JP6007716B2 - Toner for developing electrostatic image, electrostatic image developer, toner cartridge, process cartridge, image forming apparatus, image forming method, and method for producing toner for developing electrostatic image - Google Patents

Description

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

In an electrophotographic image forming apparatus, an unfixed toner image formed on a recording medium is fixed by a fixing device to form an image. As this fixing device, a contact type fixing device that fixes a toner image by pressing a rotating member such as a roll or a belt on the toner image on the recording medium, and light irradiation or heating is applied to the toner image on the recording medium. A non-contact type fixing device for fixing a toner image is known.
On the other hand, toners intended to improve developability and fixability are disclosed as toners used for electrophotographic image formation (see, for example, Patent Documents 1 to 7).

Japanese Patent Application Laid-Open No. 08-055455 JP2011-257718A Japanese Patent Laid-Open No. 2007-139813 JP 2010-170059 A JP 2011-095342 A Japanese Patent Application Laid-Open No. 07-271083 JP 2011-090135 A

  An object of the present invention is to provide an electrostatic charge image developing toner capable of obtaining a fixed image having excellent gloss.

Specific means for achieving the above object are as follows. That is,
The invention according to claim 1
A binder resin, a resin having a structure derived from rosin and having a softening point of 150 ° C. or less, and a compound represented by the general formula (A), having a structure derived from the rosin and having a softening point An electrostatic charge image developing toner comprising toner particles in which a resin having a temperature of 150 ° C. or lower is dispersed and contained .

The invention according to claim 2
The electrostatic image developing toner according to claim 1 , wherein the resin having a structure derived from rosin and having a softening point of 150 ° C. or lower is a resin having a softening point of 130 ° C. or lower .

The invention according to claim 3
An electrostatic charge image developer comprising the toner for developing an electrostatic charge image according to claim 1.

The invention according to claim 4
A toner cartridge that accommodates the electrostatic image developing toner according to claim 1 and is detachable from an image forming apparatus.

The invention according to claim 5
An image forming apparatus comprising: a developing unit that stores the electrostatic charge image developer according to claim 3 and that develops the electrostatic charge image formed on the surface of the image carrier with the electrostatic charge image developer to form a toner image. Process cartridge attached to and detached from.

The invention according to claim 6
An image carrier,
Charging means for charging the surface of the image carrier;
An electrostatic charge image forming means for forming an electrostatic charge image on the surface of the charged image carrier;
A developing unit that houses the electrostatic charge image developer according to claim 3 and that develops the electrostatic charge image formed on the surface of the image carrier with the electrostatic charge image developer to form a toner image;
Transfer means for transferring the toner image to a recording medium;
Fixing means for fixing the toner image by applying at least one of light irradiation and heating to the toner image of the recording medium;
An image forming apparatus comprising:

The invention according to claim 7 provides:
A first resin particle containing a binder resin, a second resin particle containing a resin having a structure derived from rosin and a softening point of 150 ° C. or lower, and a compound represented by the general formula (A) In a dispersion in which particles are dispersed, an aggregation step of aggregating the first resin particles, the second resin particles, and particles of the compound represented by the general formula (A) to form aggregated particles;
Heating the dispersion in which the aggregated particles are dispersed, and fusing and coalescing the aggregated particles to form fused particles;
A method for producing a toner for developing an electrostatic charge image.
The invention according to claim 8 provides:
The production method according to claim 7, wherein the resin having a structure derived from rosin and having a softening point of 150 ° C or lower is a resin having a softening point of 130 ° C or lower.

According to the first and second aspects of the invention, the toner particles are those produced by the aggregation and coalescence method without using the second resin particles, or those produced by the kneading and pulverization method. In comparison with the case, an electrostatic charge image developing toner capable of obtaining a fixed image having excellent gloss is provided .

  According to the invention of claim 3, when the toner particles are produced by an aggregation coalescence method without using the second resin particles, or when produced by a kneading pulverization method. In comparison, an electrostatic charge image developer capable of obtaining a fixed image excellent in gloss is provided.

According to the invention of claim 4, when the toner particles are produced by an aggregation and coalescence method without using the second resin particles, or when produced by a kneading and pulverizing method. In comparison, a toner cartridge capable of obtaining a fixed image having excellent gloss is provided.
According to the invention of claim 5, when the toner particles are produced by an aggregation coalescence method without using the second resin particles, or when produced by a kneading and pulverizing method. In comparison, a process cartridge capable of obtaining a fixed image excellent in gloss is provided.

  According to the invention of claim 6, when the toner particles are produced by an agglomeration and coalescence method without using the second resin particles, or when the toner particles are produced by a kneading and pulverizing method. In comparison, there are provided an image forming apparatus and an image forming method capable of obtaining a fixed image having excellent gloss.

According to the inventions according to claims 7 and 8 , a toner production method for producing toner particles by an aggregation coalescence method without using the second resin particles, and a toner production for producing toner particles by a kneading pulverization method. A method for producing a toner for developing an electrostatic image capable of obtaining a fixed image having excellent gloss as compared with the method is provided.

1 is a schematic configuration diagram illustrating an example of an image forming apparatus according to an exemplary embodiment.

  Hereinafter, an embodiment which is an example of the present invention will be described in detail.

<Toner for electrostatic image development>
The electrostatic image developing toner of the present embodiment (hereinafter also referred to as “toner”) contains toner particles.
The toner particles are dispersed in a dispersion in which first resin particles containing a binder resin and second resin particles having a structure derived from rosin and containing a resin having a softening point of 150 ° C. or lower are dispersed. Agglomeration step of aggregating the first resin particles and the second resin particles to form agglomerated particles, heating the dispersion in which the agglomerated particles are dispersed, fusing and aggregating the agglomerated particles It is produced through a fusion and coalescence step for forming fused particles, and contains the binder resin and a resin derived from the rosin and having a softening point of 150 ° C. or lower.
Hereinafter, “a structure derived from rosin” is also referred to as “rosin skeleton”, and “a resin having a structure derived from rosin and having a softening point of 150 ° C. or lower” is also referred to as “specific rosin resin”.
Further, a toner production method including a step of aggregating resin particles to form aggregated particles and a step of fusing and coalescing the aggregated particles to form fused particles is referred to as an “aggregation coalescence method”.

In the present embodiment, the “softening point” of the resin having a rosin skeleton is a value measured according to the softening point measurement method by the ring and ball method described in JIS K 5902.
The specific rosin resin is contained in the toner particles after the toner particles are dissolved in tetrahydrofuran (THF) and methanol is added little by little to precipitate the main resin component (resin constituting the first resin particles). The filtrate is collected under reduced pressure and dried, and the structure is analyzed by H ¹ -NMR, or the fraction with a molecular weight of 5000 or less is collected in a preparative GPC apparatus and the structure is analyzed by H ¹ -NMR. Confirmed by estimation.

  The toner according to the exemplary embodiment is produced by an aggregation and coalescence method in which toner particles include second resin particles containing a specific rosin resin in addition to first resin particles containing a binder resin. As a result, a fixed image having excellent gloss can be formed. The reason for this is not clear, but is presumed as follows.

The fixing means of the electrophotographic image forming apparatus includes a contact-type fixing device that fixes a toner image by pressing a rotating member such as a roll or a belt on the toner image on the recording medium, and a toner image on the recording medium. And a non-contact type fixing device for fixing a toner image by light irradiation or heating.
In the contact-type fixing device, since the rotating member presses the toner image against the recording medium, it is easier to smooth the fixed image and give a gloss than the non-contact type fixing device.
In order to obtain a fixed image with excellent gloss using a non-contact type fixing device, for example, the amount of energy applied from the fixing device is increased for the purpose of smoothing the fixed image by reducing the viscosity of the toner. In other words, measures are taken to increase the content of infrared absorbers and ultraviolet absorbers in the toner.

  On the other hand, conventionally, a toner containing a resin having a rosin skeleton produced by a kneading pulverization method is known. Resin having a rosin skeleton has a high affinity for paper and has a function of reducing the phenomenon that the toner melted on the recording medium swells in a lens shape (lens effect) and spreading it to paper. Therefore, a toner containing a resin having a rosin skeleton Is advantageous as a toner applied to an image forming apparatus provided with a non-contact type fixing device. However, if the toner is produced by the kneading and pulverizing method, segregation of the resin having a rosin skeleton tends to occur in the toner, and the lens effect reducing action of the resin may not be sufficiently obtained.

On the other hand, in the present embodiment, the resin having a rosin skeleton has a softening point of 150 ° C. or lower, and toner particles are produced by an aggregation coalescence method using resin particles containing the resin. As a result, the resin particles containing the resin are likely to be dispersed and present throughout the toner particles, and as a result, the lens effect reducing effect of the resin is easily exhibited in the entire toner, and a smooth fixed image is formed. It is considered that the gloss of the layer is excellent.
In addition, since the toner having the rosin skeleton contained therein has a softening point of 150 ° C. or less in the toner of the present embodiment, the resin itself is easily softened by applying energy from a non-contact type fixing device. It is considered that a smooth fixed image is easily formed, and thus the gloss of the image layer is excellent.

In the present embodiment, the softening point of the resin having a rosin skeleton contained in the second resin particles is 150 ° C. or less. When the softening point is higher than 150 ° C., the aggregation of the first resin particles and the second resin particles hardly occurs in the aggregation process of the aggregation and coalescence method, and the aggregation particles including both are not granulated. May not be.
The softening point is preferably 130 ° C. or lower, more preferably 120 ° C. or lower, from the viewpoint of efficiently performing the aggregation of the first resin particles and the second resin particles in the aggregation step of the aggregation and coalescence method. More preferably, the temperature is 100 ° C. or lower.
The lower limit of the softening point is preferably 20 ° C. or higher and more preferably 40 ° C. or higher from the viewpoint of toner storage stability.

  Hereinafter, each component constituting the toner and the developer according to the exemplary embodiment will be described.

(Toner particles)
The toner particles include a binder resin and a resin (specific rosin resin) having a rosin skeleton and a softening point of 150 ° C. or lower, and may further include a colorant, a release agent, an infrared absorber, and the like.

[Specific rosin resin]
The specific rosin-based resin has a structure derived from rosin (rosin skeleton) in the molecule and has a softening point of 150 ° C. or lower.
Rosin is a general term for resin acids obtained from trees, and the main component is a substance derived from natural products including abietic acid, which is one of tricyclic diterpenes, and isomers thereof. Specific examples of components include, besides abietic acid, parastrinic acid, neoabietic acid, pimaric acid, dehydroabietic acid, isopimaric acid, sandaracopimaric acid, and rosin is usually a mixture thereof.
The rosin used for the synthesis of specific rosin resins includes: raw rosin; disproportionated rosin that is a disproportionate of raw rosin; hydrogenated rosin obtained by hydrogenating raw rosin (stabilized rosin); unsaturated rosin Modified rosin added with carboxylic acid or phenol; polymerized rosin obtained by polymerizing rosin; and the like.

Specific rosin resins include, for example, rosin ester resins; rosin modified phenolic resins; rosin modified maleic acid resins;
The rosin ester resin is an esterified product of rosins, and there are rosin ester, hydrogenated rosin ester (stabilized rosin ester), modified rosin ester, polymerized rosin ester and the like depending on the type of rosin used for synthesis.
The rosin-modified phenolic resin is a resin obtained by reacting a phenol resin obtained by condensation reaction of alkylphenol and formaldehyde and rosin. A rosin-modified maleic resin is obtained by reacting rosin or rosin and polyhydric alcohol. It is a resin obtained by adding maleic acid (for example, maleic acid, fumaric acid, maleic anhydride, fumaric anhydride) to the esterified product and maleating (fumarizing) by Diels-Alder reaction.
One type of specific rosin resin may be used, or two or more types may be used.

  The weight average molecular weight of the specific rosin resin is preferably in the range of 300 to 2,000 from the viewpoint of compatibility with the main resin (resin constituting the first resin particles).

  The acid value of the specific rosin resin is desirably in the range of 1.0 mgKOH / g or more and 200 mgKOH / g or less from the viewpoint of preparing the resin particle dispersion.

  The amount of the specific rosin resin in the toner of the exemplary embodiment is preferably 1.0% by mass or more from the viewpoint of excellent gloss of the fixed image. In addition, from the viewpoint of toner fixing properties and manufacturability, it is preferably 40% by mass or less.

[Binder resin]
The toner particles contain a binder resin.
Examples of the binder resin include polyesters; homopolymers or copolymers of styrenes such as styrene, parachlorostyrene, and α-methylstyrene; methyl acrylate, ethyl acrylate, n-propyl acrylate, and butyl acrylate. , Homopolymers or copolymers of esters having vinyl groups such as lauryl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, lauryl methacrylate, 2-ethylhexyl methacrylate Homopolymers or copolymers of vinyl nitriles such as acrylonitrile and methacrylonitrile; homopolymers or copolymers of vinyl ethers such as vinyl methyl ether and vinyl isobutyl ether; vinyl methyl ketone, vinyl ethyl ketone, vinyl iso Propenylke Homopolymers or copolymers of vinyl ketones such as ethylene; Homopolymers or copolymers of olefins such as ethylene, propylene, and butadiene; non-epoxy resins, polyurethane resins, polyamide resins, cellulose resins, polyether resins, etc. Vinyl condensation resin; and the like.

As the binder resin, an amorphous resin is desirable, and it is also desirable to use a crystalline resin in combination from the viewpoint of improving low-temperature fixability.
“Crystallinity” of the resin means that it has a clear endothermic peak in differential scanning calorimetry (DSC) rather than a stepwise endothermic amount change. Specifically, at a heating rate of 10 ° C./min. It means that the half width of the endothermic peak when measured is within 6 ° C. On the other hand, a resin having a half-value width of an endothermic peak exceeding 6 ° C. or a resin in which no clear endothermic peak is observed means an amorphous resin.

When the binder resin is an amorphous resin, the glass transition temperature is preferably 40 ° C. or higher and 80 ° C. or lower, and more preferably 50 ° C. or higher and 70 ° C. or lower, from the viewpoint of storage stability and low-temperature fixability of the toner.
The glass transition temperature of the amorphous resin is determined as the peak temperature of the endothermic peak obtained by differential scanning calorimetry (DSC).

The weight average molecular weight (Mw) of the amorphous resin is preferably from 5,000 to 100,000, and more preferably from 10,000 to 50,000 from the viewpoints of low-temperature fixability of the toner, hot offset resistance, and storage stability of the recording medium after image formation. desirable.
The molecular weight of the amorphous resin is measured by gel permeation chromatography (GPC) using a tetrahydrofuran (THF) soluble component.

  The acid value of the amorphous resin is preferably 1 mgKOH / g or more and 50 mgKOH / g or less, and more preferably 3 mgKOH / g or more and 30 mgKOH / g or less from the viewpoint of chargeability of the toner.

The melting point of the crystalline resin is preferably 50 ° C. or higher and 130 ° C. or lower, and more preferably 60 ° C. or higher and 90 ° C. or lower, from the viewpoint of storage stability of the toner, blocking resistance, and low-temperature fixability.
The melting point of the crystalline resin is determined as the peak temperature of the endothermic peak obtained by differential scanning calorimetry (DSC). In addition, although crystalline resin may show a some endothermic peak, in this embodiment, the largest peak is considered as melting | fusing point.

The weight average molecular weight (Mw) of the crystalline resin is preferably from 5,000 to 100,000, and more preferably from 10,000 to 50,000, from the viewpoints of low-temperature fixability of the toner and storage stability of the recording medium after image formation.
The molecular weight of the crystalline resin is measured by gel permeation chromatography (GPC) on the tetrahydrofuran (THF) soluble component.

[Infrared absorber]
The toner of this embodiment may contain an infrared absorber that efficiently absorbs infrared rays. This provides a light fixing toner that is efficiently fixed to a recording medium by irradiation with infrared rays.
As the infrared absorber, known infrared absorbers can be used without particular limitation, but from the viewpoint of laser absorption efficiency, a squalium compound and a croconium compound having a maximum absorption wavelength (λ _max ) of 700 nm or more are desirable.

[Squarium compound]
As a squalium compound, the compound represented by the following general formula (A) is desirable.

In general formula (A), R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom or a methyl group.
In general formula (A), R ¹¹ , R ¹² , R ¹³ and R ¹⁴ each independently represents an alkyl group having 1 to 6 carbon atoms. R ¹¹ and R ¹² , R ¹³ and R ¹⁴ may be independently connected to form a ring.
Examples of the alkyl group represented by R ¹¹ , R ¹² , R ¹³ and R ¹⁴ include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a tert group. -Butyl group, n-pentyl group, isopentyl group, neopentyl group, tert-pentyl group, n-hexyl group, isohexyl group, sec-hexyl group, tert-hexyl group can be mentioned.

  Specific examples of the compound represented by the general formula (A) include the following A (1) to A (8).

The maximum absorption wavelength (λ _max ) of the above exemplified compounds in a tetrahydrofuran solution is as follows. _{A (1): λ max 807nm} , A (2): λ max 812nm, A (3): λ max 808nm, A (4): λ max 812nm, A (5): λ max 810nm, A (6): λ _max 809 nm, A (7): λ _max 807 nm, A (8): λ _max 749 nm.

  As a squalium compound, the compound represented by the following general formula (B) is also desirable.

In the general formula (B), R ²¹ , R ²² , R ²³ and R ²⁴ each independently represent a hydrogen atom or a methyl group.
In the general formula (B), R ³¹ , R ³² , R ³³ and R ³⁴ each independently represents an alkyl group having 1 to 6 carbon atoms. R ³¹ and R ³² , R ³³ and R ³⁴ may be independently connected to form a ring.
Examples of the alkyl group represented by R ³¹ , R ³² , R ³³ and R ³⁴ include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a tert group. -Butyl group, n-pentyl group, isopentyl group, neopentyl group, tert-pentyl group, n-hexyl group, isohexyl group, sec-hexyl group, tert-hexyl group can be mentioned.

  Specific examples of the compound represented by the general formula (B) include the following B (10), B (15), and B (16).

The maximum absorption wavelength (λ _max ) of the above exemplified compounds in a tetrahydrofuran solution is as follows. B (10): λ _max 809 nm, B (15): λ _max 812 nm, B (16): λ _max 811 nm.

  The squalium compound can be synthesized by, for example, the synthesis method described in JP2011-039359A, JP2010-186014A, and JP2010-077261A.

[Croconium compounds]
As the croconium compound, a croconium compound represented by the following general formula (I) is desirable.

In general formula (I), R ¹¹ , R ¹² , R ²¹ and R ²² are each independently a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a substituted or unsubstituted alkoxy group. Represents. n11 and n12 each independently represents an integer of 0 to 4, and n21 and n22 each independently represents an integer of 0 to 5. R ³¹ and R ³² each independently represents a hydrogen atom or an aliphatic group. X represents an oxygen atom or a sulfur atom.

Examples of the halogen atom represented by R ¹¹ , R ¹² , R ²¹ and R ²² in the general formula (I) include F, Cl, Br, I and the like.

The unsubstituted alkyl group represented by R ¹¹ , R ¹² , R ²¹ and R ²² in the general formula (I) preferably has 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms, and 1 carbon atom. 3 or less is more desirable. The unsubstituted alkyl group may be linear, branched, cyclic, or a combination of two or more selected from these. Examples of the unsubstituted alkyl group include linear alkyl groups such as methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, and n-hexyl group; isopropyl group, isobutyl group, Branched alkyl groups such as sec-butyl group, tert-butyl group, isopentyl group, neopentyl group, tert-pentyl group, isohexyl group, sec-hexyl group, tert-hexyl group; cyclopropyl group, cyclobutyl group, cyclopentyl group And a cyclic alkyl group such as a cyclohexyl group.

The unsubstituted alkenyl group represented by R ¹¹ , R ¹² , R ²¹ and R ²² in the general formula (I) preferably has 2 to 6 carbon atoms, more preferably 2 to 4 carbon atoms, and more preferably 2 carbon atoms. Or 3 is more desirable. Examples of the unsubstituted alkenyl group include vinyl group, allyl group, 2-butenyl group, 3-butenyl group, 2-methyl-1-propenyl group, 4-pentenyl group, 3-methyl-2-butenyl group, 5 -A hexenyl group etc. are mentioned.

The unsubstituted alkoxy group represented by R ¹¹ , R ¹² , R ²¹ and R ²² in the general formula (I) preferably has 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms, and more preferably 1 carbon atom. 3 or less is more desirable. Examples of the unsubstituted alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a hexoxy group, and a propoxy group.

  Examples of the substituent that can substitute an alkyl group, an alkenyl group, and an alkoxy group include a halogen atom.

N11 and n12 in the general formula (I) each independently represents an integer of 0 or more and 4 or less, preferably an integer of 0 or more and 2 or less, and more preferably 0 or 1.
When n11 represents an integer of 2 or more and 4 or less, the plurality of R ¹¹ may be the same or different and are bonded to each other to form a ring (eg, cyclic alkyl, cyclic alkenyl, aromatic ring (eg, benzene ring)). It may be formed.
When n12 represents an integer of 2 or more and 4 or less, the plurality of R ¹² may be the same or different and are bonded to each other to form a ring (eg, cyclic alkyl, cyclic alkenyl, aromatic ring (eg, benzene ring)). It may be formed.

N21 and n22 in the general formula (I) each independently represents an integer of 0 or more and 5 or less, preferably an integer of 0 or more and 3 or less, and more preferably 0 or 1.
When n21 represents an integer of 2 or more and 5 or less, a plurality of R ²¹ may be the same or different and are bonded to each other to form a ring (eg, cyclic alkyl, cyclic alkenyl, aromatic ring (eg, benzene ring)). It may be formed.
If n22 represents an integer of 2 to 5, a plurality of R ²² may be the same or different, ring bonded to each other (e.g., cyclic alkyl, cyclic alkenyl, an aromatic ring (e.g., benzene ring)) and It may be formed.

The aliphatic group represented by R ³¹ and R ³² in the general formula (I) preferably has 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms, and still more preferably 1 to 3 carbon atoms. Examples of the aliphatic group include linear, branched, and cyclic alkyl groups and alkenyl groups. Specific examples include a methyl group, an ethyl group, a vinyl group, and an allyl group.

  Among the croconium compounds represented by the general formula (I), croconium compounds represented by the following general formula (II) and general formula (III) are desirable.

In general formula (II), R ¹¹¹ , R ¹¹² , R ²¹¹ , and R ²¹² each independently represent a halogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted alkoxy group. n111 and n112 each independently represents an integer of 0 or more and 4 or less, and n211 and n212 each independently represents an integer of 0 or more and 5 or less. R ³¹¹ and R ³¹² each independently represent a hydrogen atom or a methyl group. X represents an oxygen atom or a sulfur atom.

R ¹¹¹ , R ¹¹² , R ²¹¹ , R ²¹² , R ³¹¹ , R ³¹² , n ¹¹¹ , n ¹¹² , n ²¹¹ , n ²¹² , and X in general formula (II) are the same as those described in general formula (I), R ¹¹ , ^{R 12, R 21, R 22} , R 31, R 32, n11, n12, n21, n22, and is synonymous with X. However, the alkenyl group is excluded from the groups represented by R ¹¹¹ , R ¹¹² , R ²¹¹ , and R ²¹² .

In general formula (III), R ²²¹ and R ²²² each independently represent a halogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted alkoxy group. n221 and n222 each independently represents an integer of 0 or more and 5 or less. R ³²¹ and R ³²² each independently represent a hydrogen atom or a methyl group. X represents an oxygen atom or a sulfur atom.

In the general formula (III), R ²²¹ , R ²²² , R ³²¹ , R ³²² , n221, n222, and X are each R ²¹ , R ²² , R ³¹ , R ³² , It is synonymous with n21, n22, and X. However, the alkenyl group is excluded from the groups represented by R ²²¹ and R ²²² .

  Specific examples of the croconium compound represented by the general formula (I) include the following compounds.

The maximum absorption wavelength (λ _max ) in the tetrahydrofuran solution of the croconium compound represented by the general formula (I) is preferably in the range of 860 nm to 1200 nm.

  The amount of the infrared absorber in the toner of the present embodiment is desirably 0.05% by mass or more and less than 3.0% by mass from the viewpoint of preventing color turbidity of the color image.

[Colorant]
The toner of this embodiment may contain a colorant. The colorant may be a dye or a pigment, but a pigment is desirable from the viewpoint of light resistance and water resistance. A surface-treated colorant or a pigment dispersant may be used.

As the pigment, a conventionally known pigment may be used without any particular limitation.
Examples of black pigments include carbon black, copper oxide, manganese dioxide, aniline black, activated carbon, nonmagnetic ferrite, and magnetite.
Examples of yellow pigments include yellow lead, zinc yellow, yellow iron oxide, cadmium yellow, chrome yellow, Hansa yellow, Hansa yellow 10G, benzidine yellow G, benzidine yellow GR, selenium yellow, and permanent yellow NCG. . Specifically, C.I. I. Pigment yellow 74, C.I. I. Pigment yellow 180, C.I. I. And CI Pigment Yellow 93.
Examples of the orange pigment include red yellow lead, molybdenum orange, permanent orange GTR, pyrazolone orange, Vulcan orange, benzidine orange GG, indanthrene brilliant orange RK, and indanthrene brilliant oren GK.
Examples of red pigments include bengara, cadmium red, red lead, mercury sulfide, watch young red, permanent red 4R, risor red, brilliantamine 3B, brilliantamine 6B, dupont oil red, pyrazolone red, rhodamine B rake, lake red C, Examples include Eoxin Red and Alizarin Lake.
Examples of purple pigments include manganese purple, fast violet B, and methyl violet lake.
Blue pigments include bitumen, cobalt blue, alkali blue lake, Victoria blue lake, fast sky blue, induslen blue BC, aniline blue, ultramarine blue, chalcoil blue, methylene blue chloride, phthalocyanine blue, phthalocyanine green, malachite green oxare. Rate and the like.
Examples of the green pigment include chromium oxide, chromium green, pigment green, malachite green lake, final yellow green G, and the like.
Examples of white pigments include zinc white, titanium oxide, antimony white, and zinc sulfide.
Examples of extender pigments include barite powder, barium carbonate, clay, silica, white carbon, talc, and alumina white.

  Examples of the dye include nigrosine, methylene blue, rose bengal, and quinoline yellow.

One colorant may be used, or two or more colorants may be used in combination.
By selecting the type of the colorant, yellow toner, magenta toner, cyan toner, black toner and the like are obtained.

  The content of the colorant in the toner is preferably 1 part by mass or more and 30 parts by mass or less with respect to 100 parts by mass of the binder resin. However, when using a magnetic body as a black coloring agent, it is good also as 30 to 100 mass parts with respect to 100 mass parts of binder resin.

〔Release agent〕
The toner of this embodiment desirably contains a release agent.
Examples of the release agent include mineral waxes such as montan wax, ozokerite, ceresin, paraffin wax, microcrystalline wax, and Fischer-Tropsch wax; petroleum wax, natural gas wax, and modified products thereof; polyethylene, polypropylene, polybutene, etc. Low molecular weight polyolefins; silicone resins that exhibit a softening point upon heating; fatty acid amides such as oleic acid amide, erucic acid amide, ricinoleic acid amide, stearic acid amide; carnauba wax, rice wax, candelilla wax, wood wax, Plant waxes such as jojoba oil; animal waxes such as beeswax; and the like. These may use 1 type and may use 2 or more types together.
Examples of the modifying auxiliary component include higher alcohols having 10 to 18 carbon atoms and mixtures thereof, higher fatty acid monoglycerides having 16 to 22 carbon atoms, and mixtures thereof.

  The melting temperature (° C.) of the release agent is preferably from 50 ° C. to 100 ° C., more preferably from 60 ° C. to 95 ° C.

  The ratio of the release agent in the total solid content of the toner is preferably 1% by mass or more and 20% by mass or less, and more preferably 5% by mass or more and 15% by mass or less based on the releasability and the fluidity of the toner.

[Other ingredients]
The toner of the exemplary embodiment may contain an internal additive or a charge control agent in addition to the above components.

  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.

  Examples of the charge control agent include quaternary ammonium salt compounds, nigrosine compounds, dyes composed of complexes of aluminum, iron, chromium, and triphenylmethane pigments.

  The total content of other components is preferably, for example, from 0.01% by mass to 5% by mass, and more preferably from 0.5% by mass to 2% by mass.

(External additive)
The toner of the present exemplary embodiment may contain various components such as inorganic particles (inorganic powder) and organic particles as external additives.

Examples of inorganic particles that can be used as external additives include SiO ₂ , TiO ₂ , Al ₂ O ₃ , CuO, ZnO, SnO ₂ , CeO ₂ , Fe ₂ O ₃ , MgO, BaO, CaO, K ₂ O, and Na ₂ O. ZrO ₂ , CaO · SiO ₂ , K ₂ O · (TiO ₂ ) _n , Al ₂ O ₃ · 2SiO ₂ , CaCO ₃ , MgCO ₃ , BaSO ₄ , MgSO _{4 and the} like.
The surface of these inorganic particles may be hydrophobized in advance. The hydrophobic treatment is performed, for example, by immersing inorganic particles in a hydrophobic treatment agent. The hydrophobizing agent is not particularly limited, and examples thereof include silane coupling agents, silicone oils, titanate coupling agents, aluminum coupling agents and the like. These may be used individually by 1 type and may use 2 or more types together.
The amount of the hydrophobizing agent is usually 1 part by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the inorganic particles, for example.

  Examples of external additives include resin particles (resin particles such as polystyrene, PMMA, and melamine resin), cleaning activators (for example, metal salts of higher fatty acids typified by zinc stearate, and particles of fluorine-based high molecular weight particles). Also mentioned.

  The external addition amount of the external additive is desirably 0.01 parts by mass or more and 5 parts by mass or less, and more desirably 0.01 parts by mass or more and 2.0 parts by mass or less with respect to 100 parts by mass of the toner particles.

[Characteristics of toner]
The volume average particle diameter D50v of the toner is preferably 3 μm to 9 μm, more preferably 3 μm to 8 μm, further preferably 4 μm to 7 μm, and particularly preferably 5 μm to 7 μm.
When the volume average particle diameter D50v is 3 μm or more, the fluidity of the toner is good and the chargeability of each toner particle is good. Further, when the volume average particle diameter D50v is 3 μm or more, the cleaning property is good.
When the volume average particle diameter D50v is 9 μm or less, the resolution of the image is good and the recent demand for high image quality is satisfied.

The volume average particle size distribution index GSDv of the toner is desirably 1.0 or more and 1.3 or less, more desirably 1.1 or more and 1.3 or less, and further desirably 1.15 or more and 1.24 or less.
When GSDv is in the above range, the presence of coarse particles and fine powder particles is small, aggregation of toners is suppressed, and charging failure and transfer failure are unlikely to occur. When GSDv is 1.3 or less, the resolution of the image is good, and when GSDv is 1.0 or more, the manufacturability is good.

The volume average particle diameter D50v and the volume average particle size distribution index GSDv are obtained by the following method.
First, the particle size distribution of the toner is measured using a Coulter Multisizer-II type (manufactured by Coulter) with an aperture diameter of 100 μm. The measurement is performed after the toner is dispersed in an electrolyte aqueous solution (isoton aqueous solution) and dispersed by ultrasonic waves for 30 seconds or more.
Then, based on the particle size distribution, a cumulative distribution of volume is drawn from the smaller diameter side with respect to the divided particle size range (channel), the particle diameter that becomes 16% cumulative is volume D16v, and the particle diameter that becomes 50% cumulative is volume. The particle diameter at which D50v is accumulated and 84% is defined as volume D84v. Using these, the volume average particle size distribution index (GSDv) is calculated as (D84v / D16v) ^1/2 .

The toner shape factor SF1 is preferably from 110 to 160, more preferably from 125 to 145, and even more preferably from 120 to 130.
When SF1 is 110 or more, a defective cleaning after transfer hardly occurs, and as a result, an image defect hardly occurs.
When SF1 is 160 or less, even if it collides with the carrier in the developing device, the increase in fine powder due to toner destruction and the exposure of the release agent are unlikely to occur, the occurrence of fog caused by the fine powder, and the image carrier due to the release agent Contamination of the surface is difficult to occur.
The shape factor SF1 is obtained by the following equation.
SF1 = (ML ² / A) × (π / 4) × 100
In the above formula, the absolute maximum length (μm) of the toner is represented, and A represents the projected area (μm ² ) of the toner.
Specifically, the shape factor SF1 is digitized by analyzing an optical microscope image or a scanning electron microscope image of the toner using an image analyzer, and is calculated as follows, for example. That is, a microscopic image of the toner spread on the surface of the slide glass is taken into a Luzex image analyzer (FT manufactured by Nireco) through a video camera, and the maximum length (ML) and projection area (A) of 50 toners are measured. SF1 is calculated for each toner by the above formula, and an average value of 50 toners is calculated to obtain a shape factor SF1.

<Method for producing toner for developing electrostatic image>
In the toner of the present embodiment, toner particles are produced by an aggregation and coalescence method. For example, an external additive is externally added to the toner particles to produce an externally added toner.

Aggregation coalescence method is a dispersion in which first resin particles containing a binder resin and second resin particles containing a resin having a structure derived from rosin and a softening point of 150 ° C. or less are dispersed. Then, the aggregation step of aggregating the first resin particles and the second resin particles to form aggregated particles,
And fusing and coalescing the aggregated particles to form fused particles by heating the dispersion in which the aggregated particles are dispersed.
More specifically, for example,
A dispersion preparation step of preparing a dispersion in which each material constituting the toner particles is dispersed in a dispersion medium;
An aggregating step of mixing the above dispersions to obtain a mixed dispersion, and aggregating the first resin particles and the second resin particles in the mixed dispersion to form aggregated particles;
And fusing and coalescing the aggregated particles to form fused particles by heating the dispersion in which the aggregated particles are dispersed.
In the aggregation step, the first resin particles, the second resin particles, and the infrared absorption are dispersed in a dispersion in which the first resin particles, the second resin particles, and the infrared absorbent particles are dispersed. It may be a step of aggregating the agent particles to form aggregated particles.
Details of each step will be described below.

[Dispersion preparation process]
In the dispersion liquid preparation step, an emulsified dispersion liquid in which main materials constituting the toner particles are each dispersed in a dispersion medium is prepared. Hereinafter, a dispersion containing the first resin particles (first resin particle dispersion) and a dispersion containing the second resin particles (second resin particle dispersion) (hereinafter referred to as “resin particle dispersion” Infrared absorbent dispersion and the like will be described.

[Resin particle dispersion]
The resin particle dispersion may be prepared by applying a shearing force to a solution obtained by mixing a dispersion medium and a resin using a disperser. At that time, particles may be formed by heating to lower the viscosity of the resin. A dispersant may be used for stabilizing the dispersed resin particles.
The dispersion medium used for the resin particle dispersion and other dispersions may be an aqueous medium. As an aqueous medium, water, alcohol, etc. are mentioned, for example, 1 type may be used individually and 2 or more types may be used together.
If the resin is oily and dissolves in a solvent with relatively low solubility in water, dissolve the resin in those solvents and then disperse in water together with the dispersant and polymer electrolyte, and then heat or reduce pressure. The solvent may be evaporated.

  Examples of the dispersant include water-soluble polymers such as polyvinyl alcohol, methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, carboxymethyl cellulose, sodium polyacrylate, and sodium polymethacrylate; sodium dodecylbenzenesulfonate, sodium octadecylsulfate, sodium oleate, Anionic surfactants such as sodium laurate and potassium stearate; Cationic surfactants such as laurylamine acetate, stearylamine acetate and lauryltrimethylammonium chloride; Zwitterionic surfactants such as lauryldimethylamine oxide; Polyoxy Nonio such as ethylene alkyl ether, polyoxyethylene alkylphenyl ether, polyoxyethylene alkylamine Sex surfactant; 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 resin particle dispersion include a homogenizer, a homomixer, a pressure kneader, an extruder, and a media disperser.

Depending on the type of resin particles, the resin particles may be dispersed using a phase inversion emulsification method.
The phase inversion emulsification method is a method in which a resin to be dispersed is dissolved in a hydrophobic organic solvent in which the resin is soluble, neutralized by adding a base to the organic continuous phase (O phase), and then an aqueous medium (W phase). ) Is converted into a discontinuous phase by converting the resin from W / O to O / W (so-called phase inversion), and the resin is dispersed in the form of particles in an aqueous medium.

The volume average particle size of the resin particles is preferably 1 μm or less, more preferably 0.01 μm or more and 1 μm or less, further preferably 50 nm or more and 400 nm or less, and particularly preferably 70 nm or more and 350 nm or less.
When the volume average particle size of the resin particles is within the above range, the particle size distribution of the finally obtained toner does not become too wide, free particles are hardly generated, and the performance and reliability are excellent. In addition, compositional uneven distribution among toners is small, and variations in performance and reliability are small.
The volume average particle size of the particles contained in the dispersion, such as resin particles, is measured with a laser diffraction particle size distribution analyzer (LA-700 manufactured by Horiba, Ltd.).

[Infrared absorber dispersion]
Examples of a method for preparing a dispersion liquid in which infrared absorbent particles are dispersed include a dispersion treatment using an ultrasonic homogenizer, and a surfactant may be used for the dispersion treatment. As the surfactant used for dispersion, the same surfactants that can be used when dispersing the binder resin may be used.

[Colorant dispersion]
As a dispersion method in preparing the colorant dispersion, a general dispersion method such as a rotary shearing homogenizer, a ball mill having a medium, a sand mill, or a dyno mill may be applied. A surfactant may be used to prepare an aqueous dispersion of the colorant, or a dispersant may be used to prepare an organic solvent dispersion of the colorant. As the surfactant and dispersant used for dispersion, the same dispersants that can be used when dispersing the binder resin may be used.

  The content of the colorant contained in the colorant dispersion may be usually 5% by mass or more and 50% by mass or less, or 10% by mass or more and 40% by mass or less. When the content is within the above range, the particle size distribution of the colorant particles is difficult to spread.

  The volume average particle diameter (median diameter) of the particles contained in the colorant dispersion may be 2 μm or less, 0.2 μm or more and 1.5 μm or less, or 0.3 μm or more and 1 μm or less. Good.

[Releasing agent dispersion]
The release agent dispersion is a dispersion treatment of the release agent in water with a polymer electrolyte such as an ionic surfactant, polymer acid or polymer base, and heated to a temperature equal to or higher than the melting temperature of the release agent. It is prepared by applying a strong shearing force using a homogenizer or a pressure discharge type disperser. Thereby, the release agent particles having a volume average particle diameter of 1 μm or less (preferably 0.1 μm or more and 0.5 μm or less) are dispersed in the dispersion medium. As the dispersion medium in the release agent dispersion liquid, the same dispersion medium used for resin dispersion may be used.

  During the dispersion treatment, an inorganic compound may be added to the dispersion. Examples of the inorganic compound include polyaluminum chloride, aluminum sulfate, highly basic polyaluminum chloride (PAC), polyaluminum hydroxide, aluminum chloride and the like.

  The release agent and other internal additives may be dispersed in the resin particle dispersion.

[Aggregation process]
In the aggregation step, the first resin particles and the second resin particles are aggregated in a dispersion in which at least the first resin particles and the second resin particles are dispersed to form aggregated particles.
In this step, for example, a flocculant is added to the mixed dispersion obtained by mixing the first resin particle dispersion, the second resin particle dispersion, and the other dispersion and heated. Then, the particles in the mixed dispersion may be aggregated to form aggregated particles.

Aggregated particles can be formed, for example, by stirring the mixed dispersion with a rotary shearing homogenizer, adding a flocculant at room temperature, adjusting the pH of the mixed dispersion to acidic, and then heating the mixed dispersion to obtain the mixed dispersion. It is carried out by agglomerating the particles dispersed in.
The mixed dispersion is preferably heated to near the glass transition temperature or melting point of the binder resin (± 20 ° C.) and to the vicinity of the softening point of the specific rosin resin (± 20 ° C.).
In order to suppress rapid aggregation of particles due to heating, the pH may be adjusted while stirring and mixing at room temperature, and a dispersion stabilizer may be added. In this embodiment, “room temperature” refers to 25 ° C.

  As the aggregating agent used in the aggregating step, a surfactant having a polarity opposite to that of the surfactant used as the dispersing agent added to the raw material dispersion, that is, an inorganic metal salt or a bivalent or higher-valent metal complex is preferably used. In particular, when a metal complex is used, the amount of surfactant used can be reduced, and charging characteristics are improved.

  Examples of inorganic metal salts that can be used as the flocculant include metal salts such as calcium chloride, calcium nitrate, barium chloride, magnesium chloride, zinc chloride, aluminum chloride, and aluminum sulfate; polyaluminum chloride, polyaluminum hydroxide, and calcium polysulfide. Inorganic metal salt polymers such as Of these, aluminum salts and polymers thereof are preferred. In order to obtain a narrower particle size distribution, the valence of the inorganic metal salt is bivalent than monovalent, trivalent than bivalent, trivalent than trivalent, and tetravalent than trivalent. Inorganic metal salt polymers are more suitable.

[Adhesion process]
After passing through the aggregation process, an adhesion process may be performed. In the attaching step, the shell layer (coating layer) can be formed by attaching the first resin particles to the surface of the aggregated particles formed through the above-described aggregation step. Thus, a toner having a core-shell structure including so-called core particles and a shell layer covering the core particles is obtained.

  The formation of the shell layer is usually performed by additionally adding a dispersion liquid containing binder resin particles to the dispersion liquid in which the aggregated particles (core particles) are formed in the aggregation process. Note that the binder resin used in the adhesion step may be the same as or different from that used in the aggregation step.

  In general, in the core-shell structure, core particles containing a crystalline resin together with a release agent are covered with an amorphous resin shell layer so that the release agent and crystalline resin contained in the core particles are exposed to the toner surface. The main purpose is to suppress. Another object of the present invention is to supplement the strength of toner particles when the strength of the toner particles is insufficient.

[Fusion and unification process]
In the coalescence coalescence process, for example, the aggregation is stopped by setting the pH of the suspension containing the aggregated particles to be in the range of 6.5 to 8.5, and then the aggregated particles are fused by heating. Let them unite. At this time, for example, the aggregated particles are fused by heating at a temperature equal to or higher than the glass transition temperature or melting point of the binder resin.

  The resin may be subjected to a crosslinking reaction during heating in the coalescence process or after the coalescence is completed. When the crosslinking reaction is performed, a crosslinking agent or a polymerization initiator is used when the toner is produced. The polymerization initiator may be preliminarily mixed with the dispersion at the stage of preparing the raw material dispersion, or may be incorporated into the aggregated particles in the aggregation process, or during or after the fusion coalescence process. It may be incorporated into the particles. In the case of introduction during the aggregation process, during the adhesion process, during the fusion and coalescence process, or after the fusion process, a solution in which the polymerization initiator is dissolved or emulsified is added to the dispersion. These polymerization initiators may be added with known crosslinking agents, chain transfer agents, polymerization inhibitors and the like for the purpose of controlling the degree of polymerization.

[Washing, drying process, etc.]
After the fusion and coalescence process is completed, toner particles are obtained through, for example, a washing process, a solid-liquid separation process, and a drying process.
In the washing step, it is desirable to perform substitution washing with ion-exchanged water in consideration of chargeability.
From the viewpoint of productivity, the solid-liquid separation step is preferably suction filtration, pressure filtration, or the like.
As the drying step, freeze drying, flash jet drying, fluidized drying, vibration fluidized drying, and the like are preferable from the viewpoint of productivity.

The toner according to the exemplary embodiment is manufactured, for example, by adding an external additive to dry toner particles and mixing them. Mixing is preferably performed by, for example, a V blender, a Henshur mixer, a Redige mixer, or the like.
Further, coarse particles of toner may be removed using an ultrasonic sieving machine, a vibration sieving machine, a wind sieving machine, or the like.

<Electrostatic image developer>
The electrostatic image developer (hereinafter, also referred to as “developer”) of the present embodiment includes the toner of the present embodiment.
The toner of this embodiment is used as it is as a one-component developer or as a two-component developer. When used as a two-component developer, it is used by mixing with a carrier.

  The carrier that can be used for the two-component developer is not particularly limited and may be a known carrier. For example, magnetic metal such as iron oxide, nickel and cobalt; magnetic oxide such as ferrite and magnetite; resin-coated carrier having a magnetic metal or magnetic oxide as a core material and a resin coating layer on the surface of the core material; conductive to matrix resin Resin-dispersed carriers in which conductive particles are dispersed; and the like.

  There are no particular restrictions on the type of coating resin or matrix resin that constitutes the carrier. For example, straight made of polyethylene, polypropylene, polystyrene, polyvinyl acetate, polyvinyl alcohol, polyvinyl butyral, polyvinyl chloride, polyvinyl ether, polyvinyl ketone, vinyl chloride-vinyl acetate copolymer, styrene-acrylic acid copolymer, organosiloxane bond Examples thereof include silicone resins or modified products thereof, fluororesins, polyesters, polycarbonates, phenol resins, epoxy resins, (meth) acrylic resins, dialkylaminoalkyl (meth) acrylic resins, and the like. Among these, dialkylaminoalkyl (meth) acrylic resins are desirable from the viewpoint of high charge amount and the like.

  Examples of the conductive material include metals such as gold, silver, and copper, carbon black, titanium oxide, zinc oxide, tin oxide, barium sulfate, aluminum borate, and potassium titanate.

Examples of the carrier core material include magnetic metals such as iron, nickel and cobalt, magnetic oxides such as ferrite and magnetite, and glass beads.
The volume average particle diameter of the core material of the carrier is, for example, 10 μm or more and 500 μm or less, and preferably 30 μm or more and 100 μm or less.

Examples of the method of coating the surface of the core material with a resin include a method of coating with a coating layer forming solution in which a coating resin and various additives are dissolved in an appropriate solvent.
Specifically, a dipping method in which the core material is immersed in the coating layer forming solution, a spray method in which the coating layer forming solution is sprayed on the surface of the core material, and a coating layer forming state in which the core material is suspended by flowing air. Examples thereof include a fluidized bed method in which a solution is sprayed and a kneader coater method in which a core material and a coating layer forming solution are mixed in a kneader coater to remove the solvent.
The solvent for the coating layer forming solution is not particularly limited, and may be selected in consideration of the type of coating resin to be used, applicability, and the like.

  The mixing ratio (mass ratio) of the toner and the carrier in the two-component developer is preferably in the range of toner: carrier = 1: 100 to 30: 100, and more preferably in the range of 3: 100 to 20: 100.

<Image forming apparatus and image forming method>
The image forming apparatus of the present embodiment includes an image carrier, a charging unit that charges the surface of the image carrier, an electrostatic charge image forming unit that forms an electrostatic image on the charged surface of the image carrier, and the image carrier. Developing means for developing the electrostatic image formed on the body surface with the developer of the present embodiment to form a toner image, transfer means for transferring the toner image to a recording medium, and the toner image on the recording medium And fixing means for fixing the toner image by applying at least one of light irradiation and heating.
The image forming apparatus according to the present embodiment uses the charging process for charging the surface of the image carrier, the electrostatic charge image forming process for forming an electrostatic charge image on the charged surface of the image carrier, and the electrostatic charge image of the present embodiment. Developing with a developer to form a toner image, a transfer step for transferring the toner image to a recording medium, and subjecting the toner image on the recording medium to light irradiation or heating to form the toner image An image forming method according to this embodiment including a fixing step for fixing is performed.

  In the image forming apparatus and the image forming method of the present embodiment, a non-contact fixing method is adopted. As the non-contact fixing method, a method of irradiating the toner image with light (light fixing method) or a method of heating the toner image may be used.

  Hereinafter, as an example of the image forming apparatus according to the present exemplary embodiment, an example of an image forming apparatus employing a light fixing method will be described with reference to the drawings. In addition, the main part shown to a figure is demonstrated and the description is abbreviate | omitted about others.

  FIG. 1 is a schematic configuration diagram illustrating an example of an image forming apparatus according to the present exemplary embodiment. The image forming apparatus shown in FIG. 1 forms an image with four color toners of black (K), yellow (Y), magenta (M), and cyan (C).

  The image forming apparatus shown in FIG. 1 includes four image forming units 312K, 312Y, 312M, and 312C arranged in parallel from the upstream side to the downstream side in the recording medium conveyance direction, and the optical fixing system is provided downstream of them. An optical fixing device 326 is provided.

  The image forming apparatus illustrated in FIG. 1 includes a paper feed roller 328, and the recording medium P is conveyed by the paper feed roller 328. The conveyance speed (process speed) of the recording medium P is preferably 1000 mm / sec or more, and more preferably 1200 mm / sec or more.

  In the image forming apparatus shown in FIG. 1, toner images are sequentially transferred by electrophotographic method on the recording medium P drawn out of the roll state by the image forming units 312K, 312Y, 312M, and 312C, and then light-fixed to the toner images. Photofixing is performed by the device 326 to form an image.

The black image forming unit 312K is a known electrophotographic image forming unit, and includes a photoreceptor 314K, a charger 316K, an exposure unit 318K, a developing device 320K, a cleaner 322K, and a transfer device 324K. The same applies to the image forming units 312Y, 312M, and 312C for yellow, magenta, and cyan.
When used for monochrome printing, only the image forming unit 312K may be provided.

  There is no restriction | limiting in particular in the light source of the optical fixing device 326, You may employ | adopt well-known light sources, such as a halogen lamp, a mercury lamp, and an infrared laser.

As a light source of the light fixing device 326, a flash lamp in which a rare gas such as xenon is enclosed is desirable in that it can emit high-output light in a short time.
When using a flash lamp, irradiation energy per unit area, 1.0 J / cm ² or more 7.0J / cm ² or less is desirable, 2J / cm ² or more 5 J / cm ² or less is more preferable. Here, the irradiation energy per unit area is the sum of the irradiation energy of each time when the toner is irradiated with light multiple times.

  As the light fixing method, a delay method in which a plurality of flash lamps emit light with a time difference is desirable. The delay system is a system in which a plurality of flash lamps are arranged, each lamp is delayed by 0.01 msec to 100 msec to emit light, and the same portion is illuminated a plurality of times. In the delay method, light energy is divided and supplied to the toner image, so that the fixing conditions are mild and it is easy to realize both void resistance and fixing property.

The number of flash lamps is preferably 1 or more and 20 or less, more preferably 2 or more and 10 or less. The time difference between one and 20 flash lamps is preferably 0.1 msec or more and 20 msec or less, and more preferably 1 msec or more and 3 msec or less. Once the irradiation energy of light emitted in one flashlamp, 0.1 J / cm ² or more 1 J / cm ² or less is preferable, 0.4 J / cm ² or more 0.8 J / cm ² or less is more preferable.

<Process cartridge, toner cartridge>
The process cartridge and the toner cartridge of the present embodiment integrally contain a plurality of members and are attached to and detached from the image forming apparatus.

The process cartridge according to the present exemplary embodiment includes a developing unit that stores the developer according to the present exemplary embodiment and develops an electrostatic charge image formed on the surface of the image holding member with the developer to form a toner image. It is attached to and detached from.
The process cartridge of this embodiment may include at least one selected from the group consisting of an image carrier, a charging unit, and a cleaning unit in addition to the developing unit.

  The toner cartridge according to the present embodiment accommodates the electrostatic charge image developing toner according to the present embodiment, and is attached to and detached from the image forming apparatus. When the amount of toner stored in the toner cartridge mounted on the image forming apparatus becomes low, the toner cartridge is replaced.

EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto. Example 1 is shown as a reference example not containing the compound represented by the general formula (A). In the following, unless otherwise specified, “part” and “%” are based on mass.

<Preparation of first resin particle dispersion>
[First resin particle dispersion (1)]
・ Styrene 320 parts ・ N-butyl acrylate 80 parts ・ Acrylic acid 10 parts ・ Dodecanethiol 10 parts ・ Nonionic surfactant (Sanyo Kasei nonipol 400) 6 parts ・ Anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd.) Neogen R) 10 parts 550 parts of ion-exchanged water The above materials were placed in a flask, dispersed and emulsified, and 50 parts of ion-exchanged water in which 4 parts of ammonium persulfate was dissolved was added while slowly stirring and mixing for 10 minutes. . Thereafter, the inside of the flask was replaced with nitrogen, and the system was heated with an oil bath while stirring to 70 ° C., and emulsion polymerization was continued as it was for 5 hours to obtain a resin particle dispersion.
When the volume average particle diameter (D50) of the resin particles was measured with a laser diffraction particle size distribution analyzer (LA-700 manufactured by Horiba, Ltd.), it was 155 nm, and a differential scanning calorimeter (DSC-50 manufactured by Shimadzu Corporation) was used. The glass transition point of the resin was measured at a heating rate of 10 ° C./min and found to be 54 ° C., and the weight average molecular weight (polystyrene conversion) was measured using THF as a solvent using a molecular weight measuring device (HLC-8020 manufactured by Tosoh Corporation). It was 33,000.

<Preparation of second resin particle dispersion>
[Second resin particle dispersion (1)]
As a polymer particle dispersion of polymerized rosin ester, Haristar Kasei Co., Ltd. Harrier Star SK-385NS (softening point 85 ° C., acid value 8.0 mgKOH / g, solid content 50%) was prepared.

[Second resin particle dispersion (2)]
As a resin particle dispersion of the rosin-modified phenol resin, Arakawa Chemical Industries Superester E-200NT (softening point 125 ° C., acid value 18.0 mgKOH / g or less, solid content 52%) was prepared.

[Second resin particle dispersion (3)]
A resin particle dispersion of a rosin-modified maleic resin (Harimak R-100 manufactured by Harima Kasei Co., Ltd., softening point 110 ° C., acid value 25 mgKOH / g) was prepared by the following method.
100 parts of the resin was dissolved in a mixed solution of 500 ml of ethyl acetate and 50 ml of ethanol, and a solution prepared by dissolving 2.375 parts of potassium hydroxide in 1.0 L of distilled water was gradually added while stirring this solution. Next, the temperature of the solution was raised to 40 ° C., ethyl acetate and ethanol were removed, and 0.1 part of an anionic surfactant (Neogen R manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) was added. Ion exchange water was added here to adjust the solid content to 50%.

[Second resin particle dispersion (4)]
A resin particle dispersion of a rosin resin having a softening point exceeding 150 ° C. was prepared by the following method.
100 parts of rosin modified special synthetic resin (Harimak AS-5 manufactured by Harima Kasei Co., Ltd., softening point 165 ° C., acid value 9.0 mgKOH / g) is dissolved in a mixture of 500 ml of ethyl acetate and 50 ml of ethanol, and this solution is stirred. While dissolving 2.375 parts of potassium hydroxide in 1.0 L of distilled water, it was gradually added. Next, the temperature of the solution was raised to 40 ° C., ethyl acetate and ethanol were removed, and 0.1 part of an anionic surfactant (Neogen R manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) was added. Ion exchange water was added here to adjust the solid content to 50%.

<Preparation of colorant dispersion>
[Colorant dispersion (K)]
・ Carbon black (Nipx35 manufactured by Tegusa) 50 parts ・ Anionic surfactant (Neogen R manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 5 parts ・ Ion-exchanged water 200 parts The above materials are mixed and a high-pressure impact disperser optimizer ( Dispersion treatment was performed for 1 hour using Sugino Machine HJP30006) to obtain a colorant dispersion (K). The colorant dispersion (K) had an average particle diameter of 190 nm and a solid content of 20%.

[Colorant dispersion (C)]
・ Cyan pigment (Pigment Blue 15: 3, manufactured by Dainichi Seika Co., Ltd.) 50 parts ・ Anionic surfactant (Neogen R, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 5 parts ・ Ion-exchanged water 200 parts Using a disperser ultimateizer (HJP30006 manufactured by Sugino Machine Co., Ltd.), a dispersion treatment was carried out for 1 hour to obtain a colorant dispersion (C). The colorant dispersion (C) had a colorant particle average particle size of 185 nm and a solid content of 20%.

<Preparation of release agent dispersion>
[Releasing agent dispersion (1)]
・ 40 parts of paraffin wax (HNP0190 manufactured by Nippon Seiwa Co., Ltd., melting point 85 ° C.) 5 parts of cationic surfactant (Sanisol B50 manufactured by Kao Corporation) 200 parts of ion-exchanged water The above materials are mixed and heated to 95 ° C. , Dispersed using a homogenizer (Ultra Turrax T50 manufactured by IKA), and then dispersed with a pressure discharge type homogenizer to obtain a release agent dispersion (1) having an average particle size of 550 nm and a release agent concentration of 2% by mass. Obtained.

<Preparation of infrared absorber dispersion>
[Infrared absorbent dispersion (1)]
-10 parts of the exemplified compound A (1) described above as an infrared absorber-1 part of an anionic surfactant (Neogen R manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)-89 parts of ion-exchanged water The above materials are mixed and an ultrasonic homogenizer (US-150T manufactured by Nippon Seiki Co., Ltd.) was used for dispersion treatment at 150 W for 5 minutes to obtain an infrared absorbent dispersion (1) having a volume average particle size of 410 nm and a solid content of 10%.

<Creation of carrier>
Ferrite particles (average particle size 35 μm, volume electric resistance 10 ⁸ Ω · cm) 100 parts toluene 14 parts perfluorooctylethyl acrylate / methyl methacrylate copolymer (copolymerization ratio 10/90, weight average molecular weight 80,000) 1.6 parts, carbon black (VXC-72 manufactured by Cabot Corporation) 0.12 parts, cross-linked melamine resin particles (number average particle size 0.3 μm) 0.3 parts The above materials other than ferrite particles are dispersed with a stirrer for 10 minutes. Then, a coating layer forming solution was prepared. The coating layer forming solution and the ferrite particles are put into a vacuum degassing kneader and stirred at 60 ° C. for 30 minutes, and then the pressure is reduced to distill off toluene to obtain a carrier having a resin coating layer on the ferrite particle surface. It was.

<Example 1>
[Production of Toner Particles (1)]
First resin particle dispersion (1) 260 parts Second resin particle dispersion (1) 20 parts Colorant dispersion (K) 32.7 parts Release agent dispersion (1) 70 parts Cationic surfactant (Sanisol B50 manufactured by Kao Corporation) 1.5 parts ・ Polyaluminum chloride 0.36 parts ・ Ion-exchanged water 1000 parts The above materials are contained in a round stainless steel flask and homogenizer (Ultra manufactured by IKA). After mixing and dispersing using TALAX T50), the flask was heated to 48 ° C. while stirring in the oil bath for heating. After maintaining at 48 ° C. for 30 minutes, it was confirmed that aggregated particles were formed with an optical microscope, and 145 parts of the first resin particle dispersion (1) was added thereto. Then, after adjusting the pH of the solution to 8.0 with a 0.5 mol / L sodium hydroxide aqueous solution, the flask is sealed, and the stirring shaft seal is magnetically sealed and heated to 90 ° C. while continuing stirring. And held for another 3 hours.

  After completion of the reaction, the reaction mixture was cooled and subjected to solid-liquid separation by Nutsche suction filtration. The solid content was redispersed in 1000 parts of ion-exchanged water at 30 ° C., stirred for 15 minutes at 300 rpm with a stirring blade, and subjected to solid-liquid separation by Nutsche suction filtration. This redispersion and suction filtration were repeated, and the washing was terminated when the filtrate had an electric conductivity of 10.0 μS / cmt or less. Subsequently, it was charged in a vacuum dryer and dried continuously for 12 hours to obtain toner particles (1) having a volume average particle diameter of 5.8 μm.

[Preparation of External Toner (1)]
After 100 parts of toner particles (1) and 1 part of hydrophobic silica (T805, manufactured by Nippon Aerosil Co., Ltd.) were stirred for 10 minutes at a peripheral speed of 32 m / sec using a Henschel mixer, coarse particles were used using a 45 μm mesh sieve. Then, an externally added toner (1) was obtained.

[Preparation of Developer (1)]
94 parts of the carrier and 6 parts of the externally added toner (1) were stirred for 20 minutes at 40 rpm using a V-blender, and then sieved with a 177 μm mesh sieve to obtain developer (1).

<Example 2>
[Production of Toner Particles (2)]
First resin particle dispersion (1) 260 parts Second resin particle dispersion (1) 20 parts Colorant dispersion (K) 27.3 parts Release agent dispersion (1) 70 parts Infrared absorbent dispersion (1) 14 parts Cationic surfactant (Sanisol B50 manufactured by Kao Corporation) 1.5 parts Polyaluminum chloride 0.36 parts Ion-exchanged water 1000 parts Toner particles using the above materials In the same manner as in the preparation of (1), toner particles (2) having a volume average particle diameter of 5.7 μm were obtained.

[Preparation of external toner (2)]
In the same manner as in the preparation of the externally added toner (1), an externally added toner (2) was obtained.

[Preparation of Developer (2)]
Developer (2) was obtained in the same manner as in the preparation of developer (1).

<Example 3>
[Production of Toner Particles (3)]
First resin particle dispersion (1) 260 parts Second resin particle dispersion (2) 20 parts Colorant dispersion (K) 27.3 parts Release agent dispersion (1) 70 parts Infrared absorbent dispersion (1) 14 parts Cationic surfactant (Sanisol B50 manufactured by Kao Corporation) 1.5 parts Polyaluminum chloride 0.36 parts Ion-exchanged water 1000 parts Toner particles using the above materials In the same manner as in the preparation of (1), toner particles (3) having a volume average particle diameter of 5.8 μm were obtained.

[Preparation of external toner (3)]
Externally added toner (3) was obtained in the same manner as in the preparation of externally added toner (1).

[Preparation of Developer (3)]
Developer (3) was obtained in the same manner as in the preparation of developer (1).

<Example 4>
[Production of Toner Particles (4)]
First resin particle dispersion (1) 260 parts Second resin particle dispersion (3) 20 parts Colorant dispersion (K) 27.3 parts Release agent dispersion (1) 70 parts Infrared absorbent dispersion (1) 14 parts Cationic surfactant (Sanisol B50 manufactured by Kao Corporation) 1.5 parts Polyaluminum chloride 0.36 parts Ion-exchanged water 1000 parts Toner particles using the above materials In the same manner as in the preparation of (1), toner particles (4) having a volume average particle diameter of 5.8 μm were obtained.

[Preparation of external toner (4)]
Externally added toner (4) was obtained in the same manner as in the preparation of externally added toner (1).

[Preparation of Developer (4)]
Developer (4) was obtained in the same manner as in the preparation of developer (1).

<Example 5>
[Production of Toner Particles (5)]
First resin particle dispersion (1) 260 parts Second resin particle dispersion (3) 20 parts Colorant dispersion (C) 27.3 parts Release agent dispersion (1) 70 parts Infrared absorbent dispersion (1) 14 parts Cationic surfactant (Sanisol B50 manufactured by Kao Corporation) 1.5 parts Polyaluminum chloride 0.36 parts Ion-exchanged water 1000 parts Toner particles using the above materials In the same manner as in the preparation of (1), toner particles (5) having a volume average particle diameter of 5.7 μm were obtained.

[Preparation of external toner (5)]
Externally added toner (5) was obtained in the same manner as in preparation of externally added toner (1).

[Preparation of Developer (5)]
Developer (5) was obtained in the same manner as in the preparation of developer (1).

<Comparative Example 1>
[Production of Toner Particles (C1)]
First resin particle dispersion (1) 260 parts Second resin particle dispersion (4) 20 parts Colorant dispersion (K) 27.3 parts Release agent dispersion (1) 70 parts Infrared absorbent dispersion (1) 14 parts Cationic surfactant (Sanisol B50 manufactured by Kao Corporation) 1.5 parts Polyaluminum chloride 0.36 parts Ion-exchanged water 1000 parts Toner particles using the above materials In the same manner as in the preparation of (1), toner particles (C1) having a volume average particle diameter of 5.7 μm were obtained.

[Preparation of Externally Added Toner (C1)]
The externally added toner (C1) was obtained in the same manner as in the preparation of the externally added toner (1).

[Preparation of Developer (C1)]
A developer (C1) was obtained in the same manner as in the preparation of the developer (1).

<Comparative example 2>
[Production of Toner Particles (C2)]
Styrene-alkyl acrylate copolymer (weight average molecular weight 6000) 1000 parts Rosin (Harima Chemical Co., Ltd. Harrier Star NL) 100 parts Carbon black (Nippx35 manufactured by Tegusa) 88 parts Paraffin wax (manufactured by Nippon Seiwa Co., Ltd.) HNP0190, melting point 85 ° C.) 88 parts The above materials were kneaded with an extruder and pulverized with a surface pulverizer. Thereafter, the step of classifying fine particles and coarse particles with an air classifier and obtaining particles having an intermediate size was repeated three times to obtain toner particles (C2) having a volume average particle size of 5.0 μm.

[Preparation of Externally Added Toner (C2)]
Externally added toner (C2) was obtained in the same manner as in the preparation of externally added toner (1).

[Preparation of Developer (C2)]
Developer (C2) was obtained in the same manner as in the preparation of developer (1).

<Evaluation>
[Image gloss]
Fuji Xerox C-2250 is used as the image forming apparatus, Fuji Xerox J paper is used as the recording medium, and the amount of applied toner is 13.5 g / m ² using the developers of the examples and comparative examples. Thus, the toner image was formed. Subsequently, the toner image was fixed using a laser irradiation apparatus at an irradiation energy of 1.5 J / cm ² per unit area and a conveyance speed of 500 mm / sec. Then, the fixed image was visually observed, and the image gloss was determined according to the following criteria. The results are shown in Table 1.
A: Image gloss is high and fixing strength and color developability are high. B: Image gloss, fixing strength and color developability are good. C: Image gloss, fixing strength and color developability are uneven and defective. Many image defects

  The developer of Comparative Example 2 did not fix at a fixing temperature of 100 ° C., and when fixing temperature was raised for fixing, white smoke was generated from an unfixed image, paper foaming called paper blister was generated, and the image was It was greatly disturbed. Therefore, Comparative Example 2 could not be evaluated according to the above criteria.

  As is clear from Table 1, Examples 1 to 5 were superior in image gloss to Comparative Example 1.

312Y, 312M, 312C, 312K Image forming units 314Y, 314M, 314C, 314K Photoconductors 316Y, 316M, 316C, 316K Chargers 318Y, 318M, 318C, 318K Exposure means 320Y, 320M, 320C, 320K Developers 322Y, 322M, 322C, 322K Cleaner 324Y, 324M, 324C, 324K Transfer device 326 Optical fixing device 328 Paper feed roller P Recording medium

Claims (8)

A binder resin, a resin having a structure derived from rosin and having a softening point of 150 ° C. or less, and a compound represented by the following general formula (A), and having a structure derived from the rosin and softening An electrostatic charge image developing toner comprising toner particles in which a resin having a point of 150 ° C. or lower is dispersed in the form of particles .

In general formula (A), R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom or a methyl group, and R ¹¹ , R ¹² , R ¹³ and R ¹⁴ each independently represent 1 carbon atom. Represents an alkyl group of 6 or less. R ¹¹ and R ¹² and R ¹³ and R ¹⁴ may be independently connected to form a ring. The electrostatic image developing toner according to claim 1 , wherein the resin having a structure derived from rosin and having a softening point of 150 ° C. or lower is a resin having a softening point of 130 ° C. or lower .   An electrostatic charge image developer comprising the toner for developing an electrostatic charge image according to claim 1.   A toner cartridge that accommodates the electrostatic image developing toner according to claim 1 and is detachable from an image forming apparatus.   An image forming apparatus comprising: a developing unit that stores the electrostatic charge image developer according to claim 3 and that develops the electrostatic charge image formed on the surface of the image carrier with the electrostatic charge image developer to form a toner image. Process cartridge attached to and detached from. An image carrier,
Charging means for charging the surface of the image carrier;
An electrostatic charge image forming means for forming an electrostatic charge image on the surface of the charged image carrier;
A developing unit that houses the electrostatic charge image developer according to claim 3 and that develops the electrostatic charge image formed on the surface of the image carrier with the electrostatic charge image developer to form a toner image;
Transfer means for transferring the toner image to a recording medium;
Fixing means for fixing the toner image by applying at least one of light irradiation and heating to the toner image of the recording medium;
An image forming apparatus comprising: First resin particles containing a binder resin, second resin particles having a structure derived from rosin and containing a resin having a softening point of 150 ° C. or lower, and the following general formula (A) In the dispersion liquid in which the compound particles are dispersed, the first resin particles, the second resin particles, and the compound particles represented by the following general formula (A) are aggregated to form aggregated particles. An aggregation process;
Heating the dispersion in which the aggregated particles are dispersed, and fusing and coalescing the aggregated particles to form fused particles;
A method for producing a toner for developing an electrostatic charge image.

In general formula (A), R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom or a methyl group, and R ¹¹ , R ¹² , R ¹³ and R ¹⁴ each independently represent 1 carbon atom. Represents an alkyl group of 6 or less. R ¹¹ and R ¹² and R ¹³ and R ¹⁴ may be independently connected to form a ring. The production method according to claim 7, wherein the resin having a structure derived from rosin and having a softening point of 150 ° C or lower is a resin having a softening point of 130 ° C or lower.