JP2007310257A - Binder resin for electrostatic image developing toner, binder resin dispersion for electrostatic image developing toner, electrostatic image developing toner and method for manufacturing the same, electrostatic image developer and image forming method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a binder resin for electrostatic image developing toner having good thermal properties and a properly controlled molecular weight, a binder resin dispersion for electrostatic image developing toner, an electrostatic image developing toner and a method for manufacturing the same, an electrostatic image developer and an image forming method. <P>SOLUTION: The binder resin for electrostatic image developing toner is obtained by a polycondensation reaction of a polycarboxylic acid and a polyol, wherein 10-95 mol% of the polyol comprises a compound represented by the formula (1): HOX<SP>1</SP><SB>h</SB>-Ph-Y-Ph-X<SP>1'</SP><SB>k</SB>OH (wherein X<SP>1</SP>and X<SP>1'</SP>are each an alkylene oxide group; Y is O(CH<SB>3</SB>)<SB>2</SB>or SO<SB>2</SB>; 1≤h≤3; and 1≤k≤3) and 5-90 mol% of the polyol comprises a compound represented by formula (2). <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a binder resin for an electrostatic charge image developing toner used when developing an electrostatic latent image formed by an electrophotographic method or an electrostatic recording method with a developer, and kneading and pulverizing the binder resin. The present invention relates to a toner for developing an electrostatic image. Furthermore, the present invention relates to a binder resin dispersion for an electrostatic charge image developing toner produced from the binder resin, and an electrostatic charge image developing toner produced using the same. The present invention also relates to an electrostatic charge image developer using the electrostatic charge image developing toner and an image forming method.

  In recent years, due to the rapid spread of digitization technology, high image quality is required for output such as printing and copying for users in general households, offices, and publishing areas. There is a growing demand for low energy and energy savings for corporate activities and products resulting from these activities. Therefore, in the image forming method such as the electrophotographic method or the electrostatic recording method, power saving is performed in the fixing process that consumes a lot of energy, and low environmental load activities are performed in the process of manufacturing a product using the material. It is necessary. Measures corresponding to the former include measures such as lowering the toner fixing temperature. By lowering the toner fixing temperature, in addition to saving power, it is possible to wait for the fixing temperature on the surface of the fixing member when power is input, shorten the warm-up time, and extend the life of the fixing member. .

Conventionally, vinyl polymers have been widely used as binder resins for toners, but high molecular weight vinyl polymers have a high softening point, so that a fixed image having excellent glossiness can be obtained. It is necessary to set the temperature of the heat roller high, which goes against energy saving.
On the other hand, the polyester resin is more flexible than the vinyl polymer, and the molecular weight when the mechanical strength is the same can be set low. This tendency is particularly remarkable when the polyester resin has a rigid aromatic ring in the chain. Furthermore, polyester is often used as a binder resin for energy-saving toner because it has the advantage of being easier to design as a low-temperature fixing resin than a vinyl binder resin in terms of molecular chain entanglement, limiting molecular weight, and the like.

Usually, the polycondensation method of polyester requires a reaction that takes 10 hours or more under stirring at high temperature exceeding 200 ° C. under high power and high vacuum, and requires a large amount of energy. For this reason, enormous capital investment is often required to obtain durability of the reaction equipment.
Recently, however, studies on methods for producing polyester resins at low temperatures have been reported. For example, Patent Document 1 discloses a method for producing a polyester using an enzyme as a catalyst, and Patent Document 2 reports a polyester synthesis at 160 to 200 ° C. using a scandium triflate catalyst.
However, the reaction at such a low temperature is that the polycondensation of the polyester does not proceed sufficiently and the molecular weight is difficult to increase, the usable monomers are limited to a part, and the thermal characteristics due to the low molecular weight There was a problem such as difficulty in controlling.

An example using a monomer having a bisphenol structure having a fluorene skeleton as a polyester resin has been reported.
For example, Patent Document 3 is a polyester polymer composed of a dicarboxylic acid or an ester-forming derivative thereof and a dihydroxy compound, wherein the dicarboxylic acid includes an alicyclic dicarboxylic acid, and the dihydroxy compound includes a fluorene compound. A polyester polymer is disclosed. However, this invention does not appropriately select the amount of dihydroxy compound, the amount of dicarboxylic acid, and other monomers to be blended as the toner resin. In particular, dihydroxy compounds having aromatic rings in the main chain and side chain, such as 1,1-bis [4- (2-hydroxyethoxy) phenyl] -1-phenylethane, bis [4- (2-hydroxyethoxy) phenyl] With respect to compounds having an aromatic ring and sulfur in the main chain such as sulfone, 10 mol% of all diol components may be used in combination. Furthermore, it is a production method in which a polycondensation reaction is performed at a high temperature using a metal catalyst.

  In Patent Document 4, an invention in which an alicyclic dicarboxylic acid or an acid anhydride thereof is esterified with a predetermined dihydroxy compound (for example, 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene) is disclosed. Although disclosed, this is a 1: 1 reaction of the above monomers and no other formulation is mentioned.

  Patent Documents 5 and 6 disclose that a polyester polymer optical element or a polymer is formed by molding from a polyester polymer in which the dicarboxylic acid contains an alicyclic dicarboxylic acid and the dihydroxy compound contains a compound containing a fluorene skeleton. However, this polymer also cannot control the thermal characteristics as a resin for toner.

Japanese Patent Laid-Open No. 11-313692 JP 2003-306535 A Japanese Patent Laid-Open No. 9-302077 Japanese Patent Laid-Open No. 11-60706 JP 2000-119379 A JP 2004-315676 A

  An object of the present invention is to provide a binder resin for an electrostatic charge image developing toner that has good thermal characteristics and has an appropriately controlled molecular weight. Furthermore, the present invention provides an electrostatic charge image developing toner, a method for producing the same, and an electrostatic charge image developer that are excellent in low-temperature fixability and image strength and have stable chargeability, using the binder resin for electrostatic charge image developing toner. The purpose is to do. Another object of the present invention is to provide an image forming method using the electrostatic image developing toner or the electrostatic image developer.

The above-described problems of the present invention have been solved by means described in the following <1> and <3> to <8>. It is described below together with <2> which is a preferred embodiment.
<1> A binder resin for an electrostatic charge image developing toner obtained by a polycondensation reaction of a polycarboxylic acid and a polyol, wherein 10 mol% or more and 95 mol% or less of the polyol is composed of a compound represented by the formula (1), A binder resin for an electrostatic charge image developing toner, wherein 5 mol% or more and 90 mol% or less of the polyol is composed of a compound represented by the formula (2):
HOX ¹ _h -Ph-Y-Ph-X ^{1 '} _k OH (1)
(X ¹ , X ^{1 ′} : alkylene oxide group, Y: C (CH ₃ ) ₂ or SO ₂ , 1 ≦ h ≦ 3, 1 ≦ k ≦ 3)

（Ｘ²、Ｘ^2'：アルキレン基、Ｒ¹〜Ｒ⁴：水素原子又は１価の置換基、Ｒ⁵、Ｒ⁶：１価の置換基、１≦ｍ≦３、１≦ｎ≦３、０≦ｐ≦４、０≦ｑ≦４）

(X ² , X ^{2 ′} : alkylene group, R ^{1 to} R ⁴ : hydrogen atom or monovalent substituent, R ⁵ , R ⁶ : monovalent substituent, 1 ≦ m ≦ 3, 1 ≦ n ≦ 3, 0 ≦ p ≦ 4, 0 ≦ q ≦ 4)

<2> The binder resin for electrostatic charge image developing toner according to <1>, wherein 50 mol% or more and 100 mol% or less of the polycarboxylic acid is composed of a compound represented by formula (3) and / or formula (4),
Q ¹ OOCA ¹ _m B ¹ _n A ^{1 ′} _l COOQ ^{1 ′} (3)
(A ¹ , A ^{1 ′} methylene group, B ¹ : aromatic hydrocarbon group, Q ¹ , Q ^{1 ′} : hydrogen atom or monovalent hydrocarbon group, 1 ≦ m + l ≦ 12, 1 ≦ n ≦ 3)
Q ² OOCA ² _p B ² _q A ^{2 ′} _r COOQ ^{2 ′} (4)
(A ² , A ^{2 ′} : methylene group, B ² : alicyclic hydrocarbon group, Q ² , Q ^{2 ′} : hydrogen atom or monovalent hydrocarbon group, 0 ≦ p ≦ 6, 0 ≦ r ≦ 6, 1 ≦ q ≦ 3)
<3> A binder resin dispersion for an electrostatic charge image developing toner in which the binder resin for an electrostatic charge image developing toner according to <1> or <2> is dispersed;
<4> Production of an electrostatic charge image developing toner comprising a step of aggregating the binder resin in a dispersion containing at least a binder resin dispersion to obtain aggregated particles, and a step of heating and aggregating the aggregated particles A method for producing an electrostatic image developing toner, wherein the binder resin dispersion is the binder resin dispersion for an electrostatic image developing toner according to <3>,
<5> An electrostatic charge image developing toner produced by the production method according to <4>,
<6> An electrostatic image developing toner produced by kneading and pulverizing the binder resin for electrostatic image developing toner according to <1>,
<7> An electrostatic charge image developer comprising the electrostatic charge image developing toner according to <5> or <6> and a carrier,
<8> A latent image forming step of forming an electrostatic latent image on the surface of the latent image holding member, and a toner image obtained by developing the electrostatic latent image formed on the surface of the latent image holding member with toner or an electrostatic charge image developer. A developing step for forming the toner image, a step for transferring the toner image formed on the surface of the latent image holding member to the surface of the recording material, and a fixing step for thermally fixing the toner image transferred to the surface of the recording material. An image forming method comprising: using the electrostatic image developing toner according to <5> or <6> as the toner, or using the electrostatic image developer according to <7> as the developer. Image forming method.

  According to the present invention, it is possible to provide a binder resin for an electrostatic charge image developing toner that has good thermal characteristics and has an appropriately controlled molecular weight. Furthermore, according to the present invention, the electrostatic charge image developing toner, the method for producing the same, and the electrostatic charge image developer, which are excellent in low temperature fixability and image strength and have stable chargeability, using the binder resin for electrostatic charge image developing toner. Can be provided. In addition, the present invention can provide an image forming method using the electrostatic image developing toner or the electrostatic image developer.

(Binding resin for electrostatic image developing toner)
The binder resin for an electrostatic charge image developing toner of the present invention is a binder resin for an electrostatic charge image developing toner obtained by a polycondensation reaction of a polycarboxylic acid and a polyol, wherein 10 mol% or more and 95 mol% or less of the polyol is represented by the formula ( It consists of a compound represented by 1), and 5 mol% or more and 90 mol% or less of the polyol is composed of a compound represented by the formula (2).
HOX ¹ _h -Ph-Y-Ph-X ^{1 '} _k OH (1)
(X ¹ , X ^{1 ′} : alkylene oxide group, Y: C (CH ₃ ) ₂ or SO ₂ , 1 ≦ h ≦ 3, 1 ≦ k ≦ 3)

（Ｘ²、Ｘ^2'：アルキレン基、Ｒ¹〜Ｒ⁴：水素原子又は１価の置換基、Ｒ⁵、Ｒ⁶：１価の置換基、１≦ｍ≦３、１≦ｎ≦３、０≦ｐ≦４、０≦ｑ≦４）
なお、本発明において、「静電荷像現像トナー」を単に「トナー」ともいうこととし、「静電荷像現像トナー用結着樹脂」を単に「結着樹脂」ともいうこととする。

(X ² , X ^{2 ′} : alkylene group, R ^{1 to} R ⁴ : hydrogen atom or monovalent substituent, R ⁵ , R ⁶ : monovalent substituent, 1 ≦ m ≦ 3, 1 ≦ n ≦ 3, 0 ≦ p ≦ 4, 0 ≦ q ≦ 4)
In the present invention, “electrostatic image developing toner” is also simply referred to as “toner”, and “binder resin for electrostatic image developing toner” is also simply referred to as “binder resin”.

  Using the polycondensable monomer structure as in the present invention, the non-crystalline polyester resin obtained by polycondensation of the polycondensable monomer has been found to have desirable physical properties as a binder resin for toner, completing the present invention. It came to do.

  Here, in the present invention, “non-crystalline” in “non-crystalline polyester resin” means a step-like endothermic change or no clear endothermic peak in differential scanning calorimetry (DSC). Specifically, it means that the half-value width of the endothermic peak when measured at a heating rate of 10 ° C./min exceeds 15 ° C. On the other hand, a resin having a half-value width of an endothermic peak within 15 ° C. means that it is crystalline.

  The compound represented by the formula (2) used in the present invention has a rigid fluorene ring and two benzene rings, thereby improving the heat resistance of the polyester polymer obtained by polycondensation thereof. Furthermore, due to the influence of the alkylene oxide group present between the benzene ring and the hydroxyl group, the compound represented by the formula (2) has a relatively low melting point and has a higher reactivity at a lower temperature than in the past. That is, it has been found that the low temperature reactivity and good thermal characteristics can be achieved by the chemical structure.

Due to such physical properties such as reactivity and melting point, a homogeneous reaction can be realized quickly even in the low-temperature polycondensation method, so that the reaction rate is increased and the remaining low molecular weight components can be reduced.
In particular, the binder resin of the present invention has a bulky fragrance, particularly when an electrostatic charge image developing toner is prepared by agglomeration and coalescence with another vinyl-based amorphous resin dispersion or a crystalline polyester resin dispersion. Compatibility with the resin to be mixed is improved in that the solubility parameter is lower than that of other polyesters that have a ring structure and have low-temperature polycondensation reactivity. It can be reduced.

  In addition, there has been no example of using a bisphenol-structure monomer having a fluorene skeleton as a polyester binder resin for toner. Until now, it was only used for molding materials for the purpose of controlling optical properties such as refractive index or thermal properties, or for controlling the thermal properties, and not for controlling the physical properties as a binder resin for toner.

  Aromatic dicarboxylic acids such as terephthalic acid and isophthalic acid, which are usually used to control thermal properties in toners, have phenolic hydroxyl groups, so stabilization due to delocalization of electrons occurs, and at low temperatures. Polycondensation reactivity is relatively low. On the other hand, when the structure of the present invention is used, a polyester having characteristics suitable for the binder resin for toner can be produced at a low temperature.

  Furthermore, the toner produced using the binder resin can ensure low-temperature fixability and improve image strength by controlling the thermal characteristics of the produced binder resin, and can further reduce the low molecular weight component in the polymer. Therefore, a uniform toner with stable aggregation and chargeability can be obtained. In addition, when this binder resin is mixed with other binder resins and waxes that have a particularly high degree of hydrophobicity, the compatibility is improved, reducing uneven distribution of colorants and waxes in the toner, exposure to the surface, and aggregation. , Image quality can be improved.

<Compound represented by Formula (1)>
The binder resin for electrostatic image developing toner of the present invention is a binder resin for toner obtained by polycondensation reaction of a polycarboxylic acid and a polyol. And a compound (diol represented by the formula (1)).
HOX ¹ _h -Ph-Y-Ph-X ^{1 '} _k OH (1)
(X ¹ , X ^{1 ′} : alkylene oxide group, Y: C (CH ₃ ) ₂ or SO ₂ , 1 ≦ h ≦ 3, 1 ≦ k ≦ 3)
The diol represented by the above formula (1) is a bisphenol S derivative (Y═SO ₂ ) or a bisphenol A derivative (Y═C (CH ₃ ) ₂ ).
Although the diol represented by Formula (1) can also be included individually by 1 type, 2 or more types of diol represented by Formula (1) can also be included. In this case, the total amount of the diol represented by the formula (1) is 10 mol% or more and 95 mol% or less of the entire polyol.

  In the present invention, by using 10 mol% or more and 95 mol% or less of a bisphenol S derivative and / or a bisphenol A derivative as a polyol component, an electrostatic charge image developing toner excellent in mechanical strength can be obtained.

In the present invention, the diol represented by the formula (1) has at least one alkylene oxide group. Examples of the alkylene oxide group include, but are not limited to, an ethylene oxide group, a propylene oxide group, and butylene oxide. Preferred are ethylene oxide and propylene oxide, and particularly preferred is ethylene oxide.
The number of alkylene oxide groups h and k is 1 or more and 3 or less in one molecule. When there is less than one alkylene oxide, that is, when no alkylene oxide group is added, electrons are delocalized by resonance stabilization of the hydroxyl group and the phenyl group, and the diol represented by the formula (1) is converted to the polycarboxylic acid. Nucleophilic aggression is weakened, and molecular weight extension and polymerization degree are suppressed. On the other hand, when more than 3 alkylene oxide groups are added, the straight chain portion in the diol represented by the formula (1) becomes too long, and the produced polyester has a crystalline property. The number of reactive functional groups in the diol represented by (1) decreases, and the reaction probability decreases.
Moreover, it is preferable that the number of alkylene oxide groups h and k is the same in order to promote an equal reaction. Further, it is preferable that the number of alkylene oxide groups h and k is 2 or 1 respectively. Moreover, when it has 2 or more alkylene oxide groups, it can also have 2 or more types of alkylene oxide groups in 1 molecule.

Examples of the diol represented by the formula (1) used in the present invention include bisphenol A and bisphenol S alkylene oxide adducts (h and k are 1 to 3). In particular, the alkylene oxide adduct is preferably a 1 mol ethylene oxide adduct (1 each of h and k) and a 1 mol propylene oxide adduct (1 each of h and k).
The bisphenol A alkylene oxide adduct has high polycondensation reactivity at low temperature due to its structure. Moreover, since melting | fusing point is comparatively low and suitable for the polycondensation at low temperature, it is preferable. By containing this monomer, the effect of dissolving other components including the compound represented by formula (2) is excellent, and the reaction is considered to proceed rapidly. Also, bisphenol S alkylene oxide adducts can be preferably used in the present invention because of their reactivity at low temperatures.
The usage-amount of the diol represented by Formula (1) is 10-95 mol%, Preferably it exceeds 10 mol and is 95 mol% or less, More preferably, it is 20-95 mol%. When it is contained in an amount of 10 mol% or more, there is an effect of smoothly proceeding the polycondensation reaction at a low temperature, and a molecular weight suitable for the toner can be obtained. Moreover, when it is 95 mol% or less, thermal characteristics can be improved, and offset resistance, strength at room temperature, and powder flowability can be controlled.

<Compound represented by Formula (2)>
The binder resin for electrostatic image developing toner of the present invention is a binder resin for toner obtained by polycondensation reaction of polycarboxylic acid and polyol, and 5 mol% or more and 90 mol% or less of the polyol is represented by the formula (2). It consists of the compound (diol represented by Formula (2)).

（Ｘ²、Ｘ^2'：アルキレン基、Ｒ¹〜Ｒ⁴：水素原子又は１価の置換基、Ｒ⁵、Ｒ⁶：１価の置換基、１≦ｍ≦３、１≦ｎ≦３、０≦ｐ≦４、０≦ｑ≦４）

(X ² , X ^{2 ′} : alkylene group, R ^{1 to} R ⁴ : hydrogen atom or monovalent substituent, R ⁵ , R ⁶ : monovalent substituent, 1 ≦ m ≦ 3, 1 ≦ n ≦ 3, 0 ≦ p ≦ 4, 0 ≦ q ≦ 4)

The compound represented by the formula (2) is a compound having a fluorene structure and two alkylene oxide chains.
Although the compound represented by Formula (2) can also be included individually by 1 type, it can also contain 2 or more types of compounds represented by Formula (2). In this case, the total amount of the compound represented by the formula (2) is 5 mol% or more and 90 mol% or less of the whole polyol.

In formula (2), X ² and X ^{2 ′} represent an alkylene group. The alkylene group is preferably a linear or branched alkylene group having 1 to 4 carbon atoms, more preferably a methylene group, an ethylene group, a propylene group, or a butylene group, and an ethylene group or a propylene group. Is more preferable, and an ethylene group is particularly preferable. X ² and X ^{2 ′} can be independently selected and may be the same or different.
In formula (2), m and n are 1 or more and 3 or less. m and n represent the number of added moles of the alkylene oxide group (OX ² ) or (OX ^{2 ′} ). m and n are preferably 1 or 2, and more preferably 1. M and n can be independently selected, but m and n are preferably the same, and m and n are more preferably 1.
In addition, the addition mole number (m and n) of an alkylene oxide group here means the maximum value, and may have distribution.
That is, the compound represented by formula (2) preferably has two ethylene oxide chains.

In formula (2), the substitution position of —O— (X ² O) _m —H and —O— (X ^{2 ′} O) _n —H is not particularly limited, but is preferably substituted at the 4-position.

In formula (2), R ^{1 to} R ⁴ are each independently a hydrogen atom or a monovalent substituent. Examples of the monovalent substituent include a halogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, a —NO ₂ group, or a —OR ₇ group, and R ₇ represents an alkyl group. Furthermore, the monovalent substituent may further have a substituent such as an alkyl group, a cycloalkyl group, an aryl group, or a halogen atom.
Examples of the alkyl group include linear or branched alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, and t-butyl group. The number of carbon atoms is preferably 1 to 7, more preferably 1 to 6, and still more preferably 1 to 4.
Examples of the aryl group include aryl groups having 6 to 12 carbon atoms such as a phenyl group and a naphthyl group.
Examples of the aralkyl group include a benzyl group, and an aralkyl group composed of an aryl group having 6 to 12 carbon atoms and an alkyl group having 1 to 4 carbon atoms is preferable.
Among these, R ^{1 to} R ⁴ are preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, an aryl group or an aralkyl group, more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, A hydrogen atom or a methyl group is more preferable, and a hydrogen atom is particularly preferable.

The substitution positions of R ^{1 to} R ⁴ are not particularly limited, but are preferably 2-position, 3-position, 4-position, 2-position and 6-position, and 3-position and 5-position.

In formula (2), R ⁵ and R ⁶ are each independently a monovalent substituent. Examples of the monovalent substituent include a halogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, a —NO ₂ group, or a —OR ₇ group, and R ₇ represents an alkyl group.
Examples of the alkyl group include linear or branched alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, and t-butyl group. The number of carbon atoms is preferably 1 to 7, more preferably 1 to 6, and still more preferably 1 to 4.
Examples of the aryl group include aryl groups having 6 to 12 carbon atoms such as a phenyl group and a naphthyl group.
Examples of the aralkyl group include a benzyl group, and an aralkyl group composed of an aryl group having 6 to 12 carbon atoms and an alkyl group having 1 to 4 carbon atoms is preferable.
Among these, when the compound represented by the formula (2) has R ⁵ and R ⁶ , it is preferably an alkyl group having 1 to 4 carbon atoms, an aryl group or an aralkyl group, and an alkyl group having 1 to 4 carbon atoms. More preferably, it is a methyl group.
p R ⁵ and q R ⁶ can be independently selected. p and q are integers of 0 or more and 4 or less. p and q are preferably 0 to 3, more preferably 0 to 2, and p and q are particularly preferably 0, ie, having no substituent.

  Examples of the compound represented by the formula (2) include 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene (also referred to as bisphenoxyethanol fluorene in the present invention), 9,9-bis [4. -(2-hydroxyethoxy) -3-methylphenyl] fluorene, 9,9-bis [4- (2-hydroxyethoxy) -3,5-dimethylphenyl] fluorene, 9,9-bis [4- (2- Hydroxyethoxy) -3-ethylphenyl] fluorene, 9,9-bis [4- (2-hydroxyethoxy) -3,5-diethylphenyl] fluorene, 9,9-bis [4- (2-hydroxyethoxy)- 3-propylphenyl] fluorene, 9,9-bis [4- (2-hydroxyethoxy) -3,5-dipropylphenyl] fluorene, 9,9 Bis [4- (2-hydroxyethoxy) -3-isopropylphenyl] fluorene, 9,9-bis [4- (2-hydroxyethoxy) -3,5-diisopropylphenyl] fluorene, 9,9-bis [4- (2-hydroxyethoxy) -3-n-butylphenyl] fluorene, 9,9-bis [4- (2-hydroxyethoxy) -3,5-di-n-butylphenyl] fluorene, 9,9-bis [ 4- (2-hydroxyethoxy) -3-isobutylphenyl] fluorene, 9,9-bis [4- (2-hydroxyethoxy) -3,5-diisobutylphenyl] fluorene, 9,9-bis [4- (2 -Hydroxyethoxy) -3- (1-methylpropyl) phenyl] fluorene, 9,9-bis [4- (2-hydroxyethoxy) -3,5-bis (1 Methylpropyl) phenyl] fluorene, 9,9-bis [4- (2-hydroxyethoxy) -3-phenylphenyl] fluorene, 9,9-bis [4- (2-hydroxyethoxy) -3,5-diphenylphenyl Fluorene, 9,9-bis [4- (2-hydroxyethoxy) -3-benzylphenyl] fluorene, 9,9-bis [4- (2-hydroxyethoxy) -3,5-dibenzylphenyl] fluorene, 9,9-bis [4- (3-hydroxypropoxy) phenyl] fluorene, 9,9-bis [4- (4-hydroxybutoxy) phenyl] fluorene and the like can be mentioned, and these can be used alone or in combination of two or more. May be used. Of these, 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene is most preferred.

  9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene is obtained, for example, by adding ethylene oxide (hereinafter abbreviated as EO) to 9,9-bis (4-hydroxyphenyl) fluorene. At this time, in addition to the 2EO adduct (9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene) in which one molecule of ethylene oxide was added to each hydroxyl group of phenol, 3EO was further added in excess of several molecules. Impurities such as adducts and 4EO adducts may be contained. That is, the added ethylene oxide has a distribution, and the 2EO adduct only needs to have a maximum distribution of 2EO adduct. In order to improve the heat resistance of the polyester polymer, the purity of the 2EO adduct is preferably 85% or more, and more preferably 95% or more.

  The usage-amount of the compound represented by Formula (2) is 5-90 mol% in all the polyols of a polycondensable resin, Preferably it is 5-80 mol%. When it is contained in an amount of 5 mol% or more, the effect of improving the thermal characteristics can be exhibited, and low molecular weight components can be reduced. Moreover, when it is 90 mol% or less, the viscosity during reaction can be maintained at an appropriate level, and the polycondensation reaction can proceed sufficiently even at low temperatures.

In the present invention, in addition to the diols represented by the formulas (1) and (2), other polyols can be used in combination.
For example, the aliphatic diol and alicyclic diol used in combination include ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,4- Butenediol, neopentyl glycol, 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, 1,18-octadecanediol, 1,14-eicosandecanediol, diethylene glycol, triethylene glycol, Dipropylene glycol , Polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol can be exemplified.
As the aromatic diol used in combination, bisphenol A, bisphenol Z, bisphenol C, bisphenol E, bisphenol F, bisphenol P, bisphenol S, bisphenol Z, biphenol, naphthalenediol, adamantanediol, adamantanedimethanol, hydrogenated bisphenol A Etc. can also be mentioned.
A dihydric or higher polyhydric alcohol can also be used in combination. Examples thereof include glycol, pentaerythritol, hexamethylol melamine, hexaethylol melamine, tetramethylol benzoguanamine, and tetraethylol benzoguanamine.
The bisphenols preferably have at least one alkylene oxide group. Examples of the alkylene oxide group include, but are not limited to, an ethylene oxide group, a propylene oxide group, and butylene oxide. Preferred are ethylene oxide and propylene oxide, and the number of moles added is preferably 1 to 3. When it is within this range, the viscoelasticity and glass transition temperature of the polyester to be produced can be appropriately controlled for use as a toner.

The added amount of the polyol used in combination is less than 85 mol% of the total polyol component, preferably 75 mol% or less, and more preferably 50 mol% or less.
It is preferable that the amount of the polyol used in combination is within the above range since a binder resin excellent in thermal characteristics and molecular weight control can be obtained.

It is preferable that 50 mol% or more and 100 mol% or less of the polycarboxylic acid used for this invention consists of a compound (dicarboxylic acid) represented by Formula (3) and / or Formula (4). In the present invention, “carboxylic acid” is intended to include esterified products and acid anhydrides thereof.
Q ¹ OOCA ¹ _m B ¹ _n A ^{1 ′} _l COOQ ^{1 ′} (3)
(A ¹ , A ^{1 ′} methylene group, B ¹ : aromatic hydrocarbon group, Q ¹ , Q ^{1 ′} : hydrogen atom or monovalent hydrocarbon group, 1 ≦ m + l ≦ 12, 1 ≦ n ≦ 3)
Q ² OOCA ² _p B ² _q A ^{2 ′} _r COOQ ^{2 ′} (4)
(A ² , A ^{2 ′} : methylene group, B ² : alicyclic hydrocarbon group, Q ² , Q ^{2 ′} : hydrogen atom or monovalent hydrocarbon group, 0 ≦ p ≦ 6, 0 ≦ r ≦ 6, 1 ≦ q ≦ 3)
Here, the monovalent hydrocarbon group represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a hydrocarbon group, or a heterocyclic group, and these groups may have an arbitrary substituent. . R ¹ , R ^{1 ′} , R ² and R ^{2 ′} are preferably a hydrogen atom or a lower alkyl group, more preferably a hydrogen atom, a methyl group or an ethyl group, and most preferably a hydrogen atom.
Moreover, the aromatic hydrocarbon group in Formula (3) and the alicyclic hydrocarbon group in Formula (4) may be substituted.

<Dicarboxylic acid represented by formula (3)>
The dicarboxylic acid represented by the formula (3) has at least one aromatic hydrocarbon group B ¹ , but its structure is not particularly limited. Examples of the aromatic hydrocarbon group B ¹ include benzene, naphthalene, acenaphthylene, fluorene, anthracene, phenanthrene, tetracene, fluoranthene, pyrene, benzofluorene, benzophenanthrene, chrysene, triphenylene, benzopyrene, perylene, anthrene, benzonaphthacene. , Benzochrysene, pentacene, pentaphen, coronene skeleton and the like, but are not limited thereto. Further, a substituent may be further added to these structures.

The number of aromatic hydrocarbon groups B ¹ contained in the dicarboxylic acid represented by the formula (3) is 1 or more and 3 or less. If it is less than 1, the non-crystallinity of the produced polyester is lost, and if it has more than 3 aromatic hydrocarbon groups, it is difficult to synthesize such a dicarboxylic acid. Not only the efficiency is lowered, but also the melting point and viscosity of the dicarboxylic acid represented by the formula (3) are increased, and the reactivity is decreased due to the size and bulkiness of the dicarboxylic acid.

  When the dicarboxylic acid represented by the formula (3) contains a plurality of aromatic hydrocarbon groups, the aromatic hydrocarbon groups may be directly bonded to each other, and other saturated aliphatic hydrocarbon groups, etc. A structure having a skeleton of Examples of the former include a biphenyl skeleton, and examples of the latter include, but are not limited to, a bisphenol A skeleton, a benzophenone, and a diphenylethene skeleton.

A group suitable as the aromatic hydrocarbon group B ¹ has a structure in which the main skeleton has C6 to C18 carbon atoms. The number of carbon atoms of the main skeleton does not include the number of carbon atoms contained in the functional group bonded to the main skeleton. Examples include benzene, naphthalene, acenaphthylene, fluorene, anthracene, phenanthrene, tetracene, fluoranthene, pyrene, benzofluorene, benzophenanthrene, chrysene, triphenylene, bisphenol A skeleton and the like. Among these, particularly preferred skeletons include benzene, naphthalene, anthracene, and phenanthrene. Most preferably, a benzene or naphthalene structure is used.
It is preferable that the main skeleton has 6 or more carbon atoms because the production of the monomer is easy. Moreover, it is preferable that the carbon number of the main skeleton is 18 or less because the size of the monomer molecule is appropriate and the reactivity is not lowered due to the limitation of molecular motion. Furthermore, the ratio of the reactive functional group in the monomer molecule is appropriate, which is preferable because the reactivity does not decrease.

The dicarboxylic acid represented by formula (3) includes at least one methylene group A ¹ or A ^{1 ′} . In formula (3), A ¹ and A ^{1 ′} can be independently selected, but A ¹ and A ^{1 ′} are preferably the same. The methylene group may be linear or branched, and for example, a methylene chain, a branched methylene chain, a substituted methylene chain and the like can be used. In the case of a branched methylene chain, the structure of the branched part is not limited and may have an unsaturated bond, further branching, a cyclic structure, or the like.
The number of methylene groups A ¹ and A ^{1 ′} is at least 1 and not more than 12 as the total m + 1 in the molecule. Preferably, m + 1 is 2 or more and 6 or less, and m and l are more preferably the same number. When m + 1 is 0, that is, when the dicarboxylic acid represented by the formula (3) does not have a methylene group, the aromatic hydrocarbon and the carboxyl groups at both ends are directly bonded. In this case, the reaction intermediate formed by the catalyst and the dicarboxylic acid represented by the formula (3) is resonance-stabilized and the reactivity is lowered. In addition, when m + 1 is larger than 12, the straight chain portion is too large with respect to the dicarboxylic acid represented by the formula (3), so that the produced polymer has crystallinity characteristics, or the glass transition temperature Tg is May decrease.

The bonding site between the methylene group A ¹ , A ^{1 ′} or carboxyl group and the aromatic hydrocarbon group B ¹ is not particularly limited, and may be any of o-position, m-position and p-position.
Examples of the dicarboxylic acid represented by the formula (3) include 1,4-phenylenediacetic acid, 1,4-phenylenedipropionic acid, 1,3-phenylenediacetic acid, 1,3-phenylenedipropionic acid, 1,2 -Phenylenediacetic acid, 1,2-phenylenedipropionic acid and the like can be mentioned, but are not limited thereto. Preferable examples include 1,4-phenylene dipropionic acid, 1,3-phenylene dipropionic acid, 1,4-phenylene diacetic acid, and 1,3-phenylene diacetic acid.

  Various functional groups may be added to any of the structures of the dicarboxylic acid represented by the formula (3). The carboxylic acid group that is a polycondensation reactive functional group may be an acid anhydride, an acid ester, or an acid chloride. However, since an intermediate between an acid ester compound and a proton is easily stabilized and tends to suppress reactivity, a carboxylic acid, a carboxylic acid anhydride, or a carboxylic acid chloride is preferably used.

<Dicarboxylic acid represented by formula (4)>
Dicarboxylic acid represented by formula (4) contains an alicyclic hydrocarbon group B ^2. The alicyclic hydrocarbon structure is not particularly limited, and cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclononane, cyclodecane, cycloundecane, cyclododecane, cyclopropene, cyclobutene, cyclopentene, cyclohexene, cycloheptene, Examples thereof include, but are not limited to, cyclooctene, norbornene, adamantane, diamantane, triamantane, tetramantane, iron, skeleton and the like. Moreover, a substituent may be added to these substances. In view of the stability of the structure, the size and bulkiness of the molecule, cyclobutane, cyclopentane, cyclohexane, norbornene, adamantane and the like are preferable.
The number of alicyclic hydrocarbon groups contained in this monomer is at least 1 and no more than 3. When it is less than 1, the non-crystallinity of the produced polyester is lost, and when it has more than 3 alicyclic hydrocarbon groups, an increase in the melting point of the dicarboxylic acid represented by the formula (4) The reactivity decreases depending on the size and bulkiness of the molecule.
In the case of containing a plurality of alicyclic hydrocarbon groups, either a structure in which aromatic hydrocarbon groups are directly bonded to each other or a structure having a skeleton such as another saturated aliphatic hydrocarbon can be taken. Examples of the former include a dicyclohexyl skeleton and the like, and examples of the latter include a hydrogenated bisphenol A skeleton, but are not limited thereto.

  A suitable alicyclic hydrocarbon group is a C3-C12 substance. The number of carbon atoms of the main skeleton does not include the number of carbon atoms contained in the functional group bonded to the main skeleton. For example, a substance having a cyclopropane, cyclobutane, cyclopentane, cyclohexane, norbornene, adamantane skeleton, or the like can be given. Among these, particularly preferable skeletons include cyclobutane, cyclopentane, cyclohexane, norbornene, and adamantane.

The dicarboxylic acid represented by the formula (4) may have a methylene group A ² and / or A ^{2 ′} in its structure. The methylene group may be linear or branched, and for example, a methylene chain, a branched methylene chain, a substituted methylene chain and the like can be used. In the case of a branched methylene chain, the structure of the branched part is not limited and may have an unsaturated bond, further branching, a cyclic structure, or the like.
As for the number of the methylene groups A ² and A ^{2 ′} , p and r are each 6 or less. When either or both of p and r are larger than 6, since the linear portion is too large for the dicarboxylic acid represented by the formula (4), the produced polymer has crystalline characteristics, The glass transition temperature Tg may decrease.

The bonding site between the methylene group A ² , A ^{2 ′} or carboxyl group and the alicyclic hydrocarbon group B ² is not particularly limited, and may be any of the o-position, m-position, and p-position.
Examples of the dicarboxylic acid represented by the formula (4) include 1,1-cyclopropanedicarboxylic acid, 1,1-cyclobutanedicarboxylic acid, 1,2-cyclobutanedicarboxylic acid, 1,1-cyclopentenedicarboxylic acid, 1,4- Examples include cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,2-cyclohexenedicarboxylic acid, norbornene-2,3-dicarboxylic acid, and adamantanedicarboxylic acid. It is not limited. Of these, a substance having a cyclobutane, cyclohexane or cyclohexane skeleton is preferably used, and 1,3-cyclohexanedicarboxylic acid or 1,4-cyclohexanedicarboxylic acid is particularly preferable.
The dicarboxylic acid represented by the formula (4) may have various functional groups added to any of its structures. The carboxylic acid group that is a polycondensation reactive functional group may be an acid anhydride, an acid ester, or an acid chloride. However, since an intermediate between an acid ester compound and a proton is easily stabilized and tends to suppress reactivity, a carboxylic acid, a carboxylic acid anhydride, or a carboxylic acid chloride is preferably used.

In this invention, it is preferable that 50 mol% or more and 100 mol% or less of the compound (dicarboxylic acid) represented by said Formula (3) and / or Formula (4) are included with respect to the whole polycarboxylic acid component. The compound represented by the above formula (3) and the compound represented by the formula (4) can be used alone or in combination.
When the ratio of the compound represented by the formula (3) and / or the formula (4) is 50 mol% or more, the reactivity can be sufficiently exerted even at the low temperature polycondensation, the molecular weight is increased, and the degree of polymerization is increased. It is preferable because it becomes a high polyester. Moreover, since a residual polycondensation component decreases, it is preferable. Thereby, there is no stickiness etc. of the hardened | cured material at normal temperature, the favorable performance of hardened | cured material is obtained, and since favorable viscoelasticity and glass transition temperature are obtained, it is preferable. The compound represented by the above formula (3) and / or the formula (4) is preferably included in an amount of 60 to 100 mol%, and the compound represented by the above formula (3) and / or the formula (4) is included in an amount of 80 to 100 mol%. It is more preferable.

In this invention, other polycarboxylic acid can also be used together with the polycarboxylic acid represented by Formula (3) and / or Formula (4).
As the polycarboxylic acid used in combination, a polycarboxylic acid containing two or more carboxyl groups in one molecule can be used. Among these, a divalent carboxylic acid is a compound containing two carboxyl groups in one molecule. For example, oxalic acid, succinic acid, itaconic acid, glutaconic acid, glutaric acid, maleic acid, adipic acid, β-methyl Adipic acid, speric acid, azelaic acid, sebacic acid, nonanedicarboxylic acid, decanedicarboxylic acid, undecanedicarboxylic acid, dodecanedicarboxylic acid, fumaric acid, citraconic acid, diglycolic acid, malic acid, citric acid, hexahydroterephthalic acid, Malonic acid, pimelic acid, tartaric acid, mucous acid, phthalic acid, isophthalic acid, terephthalic acid, tetrachlorophthalic acid, chlorophthalic acid, nitrophthalic acid, biphenyl-p, p'-dicarboxylic acid, naphthalene-1,4-dicarboxylic acid, Naphthalene-1,5-dicarboxylic acid, naphthalene-2,6-dicarbo Acid, anthracene dicarboxylic acid, n- dodecyl succinic acid, n- dodecenylsuccinic acid, iso-dodecyl succinic acid, iso-dodecenyl succinic acid, n- octyl succinic acid, and n- octenyl succinate and the like. Examples of the polyvalent carboxylic acid other than the divalent carboxylic acid include trimellitic acid, pyromellitic acid, naphthalenetricarboxylic acid, naphthalenetetracarboxylic acid, pyrenetricarboxylic acid, and pyrenetetracarboxylic acid.
Moreover, although these acid anhydrides or acid chlorides and acid esterified compounds can be mentioned, it is not limited thereto.
The polycarboxylic acid used in combination is preferably less than 50 mol%, more preferably less than 40 mol%, still more preferably less than 20 mol% of the total amount of polycarboxylic acid.

  In the present invention, it is preferable to use a dicarboxylic acid and a diol as the polycarboxylic acid component and the polyol component, and the ratio (molar ratio) between the dicarboxylic acid and the diol is the former (dicarboxylic acid) / the latter (diol) = 0. It is preferable that it is .75 / 1-1.25 / 1, More preferably, it is 0.9 / 1-1.1 / 1. It is preferable that the molar ratio of the dicarboxylic acid component and the diol component is within the above range because the polymerizability is improved.

In the present invention, polycarboxylic acid and polyol are preferably polycondensed in the presence of a catalyst, and it is preferable to use a Bronsted acid catalyst as the catalyst, and a Bronsted acid catalyst containing sulfur element (sulfur acid). More preferably, is used.
<Catalyst>
Examples of Bronsted acid catalysts include, for example, alkylbenzene sulfonic acids such as dodecylbenzene sulfonic acid, isopropyl benzene sulfonic acid, and camphor sulfonic acid, alkyl sulfonic acid, alkyl disulfonic acid, alkyl phenol sulfonic acid, alkyl naphthalene sulfonic acid, Higher fatty acid sulfates such as alkyl tetralin sulfonic acid, alkyl allyl sulfonic acid, petroleum sulfonic acid, alkyl benzimidazole sulfonic acid, higher alcohol ether sulfonic acid, alkyl diphenyl sulfonic acid, monobutyl phenyl phenol sulfuric acid, dibutyl phenyl phenol sulfuric acid, dodecyl sulfuric acid Higher alcohol sulfate, higher alcohol ether sulfate, higher fatty acid amide alkylol sulfate, higher fatty acid amide ester Killed sulfate ester, naphthenyl alcohol sulfate, sulfated fat, sulfosuccinate ester, various fatty acids, sulfonated higher fatty acid, higher alkyl phosphate ester, resin acid, resin acid alcohol sulfate, naphthenic acid, niobic acid, and all of these Although the salt compound of these can be used, it is not limited to this. Moreover, these catalysts may have a functional group in the structure. A plurality of these catalysts may be combined as necessary. Examples of the Bronsted acid catalyst preferably used include dodecylbenzenesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, and camphorsulfonic acid.

Other polycondensation catalysts generally used can be used together with the above catalyst or alone. Specific examples include metal catalysts, hydrolase type catalysts, and basic catalysts.
Examples of the metal catalyst include, but are not limited to, the following. For example, an organic tin compound, an organic titanium compound, an organic tin halide compound, and a rare earth-containing catalyst can be mentioned.
Specific examples of the rare earth-containing catalyst include scandium (Sc), yttrium (Y), and lanthanoid elements such as lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), samarium (Sm), and europium. (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), lutetium (Lu), etc. are effective. is there. Of these, alkylbenzene sulfonates, alkyl sulfate esters, and those having a triflate structure are particularly effective. Examples of the triflate include X (OSO ₂ CF ₃ ) _{3 in} the structural formula. Here, X is a rare earth element, and among these, X is preferably scandium (Sc), yttrium (Y), ytterbium (Yb), samarium (Sm), or the like.
The lanthanoid triflate is described in detail in the Journal of Synthetic Organic Chemistry, Vol. 53, No. 5, p44-54).

  When using a metal catalyst as a catalyst, the metal content derived from the catalyst in the obtained resin shall be 100 ppm or less. It is preferable to set it as 75 ppm or less, and it is more preferable to set it as 50 ppm or less. Therefore, it is preferable not to use a metal catalyst or to use a very small amount even when a metal catalyst is used.

The hydrolase type catalyst is not particularly limited as long as it catalyzes an ester synthesis reaction. Examples of the hydrolase in the present invention include EC (enzyme number) 3.1 group such as carboxyesterase, lipase, phospholipase, acetylesterase, pectinesterase, cholesterol esterase, tannase, monoacylglycerol lipase, lactonase, lipoprotein lipase and the like. (See Maruo and Tamiya's "Enzyme Handbook" Asakura Shoten, (1982), etc.) Hydrolase enzymes classified into EC 3.2 group that act on glycosyl compounds such as esterases, glucosidases, galactosidases, glucuronidases, xylosidases EC that acts on peptide bonds such as hydrolase, aminopeptidase, chymotrypsin, trypsin, plasmin, subtilisin, etc. classified into EC 3.3 group such as epoxide hydrase Hydrolase classified .4 group, mention may be made of hydrolytic enzymes such as classified into EC3.7 group such as furo retinoic hydrolase.
Among the above esterases, enzymes that hydrolyze glycerol esters to liberate fatty acids are called lipases, but lipases are highly stable in organic solvents, catalyze ester synthesis reactions in high yields, and are available at a lower price. There are advantages such as what you can do. Therefore, in the present invention, it is desirable to use lipase from the viewpoint of yield and cost.
Lipases of various origins can be used, but preferred are Pseudomonas genus, Alcaligenes genus, Achromobacter genus, Candida genus, Aspergillus genus, Rhizopus Examples include lipases obtained from microorganisms such as (Rhizopus) genus and Mucor genus, lipases obtained from plant seeds, lipases obtained from animal tissues, pancreatin, and steapsin. Of these, it is desirable to use lipases derived from microorganisms of the genus Pseudomonas, Candida, and Aspergillus.

Examples of the basic catalyst include, but are not limited to, general organic basic compounds, nitrogen-containing basic compounds, and tetraalkyl or arylphosphonium hydroxides such as tetrabutylphosphonium hydroxide. Examples of the organic base compound include ammonium hydroxides such as tetramethylammonium hydroxide and tetraethylammonium hydroxide, and examples of the nitrogen-containing basic compound include amines such as triethylamine and dibenzylmethylamine, pyridine, methylpyridine, methoxypyridine, Quinolin, imidazole, alkali metals such as sodium, potassium, lithium, cesium, and alkaline earth metals such as calcium, magnesium, barium, hydroxides, hydrides, amides, alkalis, alkaline earth metals and acids And salts with carbonates, phosphates, borates, carboxylates and phenolic hydroxyl groups.
Moreover, a compound with an alcoholic hydroxyl group, a chelate compound with acetylacetone, and the like can be exemplified, but the invention is not limited thereto.

  As a total addition amount of a catalyst, it is preferable to add in the ratio of 0.001 to 10 weight% with respect to a polycondensation component, and it is more preferable to add in the ratio of 0.01 to 5 weight%. One or more catalysts can be added.

In the present invention, the binder resin can be obtained even if the polycondensation reaction is performed at a temperature lower than the conventional reaction temperature. The reaction temperature (polycondensation temperature) is preferably 70 ° C. or higher and 150 ° C. or lower. More preferably, it is 80 degreeC or more and 140 degrees C or less.
It is preferable that the reaction temperature is 70 ° C. or higher, because no decrease in reactivity due to a decrease in monomer solubility and catalyst activity occurs, and an increase in molecular weight is not suppressed. Moreover, since it can manufacture with low energy as reaction temperature is 150 degrees C or less, it is preferable. Moreover, since coloring of resin, decomposition | disassembly of produced | generated polyester, etc. do not arise, it is preferable.

  This polycondensation reaction can be carried out by a general polycondensation method such as bulk polymerization, emulsion polymerization, suspension polymerization, or other underwater polymerization, solution polymerization, interfacial polymerization, etc., but bulk polymerization is preferably used. Although the reaction can be performed under atmospheric pressure, general conditions such as reduced pressure and nitrogen flow can be used for the purpose of increasing the molecular weight of the obtained polyester molecule.

As the binder resin for toner of the present invention, the glass transition temperature (glass transition point) Tg is preferably 35 ° C. to 95 ° C. More preferably, it is 40-90 degreeC, More preferably, it is 45-85 degreeC. When the Tg is within the above range, the cohesive force of the binder resin itself in the high temperature range is good, so that hot offset hardly occurs at the time of fixing, and further sufficient melting is obtained, and the minimum fixing temperature is increased. It is difficult to do.
Here, the glass transition temperature of the amorphous resin refers to a value measured by the method (DSC method) defined in ASTM D3418-82.
Moreover, the measurement of the glass transition temperature in this invention can be measured by "DSC-20" (made by Seiko Denshi Kogyo Co., Ltd.) according to the differential scanning calorimetry (DSC), for example, Specifically, about 10 mg of samples Can be heated at a constant rate of temperature increase (10 ° C./min), and the glass transition temperature can be obtained from the intersection of the baseline and the endothermic peak slope.

The molecular weight is a molecular weight measurement by gel permeation chromatography (GPC) method in which tetrahydrofuran (THF) is soluble, and the weight average molecular weight is preferably 1,000 to 60,000, and preferably 1,500 to 50,000. More preferably, it is more preferably 2,000-40,000. It is preferable for the weight average molecular weight to be in the above range since offset resistance is improved.
In the present invention, the molecular weight of the resin is measured with a THF solvent using a THF soluble material, such as TSK-GEL, GMH (manufactured by Tosoh Corporation), etc., and a molecular weight calibration curve prepared from a monodisperse polystyrene standard sample is obtained. Can be used to calculate the molecular weight.

In the present invention, the polycondensation step may include a polycarboxylic acid and a polyol, which are the aforementioned polycondensation components, and a polymerization reaction between a prepolymer prepared in advance. The prepolymer is not limited as long as it is a polymer that can be melted or uniformly mixed with the monomer.
Furthermore, the binder resin of the present invention includes a homopolymer of the above-mentioned polycondensation component, a copolymer in which two or more monomers including the above-described polymerizable component are combined, or a mixture, graft polymer, one It may have partial branching or a crosslinked structure.

(Electrostatic image developing toner)
Using the binder resin for toner produced according to the present invention, a mechanical manufacturing method such as a melt-kneading pulverization method, or a binder resin dispersion using the polyester (in the present invention, “binder resin particle dispersion Or “resin particle dispersion”), and the toner can be manufactured by a so-called chemical manufacturing method in which the toner is manufactured from the binder resin dispersion.

  When the binder resin of the present invention is used to produce a toner by a mechanical production method such as a melt-kneading method, the dispersibility and pulverization properties of pigments and the like are good. This includes a polycondensation component having high reactivity at low temperatures as a main component, and furthermore, polycondensation can be carried out at a lower temperature than conventional polycondensation, thereby suppressing the generation of side reactions and unreacted products. This is considered to be because a binder resin having uniform physical properties can be obtained.

  When the toner is produced by the melt-kneading pulverization method, it is preferable to stir and mix the polyester resin produced as described above with other toner raw materials in advance using a Henschel mixer, a supermixer or the like before melt-kneading. At this time, a combination of the agitator capacity, the rotation speed of the agitator, the agitation time, and the like must be selected.

Next, the agitated product of the toner binder resin and other toner raw materials is kneaded in a molten state by a known method. Kneading with a single-screw or multi-screw extruder is preferable because dispersibility is improved. At this time, the number of kneading screw zones of the kneading apparatus, the cylinder temperature, the kneading speed, etc. must all be set to appropriate values and controlled. Among the control factors at the time of kneading, the number of rotations of the kneader, the number of kneading screw zones, and the cylinder temperature have a particularly great influence on the kneading state. In general, the number of rotations is preferably 300 to 1,000 rpm, and the number of kneading screw zones is kneaded better by using a multi-stage zone such as a two-stage screw rather than a single stage. The set temperature of the cylinder is preferably determined by the softening temperature of the amorphous polyester that is the main component of the binder resin, and is usually preferably about −20 to + 100 ° C. than the softening temperature. A cylinder set temperature within the above range is preferable because sufficient kneading and dispersion can be obtained and aggregation does not occur. Further, it is preferable because a kneading share is applied, sufficient dispersion is obtained, and cooling after kneading is easy.
The melt-kneaded kneaded product is sufficiently cooled and then pulverized by a known method such as a mechanical pulverization method such as a ball mill, a sand mill, or a hammer mill, or an airflow pulverization method. If cooling by a conventional method is not sufficient, a cooling or freeze pulverization method can also be selected.

  For the purpose of controlling the particle size distribution of the toner, the pulverized toner may be classified. By eliminating particles having an inappropriate diameter by classification, there is an effect of improving toner fixing properties and image quality.

  On the other hand, in response to recent demands for high image quality, many toner chemical manufacturing methods have been adopted as technologies for reducing the diameter of toner and for low-energy manufacturing methods. As a chemical production method of the toner using the binder resin for toner of the present invention, a general production method can be used, but an aggregation and coalescence method is preferable. The aggregation coalescence method is a known aggregation method in which a latex in which a binder resin is dispersed in water is produced and aggregated (aggregated) with other toner raw materials.

The method for dispersing the binder resin produced as described above in water is not particularly limited. It can be selected from known methods such as forced emulsification, self-emulsification, and phase inversion emulsification. Among these, in consideration of energy required for emulsification, particle size controllability, stability of the obtained emulsion, forced emulsification method, self-emulsification method, phase inversion emulsification method are preferably applied, more preferably self-emulsification method, A phase inversion emulsification method is applied.
The self-emulsification method and the phase inversion emulsification method are described in “Application Technology of Ultrafine Particle Polymer” (CMC Publishing). As the polar group used in the self-emulsification method, a carboxyl group, a sulfone group, and the like can be used. In the present invention, a carboxyl group is preferably used when applied to an amorphous polyester binder resin for toner.

Using the binder resin dispersion prepared as described above, so-called latex, it is possible to produce a toner in which the toner particle diameter and distribution are controlled using an aggregation method. A step of aggregating the binder resin in a dispersion liquid containing at least the binder resin dispersion obtained as described above to obtain aggregated particles (aggregation step), and a step of heating and aggregating the aggregated particles A method for producing an electrostatic charge image developing toner comprising (a fusing step), wherein the binder resin dispersion contains the binder resin of the present invention.
More specifically, the latex (resin particle dispersion) prepared as described above is mixed with a colorant particle dispersion and a release agent particle dispersion as necessary, and a flocculant is further added to form heteroaggregation. The toner particles are formed to form aggregated particles having a toner diameter, and then heated to a temperature equal to or higher than the glass transition point or the melting point of the binder resin particles to fuse the aggregated particles, and then washed and dried. In this manufacturing method, the toner shape can be controlled from an indeterminate shape to a spherical shape by selecting a heating temperature condition.

  After completing the coalesced particle fusion step, desired toner particles are obtained through an arbitrary washing step, solid-liquid separation step, and drying step. In consideration of the charging property, the washing step is sufficiently substituted and washed with ion-exchanged water. It is desirable. Moreover, although there is no restriction | limiting in particular in a solid-liquid separation process, From the point of productivity, suction filtration, pressure filtration, etc. are suitable. Further, the drying process is not particularly limited, but freeze drying, flash jet drying, fluidized drying, vibration fluidized drying and the like are preferably used from the viewpoint of productivity.

  As a flocculant, besides a surfactant, an inorganic salt or a divalent or higher metal salt can be suitably used. In particular, when a metal salt is used, it is preferable in characteristics such as cohesion control and toner chargeability. The metal salt compound used for aggregation is obtained by dissolving a general inorganic metal compound or a polymer thereof in a resin particle dispersion, but the metal elements constituting the inorganic metal salt are a periodic table (long period table). 2A, 3A, 4A, 5A, 6A, 7A, 8, 1B, 2B, and 3B having a charge of 2 or more are preferred, and any resin that dissolves in the form of ions in the aggregated system of resin particles can be used. Good. Specific examples of preferred inorganic metal salts include metal salts such as calcium chloride, calcium nitrate, barium chloride, magnesium chloride, zinc chloride, aluminum chloride, and aluminum sulfate, and polyaluminum chloride, polyaluminum hydroxide, calcium sulfide. And inorganic metal salt polymers. Among these, an aluminum salt and a polymer thereof are particularly preferable. In general, in order to obtain a sharper particle size distribution, even if the valence of the inorganic metal salt is divalent to monovalent, bivalent to trivalent or higher, and even to the same valence, the polymerization type inorganic metal salt weight Combined is more suitable.

  In the present invention, if necessary, known additives can be blended in combination of one or more kinds within a range that does not affect the results of the present invention. For example, flame retardants, flame retardant aids, brighteners, waterproofing agents, water repellents, inorganic fillers (surface modifiers), mold release agents, antioxidants, plasticizers, surfactants, dispersants, lubricants, Fillers, extenders, binders, charge control agents and the like. These additives can be blended in any process for producing an electrostatic image developing toner.

  Examples of internal additives include various commonly used charge control agents such as quaternary ammonium salt compounds and nigrosine compounds as charge control agents. However, stability during production and reduction of wastewater contamination can be used. Therefore, materials that are difficult to dissolve in water are suitable.

Examples of mold release agents include low molecular weight polyolefins such as polyethylene, polypropylene and polybutene, silicones having a softening point upon heating, fatty acid amides such as oleic acid amide, erucic acid amide, ricinoleic acid amide, stearic acid amide and the like. Plant waxes such as ester wax, carnauba wax, rice wax, candelilla wax, tree wax, jojoba oil, animal waxes such as beeswax, montan wax, ozokerite, ceresin, paraffin wax, microcrystalline wax , Minerals such as microcrystalline wax, Fischer-Tropsch wax, petroleum-based wax, and modified products thereof can be used.
These waxes are dispersed in water together with ionic surfactants, polymer electrolytes such as polymer acids and polymer bases, and heated with a homogenizer or pressure discharge type disperser that can be heated to the melting point or higher and subjected to strong shearing. And a dispersion of particles less than 1 micron can be made.

In addition to the above polycondensable resin particle dispersion, addition polymerization resin particle dispersions prepared by using conventionally known emulsion polymerization can be used together.
Examples of addition polymerization monomers for preparing these resin particle dispersions include styrenes such as styrene and parachlorostyrene, vinyl naphthalene, vinyl chloride, vinyl bromide, vinyl fluoride, vinyl acetate, propion. Vinyl esters such as vinyl acid, vinyl benzoate, vinyl butyrate, such as methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, dodecyl acrylate, n-octyl acrylate, 2-chloroethyl acrylate, Methylene aliphatic carboxylic esters such as phenyl acrylate, methyl α-chloroacrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, acrylonitrile, methacrylonitrile, acrylamide such as vinyl methyl ether, vinyl ethyl ether, vinyl Monomers having N-containing polar groups such as vinyl ethers such as ruisobutyl ether, N-vinyl compounds such as N-vinyl pyrrole, N-vinyl carbazole, N-vinyl indole, N-vinyl pyrrolidone, methacrylic acid, acrylic Homopolymers and copolymers of vinyl monomers such as vinyl carboxylic acids such as acid, cinnamic acid and carboxyethyl acrylate, and various waxes can also be used.

  In the case of addition polymerization monomers, emulsion polymerization can be carried out using an ionic surfactant or the like to produce a resin particle dispersion, and in the case of other resins, it is oily and the solubility in water is compared. If it is soluble in a low solvent, the resin is dissolved in those solvents and dispersed in an aqueous medium with a disperser such as a homogenizer together with an ionic surfactant or polymer electrolyte, and then heated or decompressed. Then, the resin particle dispersion can be obtained by evaporating the solvent.

Examples of the surfactant used herein include anionic surfactants such as sulfate ester, sulfonate, and phosphate ester; cationic surfactants such as amine salt type and quaternary ammonium salt type; polyethylene glycol And nonionic surfactants such as polyphenols, alkylphenol ethylene oxide adducts, and polyhydric alcohols. Among these, anionic surfactants and cationic surfactants are preferable. The nonionic surfactant is preferably used in combination with the anionic surfactant or the cationic surfactant. The said surfactant may be used individually by 1 type, and may use 2 or more types together.
Anionic surfactants include sodium dodecylbenzenesulfonate, sodium alkylnaphthalenesulfonate, sodium arylalkylpolyethersulfonate, 3,3-disulfonediphenylurea-4,4-diazo-bis-amino-8-naphthol-6 Sodium sulfonate, ortho-carboxybenzene-azo-dimethylaniline, 2,2,5,5-tetramethyl-triphenylmethane-4,4-diazo-bis-β-naphthol-6-sodium sulfonate, dialkylsulfosuccinate Sodium sulfate, sodium dodecyl sulfate, sodium tetradecyl sulfate, sodium pentadecyl sulfate, sodium octyl sulfate, sodium oleate, sodium laurate, sodium caprate, sodium caprylate, caproic acid Thorium, potassium stearate, and the like calcium oleate.
Examples of the cationic surfactant include alkylbenzene dimethyl ammonium chloride, alkyl trimethyl ammonium chloride, distearyl ammonium chloride and the like. Nonionic surfactants include polyethylene oxide, polypropylene oxide, combinations of polypropylene oxide and polyethylene oxide, esters of polyethylene glycol and higher fatty acids, alkylphenol polyethylene oxide, esters of higher fatty acids and polyethylene glycol, higher fatty acids and polypropylene oxide. Examples thereof include esters and sorbitan esters.
Examples of the polymer dispersant include sodium polycarboxylate and polyvinyl alcohol, and examples of the inorganic dispersant include calcium carbonate. However, these do not limit the present invention. Further, in order to prevent the Ostwald Ripping phenomenon of the monomer emulsion particles in an ordinary aqueous medium, a higher alcohol represented by heptanol or octanol or a higher aliphatic hydrocarbon represented by hexadecane is often added as a stabilizer. It is also possible.

For these polymerizable compounds, known polymerization methods such as a method using a polymerization initiator, self-polymerization by heat, and a method using ultraviolet irradiation can be employed. A method using a polymerization initiator is preferable, and when a radical polymerizable compound is used as the polymerizable compound, it is preferable to use a radical polymerization initiator. There are oil-soluble and water-soluble radical polymerization initiators, but either polymerization initiator may be used.
Specifically, for example, 2,2′-azobis (2-methylpropionitrile), 2,2′-azobis (2-methylbutyronitrile), 2,2′-azobisisobutyronitrile, 2 , 2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (2,4-dimethyl-4-methoxyvaleronitrile), 1,1′-azobis (cyclohexanecarbonitrile), 2,2 Azobisnitriles such as' -azobis (2-amidinopropane) hydrochloride, acetyl peroxide, octanoyl peroxide, 3,5,5-trimethylhexanoyl peroxide, decanoyl peroxide, lauroyl peroxide, benzoyl peroxide Diacyl peroxide such as oxide, di-t-butyl peroxide, t-butyl-α-cumyl peroxide, dicumyl peroxide Dialkyl peroxides such as oxide, t-butyl peroxyacetate, α-cumyl peroxypivalate, t-butyl peroxyoctoate, t-butylperoxyneodecanoate, t-butylperoxylaurate, t- Peroxyesters such as butylperoxybenzoate, di-t-butylperoxyphthalate, di-t-butylperoxyisophthalate, t-butylhydroperoxide, 2,5-dimethylhexane-2,5-dihydroperoxide Hydroperoxides such as cumene hydroperoxide and di-isopropylbenzene hydroperoxide, organic peroxides such as peroxycarbonate such as t-butylperoxyisopropyl carbonate, inorganic peroxides such as hydrogen peroxide, Potassium persulfate, sodium persulfate And radical polymerization initiators such as persulfates such as ammonium persulfate. A redox polymerization initiator may be used in combination.
The polymerization initiator can be added to the oil phase, but can also be added to the aqueous medium. It can be added to either the oil phase or the aqueous medium before emulsification and dispersion, or may be added to both. Moreover, it is also preferable to add after emulsification dispersion.
Among these, it is preferable to add a polymerization initiator after emulsifying and dispersing the oil phase in an aqueous medium.

  Examples of flame retardants and flame retardant aids include, but are not limited to, bromine flame retardants that have already been widely used, antimony trioxide, magnesium hydroxide, aluminum hydroxide, and ammonium polyphosphate.

  As the coloring component (coloring agent), any of known pigments and dyes can be used. Specifically, carbon black such as furnace black, channel black, acetylene black, thermal black, inorganic pigments such as bengara, bitumen, titanium oxide, fast yellow, disazo yellow, pyrazolone red, chelate red, brilliant carmine, para brown, etc. Azo pigments, phthalocyanine pigments such as copper phthalocyanine and metal-free phthalocyanine, and condensed polycyclic pigments such as flavantron yellow, dibromoanthrone orange, perylene red, quinacridone red and dioxazine violet. Chrome Yellow, Hansa Yellow, Benzidine Yellow, Slen Yellow, Quinoline Yellow, Permanent Orange GTR, Pyrarozone Orange, Vulcan Orange, Watch Young Red, Permanent Red, Dupont Oil Red, Resol Red, Rhodamine B Lake, Lake Red C, Rose Bengal, aniline blue, ultramarine blue, calco oil blue, methylene blue chloride, phthalocyanine blue, phthalocyanine green, malachite green oxalate, C.I. I. Pigment red 48: 1, C.I. I. Pigment red 122, C.I. I. Pigment red 57: 1, C.I. I. Pigment yellow 12, C.I. I. Pigment yellow 97, C.I. I. Pigment yellow 17, C.I. I. Pigment blue 15: 1, C.I. I. Examples thereof include various pigments such as CI Pigment Blue 15: 3, and these can be used alone or in combination of two or more.

  Examples of the surfactant used in preparing the release agent particle dispersion or pigment dispersion in the method for producing an electrostatic charge image developing toner of the present invention include sulfate ester, sulfonate, and phosphoric acid. Anionic surfactants such as esters and soaps, cationic surfactants such as amine salts and quaternary ammonium salts, and nonionic interfaces such as polyethylene glycols, alkylphenol ethylene oxide adducts, and polyhydric alcohols It is also effective to use an activator in combination, and a common means such as a rotary shear type homogenizer, a ball mill having a media, a sand mill, or a dyno mill can be used for dispersion.

  Also, after drying in the same way as normal toner, inorganic particles such as silica, alumina, titania and calcium carbonate and resin fine particles such as vinyl resin, polyester and silicone are added to the surface by shearing in a dry state (external addition). It can also be used as a flow aid or cleaning aid. When the electrostatic image developing toner of the present invention has an external additive, toner particles before external addition are referred to as toner base particles. That is, when the electrostatic image developing toner of the present invention has an external additive, the electrostatic image developing toner is obtained by externally adding an external additive to toner base particles.

The toner of the present invention preferably has a cumulative volume average particle diameter (volume median diameter) (D ₅₀ ) of 3.0 μm to 20.0 μm. More preferably, the cumulative volume average particle diameter is 3.0 μm to 9.0 μm. It is preferable for D _{50 to} be 3.0 μm or more because adhesion is appropriate and developability does not deteriorate. Moreover, it is preferable that it is 20.0 μm or less because sufficient image resolution can be obtained. The cumulative volume average particle diameter (D ₅₀ ) can be measured using a laser diffraction particle size distribution measuring apparatus or the like.

The toner of the present invention preferably has a volume average particle size distribution index GSDv of 1.4 or less. In particular, in the case of a chemical toner, GSDv is more preferably 1.3 or less.
GSDv draws cumulative distribution from the small diameter side for the volume for the particle size range (channel) divided on the basis of the particle size distribution, and the particle size that becomes 16% cumulative is the volume D _16v and the particle size that is 84% cumulative. It is defined as volume D _84v . Using these, the volume average particle size distribution index (GSDv) is calculated by the following equation.
Volume average particle size distribution index GSDv = ( _D84v / _D16v ) ^0.5
A GSDv of 1.4 or less is preferable because the particle diameter is uniform, good fixability is obtained, and no device failure due to poor fixing occurs. In addition, it is preferable because it does not cause in-machine contamination or developer deterioration due to toner scattering.
The volume average particle size distribution index GSDv can be measured using a laser diffraction type particle size distribution measuring apparatus or the like.

  When the toner of the present invention is produced by a chemical production method, the shape factor SF1 is preferably from 100 to 140, more preferably from 110 to 135, from the viewpoint of image formability. At this time, SF1 is calculated as follows.

ここでＭＬは粒子の絶対最大長、Ａは粒子の投影面積である。
これらは、主に顕微鏡画像又は走査電子顕微鏡画像をルーゼックス画像解析装置によって取り込み、解析することによって数値化される。
なお、本発明において、静電荷像現像トナーの平均体積粒子径、ＧＳＤｖ及び形状係数は、上述したトナー母粒子の平均粒子径及び形状係数によって近似することもできる。

Here, ML is the absolute maximum length of the particle, and A is the projected area of the particle.
These are quantified mainly by capturing and analyzing a microscope image or a scanning electron microscope image with a Luzex image analyzer.
In the present invention, the average volume particle diameter, GSDv, and shape factor of the electrostatic image developing toner can be approximated by the above-described average particle size and shape factor of the toner base particles.

(Static charge image developer)
The electrostatic image developing toner of the present invention is used as an electrostatic image developer. The developer is not particularly limited except that it contains the electrostatic image developing toner, and can have an appropriate component composition depending on the purpose. When the electrostatic image developing toner is used alone, it is prepared as a one-component electrostatic image developer, and when used in combination with a carrier, it is prepared as a two-component electrostatic image developer.
The carrier is not particularly limited, but usually, magnetic particles such as iron powder, ferrite, iron oxide powder, nickel, etc .; the magnetic particles as a core material and the surface thereof as a styrene resin, vinyl resin, ethylene resin, rosin Resin-coated carrier formed by coating a resin such as a resin based on polyester, polyester or melamine, or a wax such as stearic acid, and forming a resin coating layer; a magnetic material obtained by dispersing magnetic particles in a binder resin Examples include a distributed carrier. Among them, the resin-coated carrier is particularly preferable because the chargeability of the toner and the resistance of the entire carrier can be controlled by the configuration of the resin coating layer.
The mixing ratio of the toner of the present invention and the carrier in the two-component electrostatic image developer is usually 2 to 10 parts by weight of the toner with respect to 100 parts by weight of the carrier. Moreover, the preparation method of a developing agent is not specifically limited, For example, the method of mixing with a V blender etc. is mentioned.

(Image forming method)
The image forming method of the present invention will be described in detail below. The image forming method of the present invention includes a latent image forming step of forming an electrostatic latent image on the surface of the latent image holding member, and developing the electrostatic latent image formed on the surface of the latent image holding member with toner or an electrostatic charge image developer. A developing process for forming a toner image (development image), a transfer process for transferring the toner image formed on the surface of the latent image holding member to the surface of the recording medium, and a toner image transferred to the surface of the recording medium. Including a fixing step for heat fixing, and further, if necessary, a cleaning step for cleaning the toner remaining on the surface of the latent image carrier, wherein the electrostatic image developing toner of the present invention is used as the toner. It is characterized by. The same effect can be obtained by using the electrostatic charge image developer of the present invention instead of the toner carried on the developer carrying member.

  The latent image forming step is a step of forming an electrostatic latent image by uniformly charging the surface of the latent image carrier with a charging means and then exposing the latent image carrier with a laser optical system or an LED array. It is. Examples of the charging means include a non-contact charger such as corotron and scorotron, and a contact method in which a latent image carrier surface is charged by applying a voltage to a conductive member in contact with the latent image carrier surface. Any type of charger may be used. However, a contact charging type charger is preferable from the viewpoint that the amount of ozone generated is small, environmentally friendly, and excellent printing durability. In the contact charging type charger, the shape of the conductive member may be any of a brush shape, a blade shape, a pin electrode shape, a roller shape, and the like, but a roller-like member is preferable. The image forming method of the present invention is not subject to any particular limitation in the latent image forming process.

  The developing step is a step of bringing a developer carrying member having a developer layer containing at least toner on the surface thereof into contact with or approaching the surface of the latent image carrying member to the electrostatic latent image on the surface of the latent image carrying member. In which a toner image (developed image) is formed on the surface of the latent image carrier. The development method can be performed using a known method, but examples of the development method using a two-component developer include a cascade method and a magnetic brush method. The image forming method of the present invention is not particularly limited with respect to the developing method.

The transfer step is a step of directly transferring the toner image formed on the surface of the latent image carrier to the recording medium or transferring the image once transferred to the intermediate transfer body to the recording medium to form a transfer image. It is.
A corotron can be used as a transfer device for transferring the toner image from the latent image carrier to paper or the like. The corotron is effective as a means for uniformly charging the paper, but a high voltage of several kV must be applied and a high voltage power source is required in order to give a predetermined charge to the paper as a recording medium. Further, since ozone is generated by corona discharge, the rubber parts and the latent image carrier are deteriorated. Therefore, a conductive transfer roll made of an elastic material is pressed against the latent image carrier to transfer the toner image onto the paper. A contact transfer method is preferred. In the image forming method of the present invention, the transfer device is not particularly limited.

The cleaning step is a step of removing toner, paper dust, dust and the like adhering to the surface of the latent image carrier by bringing a blade, a brush, a roll or the like into direct contact with the surface of the latent image carrier.
The most commonly employed method is a blade cleaning method in which a rubber blade such as polyurethane is pressed against the latent image carrier. On the other hand, a magnet is fixedly arranged inside, a rotatable cylindrical non-magnetic sleeve is provided on the outer periphery thereof, and a magnetic carrier method for collecting toner by carrying a magnetic carrier on the sleeve surface, or a semiconductive It is also possible to remove the toner by making the resin fiber or animal hair rotatable in the form of a roll and applying a bias having the opposite polarity to the toner to the roll. In the former magnetic brush system, a pretreatment corotron for cleaning may be installed. In the image forming method of the present invention, the cleaning method is preferably a cleaning step having at least a blade.

  The fixing step is a step of fixing the toner image transferred to the surface of the recording medium with a fixing device. As the fixing device, a heat fixing device using a heat roll is preferably used. The heat fixing device includes a fixing roller having a heater lamp for heating inside a cylindrical metal core, a so-called release layer formed on the outer peripheral surface by a heat resistant resin film layer or a heat resistant rubber film layer, and the fixing roller. The pressure roller or pressure belt is disposed in pressure contact with the roller and has a heat-resistant elastic body layer formed on the outer peripheral surface of the cylindrical metal core or the surface of the belt-like base material. The fixing process of the unfixed toner image is performed by inserting a recording material on which an unfixed toner image is formed between a fixing roller and a pressure roller or a pressure belt, and using a binder resin, an additive, and the like in the toner. Fix by heat melting. In the image forming method of the present invention, the fixing method is not particularly limited.

  In the image forming method of the present invention, when producing a full-color image, each of the plurality of latent image carriers has a developer carrier of each color, and the plurality of latent image carriers and developer carriers. Each color toner image is sequentially laminated on the same surface of the recording medium by a series of processes including a latent image forming process, a developing process, a transferring process, and a cleaning process, and the stacked full-color toners. An image forming method in which an image is thermally fixed in a fixing step is preferably used. By using the electrostatic image developer in the image forming method, stable development, transfer, and fixing performance can be obtained even in a tandem system suitable for, for example, downsizing and color speeding up.

Examples of the recording material to which the toner image is transferred include plain paper, OHP sheet, and the like used for electrophotographic copying machines and printers. In order to further improve the smoothness of the image surface after fixing, the surface of the recording medium is preferably as smooth as possible. For example, coated paper in which the surface of plain paper is coated with a resin or the like, art paper for printing Etc. can be used suitably.
According to the image forming method using the electrostatic charge image developing toner of the present invention, while maintaining high transfer efficiency and high image quality, the development and transfer processes are stabilized over time, and the interior of the apparatus by desorption of external additives is achieved. It is possible to obtain a high-quality image with high transfer efficiency that stably obtains an image having high image quality, particularly intermediate color reproducibility and gradation, without causing contamination.

EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited at all. In addition, unless otherwise indicated, the part in an Example shows a weight part altogether.
(1) Preparation of binder resin and binder resin particle dispersion [Example 1-1]
1,4-cyclohexanedicarboxylic acid 17.5 parts by weight Bisphenol A ethylene oxide 1 mol adduct (2 mol adduct in terms of both ends)
25.5 parts by weight (80 mol%)
9.0 parts by weight of bisphenoxyethanol fluorene (20 mol%)
0.15 parts by weight of linear dodecylbenzenesulfonic acid The above materials were mixed, put into a reactor equipped with a stirrer, and subjected to polycondensation at 120 ° C. for 24 hours. As a result, a uniform transparent amorphous polyester resin (1 )
Weight average molecular weight by GPC 18,000
Number average molecular weight by GPC 5,900
Glass transition temperature (onset) 65 ° C

In the obtained GPC curve, the area ratio obtained by dividing the peak area that appeared after 10 minutes by the area with respect to all detected peaks was 1.0%. A small peak appearing after 10 minutes suggests a monomer or an oligomer having a polymerization degree of 2 to 3 inferred from the converted molecular weight. Therefore, it can be predicted that the smaller the area ratio, the more uniformly the polycondensation reaction proceeds and the less the ultra-low molecular weight component remains.
There is no practical problem that the area ratio is 5% or less, and it is more preferably 3% or less. It is preferable that the area ratio is 5% or less because there is little remaining low molecular weight component.

The resin thus obtained was put into a three-necked flask equipped with a stirrer and a condenser, and stirring was continued while gradually adding 1N NaOH while maintaining the temperature at 95 ° C. When 50 parts by weight of NaOH aqueous solution was added in total, the resin became a slurry. The slurry was put into a flask containing 180 parts by weight of ion-exchanged water adjusted to 85 ° C., emulsified with a homogenizer (IKA, Ultra Tarrax) for 10 minutes, and then an ultra-high pressure homogenizer (Yoshida Kikai Kogyo Co., Ltd.). The resin particle dispersion (1) was obtained by emulsifying for 10 passes with a nanomizer) and then cooling the dispersion with ice. The resin median diameter was 180 nm.
The solid concentration was 28%.

[Example 1-2]
1,4-phenylenediacetic acid 20 parts by weight Bisphenol A 1 mol adduct of propylene oxide (2 mol adduct in terms of both ends)
22.5 parts by weight (65 mol%)
Bisphenol S 1 mol adduct of ethylene oxide (2 mol adduct in terms of both ends)
8.5 parts by weight (25 mol%)
Bisphenoxyethanol fluorene 4.5 parts by weight (10 mol%)
p-Chlorobenzenesulfonic acid 0.1 parts by weight The above materials were mixed, put into a reactor equipped with a stirrer, and subjected to polycondensation at 120 ° C. for 24 hours. As a result, a uniform transparent amorphous polyester resin (2) was obtained. Obtained.
Weight average molecular weight by GPC 16,500
Number average molecular weight by GPC 5,450
Glass transition temperature (onset) 61.0 ° C
Moreover, in the obtained GPC curve, the area ratio of the peak area that appeared after 10 minutes to the polymer-derived peak was 2.0%.
A resin particle dispersion (2) having a median diameter of 220 nm was produced in the same manner as in Example 1-1.
The solid concentration was 31%.

[Example 1-3]
1,4-cyclohexanedicarboxylic acid 17.5 parts by weight Bisphenol A ethylene oxide 1 mol adduct (2 mol adduct in terms of both ends)
25.5 parts by weight (80 mol%)
9,9-bis [4- (2-hydroxyethoxy) -3-methylphenyl] fluorene
9.1 parts by weight (20 mol%)
0.15 parts by weight of linear dodecylbenzenesulfonic acid The above materials were mixed, put into a reactor equipped with a stirrer, and subjected to polycondensation at 120 ° C. for 24 hours. As a result, a uniform transparent amorphous polyester resin (3 )
Weight average molecular weight by GPC 18,700
Number average molecular weight by GPC 6,450
Glass transition temperature (onset) 63.5 ℃
Moreover, in the obtained GPC curve, the area ratio of the peak area that appeared after 10 minutes to the polymer-derived peak was 3.1%.
A resin particle dispersion (3) having a median diameter of 199 nm was produced in the same manner as in Example 1-1.
The solid concentration was 29%.

[Example 1-4]
1,4-cyclohexanedicarboxylic acid 17.5 parts by weight Bisphenol A ethylene oxide 1 mol adduct (2 mol adduct in terms of both ends)
25.5 parts by weight (80 mol%)
9.0 parts by weight of bisphenoxyethanol fluorene (20 mol%)
Scandium triflate 0.2 parts by weight The above materials were mixed, put into a reactor equipped with a stirrer, and subjected to polycondensation at 120 ° C. for 24 hours. As a result, a uniform transparent amorphous polyester resin (4) was obtained.
Weight average molecular weight by GPC 15,200
Number average molecular weight by GPC 5,100
Glass transition temperature (onset) 62 ℃
Moreover, in the obtained GPC curve, the area ratio of the peak area that appeared after 10 minutes to the polymer-derived peak was 2.9%.
A resin particle dispersion (4) having a median diameter of 196 nm was produced in the same manner as in Example 1-1.
The solid content concentration was 30%.

[Comparative Example 1-1]
1,4-cyclohexanedicarboxylic acid 17.5 parts by weight Bisphenol A ethylene oxide 1 mol adduct (2 mol adduct in terms of both ends)
31.0 parts by weight Linear dodecylbenzenesulfonic acid 0.15 parts by weight The above materials were mixed, put into a reactor equipped with a stirrer, and subjected to polycondensation at 120 ° C. for 24 hours. A crystalline polyester resin (5) was obtained.
Weight average molecular weight by GPC 11,500
Weight average molecular weight by GPC 3,850
Glass transition temperature (onset) 50 ° C
In the obtained GPC curve, the area ratio of the peak area that appeared after 10 minutes to the polymer-derived peak was 3.0%.
A resin particle dispersion (5) having a median diameter of 180 nm was produced in the same manner as in Example 1-1.
The solid content concentration was 30%.

[Comparative Example 1-2]
1,4-Cyclohexanedicarboxylic acid 17.0 parts by weight Bisphenol A 1 mol adduct of ethylene oxide (2 mol adduct in terms of both ends)
1.5 parts by weight (5 mol%)
Bisphenoxyethanol fluorene 41.5 parts by weight (95 mol%)
0.15 parts by weight of linear dodecylbenzene sulfonic acid The above materials were mixed, put into a reactor equipped with a stirrer, and subjected to polycondensation at 140 ° C. for 24 hours. As a result, a uniform transparent amorphous polyester resin (6 )
Weight average molecular weight by GPC 29,000
Weight average molecular weight by GPC 6,800
Glass transition temperature (onset) 90.0 ℃
Moreover, in the obtained GPC curve, the area ratio of the peak area that appeared after 10 minutes to the polymer-derived peak was 2.7%.
The resin thus obtained was put into a three-necked flask equipped with a stirrer and a condenser, and stirring was continued while gradually adding 1N NaOH while maintaining the temperature at 98 degrees. When 50 g of NaOH aqueous solution was added in total, the resin was in a slurry state. This slurry is put into a flask containing 180 g of ion-exchanged water adjusted to 98 ° C., emulsified with a homogenizer (IKA, Ultra Tarrax) for 10 minutes, and then an ultra-high pressure homogenizer (Nanomizer, Yoshida Kikai Kogyo Co., Ltd.). The resin particle dispersion (6) was obtained by emulsifying for 10 passes and then cooling the dispersion with ice. The resin median diameter was 450 nm.
The solid concentration was 29%.

[Comparative Example 1-3]
1,4-phenylene dipropionic acid 22.0 parts by weight Bisphenol A 1 mol adduct of propylene oxide (2 mol adduct in terms of both ends)
34.0 parts by weight (98.5 mol%)
Bisphenoxyethanol fluorene 0.7 parts by weight (1.5 mol%)
p-Chlorobenzenesulfonic acid 0.1 part by weight The above materials were mixed, put into a reactor equipped with a stirrer, and subjected to polycondensation at 120 ° C. for 24 hours. As a result, a uniform transparent amorphous polyester resin (7) was obtained. Obtained.
Weight average molecular weight by GPC 13,500
Weight average molecular weight by GPC 4,050
Glass transition temperature (onset) 50.5 ° C
Moreover, in the obtained GPC curve, the area ratio of the peak area that appeared after 10 minutes to the polymer-derived peak was 2.9%.
A resin particle dispersion (7) having a median diameter of 190 nm was produced in the same manner as in Example 1-1.
The solid concentration was 33%.

[Comparative Example 1-4]
1,4-Cyclohexanedicarboxylic acid 17.0 parts by weight Bisphenol A 1 mol adduct of ethylene oxide (2 mol adduct in terms of both ends)
1.5 parts by weight (5 mol%)
9.0 parts by weight of bisphenoxyethanol fluorene (20 mol%)
Bisphenol Z 1 mol adduct 26.5 parts by weight (75 mol%)
0.15 parts by weight of linear dodecylbenzene sulfonic acid The above materials were mixed, put into a reactor equipped with a stirrer, and subjected to polycondensation at 120 ° C. for 24 hours. 8) was obtained.
Weight average molecular weight by GPC 7,500
Weight average molecular weight by GPC 2,600
Glass transition temperature (onset) 53.5 ° C
Moreover, in the obtained GPC curve, the area ratio of the peak area that appeared after 10 minutes to the polymer-derived peak was 6.2%.
When the resin particle dispersion liquid (8) was produced by the same method as in Example 1-1, the median diameter was 470 nm, but a peak also appeared in the vicinity of 1 μm, and particle aggregation was observed.
The solid concentration was 25%.

[Comparative Example 1-5]
1,4-cyclohexanedicarboxylic acid 5.5 parts by weight (30 mol%)
11.5 parts by weight of terephthalic acid (70 mol%)
Bisphenol A 1 mol adduct of ethylene oxide (2 mol adduct in terms of both ends)
1.5 parts by weight (5 mol%)
9.0 parts by weight of bisphenoxyethanol fluorene (20 mol%)
Bisphenol Z 1 mol adduct (2 mol adduct in terms of both ends)
26.5 parts by weight (75 mol%)
0.15 parts by weight of linear dodecylbenzene sulfonic acid The above materials were mixed, put into a reactor equipped with a stirrer, and subjected to polycondensation at 120 ° C. for 24 hours. As a result, a cloudy low viscosity liquid was obtained and polymerized. It was confirmed that no progress was made.
Weight average molecular weight by GPC 3,600
Number average molecular weight by GPC 1,060
Glass transition temperature (onset) 30 ° C
Moreover, in the obtained GPC curve, the area ratio of the peak area that appeared after 10 minutes to the polymer-derived peak was 26.2%.
When the resin particle dispersion (9) was prepared in the same manner as in Example 1-1, the median diameter was 560 nm, but a peak also appeared in the vicinity of 1 μm, and particle aggregation was observed.
The solid concentration was 29%.

(2) Preparation of release agent particle dispersion (W1) Polyethylene wax 30 parts by weight (manufactured by Toyo Petrolite, Polywax 725, melting point 103 ° C.)
Cationic surfactant 3 parts by weight (manufactured by Kao Corporation, Sanisol B50)
67 parts by weight of ion-exchanged water The above components were sufficiently dispersed while being heated to 95 ° C. with a homogenizer (manufactured by IKA, Ultra Tarrax T50), and then dispersed with a pressure discharge homogenizer (manufactured by Gorin, Gorin homogenizer). A release agent particle dispersion (W1) was prepared. The number average particle diameter D50n of the release agent particles in the obtained dispersion was 4,600 nm. Thereafter, ion exchange water was added to adjust the solid concentration of the dispersion to 30%.

(3) Preparation of Cyan Pigment Dispersion (C1) Cyan Pigment 20 parts by weight (Daiichi Seika Kogyo Co., Ltd., CI Pigment Blue 15: 3)
2 parts by weight of anionic surfactant (Daiichi Kogyo Seiyaku, Neogen R)
Ion-exchanged water 78 parts by weight The above components were mixed and dissolved, and dispersed for 10 minutes with a homogenizer (manufactured by IKA, Ultra Tarrax) for 5 minutes and an ultrasonic bath to obtain a cyan pigment dispersion. The number average particle diameter D50n of the pigment in the dispersion was 121 nm. Thereafter, ion exchange water was added to adjust the solid content concentration of the dispersion to 20%.

(4) Preparation of resin particle dispersion A Styrene 460 parts by weight n-butyl acrylate 140 parts by weight Acrylic acid 12 parts by weight Dodecanethiol 9 parts by weight The above components were mixed and dissolved to prepare a solution.
On the other hand, 12 parts by weight of an anionic surfactant (manufactured by Dow Chemical Co., Dowfax) was dissolved in 250 parts by weight of ion-exchanged water, and the above solution was added and dispersed and emulsified in a flask. (Monomer emulsion A)
Furthermore, 1 part by weight of an anionic surfactant (manufactured by Dow Chemical Co., Dowfax) was dissolved in 555 parts by weight of ion-exchanged water and charged into a polymerization flask.
The polymerization flask was sealed, a reflux tube was installed, and the polymerization flask was heated to 75 ° C. with a water bath while being slowly stirred while injecting nitrogen.
9 parts by weight of ammonium persulfate was dissolved in 43 parts by weight of ion-exchanged water and dropped into the polymerization flask via a metering pump over 20 minutes, and then the monomer emulsion A was added for 200 minutes through the metering pump. It was dripped over.
Thereafter, the polymerization flask was kept at 75 ° C. for 3 hours while continuing the stirring slowly to complete the polymerization.
As a result, an anionic resin particle dispersion A in which the median diameter of the fine particles was 290 nm, the glass transition temperature was 52.0 ° C., the weight average molecular weight was 30,000, and the solid content was 42% was obtained.

(5) Production of electrostatic image developer and electrostatic image developer [Example 2-1]
(Preparation of cyan toner (toner C1))
Resin particle dispersion (1) 120 parts by weight Resin particle dispersion A 40 parts by weight Release agent particle dispersion (W1) 33 parts by weight Cyan pigment dispersion (C1) 60 parts by weight Polyaluminum chloride 10% by weight aqueous solution 15 parts by weight (Asada Chemical Co., PAC1000W)
1% nitric acid aqueous solution 3 parts by weight The above components were dispersed in a round stainless steel flask for 3 minutes at 5,000 rpm using a homogenizer (manufactured by IKA, Ultra Turrax T50). The lid is equipped with a stirring device, a thermometer and a pH meter, and a heating mantle heater is set, and the whole dispersion in the flask is appropriately adjusted to the minimum number of rotations with which the stirring is performed and stirred. The mixture was heated to 1 ° C. at 1 ° C./1 min and held at 62 ° C. for 30 minutes, and the particle size of the aggregated particles was confirmed with a Coulter counter (Beckman-Coulter, Coulter Multisizer II). Immediately after the temperature rise was stopped, 50 parts by weight of the resin fine particle dispersion (1) was added and held for 30 minutes, and then an aqueous sodium hydroxide solution was added until the pH in the system reached 6.5, and then at 1 ° C./1 min. Heated to 97 ° C. After the temperature rise, an aqueous nitric acid solution was added to adjust the pH in the system to 5.0, and the aggregated particles were heated and fused by maintaining for 10 hours. Thereafter, the temperature in the system was lowered to 50 ° C., an aqueous sodium hydroxide solution was added to adjust the pH to 12.0, and the mixture was maintained for 10 minutes. After removing from the flask, sufficiently filtering with ion-exchanged water, washed with water, dispersed in ion-exchanged water so that the solid content is 10% by weight, added with nitric acid, and stirred at pH 3.0 for 10 minutes. Thereafter, the slurry obtained by sufficiently filtering and washing with water using ion exchange water again was freeze-dried to obtain cyan toner base particles (toner base particles C1).

Silica toner base particles (toner base particles C1), silica (SiO ₂ ) particles having a primary particle average particle size of 40 nm and having a surface hydrophobized with hexamethyldisilazane (hereinafter sometimes abbreviated as “HMDS”); 1% by weight of metatitanic acid compound fine particles having an average primary particle diameter of 20 nm, which is a reaction product of metatitanic acid and isobutyltrimethoxysilane, is added in each case, mixed with a Henschel mixer, and a cyan externally added toner (toner C1) is added. Produced.
The toner thus produced had a cumulative volume average particle diameter D ₅₀ of 5.8 μm, a volume average particle size distribution index GSDv of 1.22, and a toner particle shape factor of 128.
Accumulated volume average particle of the toner diameter D ₅₀ and the volume average particle size distribution index GSDv of a laser diffraction particle size distribution analyzer (manufactured by Horiba, Ltd., LA-700), also the shape factor was calculated respectively by the shape observation with a LUZEX.

[Examples 2-2 to 2-4 Comparative Examples 2-1 to 2-5]
In the same manner, using the binder resin particle dispersions obtained in Examples 1-2 to 1-4 Comparative Examples 1-1 to 1-5, the electrostatic charge image developing toner (toner base particles C2 to toner base particles) C9) and externally added toners (toner C2 to toner C9) were prepared (Examples 2-2 to 2-4 and Comparative Examples 2-1 to 2-5). For Comparative Example 2-2, the aggregation temperature was 91 ° C.

<Evaluation of toner cohesion>
When the toner coalescing is unsuitable or insufficient, at the same time, a pigment blended inside the particle or a release agent (wax) having a high hydrophobicity comes out of the particle or agglomerates.
(Evaluation of dispersibility of colorant and release agent)
For each toner base particle (toner base particle C1 to toner base particle C9) obtained in Examples 2-1 to 2-4 and Comparative Examples 2-1 to 2-5, ultra-thin sections were prepared with a cryo, It was observed and evaluated with a transmission electron microscope (TEM). The evaluation criteria are as follows.
(Double-circle): It is fine to the primary particle diameter of a coloring agent and a mold release agent, and is disperse | distributing uniformly in the inside of a toner, and is a very good level.
○: Although slight aggregation of the colorant and the release agent is confirmed, there is no problem as dispersion of the colorant and release agent in the toner if there is no uneven distribution inside the toner.
(Triangle | delta): Although the aggregation and uneven distribution of a coloring agent and a mold release agent are confirmed, it is a level which can be practically used.
X: Aggregation of large colorant and release agent is observed in the toner particles and localized on the toner surface, so that it cannot be used practically.

<Evaluation of low-temperature fixability of documents>
To the toner base particles (toner C1 to toner C9), 1.2 parts by weight of titania powder as an external additive with respect to 100 parts by weight of the toner was added and mixed with a Henschel mixer to obtain an electrostatic image developing toner. Subsequently, 5 parts by weight of each of these toners and 100 parts by weight of ferrite particles (volume average particle diameter 35 μm) covered with 1.5% of dimethyl silicone resin (SR2410, manufactured by Toray Dow Corning Silicone) were mixed to develop two-component development. An agent was prepared, and this was imaged using a Docu Center Color 500 manufactured by Fuji Xerox to obtain an unfixed image.
Next, using a belt nip type external fixing machine, the minimum fixing temperature and hot offset property of the image were evaluated while gradually increasing the fixing temperature between 90 ° C. and 220 ° C. The low-temperature fixability is determined by fixing an unfixed solid image (25 mm × 25 mm), bending it, applying a load of 250 g / cm ² for 10 seconds, returning it, and then returning the bent image The fixing temperature at which the maximum width of the image defect was 0.5 mm or less was used as a minimum fixing temperature, and was used as an index for low-temperature fixability.

<Evaluation of heat-resistant storage stability of documents>
Regarding the evaluation of the heat resistant storage stability of the document, after fixing two unfixed images created at the time of the fixing evaluation at 150 ° C. with an external fixing machine, the image portion, the non-image portion, and the image portion overlap each other. The weight was placed so as to correspond to 80 g / cm ^{2 with} respect to the overlapped portion, and left in a constant temperature and humidity chamber of 60 ° C. and 50% humidity for 3 days. After being left, the degree of image loss of the two fixed images superimposed was graded in five stages from “G1” to “G5” shown below.
G1: Since the image portions are adhered to each other, the paper on which the image is fixed is peeled off, image loss is severe, and clear image transfer to the non-image portion is observed.
G2: Since the images are bonded to each other, white spots of image defects are generated in some parts of the image portion.
G3: When separating the two superimposed images, image blurring or gloss reduction occurs on the fixing surfaces of each other, but the image has an acceptable level with almost no image loss. Some transition is seen in the non-image area.
G4: When two superimposed images are separated, a slight image shift is observed in the non-image portion, but there is no image loss and there is no problem. G5: There is no image loss or image transfer in both the image portion and the non-image. I can't.

<Evaluation of charging stability>
Each developer is housed in the Fuji Xerox Docu Center Color500 developer, and a long-term use test is performed in a high temperature and high humidity environment (30 ° C., 90% RH) and a low temperature and low humidity environment (5 ° C., 10% RH). It was carried out and the transition of charge amount was evaluated.
The criteria for each evaluation item were as follows.
(Charge maintenance)
Under high-temperature, high-humidity and low-temperature, low-humidity environments, obtain the absolute value of the amount of charge change by subtracting the amount of charge after 40,000 prints from the initial charge amount in the same environment. The larger value was judged as ○ when less than 3 μC / g, Δ when the range of 3 to 7 μC / g was larger, and x when larger than 7 μC / g.
The results are shown in the table below.

Claims (8)

A binder resin for electrostatic charge image developing toner obtained by polycondensation reaction of polycarboxylic acid and polyol,
10 mol% or more and 95 mol% or less of the polyol is composed of a compound represented by the formula (1), and 5 mol% or more and 90 mol% or less of the polyol is composed of a compound represented by the formula (2). Binder resin for charge image developing toner.
HOX ¹ _h -Ph-Y-Ph-X ^{1 '} _k OH (1)
(X ¹ , X ^{1 ′} : alkylene oxide group, Y: C (CH ₃ ) ₂ or SO ₂ , 1 ≦ h ≦ 3, 1 ≦ k ≦ 3)

(X ² , X ^{2 ′} : alkylene group, R ^{1 to} R ⁴ : hydrogen atom or monovalent substituent, R ⁵ , R ⁶ : monovalent substituent, 1 ≦ m ≦ 3, 1 ≦ n ≦ 3, 0 ≦ p ≦ 4, 0 ≦ q ≦ 4) 2. The binder resin for electrostatic image developing toner according to claim 1, wherein 50 mol% or more and 100 mol% or less of the polycarboxylic acid is composed of a compound represented by Formula (3) and / or Formula (4).
Q ¹ OOCA ¹ _m B ¹ _n A ^{1 ′} _l COOQ ^{1 ′} (3)
(A ¹ , A ^{1 ′} methylene group, B ¹ : aromatic hydrocarbon group, Q ¹ , Q ^{1 ′} : hydrogen atom or monovalent hydrocarbon group, 1 ≦ m + l ≦ 12, 1 ≦ n ≦ 3)
Q ² OOCA ² _p B ² _q A ^{2 ′} _r COOQ ^{2 ′} (4)
(A ² , A ^{2 ′} : methylene group, B ² : alicyclic hydrocarbon group, Q ² , Q ^{2 ′} : hydrogen atom or monovalent hydrocarbon group, 0 ≦ p ≦ 6, 0 ≦ r ≦ 6, 1 ≦ q ≦ 3)   A binder resin dispersion for an electrostatic charge image developing toner, wherein the binder resin for an electrostatic charge image developing toner according to claim 1 is dispersed. A step of aggregating the binder resin in a dispersion containing at least a binder resin dispersion to obtain aggregated particles; and
A method for producing an electrostatic charge image developing toner comprising a step of heating and aggregating the aggregated particles,
The method for producing an electrostatic image developing toner, wherein the binder resin dispersion is the binder resin dispersion for an electrostatic image developing toner according to claim 3.   An electrostatic charge image developing toner produced by the production method according to claim 4.   An electrostatic image developing toner produced by kneading and pulverizing the binder resin for electrostatic image developing toner according to claim 1.   An electrostatic charge image developer comprising the electrostatic charge image developing toner according to claim 5 and a carrier. A latent image forming step of forming an electrostatic latent image on the surface of the latent image holding member;
A developing step of developing the electrostatic latent image formed on the surface of the latent image holding member with toner or an electrostatic charge image developer to form a toner image;
Transferring the toner image formed on the surface of the latent image carrier to the surface of the recording medium;
A fixing step of thermally fixing the toner image transferred to the surface of the recording medium,
An image forming method using the electrostatic image developing toner according to claim 5 or 6 as the toner, or the electrostatic image developer according to claim 7 as the developer.