JP2014153691A - Toner for electrostatic charge image development, electrostatic charge image developer, toner cartridge, image forming method, and image forming apparatus - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide toner for electrostatic charge image development, configured to reduce dielectric loss, to improve transferability from a photoreceptor, and to form a metallic gloss image.SOLUTION: There is provided toner for electrostatic charge image development which contains binder resin and colorant. The colorant contains an organic compound having a group represented by the following formula (1). There are provided also electrostatic charge image developer using the toner for electrostatic charge image development, a toner cartridge, an image forming method, and an image forming apparatus. In the formula (1), Y is a hydrogen atom or a cyano group.

Description

  The present invention relates to an electrostatic charge image developing toner, an electrostatic charge image developer, a toner cartridge, an image forming method, and an image forming apparatus.

Methods for visualizing image information through an electrostatic charge image, such as electrophotography, are currently used in various fields.
In conventional electrophotography, an electrostatic latent image is formed on a photosensitive member or an electrostatic recording body by using various means, and electro-sensitive particles called toner are attached to the electrostatic latent image to form an electrostatic latent image. Generally, a method of visualizing through a plurality of steps of developing an image (toner image), transferring it to the surface of a transfer medium, and fixing it by heating or the like is generally used.
The color of an image created by electrophotography is not only a process color, but there is an increasing need to have a metallic luster such as gold and silver for decorative purposes.
As a pigment used in a metallic glossy toner (metallic toner), a metal powder pigment such as an aluminum powder or a bronze powder is used.

Examples of conventional metallic toners include Patent Documents 1 to 4.
Patent Document 1 discloses a metallic capsule toner comprising a core toner particle and a shell material covering the core toner, wherein a flaky substance having a metallic luster is present in the vicinity of the surface of the core substance. Have been described.
Patent Document 2 discloses that a domain resin composition containing a colorant and a metallic material in a domain resin, a matrix resin composition having low miscibility with the domain resin, and miscibility in both the domain resin and the matrix resin. In addition, an electrophotographic toner is described in which at least a dispersion aid having an Izod impact value higher than that of the matrix resin is included, and the domain resin composition is dispersed in the matrix resin composition via the dispersion aid.
Patent Document 3 discloses a toner including at least a binder resin and a colorant, wherein the colorant is coated with silver on flat glass flakes having an average thickness of 2 to 5 μm and an average length in the longitudinal direction of 15 to 500 μm. A golden toner for electrostatic latent image development is described which is a glitter pigment.
Patent Document 4 discloses pigment particles comprising at least one metal oxide surface additive, wherein the at least one metal oxide surface additive is covalently bonded to at least one polycondensation polymer. And pigment particles are described, wherein the pigment particles are pearlescent pigments or metallic pigments.

Moreover, what was described in patent document 5 is known as an organic colorant which has metallic luster.
Patent Document 5 describes particles for display devices in which a coating layer of a compound having at least one functional group represented by the following general formula (1) is provided on the surface of non-light-transmitting particles.

JP-A-2-6962 JP-A-5-289395 JP 2003-207941 A JP 2009-209367 A JP 2008-158092 A

  An object of the present invention is to provide a toner for developing an electrostatic charge image that has a low dielectric loss, is excellent in transferability from a photoreceptor, and can obtain a metallic glossy image.

The above-described problems of the present invention have been solved by means described in the following <1> and <3> to <6>. It is described below together with <2> which is a preferred embodiment.
<1> an electrostatic charge image developing toner comprising a binder resin and a colorant, wherein the colorant contains an organic compound having a group represented by the following formula (1):

（式（１）中、Ｙは水素原子又はシアノ基を表す。）

(In formula (1), Y represents a hydrogen atom or a cyano group.)

  <2> The electrostatic image developing toner according to <1>, wherein the organic compound having a group represented by the formula (1) is a compound represented by the following formula (2) or the formula (3): ,

（式（２）中、Ｘ¹及びＸ³はそれぞれ独立に、ＮＨ、Ｏ又はＳを表し、Ｘ²はＮ、Ｏ又はＳを表し、Ｒ¹は水素原子、アルキル基、芳香族基、複素環基、ホルミル基、アシル基、アルコキシカルボニル基又はアルケニル基を表し、Ｒ²は水素原子、２，２−ジシアノエテニル基、トリシアノエテニル基、アルキル基、芳香族基、複素環基、ホルミル基、アシル基、アルコキシカルボニル基又はアルケニル基を表し、Ｒ³及びＲ⁴はそれぞれ独立に、水素原子又は芳香族基を表し、Ｙは水素原子又はシアノ基を表し、ｎは１〜３の整数を表し、ｐは０又は１を表す。）

(In formula (2), X ¹ and X ³ each independently represent NH, O or S, X ² represents N, O or S, and R ¹ represents a hydrogen atom, an alkyl group, an aromatic group, a complex, Represents a cyclic group, a formyl group, an acyl group, an alkoxycarbonyl group or an alkenyl group, and R ² represents a hydrogen atom, 2,2-dicyanoethenyl group, tricyanoethenyl group, alkyl group, aromatic group, heterocyclic group, formyl group, An acyl group, an alkoxycarbonyl group or an alkenyl group, R ³ and R ⁴ each independently represents a hydrogen atom or an aromatic group, Y represents a hydrogen atom or a cyano group, and n represents an integer of 1 to 3. , P represents 0 or 1.)

（式（３）中、Ａ¹はｍ価の、芳香族基、複素環基、縮合多環基、脂環基、スピロ環基、ビフェニル残基、フルオレン残基又はトリフェニルアミン骨格をコアとするデンドリマー構造を表し、Ｘ⁴はそれぞれ独立に、二価の芳香族基又は二価の複素環基を表し、Ｒ⁵はそれぞれ独立に、芳香族基、複素環基、アルキル基、アルケニル基又はシクロアルキル基を表し、Ｙは水素原子又はシアノ基を表し、ｍは２以上の整数を表す。）

(In Formula (3), A ¹ is an m-valent aromatic group, heterocyclic group, condensed polycyclic group, alicyclic group, spirocyclic group, biphenyl residue, fluorene residue or triphenylamine skeleton as a core. Each of X ⁴ independently represents a divalent aromatic group or a divalent heterocyclic group, and R ⁵ each independently represents an aromatic group, a heterocyclic group, an alkyl group, an alkenyl group or Represents a cycloalkyl group, Y represents a hydrogen atom or a cyano group, and m represents an integer of 2 or more.)

<3> The electrostatic image developing toner according to <1> or <2> above, and an electrostatic image developer containing a carrier,
<4> A toner cartridge that is detachable from the image forming apparatus and contains the electrostatic charge image developing toner according to <1> or <2> above,
<5> A latent image forming step of forming an electrostatic latent image on the surface of the image carrier, a developing step of developing the electrostatic latent image formed on the surface of the image carrier with toner to form a toner image, and the toner image And a fixing step of fixing the toner image transferred to the surface of the transfer medium, wherein the toner is an electrostatic charge image according to <1> or <2> An image forming method which is a developing toner;
<6> An image holding member, a charging unit that charges the image holding member, an exposure unit that exposes the charged image holding member to form an electrostatic latent image on the surface of the image holding member, and the static with toner. A developing unit that develops the electrostatic latent image to form a toner image, a transfer unit that transfers the toner image from the image holding member to the surface of the transfer target, and a toner image transferred to the surface of the transfer target are fixed. An image forming apparatus, wherein the toner is the electrostatic image developing toner according to <1> or <2>.

According to the invention described in the above <1>, for electrostatic image development, the dielectric loss is small, the transferability from the photoreceptor is excellent, and a metallic glossy image can be obtained as compared with the case where the present configuration is not provided. Toner is provided.
According to the invention described in <2> above, the dielectric loss is smaller than when the organic compound having the group represented by the formula (1) is not a compound represented by the formula (2) or the formula (3). There is provided a toner for developing an electrostatic charge image that is less and more excellent in transferability from a photoreceptor.
According to the invention described in the above <3>, the electrostatic charge image developer has less dielectric loss, excellent transferability from the photoreceptor, and can obtain a metallic glossy image as compared with the case without the present configuration. Is provided.
According to the invention described in <4> above, for electrostatic image development, the dielectric loss is small, the transferability from the photoreceptor is excellent, and a metallic glossy image can be obtained as compared with the case without this configuration. A toner cartridge for containing toner is provided.
According to the invention described in <5> above, an image forming method in which the dielectric loss of the toner is small, the transferability from the photoreceptor is excellent, and a metallic glossy image can be obtained as compared with the case without the present configuration. Is provided.
According to the invention described in <6>, the image forming apparatus can reduce the dielectric loss of the toner, has excellent transferability from the photoreceptor, and can obtain a metallic glossy image as compared with the case where the present configuration is not provided. Is provided.

Hereinafter, the present embodiment will be described.
In the present embodiment, the description “A to B” represents not only a range between A and B but also a range including A and B which are both ends thereof. For example, if “A to B” is a numerical value range, it represents “A or more and B or less” or “B or more and A or less”.

(Static image developing toner)
The electrostatic image developing toner of the present embodiment (hereinafter also simply referred to as “toner”) contains a binder resin and a colorant, and the colorant is a group represented by the following formula (1). It contains the organic compound which has this.

（式（１）中、Ｙは水素原子又はシアノ基を表す。）

(In formula (1), Y represents a hydrogen atom or a cyano group.)

When a metal powder pigment having high electrical conductivity is used as the colorant of the metallic glossy toner, the electrical characteristics of the toner are deteriorated. In order to avoid this, it is common to coat or hydrophobize metal pigments with resin, silica, titanium, etc., but the coverage is low, the coating thickness is thin, and the strength is not sufficient. There are problems such as the metal pigment being exposed on the surface due to cracks and peeling, etc., the toner has insufficient electrical insulation, especially the dielectric loss of the toner is large, and from the image carrier (photoreceptor) The inventor has confirmed that the transferability (transfer efficiency) of the ink drops.
As a result of detailed studies by the inventor, an organic compound having a group represented by the formula (1) is used as a colorant instead of a metal pigment having high electrical conductivity. It was found that the toner dielectric loss was improved and the transferability was improved.
In addition, the metallic luster in the present embodiment means a characteristic luster specific to metals, that is, a property of reflecting light, as seen on a polished metal surface. However, the toner of the present exemplary embodiment can obtain a metallic glossy image by using the organic compound having the group represented by the formula (1). It is done. Further, the metallic glossy image obtained by the toner of the present embodiment is not particularly limited as long as it is a metallic glossy tone and has not only any color, for example, gold, silver, bronze, but also a forbidden gloss. Blue, yellow, green, purple, red, etc. may be sufficient.
Hereinafter, each component and physical property value constituting the toner will be described in detail.

<Organic Compound Having Group Represented by Formula (1)>
The toner of this embodiment contains an organic compound having a group represented by the formula (1).
In the organic compound having a group represented by the formula (1), the group represented by the formula (1) is preferably bonded to an aromatic ring or a heteroaromatic ring, and preferably bonded to a heteroaromatic ring. More preferably, it is more preferably bonded to a pyrrole ring, thiophene ring or furan ring, and particularly preferably bonded to a thiophene ring or furan ring. With the above aspect, a metallic glossy image can be obtained, and a toner excellent in transferability from a photoreceptor even in a high temperature and high humidity environment can be obtained.
The shape of the organic compound having a group represented by the formula (1) is not particularly limited, but an organic crystal having a group represented by the formula (1) or a group represented by the formula (1) An organic powder having a group represented by formula (1) is particularly preferred. In the above embodiment, the stability of the compound is excellent, and a metallic glossy image can be obtained more clearly.

The organic compound having a group represented by the formula (1) may have only one group represented by the formula (1) or may have two or more, but is represented by the formula (1). The number of groups to be formed is preferably 1 to 6, more preferably 1 to 3, and particularly preferably 1 or 2.
Further, the organic compound having a group represented by the formula (1) is preferably a compound having a molecular weight of less than 2,000, and more preferably a compound having a molecular weight of less than 1,000.
Y in the group represented by the formula (1) represents a hydrogen atom or a cyano group, and is preferably a cyano group from the viewpoint of crystallinity.
Moreover, the wavy line part in the group represented by the formula (1) represents a coupling position with another structure.
Examples of the organic compound having a group represented by the formula (1) include 2,5-dithienylpyrrole compounds and 2-thienyl-5-furanyl having at least one group represented by the formula (1). Preferred examples include pyrrole compounds, triarylamine compounds, and diarylamine compounds.
As an organic compound which has group represented by Formula (1), the compound represented by following formula (2) or Formula (3) is mentioned preferably, The compound represented by following formula (2) is mentioned more preferably. It is done.

（式（２）中、Ｘ¹及びＸ³はそれぞれ独立に、ＮＨ、Ｏ又はＳを表し、Ｘ²はＮ、Ｏ又はＳを表し、Ｒ¹は水素原子、アルキル基、芳香族基、複素環基、ホルミル基、アシル基、アルコキシカルボニル基又はアルケニル基を表し、Ｒ²は水素原子、２，２−ジシアノエテニル基、トリシアノエテニル基、アルキル基、芳香族基、複素環基、ホルミル基、アシル基、アルコキシカルボニル基又はアルケニル基を表し、Ｒ³及びＲ⁴はそれぞれ独立に、水素原子又は芳香族基を表し、Ｙは水素原子又はシアノ基を表し、ｎは１〜３の整数を表し、ｐは０又は１を表す。）

(In formula (2), X ¹ and X ³ each independently represent NH, O or S, X ² represents N, O or S, and R ¹ represents a hydrogen atom, an alkyl group, an aromatic group, a complex, Represents a cyclic group, a formyl group, an acyl group, an alkoxycarbonyl group or an alkenyl group, and R ² represents a hydrogen atom, 2,2-dicyanoethenyl group, tricyanoethenyl group, alkyl group, aromatic group, heterocyclic group, formyl group, An acyl group, an alkoxycarbonyl group or an alkenyl group, R ³ and R ⁴ each independently represents a hydrogen atom or an aromatic group, Y represents a hydrogen atom or a cyano group, and n represents an integer of 1 to 3. , P represents 0 or 1.)

（式（３）中、Ａ¹はｍ価の、芳香族基、複素環基、縮合多環基、脂環基、スピロ環基、ビフェニル残基、フルオレン残基又はトリフェニルアミン骨格をコアとするデンドリマー構造を表し、Ｘ⁴はそれぞれ独立に、二価の芳香族基又は二価の複素環基を表し、Ｒ⁵はそれぞれ独立に、芳香族基、複素環基、アルキル基、アルケニル基又はシクロアルキル基を表し、Ｙは水素原子又はシアノ基を表し、ｍは２以上の整数を表す。）

(In Formula (3), A ¹ is an m-valent aromatic group, heterocyclic group, condensed polycyclic group, alicyclic group, spirocyclic group, biphenyl residue, fluorene residue or triphenylamine skeleton as a core. Each of X ⁴ independently represents a divalent aromatic group or a divalent heterocyclic group, and R ⁵ each independently represents an aromatic group, a heterocyclic group, an alkyl group, an alkenyl group or Represents a cycloalkyl group, Y represents a hydrogen atom or a cyano group, and m represents an integer of 2 or more.)

X ¹ and X ³ in Formula (2) are each independently preferably O or S, and more preferably S. In the above embodiment, the compound is excellent in stability and crystallinity, and is easy to synthesize.
X ² in the formula (2) is preferably N, and p is preferably 1. In the above embodiment, the compound is excellent in stability and crystallinity, and becomes a compound having a stronger metallic luster color.

The alkyl group in R ¹ of formula (2) is preferably an alkyl group having 1 to 30 carbon atoms, particularly preferably an alkyl group having 1 to 18 carbon atoms. The alkyl group may be linear, branched or cyclic, and examples of the substituent of the alkyl group include an alkoxy group having 1 to 18 carbon atoms, a phenyl group, a naphthyl group, a benzothienyl group, an indolyl group, and a pyridyl group. Aromatic groups such as phenoxy group, naphthyloxy group, bromine atom, iodine atom, chlorine atom and fluorine atom are particularly preferred.
As an aromatic group in R < ¹ > of Formula (2), a phenyl group, a naphthyl group, a thienyl group, a benzothienyl group, an indolyl group, and a pyridyl group are preferable. As the substituent of the aromatic group, an alkyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, a phenoxy group, a naphthyloxy group, a bromine atom, an iodine atom, a chlorine atom, a fluorine atom, a monoalkylamino group , A dialkylamino group, a monoarylamino group, a diarylamino group and a thioalkyl group are preferred, and the alkyl group constituting the thioalkyl group preferably has 1 to 30 carbon atoms, and more preferably 1 to 18 carbon atoms.
The aromatic group in R ² of the formula (2) is preferably a group derived from a compound group composed of an aromatic ring having 6 to 30 carbon atoms, and is a substituted or unsubstituted phenyl group or biphenyl group. Or it is more preferable that it is a naphthyl group.
As the heterocyclic group in R ² of the formula (2), a pyridine ring, a pyrazine ring, a pyrimidine ring, a pyridazine ring, a triazine ring, an indoline ring, a quinoline ring, an acridine ring, a carbazole ring, a furan ring, a thiophene ring, an oxazole ring, Derived from a compound group composed of C2-C30 heterocycles such as oxadiazole ring, benzoxazole ring, thiazole ring, thiadiazole ring, benzothiazole ring, triazole ring, benzotriazole ring, imidazole ring, benzimidazole ring It is preferred that
The aromatic group in R ³ and R ⁴ in the formula (2) is preferably a group derived from a compound group composed of an aromatic ring having 6 to 30 carbon atoms, and a substituted or unsubstituted phenyl group , Biphenyl group or naphthyl group is preferable.

R ¹ in formula (2) is preferably an aromatic group, more preferably a substituted or unsubstituted phenyl group, further preferably a phenyl group having a substituent, and a substituent at the p-position. Particularly preferred is a phenyl group having only one group. In the above embodiment, the compound is excellent in stability and crystallinity, and a compound having a desired color can be easily synthesized.
As the substituent of the phenyl group in R ¹ of the formula (2), an alkyl group, an alkoxy group, a phenoxy group, a naphthyloxy group, a bromine atom, an iodine atom, a chlorine atom, a fluorine atom, a monoalkylamino group, a dialkylamino group It is preferably a group selected from the group consisting of a monoarylamino group, a diarylamino group, and a thioalkyl group, an alkyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, a bromine atom, chlorine It is more preferably a group selected from the group consisting of an atom, a fluorine atom, and a thioalkyl group having 1 to 18 carbon atoms, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, and a bromine atom. More preferably a group selected from the group consisting of a chlorine atom, a fluorine atom, and a thioalkyl group having 1 to 8 carbon atoms. Particularly preferably 8 alkyl group, and most preferably an alkyl group having 14 to 18 carbon atoms. In the above embodiment, the stability and crystallinity of the compound is excellent, and the toner dielectric loss is smaller.
R ² in Formula (2) is preferably a hydrogen atom, a 2,2-dicyanoethenyl group or a tricyanoethenyl group, and more preferably a hydrogen atom or a tricyanoethenyl group. In the above embodiment, the compound is excellent in stability and crystallinity, and is easy to synthesize.
R ³ and R ⁴ in formula (2) are preferably both hydrogen atoms.
Y in Formula (2) is preferably a cyano group. In the above embodiment, the compound is excellent in stability and crystallinity, and becomes a compound having a stronger metallic luster color.
N in Formula (2) is preferably 1 or 2, and particularly preferably 1. In the above embodiment, the compound is excellent in crystallinity and has a stronger metallic luster color.

The m-valent aromatic group in A ¹ of Formula (3) is preferably an m-valent group derived from a compound group composed of an aromatic ring having 6 to 30 carbon atoms, such as a benzene ring, a biphenyl ring, And a group obtained by removing m hydrogen atoms from a ring selected from the group consisting of naphthalene rings, and a group obtained by removing m hydrogen atoms from a ring selected from the group consisting of benzene rings and biphenyl rings. More preferably, it is a group obtained by removing m hydrogen atoms from the biphenyl ring.
The heterocyclic group in A ¹ of the formula (3) is preferably an m-valent group derived from a compound group composed of a heterocyclic ring having 2 to 30 carbon atoms, and includes a pyridine ring, a pyrazine ring, a pyrimidine ring, Pyridazine ring, triazine ring, indoline ring, quinoline ring, acridine ring, carbazole ring, furan ring, thiophene ring, oxazole ring, oxadiazole ring, benzoxazole ring, thiazole ring, thiadiazole ring, benzothiazole ring, triazole ring, benzo A group obtained by removing m hydrogen atoms from a ring selected from the group consisting of a triazole ring, an imidazole ring, and a benzimidazole ring is more preferable.
The condensed polycyclic residue in A ¹ of the formula (3) is a group derived from a compound in which an aromatic ring or a heterocyclic ring is further condensed by sharing one or more sides with the above aromatic group or heterocyclic group. Say. Among these, a group obtained by removing m hydrogen atoms from the fluorene ring is preferable.
The alicyclic group in A ¹ of formula (3) is a saturated cyclic carbon compound derivative such as cyclopropane, cyclobutane, cyclopentane, or cyclohexane, or an unsaturated cyclic carbon compound derivative that is not an aromatic ring in which a part of the ring is unsaturated. , Means a spirocyclic carbon compound derivative containing a spiro atom as part of its structure. Among them, a group obtained by removing m hydrogen atoms from a structure in which two fluorene rings are bonded by a central carbon atom to form a spiro ring is preferable.
The triarylamine residue in A ¹ of the formula (3) refers to a group derived from a compound containing a dendrimer structure having a triarylamine structure as a core in a part of the structure.

Each group in A ¹ , X ⁴ and R ⁵ in formula (3) may have a substituent, if possible. As the substituent, an alkyl group that may have a substituent, a cycloalkyl group that may have a substituent, an alkenyl group that may have a substituent, an aryl group that may have a substituent, A heterocyclic group that may have a substituent, an alkoxy group that may have a substituent, an alkylthio group that may have a substituent, an aryloxy group that may have a substituent, and a substituent; An arylthio group which may have a substituent, an alkenyloxy group which may have a substituent, an acyloxy group, an alkoxycarbonyl group, a carbamoyl group, an acylamino group, an amino group which may have a substituent, an acyl group, a sulfonamide group, Cyano group, nitro group, halogen atom, silyl group, carboxyl group, phosphoryl group, phosphonyl group, sulfonyl group, sulfonic acid group, hydroxy group, thiol group, hydroxamic acid group, etc. Is not limited to this, one type of group multiple or two or more kinds of substituents may be one by one or a plurality. In addition, substituents may be bonded to form a ring, and a salt may be formed with an alkali metal, alkaline earth metal, quaternary ammonium, or the like depending on the application.

A ¹ in Formula (3) is preferably an m-valent aromatic group or an m-valent alicyclic group, and more preferably an m-valent aromatic group.
In formula (3), each X ⁴ is independently a divalent fragrance having 6 or more carbon atoms such as a phenylene group from the viewpoint of enhancing the interaction between molecules by the π-electron system and improving the crystallinity due to the stack structure. It is preferably a group group, and more preferably a phenylene group.
In the formula (3), each R ⁵ is preferably an aromatic group from the viewpoint of strengthening the interaction between molecules by the π-electron system and forming the crystallinity by the stack structure, and is a phenyl group or a naphthyl group. More preferably.
Y in Formula (3) is preferably a cyano group. In the above embodiment, the compound is excellent in stability and crystallinity, and becomes a compound having a stronger metallic luster color.
M in Formula (3) is preferably an integer of 2 to 100, more preferably an integer of 2 to 6, and still more preferably 2 or 3.

  The compound represented by the formula (2) is preferably a compound represented by the following formula (4) to formula (6).

R ^{6 to} R ⁸ in formula (4) to formula (6) are each independently an alkyl group, alkoxy group, phenoxy group, naphthyloxy group, bromine atom, iodine atom, chlorine atom, fluorine atom, monoalkylamino group, Represents a group selected from the group consisting of a dialkylamino group, a monoarylamino group, a diarylamino group, and a thioalkyl group, an alkyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, a bromine atom, chlorine It is preferably a group selected from the group consisting of an atom, a fluorine atom, and a thioalkyl group having 1 to 18 carbon atoms, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a bromine atom, It is more preferably a group selected from the group consisting of a chlorine atom, a fluorine atom, and a thioalkyl group having 1 to 8 carbon atoms, and is an alkyl group having 1 to 18 carbon atoms. It is more preferable, and particularly preferably an alkyl group having 14 to 18 carbon atoms. In the above embodiment, the stability and crystallinity of the compound is excellent, and the toner dielectric loss is smaller.

  As a compound represented by Formula (3), the compound shown below is mentioned preferably.

The organic compound which has group represented by Formula (1) may contain individually by 1 type, or may contain 2 or more types.
The content of the organic compound having a group represented by the formula (1) is preferably 0.1 to 50 parts by weight, and preferably 0.2 to 20 parts by weight with respect to 100 parts by weight of the toner. More preferred is 0.5 to 10 parts by weight.
As a method for dispersing the organic compound having the group represented by the formula (1), an arbitrary method, for example, a general dispersion method such as a rotary shear type homogenizer, a ball mill having a medium, a sand mill, or a dyno mill may be used. Yes, it is not limited at all. Moreover, the organic compound which has group represented by Formula (1) may be added to a mixed solvent at once with other components, and may be divided and added in multiple steps.
The average primary particle size of the organic compound having a group represented by the formula (1) in the toner of the exemplary embodiment is preferably 0.1 to 100 μm, and more preferably 5 to 35 μm.
In addition, the dielectric loss factor in the toner of the exemplary embodiment is preferably 0 to 0.030, and more preferably 0.005 to 0.030.
The dielectric loss ratio in the toner is preferably measured by the following method.
Using a compression molding machine (BRIQUETING PRESS) manufactured by Maekawa Tester Mfg. Co., Ltd., 6 g of toner is compressed with a load of 10 t and pressurization for 60 seconds to produce a molding disk having a diameter of 50 mm and a thickness of 3.0 mm. A molding disk left for 24 hours in an atmosphere of 90 ° C and humidity of 90 ° C was measured with a dielectric property measuring machine (WAYNE PRECISION COMPONENT ANALYZER) manufactured by Toyo Technica Co., Ltd., with an AC frequency of 1,000 Hz and a repeat count of 100 times. Set and measure the dielectric loss factor. Regarding the measurement, the measurement is repeated 100 times under the above conditions, and the average value is adopted as the value of the dielectric loss factor.

<Binder resin>
The toner of this embodiment contains a binder resin.
Examples of the binder resin include polycondensation resins and addition polymerization resins. For example, polyolefin resins such as polyethylene and polypropylene, styrene resins mainly composed of polystyrene, poly (α-methylstyrene), and polymethyl. Examples include (meth) acrylic resins, styrene- (meth) acrylic copolymer resins, polyamide resins, polycarbonate resins, polyether resins, polyester resins, and copolymer resins mainly composed of methacrylate, polyacrylonitrile, and the like. .
Among these, a polyester resin is preferable as the binder resin. Since the polyester resin is hydrophilic, it is well dispersed during toner formation, and the europium colorant is taken into the toner base particles in a more uniform state.

As the polycondensation resin, for example, polyester resin and polyamide resin can be preferably exemplified, and in particular, a polyester resin obtained by using a polycarboxylic acid and a polyol as a polycondensable monomer. It is preferable.
Examples of the polycondensable monomer that can be used in this embodiment include polycarboxylic acids, polyols, hydroxycarboxylic acids, polyamines, and mixtures thereof. In particular, the polycondensable monomer is preferably a polyvalent carboxylic acid, a polyol, and further an ester compound (oligomer and / or prepolymer) thereof. After undergoing a direct ester reaction or transesterification reaction, a polyester is obtained. What obtains resin is good.
In the present embodiment, the polycondensation resin is obtained by polycondensation of at least one selected from the group consisting of polycondensable monomers, oligomers thereof and prepolymers. Is preferably used.

The polyvalent carboxylic acid is a compound containing two or more carboxyl groups in one molecule. Among these, dicarboxylic acid is a compound containing two carboxyl groups in one molecule. For example, oxalic acid, succinic acid, glutaric acid, maleic acid, adipic acid, β-methyladipic acid, azelaic acid, sebacic acid, Nonanedicarboxylic acid, decanedicarboxylic acid, undecanedicarboxylic acid, dodecanedicarboxylic acid, fumaric acid, citraconic acid, diglycolic acid, cyclohexane-3,5-diene-1,2-carboxylic acid, hexahydroterephthalic acid, malonic acid, pimeline Acid, peric acid, phthalic acid, isophthalic acid, terephthalic acid, tetrachlorophthalic acid, chlorophthalic acid, nitrophthalic acid, p-carboxyphenylacetic acid, p-phenylenediacetic acid, m-phenylenediacetic acid, o-phenylenediacetic acid, diphenyl Acetic acid, diphenyl-p, p'-dicarboxylic acid, naphth Ren-1,4-dicarboxylic acid, naphthalene-1,5-dicarboxylic acid, naphthalene-2,6-dicarboxylic acid, anthracene dicarboxylic acid, and cyclohexane dicarboxylic acid.
Examples of the polycarboxylic acid other than dicarboxylic acid include trimellitic acid, trimesic acid, pyromellitic acid, naphthalenetricarboxylic acid, naphthalenetetracarboxylic acid, pyrenetricarboxylic acid, pyrenetetracarboxylic acid, itaconic acid, glutaconic acid, Examples thereof include n-dodecyl succinic acid, n-dodecenyl succinic acid, isododecyl succinic acid, isododecenyl succinic acid, n-octyl succinic acid, n-octenyl succinic acid, and the like, and lower esters thereof. Furthermore, acid halides and acid anhydrides are not limited to this.
These may be used individually by 1 type and may use 2 or more types together.
In addition, a lower ester shows that the carbon number of the alkoxy part of ester is 1-8. Specific examples include methyl ester, ethyl ester, n-propyl ester, isopropyl ester, n-butyl ester, and isobutyl ester.

A polyol is a compound containing two or more hydroxyl groups in one molecule. Among these, diol is a compound containing two hydroxyl groups in one molecule. Specifically, for example, as diol, ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,13-tridecanediol, 1,14-tetradecanediol, 1,18-octadecanediol, 1,14-eicosandecanediol, diethylene glycol, triethylene glycol , Dipropylene glycol, polyester Lenglycol, polypropylene glycol, polytetramethylene ether glycol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, 1,4-butenediol, neopentyl glycol, 1,4-cyclohexanediol, polytetramethylene glycol, Examples include hydrogenated bisphenol A, bisphenol A, bisphenol F, bisphenol S, and alkylene oxide (ethylene oxide, propylene oxide, butylene oxide, etc.) adducts of the above bisphenols. Among these, preferred are alkylene glycols having 2 to 12 carbon atoms and alkylene oxide adducts of bisphenols, and particularly preferred are alkylene oxide adducts of bisphenols and alkylene glycols having 2 to 12 carbon atoms. It is combined use with.
Moreover, in order to make water dispersibility easy, a 2, 2- dimethylol propionic acid, a 2, 2- dimethylol butanoic acid, a 2, 2- dimethylol valeric acid etc. are illustrated, for example.

Examples of trihydric or higher alcohols include glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, hexamethylolmelamine, hexaethylolmelamine, tetramethylolbenzoguanamine, tetraethylolbenzoguanamine, sorbitol, trisphenol PA, phenol novolac, Examples thereof include cresol novolac, and alkylene oxide adducts of the above trivalent or higher polyphenols. These may be used individually by 1 type and may use 2 or more types together.
In addition, an amorphous resin or a crystalline resin can be easily obtained by combining these polycondensable monomers.

  Hydroxycarboxylic acid can also be used. Specific examples of the hydroxycarboxylic acid include hydroxyheptanoic acid, hydroxyoctanoic acid, hydroxydecanoic acid, hydroxyundecanoic acid, malic acid, tartaric acid, mucoic acid, and citric acid.

  Polyamines include ethylenediamine, diethylenediamine, 1,2-propanediamine, 1,3-propanediamine, 1,4-butanediamine, 1,4-butenediamine, 2,2-dimethyl-1,3-butane. Examples include diamine, 1,5-pentanediamine, 1,6-hexanediamine, 1,4-cyclohexanediamine, 1,4-cyclohexanebis (methylamine), and the like.

  The weight average molecular weight of the polycondensation resin obtained by polycondensation of the polycondensable monomer is preferably 1,500 or more and 40,000 or less, and preferably 3,000 or more and 30,000 or less. More preferred. When the weight average molecular weight is 1,500 or more, the cohesive force of the binder resin is good and the hot offset property is excellent, and when it is 40,000 or less, the hot offset property is excellent and the minimum fixing temperature is excellent. This is preferable. Further, it may be partially branched or cross-linked by selecting the carboxylic acid valence or alcohol valence of the monomer.

Moreover, it is preferable that the acid value of the polyester resin obtained is 1 mg * KOH / g or more and 50 mg * KOH / g or less. The first reason is that control of the particle size and distribution of the toner in the aqueous medium is indispensable for practical use as a high-quality toner, and the acid value is 1 mg · KOH / g or more. In the granulation step, sufficient particle size and distribution can be achieved, and when used in toner, sufficient chargeability can be obtained. Further, when the acid value of the polyester to be polycondensed is 50 mg · KOH / g or less, a sufficient molecular weight for obtaining image quality strength as a toner at the time of polycondensation can be obtained, and the chargeability of the toner under high humidity can be obtained. Is less dependent on the environment and has excellent image reliability.
Although there is no restriction | limiting in particular as a measuring method of an acid value, It is preferable to measure according to JISK0070.

When an amorphous polyester resin is used, the glass transition temperature Tg of the amorphous polyester resin is preferably 50 to 80 ° C, and more preferably 50 to 65 ° C. When the Tg is 50 ° C. or more, the cohesive force of the binder resin itself in a high temperature range is good, and thus the hot offset property is excellent at the time of fixing. Further, when Tg is 80 ° C. or less, sufficient melting is obtained and the minimum fixing temperature is hardly increased.
The glass transition temperature of the binder resin refers to a value measured by a method (DSC method) defined in ASTM D3418-82.

Examples of the addition polymerizable monomer used for the preparation of the addition polymerization type resin include a cationic polymerizable monomer and a radical polymerizable monomer, and a radical polymerizable monomer is preferable.
As radically polymerizable monomers, styrenic monomers, unsaturated carboxylic acids, (meth) acrylates ("(meth) acrylate" means acrylate and methacrylate, and so on. N-vinyl compounds, vinyl esters, halogenated vinyl compounds, N-substituted unsaturated amides, conjugated dienes, polyfunctional vinyl compounds, polyfunctional (meth) acrylates, and the like. . Among these, N-substituted unsaturated amides, conjugated dienes, polyfunctional vinyl compounds, polyfunctional (meth) acrylates, and the like may cause a crosslinking reaction in the produced polymer. it can. These can be used alone or in combination.

Examples of the addition polymerizable monomer that can be used in this embodiment include a radical polymerizable monomer, a cationic polymerizable monomer, or an anion polymerizable monomer. Preferably there is.
The radically polymerizable monomer is preferably a compound having an ethylenically unsaturated bond, and has an aromatic ethylenically unsaturated compound (hereinafter also referred to as “vinyl aromatic”) or an ethylenically unsaturated bond. Carboxylic acids (unsaturated carboxylic acids), derivatives of unsaturated carboxylic acids such as esters, aldehydes, nitriles or amides, N-vinyl compounds, vinyl esters, halogenated vinyl compounds, N-substituted unsaturated amides, conjugated dienes, many It is more preferably a functional vinyl compound or a polyfunctional (meth) acrylate.

  Specifically, for example, unsubstituted vinyl aromatics such as styrene and p-vinylpyridine, α-substituted styrene such as α-methylstyrene and α-ethylstyrene, m-methylstyrene, p-methylstyrene, 2, Aromatic nucleus substituted styrene such as 5-dimethylstyrene, vinyl aromatics such as aromatic nucleus halogen substituted styrene such as p-chlorostyrene, p-bromostyrene, dibromostyrene, (meth) acrylic acid (in addition, “(meth) acrylic” "Means acrylic and methacrylic, and the same shall apply hereinafter.), Unsaturated carboxylic acids such as crotonic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, methyl (meth) acrylate, ethyl ( (Meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate Unsaturated carboxylic acid esters such as hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, glycidyl (meth) acrylate, benzyl (meth) acrylate, (meth) acrylaldehyde, (meth) acrylonitrile, (meth) acrylamide, etc. Unsaturated carboxylic acid derivatives, N-vinyl compounds such as N-vinyl pyridine and N-vinyl pyrrolidone, vinyl esters such as vinyl formate, vinyl acetate and vinyl propionate, vinyl chloride, vinyl bromide, vinylidene chloride, etc. Halogenated vinyl compounds, N-methylol acrylamide, N-ethylol acrylamide, N-propanol acrylamide, N-methylol maleamic acid, N-methylol maleamic acid ester, N-methylol maleimide, N-ethylo N-substituted unsaturated amides such as lumaleimide, conjugated dienes such as butadiene and isoprene, polyfunctional vinyl compounds such as divinylbenzene, divinylnaphthalene and divinylcyclohexane, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate , Propylene glycol di (meth) acrylate, tetramethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, hexamethylene glycol di (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane tri ( (Meth) acrylate, glycerol di (meth) acrylate, glycerol tri (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythrito Tritri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol di (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, Examples include polyfunctional acrylates such as dipentaerythritol hexa (meth) acrylate, sorbitol tri (meth) acrylate, sorbitol tetra (meth) acrylate, sorbitol penta (meth) acrylate, and sorbitol hexa (meth) acrylate. Moreover, the sulfonic acid and phosphonic acid which have an ethylenically unsaturated bond, and those derivatives can also be used. Among these, N-substituted unsaturated amides, conjugated dienes, polyfunctional vinyl compounds, polyfunctional acrylates, and the like can also cause a crosslinking reaction in the produced polymer. These addition polymerizable monomers may be used alone or in combination of two or more.

  Further, the content of the binder resin in the toner of the exemplary embodiment is preferably 10 to 90% by weight, more preferably 30 to 85% by weight, and more preferably 50 to 80% by weight with respect to the total weight of the toner. % Is more preferable.

<Other colorants>
The toner of the exemplary embodiment may contain a colorant other than the organic compound having a group represented by the formula (1) as necessary.
As the colorant, known ones can be used, and may be arbitrarily selected from the viewpoints of hue angle, saturation, brightness, weather resistance, OHP permeability, and dispersibility in the toner.
Specifically, various pigments such as watch young red, permanent red, brilliantamine 3B, brilliantamine 6B, dapon oil red, pyrazolone red, resol red, rhodamine B lake, lake red C rose bengal, and acridine series , Xanthene, azo, benzoquinone, azine, anthraquinone, thioindico, dioxazine, thiazine, azomethine, indico, thioindico, phthalocyanine, aniline black, polymethine, triphenylmethane, diphenylmethane Examples thereof include various colorants such as those based on thiazine, thiazine, thiazole and xanthene.

  Specific examples of the colorant include carbon black, nigrosine dye (CI No. 50415B), aniline blue (CI No. 50405), calco oil blue (CI No. azoic Blue 3), chrome yellow (CI No.14090), Ultramarine Blue (CINo.77103), DuPont Oil Red (CINo.26105), Quinoline Yellow (CINo.47005), Methylene Blue Chloride (CINo.52015), Phthalocyanine Blue (CINo.74160) ), Malachite green oxalate (CI No. 42000), lamp black (CI No. 77266), rose bengal (CI No. 45435), and mixtures thereof can be preferably used.

The content of the other colorant in the toner of the exemplary embodiment is preferably smaller than the content of the organic compound having a group represented by the formula (1). Moreover, as a coloring agent, these pigments, dyes, etc. can be used individually by 1 type, or 2 or more types can be used together.
As a method for dispersing the colorant, an arbitrary method, for example, a general dispersion method such as a rotary shear type homogenizer, a ball mill having a medium, a sand mill, or a dyno mill can be used, and the method is not limited at all. These colorant particles may be added to the mixed solvent at the same time as other particle components, or may be divided and added in multiple stages.

<Release agent>
The electrostatic image developing toner of the present embodiment preferably contains a release agent.
Specific examples of the release agent include, for example, ester wax, polyethylene, polypropylene, or a copolymer of polyethylene and polypropylene, but polyglycerin wax, microcrystalline wax, paraffin wax, carnauba wax, sazol wax, and montanic acid ester. Wax, deacidified carnauba wax, palmitic acid, stearic acid, montanic acid, blandic acid, eleostearic acid, valinalic acid and other unsaturated fatty acids, stearyl alcohol, aralkyl alcohol, bephenyl alcohol, carnauvyl alcohol, ceryl alcohol , Saturated alcohols such as long chain alkyl alcohols having a long chain alkyl group; polyhydric alcohols such as sorbitol; linoleic acid amides Fatty acid amides such as oleic acid amide and lauric acid amide; saturated fatty acid bisamides such as methylene bis stearic acid amide, ethylene bis capric acid amide, ethylene bis lauric acid amide, hexamethylene bis stearic acid amide, ethylene bis oleic acid amide, Unsaturated fatty acid amides such as hexamethylene bisoleic acid amide, N, N′-dioleyl adipic acid amide, N, N′-dioleyl sebacic acid amide; m-xylene bisstearic acid amide, N, N′— Aromatic bisamides such as distearyl isophthalic acid amide; fatty acid metal salts such as calcium stearate, calcium laurate, zinc stearate, magnesium stearate (generally called metal soap); aliphatic hydrocarbon wax and styrene Waxes grafted with vinyl monomers such as acrylic acid; Partially esterified products of fatty acids such as behenic acid monoglyceride and polyhydric alcohols; Methyl ester compounds having hydroxyl groups obtained by hydrogenation of vegetable oils, etc. Is mentioned.

The said mold release agent may be used individually by 1 type, or may use 2 or more types together.
The content of the release agent in the toner of the exemplary embodiment is preferably 1 to 20% by weight and more preferably 3 to 15% by weight with respect to 100% by weight of the binder resin. Within the above range, both good fixing and image quality characteristics can be achieved.

<Other ingredients>
In addition to the above components, various components such as an internal additive, a charge control agent, inorganic powder (inorganic particles), and organic particles may be added to the toner as necessary.
Examples of the internal additive include metals such as ferrite, magnetite, reduced iron, cobalt, nickel and manganese, alloys, and magnetic materials such as compounds containing these metals. When the magnetic material is used as a magnetic toner, the ferromagnetic particles preferably have an average particle size of 2 μm or less, more preferably about 0.1 to 0.5 μm. The amount contained in the toner is preferably 20 to 200 parts by weight with respect to 100 parts by weight of the resin component, and particularly preferably 40 to 150 parts by weight with respect to 100 parts by weight of the resin component. Further, it is preferable that the magnetic characteristics at the application of 10K oersted are those having a coercive force (Hc) of 20 to 300 oersted, saturation magnetization (σs) of 50 to 200 emu / g, and residual magnetization (σr) of 2 to 20 emu / g.

  Examples of the charge control agent include fluorine surfactants, salicylic acid metal complexes, metal-containing dyes such as azo metal compounds, polymer acids such as polymers containing maleic acid as a monomer component, and quaternary ammonium salts. And azine dyes such as nigrosine.

  The toner may contain an inorganic powder for the purpose of adjusting viscoelasticity. Examples of inorganic powders include silica, alumina, titania, calcium carbonate, magnesium carbonate, calcium phosphate, and cerium oxide. Can be mentioned.

<External additive>
An external additive may be externally added to the surface of the toner as necessary. Examples of the external additive externally added to the surface include inorganic particles and organic particles.
Examples of inorganic particles include silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, zinc oxide, silica sand, clay, mica, wollastonite, diatomaceous earth, cerium chloride, Examples include Bengala, chromium oxide, cerium oxide, antimony trioxide, magnesium oxide, zirconium oxide, silicon carbide, and silicon nitride.
Inorganic particles are generally used for the purpose of improving fluidity. The average primary particle size of the inorganic particles is preferably in the range of 1 to 200 nm. The addition amount of the inorganic particles is preferably in the range of 0.01 to 20 parts by weight with respect to 100 parts by weight of the toner.

It is preferable that the surface of the inorganic particles is previously hydrophobized. This hydrophobization treatment is more effective for improving the powder fluidity of the toner, as well as the environmental dependency of charging and the resistance to carrier contamination.
The hydrophobizing treatment may be performed by immersing the inorganic particles in a hydrophobizing agent. Although there is no restriction | limiting in particular as said hydrophobic treatment agent, For example, a silane coupling agent, a silicone oil, a titanate coupling agent, an aluminum coupling agent etc. are mentioned. These may be used individually by 1 type and may use 2 or more types together. Among these, silane coupling agents are preferable.

  Organic particles are generally used for the purpose of improving cleaning properties and transfer properties. Specifically, for example, fluorine resin powders such as polyvinylidene fluoride and polytetrafluoroethylene, fatty acid metal salts such as zinc stearate and calcium stearate. , Polystyrene, polymethyl methacrylate and the like.

Among these, it is preferable to use inorganic oxides such as titania and silica from the viewpoint of improving fluidity and charging characteristics.
Moreover, an external additive may be used individually by 1 type, or may use 2 or more types together.
The ratio of the external additive externally added to the toner base particles before external addition is preferably in the range of 0.01 to 5 parts by weight, and in the range of 0.1 to 3.0 parts by weight with respect to 100 parts by weight of the toner base particles. Is more preferable.

<Toner shape>
The volume average particle diameter (D _50v ) of the toner of the exemplary embodiment is preferably 2 μm or more and 20 μm or less, more preferably 3 μm or more and 15 μm or less, and further preferably 3 μm or more and 12 μm or less. Within the above range, transfer unevenness in a high temperature and high humidity environment is further suppressed.
Further, the volume average particle diameter (D _50v ) of the toner base particles in the toner of the exemplary embodiment is preferably 2 μm or more and 20 μm or less, more preferably 3 μm or more and 15 μm or less, and further preferably 3 μm or more and 12 μm or less. Within the above range, transfer unevenness in a high temperature and high humidity environment is further suppressed.
The toner preferably has a narrow particle size distribution, and more specifically, the ratio of the 16% diameter (D _16p ) and the 84% diameter (D _84p ) in _terms of the square root in terms of the smaller number particle size of the toner. (GSDp), that is, GSDp represented by the following formula is preferably 1.40 or less, more preferably 1.31 or less, and particularly preferably 1.27 or less. Moreover, it is preferable that GSDp is 1.15 or more.
_{GSDp = {(D 84p) /} (D 16p)} 0.5
If the volume average particle size and GSDp are both in the above ranges, extremely small particles do not exist, and therefore, it is possible to suppress a decrease in developability due to an excessive charge amount of the small particle size toner.

A Coulter Multisizer II type (manufactured by Beckman Coulter, Inc.) can be used to measure the average particle size of particles such as toner. In this case, measurement can be performed using an optimum aperture depending on the particle size level of the particles. The particle diameter of the measured particle is expressed by a volume average particle diameter.
When the particle size is about 5 μm or less, the particle size can be measured using a laser diffraction / scattering particle size distribution measuring device (LA-700, manufactured by Horiba, Ltd.).
Furthermore, when the particle size is on the order of nanometers, it can be measured using a BET specific surface area measuring device (Flow Sorb II 2300, manufactured by Shimadzu Corporation).

In this embodiment, the toner shape factor SF1 is preferably in the range of 110 to 160, and more preferably in the range of 120 to 150. Within the above range, transfer unevenness in a high temperature and high humidity environment is further suppressed.
The shape factor SF1 is a shape factor indicating the degree of unevenness on the particle surface, and is calculated by the following equation.

In the formula, ML indicates the maximum length of the particle, and A indicates the projected area of the particle.
As a specific measurement method of SF1, for example, first, an optical microscope image of toner spread on a slide glass is taken into an image analysis device through a video camera, SF1 is calculated for 50 toners, and an average value is obtained. Is mentioned.

The method for producing the toner of the exemplary embodiment is not particularly limited, and a known method can be used. Specific examples include the following methods.
The toner is manufactured, for example, by a kneading pulverization method in which a binder resin, a colorant, a release agent, and, if necessary, a charge control agent are kneaded, pulverized, and classified; particles obtained by a kneading pulverization method A method of changing the shape by mechanical impact force or thermal energy; a dispersion in which a binder resin is emulsified and dispersed; a dispersion of a colorant, a release agent, and, if necessary, a charge control agent; An emulsion aggregation method in which toner particles are obtained by mixing, agglomerating and heat fusing; emulsion polymerization of a polymerizable monomer of a binder resin, a formed dispersion, a colorant, a release agent, and necessary Depending on the type, an emulsion polymerization aggregation method in which a dispersion liquid such as a charge control agent is mixed, aggregated, and heat-fused to obtain toner particles; a polymerizable monomer to obtain a binder resin, a colorant, and a release agent A suspension polymerization method in which an agent and, if necessary, a solution such as a charge control agent are suspended in an aqueous solvent for polymerization; a binder resin Coloring agents, release agents, and, dissolution suspension method and granulated with a solution such as a charge control agent is suspended in an aqueous solvent optionally; or the like can be used. In addition, a manufacturing method may be performed in which the toner base particles obtained by the above method are used as a core, and aggregated particles are further adhered and heat-fused to have a core-shell structure.
Among these, the toner of the exemplary embodiment is preferably a toner (emulsion aggregation toner) obtained by an emulsion aggregation method or an emulsion polymerization aggregation method.
The toner manufacturing method of the present embodiment includes an aggregation step of aggregating particles contained in a dispersion containing at least a binder resin and an organic compound having a group represented by formula (1) to form an aggregate, and It is preferable to include a fusion step in which the obtained aggregated particles are fused by heating.

-Aggregation process-
The toner manufacturing method according to the exemplary embodiment includes an aggregation step of aggregating particles contained in a dispersion containing at least a binder resin and an organic compound having a group represented by Formula (1) to form an aggregate. preferable.
In the aggregation step, resin particle dispersions mixed with each other, an organic compound having a group represented by formula (1) or a dispersion or solution thereof, and, if necessary, a colorant dispersion, It is preferable that the particles in the release agent dispersion are aggregated in an aqueous medium to form aggregated particles having a desired volume average particle size. The aggregated particles are formed by heteroaggregation or the like, and a surfactant or an aggregating agent may be added for the purpose of stabilizing the aggregated particles and controlling the particle size / particle size distribution. In addition, the formation of the agglomerated particles is preferably performed by adding an aggregating agent at 10 to 35 ° C. while stirring with a rotary shearing homogenizer.
In the present embodiment, the resin particle dispersion, the organic compound having the group represented by the formula (1) or the dispersion or solution thereof, and the group represented by the formula (1) are used depending on the purpose. Other components (particles) such as an internal additive, a charge control agent, an inorganic particle, an organic particle, a lubricant, and an abrasive are dispersed in at least one of the organic compound dispersion and the release agent dispersion. Also good. Further, for example, other components (particles) are dispersed in at least one of a binder resin dispersion, a dispersion of an organic compound having a group represented by the formula (1), and a release agent dispersion. Alternatively, other components (particles) may be dispersed in a mixture obtained by mixing a resin particle dispersion, a dispersion of an organic compound having a group represented by the formula (1), and a release agent dispersion. You may mix the dispersion liquid.

Examples of the dispersion medium in the dispersion of the resin particle dispersion, the dispersion of the organic compound having the group represented by the formula (1), the colorant dispersion, and the release agent dispersion include an aqueous medium. Etc.
Examples of the aqueous medium used in the present embodiment include water such as distilled water and ion exchange water, and alcohols such as ethanol and methanol. Among these, ethanol and water are preferable, and water such as distilled water and ion-exchanged water is particularly preferable. These may be used individually by 1 type and may use 2 or more types together.
The aqueous medium may contain a water-miscible organic solvent. Examples of the water-miscible organic solvent include acetone and acetic acid.
Further, the solvent in the solution of the organic compound having the group represented by the formula (1) is not particularly limited as long as it is a solvent in which the organic compound having the group represented by the formula (1) is dissolved. These solvents are used.

[Surfactant]
In the present embodiment, for example, for the purpose of dispersion stability during the production of the toner, for example, the resin particle dispersion in the aggregation process, the dispersion of the organic compound having a group represented by the formula (1), and the release agent dispersion. A surfactant can be used.
Examples of the surfactant include anionic surfactants such as sulfate ester, sulfonate, phosphate ester, and soap; cationic surfactants such as amine salt type and quaternary ammonium salt type; polyethylene Nonionic surfactants such as glycols, alkylphenol ethylene oxide adducts, polyhydric alcohols and the like can be mentioned. Among these, an ionic surfactant is preferable, and an anionic surfactant and a cationic surfactant are more preferable.

In toners, anionic surfactants generally have a strong dispersing power and are excellent in dispersing resin particles and colorants. Moreover, it is advantageous to use an anionic surfactant as the surfactant for dispersing the release agent.
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.

  Specific examples of anionic surfactants include fatty acid soaps such as potassium laurate, sodium oleate, and castor oil sodium; sulfate esters such as octyl sulfate, lauryl sulfate, lauryl ether sulfate, and nonyl phenyl ether sulfate; lauryl sulfonate , Sodium alkylnaphthalene sulfonate such as dodecylbenzene sulfonate, triisopropyl naphthalene sulfonate, dibutyl naphthalene sulfonate; sulfones such as naphthalene sulfonate formalin condensate, monooctyl sulfosuccinate, dioctyl sulfosuccinate, lauric acid amide sulfonate, oleic acid amide sulfonate Acid salts; lauryl phosphate, isopropyl phosphate, nonylphenyl ether Phosphoric acid esters such as Sufeto; dialkyl sulfosuccinate salts such as sodium dioctyl sulfosuccinate; and sulfosuccinate salts such as lauryl disodium sulfosuccinate, and the like.

  Specific examples of the cationic surfactant include laurylamine hydrochloride, stearylamine hydrochloride, oleylamine acetate, stearylamine acetate, stearylaminopropylamine acetate, and other amine salts; lauryltrimethylammonium chloride, dilauryldimethylammonium Chloride, distearyldimethylammonium chloride, distearyldimethylammonium chloride, lauryldihydroxyethylmethylammonium chloride, oleylbispolyoxyethylenemethylammonium chloride, lauroylaminopropyldimethylethylammonium ethosulphate, lauroylaminopropyldimethylhydroxyethylammonium perchlorate, alkylbenzene Trimethylammonium chloride, Such as quaternary ammonium salts such as quilts trimethyl ammonium chloride.

  Specific examples of nonionic surfactants include alkyl ethers such as polyoxyethylene octyl ether, polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether; polyoxyethylene octylphenyl ether, polyoxyethylene Alkyl phenyl ethers such as nonylphenyl ether; alkyl esters such as polyoxyethylene laurate, polyoxyethylene stearate, polyoxyethylene oleate; polyoxyethylene lauryl amino ether, polyoxyethylene stearyl amino ether, polyoxyethylene oleyl Alkylamines such as amino ether, polyoxyethylene soybean amino ether, polyoxyethylene beef tallow amino ether; polyoxy Alkyl amides such as ethylene lauric acid amide, polyoxyethylene stearic acid amide, polyoxyethylene oleic acid amide; vegetable oil ethers such as polyoxyethylene castor oil ether and polyoxyethylene rapeseed oil ether; lauric acid diethanolamide, stearic acid Alkanolamides such as diethanolamide and oleic acid diethanolamide; sorbitan ester ethers such as polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan monooleate Etc.

  The content of the surfactant in each dispersion may be a level that does not hinder the present embodiment, and is generally a small amount, specifically, 0.01 wt% or more and 3 wt% or less. The range is preferably 0.05% by weight or more and 2% by weight or less, more preferably 0.1% by weight or more and 1% by weight or less. Within the above range, each dispersion such as a resin particle dispersion, a colorant dispersion, and a release agent dispersion is stable, does not cause aggregation or release of specific particles, and affects the amount of copper compound added. The effect of the present embodiment can be sufficiently obtained. In general, a suspension-polymerized toner dispersion having a large particle size is stable even when a small amount of a surfactant is used.

[Flocculant]
In the aggregating step, agglomeration is caused by pH change or the like, and toner particle diameter particles containing a binder resin and an organic compound having a group represented by the formula (1) can be prepared. At the same time, an aggregating agent may be added in order to stably and rapidly aggregate the particles or to obtain aggregated particles having a narrower particle size distribution.
As the flocculant, a compound having a monovalent or higher charge is preferable, and specific examples of the compound include water-soluble surfactants such as the above-mentioned ionic surfactants and nonionic surfactants, hydrochloric acid, sulfuric acid, Acids such as nitric acid, acetic acid, oxalic acid, magnesium chloride, sodium chloride, aluminum sulfate, calcium sulfate, aluminum nitrate, silver nitrate, copper sulfate, sodium carbonate and other inorganic acid metal salts, sodium acetate, potassium formate, sodium oxalate, Examples thereof include aliphatic acids such as sodium phthalate and potassium salicylate, metal salts of aromatic acids, and metal salts of phenols such as sodium phenolate.

In consideration of the stability of the aggregated particles, the stability of the coagulant with respect to heat and time, and the removal during washing, a metal salt of an inorganic acid is preferable as the coagulant in terms of performance and use. Specific examples include metal salts of inorganic acids such as magnesium chloride, sodium chloride, aluminum sulfate, calcium sulfate, aluminum nitrate, silver nitrate, copper sulfate, and sodium carbonate.
The amount of these flocculants to be added varies depending on the valence of the charge, but it is preferable that all of them are small in quantity. Is preferably 0.5% by weight or less. Since the amount of the flocculant is preferably small, it is preferable to use a compound having a large valence.

[Method for preparing resin particle dispersion]
The method for producing the resin particle dispersion is not particularly limited, but it is preferably produced by emulsion polymerization or emulsification, and a known emulsion polymerization method or a known emulsion method is used.
For example, the production of the resin particle dispersion is preferably performed by applying a shearing force to a solution obtained by mixing an aqueous medium and a resin with a disperser. At that time, it is more preferable to form particles by lowering the viscosity of the resin component by heating. A dispersant may be used for stabilizing the dispersed resin particles. Further, if the resin is oily and dissolves in a solvent having a relatively low solubility in water, the resin is dissolved in these solvents and dispersed together with a dispersant and a polymer electrolyte in an aqueous medium and then heated or The resin particle dispersion may be prepared by evaporating the solvent under reduced pressure.
Examples of the aqueous medium include water such as distilled water and ion-exchanged water; alcohols; and the like, but preferably only water.
Examples of the dispersant used for emulsification include water-soluble polymers such as polyvinyl alcohol, methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, carboxymethyl cellulose, sodium polyacrylate, and sodium polymethacrylate; sodium dodecylbenzenesulfonate, octadecyl Anionic surfactants such as sodium sulfate, sodium oleate, sodium laurate, potassium stearate, cationic surfactants such as laurylamine acetate, stearylamine acetate, lauryltrimethylammonium chloride, zwitterions such as lauryldimethylamine oxide Surfactant, polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene Surfactants such as nonionic surface active agents such as Rukiruamin; and the like are; tricalcium phosphate, aluminum hydroxide, calcium sulfate, calcium carbonate, inorganic salts such as barium carbonate.

Examples of the disperser used for preparing the emulsion include a homogenizer, a homomixer, a pressure kneader, an extruder, and a media disperser.
As the size of the resin particles, the average particle size (volume average particle size) is preferably in the range of 60 nm to 300 nm, and more preferably in the range of 150 nm to 250 nm. Within the above range, the cohesiveness of the resin particles is sufficient, and the particle size distribution of the toner can be narrowed.

The volume average particle diameter of the resin particle dispersion thus obtained is preferably measured, for example, with a laser diffraction particle size distribution analyzer (LA-700, manufactured by Horiba, Ltd.).
Specific examples of the measuring method include the following methods.
The sample in the state of dispersion is adjusted so as to have a solid content of about 2 g, and ion exchange water is added thereto to make about 40 ml. This is put into the cell until an appropriate concentration is reached, waits for about 2 minutes, and is measured when the concentration in the cell becomes almost stable. The obtained volume average particle diameter for each channel is accumulated from the smaller volume average particle diameter, and the volume average particle diameter (D ₅₀ ) is defined as 50%.

[Production method of colorant dispersion]
The colorant dispersion is formed by dispersing at least a colorant.
The colorant is dispersed by a known method. For example, a rotary-type homogenizer, a ball-type mill, a sand mill, an attritor-type media type dispersing machine, a high-pressure counter-collision type dispersing machine, or the like is preferably used. The colorant may be an ionic surfactant having polarity and dispersed in an aqueous solvent using a homogenizer as described above to produce a colorant particle dispersion. A coloring agent may be used individually by 1 type, and may use 2 or more types together. The volume average particle size of the colorant (hereinafter sometimes simply referred to as an average particle size) is preferably 1 μm or less, more preferably 0.5 μm or less, and 0.01 to 0.5 μm. Is particularly preferred.
In addition, rosin, rosin derivatives, coupling agents, polymer dispersions are added as dispersants to further stabilize the dispersion stability of the colorant in the aqueous medium and lower the energy of the colorant in the toner. Agents and the like.

[Method for preparing release agent dispersion]
The release agent dispersion is formed by dispersing at least a release agent.
The release agent is dispersed by a known method, and for example, a rotary shearing type homogenizer, a media type dispersing machine such as a ball mill, a sand mill, or an attritor, a high pressure opposed collision type dispersing machine or the like is preferably used. The release agent may be a ionic surfactant having polarity and dispersed in an aqueous solvent using a homogenizer as described above to prepare a release agent particle dispersion. In this embodiment, a mold release agent may be used individually by 1 type, and may use 2 or more types together. The average particle size of the release agent particles is preferably 1 μm or less, and more preferably 0.01 to 1 μm.

-Fusion process-
The toner manufacturing method of the present embodiment preferably includes a fusing step of fusing the obtained aggregated particles by heating.
In the fusing step, the binder resin in the aggregate is melted under a temperature condition equal to or higher than its melting point or glass transition temperature, and the aggregated particles change from an indeterminate shape to a more spherical shape.
The heating temperature in the fusion step is preferably in the range of (melting temperature of the used crystalline resin +0 to 50) ° C. or (glass transition temperature of the used amorphous resin particles +0 to 50) ° C. The melting temperature of the crystalline resin used + 0 to 40) ° C. or (the glass transition temperature of the amorphous polyester resin particles + 10 to 40) ° C. is more preferable.
The heating time may be as long as fusion between particles is performed, and is preferably 0.5 to 10 hours.
Cooling is performed after the aggregated particles are fused to obtain fused particles. Also, in the cooling process, the cooling rate is increased in the vicinity of the melting temperature of the release agent and binder resin (melting temperature ± 10 ° C range), so-called rapid cooling enables recrystallization of the release agent and binder resin. It may be suppressed to suppress surface exposure.

-Other processes-
After completion of the fusion process, a desired toner may be obtained through an arbitrary washing process, solid-liquid separation process, drying process, external addition process, and the like.
In the washing step, it is preferable to sufficiently perform substitution washing with ion-exchanged water from the viewpoint of chargeability. The solid-liquid separation step is not particularly limited, but suction filtration, pressure filtration, and the like are preferably used from the viewpoint of productivity. Furthermore, the drying process is not particularly limited, but freeze drying, flash jet drying, fluidized drying, vibration fluidized drying, etc. are preferably used from the viewpoint of productivity. In the toner of the present exemplary embodiment, the moisture content after drying is preferably adjusted to 1.0% by weight or less, and more preferably adjusted to 0.5% by weight or less.
The method for externally adding inorganic particles such as silica and titania to the surface of the toner base particles in the external addition step is not particularly limited, and a known method is used, for example, adhesion by a mechanical method or a chemical method. The method of letting it be mentioned.

(Electrostatic image developer)
The electrostatic image developer of the present embodiment (hereinafter sometimes referred to as “developer”) is not particularly limited as long as it contains the electrostatic image developing toner of the present embodiment. A single-component developer used alone or a two-component developer containing a toner and a carrier may be used. In the case of a one-component developer, a toner containing magnetic metal particles or a non-magnetic one-component toner containing no magnetic metal particles may be used.

The carrier is not particularly limited as long as it is a known carrier, and iron powder carriers, ferrite carriers, surface-coated ferrite carriers, and the like are used. Each surface-added powder may be used after a desired surface treatment.
Specific examples of the carrier include the following resin-coated carriers. Examples of the carrier core particle include normal iron powder, ferrite, and magnetite molding, and the volume average particle size is preferably 30 to 200 μm.

  Examples of the coating resin for the resin-coated carrier include styrenes such as styrene, parachlorostyrene, and α-methylstyrene; methyl acrylate, ethyl acrylate, n-propyl acrylate, lauryl acrylate, acrylic acid 2 -Α-methylene fatty acid monocarboxylic acids such as ethylhexyl, methyl methacrylate, n-propyl methacrylate, lauryl methacrylate, 2-ethylhexyl methacrylate; nitrogen-containing acrylics such as dimethylaminoethyl methacrylate; acrylonitrile, methacrylonitrile, etc. Vinyl nitriles; vinyl pyridines such as 2-vinyl pyridine and 4-vinyl pyridine; vinyl ethers such as vinyl methyl ether and vinyl isobutyl ether; vinyl methyl ketone, vinyl ethyl ketone, vinyl isopropenyl Homopolymers such as vinyl ketones such as ketones; olefins such as ethylene and propylene; vinyl-based fluorine-containing monomers such as vinylidene fluoride, tetrafluoroethylene and hexafluoroethylene; and copolymers comprising two or more types of monomers Furthermore, silicone resins containing methyl silicone, methyl phenyl silicone, etc., polyesters containing bisphenol, glycol, etc., epoxy resins, polyurethane resins, polyamide resins, cellulose resins, polyether resins, polycarbonate resins and the like can be mentioned. These resins may be used alone or in combination of two or more. The coating amount of the coating resin is preferably in the range of about 0.1 to 10 parts by weight and more preferably in the range of 0.5 to 3.0 parts by weight with respect to 100 parts by weight of the core particles.

  For the production of the carrier, a heating type kneader, a heating type Henschel mixer, a UM mixer, or the like is used. Depending on the amount of the coating resin, a heating type fluidized rolling bed, a heating type kiln, or the like is used.

When a carrier in which ferrite particles are used as a core and coated with a resin in which carbon black or the like as a conductive agent and melamine beads or the like as a charge control agent are dispersed in methyl acrylate or ethyl acrylate and styrene or the like is used as a carrier, Since the resistance controllability is excellent even when the film thickness is increased, the image quality and the image quality maintenance are excellent, which is more preferable.
The mixing ratio of the toner and the carrier in the developer is not particularly limited and is selected according to the purpose.

(Image forming method)
An image forming method using the toner of this embodiment will be described. The toner of the exemplary embodiment is used in an image forming method using a known electrophotographic method. Specifically, it is used in an image forming method having the following steps.
That is, a preferable image forming method includes a charging step for uniformly charging the surface of the electrostatic charge image holding member, a latent image forming step for forming a latent image on the surface of the charged electrostatic charge image holding member, and the electrostatic charge image. Developing a latent image formed on the surface of the holding body with a developer containing at least toner to form a toner image, and transferring the toner image formed on the surface of the electrostatic image holding body to the transfer target A transfer step for fixing, a fixing step for fixing the toner image transferred to the transfer target, and a cleaning step for removing residual toner on the surface of the electrostatic charge image holding member after transfer. The toner of the present embodiment described above is used. Further, the transfer step may use an intermediate transfer member that mediates transfer of the toner image from the electrostatic latent image holding member to the transfer target.

Each of the above steps is a general step per se, and is described in, for example, JP-A-56-40868 and JP-A-49-91231. Note that the image forming method of the present embodiment can be carried out by using a known image forming apparatus such as a copying machine or a facsimile machine.
The electrostatic latent image forming step is a step of forming an electrostatic latent image on an image carrier (photoconductor).
The developing step is a step of developing the electrostatic latent image with a developer layer on a developer holding member to form a toner image. The developer layer is not particularly limited as long as it contains the electrostatic image developing toner of this embodiment.
The transfer step is a step of transferring the toner image onto a transfer target. Examples of the transfer medium in the transfer process include an intermediate transfer medium and a recording medium such as paper.
In the fixing step, for example, there is a method of forming a copy image by fixing the toner image transferred onto the transfer paper by a heating roller fixing device in which the temperature of the heating roller is set to a constant temperature.
The cleaning step is a step of removing the electrostatic charge image developer remaining on the image carrier.
As the transfer target, a recording medium such as an intermediate transfer member or paper can be used.
Examples of the recording medium include paper used for electrophotographic copying machines and printers, OHP sheets, etc., for example, coated paper whose surface is coated with resin, art paper for printing, and the like. Etc. can be used suitably.

  The image forming method of the present embodiment may further include a recycling step. The recycling step is a step of transferring the electrostatic image developing toner collected in the cleaning step to the developer layer. The image forming method including the recycling process is performed using an image forming apparatus such as a toner recycling system type copying machine or facsimile machine. Further, the present invention may be applied to a recycling system in which the cleaning process is omitted and toner is collected simultaneously with development.

(Image forming device)
As the image forming apparatus according to the present embodiment, an image forming apparatus using the electrostatic charge image developing toner according to the present embodiment will be described.
The image forming apparatus according to this embodiment includes an image carrier, a charging unit that charges the image carrier, and an exposure unit that exposes the charged image carrier to form an electrostatic latent image on the surface of the image carrier. Developing means for developing the electrostatic latent image with toner to form a toner image; transfer means for transferring the toner image from the image carrier to the surface of the transfer body; and transferring the toner image to the surface of the transfer body. A fixing means for fixing the toner image, and the toner is preferably the electrostatic image developing toner of the present embodiment.
The image forming apparatus of the present embodiment is not particularly limited as long as it includes at least the image holding member, the charging unit, the exposure unit, the developing unit, and the transfer unit as described above, but other necessary. Depending on the situation, a fixing means, a cleaning means, a static elimination means and the like may be included.
In the transfer unit, the transfer may be performed twice or more using an intermediate transfer member. Examples of the transfer medium in the transfer unit include an intermediate transfer medium and a recording medium such as paper.

The image carrier and each of the above-described units can preferably use the configurations described in the respective steps of the image forming method. As each of the above-described means, a known means in the image forming apparatus can be used. In addition, the image forming apparatus according to the present embodiment may include means and devices other than the above-described configuration. Further, the image forming apparatus according to the present embodiment may simultaneously perform a plurality of the above-described means.
The image forming apparatus according to the present exemplary embodiment preferably includes a cleaning unit that removes the electrostatic charge image developer remaining on the image carrier.
Examples of the cleaning means include a cleaning blade and a cleaning brush, and a cleaning blade is preferable.

  In this image forming apparatus, for example, the portion including the developing unit may be a cartridge structure (process cartridge) that is detachable from the image forming apparatus main body. As the process cartridge, a developer holding body is used. The process cartridge of the present embodiment is preferably used that includes at least the electrostatic charge image developing developer of the present embodiment.

(Toner cartridge, developer cartridge, and process cartridge)
The toner cartridge of this embodiment is a toner cartridge that contains at least the toner for developing an electrostatic charge image of this embodiment.
The developer cartridge of this embodiment is a developer cartridge that contains at least the electrostatic charge image developer of this embodiment.
The process cartridge of the present embodiment is a process cartridge including a developer holder that contains the electrostatic charge image developer of the present embodiment and holds and conveys the electrostatic charge image developer. The electrostatic latent image formed on the surface is developed with the electrostatic charge image developing toner or the electrostatic charge image developer to form a toner image, and the image carrier and the surface of the image carrier are charged. And at least one selected from the group consisting of a cleaning means for removing the toner remaining on the surface of the image carrier, and the electrostatic charge image developing toner of this embodiment, or The process cartridge preferably contains at least the electrostatic charge image developer of the present embodiment.

The toner cartridge of this embodiment is preferably detachable from the image forming apparatus. That is, in the image forming apparatus having a configuration in which the toner cartridge can be attached and detached, the toner cartridge of the present embodiment in which the toner of the present embodiment is stored is preferably used.
The developer cartridge of the present embodiment is not particularly limited as long as it contains the electrostatic charge image developer including the electrostatic image developing toner of the present embodiment. The developer cartridge is, for example, attached to and detached from an image forming apparatus including a developing unit, and includes the electrostatic image developer according to the present embodiment as a developer to be supplied to the developing unit. Is stored.
The developer cartridge may be a cartridge that stores toner and a carrier, or may be a cartridge that stores toner alone and a cartridge that stores a carrier separately.
It is preferable that the process cartridge of the present embodiment is attached to and detached from the image forming apparatus.
In addition, the process cartridge according to the present embodiment may include other members such as a static elimination unit as necessary.
As the toner cartridge and the process cartridge, known configurations may be adopted. For example, Japanese Patent Application Laid-Open No. 2008-209489 and Japanese Patent Application Laid-Open No. 2008-233863 are referred to.

Hereinafter, the present embodiment will be described in more detail with reference to examples and comparative examples, but the present embodiment is not limited to these examples.
In the following examples, “part” means “part by weight” and “%” means “% by weight” unless otherwise specified.

(Measuring method)
<Measurement method of volume average particle diameter of toner>
The volume average particle size of the toner was measured using a Coulter Multisizer II (manufactured by Beckman-Coulter). As the electrolytic solution, ISOTON-II (manufactured by Beckman-Coulter) was used.
As a measuring method, first, 0.5 mg to 50 mg of a measurement sample is added to 2 ml of a 5% aqueous solution of a surfactant, preferably sodium alkylbenzenesulfonate as a dispersant, and this is added to 100 ml to 150 ml of the electrolytic solution. Added. The electrolytic solution in which the measurement sample is suspended is subjected to a dispersion treatment with an ultrasonic disperser for about 1 minute, and the particle size is 2.0 μm or more and 60 μm or less using the Coulter Multisizer II with an aperture having an aperture diameter of 100 μm. The particle size distribution of particles in the range was measured. The number of particles to be measured was 50,000.
For the divided particle size range (channel), draw the cumulative distribution from the small diameter side with respect to the divided particle size range (channel), and define the 50% cumulative particle size as the weight average particle size or volume average particle size, respectively. To do.

The NMR spectrum analysis was performed using a ¹ H-NMR apparatus (JNM AL400, manufactured by JEOL Ltd.) under the measurement conditions of a 5 mm glass tube, a 5 wt% deuterated chloroform solution, and a measurement temperature of 25 ° C.
Ultraviolet-visible absorption spectrum measurement was performed using an ultraviolet-visible spectrophotometer (SHIMADZU UV 2100, manufactured by Shimadzu Corporation), optical path length: 10 mm, slit width: 2 nm, measurement range: 200 to 700 nm, solvent: tetrahydrofuran (THF). Measurement temperature: 25 ° C.
The melting temperature was determined by a DSC (Differential Scanning Calorimeter) measurement method, and was determined from the main maximum peak measured in accordance with ASTM D3418-8. DSC-7 manufactured by PerkinElmer was used for measurement of the main maximum peak. The temperature correction of the detection part of this apparatus was performed using the melting point of indium and zinc, and the heat quantity was corrected using the heat of fusion of indium. As the sample, an aluminum pan was used, an empty pan was set as a control, and the measurement was performed at a heating rate of 10 ° C./min.

Example 1
<Synthesis of Organic Crystal (1)>
1-phenyl-2,5-di (2-thienyl) pyrrole: 50 parts Tetracyanoethylene: 30 parts Dimethylformamide (DMF): 5,000 parts After stirring at 30 ° C. for 12 hours, pure water was added and extracted with toluene. . This was repeated three times.
The obtained organic layer was dried over anhydrous sodium sulfate, further dried under reduced pressure with an evaporator, and then separated by silica gel column chromatography. In addition, toluene was used as an elution solvent. Furthermore, recrystallization was performed using a chloroform-hexane mixed solvent.
The melting temperature, properties, ¹ HNMR, and UV-visible absorption spectrum of the organic crystal (1) were measured, and the chemical structure shown in Table 1 was confirmed.

<Preparation of Colorant Dispersion (1)>
Organic crystal (1): 40 parts Nonionic surfactant (Nonipol 400: manufactured by Sanyo Chemical Co., Ltd.): 5 parts Ion-exchanged water: 160 parts The above ingredients are mixed, dissolved, and homogenizer (Ultra Turrax T50: A colorant dispersant (solid pigment) in which colorant (gold pigment) particles having an average particle diameter of 11.1 μm are dispersed by stirring for 10 minutes using an IKA) Minor concentration: 20%).

<Preparation of polyester resin dispersion (1)>
-Dimethyl adipate: 74 parts-Dimethyl terephthalate: 192 parts-Bisphenol A ethylene oxide 2-mole adduct: 216 parts-Ethylene glycol: 38 parts-Tetrabutoxy titanate (catalyst): 0.037 parts

The above components were placed in a heat-dried two-necked flask, and nitrogen gas was introduced into the container, and the temperature was raised while stirring in an inert atmosphere. Then, a copolycondensation reaction was performed at 160 ° C. for 7 hours, and then gradually until 10 Torr. The temperature was raised to 220 ° C. while reducing the pressure to 4 hours. The pressure was returned to normal pressure, 9 parts of trimellitic anhydride was added, the pressure was gradually reduced to 10 Torr, and the pressure was maintained at 220 ° C. for 1 hour to synthesize polyester resin (1).
It was 65 degreeC when the glass transition temperature of the obtained polyester resin (1) was measured using the differential scanning calorimeter (DSC). When the molecular weight of the obtained polyester resin (1) was measured using GPC, the weight average molecular weight (Mw) was 12,000 and the number average molecular weight (Mn) was 4,000.

  Next, the obtained polyester resin (1): 160 parts, ethyl acetate: 233 parts, and sodium hydroxide aqueous solution (0.3N): 0.1 part were put into a separable flask and heated at 70 ° C. A resin mixed solution was prepared by stirring with a motor (manufactured by Shinto Kagaku Co., Ltd.). While further stirring this resin mixture, 373 parts of ion-exchanged water was gradually added, phase-inversion emulsification and solvent removal were carried out to obtain a polyester resin particle dispersion (1) (solid content concentration: 30%). The volume average particle diameter of the resin particles in the dispersion was 160 nm.

<Preparation of polyester resin particle dispersion (2)>
-Bisphenol A ethylene oxide 2-mole adduct: 114 parts-Bisphenol A propylene oxide 2-mole adduct: 84 parts-Fumaric acid dimethyl ester: 75 parts-Dodecenyl succinic acid: 19.5 parts-Trimellitic acid: 7.5 parts

The above components were put into a flask equipped with a stirrer, a nitrogen introduction tube, a temperature sensor, and a rectifying tower. After 1 hour, the temperature was raised to 190 ° C., and the reaction system was stirred, and then dibutyltin oxide 3.0 Department was put in. Further, 6 hours were required while distilling off the generated water, the temperature was raised from 190 ° C. to 240 ° C., and the dehydration condensation reaction was continued at 240 ° C. for another 2 hours to synthesize polyester resin (2).
The obtained polyester resin (2) had a glass transition temperature of 57 ° C., an acid value of 15.0 mgKOH / g, a weight average molecular weight (Mw) of 58,000, and a number average molecular weight (Mn) of 5,600.

  Next, the obtained polyester resin (2): 160 parts, ethyl acetate: 233 parts, and sodium hydroxide aqueous solution (0.3N): 0.1 part were put into a separable flask and heated at 70 ° C. A resin mixed solution was prepared by stirring with a motor (manufactured by Shinto Kagaku Co., Ltd.). While further stirring this resin mixture, 373 parts of ion-exchanged water was gradually added to effect phase inversion emulsification and solvent removal to obtain a polyester resin particle dispersion (2) (solid content concentration: 30%). The volume average particle diameter of the resin particles in the dispersion was 180 nm.

<Preparation of wax dispersion (1)>
Fischer-Tropsch wax (Nippon Seiki Co., Ltd., trade name: FNP-0090, melting temperature = 90 ° C.): 270 parts Anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd., Neogen RK): 1 0.0 part, ion-exchanged water: 400 parts The above was mixed and heated to 95 ° C., dispersed using a homogenizer (Ultra Tlux T50, manufactured by IKA), and then 360 using a Manton Gorin high-pressure homogenizer (manufactured by Gorin). A wax dispersion (1) (solid content concentration: 20%) in which a release agent having a volume average particle diameter of 0.23 μm was dispersed was prepared by performing a dispersion treatment for a minute.

<Production of toner>
Ion-exchanged water: 450 parts by weight Polyester resin particle dispersion (1): 210 parts by weight Polyester resin particle dispersion (2): 210 parts by weight Wax dispersion (1): 100 parts by weight Anionic surfactant (Daiichi Kogyo) Pharmaceutical Co., Ltd. Neogen RK, 20% by weight): 2.8 parts by weight The above components are put into a reaction vessel equipped with a thermometer, pH meter, and stirrer, and the temperature is controlled with a mantle heater from the outside. The temperature was maintained at 30 ° C. and a stirring speed of 150 rpm for 30 minutes.
Colorant dispersion (1) 182.5 parts by mass (20% by weight of the total toner) was added and held for 5 minutes. The 1.0 wt% nitric acid aqueous solution was added as it was, and the pH in the aggregation process was adjusted to 3.0.

While dispersing with a homogenizer (manufactured by IKA Japan: Ultra Tarax T50), 0.4 parts by weight of polyaluminum chloride was added, the temperature was raised to 50 ° C. while stirring, and the particle size was measured. The diameter was 5.5 μm. Thereafter, 110 parts by weight of the polyester resin particle dispersion (1) and 73 parts by weight of the polyester resin particle dispersion (2) were additionally added.
Thereafter, the pH was adjusted to 9.0 using a 5% by weight aqueous sodium hydroxide solution, the temperature was raised to 90 ° C. at a rate of temperature increase of 0.05 ° C./min, held at 90 ° C. for 3 hours, and then cooled. Filtration, further redispersion with ion-exchanged water, filtration, washing repeatedly until the electrical conductivity of the filtrate is 20 μS / cm or less, and then vacuum drying in an oven at 40 ° C. for 5 hours, Toner particles were obtained.

  To 100 parts by weight of the toner particles obtained, 1.5 parts by weight of hydrophobic silica (manufactured by Nippon Aerosil Co., Ltd., RY50) and 1.0 weight of hydrophobic titanium oxide (manufactured by Nippon Aerosil Co., Ltd., T805) Were mixed and blended at 10,000 rpm for 30 seconds using a sample mill. Thereafter, the toner (1) was prepared by sieving with a vibration sieve having an opening of 45 μm. The toner (1) obtained had a volume average particle diameter of 6.1 μm.

(Examples 2 to 24)
According to the same operation as in Example 1, the compounds (organic crystals) of each Example listed in Table 1 were produced, and their melting points, properties, ¹ HNMR, and UV-visible absorption spectra were measured. Table 1 shows the formula number and substituent R of each compound.
Using the obtained organic crystals, toners of Examples 2 to 24 having metallic luster were obtained in the same manner as in Example 1. Table 1 also shows the metallic gloss color of the toner obtained.

(Comparative Examples 1-7)
<Production of toner>
The toners of Comparative Examples 1 to 7 were obtained in the same manner as in Example 1 except that the organic crystals (1) in Example 1 were changed to the compounds shown below.
Comparative Example 1: Iron (manufactured by ECKART, STAPA IL Ferricon Resist 200, with an average primary particle size of 17.1 μm filtered and washed with water)
Comparative Example 2: Stainless steel (manufactured by ECKART, STAY / STEEL 316L Flak Standard Grade, average primary particle size 34.7 μm)
Comparative Example 3: Copper (manufactured by ECKART, STANDART Copper Powder Doloran 17/0, average primary particle size 17.5 μm)
Comparative Example 4: Copper zinc alloy (manufactured by ECKART, STANDART Bronze Powder RESIST AT Rich Gold, average primary particle size 14.2 μm)
Comparative Example 5: Zinc (manufactured by ECKART, STANDART Zinc flake AT, average primary particle size 19.3 μm)
Comparative Example 6: Glass flake whose surface was coated with silver (manufactured by Nippon Sheet Glass Co., Ltd., Metashine 1030PS, average primary particle size 30.5 μm)
Comparative Example 7: Glass flake whose surface is coated with gold (manufactured by Nippon Sheet Glass Co., Ltd., Metashine 1030GP, average primary particle size 31.2 μm)

<Evaluation>
The obtained toners of Examples 1 to 24 and Comparative Examples 1 to 7 were evaluated by the following methods. The evaluation results are summarized in Table 1.

(Electrical characteristics evaluation)
-Dielectric loss factor-
By using a compression molding machine (BRIQUETING PRESS) manufactured by Maekawa Tester Manufacturing Co., Ltd., 6 g of toner was compressed with a load of 10 t and a pressurization of 60 seconds to obtain a molded disk having a diameter of 50 mm and a thickness of 3.0 mm. A molding disk left for 24 hours in an atmosphere of 30 ° C and humidity 90% RH is measured with a dielectric property measuring instrument (WAYNE PRECISION COMPONENT ANALYZER) manufactured by Toyo Technica Co., Ltd., with an AC frequency of 1,000 Hz and a repeat count of 100 times. The dielectric loss factor was measured. Regarding the measurement, the measurement was repeated 100 times under the above conditions, and the average value was adopted as the value of the dielectric loss factor.

(Transferability evaluation)
The transferability of each color toner obtained was evaluated using a modified DocuCenter Color 450a (Fuji Xerox Co., Ltd.) modified so that transfer and reverse development with a bias roller could be performed.
The transferability was evaluated based on the following criteria by measuring the weight before and after transferring the image on the photosensitive member to a tape using a solid patch and transferring it to plain paper.
X: Transfer rate of less than 85% Δ: Transfer rate of 85% or more and less than 90% ○: Transfer rate of 90% or more and less than 95% ◎: Transfer rate of 95% or more

In Table 1, the colorant used in Examples 1 to 24 is a compound represented by any of the following formulas (4) to (6), and R ^{6 to} R ⁸ are groups shown in Table 1. .

Claims (6)

Contains a binder resin and a colorant,
The toner for developing an electrostatic charge image, wherein the colorant contains an organic compound having a group represented by the following formula (1).

(In formula (1), Y represents a hydrogen atom or a cyano group.) The electrostatic image developing toner according to claim 1, wherein the organic compound having a group represented by the formula (1) is a compound represented by the following formula (2) or formula (3).

(In formula (2), X ¹ and X ³ each independently represent NH, O or S, X ² represents N, O or S, and R ¹ represents a hydrogen atom, an alkyl group, an aromatic group, a complex, Represents a cyclic group, a formyl group, an acyl group, an alkoxycarbonyl group or an alkenyl group, and R ² represents a hydrogen atom, 2,2-dicyanoethenyl group, tricyanoethenyl group, alkyl group, aromatic group, heterocyclic group, formyl group, An acyl group, an alkoxycarbonyl group or an alkenyl group, R ³ and R ⁴ each independently represents a hydrogen atom or an aromatic group, Y represents a hydrogen atom or a cyano group, and n represents an integer of 1 to 3. , P represents 0 or 1.)

(In Formula (3), A ¹ is an m-valent aromatic group, heterocyclic group, condensed polycyclic group, alicyclic group, spirocyclic group, biphenyl residue, fluorene residue or triphenylamine skeleton as a core. Each of X ⁴ independently represents a divalent aromatic group or a divalent heterocyclic group, and R ⁵ each independently represents an aromatic group, a heterocyclic group, an alkyl group, an alkenyl group or Represents a cycloalkyl group, Y represents a hydrogen atom or a cyano group, and m represents an integer of 2 or more.)   An electrostatic charge image developer comprising: the electrostatic charge image developing toner according to claim 1; and a carrier.   A toner cartridge which is detachable from an image forming apparatus and contains toner for developing an electrostatic charge image according to claim 1. A latent image forming step for forming an electrostatic latent image on the surface of the image carrier;
A developing step of developing the electrostatic latent image formed on the surface of the image carrier with toner to form a toner image;
A transfer step of transferring the toner image onto the surface of the transfer target; and
A fixing step of fixing the toner image transferred to the surface of the transfer target,
An image forming method, wherein the toner is the electrostatic charge image developing toner according to claim 1. An image carrier,
Charging means for charging the image carrier;
Exposure means for exposing the charged image carrier to form an electrostatic latent image on the surface of the image carrier;
Developing means for developing the electrostatic latent image with toner to form a toner image;
Transfer means for transferring the toner image from the image carrier to the surface of the transfer target;
Fixing means for fixing the toner image transferred to the surface of the transfer target,
An image forming apparatus, wherein the toner is the electrostatic image developing toner according to claim 1.