JP2015224312A - Resin for toner and toner for electrostatic image development - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyester resin for a toner having both sufficient low-temperature fixability and storage property and excellent charge stability, fluidity, and a transfer rate in a long period of time in a high-temperature and high humidity environment.SOLUTION: The polyester resin for a toner comprises a polyol-based structural moiety, a polycarboxylic acid-based structural moiety, and a fluorine-containing bisphenol-based structural moiety.

Description

  The present invention relates to an electrostatic image developing toner and a toner resin.

In electrophotographic devices and electrostatic recording devices, toner is attached to an electrostatic latent image formed on a photoreceptor, transferred to a transfer material, and then fixed to the transfer material by heat to form a toner image. doing.
Also, full-color image formation is generally performed by using four color toners of black, yellow, magenta, and cyan. Each toner is developed, and each toner layer is superimposed on a transfer material. To obtain a full-color image.
However, for users who are familiar with printing in general, images on full-color copiers are not yet satisfactory, and there is a demand for higher image quality that satisfies photography, high-definition, and high resolution. It is known to use a toner having a small particle size and a narrow particle size distribution to improve the image quality.

A conventional pulverized toner is obtained by melting and uniformly dispersing a colorant, a charge control agent, an offset preventing agent, etc. in a thermoplastic resin (binder resin), and pulverizing and classifying the resulting composition. In such a toner manufacturing method, a high-range particle size distribution is easily formed, and when trying to obtain a copy image having good resolution and gradation, for example, a fine powder having a particle size of 5 μm or less is used. The coarse powder of 20 μm or more must be removed by classification, and there is a disadvantage that the yield becomes very low.
Particularly in the case of a color toner, it is difficult to uniformly disperse a colorant, a charge control agent and the like in a thermoplastic resin by the pulverization method.
The non-uniform dispersion of the compounding agent adversely affects toner fluidity, developability, durability, image quality, and the like.

In recent years, in order to overcome these problems in the pulverization method, a toner production method by a suspension polymerization method has been proposed and implemented.
A technique for producing a toner for developing an electrostatic latent image by a polymerization method is known. For example, toner particles are obtained by a suspension polymerization method.
According to the polymerization method, the conventional pulverization process and kneading process can be omitted, energy saving, shortening of production time, improvement of process yield, etc. contribute greatly to cost reduction. At the same time, it is easy to make the particle size distribution sharper than that of the pulverization method, and the contribution to high image quality is great.
In addition, in order to increase the image quality of a full-color image as in printing in electrophotography, it is necessary that each toner has a wide color reproducibility.
In order to achieve the above object without any problems, it is necessary to highly disperse a colorant excellent in transparency, light resistance and heat resistance in the toner particles.
Further, the toner to be used is first required to have an appropriate charge amount in order to obtain a clear developed image free from fog or the like.
Further, there is a demand that there is no change in charge amount with time, and that there is no significant change in charge amount attenuation or aggregation due to environmental changes such as humidity changes.
This is because when the charge amount is attenuated and reduced from the initially set value, toner scattering increases, causing problems such as background fogging and toner contamination around the developing device.

In order to meet the above requirements, a charge control agent is usually added to the toner, or charge control is performed on the surface of an external additive or the like (see, for example, Patent Documents 1, 2, and 3).
However, when charge control is performed using a charge control agent, for example, a calixarene compound known as a charge control agent has a large particle size and is difficult to uniformly disperse the charge control agent in the toner particles. The surface is subject to great stress and easily deteriorates. As a result, toner performance such as charging characteristics for each toner particle varies, and as a result, toner scattering and a toner fog problem occur in a copy image. These problems are particularly noticeable in a high temperature and high humidity environment.

  In recent years, toners are required to have improved low-temperature fixability in order to save energy. However, particularly in a high-temperature and high-humidity environment, the melting of the toner tends to proceed, and there is a problem in that the fluidity of the toner decreases and the transfer rate decreases due to aggregation in the developing device.

  The object of the present invention is to solve the above-mentioned problems, satisfy both low-temperature fixability and storability at the same time, and have excellent charging stability, fluidity, and transfer rate over a long period of time in a high temperature and high humidity environment. It is to provide a polyester resin.

The above problem is solved by the “polyester resin for toner” described in the following (1) of the present invention.
(1) “A polyester resin for toner, comprising a polyol-based structural part, a polycarboxylic acid-based structural part, and a fluorine-containing bisphenol-based structural part represented by the following general formula (1):

（一般式（１）中、Ｒ_１、Ｒ_２は、アルキル基内に含まれる少なくとも１つ以上の水素原子がフッ素原子で置換されておりそれぞれ同一でも異なっていてもよい含フッ素アルキル基を表し、Ｒ_３、Ｒ_４は、水素原子、又はアミノ基、スルホ基、ハロゲン原子及び炭化水素基よりなる群より選ばれそれぞれ同一であっても異なっていてもよい１個乃至４個の置換基を表し、Ｘはカルボキシル基由来のカルボニル基（＊−ＣＯ−）、イソシアネート基由来のオキシカルバモイル残基（＊−ＯＣＯＮＨ−）若しくはアミノカルボニルオキシ残基（＊−ＮＨＣＯ−Ｏ−）、イソシアネート基由来のウレイレニル基（＊−ＨＮＣＯＮＨ−）、又は次の一般式（２）で表される末端オキシル基を表わす。）
−Ｏ（Ｒ_５Ｏ）_ｍ−・・・一般式（２）
（一般式（２）中、Ｒ_５はアルキニル基を表し、ｍは０以上の整数を表す。）。」

(In the general formula (1), R ₁ and R ₂ each represents a fluorine-containing alkyl group in which at least one hydrogen atom contained in the alkyl group is substituted with a fluorine atom and may be the same or different from each other. , R ₃ and R ₄ are each selected from the group consisting of a hydrogen atom, an amino group, a sulfo group, a halogen atom and a hydrocarbon group, and may be the same or different and each may have 1 to 4 substituents. X represents a carbonyl group derived from a carboxyl group (* -CO-), an oxycarbamoyl residue derived from an isocyanate group (* -OCONH-) or an aminocarbonyloxy residue (* -NHCO-O-), derived from an isocyanate group A ureylenyl group (* -HNCONH-) or a terminal oxyl group represented by the following general formula (2):
_{-O (R 5 O) m -} ··· formula (2)
(In the general formula (2), R ₅ represents an alkynyl group, and m represents an integer of 0 or more.) "

  According to the present invention, the conventional problems are solved, low-temperature fixability and storage stability are satisfied at the same time, and long-term charging stability, fluidity, and transfer rate are excellent in a high-temperature and high-humidity environment. A very excellent effect that a resin for toner can be provided is exhibited.

1 is a schematic configuration diagram illustrating an example of an image forming apparatus of the present invention. It is a schematic block diagram which shows another example of the image forming apparatus of this invention. It is a schematic block diagram which shows another example of the image forming apparatus of this invention. FIG. 4 is a partially enlarged view of FIG. 3. It is a schematic block diagram which shows an example of a process cartridge.

Hereinafter, the “polyester resin for toner (hereinafter, this resin is sometimes referred to as“ polyester resin A ”)” described in (1) will be described in detail. The “polyester resin A” described in (1) The embodiment of “polyester resin A” described in the following (2) to (5) is included. In addition, the present invention includes embodiments of “toner”, “developer”, and “image forming apparatus” described in the following (6) to (10), and these will be described in detail together.
(2) “The polyester resin for toner according to (1) above, which contains 1 to 10 mol% of any one or more structural parts derived from the fluorine-containing bisphenol compound of the general formula (1). "
(3) “The hydrogen atom contained in the alkyl group of R ₁ and R _{2 in} the general formula (1) is substituted with three fluorine atoms,” described in (1) or (2) above Polyester resin for toner. "
(4) “For toner according to any one of (1) to (3) above, wherein the glass transition temperature is 40 ° C. or higher and lower than 70 ° C., and the weight average molecular weight is 4000 or higher and 25000 or lower. Polyester resin. "
(5) The above-mentioned (1), wherein a structural part derived from a trivalent or higher aliphatic alcohol is contained in an amount of 0.5 parts by mass or more and 6.5 parts by mass or less in 100 parts by mass of the total mass of the polyol-based structural part The polyester resin for toner according to any one of (1) to (4).
(6) “Toner containing the resin according to (1)”.
(7) “The polyester resin according to any one of the above (1) to (5)” (hereinafter sometimes referred to as “polyester resin A”), a structural part derived from a diol component and a cross-linking as a constituent component The structural part derived from the component, wherein the diol component contains 50 mol% or more of an aliphatic diol having 3 to 10 carbon atoms, and the crosslinking component contains a polyester resin B containing a trihydric or higher aliphatic alcohol ( The toner according to 6). "
(8) The toner according to (6), wherein the first glass transition temperature (Tg1st) of the differential scanning calorimetry (DSC) of the toner is 20 ° C. or more and 50 ° C. or less. "
(9) “A developer comprising the toner according to any one of (6) to (8)”.
(10) “An electrostatic latent image carrier, an electrostatic latent image forming unit for forming an electrostatic latent image on the surface of the electrostatic latent image carrier, and developing the electrostatic latent image using a developer. An image forming apparatus having at least developing means for forming a visible image, transfer means for transferring the visible image to a recording medium, and fixing means for fixing the transferred image transferred to the recording medium, An image forming apparatus, wherein the developer is the developer described in (9). "

<Polyester resin A>
-Fluorine-containing monomer-
The polyester resin A preferably contains a fluorine-containing bisphenol-based structural moiety of the general formula (1), and is preferably 1 to 10 mol% from the viewpoints of low-temperature fixability, charging stability, transfer rate, and fluidity. More preferred. When no fluorine-containing monomer is contained, long-term charging stability, transfer rate, and fluidity in a high-temperature and high-humidity environment are disadvantageous.
As the fluorine-containing monomer therefor, for example, as shown in the following table, 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 2,2-bis (3-amino-4-hydroxyphenyl) ) Hexafluoropropane, 2,2-bis (4-carboxyphenyl) hexafluoropropane, bisphenol AF, 2,2-bis (4-isocyanatophenyl) hexafluoropropane, and the like.

-Polyol-
Examples of the polyol include glycols such as ethylene glycol, diethylene glycol, triethylene glycol, and propylene glycol, etherified bisphenols such as 1,4-bis (hydroxymethyl) cyclohexane and bisphenol A, and other dihydric alcohols. Examples include the body.

-Polycarboxylic acid-
Examples of the polycarboxylic acid include divalent organic acid monomers such as adipic acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid, terephthalic acid, succinic acid, and malonic acid.

-Branch component-
Examples of the branched component include a trivalent or higher polyol, a trivalent or higher polyvalent carboxylic acid, and the like. Examples of the branched component include 1,2,4-benzenetricarboxylic acid, 1,2,5-benzenetricarboxylic acid, 1,2,4-cyclohexanetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, And trivalent or higher polyvalent carboxylic acid monomers such as 2,5-hexanetricarboxylic acid, 1,3-dicarboxyl-2-methylenecarboxypropane, 1,2,7,8-octanetetracarboxylic acid, and the like. .
Among these, a tri- or tetravalent aliphatic alcohol is preferable from the viewpoint of excellent low-temperature fixing.
There is no restriction | limiting in particular as the quantity of the said branch component in the structural component of the polyester resin A, Although it can select suitably according to the objective, 0.5-6.5 mol of branch components derived from an alcohol component with respect to an alcohol component. % Is preferable, and 2 to 4 mol% is more preferable from the viewpoint of low-temperature fixability and storage stability. When the branched component derived from the alcohol component is less than 0.5 mol%, the storage stability may be inferior, and when it exceeds 6.5 mol%, the low-temperature fixability may be inferior.

<Polyester resin B>
The toner for electrostatic image development in the present invention contains the polyester resin A for toner according to the present invention, but may contain and preferably contain the polyester resin B described below. Furthermore, it may contain the polyester resin C demonstrated in detail below simultaneously, and it is more preferable to contain.
There is no restriction | limiting in particular as the polyester resin B, Although it can select suitably according to the objective, A diol component is included as a structural component, The said diol component contains 50 mol% or more of C3-C10 aliphatic diol. In addition, it is preferable to contain at least one of a trivalent or higher acid and a trivalent or higher alcohol as a crosslinking component.
Polyester resin B may be used alone or in combination of two or more.
The polyester resin B contains, for example, the diol component and the dicarboxylic acid component as its constituent components, and preferably contains at least one of the trivalent or higher acid and the trivalent or higher alcohol as the crosslinking component. .
The polyester resin B preferably has at least one of a urethane bond and a urea bond, and more preferably has a urethane bond and a urea bond, from the viewpoint of better adhesion to a recording medium such as paper. Further, since the polyester resin B has either a urethane bond or a urea bond, the urethane bond or the urea bond behaves like a quasi-branching point, and the rubber property of the polyester resin B becomes stronger, and the heat resistance of the toner is increased. Excellent storage stability and high-temperature offset resistance.

-Reactive precursor-
The polyester resin B is preferably obtained by a reaction between a reactive precursor and a curing agent.
The reactive precursor is not particularly limited as long as it is a polyester resin having a group capable of reacting with the curing agent (hereinafter sometimes referred to as “prepolymer”), and is appropriately selected according to the purpose. be able to.
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 of the group capable of reacting with the active hydrogen group include an isocyanate group, an epoxy group, a carboxylic acid, and an acid chloride group. Among these, an isocyanate group is preferable because a urethane bond or a urea bond can be introduced into the polyester resin B.
The prepolymer is preferably non-linear. The non-linear means having a branched structure imparted by at least one of a trivalent or higher alcohol and a trivalent or higher carboxylic acid.
As the prepolymer, a polyester resin containing an isocyanate group is preferable.

--Polyester resin containing isocyanate group--
There is no restriction | limiting in particular as the polyester resin containing 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 polycondensation of diol, dicarboxylic acid, trivalent or higher alcohol and 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 containing the isocyanate group.

--- Diol ---
Examples of the diol include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, , 8-octanediol, 1,10-decanediol, 1,12-dodecanediol and other aliphatic diols; diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol and other oxyalkylene groups Diols such as 1,4-cyclohexanedimethanol and hydrogenated bisphenol A; alkylene oxides such as ethylene oxide, propylene oxide and butylene oxide are added to the alicyclic diols. Ones; bisphenol A, bisphenol F, bisphenol such as bisphenol S; the bisphenols include ethylene oxide, propylene oxide, etc. bisphenols alkylene oxide adducts such as those obtained by adding alkylene oxides such as butylene oxide.
Among these, an aliphatic diol having 3 to 10 carbon atoms is preferable.
These diols may be used alone or in combination of two or more.
Furthermore, the number of carbon atoms in the main chain of the diol constituting the diol is an odd number, and having an alkyl group in the side chain exhibits rubber elasticity while exhibiting high thermal deformability of the resin in the fixing temperature region. The toner can be more excellent in low-temperature fixability and blocking resistance.

--- Dicarboxylic acid ---
There is no restriction | limiting in particular as said dicarboxylic acid, According to the objective, it can select suitably, For example, aliphatic dicarboxylic acid, aromatic dicarboxylic acid, etc. are mentioned. Moreover, these anhydrides may be used, a lower (C1-C3) alkyl esterified material may be used, and a halide may be used.
The aliphatic dicarboxylic acid is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include succinic acid, adipic acid, sebacic acid, dodecanedioic acid, maleic acid, and fumaric acid.
The aromatic dicarboxylic acid is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include phthalic acid, isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid, etc. Among these, carbon number of 4 or more Twelve or less aliphatic dicarboxylic acids are preferred.
These dicarboxylic acids may be used alone or in combination of two or more.

--- 3 or higher valent alcohol, trivalent or higher carboxylic acid ---
The trivalent or higher carboxylic acid and the trivalent or higher alcohol are not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol, Examples include dipentaerythritol, trimellitic acid, and pyromellitic acid.
Among these, a trivalent to tetravalent acid and a trivalent to tetravalent alcohol are preferable. These may be used individually by 1 type and may use 2 or more types together.
When the polyester resin B contains these trivalent or higher acid or trivalent or higher alcohol as a constituent component, it exhibits rubber elasticity and is more excellent in blocking resistance. Furthermore, a tri- or tetravalent acid can be developed from the viewpoint that rubber elasticity can be exhibited while having high thermal deformability of the resin in the fixing temperature region, and the low-temperature fixing property and blocking resistance of the toner are more excellent. Trivalent to tetravalent alcohols are preferred.
Further, among trivalent to tetravalent acids or trivalent to tetravalent alcohols, aliphatic alcohols are preferable from the viewpoint of excellent low-temperature fixing.

--- 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.
The aliphatic diisocyanate is not particularly limited and may be appropriately selected depending on the intended purpose. For example, tetramethylene diisocyanate, hexamethylene diisocyanate, methyl 2,6-diisocyanatocaproate, octamethylene diisocyanate, decametin Examples thereof include diisocyanate, dodecamethylene diisocyanate, tetradecamethylene diisocyanate, trimethylhexane diisocyanate, and tetramethylhexane diisocyanate.
The alicyclic diisocyanate is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include isophorone diisocyanate and cyclohexylmethane diisocyanate.
The aromatic diisocyanate is not particularly limited and may be appropriately selected depending on the intended purpose. For example, tolylene diisocyanate, diisocyanatodiphenylmethane, 1,5-naphthylene diisocyanate, 4,4′-diisocyanato Examples include diphenyl, 4,4′-diisocyanato-3,3′-dimethyldiphenyl, 4,4′-diisocyanato-3-methyldiphenylmethane, 4,4′-diisocyanato-diphenyl ether, and the like.
The araliphatic diisocyanate is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include α, α, α ′, α′-tetramethylxylylene diisocyanate.
There is no restriction | limiting in particular as said isocyanurates, According to the objective, it can select suitably, For example, a tris (isocyanatoalkyl) isocyanurate, a tris (isocyanatocycloalkyl) isocyanurate, etc. are mentioned.
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 reacts with the prepolymer, and can be appropriately selected according to the purpose. Examples thereof include an active hydrogen group-containing compound.

-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. 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.
The amines are not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include diamines, trivalent or higher valent amines, amino alcohols, amino mercaptans, amino acids, and those obtained by blocking these amino groups. Can be mentioned. These may be used individually by 1 type and may use 2 or more types together.
Among these, diamine and a mixture of a diamine and a small amount of a trivalent or higher amine are preferable.
There is no restriction | limiting in particular as said diamine, According to the objective, it can select suitably, For example, aromatic diamine, alicyclic diamine, aliphatic diamine etc. are mentioned. There is no restriction | limiting in particular as said aromatic diamine, According to the objective, it can select suitably, For example, phenylenediamine, diethyltoluenediamine, 4,4'- diaminodiphenylmethane etc. are mentioned. The alicyclic diamine is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include 4,4′-diamino-3,3′-dimethyldicyclohexylmethane, diaminocyclohexane and isophorone diamine. It is done. There is no restriction | limiting in particular as said aliphatic diamine, According to the objective, it can select suitably, For example, ethylenediamine, tetramethylenediamine, hexamethylenediamine etc. are mentioned.
The trivalent or higher amine is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include diethylenetriamine and triethylenetetramine.
The amino alcohol is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include ethanolamine and hydroxyethylaniline.
The amino mercaptan is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include aminoethyl mercaptan and aminopropyl mercaptan.
The amino acid is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include aminopropionic acid and aminocaproic acid.
There is no restriction | limiting in particular as what blocked the said amino group, According to the objective, it can select suitably, For example, it is obtained by blocking an amino group with ketones, such as acetone, methyl ethyl ketone, and methyl isobutyl ketone. Examples include ketimine compounds and oxazoline compounds.

The molecular structure of the 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 .
There is no restriction | limiting in particular as content of the polyester resin B, Although it can select suitably according to the objective, 5 mass parts-25 mass parts are preferable with respect to 100 mass parts of said toner, 10 mass parts-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 is more than 25 parts by mass, the heat-resistant storage stability is deteriorated, and the glossiness of the image obtained after fixing is obtained. The degree may decrease. When the content is within the more preferable range, it is advantageous in that it is excellent in all of low-temperature fixability, high-temperature offset resistance, and blocking resistance.

<Crystalline polyester resin C>
Since the crystalline polyester resin C has high crystallinity, the crystalline polyester resin C exhibits a heat-melting characteristic showing a rapid viscosity decrease near the fixing start temperature. By using the crystalline polyester resin C having such characteristics together with the polyester resin A, the heat resistant storage stability due to the crystallinity is good until just before the melting start temperature, and at the melting start temperature, the crystalline polyester resin C is rapidly melted by melting. Cause a significant decrease in viscosity (sharp melt properties). It is compatible with the polyester resin A as the viscosity is rapidly reduced by melting, and is fixed by rapidly decreasing the viscosity together. As a result, a toner having both good heat storage stability and low-temperature fixability can be 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 is obtained 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.
In the present invention, the crystalline polyester resin C is, as described above, 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 refers to what is obtained by using. A modified polyester resin, for example, the prepolymer and a resin obtained by branching and / or extending the prepolymer do not belong to the crystalline polyester resin C.

-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 of the saturated aliphatic diol include linear saturated aliphatic diols and branched saturated aliphatic diols. Among these, linear saturated aliphatic diols are preferable, and linear saturated fats having 2 to 12 carbon atoms are preferred. Group diols are more preferred. 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. The number of carbon atoms is more preferably 12 or less.
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, the crystalline polyester resin C has 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. preferable. By doing so, since crystallinity is high and it is excellent in sharp melt property, it is preferable at the point which can exhibit the outstanding low-temperature fixability.
There is no restriction | limiting in particular as melting | fusing point of the said crystalline polyester resin C, Although it can select suitably according to the objective, It is preferable that it is 60 to 80 degreeC. When the melting point is less than 60 ° C., the crystalline polyester resin C is easily melted at a low temperature and the heat-resistant storage stability of the toner may be lowered. When the melting point is higher than 80 ° C., the crystalline polyester resin is heated by fixing. Insufficient melting of C may reduce the low-temperature fixability.
The molecular weight of the crystalline polyester resin C is not particularly limited and may be appropriately selected depending on the intended purpose. A component having a sharp molecular weight distribution and low molecular weight is excellent in low-temperature fixability and has a low molecular weight. If the amount is too large, the heat-resistant storage stability is lowered. From this point of view, the soluble content of orthodichlorobenzene in the crystalline polyester resin C is determined by GPC measurement to have a weight average molecular weight (Mw) of 2,000 to 30,000 and a number average molecular weight (Mn) of 5,000 to 10,000. 000 and Mw / Mn of 1.0 to 10 are preferable. When the molecular weight is 2,000 or less, the residual oligomer may be insufficient in heat-resistant storage property and high-temperature and high-humidity storage property. When the molecular weight is 3,0000 or more, low-temperature fixability may be impaired.
The acid value of the crystalline polyester resin C is not particularly limited and may be appropriately selected depending on the intended purpose. From the viewpoint of the affinity between paper and resin, in order to achieve a desired low-temperature fixability. Is preferably 5 mgKOH / g or more, more preferably 10 mgKOH / g or more. On the other hand, 45 mgKOH / g or less is preferable in order to improve the high temperature offset resistance.
The hydroxyl value of the crystalline polyester resin C is not particularly limited and may be appropriately selected depending on the purpose.To achieve desired temperature fixability and good charging characteristics, 0 mgKOH / g to 50 mgKOH / g is preferable, and 5 mgKOH / g to 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 the crystalline polyester resin C having an absorption based on δCH (out-of-plane variable angular vibration) of olefin at 965 ± 10 cm ⁻¹ or 990 ± 10 cm ⁻¹ can be mentioned.
There is no restriction | limiting in particular as content of the said crystalline polyester resin C, Although it can select suitably according to the objective, 3 mass parts-20 mass parts are preferable with respect to 100 mass parts of said toners, and 5 masses. Part-15 mass parts is more preferable. When the content is less than 3 parts by mass, the low-temperature fixability may be inferior because sharp melting with the crystalline polyester resin C is insufficient, and when the content exceeds 20 parts by mass, the heat resistant storage stability is lowered. , And image fogging 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>
Examples of the other components include a release agent, a colorant, a charge control agent, an external additive, a fluidity improver, a cleaning property improver, and a magnetic material.

<< Releasing agent >>
There is no restriction | limiting in particular as said mold release agent, It can select suitably from well-known things.
Examples of release agents for 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; And natural waxes such as petroleum waxes such as paraffin, microcrystalline, and 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.
There is no restriction | limiting in particular as melting | fusing point of the said mold release agent, Although it can select suitably according to the objective, 60 to 80 degreeC is preferable. When the melting point is less than 60 ° C., the release agent is likely to melt at a low temperature, 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 range, the release agent may not be sufficiently melted, resulting in fixing offset and image loss.
There is no restriction | limiting in particular as content of the said mold release agent, Although it can select suitably according to the objective, 2 mass parts-10 mass parts are preferable with respect to 100 mass parts of said toner, 3 mass parts- 8 parts by mass is more preferable. When the content is less than 2 parts by mass, the high-temperature offset resistance during fixing and the low-temperature fixability may be inferior. When the content exceeds 10 parts by mass, the heat-resistant storage stability is deteriorated, and image fogging occurs. Etc. may occur easily. When the content is within the more preferable range, it is advantageous in terms of improving image quality and improving fixing stability.

<< Colorant >>
The colorant is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof 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, Anthrazan Yellow BGL, Isoindolinone Yellow, Bengala, Red Tan, Lead Zhu, Cadmium Red, Cadmium Mercury Red, Antimon Zhu, Permanent Red 4R, Para Red, Phisa red, para Lortho Nitroaniline Red, Resol Fast Scarlet G, Brilliant Fast Scarlet, Brilliant Carnmin 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, Tolujing 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, Lazolone Red, Polyazo Red, Chrome Vermilion, Benzidine Orange, Perinone Orange, Oil Orange, Cobalt Blue, Cerulean Blue, Alkaline Blue Lake, Peacock Blue Lake, Victoria Blue Lake, Metal Free Phthalocyanine Blue, Phthalocyanine Blue, Fast Sky Blue, Indance Ren 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, Chrome Oxide, Pyridian, Emerald Green , Pigment Green B, Naphthol Green B, Green Gold, Acid Green Lake, Malachite Grits Enlake, phthalocyanine green, anthraquinone green, titanium oxide, zinc white, lithopone and the like.

The colorant can also be used as a master batch combined with a resin. Examples of the resin to be kneaded with the production of the master batch or the master batch include, in addition to the polyester resin A, styrene such as polystyrene, poly p-chlorostyrene, and polyvinyl toluene, or a polymer of its substitution product; 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-chloromethyl methacrylate copolymer Coalescence, styrene-acrylonitrile Polymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-acrylonitrile-indene copolymer, styrene-maleic acid copolymer, styrene-maleic acid ester copolymer Styrene copolymers such as coalescence; polymethyl methacrylate, polybutyl methacrylate, polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, polyester, epoxy resin, epoxy polyol resin, polyurethane, polyamide, polyvinyl butyral, polyacrylic acid resin, Examples thereof include rosin, modified rosin, terpene resin, aliphatic or alicyclic hydrocarbon resin, aromatic petroleum resin, chlorinated paraffin, and paraffin wax. These may be used individually by 1 type and may use 2 or more types together.
The masterbatch can be obtained by mixing a masterbatch resin and a colorant under high shear force and kneading to obtain a masterbatch. In this case, an organic solvent can be used in order to enhance the interaction between the colorant and the resin. In addition, a so-called flushing method, which is a wet method of colorant, is a method of mixing and kneading an aqueous paste containing water of a colorant together with a resin and an organic solvent, transferring the colorant to the resin side, and removing moisture and organic solvent components. Since the cake can be used as it is, it does not need to be dried and is preferably used. For mixing and kneading, a high shear dispersion device such as a three-roll mill is preferably used.
There is no restriction | limiting in particular as content of the said coloring agent, Although it can select suitably according to the objective, 1 mass part-15 mass parts are preferable with respect to 100 mass parts of said toners, and 3 mass parts-10 parts. Part by mass is more preferable.

<< Charge Control Agent >>
The charge control agent is not particularly limited and may be appropriately selected depending on the intended purpose.For example, 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), alkylamides, phosphorus simple substances or compounds, tungsten simple substances or compounds, fluorine activators, salicylic acid metal salts, metal salts of salicylic acid derivatives, etc. Is mentioned. 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 phenol-based condensate (above, manufactured by Orient Chemical Co., Ltd.), TP-302, TP-415 of quaternary ammonium salt molybdenum complex (above, manufactured by Hodogaya Chemical Co., Ltd.), LRA- 901, boron complex LR-147 (manufactured by Nippon Carlit Co., Ltd.), copper phthalocyanine, perylene, quinacridone, azo pigment, other polymer compounds having functional groups such as sulfonic acid group, carboxyl group, quaternary ammonium salt Etc.
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 parts by mass to 10 parts by mass with respect to 100 parts by mass of the toner. 2 mass parts-5 mass parts are more preferable. When the content exceeds 10 parts by mass, the chargeability of the toner is too large, the effect of the main charge control agent is reduced, the electrostatic attraction force with the developing roller is increased, and the flowability of the developer is reduced. The image density may be reduced. These charge control agents can be dissolved and dispersed after being melt-kneaded with a masterbatch and resin, or of course, may be added when directly dissolving or dispersing in an organic solvent, or may be fixed on the toner surface after preparation of toner particles. May be.

<< External additive >>
As the external additive, in addition to oxide fine particles, inorganic fine particles and hydrophobized inorganic particles can be used in combination, but the average particle size of the hydrophobized primary particles is preferably 1 nm to 100 nm, and 5 nm 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 primary particles subjected to the hydrophobization treatment is contained, and at least one kind of inorganic fine particles having a diameter of 30 nm or more is contained.
In addition, the specific surface area by BET method ^is preferably 20m ² / g~500m 2 / g.
There is no restriction | limiting in particular as said external additive, According to the objective, it can select suitably. Examples thereof include silica fine particles, hydrophobic silica, fatty acid metal salts (such as zinc stearate and aluminum stearate), metal oxides (such as titania, alumina, tin oxide, and antimony oxide), 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.). Moreover, as titania fine particles, for example, P-25 (manufactured by Nippon Aerosil Co., Ltd.), STT-30, STT-65C-S (both manufactured by Titanium Industry Co., Ltd.), TAF-140 (manufactured by Fuji Titanium Industry Co., Ltd.), MT-150W, MT-500B, MT-600B, MT-150A (all manufactured by Teika Co., Ltd.) and the like can be mentioned.
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- Examples include 1500T (all manufactured by Fuji Titanium Industry Co., Ltd.), MT-100S, MT-100T (all manufactured by Teika Co., Ltd.), IT-S (manufactured 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, hydrophilic fine particles such as methyltrimethoxysilane and methyltriethoxysilane. It can be obtained by treatment 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. Examples include 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, and α-methylstyrene-modified silicone oil.
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, Examples include wollastonite, 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.
There is no restriction | limiting in particular as an 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 nm or more and 70 nm or less are more preferable. If it is smaller than this range, the inorganic fine particles are buried in the toner, and the function is hardly exhibited effectively. On the other hand, if it is larger than this range, the surface of the photoreceptor is undesirably damaged.
There is no restriction | limiting in particular as content of the said external additive, Although it can select suitably according to the objective, 0.1 mass part-5 mass parts are preferable with respect to 100 mass parts of the said toner. 3 mass parts-3 mass parts are more preferable.

<< Flowability improver >>
The fluidity improver is not particularly limited as long as it is surface-treated to increase hydrophobicity and prevent deterioration of flow characteristics and charging characteristics even under high humidity, and is appropriately selected according to the purpose. can do. For example, a silane coupling agent, a silylating agent, a silane coupling agent having a fluorinated alkyl group, an organic titanate coupling agent, an aluminum coupling agent, silicone oil, modified silicone oil and the like can be mentioned. It is particularly preferable that the silica and the titanium oxide are surface-treated with such a fluidity improver and used as hydrophobic silica and 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 photosensitive member or the primary transfer medium, and is appropriately selected according to the purpose. 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 μm 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, magnetite, a ferrite, etc. are mentioned. Among these, white is preferable in terms of color tone.

<Glass transition temperature [Tg1st (toner)]>
The toner preferably has a glass transition temperature [Tg1st (toner)] of 20 ° C. or more and 50 ° C. or less at the first temperature increase in differential scanning calorimetry (DSC).
In the case of a conventional toner, when the Tg is about 50 ° C. or less, toner aggregation is likely to occur due to temperature changes in the summer environment and the tropical region during transportation of the toner and in a storage environment.
As a result, solidification in the toner bottle and fixation of the toner in the developing machine occur. Also, 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.
Even if the toner of the present invention has a Tg lower than that of the conventional toner, if the polyester resin B, which is a low Tg component in the toner, is non-linear, the toner of the present invention retains heat-resistant storage stability. be able to. In particular, when the polyester resin B has a urethane bond or a urea bond having a high cohesive force, the effect of maintaining the heat-resistant storage stability becomes more remarkable.
When [Tg1st (toner)] is less than 20 ° C., heat resistance storage stability, blocking in the developing machine, and filming on the photoreceptor may occur. Low temperature fixability may be reduced.
There is no restriction | limiting in particular as melting | fusing point of the said toner, According to the objective, it can select suitably. 60 degreeC or more and 80 degrees C or less are preferable.
The volume average particle diameter of the toner is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 3 μm or more and 7 μm or less. The ratio of the volume average particle diameter to the number average particle diameter is preferably 1.2 or less. Further, it is preferable to contain 1% by number or more and 10% by number or less of a component having a volume average particle diameter of 2 μm or less.

<Calculation method and analysis method of various characteristics of toner and toner component>
The Tg, acid value, hydroxyl value, molecular weight, and melting point of the polyester resin B, the polyester resin A, the crystalline polyester resin C, and the release agent may be measured on their own. Further, by separating the actual toner by gel permeation chromatography (GPC) or the like and applying the analysis method described later for each separated component, the Tg, molecular weight, melting point, and mass ratio of the constituent components can be calculated. Good.
Separation of each component by GPC can be performed, for example, by the following method.
In GPC measurement using THF (tetrahydrofuran) 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 surface 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 THF, and 1H-NMR measurement is performed. From the integration ratio of each element, the composition of the resin in the eluted component The monomer ratio is calculated.
Another method is to calculate the constituent monomer ratio by concentrating the eluate, hydrolyzing with sodium hydroxide, etc., and performing qualitative quantitative analysis of the decomposition products using high performance liquid chromatography (HPLC). In this case, check the compatibility with the values obtained by the 1H-NMR measurement method in advance, or if there is a difference between the two values, check the conversion table between the differences. Is preferred.
In the case where the toner manufacturing method forms toner base particles while generating the amorphous polyester resin A by an extension reaction and / or a branching reaction between the nonlinear reactive precursor and the curing agent. Alternatively, the Tg of the polyester resin B may be obtained by separating the actual toner by GPC or the like. Alternatively, an amorphous polyester resin A is synthesized by an elongation reaction and / or a branching reaction between the nonlinear reactive precursor and the curing agent, and Tg and the like are measured from the synthesized amorphous polyester resin A. May be.

<< Toner component separation means >>
An example of the separation means for each component when analyzing the toner will be described in detail.
First, 1 g of toner is put into 100 mL of THF, and a solution in which the soluble components are dissolved is obtained while stirring for 30 minutes at 25 ° C.
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 discharge port 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 5 mm diameter glass tube for NMR measurement, 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 polyester resin B, the polyester resin A, and the crystalline polyester resin C contained in the toner can be obtained from the peak integration ratio of the obtained spectrum.
For example, peak assignment is performed as follows, and the component ratio of the constituent monomer is determined from each integral ratio.
The attribution of the peak is, for example,
Near 8.25 ppm: derived from benzene ring of trimellitic acid (for one hydrogen),
8.07 ppm to around 8.10 ppm: derived from benzene ring of terephthalic acid (for 4 hydrogens),
7.1 ppm to around 7.25 ppm: derived from benzene ring of bisphenol A (for 4 hydrogens),
Around 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 ppm to around 5.4 ppm: derived from methine of bisphenol A propylene oxide adduct (one hydrogen),
3.7 ppm to around 4.7 ppm: 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),
It can be.
From these results, for example, the extract recovered in the fraction in which the polyester resin B accounts for 90% or more can be treated as the polyester resin B.
Similarly, the extract recovered in the fraction in which the polyester resin A accounts for 90% or more can be treated as the polyester resin A. The extract recovered in the fraction in which the crystalline polyester resin C accounts for 90% or more can be handled as the crystalline polyester resin C.

<< Method for measuring hydroxyl value and acid value >>
The hydroxyl value can be measured using a method based on JIS K0070-1966.
Specifically, first, 0.5 g of a sample is precisely weighed into a 100 mL volumetric flask, and 5 mL of an acetylating reagent is added thereto. Next, after heating in a 100 ± 5 ° C. warm bath for 1 to 2 hours, the flask is removed from the warm bath and allowed to cool. Furthermore, water is added and shaken to decompose acetic anhydride. Next, in order to completely decompose acetic anhydride, the flask is again heated in a warm bath for 10 minutes or more and allowed to cool, and then the wall of the flask is thoroughly washed with an organic solvent.
Furthermore, the hydroxyl value was measured at 23 ° C. using an automatic potentiometric titrator DL-53 Titator (manufactured by METTLER TOLEDO) and electrode DG113-SC (manufactured by METTLER TOLEDO), and analysis software LabX Light Version 1.00 Analyze using .000.
For calibration of the apparatus, a mixed solvent of 120 mL of toluene and 30 mL of ethanol is used.
At this time, the measurement conditions are as follows.
〔Measurement condition〕
Still
Speed [%] 25
Time [s] 15
EQP titration
Titrant / Sensor
Titrant CH3ONa
Concentration [mol / L] 0.1
Sensor DG115
Unit of measurement mV
Predispensing to volume
Volume [mL] 1.0
Wait time [s] 0
Titrant addition Dynamic
dE (set) [mV] 8.0
dV (min) [mL] 0.03
dV (max) [mL] 0.5
Measurement mode Equilibrium controlled
dE [mV] 0.5
dt [s] 1.0
t (min) [s] 2.0
t (max) [s] 20.0
Recognition
Threshold 100.0
Steppes jump only No
Range No
Tendency None
Termination
at maximum volume [mL] 10.0
at potential No
at slope No
after number EQPs Yes
n = 1
comb. termination conditions No
Evaluation
Procedure Standard
Potential1 No
Potentialial No
Stop for revaluation No
The acid value can be measured using a method based on JIS K0070-1992.
Specifically, first, 0.5 g of a sample (0.3 g in the case where ethyl acetate is soluble) is added to 120 mL of toluene and dissolved by stirring at 23 ° C. for about 10 hours. Next, 30 mL of ethanol is added to prepare a sample solution. When the sample does not dissolve, a solvent such as dioxane or tetrahydrofuran is used. Furthermore, an acid value was measured at 23 ° C. using an automatic potentiometric titrator DL-53 Titator (manufactured by METTLER TOLEDO) and electrode DG113-SC (manufactured by METTLER TOLEDO), and analysis software LabX Light Version 1.00 Analyze using .000. For calibration of the apparatus, a mixed solvent of 120 mL of toluene and 30 mL of ethanol is used.
At this time, the measurement conditions are the same as in the case of the hydroxyl value described above.
The acid value can be measured as described above. Specifically, titration is performed with a 0.1N potassium hydroxide / alcohol solution standardized in advance, and the acid value [mg KOH / g] = The acid value is calculated by titration [mL] × N × 56.1 [mg / mL] / sample [g] (where N is a factor of 0.1 N potassium hydroxide / alcohol solution).

<< Measurement Method of Melting Point and Glass Transition Temperature (Tg) >>
The melting point and glass transition temperature (Tg) in the present invention can be measured using, for example, a DSC system (differential scanning calorimeter) (“Q-200”, manufactured by TA Instruments).
Specifically, the melting point and glass transition temperature of the target sample 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 decreased from 150 ° C. to −80 ° C. at a temperature decrease rate of 10 ° C./min, and further heated to 150 ° C. at a temperature increase rate of 10 ° C./min (second temperature increase). In each of the first temperature increase and the second temperature increase, the 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 glass transition temperature 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 glass transition temperature at the second temperature increase of the target sample 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, a 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 this specification, when the 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 this specification, the polyester resin B, the polyester resin A, the crystalline polyester resin C, and the glass transition temperature and the melting point of other components such as the release agent are the second time unless otherwise specified. The endothermic peak top temperature and Tg at the time of temperature rise are defined as the melting point and Tg of each target sample.

<< Measurement Method of Particle Size Distribution >>
For the volume average particle diameter (D4) and number average particle diameter (Dn) of the toner, the ratio (D4 / Dn) is, for example, Coulter Counter TA-II, Coulter Multisizer II (both manufactured by Coulter Co., Ltd.), etc. Can be measured. In the present invention, Coulter Multisizer II is used. The measurement method is described below.
First, 0.1 mL to 5 mL of a surfactant (preferably polyoxyethylene alkyl ether (nonionic surfactant)) as a dispersant is added to 100 mL 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. Here, 2 mg to 20 mg of a measurement sample is further added. The electrolytic aqueous solution in which the sample is suspended is subjected to a dispersion treatment with an ultrasonic disperser for about 1 to 3 minutes, and the measurement device is used to measure the volume and number of toner particles or toner using a 100 μm aperture as the aperture. Calculate volume distribution and 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.

<< Measurement of molecular weight >>
The molecular weight of each component of the toner can be measured, for example, by the following method.
Gel permeation chromatography (GPC) measuring device: GPC-8220GPC (manufactured by Tosoh Corporation)
Column: TSKgel SuperHZM-H 15 cm triple (manufactured by Tosoh Corporation)
Temperature: 40 ° C
Solvent: THF
Flow rate: 0.35 mL / min
Sample: 0.4 mL injection of 0.15% by mass sample Pretreatment of sample: Toner was dissolved in tetrahydrofuran THF (made by Wako Pure Chemical Industries, Ltd.) at 0.15% by mass and filtered through a 0.2 μm filter. The filtrate is used as a sample.
100 μL of the THF sample solution is injected and measured. In 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.

<Toner production method>
There is no restriction | limiting in particular as a manufacturing method of the said toner, According to the objective, it can select suitably. The toner includes, for example, polyester resin B, polyester resin A, and crystalline polyester resin C, and if necessary, an oil phase containing the release agent, the colorant, and the like is dispersed in an aqueous medium. Is preferably granulated.
The toner includes the nonlinear reactive precursor, the polyester resin A, and the crystalline polyester resin C. If necessary, the toner further includes the curing agent, the release agent, and the colorant. It is preferable that the oil phase is granulated by dispersing it in an aqueous medium.
An example of such a method for producing the toner is a known dissolution suspension method.
As an example of the method for producing the toner, a method of forming toner base particles while producing a polyester resin B by an elongation reaction and / or a branching reaction between the non-linear reactive precursor and the curing agent is described below. Show. In such a 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. The amount of the resin particles added to the aqueous medium is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 0.5 parts by mass to 10 parts by mass with respect to 100 parts by mass of the aqueous medium. .
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 oil phase containing the toner material is prepared by including at least the non-linear reactive precursor, the polyester resin A, and the crystalline polyester resin C, and if necessary, the curing agent and the release agent. It can be carried out by dissolving or dispersing a toner material containing a mold agent, the colorant and the like in an organic solvent.
There is no restriction | limiting in particular as said organic solvent, According to the objective, it can select suitably.
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 the toner material is emulsified or dispersed, the curing resin and the non-linear reactive precursor are subjected to an extension reaction and / or a branch reaction to produce a polyester resin B.

The polyester resin B can be produced by, for example, 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 A method of producing polyester resin B by subjecting to elongation reaction and / or branching 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 polyester resin B by subjecting the body to an elongation reaction and / or a branching 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. A method of producing a polyester resin B by subjecting the non-linear reactive precursor to an extension reaction and / or a branch reaction.

When the curing agent and the non-linear reactive precursor are subjected to an extension reaction and / or a branch reaction from the particle interface, the polyester resin B is preferentially formed on the surface of the produced toner, and the polyester is contained in the toner. A concentration gradient of the resin B can also be provided.
The reaction conditions (reaction time, reaction temperature) for producing the polyester resin B are not particularly limited and may be appropriately selected according to the combination of the curing agent and the non-linear reactive precursor. Can do.
There is no restriction | limiting in particular as said reaction time, Although it can select suitably according to the objective, 10 minutes-40 hours are preferable, and 2 hours-24 hours are more preferable.
There is no restriction | limiting in particular as said reaction temperature, Although it can select suitably according to the objective, 0 to 150 degreeC is preferable and 40 to 98 degreeC is more preferable.
The method for stably forming the dispersion containing the non-linear reactive precursor in the aqueous medium is not particularly limited and may be appropriately selected depending on the intended purpose. For example, the aqueous medium phase Examples thereof include a method in which an oil phase prepared by dissolving or dispersing a toner material in a solvent is added and dispersed by shearing force.
The disperser for the dispersion is not particularly limited and can be appropriately selected according to the purpose. For example, a low-speed shear disperser, a high-speed shear disperser, a friction disperser, and a high-pressure jet disperser. And an ultrasonic disperser.
Among these, a high-speed shearing disperser is preferable in that the particle diameter of the dispersion (oil droplets) can be controlled to 2 μm 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.
There is no restriction | limiting in particular as said rotation speed, Although it can select suitably according to the objective, 1,000 rpm-30,000 rpm are preferable, and 5,000 rpm-20,000 rpm are more preferable.
There is no restriction | limiting in particular as said dispersion | distribution time, Although it can select suitably according to the objective, In the case of a batch system, 0.1 minute-5 minutes are preferable.
There is no restriction | limiting in particular as said dispersion | distribution temperature, Although it can select suitably according to the objective, 0 degreeC-150 degreeC is preferable under pressure, and 40 degreeC-98 degreeC is more preferable. 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 50 mass parts to 100 mass parts of the toner material. 2,000 parts by mass is preferable, and 100 parts by mass to 1,000 parts by mass 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, and the amount exceeds 2,000 parts by mass. The production cost may increase.
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 as said dispersing agent, According to the objective, it can select suitably. For example, surfactants, sparingly water-soluble inorganic compound dispersants, polymeric protective colloids and the like can be 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, an anionic surfactant, a cationic surfactant, a nonionic surfactant, an amphoteric surfactant and the like can be used.
There is no restriction | limiting in particular as said anionic surfactant, According to the objective, it can select suitably, For example, alkylbenzene sulfonate, (alpha) -olefin sulfonate, phosphate ester etc. are mentioned.
Among these, those having a fluoroalkyl group are preferable.
A catalyst can be used for the elongation reaction and / or branching reaction when the polyester resin B is produced.
The catalyst is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include dibutyltin laurate and dioctyltin laurate.

<< 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, Examples include a method of evaporating the organic solvent, and a method of removing the organic solvent in the oil droplets by spraying the dispersion into 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.
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 can be appropriately selected depending on the purpose. For example, a method for applying the impact force to the mixture using blades rotating at high speed, For example, a method may be used in which the mixture is charged and accelerated to cause the particles or particles to collide with an appropriate collision plate.
The apparatus used in the above method is not particularly limited and may be appropriately selected depending on the purpose. And 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 that supports an increase in information processing speed in recent years, the lifetime is shortened. A two-component developer is preferred because it improves.
When the developer is used as a one-component developer, even if the balance of the toner is performed, there is little fluctuation in the toner particle diameter, and the filming of the toner on the developing roller and a member such as a blade for thinning the toner The toner is less fused to the toner, 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, even if the toner balance for a long period of time is performed, the fluctuation of the toner particle diameter is small, and good and stable developability and images can be obtained even with long-term stirring in the developing device. can get.

<Career>
There is no restriction | limiting in particular as 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 >>
The material for the core material is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include 50 emu / g to 90 emu / g manganese-strontium-based material, 50 emu / g to 90 emu / g manganese- Examples include magnesium-based materials. 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 emu / g to 120 emu / g. In addition, since the impact of the developer in the standing state on the photoconductor can be alleviated and it is advantageous for high image quality, a low-magnetization material such as a copper-zinc system of 30 emu / g to 80 emu / g should be used. Is preferred.
These may be used individually by 1 type and may use 2 or more types together.
There is no restriction | limiting in particular as a volume average particle diameter of the said core material, Although it can select suitably according to the objective, 10 micrometers-150 micrometers are preferable, and 40 micrometers-100 micrometers are more preferable. When the volume average particle diameter is less than 10 μm, fine powder is increased in the carrier, and magnetization per particle may be reduced to cause scattering of the carrier. In the case of a full color with many solid portions, reproduction of the solid portions may be deteriorated.
When the toner is used for a two-component developer, it may be used by mixing with the carrier. The content of the carrier in the two-component developer is not particularly limited and may be appropriately selected depending on the intended purpose. It is 90 to 98 parts by mass with respect to 100 parts by mass of the two-component developer. Part is preferable, and 93 parts by mass to 97 parts by mass is more preferable.
The developer of the present invention can be suitably used for image formation by various known electrophotographic methods such as a magnetic one-component development method, a non-magnetic one-component development method, and a two-component development method.

(Developer container)
The developer container according to the present invention contains the developer according to the present invention. However, the container is not particularly limited and can be appropriately selected from known ones, but has a container body and a cap. Etc.
In addition, the size, shape, structure, material, etc. of the container body are not particularly limited, but the shape is preferably cylindrical, etc., spiral irregularities are formed on the inner peripheral surface, and by rotating, It is particularly preferable that the developer as the contents can move to the discharge port side, and that some or all of the spiral irregularities have a bellows function. Furthermore, the material is not particularly limited, but is preferably one having good dimensional accuracy. For example, polyester resin, polyethylene resin, polypropylene resin, polystyrene resin, polyvinyl chloride resin, polyacrylic acid, polycarbonate resin, ABS resin, Examples thereof include resin materials such as polyacetal resin.
Since the developer container is easy to store and transport and has excellent handleability, the developer container can be detachably attached to a process cartridge, an image forming apparatus, etc., which will be described later, and used for replenishing the developer.

(Image forming apparatus and image forming method)
The image forming apparatus of the present invention includes at least an electrostatic latent image carrier, an electrostatic latent image forming unit, and a developing unit, and further includes other units as necessary.
The image forming method according to the present invention includes at least an electrostatic latent image forming step and a developing step, and further includes other steps as necessary.
The image forming method can be preferably performed by the image forming apparatus, the electrostatic latent image forming step can be preferably performed by the electrostatic latent image forming unit, and the developing step can be performed by the developing unit. The other steps can be preferably performed by the other means.

<Electrostatic latent image carrier>
The material, structure, and size of the electrostatic latent image carrier are not particularly limited and may be appropriately selected from known materials. Examples of the material include inorganic photoreceptors such as amorphous silicon and selenium. And organic photoreceptors such as polysilane and phthalopolymethine. Among these, amorphous silicon is preferable in terms of long life.
As the amorphous silicon photoreceptor, for example, a support is heated to 50 ° C. to 400 ° C., and a vacuum deposition method, a sputtering method, an ion plating method, thermal CVD (chemical vapor deposition, Chemical Vapor Deposition) is formed on the support. ), A photo-CVD method, a plasma CVD method, or other film forming methods can be used to provide a photoconductor having a photoconductive layer made of a-Si. Among these, a plasma CVD method, that is, a method in which a source gas is decomposed by direct current, high frequency or microwave glow discharge to form an a-Si deposited film on a support is preferable.
There is no restriction | limiting in particular as a shape of the said electrostatic latent image carrier, Although it can select suitably according to the objective, A cylindrical shape is preferable. The outer diameter of the cylindrical electrostatic latent image carrier is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 3 mm to 100 mm, more preferably 5 mm to 50 mm, and more preferably 10 mm to 30 mm. Particularly preferred.

<Electrostatic latent image forming means and electrostatic latent image forming step>
The electrostatic latent image forming means is not particularly limited as long as it is a means for forming an electrostatic latent image on the electrostatic latent image carrier, and can be appropriately selected according to the purpose. Examples thereof include at least a charging member that charges the surface of the electrostatic latent image carrier and an exposure member that exposes the surface of the electrostatic latent image carrier imagewise.
The electrostatic latent image forming step is not particularly limited as long as it is a step of forming an electrostatic latent image on the electrostatic latent image carrier, and can be appropriately selected according to the purpose. After the surface of the electrostatic latent image carrier is charged, the imagewise exposure can be performed, and the electrostatic latent image forming unit can be used.

<< Charging member and charging >>
The charging member is not particularly limited and may be appropriately selected depending on the purpose. For example, a known contact charger including a conductive or semiconductive roller, brush, film, rubber blade, etc. And non-contact chargers utilizing corona discharge such as corotron and scorotron.
The charging can be performed, for example, by applying a voltage to the surface of the electrostatic latent image carrier using the charging member.
The shape of the charging member may take any form such as a magnetic brush or a fur brush in addition to a roller, and can be selected according to the specifications and form of the image forming apparatus.
The charging member is not limited to the contact-type charging member, but it is preferable to use a contact-type charging member because an image forming apparatus in which ozone generated from the charging member is reduced can be obtained.

<< Exposure member and exposure >>
The exposure member is not particularly limited and may be appropriately selected depending on the purpose, as long as the surface of the electrostatic latent image carrier charged by the charging member can be exposed like an image to be formed. Examples thereof include various exposure members such as a copying optical system, a rod lens array system, a laser optical system, and a liquid crystal shutter optical system.
There is no restriction | limiting in particular as a light source used for the said exposure member, According to the objective, it can select suitably, For example, a fluorescent lamp, a tungsten lamp, a halogen lamp, a mercury lamp, a sodium lamp, a light emitting diode (LED), a semiconductor laser General light emitting materials such as (LD) and electroluminescence (EL).
In addition, various types of filters such as a sharp cut filter, a band pass filter, a near infrared cut filter, a dichroic filter, an interference filter, and a color temperature conversion filter can be used to irradiate only light in a desired wavelength range.
The exposure can be performed, for example, by exposing the surface of the latent electrostatic image bearing member imagewise using the exposure member.
In the present invention, a back light system in which imagewise exposure is performed from the back side of the electrostatic latent image carrier may be employed.

<Developing means and development process>
The developing unit is not particularly limited as long as it is a developing unit including toner that develops the electrostatic latent image formed on the electrostatic latent image carrier to form a visible image. Can be selected as appropriate.
The development step is not particularly limited as long as it is a step of developing the latent electrostatic image formed on the latent electrostatic image bearing member with toner to form a visible image. For example, it can be carried out by the developing means.
The developing means may be of a dry development type or a wet development type. Further, it may be a single color developing means or a multicolor developing means.
The developing means includes a stirrer for charging the toner by frictional stirring and a magnetic field generating means fixed inside, and a developer carrying that can carry and rotate the developer containing the toner on the surface. A developing device having a body is preferred.
In the developing means, for example, the toner and the carrier are mixed and stirred, and the toner is charged by friction at that time, and held on the surface of the rotating magnet roller in a raised state, thereby forming a magnetic brush. . The magnet roller is disposed in the vicinity of the electrostatic latent image carrier. Therefore, a part of the toner constituting the magnetic brush formed on the surface of the magnet roller moves to the surface of the electrostatic latent image carrier by an electric attractive force. As a result, the electrostatic latent image is developed with the toner, and a visible image is formed with the toner on the surface of the electrostatic latent image carrier.

<Other means and other processes>
Examples of the other means include a transfer means, a fixing means, a cleaning means, a static elimination means, a recycling means, and a control means.
Examples of the other processes include a transfer process, a fixing process, a cleaning process, a static elimination process, a recycling process, and a control process.

<< Transfer means and transfer process >>
The transfer means is not particularly limited as long as it is a means for transferring a visible image to a recording medium, and can be appropriately selected according to the purpose. However, the visible image is transferred onto an intermediate transfer member and combined. An embodiment having a primary transfer unit for forming a transfer image and a secondary transfer unit for transferring the composite transfer image onto a recording medium is preferable.
The transfer step is not particularly limited as long as it is a step of transferring a visible image to a recording medium, and can be appropriately selected according to the purpose. However, an intermediate transfer member is used, and the transfer step can be performed on the intermediate transfer member. It is preferable that the visual image is firstly transferred and then the visible image is secondarily transferred onto the recording medium.
The transfer step can be performed by, for example, charging the visible image using a transfer charger and the transfer unit.
Here, when the image to be secondarily transferred onto the recording medium is a color image composed of a plurality of colors of toner, the toner of each color is sequentially superimposed on the intermediate transfer member by the transfer means. An image can be formed on the body, and the image on the intermediate transfer body can be collectively transferred onto the recording medium by the intermediate transfer unit.
The intermediate transfer member is not particularly limited and can be appropriately selected from known transfer members according to the purpose. For example, a transfer belt and the like are preferable.
The transfer unit (the primary transfer unit and the secondary transfer unit) preferably includes at least a transfer unit that peels and charges the visible image formed on the photoconductor toward the recording medium. Examples of the transfer device include a corona transfer device using corona discharge, a transfer belt, a transfer roller, a pressure transfer roller, and an adhesive transfer device.
The recording medium is typically plain paper, but is not particularly limited as long as it can transfer an unfixed image after development, and can be appropriately selected according to the purpose. A PET base or the like can also be used.

<< Fixing means and fixing process >>
The fixing unit is not particularly limited as long as it is a unit that fixes the transferred image transferred to the recording medium, and can be appropriately selected according to the purpose. However, a known heating and pressing member is preferable. Examples of the heating and pressing member include a combination of a heating roller and a pressing roller, and a combination of a heating roller, a pressing roller, and an endless belt.
The fixing step is not particularly limited as long as it is a step of fixing the visible image transferred to the recording medium, and can be appropriately selected according to the purpose. For example, the recording medium for each color toner May be performed every time the toner is transferred to the toner image, or may be performed simultaneously at the same time in a state where the toners of the respective colors are stacked.
The fixing step can be performed by the fixing unit.
The heating in the heating and pressing member is usually preferably 80 ° C to 200 ° C.
In the present invention, for example, a known optical fixing device may be used together with or in place of the fixing unit depending on the purpose.
The surface pressure in the fixing step is not particularly limited and may be appropriately selected depending on the intended ^purpose, is preferably ^{10N / cm 2 ~80N / cm 2} .

<< Cleaning means and cleaning process >>
The cleaning means is not particularly limited as long as it can remove the toner remaining on the photoreceptor, and can be appropriately selected according to the purpose. For example, a magnetic brush cleaner, an electrostatic brush cleaner, Examples thereof include a magnetic roller cleaner, a blade cleaner, a brush cleaner, and a web cleaner.
The cleaning step is not particularly limited as long as it can remove the toner remaining on the photoreceptor, and can be appropriately selected according to the purpose. For example, the cleaning step can be performed by the cleaning unit.

<< Static elimination means and static elimination process >>
The neutralizing means is not particularly limited as long as it is a means for neutralizing by applying a neutralizing bias to the photosensitive member, and can be appropriately selected according to the purpose. Examples thereof include a neutralizing lamp.
The neutralization step is not particularly limited as long as it is a step of neutralizing by applying a neutralization bias to the photoconductor, and can be appropriately selected according to the purpose. For example, it can be performed by the neutralization unit. .

<< Recycling means and recycling process >>
The recycling unit is not particularly limited as long as it is a unit that causes the developing device to recycle the toner removed in the cleaning step, and can be appropriately selected depending on the purpose. Can be mentioned.
The recycling process is not particularly limited as long as it is a process for recycling the toner removed in the cleaning process to the developing device, and can be appropriately selected according to the purpose. For example, the recycling unit performs the recycling process. Can do.

<< Control means and control process >>
The control means is not particularly limited as long as it can control the movement of each means, and can be appropriately selected according to the purpose. Examples thereof include devices such as a sequencer and a computer.
The control process is not particularly limited as long as it can control the movement of each process, and can be appropriately selected according to the purpose. For example, the control process can be performed by the control means.

Next, one mode for carrying out the method of forming an image by the image forming apparatus of the present invention will be described with reference to FIG. A color image forming apparatus 100A shown in FIG. 1 includes a photosensitive drum 10 as the electrostatic latent image carrier (hereinafter also referred to as “photosensitive member 10”), a charging roller 20 as the charging unit, and the An exposure apparatus 30 as an exposure means, a developing device 40 as the development means, an intermediate transfer member 50, a cleaning device 60 as the cleaning means having a cleaning blade, and a static elimination lamp 70 as the static elimination means. .
The intermediate transfer member 50 is an endless belt, and is designed to be movable in the direction of an arrow by three rollers 51 that are arranged inside and stretched. Part of the three rollers 51 also functions as a transfer bias roller that can apply a predetermined transfer bias (primary transfer bias) to the intermediate transfer member 50. A cleaning device 90 having a cleaning blade is disposed in the vicinity of the intermediate transfer member 50. Also, in the vicinity of the intermediate transfer member 50, there is a transfer roller 80 as the transfer means capable of applying a transfer bias for transferring (secondary transfer) a developed image (toner image) onto a transfer sheet 95 as a recording medium. The intermediate transfer member 50 is disposed opposite to the intermediate transfer member 50. Around the intermediate transfer member 50, a corona charger 58 for applying a charge to the toner image on the intermediate transfer member 50 is arranged between the photosensitive member 10 and the intermediate transfer member 50 in the rotation direction of the intermediate transfer member 50. It is disposed between the contact portion and the contact portion between the intermediate transfer member 50 and the transfer paper 95.
The developing device 40 includes a developing belt 41 as the developer carrying member, and a black developing unit 45K, a yellow developing unit 45Y, a magenta developing unit 45M, and a cyan developing unit 45C provided around the developing belt 41. . The black developing unit 45K includes a developer accommodating portion 42K, a developer supply roller 43K, and a developing roller 44K. The yellow developing unit 45Y includes a developer container 42Y, a developer supply roller 43Y, and a developing roller 44Y. The magenta developing unit 45M includes a developer container 42M, a developer supply roller 43M, and a developing roller 44M. The cyan developing unit 45C includes a developer container 42C, a developer supply roller 43C, and a developing roller 44C. Further, the developing belt 41 is an endless belt, is rotatably stretched around a plurality of belt rollers, and a part thereof is in contact with the electrostatic latent image carrier 10.
In the color image forming apparatus 100A shown in FIG. 1, for example, the charging roller 20 charges the photosensitive drum 10 uniformly. The exposure device 30 performs imagewise exposure on the photosensitive drum 10 to form an electrostatic latent image. The electrostatic latent image formed on the photosensitive drum 10 is developed by supplying toner from the developing device 40 to form a toner image. The toner image is transferred (primary transfer) onto the intermediate transfer member 50 by the voltage applied from the roller 51 and further transferred (secondary transfer) onto the transfer paper 95. As a result, a transfer image is formed on the transfer paper 95. The residual toner on the photoconductor 10 is removed by the cleaning device 60, and the charge on the photoconductor 10 is temporarily removed by the charge eliminating lamp 70.

  FIG. 2 shows another example of the image forming apparatus of the present invention. In the image forming apparatus 100B, the black developing unit 45K, the yellow developing unit 45Y, the magenta developing unit 45M, and the cyan developing unit 45C are arranged directly facing each other around the photosensitive drum 10 without providing the developing belt 41. Other than this, the configuration is the same as that of the image forming apparatus 100A shown in FIG.

FIG. 3 shows another example of the image forming apparatus of the present invention. The image forming apparatus shown in FIG. 3 includes a copying apparatus main body 150, a paper feed table 200, a scanner 300, and an automatic document feeder (ADF) 400.
The copying apparatus main body 150 is provided with an endless belt-like intermediate transfer member 50 at the center. The intermediate transfer member 50 is stretched around the support rollers 14, 15 and 16, and can be rotated clockwise in FIG. 3. An intermediate transfer member cleaning device 17 for removing residual toner on the intermediate transfer member 50 is disposed in the vicinity of the support roller 15. The intermediate transfer member 50 stretched between the support roller 14 and the support roller 15 is a tandem type in which four image forming units 18 of yellow, cyan, magenta, and black are arranged to face each other along the conveyance direction. A developing device 120 is disposed. In the vicinity of the tandem developing device 120, an exposure device 21 as the exposure member is disposed. A secondary transfer device 22 is disposed on the side of the intermediate transfer member 50 opposite to the side on which the tandem developing device 120 is disposed. In the secondary transfer device 22, a secondary transfer belt 24, which is an endless belt, is stretched around a pair of rollers 23, and the transfer paper conveyed on the secondary transfer belt 24 and the intermediate transfer body 50 are in contact with each other. Is possible. In the vicinity of the secondary transfer device 22, a fixing device 25 as the fixing means is arranged. The fixing device 25 includes a fixing belt 26 that is an endless belt, and a pressure roller 27 that is pressed against the fixing belt 26.
In the tandem image forming apparatus, a sheet reversing device 28 for reversing the transfer paper for image formation on both sides of the transfer paper is disposed in the vicinity of the secondary transfer device 22 and the fixing device 25. .

Next, formation of a full-color image (color copy) using the tandem developing device 120 will be described. That is, first, a document is set on the document table 130 of the automatic document feeder (ADF) 400, or the automatic document feeder 400 is opened and the document is set on the contact glass 32 of the scanner 300. 400 is closed.
When a start switch (not shown) is pressed, when the document is set on the automatic document feeder 400, the document is transported and moved onto the contact glass 32, and then the document is set on the contact glass 32. Immediately after that, the scanner 300 is driven. Then, the first traveling body 33 and the second traveling body 34 travel. At this time, light from the light source is irradiated by the first traveling body 33 and reflected light from the document surface is reflected by the mirror in the second traveling body 34 and is received by the reading sensor 36 through the imaging lens 35 to be color. An original (color image) is read and used as black, yellow, magenta, and cyan image information.
Each image information of black, yellow, magenta, and cyan is stored in each image forming unit 18 (black image forming unit, yellow image forming unit, magenta image forming unit, and cyan image) in the tandem developing device 120. Forming means). In each image forming unit, black, yellow, magenta, and cyan toner images are formed. That is, each image forming means 18 (black image forming means, yellow image forming means, magenta image forming means, and cyan image forming means) in the tandem type developing device 120 is a static image as shown in FIG. An electrostatic latent image carrier 10 (black electrostatic latent image carrier 10K, yellow electrostatic latent image carrier 10Y, magenta electrostatic latent image carrier 10M, and cyan electrostatic latent image carrier 10C); The electrostatic latent image carrier 10 is exposed to each color image corresponding to each color image based on each color image information, with the charging device 160 as the charging means for uniformly charging the electrostatic latent image carrier 10 (FIG. 4). L), and an exposure device for forming an electrostatic latent image corresponding to each color image on the electrostatic latent image carrier, and the electrostatic latent image for each color toner (black toner, yellow toner, magenta toner). And cyan tona ), A developing device 61 as the developing means for forming a toner image with each color toner, a transfer charger 62 for transferring the toner image onto the intermediate transfer member 50, a cleaning device 63, The static eliminator 64 is provided. Each image forming unit 18 can form each monochrome image (black image, yellow image, magenta image, and cyan image) based on the image information of each color. The black image, the yellow image, the magenta image, and the cyan image formed in this way are respectively transferred to the black electrostatic latent image carrier 10K on the intermediate transfer member 50 that is rotationally moved by the support rollers 14, 15, and 16. Black image formed on top, yellow image formed on electrostatic latent image carrier 10Y for yellow, magenta image formed on electrostatic latent image carrier 10M for magenta, and electrostatic latent image carrier for cyan The cyan image formed on 10C is sequentially transferred (primary transfer). Then, the black image, the yellow image, the magenta image, and the cyan image are superimposed on the intermediate transfer member 50 to form a composite color image (color transfer image).

On the other hand, in the paper feed table 200, one of the paper feed rollers 142 is selectively rotated to feed out a sheet (recording paper) from one of the paper feed cassettes 144 provided in multiple stages in the paper bank 143. The sheets are separated one by one by the separation roller 145, sent to the paper feed path 146, transported by the transport roller 147, guided to the paper feed path 148 in the copier body 150, and abutted against the registration roller 49 to stop. It is done. Alternatively, the sheet feed roller 142 is rotated to feed out sheets (recording paper) on the manual feed tray 54, separated one by one by the separation roller 52, put into the manual feed path 53, and abutted against the registration roller 49 and stopped. . The registration roller 49 is generally used while being grounded, but may be used in a state where a bias is applied to remove paper dust from the sheet. Then, the registration roller 49 is rotated in synchronization with the synthesized color image (color transfer image) synthesized on the intermediate transfer member 50, and a sheet (recording paper) is interposed between the intermediate transfer member 50 and the secondary transfer device 22. Then, the composite color image (color transfer image) is transferred (secondary transfer) onto the sheet (recording paper) by the secondary transfer device 22. By doing so, a color image is transferred and formed on the sheet (recording paper). The residual toner on the intermediate transfer member 50 after image transfer is cleaned by the intermediate transfer member cleaning device 17.
The sheet (recording paper) on which the color image has been transferred is conveyed by the secondary transfer device 22 and sent to the fixing device 25, where the combined color image (color) is generated by heat and pressure. (Transfer image) is fixed on the sheet (recording paper). Thereafter, the sheet (recording paper) is switched by a switching claw 55 and discharged by a discharge roller 56 and is stacked on a discharge tray 57. Alternatively, the sheet is switched by the switching claw 55 and reversed by the sheet reversing device 28 and guided to the transfer position again. After the image is recorded on the back surface, the sheet is discharged by the discharge roller 56 and stacked on the discharge tray 57. Is done.

(Process cartridge)
The process cartridge according to the present invention is detachably molded in various image forming apparatuses, and includes an electrostatic latent image carrier that carries an electrostatic latent image, and an electrostatic latent image carried on the electrostatic latent image carrier. And at least developing means for forming a toner image by developing with the developer of the present invention. The process cartridge of the present invention may further include other means as necessary.
The developing means includes at least a developer container that contains the developer of the present invention and a developer carrier that carries and conveys the developer contained in the developer container.
The developing means may further include a regulating member or the like for regulating the thickness of the developer carried.

  FIG. 5 shows an example of a process cartridge according to the present invention. The process cartridge 110 includes a photosensitive drum 10, a corona charger 58, a developing device 40, a transfer roller 80, and a cleaning device 90.

Examples of the present invention will be described below, but the present invention is not limited to the following examples. Unless otherwise specified, “part” refers to “part by mass”, and “%” refers to “mass%”.
Each measured value in the following examples was measured by the method described in this specification. In addition, Tg, Tm, and molecular weight, such as polyester resin A, polyester resin B, and crystalline polyester resin, were measured from each resin obtained in the production examples.

(Example A)
<Manufacture of polyester resin A>
<< Synthesis of Polyester Resin A-1 >>
A four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple was added to a bisphenol AF ethylene oxide 2-mole adduct (BisAF-EO) and a bisphenol A propylene oxide 3-mole adduct (BisA-) having the following structure. PO), trimethylolpropane (TMP), terephthalic acid, and adipic acid in a molar ratio (bisphenol AF ethylene), bisphenol AF ethylene oxide 2 mol adduct, bisphenol A propylene oxide 3 mol adduct, and trimethylolpropane. It was 37/55/3/5 in terms of oxide 2 mol adduct / bisphenol A propylene oxide 3 mol adduct / trimethylolpropane / bisphenol AF-EO), and the molar ratio of terephthalic acid to adipic acid (terephthalic acid / adipine) 85) 15 and charged so that OH / COOH, which is the molar ratio of hydroxyl group to carboxyl group, was 1.12, and reacted with titanium tetraisopropoxide (500 ppm with respect to the resin component) at 230 ° C. for 8 hours at normal pressure. Furthermore, after reacting at a reduced pressure of 10 mmHg to 15 mmHg for 4 hours, trimellitic anhydride was added to the reaction vessel so as to be 1 mol% with respect to all resin components, and reacted at 180 ° C. and normal pressure for 3 hours. -1] was obtained. The physical property values are shown in Table 2.

<< Synthesis of Polyester Resin A-2 to A-14 >>
The acid component, alcohol component, OH / COO ratio, F-containing monomer type, F-containing monomer amount, branching component type, and branching component amount are shown in Table 2. Acid component, alcohol component, OH / COO ratio, F-containing monomer type [Polyester Resin A-2] to [Polyester Resin A-14] in the same manner as in the synthesis of [Polyester Resin A-1] except that the amount of F-containing monomer, branching component type, and branching component amount are changed. Obtained. The physical property values are shown in Table 2.
In Table 2, bisphenol AF and 2,2-bis (4-isocyanatophenyl) hexafluoropropane, which are fluorine-containing monomer species, are in mol% or 2,2-bis (4-carboxy) in the alcohol component. Phenyl) hexafluoropropane is in mole percent relative to the acid component. Moreover, the amount of branched components is the mol% of trihydric or higher aliphatic alcohol with respect to the alcohol component.

(Synthesis of ketimine)
170 parts of isophoronediamine 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 of prepolymer B)
<Synthesis of Non-Linear Polyester Resin B-1 (Prepolymer B-1) Having Reactive Group>
In a reaction vessel equipped with a condenser, a stirrer, and a nitrogen introduction tube, 97 mol% of 3-methyl-1,5-pentanediol as an alcohol component, 3 mol% of trimethylolpropane (TMP), and adipine as an acid component The acid was 50 mol% and terephthalic acid 50 mol%, and was added together with titanium tetraisopropoxide (300 ppm to resin component) so that the molar ratio of hydroxyl group to carboxyl group was OH / COOH = 1.1. . 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 mmHg-15 mmHg for 5 hours, and [intermediate polyester B-1] was obtained.
Next, in a reaction vessel equipped with a cooling pipe, a stirrer, and a nitrogen introduction pipe, [middle ratio of intermediate polyester B-1] and isophorone diisocyanate (IPDI) (IPDI isocyanate group / hydroxyl group of intermediate polyester) 2.1, and diluted with ethyl acetate to a 48% ethyl acetate solution, and then reacted at 100 ° C. for 5 hours to produce a non-linear polyester resin B-1 having a reactive group [prepolymer B- 1] was obtained. The number average molecular weight (Mn) of this resin was 5,800, the weight average molecular weight (Mw) was 26,000, and Tg was −5 ° C.

(Production of crystalline polyester resin C)
<Synthesis of Crystalline Polyester Resin C-1>
In a 5 L four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple, sebacic acid and 1,6-hexanediol were mixed with OH / COOH, which is the molar ratio 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-1. The physical property values are shown in Table 2.

[Example 1]
<Manufacture of master batch 1>
1,200 parts of water, carbon black (Printex 35, manufactured by Dexa) [DBP oil absorption = 42 mL / 100 mg, pH = 9.5], 500 parts, and 500 parts of polyester resin A-1 were added. The mixture was kneaded at 150 ° C. for 30 minutes using two rolls, rolled and cooled, and pulverized with a pulverizer to obtain [Masterbatch 1].

<Manufacture of masterbatch 2>
1200 parts by mass of water, 349 parts by mass of CRAYTONE APA manufactured by SCP, and 1400 parts by mass of the above-mentioned [Polyester resin A] are mixed with a Henschel mixer (manufactured by Nihon Coke Industries, Ltd.), and the mixture is used at 150 ° C. using two rolls. After kneading for 30 minutes, it was rolled and cooled, and pulverized with a pulverizer to obtain [Masterbatch 2].

<Synthesis of WAX dispersant>
In an autoclave reaction vessel equipped with a thermometer and a stirrer, 480 parts of xylene and 100 parts of low molecular weight polyethylene (Sanwax 151P manufactured by Sanyo Chemical Industries, Ltd .: melting point 108 ° C., weight average molecular weight 1,000) are sufficiently dissolved. After substitution with nitrogen, a mixed solution of 805 parts of styrene, 50 parts of acrylonitrile, 45 parts of butyl acrylate, 36 parts of di-t-butyl peroxide, and 100 parts of xylene was added dropwise at 170 ° C. for 3 hours for polymerization, and this temperature was further increased. For 30 minutes. Next, the solvent was removed to obtain [WAX dispersant].
The weight average molecular weight of the acrylic resin in the WAX dispersant was 16,000.
The WAX dispersant had a weight average molecular weight of 18,000, a number average molecular weight of 3,300, and a Tg of 65 ° C.

<Preparation of WAX dispersion>
In a container equipped with a stir bar and a thermometer, 300 parts of paraffin wax (manufactured by Nippon Seiki Co., Ltd., HNP-9, hydrocarbon wax, melting point 75 ° C.), 150 parts of [WAX dispersant], and acetic acid 1,800 parts of ethyl was charged, heated to 80 ° C. with stirring, held at 80 ° C. for 5 hours, cooled to 30 ° C. in 1 hour, and using a bead mill (Ultra Visco Mill, manufactured by Imex Corporation), Dispersion was carried out under the conditions of a liquid feed speed of 1 kg / hr, a disk peripheral speed of 6 m / sec, a zirconia bead of 0.5 mm in diameter and 80% by volume filled in 3 passes to obtain [WAX Dispersion 1].

<Preparation of crystalline polyester resin dispersion>
308 parts of crystalline polyester resin C-1 and 1900 parts of ethyl acetate were charged in a container equipped with a stirring bar and a thermometer, heated to 80 ° C. with stirring, held at 80 ° C. for 5 hours, and then for 1 hour. At 30 ° C., and using a bead mill (Ultra Visco Mill, manufactured by Imex Co., Ltd.), a liquid feeding speed of 1 kg / hr, a disk peripheral speed of 6 m / second, 80% by volume of 0.5 mm zirconia beads, 3 pass conditions Then, dispersion was carried out to obtain [Crystalline polyester resin dispersion 1].

<Preparation of oil phase>
[WAX Dispersion 1] 190 parts, [Prepolymer B-1] 32 parts, [Crystalline Polyester Resin Dispersion 1] 290 parts, [Polyester Resin A-1] 65 parts, [Masterbatch 1] 100 parts and [ 0.2 parts of ketimine compound 1] was put in a container and mixed for 60 minutes at 7,000 rpm with a TK homomixer (manufactured by PRIMIX Corporation) to obtain [Oil Phase 1].

<Synthesis of organic fine particle emulsion (fine particle dispersion)>
In a reaction vessel equipped with a stirrer and a thermometer, 683 parts of water, 11 parts of a sodium salt of ethylene oxide methacrylate adduct sulfate (Eleminol RS-30: Sanyo Chemical Industries, Ltd.), 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, and a white emulsion was obtained. The system was heated to raise the system temperature 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 (a copolymer of styrene-methacrylic acid-methacrylic acid ethylene oxide adduct sulfate sodium salt) [fine particles Dispersion 1] was obtained.
The volume average particle size of the [fine particle dispersion 1] measured with LA-920 (manufactured by HORIBA) was 0.14 μm. A portion of [Fine Particle Dispersion 1] was dried to isolate the resin component.

<Preparation of aqueous phase>
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: Sanyo Chemical Industries, Ltd.) and 90 parts of ethyl acetate are mixed and stirred. A milky white liquid was obtained. This was designated as [Aqueous Phase 1].

<Emulsification / desolvation>
1,200 parts of [Aqueous phase 1] was added to a container containing [Oil phase 1], and mixed with a TK homomixer at a rotation speed of 8,000 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,
(1): 100 parts of ion-exchanged water was added to the filter cake, mixed with a TK homomixer (10 minutes at 12,000 rpm), and then filtered.
(2): 100 parts of a 10% aqueous sodium hydroxide solution was added to the filter cake of (1), mixed with a TK homomixer (30 minutes at 12,000 rpm), and then filtered under reduced pressure.
(3): 100 parts of 10% hydrochloric acid was added to the filter cake of (2), mixed with a TK homomixer (rotation speed: 12,000 rpm for 10 minutes), and then filtered.
(4): Add 300 parts of ion exchange water to the filter cake of (3), mix with TK homomixer (10 minutes at 12,000 rpm), and then filter.
The operations (1) to (4) were performed twice to obtain [Filter cake 1].
[Filtration cake 1] was dried at 45 ° C. for 48 hours with a circulating dryer, and sieved with a mesh having an opening of 75 μm to obtain [Mother toner particles 1].
100 parts of the obtained [toner base particles 1], 0.7 part of hydrophobic silica HDK-2000 (manufactured by Asahi Kasei Wacker Silicone) having an average primary particle size of 20 nm, and hydrophobic titanium oxide having an average primary particle size of 20 nm Three parts were mixed using a Henschel mixer (Mitsui Mining Co., Ltd.) to obtain [Toner 1].
Table 2 shows the composition ratio and physical properties of the obtained toner.

[Example 2]
[Toner 2] was obtained in the same manner as in Example 1, except that the oil phase was prepared so as to have the material composition and composition ratio shown in Table 2.

Example 3
[Toner 3] was obtained in the same manner as in Example 1 except that the oil phase was prepared so as to have the material composition and composition ratio shown in Table 2.

Example 4
[Toner 4] was obtained in the same manner as in Example 1 except that the oil phase was prepared so as to have the material composition and composition ratio shown in Table 2.

Example 5
[Toner 5] was obtained in the same manner as in Example 1 except that the oil phase was prepared so as to have the material composition and composition ratio shown in Table 2.

Example 6
[Toner 6] was obtained in the same manner as in Example 1 except that the oil phase was prepared so as to have the material composition and composition ratio shown in Table 2.

Example 7
[Toner 7] was obtained in the same manner as in Example 1 except that the oil phase was prepared so as to have the material composition and composition ratio shown in Table 2.

Example 8
[Toner 8] was obtained in the same manner as in Example 1 except that the oil phase was prepared so as to have the material composition and composition ratio shown in Table 2.

Example 9
[Toner 9] was obtained in the same manner as in Example 1 except that the oil phase was prepared so as to have the material composition and composition ratio shown in Table 2.

Example 10
[Toner 10] was obtained in the same manner as in Example 1 except that the oil phase was prepared so as to have the material composition and composition ratio shown in Table 2.

[Comparative Example 1]
[Toner 11] was obtained in the same manner as in Example 1 except that the oil phase was prepared so as to have the material composition and composition ratio shown in Table 2.

[Comparative Example 2]
A filter cake was obtained in the same manner as in Example 1 except that the oil phase was adjusted to have the material composition and the composition ratio shown in Table 2. Thereafter, N, N, N is added to the toner base in an aqueous solvent tank in which N, N, N-trimethyl- [3- (4-perfluorononenyloxybenzamido) propyl] ammonium iodide is dispersed at a concentration of 1 wt%. -Trimethyl- [3- (4-perfluorononenyloxybenzamido) propyl] ammonium iodide was mixed so as to have a concentration of 0.1 wt., And a fluorine compound was adhered (bonded), followed by 45 ° C. in a circulating dryer. For 48 hours.
Thereafter, the mixture was sieved with a mesh of 75 μm to obtain [toner mother particles 11]. 100 parts of the obtained [toner base particle 11], 0.7 part of hydrophobic silica HDK-2000 (manufactured by Asahi Kasei Wacker Silicone) having an average primary particle diameter of 20 nm, and hydrophobic titanium oxide having an average primary particle diameter of 20 nm Three parts were mixed using a Henschel mixer (Mitsui Mining Co., Ltd.) to obtain [Toner 12].
Table 2 shows the composition ratio and physical properties of the obtained toner.

[Comparative Example 3]
[Toner 13] was obtained in the same manner as in Example 1 except that the oil phase was prepared so as to have the material composition and composition ratio shown in Table 2.

[Comparative Example 4]
[Toner 14] was obtained in the same manner as in Example 1 except that the oil phase was prepared so as to have the material composition and composition ratio shown in Table 2.

<Evaluation>
A developer was prepared for the obtained toner by the following method, and the following evaluation was performed. The results are shown in Table 2.

<< Developer >>
-Production of carrier-
Add 100 parts of silicone resin organostraight silicone, 5 parts of γ- (2-aminoethyl) aminopropyltrimethoxysilane, and 10 parts of carbon black to 100 parts of toluene, disperse with a homomixer for 20 minutes, and apply resin layer A liquid was prepared. Using a fluid bed type coating device, the resin layer coating solution was applied to the surface of 1,000 parts of spherical magnetite having an average particle size of 50 μm to prepare a carrier.

-Production of developer-
Using a ball mill, 5 parts of each toner and 95 parts of the carrier were mixed, and toner Nos. 1 to 10 and toner No. for comparison. Developer Nos. 11 to 14 respectively. 1 to developer No. 1 14 was produced.

<< Low-temperature fixability and high-temperature offset resistance >>
A copying test was performed on type 6200 paper (manufactured by Ricoh Co., Ltd.) using an apparatus obtained by modifying the fixing unit of a copier Imagio MF2200 (manufactured by Ricoh Co., Ltd.) using a Teflon (registered trademark) roller as a fixing roller.
Specifically, the cold offset temperature (fixing lower limit temperature) and the high temperature offset temperature (fixing upper limit temperature) were determined by changing the fixing temperature.
The evaluation conditions for the minimum fixing temperature were a paper feed linear velocity of 120 mm / second to 150 mm / second, a surface pressure of 1.2 kgf / cm ² , and a nip width of 3 mm.
The evaluation conditions for the upper limit fixing temperature were a paper feed linear velocity of 50 mm / sec, a surface pressure of 2.0 kgf / cm ² , and a nip width of 4.5 mm.

<< Heat resistant storage stability >>
The toner was stored at 50 ° C. for 8 hours and then sieved with a 42 mesh sieve for 2 minutes, and the residual rate on the wire mesh was measured. At this time, the toner having better heat-resistant storage stability has a smaller remaining rate.
The evaluation criteria for heat resistant storage stability were as follows.
〔Evaluation criteria〕
A: Residual rate is less than 10%.
○: Residual rate is 10% or more and less than 20%.
Δ: Residual rate is 20% or more and less than 30%.
X: Residual rate is 30% or more.

<< Charge amount >>
1) 15 seconds stirring charge amount 10 g of each toner and 100 g of ferrite carrier were placed in a stainless steel pot up to 30% of the internal volume in an environment with a temperature of 28 ° C. and a humidity of 80%, and stirred for 15 seconds at a stirring speed of 100 rpm. The charge amount (μC / g) of the developer was measured with [Toshiba Chemical Co., Ltd .: TB-200].
The charge amount of the toner was measured by the blow-off method.
2) Charge amount when stirred for 5 minutes Charge amount when stirred for 5 minutes as in 1) 3) Charge amount when stirred for 10 minutes As in 1) Charge amount when stirred for 10 minutes

<< Charging stability >>
(1) High-temperature and high-humidity environment In an environment where the charging stability temperature is 40 ° C. and the humidity is 90%, the image chart of 7% image area in a monochrome mode is running 100,000 sheets on a digital full-color copier (Imagio Color 2800 manufactured by Ricoh). During output, a part of the developer was sampled every 1000 sheets, and the charge amount was measured by the blow-off method to evaluate the charging stability.
When the change in the charge amount was 5 μc / g or less, it was evaluated as ◯, when it was 10 μc / g or less, Δ when it exceeded 10 μc / g.
(2) Low-temperature, low-humidity environment Charging stability temperature of 10 ° C, humidity of 15% In a monochrome mode, an image chart with a 7% image area is output on a digital full-color copier (Imagio Color 2800 manufactured by Ricoh) with 100,000 sheets output. In the meantime, a part of the developer was sampled every 1000 sheets, and the charge amount was measured by the blow-off method to evaluate the charging stability.
When the change in the charge amount was 5 μc / g or less, it was evaluated as ◯, when it was 10 μc / g or less, Δ when it exceeded 10 μc / g.
The charge amount measurement by the blow-off method (1) and (2) was performed as follows.
In a test room with a temperature of 20 ° C. and a humidity of 50%, 10 g of each toner and 100 g of ferrite carrier are placed in a stainless steel pot up to 30% of the internal volume, and stirred for 10 minutes at a stirring speed of 100 rpm. g) was measured with [Toshiba Chemical Co., Ltd .: TB-200].

<< Toner T Scattering >>
Using a digital full-color copying machine (image Color 2800 manufactured by Ricoh), the degree of toner contamination in the machine was confirmed after continuous printing of 50,000 sheets.
A problem-free level was indicated by “◯”, a toner was observed, but a problem-free level was indicated by “Δ”, and a markedly contaminated and problematic problem was indicated by “X”.

<< Soil dirt >>
Using a digital full-color copier (Imagio Color 2800, manufactured by Ricoh Co., Ltd.), after running 30,000 image charts with 50% image area in single color mode, the blank image is stopped during development, and the developed photoreceptor The developer was transferred to tape, and the difference from the image density of the untransferred tape was measured with a 938 spectrodensitometer (manufactured by X-Rite).
The smaller the difference in image density, the better the background stain, and the better ones were ranked in the order of “◎”, “◯”, “Δ”, “×”.

<< Fluidity >>
Using a flowable powder tester (manufactured by Hosokawa Micron Corporation), sieves with openings of 63 μm, 45 μm, and 22 μm are arranged in this order from above, and 2 g of toner that has been air-sieved with a sieve of openings of 63 μm is added, and the amplitude is 30 mm at 1 mm. Vibration was applied for 2 seconds, and the weight of the toner on each sieve after vibration was measured.
Here, the smaller the obtained value, the better the fluidity of the toner.

<< Transfer rate >>
Using a digital full-color copier (Imagio Color 2800, manufactured by Ricoh), the copier was stopped during the transfer to the transfer paper, and the amount of toner remaining on the intermediate transfer belt was visually confirmed and ranked as follows. .
◎: Transfer residual toner is very small and transfer performance is excellent ○: Transfer residual toner is low and transfer performance is excellent △: Transfer performance equivalent to that of conventional color toner containing a release agent ×: Transfer residual toner is very large In Table 2, “Composition ratio (mass%)” is the composition ratio (mass%) relative to the total amount of the first polyester resin, second polyester resin B, crystalline polyester resin C, release agent, and colorant. ).
"BisA-EO" represents a bisphenol A ethylene oxide 2 molar adduct.
“BisA-PO” represents a bisphenol A propylene oxide 3 molar adduct.

(About Fig. 1 and Fig. 2)
DESCRIPTION OF SYMBOLS 100A Image forming apparatus 100B Image forming apparatus 10 Photosensitive drum 20 Charging roller 30 Exposure apparatus 40 Developer 41 Developing belt 42K, 42Y, 42M, 42C Developer accommodating part 43K, 43Y, 43M, 43C Developer supply roller 44K, 44Y, 44M, 44C Developing roller 45K, 45Y, 45M, 45C Developing unit 50 Intermediate transfer member 51 Roller 58 Corona charger 60 Cleaning device 70 Static elimination lamp 80 Transfer roller 90 Cleaning device 95 Transfer paper (About FIGS. 3 and 4)
10K, 10Y, 10M, 10C Electrostatic latent image carrier 14, 15, 16 Support roller 17 Intermediate transfer member cleaning device 18 Image forming means 21 Exposure device 22 Secondary transfer device 23 Roller 24 Secondary transfer belt 25 Fixing device 26 Fixing Belt 27 Pressure roller 28 Sheet reversing device 32 Contact glass 33 First traveling body 34 Second traveling body 35 Imaging lens 36 Reading sensor 49 Registration roller 50 Intermediate transfer body 52 Separating roller 53 Manual feed path 54 Manual feed tray 55 Switching claw 56 discharge roller 57 discharge tray 61 developing device 62 transfer charger 63 cleaning device 64 static eliminator 120 tandem type developer 130 document table 142 paper feed roller 143 paper bank 144 paper feed cassette 145 separation roller 146 paper feed path 147 transport roller 14 Feeding path 150 copying apparatus main body 160 a charging device 200 feeder table 300 Scanner 400 automatic document feeder (ADF)
L Exposure (About Figure 5)
DESCRIPTION OF SYMBOLS 10 Photosensitive drum 40 Developing device 58 Corona charger 80 Transfer roller 90 Cleaning device 95 Recording paper 110 Process cartridge

JP 2007-279700 A JP 2005-115213 A JP 2003-280266 A

Claims (10)

A polyester resin for toner, comprising a polyol-based structural part, a polycarboxylic acid-based structural part, and a fluorine-containing bisphenol-based structural part represented by the following general formula (1).

(In the general formula (1), R ₁ and R ₂ each represents a fluorine-containing alkyl group in which at least one hydrogen atom contained in the alkyl group is substituted with a fluorine atom and may be the same or different from each other. , R ₃ and R ₄ are each selected from the group consisting of a hydrogen atom, an amino group, a sulfo group, a halogen atom and a hydrocarbon group, and may be the same or different and each may have 1 to 4 substituents. X represents a carbonyl group derived from a carboxyl group (* -CO-), an oxycarbamoyl residue derived from an isocyanate group (* -OCONH-) or an aminocarbonyloxy residue (* -NHCO-O-), derived from an isocyanate group A ureylenyl group (* -HNCONH-) or a terminal oxyl group represented by the following general formula (2):
_{-O (R 5 O) m -} ··· formula (2)
(In general formula (2), R ₅ represents an alkynyl group, and m represents an integer of 0 or more.)   2. The polyester resin for toner according to claim 1, comprising 1 to 10 mol% of any one or more of structural parts derived from the fluorine-containing bisphenol compound of the general formula (1). 3. The polyester resin for toner according to claim 1, wherein three hydrogen atoms contained in the alkyl groups of R ₁ and R _{2 in} the general formula (1) are substituted with fluorine atoms. 4.   4. The polyester resin for toner according to claim 1, having a glass transition temperature of 40 ° C. or higher and lower than 70 ° C. and a weight average molecular weight of 4000 or more and 25000 or less.   The structural part derived from a trihydric or higher aliphatic alcohol is contained in an amount of 0.5 parts by mass or more and 6.5 parts by mass or less in 100 parts by mass of the total mass of the polyol-based structural part. 2. A polyester resin for toner according to 1.   A toner comprising the resin according to claim 1.   A polyester resin according to any one of claims 1 to 5 and a structural component derived from a diol component and a structural component derived from a crosslinking component as constituent components, wherein the diol component contains 50 mol of an aliphatic diol having 3 to 10 carbon atoms. The toner according to claim 6, wherein the toner contains a polyester resin B containing at least% and the crosslinking component contains a trihydric or higher aliphatic alcohol.   7. The toner according to claim 6, wherein the glass transition temperature (Tg1st) of the first temperature increase in differential scanning calorimetry (DSC) of the toner is 20 ° C. or more and 50 ° C. or less.   A developer comprising the toner according to claim 6.   An electrostatic latent image carrier, electrostatic latent image forming means for forming an electrostatic latent image on the surface of the electrostatic latent image carrier, and developing the electrostatic latent image using a developer to form a visible image An image forming apparatus having at least a developing unit to form, a transferring unit for transferring the visible image to a recording medium, and a fixing unit for fixing the transferred image transferred to the recording medium, wherein the developer is An image forming apparatus comprising the developer according to claim 9.

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