide side 2 mol adduct and bisphenol A propylene oxide 3 mol adduct is 85/15, and terephthalic acid and Titanium tetraisopropoxide (500 ppm with respect to all resin components) was added so that the molar ratio of adipic acid was 80/20. Then, after reacting under normal pressure at 230 ° C. for 8 hours and further reacting under reduced pressure of 10 to 15 mmHg for 4 hours, trimellitic anhydride was added to the reaction vessel so as to be 1 mol% based on the total resin components, Reaction was performed at 180 ° C. under normal pressure for 3 hours to obtain an amorphous polyester resin B5.

(Production Example C)
<Synthesis of crystalline polyester resin C>
In a 5 L four-necked flask equipped with a nitrogen inlet tube, a dehydrating tube, a stirrer, and a thermocouple, sebacic acid and 1,6-hexanediol were mixed at a molar ratio of “OH / COOH” of hydroxyl group to carboxyl group. The mixture was charged to 0.9, and reacted with titanium tetraisopropoxide (500 ppm with respect to the resin component) at 180 ° C. for 10 hours, then heated to 200 ° C. and reacted for 3 hours, and further 8.3 kPa. For 2 hours to obtain a crystalline polyester resin C.

(Preparation of Toner 1)
<Synthesis of Masterbatch 1>
Add 1200 parts of water, 500 parts of carbon black (Printex 35, manufactured by Dexa) [DBP oil absorption = 42 mL / 100 mg, pH = 9.5] and 500 parts of amorphous polyester resin B1, and add a Henschel mixer (made by Mitsui Mining Co., Ltd.). ) Was kneaded at 150 ° C. for 30 minutes using two rolls, rolled and cooled, and pulverized with a pulverizer to obtain [Masterbatch 1].

<Preparation of WAX dispersion 1>
In a container in which a stir bar and a thermometer are set, 50 parts of paraffin wax (manufactured by Nippon Seiki Co., Ltd., HNP-9, hydrocarbon wax, melting point 75 ° C., SP value 8.8) as release agent 1 and ethyl acetate 450 parts were charged, the temperature was raised to 80 ° C. with stirring, and the temperature was maintained at 80 ° C. for 5 hours. Next, it is cooled to 30 ° C. over 1 hour, and using a bead mill (Ultra Visco Mill, manufactured by Imex Co., Ltd.), liquid feeding speed is 1 kg / hour, disk peripheral speed is 6 m / second, and 0.5 mm zirconia beads are 80% by volume. Dispersion was performed under conditions of filling and 3 passes to obtain [WAX Dispersion 1].

<Preparation of crystalline polyester resin dispersion 1>
In a container equipped with a stirring rod and a thermometer, 50 parts of crystalline polyester resin C and 450 parts of ethyl acetate were charged, heated to 80 ° C. with stirring, and maintained at 80 ° C. for 5 hours. Next, it is cooled to 30 ° C. over 1 hour and filled with 80% by volume of 0.5 mm zirconia beads using a bead mill (Ultra Visco Mill, manufactured by Imex) with a liquid feeding speed of 1 kg / hour, a disk peripheral speed of 6 m / sec. Dispersion was performed under conditions of 3 passes to obtain [Crystalline Polyester Resin Dispersion 1].

<Preparation of oil phase 1>
[WAX Dispersion 1] 50 parts, [Non-Linear Amorphous Polyester Resin A1] 150 parts, [Crystalline Polyester Resin Dispersion 1] 50 parts, [Amorphous Polyester Resin B1] 750 parts, [Masterbatch 1] 50 parts and 2 parts of [ketimine compound 1] were put in a container and mixed with a TK homomixer (manufactured by Tokushu Kika Co., Ltd.) at 5000 rpm for 60 minutes to obtain [Oil Phase 1].

<Synthesis of fine particle dispersion 1 (organic fine particle emulsion)>
In a reaction vessel equipped with a stirrer and a thermometer, 683 parts of water, 11 parts of sodium salt of ethylene oxide methacrylate adduct sulfate (Eleminol RS-30: manufactured by Sanyo Chemical Industries), 138 parts of styrene, 138 parts of methacrylic acid , And 1 part of ammonium persulfate were added and stirred at 400 rpm for 15 minutes to obtain a white emulsion. This was heated to raise the temperature in the system to 75 ° C. and reacted for 5 hours. Further, 30 parts of a 1% ammonium persulfate aqueous solution was added, and the mixture was aged at 75 ° C. for 5 hours, and an aqueous dispersion of a vinyl resin (styrene salt copolymer of styrene-methacrylic acid-methacrylic acid ethylene oxide adduct sulfate) [ A fine particle dispersion 1] was obtained.
The volume average particle size of [Fine Particle Dispersion 1] measured with LA-920 (manufactured by HORIBA) was 0.14 μm.

<Preparation of aqueous phase 1>
990 parts of water, 83 parts of [fine particle dispersion 1], 37 parts of a 48.5% aqueous solution of sodium dodecyl diphenyl ether disulfonate (Eleminol MON-7: manufactured by Sanyo Chemical Industries) and 90 parts of ethyl acetate were mixed and stirred to give a milky white color Obtained liquid. This was designated as [Aqueous Phase 1].

<Emulsification / desolvation>
[Oil Phase 1] 1200 parts of [Aqueous Phase 1] was added to a container containing the entire amount, and was mixed with a TK homomixer at 13,000 rpm for 20 minutes to obtain [Emulsion Slurry 1].
[Emulsion slurry 1] was put into a container equipped with a stirrer and a thermometer, and after removing the solvent at 30 ° C. for 8 hours, aging was carried out at 45 ° C. for 4 hours to obtain [Dispersion slurry 1].

<Washing and drying>
[Dispersion Slurry 1] After filtering 100 parts under reduced pressure, the following operations (1) to (4) were performed twice on the obtained filter cake to obtain [Filter Cake 1].
(1): Add 100 parts of ion-exchanged water to the filter cake, mix with a TK homomixer (10 minutes at 12,000 rpm), and then filter.
(2): Add 100 parts of a 10% aqueous sodium hydroxide solution to the filter cake of (1), mix with a TK homomixer (30 minutes at 12,000 rpm), and then filter under reduced pressure.
(3): 100 parts of 10% hydrochloric acid is added to the filter cake of (2), mixed with a TK homomixer (rotation speed: 12000 rpm for 10 minutes), and then filtered.
(4): Add 300 parts of ion-exchanged water to the filter cake of (3), mix with a TK homomixer (rotation speed 12000 rpm for 10 minutes), and then filter.

Next, [Filter cake 1] was dried with a circulating dryer at 45 ° C. for 48 hours, and sieved with an opening of 75 μm mesh to obtain [Toner base 1]. Table 1 shows Tg1st, storage elastic modulus G ′ (50) at 50 ° C., and storage elastic modulus G ′ (100) at 100 ° C. of [Toner Base 1].

<External additive mixing>
[Toner base 1] To 100 parts by mass, 0.5 part of titanium oxide (JMT-150IB manufactured by Denka), 1 part of first silica (UFP-35 manufactured by Denka), and second silica (HDK) -2000H, volume average particle size 22 nm) was added in this order in this order.
Using a Henschel mixer (Mitsui Mining Co., Ltd.), JMT-150IB was first charged, mixed for 30 seconds, and rested for 1 minute. Next, UFP-35 was added, mixed for 30 seconds, and rested for 1 minute. Finally, HDK-2000 was added and mixed for 30 seconds, and then sieved with a mesh having an opening of 35 μm to prepare [Toner 1].

(Preparation of Toner 2)
In the preparation of Toner 1 in <Preparation of oil phase 1>, except that the input amount of the non-linear amorphous polyester resin A1 is changed to 120 parts and the input amount of the amorphous polyester resin B1 is changed to 780 parts. Produced [Toner 2] in the same manner as in the preparation of Toner 1.

(Preparation of Toner 3)
In the preparation of Toner 1 in <Preparation of Oil Phase 1>, except that the input amount of the non-linear amorphous polyester resin A1 is changed to 180 parts and the input amount of the amorphous polyester resin B1 is changed to 720 parts. Produced [Toner 3] in the same manner as in the preparation of Toner 1.

(Preparation of Toner 4)
[Toner 4] was obtained in the same manner as in the preparation of the toner 1 except that the non-linear amorphous polyester resin A1 was changed to the non-linear amorphous polyester resin A2 in the preparation of the toner 1.

(Preparation of Toner 5)
[Toner 5] was obtained in the same manner as in the preparation of the toner 1 except that the amorphous polyester resin B1 was changed to the amorphous polyester resin B2 in the preparation of the toner 1.

(Preparation of Comparative Toner 11)
In <Preparation of oil phase 1> in the production of toner 1, the non-linear amorphous polyester resin A1 is changed to the non-linear amorphous polyester resin A5, and the amorphous polyester resin B1 is changed to the amorphous polyester resin. Except for the change to B4, [Toner 11] was obtained in the same manner as in the preparation of Toner 1.

(Preparation of Comparative Toner 12)
In <Preparation of oil phase 1> in the production of toner 1, the non-linear amorphous polyester resin A1 is changed to the non-linear amorphous polyester resin A5, and the amorphous polyester resin B1 is changed to the amorphous polyester resin. Except for the change to B5, [Toner 12] was obtained in the same manner as in the preparation of Toner 1.

(Preparation of Comparative Toner 13)
In <Preparation of oil phase 1> in the production of toner 1, the non-linear amorphous polyester resin A1 is changed to the non-linear amorphous polyester resin A3, and the amorphous polyester resin B1 is changed to the amorphous polyester resin. Except for the change to B2, [Toner 13] was obtained in the same manner as in the preparation of Toner 1.

(Preparation of Comparative Toner 14)
In <Preparation of oil phase 1> in the production of toner 1, the non-linear amorphous polyester resin A1 is changed to a non-linear amorphous polyester resin A4, and the amorphous polyester resin B1 is changed to an amorphous polyester resin. [Toner 14] was obtained in the same manner as in the preparation of the toner 1 except that the crystalline polyester resin dispersion 1 was not used instead of the B3.

The properties of the obtained toners were evaluated as follows.
-Soxhlet extraction-
1 part of each toner was refluxed with 100 parts of THF for 6 hours to separate a THF-insoluble part and a THF-soluble part. The solid content of THF-insoluble matter was dried at 40 ° C. for 20 hours, and the THF-insoluble matter was subjected to storage elastic modulus (G ′) measurement and DSC measurement. The results are shown in Table 1.

<Heat resistant storage stability>
After filling each toner in a 50 mL glass container and leaving it in a constant temperature bath at 50 ° C. for 24 hours,
Cooled to 24 ° C. Subsequently, the penetration [mm] was measured by a penetration test (JISK2235-1991), and the heat resistant storage stability was evaluated. The results are shown in Table 2.
〔Evaluation criteria〕
◎: Needle penetration 20 mm or more ○: Needle penetration 15 mm or more and less than 20 mm △: Needle penetration 10 mm or more and less than 15 mm ×: Needle penetration less than 10 mm

<High temperature and high humidity storage stability>
After 5 g of each toner was stored in an environment of 40 ° C. and 70% for 2 weeks, it was sieved with a mesh sieve having an opening of 106 μm for 5 minutes, and the amount of toner on the wire mesh was measured and evaluated according to the following criteria. The results are shown in Table 2.
〔Evaluation criteria〕
A: Toner amount on wire mesh is 0 mg
○: Toner amount on wire mesh is less than 2 mg Δ: Toner amount on wire mesh is 2 mg or more, less than 50 mg ×: Toner amount on wire mesh is 50 mg or more

Using each toner, a developer was prepared and evaluated by the following method. The results are shown in Table 2.

<< Development of Developer >>
-Production of carrier-
To 100 parts of toluene, 100 parts of silicone resin organostraight silicone, 5 parts of γ- (2-aminoethyl) aminopropyltrimethoxysilane, and 10 parts of carbon black are added and dispersed with a homomixer for 20 minutes to form a resin layer. A coating solution was prepared. Next, the resin layer coating solution was applied to the surface of 1000 parts of spherical magnetite having an average particle diameter of 50 μm using a fluidized bed type coating apparatus to prepare a carrier.

-Production of developer-
Using a ball mill, 7 parts of toners 1 to 5 and 11 to 14 and 93 parts of the carrier were mixed to prepare a developer.

<Offset resistance>
After each developer is put in the unit of imageo MP C5002 (manufactured by Ricoh), a rectangular solid image of 2 cm × 15 cm is applied to the PPC paper type 6000 <70W> A4T (manufactured by Ricoh), and the amount of toner attached is It was formed to be 0.85 mg / cm ² for cold and 0.20 mg / cm ² for hot. At this time, the surface temperature of the fixing roller was changed, and it was observed whether or not an offset at which a solid developed image was fixed at a place other than a desired place was generated, and the offset resistance was evaluated according to the following criteria. The results are shown in Table 2.

[Cold offset evaluation criteria]
◎: Less than 110 ° C ○: 110 ° C or more, less than 120 ° C △: 120 ° C or more, less than 130 ° C ×: 130 ° C or more

[Hot offset evaluation criteria]
A: 170 ° C. or higher ○: 160 ° C. or higher, lower than 170 ° C. Δ: 150 ° C. or higher, lower than 160 ° C. ×: lower than 150 ° C.

(Examples 1-9, Comparative Examples 1-13)
Transfer toner loss was measured and evaluated using toners 1 to 5 and 11 to 14, respectively. The results are shown in Table 2.

<Evaluation during transfer failure 1>
Regarding the mechanical conditions, the imageo MP C5002 photoconductor, photoconductor drive unit, and intermediate transfer belt were modified. Each end was marked, the marks were read by a sensor to check the linear velocity, and the linear velocity of the drum motor was adjusted. Table 2 shows values (linear velocity difference%) of “{(Vopc−Vtrans) / Vtrans} × 100” regarding the linear velocity difference between the linear velocity of the photosensitive member and the linear velocity of the intermediate transfer belt. This time, the linear speed of the drum motor was adjusted, and the linear speed of the intermediate transfer bell t was fixed at 230 mm / sec.
Further, the surface friction coefficient of the photosensitive member was adjusted by adjusting the spring pressure of the coating mechanism for applying the lubricant by using the process as shown in FIG. As a lubricant, a mixture of 90 parts of zinc stearate and 10 parts of boron nitride was used. The surface friction coefficient (μpc) of the photoreceptor and the friction coefficient (μtrans) of the intermediate transfer belt are shown together in Table 2.

The carrier used for imageo MP C5002 (manufactured by Ricoh Co., Ltd.) and each toner were mixed so that the toner concentration would be 7% to obtain each developer.
After loading each developer into the unit of imageo MP C5002 (manufactured by Ricoh), a grid-like image consisting of vertical and horizontal 600 dpi 1 dot line, 2 dot line, 4 dot line, and 6 dot line is created, and line omission and line intersection Evaluated the void. Further, not only the CMYK line but also the RGB line which is disadvantageous due to a large amount of adhesion was evaluated. The paper used for the evaluation was My Paper A4T (manufactured by Ricoh).
〔Evaluation criteria〕
A: No void occurred.
○: Some of the intersections with the RGB lines are missing.
Δ: The RGB vertical lines are completely missing, and some CMYK lines are also missing.
Is seen.
×: All the vertical lines have hollows, and the horizontal lines have a hollow part.
It is.

(Examples 10 to 14)
<Evaluation during transfer failure 2>
Subsequently, 0.1 part of zinc stearate as a lubricant is added to 100 parts of each toner of toners 1 to 5, and mixed using a Henschel mixer (manufactured by Mitsui Mining Co., Ltd.) at a peripheral speed of 30 m / second for 30 seconds. When stearic acid is added, it becomes difficult to pass through the sieve, and therefore, sieved with a mesh having an aperture of 106 μm, toners 21 to 25 were obtained.
Using this toner, the same transfer omission evaluation as in <Transfer omission evaluation 1> was performed. The results are shown in Table 3.

(Examples 15 to 19)
<Transfer dropout evaluation 3>
On the surface of the photoconductor, 10 parts of polytetrafluoroethylene mixed with 100 parts of the material for the charge transport layer was spray-coated at a thickness of 3 μm to obtain a low μ photoconductor.
Table 4 shows the results of evaluation of transfer loss when toners 1 to 5 are used for this photoreceptor.
Here, since it is necessary to evaluate that the photoconductor is worn over time, a running test up to 100,000 sheets was performed. The relationship between the coefficient of friction (μpc) of the photoconductor, the coefficient of friction (μtrans) of the transfer belt, and the transfer dropout at each sheet passing number is shown.
The linear speed ratio between the photoconductor and the intermediate transfer belt was fixed at 0.1.

1Y yellow photosensitive drum (latent image carrier)
1M Magenta photosensitive drum (latent image carrier)
1C Cyan photoreceptor drum (latent image carrier)
1K black photosensitive drum (latent image carrier)
2a cleaning blade 2Y yellow cleaning unit 2M magenta cleaning unit 2C cyan cleaning unit 2K black cleaning unit 4Y yellow charging unit 4M magenta charging unit 4C cyan charging unit 4K black charging unit 5Y yellow developing device (developing unit)
5M magenta developing device (developing part)
5C cyan developing device (developing part)
5K black developing device (developing part)
6Y Yellow imaging unit 6M Magenta imaging unit 6C Cyan imaging unit 6K Black imaging unit 7 Exposure unit (exposure device)
8 Intermediate transfer belt 9Y Yellow primary transfer bias roller 9M Magenta primary transfer bias roller 9C Cyan primary transfer bias roller 9K Black primary transfer bias roller 10 Intermediate transfer cleaning unit 12Y Yellow secondary transfer bias roller 12M Magenta secondary transfer bias Roller 12C Cyan secondary transfer bias roller 12K Black secondary transfer bias roller 13 Cleaning backup roller 14 Tension roller 15 Intermediate transfer unit (intermediate transfer member)
19 Secondary transfer roller 20 Fixing portion 26 Paper feed portion 27 Paper feed roller 28 Registration roller pair 29 Paper discharge roller pair 30 Stack portion 31 Toner replenishing device 32Y Yellow toner cartridge (toner container)
32M magenta toner cartridge (toner container)
32C cyan toner cartridge (toner container)
32K black toner cartridge (toner container)
38Y Yellow toner cartridge ID chip 38M Magenta toner cartridge ID chip 38C Cyan toner cartridge ID chip 38K Black toner cartridge ID chip 43Y Toner replenishment port 51Y Developer sleeve 52Y Doctor blade 53Y Agent separation point 54Y Developer 55Y Conveying screw 56Y Yellow Toner density sensor 56M Magenta toner density sensor 56C Cyan toner density sensor 56K Black toner density sensor 100 Image forming apparatus main body 101 Electrical board 102 Toner supply motor 201Y Yellow brush 202Y Yellow rod-like lubricant 203Y Yellow coating blade G Force gauge L Laser light P Transfer material (recording material)
S Cylindrical photoconductor surface W Load

JP 2000-19858 A Japanese Unexamined Patent Publication No. 8-21755 JP 2007-25096 A JP 2008-24234 A Japanese Patent No. 4820687 Japanese Patent No. 4854645 JP 2008-3554 A

Claims (5)

When the storage elastic modulus G ′ (40) at 40 ° C. containing at least a polyester resin is X and the storage elastic modulus G ′ (100) at 100 ° C. is Y, Y is 1.0 × 10 ^5. an ~1.0 × ¹⁰ 7 Pa, an image forming method of the electrophotographic method using a toner as a X / Y ≦ 3.5 × 10, and the friction coefficient of the photoconductor (mu PC), photoreceptor The friction coefficient (μtrans) of the toner image transfer medium in contact satisfies the relationship of “μpc <μtrans”, and the linear velocity difference between the linear velocity (Vopc) of the photoreceptor and the linear velocity (Vtrans) of the toner image transfer medium is | {(Vopc−Vtrans) / Vtrans} × 100 | ≦ 0.5 is satisfied.   The image forming method according to claim 1, wherein a lubricant is applied to the photoreceptor.   The image forming method according to claim 1, wherein the toner to which the lubricant is added is supplied to the surface of the photoreceptor through a development process, and the lubricant is supplied to a cleaning portion of the photoreceptor.   4. The image forming method according to claim 1, wherein a layer containing a fluororesin is provided as a surface layer of the charge transport layer of the photoreceptor.   5. An image forming apparatus used for carrying out the image forming method according to claim 1, wherein a toner image transfer unit, a mechanism for controlling a friction coefficient of the photosensitive member, and a photosensitive member motor are adjusted by adjusting a photosensitive member motor. It has a mechanism that can finely adjust the linear velocity with respect to the linear velocity of the toner image transfer medium, and the friction coefficient (μpc) of the photoconductor and the friction coefficient (μtrans) of the toner image transfer medium in contact with the photoconductor are “μpc”. <Μtrans ”and the difference between the linear velocity (Vopc) of the photoreceptor and the linear velocity (Vtrans) of the toner image transfer medium is | {(Vopc−Vtrans) / Vtrans} × 100 | ≦ 0. 5. An image forming apparatus that is controllable so as to satisfy the relationship 5.

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