JP7151308B2 - TONER, TONER CONTAINING UNIT, IMAGE FORMING APPARATUS, AND IMAGE FORMING METHOD - Google Patents

Description

The present invention relates to toner, a toner storage unit, an image forming apparatus, and an image forming method.

In recent years, toners have become smaller in size to improve the quality of output images, have high-temperature offset resistance, have low-temperature fixability to save energy, and can withstand high temperatures and high humidity during storage and transportation after manufacturing. There is a demand for good heat-resistant storage stability. In particular, since the power consumption during fixing accounts for most of the power consumption in the image forming process, it is very important to improve the low-temperature fixability.

Conventionally, a toner produced by a kneading pulverization method has been used. It is difficult to reduce the particle size of the toner produced by the kneading pulverization method, and the shape of the toner is irregular and the particle size distribution is broad. There were problems such as In addition, when wax (release agent) is added to improve fixability, the toner produced by kneading and pulverizing cracks at the wax interface during pulverization, so a large amount of wax exists on the toner surface. Resulting in. As a result, while the release effect is obtained, the toner tends to adhere (filming) to the carrier, photoreceptor, and blade, and the overall performance is unsatisfactory.

Therefore, in order to overcome the above-mentioned problems caused by the kneading pulverization method, a method for producing toner by a polymerization method has been proposed. The toner produced by the polymerization method can be easily made into a small particle size, has a sharper particle size distribution than the toner produced by the pulverization method, and can contain a release agent. . As a method of producing a toner by a polymerization method, a method of producing a toner from an elongation reaction product of a urethane-modified polyester as a toner binder is disclosed for the purpose of improving low-temperature fixability and high-temperature offset resistance. (See Patent Document 1, for example).
In addition, a method for producing a toner that is excellent in powder fluidity and transferability in the case of a small particle size toner and is excellent in all of heat-resistant storage stability, low-temperature fixability, and high-temperature offset resistance is disclosed (for example, , see Patent Documents 2 and 3).
Further, a method for producing a toner having an aging process for producing a toner binder with a stable molecular weight distribution and achieving both low-temperature fixability and high-temperature offset resistance is disclosed (see, for example, Patent Documents 4 and 5). .
However, these proposed techniques do not satisfy the high level of low-temperature fixability required in recent years.

Therefore, in order to obtain a high level of low-temperature fixability, a toner has been proposed which contains a resin containing a crystalline polyester resin and a release agent, and has a sea-island phase separation structure in which the resin and wax are incompatible with each other. (See Patent Document 6, for example).
Also, a toner containing a crystalline polyester resin, a releasing agent and a graft polymer has been proposed (see, for example, Patent Document 7).
In these proposed techniques, since the crystalline polyester resin melts more rapidly than the amorphous polyester resin, low-temperature fixing can be achieved. However, even if the crystalline polyester resin corresponding to the islands in the sea-island phase separation structure melts, most of the amorphous polyester resin corresponding to the sea still does not melt. In this case, both the crystalline polyester resin and the amorphous polyester resin need to be melted to a certain extent to fix the toner. Therefore, these proposed techniques do not satisfy the high level of low-temperature fixability that has been increasing in recent years.

For the purpose of obtaining a higher level of low-temperature fixability, a toner comprising an amorphous polyester obtained by reacting a reactive precursor having a branched structure with a very low glass transition temperature with a curing agent has been proposed. (See Patent Document 8, for example).
This proposed technology utilizes the property that polyester resin, which has a very low glass transition temperature, deforms at low temperatures. Take advantage of the ease of use. In addition, since the reactive precursor is non-linear, it has a branched structure in the molecular skeleton and the molecular chain has a three-dimensional network structure, so it deforms at low temperatures but does not flow like rubber. have the property Therefore, it is possible to maintain the heat-resistant storage stability and high-temperature offset resistance of the toner.

However, according to this technique, the three-dimensional network structure is obtained by an ester reaction of diols, dicarboxylic acids, polyhydric alcohols, or acids, and polyhydric alcohols or acids that form branched structures exist nonuniformly. Therefore, there are loose portions and dense portions in the network structure, and the loose portions cause deterioration in heat-resistant storage stability, while the dense portions cause deterioration in low-temperature fixability, image gloss, image density, and color reproducibility.
In addition, the portion forming the branches is an ester structure, and the cohesive force as a cross-linking point of the resin is weak. Good low-temperature fixability and image gloss cannot be obtained. Therefore, it does not satisfy the high level of low-temperature fixability and image quality which have been increasing in recent years.

Further, for the purpose of improving heat-resistant storage stability, a toner containing two types of amorphous polyester resins having different glass transition points has been proposed (see, for example, Patent Document 9).
In this proposed technique, an amorphous polyester resin, which has a glass transition temperature in the ultra-low temperature range but has a high melt viscosity and is difficult to flow, is combined with other amorphous polyester resins in a compatible state. Therefore, even if the glass transition temperature of the toner is set low, it is possible to maintain heat-resistant storage stability and offset resistance.

However, according to this technique, the low-Tg polyester resin, which is advantageous in low-temperature fixing, has an aromatic trimellitic acid skeleton, and the trimellitic acid skeleton is disadvantageous in low-temperature fixing. Therefore, the high level of low-temperature fixability required in recent years is not satisfied.

Therefore, at present, there is a demand for a toner having excellent low-temperature fixability, high glossiness, and heat-resistant storage stability.

An object of the present invention is to provide a toner having excellent low-temperature fixability, glossiness, and heat-resistant storage stability.

The above problem is solved by the following configuration 1).
1) A toner containing at least a colorant, a release agent, and a binder resin,
including a crystalline polyester resin and an amorphous polyester resin as the binder resin,
The amorphous polyester resin includes an amorphous polyester resin A having an isocyanurate skeleton and urethane and/or urea bonds, and an amorphous polyester resin having a trimellitic acid skeleton and urethane and/or urea bonds. A toner characterized by containing B.

According to the present invention, it is possible to provide a toner having excellent low-temperature fixability, glossiness, and heat-resistant storage stability.

1 is a schematic configuration diagram showing an example of an image forming apparatus of the present invention; FIG. FIG. 3 is a schematic configuration diagram showing another example of the image forming apparatus of the present invention; FIG. 3 is a schematic configuration diagram showing another example of the image forming apparatus of the present invention; 4 is a partially enlarged view of FIG. 3; FIG. 1 is a schematic configuration diagram showing an example of a process cartridge; FIG. It is an image diagram for explaining the branched structure of a conventional polyester resin. It is an image diagram for explaining the branched structure of the polyester resin defined in the present invention.

The toner of the present invention contains at least a colorant, a release agent, and a binder resin, and includes a crystalline polyester resin and an amorphous polyester resin as the binder resin, and the amorphous polyester resin is isocyanate. characterized by containing an amorphous polyester resin A having a nurate skeleton and urethane and/or urea bonds, and an amorphous polyester resin B having a trimellitic acid skeleton and urethane and/or urea bonds do.

In order to improve the low-temperature fixability, a method of lowering the glass transition temperature or reducing the molecular weight is conceivable so that the polyester resin (for example, amorphous polyester resin) melts together with the crystalline polyester resin. However, if the melt viscosity is simply lowered by lowering the glass transition temperature or the molecular weight of the polyester resin, it is easily imagined that the heat-resistant storage stability of the toner and the high-temperature offset property during fixing will be deteriorated. be.
On the other hand, in the toner of the present invention, the amorphous polyester resin A has a branched structure in the molecular skeleton due to urethane and/or urea bonds, and the molecular chain has a three-dimensional network structure. It has a rubber-like property that it deforms at , but does not flow. Therefore, even when the glass transition temperature of the amorphous polyester resin A is made very low, the heat-resistant storage stability and high-temperature offset resistance of the toner can be maintained.

In addition, if the network structure is non-uniform, the flow of the resin is not sufficiently suppressed in the coarse-mesh portion, resulting in deterioration of the heat-resistant storage stability, and in the dense-mesh portion, the deformability of the resin is insufficient. Therefore, low-temperature fixability and image gloss are lowered.
For example, in the polyester resin described in Japanese Patent No. 5408210 (corresponding to Patent Document 8 above) described in Background Art, when the portion forming the branch is an ester structure, as shown in the image diagram of FIG. Since the branched structure exists non-uniformly in each layer, the low-temperature fixability and image gloss are not sufficiently satisfactory. FIG. 6 is a schematic diagram of a branched structure of a polyester resin obtained by a conventional synthesis method.
As described above, it is not easy for conventional polyester resins to satisfy all of these items, that is, good low-temperature fixability and image glossiness, as well as good heat-resistant storage stability and high-temperature offset resistance.

However, in a preferred form of the amorphous polyester resin A of the present invention, after synthesizing R2, which is a polyester or modified polyester moiety, it is possible to combine R1 with a urethane or urea group to form a network structure. By narrowing the molecular weight distribution of the R2 portion, it is possible to homogenize the network structure.
The state of the amorphous polyester resin A defined in the present invention is shown as an image diagram in FIG. FIG. 7 is a schematic diagram of the branched structure of the amorphous polyester resin A obtained by the synthesis method of the invention described below. Since the straight-chain polyester resin portion of the R2 portion has the same length, the branched structure of the amorphous polyester resin A is made uniform as shown in FIG.
As described above, the network structure of the amorphous polyester resin A is made uniform, so that the heat-resistant storage stability, low-temperature fixability, image glossiness, and high-temperature offset resistance of the toner can be achieved at the same time.

Furthermore, the amorphous polyester resin A has a urethane bond or a urea bond with high cohesive energy in the branched structure portion, so that it behaves like a strong cross-linking point. Since the effect of suppressing resin flow is strong, it is possible to achieve both heat-resistant storage stability, low-temperature fixability, image gloss, and high-temperature offset resistance of the toner.

In the present invention, for the purpose of further improving high-temperature offset resistance and heat-resistant storage stability while satisfying excellent low-temperature fixability, high gloss, and high color reproducibility, the above-mentioned non-polyester resin, which is an ultra-low Tg polyester resin, is used. A crystalline polyester resin A and a high Tg amorphous polyester resin B are used in combination in the toner. Since the amorphous polyester resin A facilitates deformation at low temperatures, excellent low-temperature fixability, high gloss, and high color reproducibility are exhibited. Furthermore, since the amorphous polyester resin B increases the elastic modulus at high temperatures, high-temperature offset resistance and heat-resistant storage stability are improved.
In this way, the amorphous polyester resin A and the amorphous polyester resin B, which have different glass transition points, are contained in combination in the toner, whereby excellent low-temperature fixability, high-temperature offset resistance, high glossiness, It is possible to achieve both high color reproducibility and heat resistant storage stability.

<Polyester resin>
(Amorphous polyester resin A)
The amorphous polyester resin A has a structure represented by any one of the following structural formulas 1) to 3), wherein R2, which is a polyester or modified polyester moiety, and R1, which corresponds to a branched structure, are urethane or urea It has a structure linked by groups.
1) R1-(NHCONH-R2)n-
2) R1-(NHCOO-R2)n-
3) R1-(OCONH-R2)n-
(In the above formula, n = 3, R1 represents an isocyanurate skeleton, and R2 represents a group derived from either a polyester containing a polycarboxylic acid and a polyol or a modified polyester in which the polyester is isocyanate-modified. .)
Since the amorphous polyester resin A has at least one of a urethane bond and a urea bond in the branched structure portion, the urethane bond or the urea bond behaves like a pseudo-crosslinking point, and the amorphous polyester resin A The rubber-like properties of the resin A are strengthened, and a toner excellent in heat-resistant storage stability and high-temperature offset resistance can be produced.
The amorphous polyester resin A contains a diol component as a constituent component, more preferably a dicarboxylic acid component as a constituent component.

The amorphous polyester resin A is not particularly limited as long as R2 corresponding to the polyester or modified polyester portion and R1 corresponding to the branched structure portion are bonded by a urethane or urea group, and may be used appropriately depending on the purpose. can be selected.
The method for combining R1 and R2 is not limited to the following, but includes, for example, the following method.

a) A method in which a diol component and a dicarboxylic acid component are subjected to an ester reaction to prepare a polyester polyol (R2) having a terminal hydroxyl group, and the obtained polyester polyol is reacted with an isocyanurate (R1).
b) esterification of a diol component and a dicarboxylic acid component to prepare a polyester polyol (R2) having a terminal hydroxyl group, reaction of the obtained polyester polyol with a divalent polyisocyanate to obtain an isocyanate-modified polyester (R2); A method of reacting an isocyanurate (R1) with the obtained isocyanate-modified polyester in the presence of pure water.
It is also possible to react the hydroxyl groups remaining in the polyol obtained by any one of the above a) to b) with a polyisocyanate having a valence of 2 or more to obtain a polyester prepolymer, which is reacted with a curing agent in the toner production process and used. .
During the toner production process, urethane and urea bonds are generated by reaction with the curing agent, and by exhibiting behavior like a strong cross-linking point, the rubber-like properties of the amorphous polyester resin A are strengthened, and heat-resistant storage stability is achieved. Further, it is more preferable to use a modified polyester resin in which the R2 portion is modified with isocyanate, since it is more excellent in high-temperature offset resistance.

In order to lower the Tg of the amorphous polyester resin A and easily impart the property of being deformed at a low temperature, the amorphous polyester resin A contains a diol component as a constituent component, and the diol component has a carbon number of It preferably contains an aliphatic diol having 3 to 12 carbon atoms, and more preferably contains an aliphatic diol having 4 to 12 carbon atoms.

The amorphous polyester resin A preferably contains 50 mol % or more, more preferably 80 mol % or more, and even more preferably 90 mol % or more of the aliphatic diol having 3 to 12 carbon atoms.

Examples of the aliphatic diol having 3 to 12 carbon atoms include 1,3-propanediol, 1,4-butanediol, 2-methyl-1,3-propanediol, 1,5-pentanediol, 3-methyl -1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol, 1,12-dodecanediol and the like.

In particular, in the amorphous polyester resin A, the diol component is an aliphatic diol having 4 to 12 carbon atoms, the main chain portion of the diol component has an odd number of carbon atoms, and the diol component However, it is more preferable to have an alkyl group on the side chain.
Examples of aliphatic diols having 4 to 12 carbon atoms in the main chain portion having an odd number of carbon atoms and alkyl groups in side chains include aliphatic diols represented by the following general formula (1).
HO—(CR1R2)n—OH General formula (1)
However, in the general formula (1), R1 and R2 each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. n represents an odd number from 3 to 9; In n repeating units, R1 may be the same or different. Moreover, in n repeating units, R2 may be the same or different.

In addition, in order to lower the Tg of the amorphous polyester resin A and easily impart the property of being deformed at low temperatures, the amorphous polyester resin A contains fats having 3 or more and 12 or less carbon atoms in the total alcohol component. It is preferable to contain group diols in an amount of 50 mol % or more.

In order to lower the Tg of the amorphous polyester resin A and easily impart the property of being deformed at a low temperature, the amorphous polyester resin A contains a dicarboxylic acid component as a constituent component, and the dicarboxylic acid component is It is preferable to contain an aliphatic dicarboxylic acid having 4 to 12 carbon atoms.

The polyester resin preferably contains 30 mol % or more of the aliphatic dicarboxylic acid having 4 to 12 carbon atoms.
Examples of the aliphatic dicarboxylic acids having 4 to 12 carbon atoms include succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid and dodecanedioic acid.

-Diol component-
The diol component is not particularly limited and can be appropriately selected depending on the intended purpose. methyl-1,3-propanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol, 1, Aliphatic diols such as 12-dodecanediol; diols having an oxyalkylene group such as diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol; 1,4-cyclohexanedimethanol, hydrogenated bisphenol Alicyclic diols such as A; alicyclic diols to which alkylene oxides such as ethylene oxide, propylene oxide and butylene oxide are added; bisphenols such as bisphenol A, bisphenol F and bisphenol S; bisphenols, ethylene oxide and propylene Examples include alkylene oxide adducts of bisphenols, such as oxides and alkylene oxide adducts such as butylene oxide. Among these, aliphatic diols having 4 to 12 carbon atoms are preferred.
These diols may be used singly or in combination of two or more.

-Dicarboxylic acid component-
The dicarboxylic acid component is not particularly limited and can be appropriately selected depending on the intended purpose. Examples thereof include aliphatic dicarboxylic acids and aromatic dicarboxylic acids. Anhydrides of these may be used, lower alkyl esters (having 1 to 3 carbon atoms), or halides thereof may be used.
The aliphatic dicarboxylic acid is not particularly limited and can be appropriately selected depending on the intended purpose. Examples thereof include succinic acid, adipic acid, sebacic acid, dodecanedioic acid, maleic acid and fumaric acid.
The aromatic dicarboxylic acid is not particularly limited and can be appropriately selected depending on the intended purpose, but an aromatic dicarboxylic acid having 8 to 20 carbon atoms is preferable.
The aromatic dicarboxylic acid having 8 to 20 carbon atoms is not particularly limited and can be appropriately selected depending on the intended purpose. Examples thereof include phthalic acid, isophthalic acid, terephthalic acid and naphthalenedicarboxylic acid.
Among these, aliphatic dicarboxylic acids having 4 to 12 carbon atoms are preferred.
These dicarboxylic acids may be used individually by 1 type, and may use 2 or more types together.

-Trihydric or higher alcohol-
The trihydric or higher alcohol is not particularly limited and can be appropriately selected depending on the intended purpose. and oxide adducts.
Examples of trihydric or higher aliphatic alcohols include glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, and sorbitol.
Examples of the trivalent or higher polyphenols include trisphenol PA, phenol novolak, and cresol novolak.
Examples of the alkylene oxide adducts of trihydric or higher polyphenols include those obtained by adding alkylene oxides such as ethylene oxide, propylene oxide and butylene oxide to trihydric or higher polyphenols.

- Polyisocyanate -
The polyisocyanate is not particularly limited and can be appropriately selected depending on the intended purpose. Examples thereof include diisocyanate and trivalent or higher isocyanate.
Examples of the diisocyanate include aliphatic diisocyanates, alicyclic diisocyanates, aromatic diisocyanates, araliphatic diisocyanates, isocyanurates, and those obtained by blocking these with phenol derivatives, oximes, caprolactam, and the like.
Examples of the trivalent or higher isocyanate include lysine triisocyanate, a product obtained by reacting a trivalent or higher alcohol with a diisocyanate, and a product obtained by reacting a polyisocyanate to form an isocyanurate.
Among them, it is more preferable to use a polyisocyanate having an isocyanurate skeleton because it acts as a stronger cross-linking point and is more excellent in heat resistant storage stability and high temperature offset resistance.

The content of the trivalent isocyanate component is preferably 0.2 mol % or more and 1.0 mol % or less with respect to the resin component in the THF-insoluble matter of the toner. When a crosslinked structure is formed with a trivalent isocyanate component, the cohesive force of the molecular chains increases due to pseudo-crosslinking due to urethane or urea bonds at the crosslink points. A high level of fixability can be achieved. If the content of the trivalent isocyanate component is less than 0.2 mol %, the formation of the branched structure becomes insufficient, and the portion where the network structure becomes non-uniform becomes the starting point, thereby deteriorating heat-resistant storage stability and filming resistance. Sometimes. When the trivalent isocyanate component is more than 1.0 mol %, the low-temperature fixability may deteriorate due to the formation of a dense crosslinked structure.
The aliphatic diisocyanate is not particularly limited and can be appropriately selected depending on the intended purpose. diisocyanate, dodecamethylene diisocyanate, tetradecamethylene diisocyanate, trimethylhexane diisocyanate, tetramethylhexane diisocyanate and the like.
The alicyclic diisocyanate is not particularly limited and can be appropriately selected depending on the intended purpose. Examples thereof include isophorone diisocyanate and cyclohexylmethane diisocyanate.
The aromatic diisocyanate is not particularly limited and can be appropriately selected depending on the intended purpose. diphenyl, 4,4'-diisocyanato-3,3'-dimethyldiphenyl, 4,4'-diisocyanato-3-methyldiphenylmethane, 4,4'-diisocyanato-diphenyl ether and the like.
The araliphatic diisocyanate is not particularly limited and can be appropriately selected depending on the intended purpose. Examples thereof include α,α,α',α'-tetramethylxylylene diisocyanate.
The isocyanurates are not particularly limited and can be appropriately selected depending on the intended purpose. Examples thereof include tris(isocyanatoalkyl)isocyanurate and tris(isocyanatocycloalkyl)isocyanurate.
These polyisocyanates may be used singly or in combination of two or more.

-Curing agent-
The curing agent is a curing agent capable of reacting with a polyester prepolymer (a reaction product of the polyester portion of R2 and the polyisocyanate, that is, a reaction precursor to be reacted with a curing agent) to generate the polyester resin. If there is, there is no particular limitation, and it can be appropriately selected depending on the purpose. Examples thereof include active hydrogen group-containing compounds.

-Compound containing active hydrogen group-
The active hydrogen group in the active hydrogen group-containing compound is not particularly limited and can be appropriately selected depending on the intended purpose. etc. These may be used individually by 1 type, and may use 2 or more types together.

The active hydrogen group-containing compound is not particularly limited and can be appropriately selected depending on the intended purpose, but amines are preferable because they can form a urea bond.

The amines are not particularly limited and can be appropriately selected depending on the intended purpose. mentioned. These may be used individually by 1 type, and may use 2 or more types together.
Among these, diamines and mixtures of diamines and a small amount of trivalent or higher amines are preferred.

The diamine is not particularly limited and can be appropriately selected depending on the intended purpose. Examples thereof include aromatic diamines, alicyclic diamines, and aliphatic diamines. The aromatic diamine is not particularly limited and can be appropriately selected depending on the intended purpose. Examples thereof include phenylenediamine, diethyltoluenediamine, 4,4'-diaminodiphenylmethane and the like. The alicyclic diamine is not particularly limited and can be appropriately selected depending on the intended purpose. be done. The aliphatic diamine is not particularly limited and can be appropriately selected depending on the intended purpose. Examples thereof include ethylenediamine, tetramethylenediamine and hexamethylenediamine.

The trivalent or higher amine is not particularly limited and can be appropriately selected depending on the intended purpose. Examples thereof include diethylenetriamine and triethylenetetramine.
The aminoalcohol is not particularly limited and can be appropriately selected depending on the intended purpose. Examples thereof include ethanolamine and hydroxyethylaniline.
The aminomercaptan is not particularly limited and can be appropriately selected depending on the intended purpose. Examples thereof include aminoethylmercaptan and aminopropylmercaptan.
The amino acid is not particularly limited and can be appropriately selected depending on the intended purpose. Examples thereof include aminopropionic acid and aminocaproic acid.
The blocked amino group is not particularly limited and can be appropriately selected depending on the intended purpose. ketimine compounds, oxazoline compounds, and the like.

The glass transition temperature of the amorphous polyester resin A is preferably -60°C or higher and 0°C or lower, more preferably -40°C or higher and -20°C or lower.
If the glass transition temperature is less than −60° C., the flow of the toner at low temperatures cannot be suppressed, resulting in poor heat-resistant storage stability and filming resistance.
If the glass transition temperature exceeds 0° C., the toner cannot be sufficiently deformed by heat and pressure during fixation, resulting in insufficient low-temperature fixability.

In the amorphous polyester resin A, in the above structural formulas 1) to 3), R1 has an isocyanurate skeleton represented by the following structural formula (I). It is preferable in terms of sex.

In the amorphous polyester resin A, although the detailed reason is not clear, the three-dimensional molecular network structure is suitable for achieving both low-temperature fixability, image gloss, heat-resistant storage stability, and offset resistance. In the above structural formulas 1) to 3), it is more preferable that n is 3.

The weight-average molecular weight of the amorphous polyester resin A is not particularly limited and can be appropriately selected depending on the intended purpose. The following are preferred.
The weight average molecular weight of the amorphous polyester resin A refers to the molecular weight of the reaction product obtained by reacting the reactive precursor with the curing agent.
If the weight-average molecular weight is less than 20,000, the toner tends to flow at low temperatures, which may result in poor heat-resistant storage stability.
Moreover, the viscosity at the time of melting becomes low, and the high-temperature offset property may deteriorate.

The content of the amorphous polyester resin A is not particularly limited and can be appropriately selected depending on the intended purpose. ~5 parts by mass is more preferred.

(Amorphous polyester resin B)
The amorphous polyester resin B contains, for example, a diol component and a dicarboxylic acid component as constituent components. The amorphous polyester resin B, like the amorphous polyester resin A, contains urethane or urea bonds.

The amorphous polyester resin B can be produced in the same manner as the amorphous polyester resin A. However, in the amorphous polyester resin B, R1 is trimellitic acid.

The glass transition temperature of the amorphous polyester resin B is 30° C. or more and less than 70° C. according to the method for measuring the glass transition temperature described later.
If the glass transition temperature is too low, the toner may have poor heat-resistant storage stability and durability against stress such as agitation in the developing device. This is because the low-temperature fixability may be inferior.

-Diol component-
The diol component is not particularly limited and can be appropriately selected depending on the purpose. Examples include polyoxypropylene (2.2)-2,2-bis(4-hydroxyphenyl)propane, polyoxyethylene ( 2.2) -2,2-bis(4-hydroxyphenyl)propane and other alkylene (carbon number 2-3) oxide (average addition mole number 1-10) adducts of bisphenol A; ethylene glycol, propylene glycol, water Added bisphenol A, or their alkylene (carbon number 2-3) oxide (average addition mole number 1-10) adducts, and the like. These may be used individually by 1 type, and may use 2 or more types together.

-Dicarboxylic acid component-
The dicarboxylic acid component is not particularly limited and can be appropriately selected depending on the purpose. Examples include dicarboxylic acids such as adipic acid, phthalic acid, isophthalic acid, terephthalic acid, fumaric acid, and maleic acid; Succinic acid substituted with an alkyl group having 1 to 20 carbon atoms or an alkenyl group having 2 to 20 carbon atoms, such as octyl succinic acid. These may be used individually by 1 type, and may use 2 or more types together.

As the isocyanate component, those mentioned for the amorphous polyester resin A can be used.
Preferred are aromatic diisocyanates having 6 to 15 carbon atoms, aliphatic diisocyanates having 4 to 12 carbon atoms, and alicyclic diisocyanates having 4 to 15 carbon atoms, and particularly preferred are TDI, MDI, HDI, hydrogenated MDI, and IPDI.

In the present invention, for the purpose of adjusting the acid value and hydroxyl value, trivalent or higher polycarboxylic acids such as trimellitic acid, pyromellitic acid and their anhydrides, glycerin, pentaerythritol and trimethylolpropane are added to the ends of the resin chain. It may also contain a polyol having a valence of 3 or more.

The acid value of the amorphous polyester resin B is not particularly limited and can be appropriately selected depending on the intended purpose. . When the acid value is 1 mgKOH/g or more, the toner tends to be negatively charged, and when fixing onto paper, the affinity between the toner and paper is improved, and the low-temperature fixability can be improved. . If the acid value exceeds 50 mgKOH/g, the charging stability, particularly the charging stability against environmental fluctuations, may deteriorate.

The hydroxyl value of the amorphous polyester resin B is not particularly limited and can be appropriately selected depending on the intended purpose, but is preferably 5 mgKOH/g or more.

The content of the amorphous polyester resin B is not particularly limited and can be appropriately selected depending on the intended purpose. ~7 parts by mass is more preferred.

The molecular structures of the amorphous polyester resins A and B can be confirmed by X-ray diffraction, GC/MS, LC/MS, IR measurements, etc., in addition to NMR measurements using solutions and solids. A simple method is to detect an amorphous polyester resin that does not have absorption based on δCH (out-of-plane bending vibration) of an olefin at 965±10 cm ⁻¹ and 990±10 cm ⁻¹ in the infrared absorption spectrum. .

<Other polyester resins>
The toner of the present invention may contain polyester resins other than those described above as a binder resin, if necessary.
Other polyester resins have a skeleton derived from an alcohol component and a skeleton derived from a carboxylic acid component.
The alcohol component contains a trihydric or higher aliphatic alcohol.
The other polyester resin satisfies the following formulas (1) to (3).

4,000≦weight average molecular weight (Mw)≦25,000 Formula (2)
0.5 ≤ (amount of trihydric or higher aliphatic alcohol) ≤ 6.5 Formula (3)

However, the amount of the trivalent or higher fatty alcohol in the formulas (1) and (3) (hereinafter sometimes referred to as the "branching component amount") is the trivalent or higher fat with respect to the alcohol component is the mole percent of group alcohols.

Here, when there are two or more types of the trihydric or higher fatty alcohol in the alcohol component, the "valence of the trihydric or higher fatty alcohol" is obtained from the molar fraction of the trihydric or higher fatty alcohol. is the average valence For example, in the trihydric or higher aliphatic alcohol, when the trihydric aliphatic alcohol and the tetrahydric aliphatic alcohol each contain 50 mol%, the "valence of the trihydric or higher aliphatic alcohol" is 3*0.5+4*0.5=3.5. Further, for example, when the trihydric or higher aliphatic alcohol contains 60 mol% of the trihydric aliphatic alcohol and 40 mol% of the hexahydric aliphatic alcohol, the "trihydric or higher aliphatic alcohol valence" is 3×0.6+6×0.4=4.2.

When the other polyester resin satisfies the formulas (1) to (3), the toner can be improved in low-temperature fixability, stress resistance, and blocking resistance of the toner image.

The following part of the formula (1) represents the average distance between branches of the polyester resin (hereinafter sometimes referred to as "distance between branches").

The other polyester resin preferably satisfies the above formula (1) and the following formula (1-1).

However, the amount of the fatty alcohol having a valence of 3 or higher in the formula (1-1) is the mol % of the fatty alcohol having a valence of 3 or higher with respect to the alcohol component.

If the branch-to-branch distance exceeds 4,000, the melt viscosity hardly decreases, which is disadvantageous for low-temperature fixability. When the distance between branches is less than 500, the distance between branches becomes short, and the molecular size becomes small, so that the stress resistance of the toner decreases. In addition, the start of molecular entanglement is delayed when cooled from a high temperature state, and the blocking resistance of the output toner image is lowered.

A polyester resin having a branched structure can lower the melt viscosity in a high temperature range while maintaining the glass transition temperature, and thus can improve low-temperature fixability and heat-resistant storage stability. On the other hand, by increasing the amount of branching components inside, it has a dense three-dimensional structure portion, so that deformation is suppressed even when a large stress is applied.

The weight average molecular weight of the other polyester resin preferably satisfies the above formula (2) and the following (2-1).
8,000 ≤ weight average molecular weight (Mw) ≤ 20,000 Formula (2-1)
When the weight-average molecular weight of the other polyester resin is less than 4,000, the toner has poor high-temperature, high-humidity storage stability and stress resistance. Therefore, the low-temperature fixability of the toner cannot be exhibited.

The other polyester resin preferably satisfies the above formula (3) and the following formula (3-1).
2.0 ≤ (amount of trihydric or higher aliphatic alcohol) ≤ 4.0 Formula (3-1)
However, the amount of the fatty alcohol having a valence of 3 or higher in the formula (3-1) is the mol % of the fatty alcohol having a valence of 3 or higher with respect to the alcohol component.
When the above-mentioned "amount of trihydric or higher aliphatic alcohol" (amount of branching component) is less than 0.5 mol%, high-temperature and high-humidity storage resistance and filming property are poor, and when it exceeds 6.5 mol%, image gloss , and poor low-temperature fixability.

As a method for producing the other polyester resin, a method of reacting an alcohol component containing a trihydric or higher aliphatic alcohol with a carboxylic acid component is preferable. By doing so, a polyester resin having a branched structure can be formed.

The glass transition temperature (Tg) of the other polyester resin is preferably 40° C. or higher and 70° C. or lower, more preferably 50° C. or higher and 60° C. or lower.
If the glass transition temperature is less than 40° C., the toner may have poor heat-resistant storage stability and durability against stress such as agitation in a developing machine, and filming resistance may deteriorate.
If the glass transition temperature exceeds 70° C., deformation due to heat and pressure during fixation of the toner may be insufficient, resulting in insufficient low-temperature fixability.

The other polyester resin is preferably soluble in tetrahydrofuran (THF) from the viewpoint of low-temperature fixability and high gloss of images.

<Alcohol component>
Examples of the alcohol component include dihydric alcohols and trihydric or higher alcohols.
The alcohol component contains a trihydric or higher aliphatic alcohol.

Examples of the dihydric alcohol include aliphatic diols, diols having an oxyalkylene group, alicyclic diols, alicyclic diols to which alkylene oxides (ethylene oxide, propylene oxide, butylene oxide, etc.) are added, and bisphenols. , and alkylene oxide adducts of bisphenols.

Examples of the aliphatic diol include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 3-methyl-1,5-pentanediol, and 1,6-hexanediol. , 1,8-octanediol, 1,10-decanediol, 1,12-dodecanediol, and the like.
Examples of diols having an oxyalkylene group include diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, and polytetramethylene glycol.
Examples of the alicyclic diol include 1,4-cyclohexanedimethanol and hydrogenated bisphenol A.
Examples of the bisphenols include bisphenol A, bisphenol F, bisphenol S and the like.
Examples of the alkylene oxide adducts of bisphenols include those obtained by adding alkylene oxides such as ethylene oxide, propylene oxide and butylene oxide to bisphenols.

Examples of the trihydric or higher alcohol include the trihydric or higher aliphatic alcohol.
Examples of trihydric or higher aliphatic alcohols include glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol, and dipentaerythritol.

As the trihydric or higher aliphatic alcohol, a trihydric to tetrahydric aliphatic alcohol is preferable.

<Carboxylic acid component>
Examples of the carboxylic acid component include divalent carboxylic acids and trivalent or higher carboxylic acids. Anhydrides of these may be used, lower alkyl esters (having 1 to 3 carbon atoms), or halides thereof may be used.

Examples of the divalent carboxylic acid include aliphatic dicarboxylic acids and aromatic dicarboxylic acids.

The aliphatic dicarboxylic acid is not particularly limited and can be appropriately selected depending on the intended purpose. Examples thereof include succinic acid, adipic acid, sebacic acid, dodecanedioic acid, maleic acid and fumaric acid.
The aromatic dicarboxylic acid is not particularly limited and can be appropriately selected depending on the intended purpose. Examples thereof include phthalic acid, isophthalic acid, terephthalic acid and naphthalenedicarboxylic acid.

Examples of the trivalent or higher carboxylic acid include trimellitic acid and pyromellitic acid.

These carboxylic acid components may be used singly or in combination of two or more.

<Crystalline polyester resin>
Since the crystalline polyester resin has high crystallinity, it exhibits a heat melting characteristic that exhibits a rapid viscosity drop near the fixing start temperature. By using the crystalline polyester resin having such properties together with the amorphous polyester resin, the heat resistance storage stability due to the crystallinity is good until just before the melting start temperature, and at the melting start temperature, the crystalline polyester resin melts rapidly. A toner having both good heat-resistant preservability and low-temperature fixability because it causes a sharp viscosity decrease (sharp melt), and is compatible with the amorphous polyester resin along with it, and is fixed by abrupt viscosity decrease. is obtained. Good results are also obtained with respect to the release width (difference between minimum fixing temperature and high-temperature offset generating temperature).

The crystalline polyester resin is obtained by using a polyhydric alcohol, a polycarboxylic acid such as a polycarboxylic acid, a polycarboxylic acid anhydride, a polycarboxylic acid ester, or a derivative thereof.
In the present invention, the crystalline polyester resin is, as described above, a polyhydric alcohol, a polycarboxylic acid such as a polycarboxylic acid, a polycarboxylic anhydride, a polycarboxylic acid ester, or a derivative thereof. Modified polyester resins, such as the prepolymers and resins obtained by cross-linking and/or elongation reactions of the prepolymers, do not belong to the crystalline polyester resins.

The presence or absence of crystallinity of the crystalline polyester resin in the present invention can be confirmed by a crystal analysis X-ray diffraction device (for example, X'Pert Pro MRD, Philips). The measurement method is described below.
First, a target sample is ground in a mortar to prepare a sample powder, and the obtained sample powder is uniformly applied to a sample holder. After that, the sample holder is set in the diffractometer, measurement is performed, and a diffraction spectrum is obtained.
Crystallinity is judged to be present when the half-value width of the peak having the highest peak intensity among the diffraction peaks obtained in the range of 20°<2θ<25° is 2.0 or less.
In the present invention, a polyester resin that does not exhibit the above-described state is referred to as an amorphous polyester resin in contrast to the crystalline polyester resin.
The measurement conditions for X-ray diffraction are described below.
〔Measurement condition〕
Tension kV: 45 kV
Current: 40mA
MPSS
Upper
Gonio
Scan mode: continuous
Start angle: 3°
End angle: 35°
Angle Step: 0.02°
Lucident beam optics
Divergence slit: Div slit 1/2
Difflection beam optics
Anti-scatter slit: As Fixed 1/2
Receiving slit: Prog rec slit

-Polyhydric alcohol-
The polyhydric alcohol is not particularly limited and can be appropriately selected depending on the intended purpose. Examples thereof include diols and trihydric or higher alcohols.

Examples of the diols include saturated aliphatic diols. Examples of the saturated aliphatic diol include linear saturated aliphatic diols and branched saturated aliphatic diols. Group diols are more preferred. If the saturated aliphatic diol is branched, the crystallinity of the crystalline polyester resin may be lowered, and the melting point may be lowered. Moreover, when the number of carbon atoms of the saturated aliphatic diol exceeds 12, it becomes difficult to obtain the material for practical use. It is more preferable that the number of carbon atoms is 12 or less.

Examples of the saturated aliphatic diol include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1, 8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,13-tridecanediol, 1,14-tetradecanediol, 1, 18-octadecanediol, 1,14-eicosanediol and the like. Among these, ethylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, 1,10 -decanediol, 1,12-dodecanediol are preferred.

Examples of the trihydric or higher alcohol include glycerin, trimethylolethane, trimethylolpropane, and pentaerythritol. These may be used individually by 1 type, and may use 2 or more types together.

-Polyvalent carboxylic acid-
The polyvalent carboxylic acid is not particularly limited and can be appropriately selected depending on the intended purpose. Examples thereof include divalent carboxylic acid and trivalent or higher carboxylic acid.

Examples of the divalent carboxylic acid include oxalic acid, succinic acid, glutaric acid, adipic acid, superic acid, azelaic acid, sebacic acid, 1,9-nonanedicarboxylic acid, 1,10-decanedicarboxylic acid, 1, saturated aliphatic dicarboxylic acids such as 12-dodecanedicarboxylic acid, 1,14-tetradecanedicarboxylic acid and 1,18-octadecanedicarboxylic acid; phthalic acid, isophthalic acid, terephthalic acid, naphthalene-2,6-dicarboxylic acid, malonic acid, Aromatic dicarboxylic acids such as dibasic acids such as mesaconic acid; and the like, and also their anhydrides and lower alkyl esters (having 1 to 3 carbon atoms).

Examples of the trivalent or higher carboxylic acid include 1,2,4-benzenetricarboxylic acid,
Examples include 1,2,5-benzenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, anhydrides thereof, and lower alkyl esters (having 1 to 3 carbon atoms) thereof.

In addition to the saturated aliphatic dicarboxylic acid and the aromatic dicarboxylic acid, the polyvalent carboxylic acid may contain a dicarboxylic acid having a sulfonic acid group. Furthermore, in addition to the saturated aliphatic dicarboxylic acid and aromatic dicarboxylic acid, a dicarboxylic acid having a double bond may be contained. These may be used individually by 1 type, and may use 2 or more types together.

The crystalline polyester resin is preferably composed of a linear saturated aliphatic dicarboxylic acid having 4 to 12 carbon atoms and a linear saturated aliphatic diol having 2 to 12 carbon atoms.
That is, the crystalline polyester resin preferably has a structural unit derived from a saturated aliphatic dicarboxylic acid having 4 to 12 carbon atoms and a structural unit derived from a saturated aliphatic diol having 2 to 12 carbon atoms. . By doing so, the crystallinity is high and the sharp melt property is excellent, which is preferable in that excellent low-temperature fixability can be exhibited.

The melting point of the crystalline polyester resin is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 60° C. or higher and 80° C. or lower. When the melting point is less than 60°C, the crystalline polyester resin tends to melt at a low temperature, and the heat-resistant storage stability of the toner may deteriorate. Insufficient melting may result in poor low-temperature fixability.

The molecular weight of the crystalline polyester resin is not particularly limited, and can be appropriately selected according to the purpose. However, those having a sharp molecular weight distribution and low molecular weight are excellent in low-temperature fixability and have many components with low molecular weight. From the viewpoint that the heat-resistant storage stability deteriorates when the heat resistance is reduced, the ortho-dichlorobenzene soluble portion of the crystalline polyester resin has a weight average molecular weight (Mw) of 3,000 to 30,000 and a number average molecular weight (Mn) of 3,000 to 30,000 in GPC measurement. It is preferably 1,000 to 10,000 and Mw/Mn 1.0 to 10. Furthermore, it is preferable that the weight average molecular weight (Mw) is 5,000 to 15,000, the number average molecular weight (Mn) is 2,000 to 10,000, and the Mw/Mn is 1.0 to 5.0.

The acid value of the crystalline polyester resin is not particularly limited and can be appropriately selected depending on the intended purpose. , preferably 5 mgKOH/g or more, more preferably 10 mgKOH/g or more. On the other hand, 45 mgKOH/g or less is preferable in order to improve high temperature offset resistance.

The hydroxyl value of the crystalline polyester resin is not particularly limited and can be appropriately selected depending on the intended purpose. /g to 50 mgKOH/g, more preferably 5 mgKOH/g to 50 mgKOH/g.

The molecular structure of the crystalline polyester resin can be confirmed by X-ray diffraction, GC/MS, LC/MS, IR measurement, etc., in addition to NMR measurement using a solution or solid. A simple method is to detect a crystalline polyester resin having an absorption based on δCH (out-of-plane bending vibration) of an olefin at 965±10 cm ⁻¹ or 990±10 cm ⁻¹ in an infrared absorption spectrum.

The content of the crystalline polyester resin is not particularly limited and can be appropriately selected according to the intended purpose. ~15 parts by mass is more preferred. If the content is less than 3 parts by mass, sharp melting by the crystalline polyester resin may be insufficient, resulting in poor low-temperature fixability. In addition, image fogging may easily occur. When the content is within the range more preferable than the above, it is advantageous in that both high image quality and low-temperature fixability are excellent.

<Other ingredients>
The toner of the present invention contains a release agent and a colorant as essential components, and may contain other components such as a charge control agent, an external additive, a fluidity improver, a cleanability improver, and a magnetic material.

-Release agent-
The release agent is not particularly limited and can be appropriately selected from known ones.
Release agents for waxes and waxes include, for example, plant waxes such as carnauba wax, cotton wax and wood wax rice wax; animal waxes such as beeswax and lanolin; mineral waxes such as ozokerite and cersin; petroleum waxes such as , microcrystalline, petrolatum; and other natural waxes.

In addition to these natural waxes, synthetic hydrocarbon waxes such as Fischer-Tropsch wax, polyethylene and polypropylene; synthetic waxes such as esters, ketones and ethers;

Furthermore, fatty acid amide compounds such as 12-hydroxystearic acid amide, stearic acid amide, phthalic anhydride, and chlorinated hydrocarbons; poly-n-stearyl methacrylate and poly-n, which are low-molecular-weight crystalline polymer resins; -Polyacrylate homopolymers or copolymers such as lauryl methacrylate (e.g., n-stearyl acrylate-ethyl methacrylate copolymers); crystalline polymers having long alkyl groups in side chains; good.

Among these, hydrocarbon waxes such as paraffin wax, microcrystalline wax, Fischer-Tropsch wax, polyethylene wax and polypropylene wax are preferred.

The melting point of the release agent is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 60° C. or higher and 80° C. or lower. When the melting point is lower than 60°C, the releasing agent tends to melt at low temperatures, which may result in poor heat-resistant storage stability. If the melting point exceeds 80° C., even if the resin melts and is within the fixing temperature range, the releasing agent may not melt sufficiently, causing fixation offset and image defects.

The content of the release agent is not particularly limited and can be appropriately selected according to the purpose. 8 parts by mass is more preferred. When the content is less than 2 parts by mass, high-temperature offset resistance and low-temperature fixability during fixing may be deteriorated. etc. may occur more easily. When the content is within the range more preferable than the above, it is advantageous in terms of improving image quality and fixing stability.

-coloring agent-
The coloring agent is not particularly limited and can be appropriately selected depending on the intended purpose. Yellow iron oxide, ocher, yellow lead, titanium yellow, polyazo yellow, oil yellow, Hansa yellow (GR, A, RN, R), pigment yellow L, benzidine yellow (G, GR), permanent yellow (NCG), Vulcan Fast yellow (5G, R), tartrazine lake, quinoline yellow lake, anthrazane yellow BGL, isoindolinone yellow, red iron oxide, red lead, red lead, cadmium red, cadmium mercury red, antimony vermillion, permanent red 4R, para red, Phise Red, Parachlororthonitroaniline Red, Lithol Fast Scarlet G, Brilliant Fast Scarlet, Brilliant Carnmine BS, Permanent Red (F2R, F4R, FRL, FRLL, F4RH), Fast Scarlet VD, Belkan Fastlubin B, Brilliant Scarlet G, Risol Rubin GX, Permanent Red F5R, Brilliant Carmine 6B, Pigment Scarlet 3B, Bordeaux 5B, Toluidine Maroon, Permanent Bordeaux F2K, Helio Bordeaux BL, Bordeaux 10B, Bon Maroon Light, Bon Maroon Medium, Eosin Lake, Rhodamine Lake B, Rhodamine lake Y, alizarin lake, thioindigo red B, thioindigo maroon, oil red, quinacridone red, pyrazolone red, polyazo red, chrome vermillion, benzidine orange, perinone orange, oil orange, cobalt blue, cerulean blue, alkali blue lake , Peacock Blue Lake, Victoria Blue Lake, Metal-Free Phthalocyanine Blue, Phthalocyanine Blue, Fast Sky Blue, Indanthrene Blue (RS, BC), Indigo, Ultramarine Blue, Prussian Blue, Anthraquinone Blue, Fast Violet B, Methyl Violet Lake, Cobalt Purple , manganese purple, dioxane violet, anthraquinone violet, chromium green, zinc green, chromium oxide, pyridian, emerald green, pigment green B, naphthol green B, green gold, acid green lake, malachite glyc green lakes, phthalocyanine greens, anthraquinone greens, titanium oxide, zinc white, litbon and the like.

The content of the coloring agent is not particularly limited and can be appropriately selected according to the intended purpose. Parts by mass are more preferred.

The colorant can also be used as a masterbatch combined with a resin. Examples of the resins to be used in the production of the masterbatch or kneaded together with the masterbatch include, in addition to the other polyester resins described above, styrene such as polystyrene, poly-p-chlorostyrene, and polyvinyltoluene, or polymers of substituted styrenes thereof; styrene-p- Chlorostyrene copolymer, styrene-propylene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene-methyl acrylate copolymer, styrene-ethyl acrylate copolymer, styrene-acrylic Butyl acid copolymer, styrene-octyl acrylate copolymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer, styrene-α-methyl chloromethacrylate Copolymers, styrene-acrylonitrile copolymers, styrene-vinyl methyl ketone copolymers, styrene-butadiene copolymers, styrene-isoprene copolymers, styrene-acrylonitrile-indene copolymers, styrene-maleic acid copolymers , Styrene-based copolymers such as styrene-maleic acid ester copolymer; polymethyl methacrylate, polybutyl methacrylate, polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, polyester, epoxy resin, epoxy polyol resin, polyurethane, polyamide, Polyvinyl butyral, polyacrylic resin, rosin, modified rosin, terpene resin, aliphatic or alicyclic hydrocarbon resin, aromatic petroleum resin, chlorinated paraffin, paraffin wax and the like. These may be used individually by 1 type, and may use 2 or more types together.

The masterbatch can be obtained by mixing and kneading a masterbatch resin and a colorant by applying a high shearing force. At this time, an organic solvent can be used in order to enhance the interaction between the colorant and the resin. In addition, a so-called flushing method, in which an aqueous paste containing colorant water is mixed and kneaded with a resin and an organic solvent, the colorant is transferred to the resin side, and the water and organic solvent components are removed. Since the cake can be used as it is, there is no need to dry it, and it is preferably used. For mixing and kneading, a high-shear dispersing device such as a three-roll mill is preferably used.

- Charge control agent -
The charge control agent is not particularly limited and can be appropriately selected depending on the intended purpose. Alkoxy-based amines, quaternary ammonium salts (including fluorine-modified quaternary ammonium salts), alkylamides, phosphorus elements or compounds, tungsten elements or compounds, fluorine-based activators, salicylic acid metal salts, metal salts of salicylic acid derivatives, etc. are mentioned.

Specifically, nigrosine-based dye Bontron 03, quaternary ammonium salt Bontron P-51, metal-containing azo dye Bontron S-34, oxynaphthoic acid-based metal complex E-82, salicylic acid-based metal complex E- 84, E-89 of phenolic condensate (manufactured by Orient Chemical Industry Co., Ltd.), TP-302, TP-415 of quaternary ammonium salt molybdenum complex (manufactured by Hodogaya Chemical Industry Co., Ltd.), LRA- 901, LR-147 (manufactured by Nihon Carlit Co., Ltd.), which is a boron complex, copper phthalocyanine, perylene, quinacridone, azo pigments, and other polymeric compounds having functional groups such as sulfonic acid groups, carboxyl groups, and quaternary ammonium salts. is mentioned.

The content of the charge control agent is not particularly limited and can be appropriately selected according to the intended purpose. 2 parts by mass to 5 parts by mass is more preferable. If the content exceeds 10 parts by mass, the chargeability of the toner is too high, the effect of the main charge control agent is reduced, the electrostatic attraction force with the developing roller is increased, and the fluidity of the developer is reduced. , the image density may be lowered. These charge control agents can be dissolved and dispersed after being melted and kneaded together with the masterbatch and resin. Alternatively, they can be directly added to an organic solvent during dissolution and dispersion, or they can be fixed on the toner surface after the toner particles are produced. may

-External Additives-
As the external additive, oxide microparticles, inorganic microparticles, and hydrophobized inorganic microparticles can be used in combination. The average particle size of the hydrophobized primary particles is preferably 1 nm to 100 nm, and the inorganic microparticles of 5 nm to 70 nm. is more preferred.

In addition, it is preferable that at least one type of inorganic fine particles having an average particle size of 20 nm or less and at least one type of inorganic fine particles having an average particle size of 30 nm or more are included. Moreover, the specific surface area by the BET method is preferably 20 m ² /g to 500 m ² /g.

The external additive is not particularly limited and can be appropriately selected depending on the intended purpose. (eg, titania, alumina, tin oxide, antimony oxide, etc.), fluoropolymers, and the like.

Suitable additives include hydrophobized silica, titania, titanium oxide, alumina particulates. Examples of silica fine particles include R972, R974, RX200, RY200, R202, R805, and R812 (all manufactured by Nippon Aerosil Co., Ltd.). Examples of titania fine particles include P-25 (manufactured by Nippon Aerosil Co., Ltd.), STT-30, STT-65C-S (all manufactured by Titan Kogyo Co., Ltd.), TAF-140 (manufactured by Fuji Titanium Kogyo Co., Ltd.), Examples include MT-150W, MT-500B, MT-600B, and MT-150A (all manufactured by Tayca Corporation).

Hydrophobized titanium oxide fine particles include, for example, T-805 (manufactured by Nippon Aerosil Co., Ltd.), STT-30A, STT-65S-S (all manufactured by Titan Kogyo Co., Ltd.), TAF-500T, TAF- 1500T (both manufactured by Fuji Titanium Industry Co., Ltd.), MT-100S, MT-100T (both manufactured by Tayca Corporation), IT-S (manufactured by Ishihara Sangyo Co., Ltd.), and the like.

Hydrophobic oxide microparticles, hydrophobilizing silica microparticles, hydrophobilizing titania microparticles, and hydrophobilizing alumina microparticles include hydrophilic microparticles such as methyltrimethoxysilane and methyltriethoxysilane. , octyltrimethoxysilane, or other silane coupling agent. Also suitable are silicon oil-treated oxide fine particles and inorganic fine particles, which are obtained by heating silicone oil if necessary to form inorganic fine particles.

Examples of the silicone oil include dimethyl silicone oil, methylphenyl silicone oil, chlorophenyl silicone oil, methyl hydrogen silicone oil, alkyl-modified silicone oil, fluorine-modified silicone oil, polyether-modified silicone oil, alcohol-modified silicone oil, amino Modified silicone oil, epoxy-modified silicone oil, epoxy/polyether-modified silicone oil, phenol-modified silicone oil, carboxyl-modified silicone oil, mercapto-modified silicone oil, methacryl-modified silicone oil, α-methylstyrene-modified silicone oil and the like.

Examples of the inorganic fine particles include silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, iron oxide, copper oxide, zinc oxide, tin oxide, silica sand, clay, mica, Wollastonite, diatomaceous earth, chromium oxide, cerium oxide, red iron oxide, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, silicon carbide, silicon nitride, and the like. Among these, silica and titanium dioxide are particularly preferred.

The content of the external additive is not particularly limited and can be appropriately selected according to the purpose. 3 parts by mass to 3 parts by mass is more preferable.

The average particle diameter of the primary particles of the inorganic fine particles is not particularly limited and can be appropriately selected depending on the intended purpose. If it is smaller than this range, the inorganic fine particles are buried in the toner, making it difficult to effectively exhibit their functions. On the other hand, if it exceeds this range, the surface of the photoreceptor is unevenly damaged, which is not preferable.

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

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

－Magnetic materials－
The magnetic material is not particularly limited and can be appropriately selected depending on the intended purpose. Examples thereof include iron powder, magnetite, and ferrite. Among these, white ones are preferable in terms of color tone.

<T1/2>
The toner of the present invention preferably has a T1/2 of 105° C. or higher and 125° C. or lower as determined by a flow tester heating method. By satisfying this T1/2, it is possible to achieve both the separation stability of the toner and high glossiness.
T1/2 of the toner is more preferably 110° C. or higher and 120° C. or lower.
Further, the T1/2 of the toner can be determined from a flow curve measured using, for example, an elevated flow tester CFT500 (manufactured by Shimadzu Corporation). An example of measurement conditions is shown below.
[Measurement condition]
Load: 30kg/ ^cm2
Heating rate: 3.0°C/min
Die diameter: 0.50mm
Die length: 1.0mm
Measurement temperature: 40°C to 200°C

<Glass transition temperature [Tg1st (toner)]>
The toner preferably has a glass transition temperature [Tg1st (toner)] of 20° C. or more and 65° C. or less, more preferably 50° C. or more and 65° C., in the endothermic curve measured using a differential scanning calorimeter. More preferably:

In conventional toners, if the Tg is about 50° C. or less, aggregation of the toner tends to occur due to temperature changes during transportation of the toner, assuming summertime or tropical regions, and in the storage environment. As a result, solidification in the toner bottle and toner sticking in the developing machine occur. In addition, insufficient replenishment due to toner clogging in the toner bottle and image abnormality due to toner sticking in the developing machine tend to occur.

The toners of the present invention have a lower Tg than conventional toners. However, since the polyester resin having the structure represented by any one of the above structural formulas 1) to 3), which is the low Tg component in the toner, is non-linear, the toner of the present invention does not have heat resistant storage stability. can hold. In particular, when the polyester resin having a structure represented by any one of the above structural formulas 1) to 3) has a urethane bond or a urea bond with high cohesion, the effect of maintaining heat-resistant storage stability becomes more pronounced. .
When the Tg1st (toner) is 20° C. or higher, preferably 50° C. or higher, the heat-resistant storage stability is improved, blocking in the developing machine and filming on the photoreceptor can be prevented, and when the Tg1st is 65° C. or lower, , the low-temperature fixability of the toner is further improved.

In a preferred embodiment of the present invention, the polyester resin contains a polyester resin having a structure represented by any one of the above 1) to 3) and the other polyester resin, and the [Tg1st (toner)] is 20. C. or more and 65.degree. C. or less.

Further, the difference (Tg1st−Tg2nd) between the glass transition temperature [Tg1st (toner)] at the first temperature increase and the glass transition temperature [Tg2nd (toner)] at the second temperature increase in differential scanning calorimetry (DSC) of the toner. is not particularly limited and can be appropriately selected depending on the purpose, but it is more preferably 10°C or higher. The upper limit of the difference is not particularly limited and can be appropriately selected according to the purpose, but the difference (Tg1st−Tg2nd) is preferably 50° C. or less.

When the difference is 10° C. or more, it is advantageous in terms of excellent low-temperature fixability. The fact that the difference is 10 ° C. or more means that the crystalline polyester resin that was present in an incompatible state before heating (before the first temperature increase) and the amorphous polyester resin are (After the first temperature rise) means a compatible state.
In addition, the compatible state after heating does not need to be a complete compatible state.

<Volume average particle size>
The volume average particle diameter of the toner is not particularly limited and can be appropriately selected according to the purpose, but is preferably 3 μm or more and 7 μm or less. Also, the ratio of the volume average particle diameter to the number average particle diameter is preferably 1.2 or less. Moreover, it is preferable to contain 1% by number or more and 10% by number or less of a component having a volume-based particle size of 2 μm or less.

<<Calculation method and analysis method for various characteristics of toner and toner constituents>>
The SP value, Tg, acid value, hydroxyl value, molecular weight, and melting point of the amorphous polyester resin, the crystalline polyester resin, and the release agent may be measured on their own, but may be measured on the actual toner. The SP value, Tg, molecular weight, melting point, and mass ratio of the constituent components may be calculated by separating the separated components by gel permeation chromatography (GPC) or the like and adopting the analysis method described later.

Separation of each component by GPC can be performed, for example, by the following method.
In the GPC measurement using THF (tetrahydrofuran) as a mobile phase, the eluate is fractionated with a fraction collector or the like, and the fractions corresponding to the desired molecular weight portion from the total integration of the elution curve are collected.

After concentrating and drying the combined eluate with an evaporator or the like, the solid content is dissolved in a heavy solvent such as heavy chloroform or heavy THF, 1H-NMR measurement is performed, and from the integral ratio of each element, the resin in the eluted component Calculate the constituent monomer ratio.

As another method, after concentrating the eluate, it is hydrolyzed with sodium hydroxide or the like, and the decomposition products are qualitatively and quantitatively analyzed by high performance liquid chromatography (HPLC) or the like to calculate the constituent monomer ratio.

In the case where the toner manufacturing method forms toner base particles while generating a polyester resin through an elongation reaction and/or a cross-linking reaction between the non-linear reactive precursor and the curing agent, in practice, The toner may be separated from the toner by GPC or the like to determine the Tg of the polyester resin, or the polyester resin may be separately subjected to an elongation reaction and/or a cross-linking reaction between the non-linear reactive precursor and the curing agent. may be synthesized and Tg and the like may be measured from the synthesized polyester resin.

<<Means for Separating Toner Components>>
An example of means for separating each component when analyzing the toner will be described in detail.
First, 1 g of toner is put into 100 mL of THF and stirred for 30 minutes at 25° C. to obtain a solution in which soluble components are dissolved.
This is filtered through a membrane filter with an opening of 0.2 μm to obtain a THF-soluble component in the toner.
Next, this is dissolved in THF to prepare a sample for GPC measurement, and the sample is injected into the GPC used for molecular weight measurement of each resin described above.
On the other hand, a fraction collector is placed at the eluate outlet of GPC, and the eluate is collected at predetermined counts, and the eluate is collected every 5% in terms of area ratio from the elution start of the elution curve (curve rise). get
For each elution, 30 mg of sample is then dissolved in 1 mL of deuterated chloroform and 0.05% by volume of tetramethylsilane (TMS) is added as a reference substance.
The solution is filled in a glass tube for NMR measurement with a diameter of 5 mm, and a nuclear magnetic resonance apparatus (JNM-AL400 manufactured by JEOL Ltd.) is used to perform integration 128 times at a temperature of 23 ° C. to 25 ° C. to obtain a spectrum. .
The composition and composition ratio of monomers such as the polyester resin and the crystalline polyester resin contained in the toner can be obtained from the peak integral ratio of the obtained spectrum.

For example, the peaks are assigned as follows, and the component ratio of the constituent monomers is obtained from the respective integral ratios.
Peak assignments are, for example,
Around 8.25 ppm: Derived from the benzene ring of trimellitic acid (for one hydrogen)
Around 8.07 ppm to 8.10 ppm: Derived from the benzene ring of terephthalic acid (for 4 hydrogen atoms)
Around 7.1 ppm to 7.25 ppm: Derived from the benzene ring of bisphenol A (4 hydrogen atoms)
Around 6.8 ppm: Derived from the benzene ring of bisphenol A (4 hydrogens) and from the double bond of fumaric acid (2 hydrogens)
Around 5.2 ppm to 5.4 ppm: derived from methine of bisphenol A propylene oxide adduct (for one hydrogen)
Around 3.7 ppm to 4.7 ppm: derived from methylene of bisphenol A propylene oxide adduct (2 hydrogens) and methylene derived from bisphenol A ethylene oxide adduct (4 hydrogens)
Around 1.6 ppm: Derived from the methyl group of bisphenol A (for 6 hydrogens)
can be

From these results, for example, the extract collected in the fraction containing 90% or more of the amorphous polyester resin having the structure represented by any one of the structural formulas 1) to 3) is 3) can be treated as a polyester resin having a structure represented by any one of the above.
Similarly, the extract collected in the fraction containing 90% or more of the other polyester resin can be treated as the other polyester resin.
In addition, the extract collected in the fraction containing 90% or more of the crystalline polyester resin can be treated as the crystalline polyester resin.

<<Analysis of THF Insoluble Content of Toner>>
The THF-insoluble matter of the toner can be extracted, for example, as follows.
After adding 1 part of toner to 40 parts of THF and refluxing for 6 hours, the insoluble components are sedimented by a centrifugal separator to separate the insoluble components from the supernatant. The insoluble matter is dried at 40° C. for 20 hours to obtain a THF insoluble matter. The THF-insoluble matter corresponds to a non-linear polyester resin. Therefore, the THF-insoluble matter contains a plurality of structural moieties derived from trivalent isocyanate.
The composition of the THF-insoluble matter can be analyzed by NMR measurement by solution or solid, X-ray diffraction, GC/MS, LC/MS, IR measurement, and the like.
Conveniently, analysis can be performed by the following method, for example, by thermal decomposition simultaneous methylation GC-MS method using a methylation reaction reagent.
Device name: Shimadzu Corporation QP2010 Frontier Lab Py2020D
Data analysis software: GCMSsolution manufactured by Shimadzu Corporation
Heating temperature: 280°C
Reaction pyrolysis temperature: 300°C
Column name: Ultra ALLOY-5 L = 30 m ID = 0.25 mm Film = 0.25 μm
Constant temperature bath temperature: 50°C (holding 1 minute) - 10°C/min - 330°C (holding 11 minutes)
Carrier gas: 53.6 kPa constant, He 1.0 mL/min
Injection mode: Split (1:100)
Ionization method: EI method (70 eV)
Measurement mode: Scan mode Library: NIST 20 MASS SPECTRAL

<<Method for measuring hydroxyl value and acid value>>
A hydroxyl value can be measured using a method based on JIS K0070-1966.
Specifically, first, 0.5 g of a sample is accurately weighed into a 100 mL volumetric flask, and 5 mL of an acetylation reagent is added thereto. After heating in a hot bath at 100±5° C. for 1 to 2 hours, the flask is removed from the hot bath and allowed to cool. Further, water is added and shaken to decompose acetic anhydride.
Next, in order to completely decompose the acetic anhydride, the flask is again heated in the hot bath for 10 minutes or more and allowed to cool, and then the walls of the flask are thoroughly washed with an organic solvent. Furthermore, using a potentiometric automatic titrator DL-53 Titrator (manufactured by Mettler Toledo) and an electrode DG113-SC (manufactured by Mettler Toledo), the hydroxyl value was measured at 23 ° C., and analysis software LabX Light Version 1.00 Analyze using .000. A mixed solvent of 120 mL of toluene and 30 mL of ethanol is used for calibrating the apparatus.
At this time, the measurement conditions are as follows.

〔Measurement condition〕
Stir
Speed [%] 25
Time[s] 15
EQP titration
Titan/Sensor
Titrant CH3ONa
Concentration [mol/L] 0.1
Sensor DG115
Unit of measurement mV
Predispensing to volume
Volume [mL] 1.0
Wait time [s] 0
Titrant addition Dynamic
dE(set) [mV] 8.0
dV (min) [mL] 0.03
dV(max) [mL] 0.5
Measure mode Equilibrium controlled
dE [mV] 0.5
dt[s] 1.0
t (min) [s] 2.0
t(max) [s] 20.0
Recognition
Threshold 100.0
Steepest jump only No
Range No.
Tendency None
Termination
at maximum volume [mL] 10.0
at potential no
at slope no
After number EQPs Yes
n=1
comb. Termination conditions No
Evaluation
Procedure Standard
Potential 1 No
Potential 2 No
Stop for revaluation No

The acid value can be measured using a method based on JIS K0070-1992.
Specifically, first, 0.5 g of a sample (0.3 g of ethyl acetate solubles) is added to 120 mL of toluene and dissolved by stirring at 23° C. for about 10 hours. Next, 30 mL of ethanol is added to obtain a sample solution. If the sample does not dissolve, use a solvent such as dioxane or tetrahydrofuran.
Furthermore, using a potentiometric automatic titrator DL-53 Titrator (manufactured by Mettler Toledo) and an electrode DG113-SC (manufactured by Mettler Toledo), the acid value was measured at 23 ° C., and analysis software LabX Light Version 1.00 Analyze using .000. A mixed solvent of 120 mL of toluene and 30 mL of ethanol is used for calibrating the apparatus.
At this time, the measurement conditions are the same as those for the hydroxyl value described above.

The acid value can be measured as described above. Specifically, it is titrated with a pre-standardized 0.1N potassium hydroxide/alcohol solution, and from the titration amount, the acid value [mgKOH/g] = The acid value is calculated by titration amount [mL]×N×56.1 [mg/mL]/sample [g] (where N is the factor of 0.1N potassium hydroxide/alcohol solution).

<<Method for measuring melting point and glass transition temperature (Tg)>>
The melting point and glass transition temperature (Tg) in the present invention can be measured using, for example, a DSC system (differential scanning calorimeter) (“Q-200”, manufactured by TA Instruments).
Specifically, the melting point and glass transition temperature of the target sample can be measured by the following procedure.
First, about 5.0 mg of a target sample is placed in an aluminum sample container, the sample container is placed on a holder unit, and set in an electric furnace. Next, in a nitrogen atmosphere, it is heated from −80° C. to 150° C. at a rate of temperature increase of 10° C./min (first temperature increase). After that, it is cooled from 150° C. to −80° C. at a temperature decrease rate of 10° C./min, and further heated to 150° C. at a temperature increase rate of 10° C./min (second temperature increase). In each of the first temperature rise and the second temperature rise, a DSC curve is measured using a differential scanning calorimeter (“Q-200”, manufactured by TA Instruments).

From the obtained DSC curve, the analysis program in the Q-200 system can be used to select the DSC curve at the time of the first heating, and the glass transition temperature of the target sample at the first heating can be obtained. Similarly, by selecting the DSC curve at the time of the second temperature rise, the glass transition temperature of the target sample at the second time of temperature rise can be obtained.

Also, from the obtained DSC curve, using the analysis program in the Q-200 system, select the DSC curve at the time of the first heating, and obtain the endothermic peak top temperature at the first heating of the target sample as the melting point. can be done. Similarly, by selecting the DSC curve at the time of the second temperature rise, the endothermic peak top temperature of the target sample at the second time of temperature rise can be determined as the melting point.

In this specification, when toner is used as the target sample, the glass transition temperature at the first heating is Tg1st (toner), and the glass transition temperature at the second heating is Tg2nd (toner).

Further, in this specification, unless otherwise specified, the glass transition temperature and melting point of the polyester resin, the crystalline polyester resin, and other components such as the release agent are endothermic at the time of the second temperature rise. Let the peak top temperature, Tg, be the melting point, Tg, of each target sample.

<<Method for measuring particle size distribution>>
The volume-average particle diameter (D4) and number-average particle diameter (Dn) of the toner and their ratio (D4/Dn) are determined using, for example, Coulter Counter TA-II and Coulter Multisizer II (both manufactured by Coulter). can be measured by
Coulter Multisizer II was used in the present invention.
The measurement method is described below.
First, 0.1 mL to 5 mL of a surfactant (preferably polyoxyethylene alkyl ether (nonionic surfactant)) is added as a dispersing agent to 100 mL to 150 mL of the electrolytic aqueous solution. Here, the electrolytic aqueous solution is a 1 mass % NaCl aqueous solution prepared using primary sodium chloride, and for example, ISOTON-II (manufactured by Coulter) can be used. Here, 2 mg to 20 mg of the measurement sample is added.
The electrolytic aqueous solution in which the sample is suspended is subjected to dispersion treatment for about 1 to 3 minutes in an ultrasonic disperser, and the volume and number of toner particles or toner are measured by the measuring device using a 100 μm aperture as an aperture. , to calculate the volume distribution and the number distribution.
From the obtained distribution, the volume average particle diameter (D4) and number average particle diameter (Dn) of the toner can be obtained.
2.00 to less than 2.52 μm; 2.52 to less than 3.17 μm; 3.17 to less than 4.00 μm; 8.00 μm or more and less than 10.08 μm; 10.08 μm or more and less than 12.70 μm; 12.70 μm or more and less than 16.00 μm; 25.40 μm to less than 32.00 μm; 32.00 μm to less than 40.30 μm using 13 channels, targeting particles with a particle size of 2.00 μm to less than 40.30 μm.

<<Measurement of molecular weight>>
The molecular weight of each component of the toner can be measured, for example, by the following method.
Gel permeation chromatography (GPC) measurement device: GPC-8220GPC (manufactured by Tosoh Corporation)
Column: TSKgel SuperHZM-H 15 cm triple (manufactured by Tosoh Corporation)
Temperature: 40°C
Solvent: Tetrahydrofuran (THF)
Flow rate: 0.35mL/min
Sample: 0.4 mL of 0.15% by mass sample was injected. The filtrate is used as sample.
100 μL of the THF sample solution is injected and measured.
In measuring the molecular weight of a sample, the molecular weight distribution of the sample is calculated from the relationship between the logarithmic value of a calibration curve prepared from several types of monodisperse polystyrene standard samples and the number of counts.
As a standard polystyrene sample for preparing a calibration curve, Showdex STANDARD Std. No. S-7300, S-210, S-390, S-875, S-1980, S-10.9, S-629, S-3.0, S-0.580 are used.
An RI (refractive index) detector is used as the detector.

<Toner manufacturing method>
The method for producing the toner is not particularly limited and can be appropriately selected according to the intended purpose. It is preferable to granulate by dispersing an oil phase containing the releasing agent, the coloring agent, etc. in an aqueous medium.

An example of such a method for producing the toner includes a known dissolution suspension method. As an example of the method for producing the toner, a polyester resin having a structure represented by any one of the above structural formulas 1) to 3) is produced by an elongation reaction and/or a cross-linking reaction between the polyester prepolymer and the curing agent. However, a method for forming the toner base particles is shown below. In such a method, an aqueous medium is prepared, an oil phase containing a toner material is prepared, the toner material is emulsified or dispersed, and an organic solvent is removed.

-Preparation of aqueous medium (aqueous phase)-
The aqueous medium can be prepared, for example, by dispersing the resin particles in the aqueous medium. The amount of the resin particles to be added to the aqueous medium is not particularly limited and can be appropriately selected according to the purpose. .

The aqueous medium is not particularly limited and can be appropriately selected depending on the intended purpose. Examples thereof include water, water-miscible solvents, and mixtures thereof. These may be used individually by 1 type, and may use 2 or more types together. Among these, water is preferred.

The water-miscible solvent is not particularly limited and can be appropriately selected depending on the intended purpose. Examples thereof include alcohols, dimethylformamide, tetrahydrofuran, cellosolves, lower ketones and the like. The alcohol is not particularly limited and can be appropriately selected depending on the intended purpose. Examples thereof include methanol, isopropanol, ethylene glycol and the like. The lower ketones are not particularly limited and can be appropriately selected depending on the intended purpose. Examples thereof include acetone and methyl ethyl ketone.

-Preparation of oil phase-
Preparation of the oil phase containing the toner material includes at least the precursor of the amorphous polyester and the crystalline polyester resin, and if necessary, the curing agent, the releasing agent, the coloring agent, and the like. can be carried out by dissolving or dispersing the toner material containing in an organic solvent.

The organic solvent is not particularly limited and can be appropriately selected depending on the intended purpose, but an organic solvent having a boiling point of less than 150° C. is preferable because it is easy to remove.

The organic solvent having a boiling point of less than 150° C. is not particularly limited and can be appropriately selected depending on the intended purpose. , 1,2-trichloroethane, trichloroethylene, chloroform, monochlorobenzene, dichloroethylidene, methyl acetate, ethyl acetate, methyl ethyl ketone, methyl isobutyl ketone and the like. These may be used individually by 1 type, and may use 2 or more types together.

Among these, ethyl acetate, toluene, xylene, benzene, methylene chloride, 1,2-dichloroethane, chloroform, carbon tetrachloride and the like are preferred, and ethyl acetate is more preferred.

- Emulsification or dispersion -
The emulsification or dispersion of the toner material can be performed by dispersing the oil phase containing the toner material in the aqueous medium. Then, when emulsifying or dispersing the toner material, the amorphous polyester resin is produced by subjecting the curing agent and the polyester prepolymer to elongation reaction and/or cross-linking reaction.

The amorphous polyester resin can be produced, for example, by the following methods (1) to (3).
(1) A method of emulsifying or dispersing an oil phase containing the polyester prepolymer and the curing agent in an aqueous medium, and subjecting the curing agent and the polyester prepolymer to elongation reaction and/or crosslinking reaction in the aqueous medium. .
(2) The oil phase containing the polyester prepolymer is emulsified or dispersed in an aqueous medium to which the curing agent is added in advance, and the curing agent and the polyester prepolymer are subjected to elongation reaction and/or cross-linking reaction in the aqueous medium. how to let
(3) After emulsifying or dispersing the oil phase containing the polyester prepolymer in an aqueous medium, the curing agent is added to the aqueous medium, and the curing agent and the polyester prepolymer are mixed from the particle interface in the aqueous medium. A method of elongation reaction and / or cross-linking reaction.

The reaction conditions (reaction time, reaction temperature) for producing the amorphous polyester resin are not particularly limited, and can be appropriately selected according to the combination of the curing agent and the polyester prepolymer. .

The reaction time is not particularly limited and can be appropriately selected depending on the intended purpose, preferably 10 minutes to 40 hours, more preferably 2 hours to 24 hours.

The reaction temperature is not particularly limited and can be appropriately selected depending on the intended purpose.

The method for stably forming the dispersion containing the polyester prepolymer in the aqueous medium is not particularly limited and can be appropriately selected according to the purpose. is added to the oil phase prepared by dissolving or dispersing in a solvent, and dispersing by shearing force.

The disperser for the dispersion is not particularly limited and can be appropriately selected according to the purpose. , an ultrasonic disperser, and the like.

Among these, a high-speed shear type disperser is preferable because the particle size of the dispersion (oil droplets) can be controlled to 2 μm to 20 μm.

When the high-speed shear type disperser is used, the conditions such as rotation speed, dispersion time, and dispersion temperature can be appropriately selected according to the purpose.

The number of revolutions is not particularly limited and can be appropriately selected according to the purpose.

The dispersion time is not particularly limited and can be appropriately selected according to the purpose.
In the case of a batch system, 0.1 to 5 minutes is preferred.

The amount of the aqueous medium used in emulsifying or dispersing the toner material is not particularly limited and can be appropriately selected according to the intended purpose. ,000 parts by mass, and more preferably 100 to 1,000 parts by mass.

When the amount of the aqueous medium used is less than 50 parts by mass, the dispersion state of the toner material deteriorates, and toner base particles having a predetermined particle size may not be obtained. and production costs can be high.

When emulsifying or dispersing the oil phase containing the toner material, it is preferable to use a dispersant from the viewpoint of stabilizing the dispersion such as oil droplets, forming a desired shape, and sharpening the particle size distribution. .

The dispersant is not particularly limited and can be appropriately selected depending on the intended purpose. Examples thereof include surfactants, poorly water-soluble inorganic compound dispersants, polymeric protective colloids, and the like.
These may be used individually by 1 type, and may use 2 or more types together. Among these, surfactants are preferred.

The surfactant is not particularly limited and can be appropriately selected depending on the purpose. For example, anionic surfactants, cationic surfactants, nonionic surfactants, amphoteric surfactants, etc. be able to.

The anionic surfactant is not particularly limited and can be appropriately selected depending on the intended purpose. Examples thereof include alkylbenzene sulfonates, α-olefin sulfonates and phosphate esters. Among these, those having a fluoroalkyl group are preferred.

-Removal of organic solvent-
The method for removing the organic solvent from the dispersion such as the emulsified slurry is not particularly limited and can be appropriately selected according to the purpose. A method of evaporating the organic solvent, a method of spraying the dispersion into a dry atmosphere to remove the organic solvent in the oil droplets, and the like can be mentioned.

When the organic solvent is removed, toner base particles are formed. The toner base particles can be washed, dried, etc., and further classified. The classification may be carried out by removing fine particles in a liquid using a cyclone, decanter, centrifugation, or the like, or may be carried out after drying.

The obtained toner base particles may be mixed with particles such as the external additive and the charge control agent. At this time, by applying a mechanical impact force, it is possible to suppress detachment of the particles such as the external additive from the surface of the toner base particles.

The method for applying the mechanical impact force is not particularly limited and can be appropriately selected according to the purpose. The mixture is put into the chamber and accelerated to collide the particles with each other or against a suitable collision plate.

The apparatus used in the above method is not particularly limited and can be appropriately selected according to the purpose. apparatus with lowered pressure, hybridization system (manufactured by Nara Machinery Co., Ltd.), kryptron system (manufactured by Kawasaki Heavy Industries, Ltd.), automatic mortar, and the like.

(developer)
The developer of the present invention contains at least the toner described above, and optionally other components such as a carrier that are appropriately selected.
Therefore, it is possible to stably form a high-quality image with excellent transferability, chargeability, and the like. The developer may be a one-component developer or a two-component developer. Two-component developers are preferred because of their improved performance.

When the developer is used as a one-component developer, even if the toner balance is performed, the variation in the particle size of the toner is small, and the filming of the toner on the developing roller and members such as blades that thin the toner layer. The toner is less fused to the toner, and good and stable developability and images can be obtained even during long-term agitation in the developing device.

When the developer is used as a two-component developer, even if the toner balance is maintained over a long period of time, the toner particle size fluctuates little, and good and stable developability and images can be obtained even during long-term agitation in the developing device. can get.

<Carrier>
The carrier is not particularly limited and can be appropriately selected according to the purpose.
Those having a core material and a resin layer covering the core material are preferable.

-core material-
The material of the core material is not particularly limited and can be appropriately selected according to the purpose. Examples include magnesium-based materials. Further, in order to ensure image density, it is preferable to use a highly magnetized material such as iron powder of 100 emu/g or more and magnetite of 75 emu/g to 120 emu/g. In addition, a low magnetization material such as a copper-zinc system with a concentration of 30 emu/g to 80 emu/g can be used because it is possible to reduce the impact of the standing developer on the photoreceptor, which is advantageous for achieving high image quality. is preferred.

These may be used individually by 1 type, and may use 2 or more types together.

The volume-average particle size of the core material is not particularly limited and can be appropriately selected depending on the intended purpose. If the volume average particle size is less than 10 μm, the carrier contains a large amount of fine powder, and the magnetization per particle may decrease, resulting in scattering of the carrier. In full-color printing, which has many solid areas, the reproduction of solid areas is particularly poor.

When the toner is used in a two-component developer, it may be used by being mixed with the carrier. The content of the carrier in the two-component developer is not particularly limited and can be appropriately selected according to the purpose. parts are preferred, and 93 to 97 parts by mass are more preferred.
The developer of the present invention can be suitably used for image formation by various known electrophotographic methods such as a magnetic one-component development method, a non-magnetic one-component development method, and a two-component development method.

The toner containing unit in the present invention means a unit having a function of containing toner and containing toner. Here, examples of the toner storage unit include a toner storage container, a developing device, a process cartridge, and the like.
A toner container is a container containing toner.
A developing device means a device having a means for storing and developing toner.
A process cartridge is a cartridge that integrates at least an image carrier and developing means, stores toner, and is detachable from an image forming apparatus. The process cartridge may further comprise at least one selected from charging means, exposure means and cleaning means.
By mounting the toner containing unit of the present invention on an image forming apparatus to form an image, excellent low-temperature fixability, high-temperature offset resistance, high glossiness, high color reproducibility, and heat-resistant storage stability can be achieved without filming. It is possible to perform image formation by making the most of the characteristics of the toner that it has.
In the following, a developer storage container that stores a developer containing toner in particular will be described.

(Developer storage container)
The developer storage container related to the present invention stores the developer of the present invention, but the container is not particularly limited and can be appropriately selected from known ones, but the container has a container body and a cap. etc.

In addition, the size, shape, structure, material, etc. of the container body are not particularly limited, but the shape is preferably cylindrical, etc. Spiral irregularities are formed on the inner peripheral surface, and by rotating, It is particularly preferable that the developer, which is the content, can move to the discharge port side, and that part or all of the spiral unevenness has a bellows function. Further, the material is not particularly limited, but preferably has good dimensional accuracy. Examples include polyester resin, polyethylene resin, polypropylene resin, polystyrene resin, polyvinyl chloride resin, polyacrylic acid, polycarbonate resin, ABS resin, Resin materials such as polyacetal resin can be used.

Since the developer storage container is easy to store, transport, etc., and is excellent in handleability, it can be detachably attached to a process cartridge, an image forming apparatus, etc., which will be described later, and used to replenish the developer.

(Image forming apparatus and image forming method)
The image forming apparatus of the present invention has at least an electrostatic latent image carrier, an electrostatic latent image forming means, and a developing means, and further has other means as necessary.
The image forming method of the present invention includes a charging process, an exposure process, a developing process, a primary transfer process, a secondary transfer process, a fixing process, a cleaning process, and, if necessary, other processes.
The image forming method can be preferably performed by the image forming apparatus, the charging step and the exposure step can be preferably performed by the electrostatic latent image forming means, and the developing step can be performed by the developing means. It can be suitably performed, and the above-mentioned other steps can be suitably performed by the above-mentioned other means.

<Electrostatic latent image carrier>
The material, structure, and size of the electrostatic latent image carrier are not particularly limited, and can be appropriately selected from known ones. , polysilane, and phthalopolymethine. Among these, amorphous silicon is preferable in terms of long life.

For the amorphous silicon photoreceptor, for example, a support is heated to 50° C. to 400° C., and vacuum deposition, sputtering, ion plating, thermal CVD (Chemical Vapor Deposition) is performed on the support. ) method, optical CVD method, plasma CVD method, and the like, a photosensitive member having a photoconductive layer made of a-Si can be used. Among these, the plasma CVD method, that is, the method of decomposing a raw material gas by direct current, high frequency or microwave glow discharge to form an a-Si deposition film on a support is preferable.

The shape of the electrostatic latent image carrier is not particularly limited and can be appropriately selected depending on the intended purpose, but a cylindrical shape is preferred. The outer diameter of the cylindrical electrostatic latent image bearing member is not particularly limited and can be appropriately selected according to the purpose. Especially preferred.

<Electrostatic latent image forming means and electrostatic latent image forming step>
The electrostatic latent image forming means is not particularly limited as long as it is means for forming an electrostatic latent image on the electrostatic latent image carrier, and can be appropriately selected according to the purpose. Examples include means having at least a charging member for charging the surface of the electrostatic latent image carrier and an exposure member for imagewise exposing the surface of the electrostatic latent image carrier.
The electrostatic latent image forming step is not particularly limited as long as it is a step of forming an electrostatic latent image on the electrostatic latent image carrier, and can be appropriately selected according to the purpose. After the surface of the electrostatic latent image carrier is charged, it can be exposed imagewise, and can be carried out using the electrostatic latent image forming means.

- Charging member and charging -
The charging member is not particularly limited and can be appropriately selected according to the intended purpose. , corotron, scorotron, and other non-contact chargers using corona discharge.
The charging can be performed, for example, by applying a voltage to the surface of the electrostatic latent image carrier using the charging member.

The shape of the charging member may be a roller, a magnetic brush, a fur brush, or any other shape, and can be selected according to the specifications and shape of the image forming apparatus.
The charging member is not limited to the contact-type charging member, but it is preferable to use the contact-type charging member because an image forming apparatus in which ozone generated from the charging member is reduced can be obtained.

- Exposure member and exposure -
As the exposure member, on the surface of the electrostatic latent image carrier charged by the charging member,
There is no particular limitation as long as the image-wise exposure to be formed can be performed, and it can be appropriately selected according to the purpose. Examples include copying optical systems, rod lens array systems, laser optical systems, liquid crystal shutter optical systems, and the like. and various exposure members.
The light source used for the exposure member is not particularly limited and can be appropriately selected depending on the intended purpose. (LD) and electroluminescence (EL).
Moreover, various filters such as a sharp cut filter, a bandpass filter, a near-infrared cut filter, a dichroic filter, an interference filter, and a color temperature conversion filter can be used in order to irradiate only light in a desired wavelength range.
The exposure can be performed, for example, by imagewise exposing the surface of the electrostatic latent image carrier using the exposure member.
In addition, in the present invention, a light rear surface method in which imagewise exposure is performed from the rear surface side of the electrostatic latent image carrier may be employed.

<Developing means and developing process>
The developing means is not particularly limited as long as it is a developing means equipped with toner that develops the electrostatic latent image formed on the electrostatic latent image bearing member to form a visible image. can be selected as appropriate.
The developing step is not particularly limited as long as it is a step of developing the electrostatic latent image formed on the electrostatic latent image carrier with toner to form a visible image, depending on the purpose. For example, it can be carried out by the developing means.

The developing means may be of a dry developing system or may be of a wet developing system. Further, it may be a single-color developing means or a multi-color developing means.
The developing means includes a stirrer for frictionally stirring and charging the toner, and a magnetic field generating means fixed inside, and a rotatable developer carrying developer containing the toner on its surface. A developing device having a body is preferred.
In the developing means, for example, the toner and the carrier are mixed and agitated, and the toner is charged by friction at that time and held in a bristling state on the surface of a rotating magnet roller to form a magnetic brush. . The magnet roller is arranged near the electrostatic latent image carrier. Therefore, part of the toner forming the magnetic brush formed on the surface of the magnet roller moves to the surface of the electrostatic latent image carrier due to the electric attractive force. As a result, the electrostatic latent image is developed with the toner to form a visible image with the toner on the surface of the electrostatic latent image carrier.

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

-Transfer Means and Transfer Process-
The transfer means is not particularly limited as long as it is a means for transferring a visible image to a recording medium, and can be appropriately selected according to the purpose. An embodiment having primary transfer means for forming a transfer image and secondary transfer means for transferring the composite transfer image onto a recording medium is preferred.
The transfer step is not particularly limited as long as it is a step of transferring a visible image to a recording medium, and can be appropriately selected according to the purpose. It is preferable that the visual image is primarily transferred and then the visible image is secondarily transferred onto the recording medium.
The transfer step can be performed, for example, by charging the visible image to the photoreceptor using a transfer charger, and can be performed by the transfer means.
Here, when the image to be secondarily transferred onto the recording medium is a color image made of toner of a plurality of colors, the transfer means sequentially superimposes the toners of each color on the intermediate transfer body to perform the intermediate transfer. An image may be formed on the medium, and the intermediate transfer means may secondary transfer the image on the intermediate transfer medium onto the recording medium all at once.
The intermediate transfer member is not particularly limited, and can be appropriately selected from known transfer members depending on the intended purpose. For example, a transfer belt is suitable.
The linear velocity for transferring the toner image onto the recording medium (recording material) is preferably 100 to 1000 mm/sec, and the transfer time at the nip portion of the secondary transfer means is preferably 0.5 to 60 msec. By satisfying these requirements, both productivity (printing efficiency) and transferability can be achieved.

Preferably, the transfer means (the primary transfer means, the secondary transfer means) has at least a transfer device that separates and charges the visible image formed on the photoreceptor to the recording medium side. Examples of the transfer device include a corona transfer device using corona discharge, a transfer belt, a transfer roller, a pressure transfer roller, an adhesive transfer device, and the like.
The recording medium is typically plain paper, but is not particularly limited as long as it can transfer an unfixed image after development, and can be appropriately selected according to the purpose. A PET base or the like can also be used.

- Fixing means and fixing process -
If the fixing means is means for fixing the transferred image transferred to the recording medium,
There is no particular limitation, and it can be appropriately selected depending on the purpose, but a known heating and pressurizing member is preferable. Examples of the heating and pressing member include a combination of a heating roller and a pressure roller, and a combination of a heating roller, a pressure roller and an endless belt.
As the fixing step, if it is a step of fixing the visible image transferred to the recording medium,
There is no particular limitation, and it can be appropriately selected according to the purpose. For example, it may be performed each time the toner of each color is transferred to the recording medium, or it may be performed at once in a state in which the toner of each color is laminated. You can go at the same time.
The fixing step can be performed by the fixing means.
Heating in the heating and pressurizing member is usually preferably from 80°C to 200°C.
In addition, in the present invention, depending on the purpose, for example, a known optical fixing device may be used together with or in place of the fixing means.

The surface pressure in the fixing step is not particularly limited and can be appropriately selected according to the purpose, but is preferably 10 N/cm ² to 80 N/cm ² .

-Cleaning means and cleaning process-
The cleaning means is not particularly limited as long as it can remove the toner remaining on the photoreceptor, and can be appropriately selected according to the purpose. Magnetic roller cleaners, blade cleaners, brush cleaners, web cleaners, and the like.
The cleaning step is not particularly limited as long as it can remove the toner remaining on the photoreceptor, and can be appropriately selected according to the purpose. For example, the cleaning means can be used.

- Static Eliminating Means and Static Eliminating Step -
The charge removing means is not particularly limited as long as it removes charges by applying a charge removing bias to the photoreceptor, and can be appropriately selected according to the purpose. Examples thereof include a charge removing lamp.
The static elimination process is not particularly limited as long as it is a process of applying a static elimination bias to the photosensitive member to eliminate static electricity, and can be appropriately selected according to the purpose. .

- Recycling means and recycling process -
The recycling means is not particularly limited as long as it is a means for recycling the toner removed in the cleaning step to the developing device, and can be appropriately selected according to the purpose. mentioned.
The recycling step is not particularly limited as long as it is a step of recycling the toner removed in the cleaning step to the developing device, and can be appropriately selected according to the purpose. can be done.

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

Next, one aspect of implementing a method of forming an image by the image forming apparatus of the present invention will be described with reference to FIG. A color image forming apparatus 100A shown in FIG. It comprises an exposure device 30 as exposure means, a developing device 40 as the development means, an intermediate transfer body 50, a cleaning device 60 as the cleaning means having a cleaning blade, and a static elimination lamp 70 as the static elimination means. .

The intermediate transfer member 50 is an endless belt, and is designed to be movable in the direction of the arrow by means of three rollers 51 arranged inside and stretched thereon. Some of the three rollers 51 also function as transfer bias rollers capable of applying a predetermined transfer bias (primary transfer bias) to the intermediate transfer member 50 . A cleaning device 90 having a cleaning blade is arranged near the intermediate transfer member 50 . Further, in the vicinity of the intermediate transfer member 50, there is a transfer roller 80 as the transfer means capable of applying a transfer bias for transferring (secondary transfer) the developed image (toner image) onto the transfer paper 95 as the recording medium. , are arranged to face the intermediate transfer member 50 . Around the intermediate transfer body 50 , a corona charger 58 for imparting electric charge to the toner image on the intermediate transfer body 50 is arranged so that the photoreceptor 10 and the intermediate transfer body 50 are in contact with each other in the rotation direction of the intermediate transfer body 50 . It is arranged between the contact portion and the contact portion between the intermediate transfer member 50 and the transfer paper 95 .

The developing device 40 is composed of a developing belt 41 as the developer carrying member, and a black developing unit 45K, a yellow developing unit 45Y, a magenta developing unit 45M and a cyan developing unit 45C which are provided side by side around the developing belt 41. . The black developing unit 45K includes a developer container 42K, a developer supply roller 43K, and a developing roller 44K. The yellow developing unit 45Y includes a developer container 42Y, a developer supply roller 43Y, and a developing roller 44Y. The magenta developing unit 45M includes a developer container 42M, a developer supply roller 43M, and a developing roller 44M. The cyan developing unit 45C includes a developer container 42C, a developer supply roller 43C, and a developing roller 44C. The developing belt 41 is an endless belt and is rotatably stretched around a plurality of belt rollers, and a part of the developing belt 41 is in contact with the electrostatic latent image carrier 10 .

In the color image forming apparatus 100A shown in FIG. 1, for example, the charging roller 20 uniformly charges the photosensitive drum 10. As shown in FIG. The exposure device 30 imagewise exposes the photosensitive drum 10 to form an electrostatic latent image. The electrostatic latent image formed on the photosensitive drum 10 is developed by supplying toner from the developing device 40 to form a toner image. The toner image is transferred (primary transfer) onto the intermediate transfer member 50 by the voltage applied from the roller 51 and further transferred onto the transfer paper 95 (secondary transfer). As a result, a transfer image is formed on the transfer paper 95 . Toner remaining on the photoreceptor 10 is removed by the cleaning device 60 , and the charge on the photoreceptor 10 is temporarily removed by the charge removal lamp 70 .

FIG. 2 shows another example of the image forming apparatus of the present invention. The image forming apparatus 100B does not have a developing belt 41, and has a black developing unit 45K, a yellow developing unit 45Y, a magenta developing unit 45M, and a cyan developing unit 45C arranged around the photosensitive drum 10 so as to directly face each other. Other than that, it has the same configuration as the image forming apparatus 100A shown in FIG.

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

Next, formation of a full-color image (color copy) using the tandem developing device 120 will be described. That is, first, a document is set on the document platen 130 of the automatic document feeder (ADF) 400, or the document is set on the contact glass 40 of the scanner 300 by opening the automatic document feeder 400, and then the automatic document feeder is operated. Close 400.

When a start switch (not shown) is pressed, when a document is set on the automatic document feeder 400, the document is conveyed and moved onto the contact glass 32, and then set on the contact glass 32. Immediately after this, the scanner 300 is driven. Then, the first running body 33 and the second running body 34 run. At this time, the light from the light source is irradiated by the first traveling member 33, and the reflected light from the surface of the document is reflected by the mirror of the second traveling member 34, and is received by the reading sensor 36 through the imaging lens 35, resulting in a color image. A document (color image) is read to obtain black, yellow, magenta, and cyan image information.

Then, each image information of black, yellow, magenta, and cyan is processed by each image forming means 18 (black image forming means, yellow image forming means, magenta image forming means, and cyan image forming means) in the tandem type developing device 120 . forming means). Then, each image forming means forms black, yellow, magenta, and cyan toner images. That is, each of the image forming units 18 (black image forming unit, yellow image forming unit, magenta image forming unit, and cyan image forming unit) in the tandem type developing device 120 is static as shown in FIG. an electrostatic latent image carrier 10 (a black electrostatic latent image carrier 10K, a yellow electrostatic latent image carrier 10Y, a magenta electrostatic latent image carrier 10M, and a cyan electrostatic latent image carrier 10C); A charging device 160 which is the charging means for uniformly charging the electrostatic latent image carrier 10, and an imagewise exposure of the electrostatic latent image carrier 10 corresponding to each color image based on each color image information (FIG. 4). medium, L), an exposure device for forming an electrostatic latent image corresponding to each color image on the electrostatic latent image carrier, and an exposure device for forming the electrostatic latent image on each color toner (black toner, yellow toner, magenta toner); , and cyan toner) to form a toner image of each color toner, a transfer charger 62 for transferring the toner image onto the intermediate transfer member 50, A cleaning device 63 and a static eliminator 64 are provided. Each image forming unit 18 can form each monochromatic image (a black image, a yellow image, a magenta image, and a cyan image) based on the respective color image information. The black image, the yellow image, the magenta image and the cyan image thus formed are transferred onto an intermediate transfer member 50 which is rotationally moved by support rollers 14, 15 and 16, respectively. A black image formed on the top, a yellow image formed on the electrostatic latent image carrier 10Y for yellow, a magenta image formed on the electrostatic latent image carrier 10M for magenta, and an electrostatic latent image carrier for cyan. The cyan image formed on 10C is sequentially transferred (primary transfer). Then, the black image, the yellow image, the magenta image, and the cyan image are superimposed on the intermediate transfer member 50 to form a composite color image (color transfer image).

On the other hand, in the paper feed table 200 , one of the paper feed rollers 142 is selectively rotated to feed a sheet (recording paper) from one of the paper feed cassettes 144 provided in multiple stages in the paper bank 143 . The sheet is separated one by one by a separation roller 145 and sent to a paper feed path 146, conveyed by a conveying roller 147, guided to a paper feed path 148 in the main body 150 of the copying machine, and stopped by being abutted against a registration roller 49. be done. Alternatively, the sheet (recording paper) on the manual feed tray 54 is fed out by rotating the paper feed roller 142 , separated one by one by the separation roller 52 , put into the manual feed path 53 , and stopped by hitting the registration roller 49 . . Although the registration roller 49 is generally grounded and used, it may be used with a bias applied to remove paper dust from the sheet. Then, the registration rollers 49 are rotated in synchronization with the synthesized color image (color transfer image) synthesized on the intermediate transfer member 50 , and a sheet (recording paper) is placed between the intermediate transfer member 50 and the secondary transfer device 22 . , and the secondary transfer device 22 transfers (secondary transfer) the composite color image (color transfer image) onto the sheet (recording paper). By doing so, a color image is transferred and formed on the sheet (recording paper). The intermediate transfer member cleaning device 17 cleans residual toner on the intermediate transfer member 50 after image transfer.

The sheet (recording paper) on which the color image is transferred is conveyed by the secondary transfer device 22 and sent to the fixing device 25. In the fixing device 25, the composite color image (color image) is applied by heat and pressure. A transferred image) is fixed on the sheet (recording paper). After that, the sheet (recording paper) is switched by a switching claw 55 and discharged by a discharge roller 56 to be stacked on a paper discharge tray 57 . Alternatively, the sheet is switched by the switching claw 55, reversed by the sheet reversing device 28, and led to the transfer position again. be done.

(process cartridge)
A process cartridge according to the present invention is molded so as to be detachable from various image forming apparatuses. with the toner of the present invention to form a toner image. Incidentally, the process cartridge of the present invention may further have other means as required.

The developing means includes at least a developer storage container that stores the developer of the present invention and a developer carrier that carries and conveys the developer stored in the developer storage container. The developing means may further have a regulating member or the like for regulating the thickness of the developer to be carried.

FIG. 5 shows an example of a process cartridge relating to the present invention. The process cartridge 110 has a photosensitive drum 10 , a corona charger 58 , a developer 40 , a transfer roller 80 and a cleaning device 90 . Reference numeral 95 denotes transfer paper, and L denotes exposure light.

Examples of the present invention will be described below, but the present invention is not limited to the following examples. "Parts" means "mass parts" unless otherwise specified. "%" represents "% by mass" unless otherwise specified.
Each measured value in the following examples was measured by the method described in this specification. The Tg and molecular weight of the amorphous polyester resin, the crystalline polyester resin, etc. were measured from each resin obtained in the production examples.

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

(Production example A)
<Synthesis of Amorphous Polyester Resin A>
-Synthesis of Prepolymer A-
3-Methyl-1,5-pentanediol, terephthalic acid, and adipic acid were added to a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen tube, and the molar ratio of hydroxyl groups to carboxyl groups, OH/COOH, was 1. .2, the composition of the diol component is 100 mol % of 3-methyl-1,5-pentanediol, and the composition of the dicarboxylic acid component is 50 mol % of terephthalic acid and 50 mol % of adipic acid. (1,000 ppm relative to the resin component).
After that, the temperature was raised to 200° C. over about 4 hours, then to 230° C. over 2 hours, and the reaction was carried out until no water flowed out.
After that, the mixture was further reacted under reduced pressure of 10 mmHg to 15 mmHg for 5 hours to obtain an intermediate polyester A'.
The resulting intermediate polyester A' had a Tg of -40°C, an Mw of 15,000, and an Mw/Mn of 2.0.
Next, in a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen inlet tube, the molar ratio of intermediate polyester A' and hexamethylene diisocyanate (HDI) trimer (isocyanate group of HDI / hydroxyl group of intermediate polyester ) 0.2, diluted with ethyl acetate to give a 50% ethyl acetate solution, and reacted at 100° C. for 5 hours to obtain an intermediate polyester A solution.
The obtained intermediate polyester A had a Tg of −35° C., an Mw of 20,000, and an Mw/Mn of 2.2.
Next, the intermediate polyester A solution and isophorone diisocyanate (IPDI) were mixed in a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen inlet tube at a molar ratio (isocyanate group of IPDI/hydroxyl group of intermediate polyester) of 1.5. and diluted with ethyl acetate to give a 50% ethyl acetate solution, followed by reaction at 100° C. for 5 hours to obtain a prepolymer A solution.

-Synthesis of Amorphous Polyester Resin A-
The obtained prepolymer A is stirred in a reaction vessel equipped with a heating device, a stirrer and a nitrogen inlet tube, and the amount of amine in [ketimine compound 1] becomes equimolar to the amount of isocyanate in prepolymer A. An amount of [ketimine compound 1] was dropped into the reaction vessel, and after stirring at 45°C for 10 hours, the prepolymer elongation product was taken out.
The resulting prepolymer stretched product was dried under reduced pressure at 50° C. until the residual ethyl acetate content was 100 ppm or less, and an amorphous polyester resin A was obtained.
The Tg of the amorphous polyester resin A was -25°C.

(Manufacturing Example B-1 )
<Synthesis of Amorphous Polyester Resin B-1 >
-Synthesis of Prepolymer B-
A four-necked flask equipped with a nitrogen inlet tube, a dehydration tube, a stirrer and a thermocouple was charged with a bisphenol A ethylene oxide side 2 mol adduct/bisphenol A propylene oxide 3 mol adduct in a molar ratio of 85/15 and isophthalic acid. and adipic acid at a molar ratio of 80/20, charged with an OH/COOH molar ratio of hydroxyl groups and carboxyl groups of 1.4, reacted with 500 ppm of titanium tetraisopropoxide at 230 ° C. under normal pressure for 8 hours, and further The mixture was reacted under a reduced pressure of 10 mmHg to 15 mmHg for 4 hours , trimellitic anhydride was added to the reaction vessel so as to be 1 mol % of the total resin components, and reacted at 180° C. under normal pressure for 3 hours to obtain an intermediate polyester B. .
Next, intermediate polyester B and isophorone diisocyanate (IPDI) were mixed in a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen inlet tube at a molar ratio (isocyanate group of IPDI/hydroxyl group of intermediate polyester) of 1.5. After diluting with ethyl acetate to give a 50% ethyl acetate solution, reaction was carried out at 100° C. for 5 hours to obtain a prepolymer B solution.
-Synthesis of Amorphous Polyester Resin B-1-
The obtained prepolymer B is stirred in a reaction vessel equipped with a heating device, a stirrer and a nitrogen inlet tube, and the amount of amine in [ketimine compound 1] becomes equimolar to the amount of isocyanate in prepolymer B. An amount of [ketimine compound 1] was dropped into the reaction vessel, and after stirring at 45°C for 10 hours, the prepolymer elongation product was taken out.
The resulting prepolymer stretched product was dried under reduced pressure at 50° C. until the residual ethyl acetate amount was 100 ppm or less, to obtain amorphous polyester resin B-1 .
The Tg of the amorphous polyester resin B-1 was 45°C.

(Manufacturing example C)
<Synthesis of crystalline polyester resin C>
Dodecanedioic acid and 1,6-hexanediol were added to a 5 L four-necked flask equipped with a nitrogen inlet tube, a dehydration tube, a stirrer and a thermocouple, and OH/COOH, which is the molar ratio of hydroxyl groups to carboxyl groups. is 0.9, reacted with titanium tetraisopropoxide (500 ppm relative to the resin component) at 180° C. for 10 hours, then heated to 200° C. and reacted for 3 hours. A crystalline polyester resin C was obtained by reacting for 2 hours at a pressure of 3 kPa.

(Manufacturing example D)
<Synthesis of polyester resin D-1>
A bisphenol A ethylene oxide 2 mol adduct (BisA-EO), a bisphenol A propylene oxide 3 mol adduct (BisA-PO), Trimethylolpropane (TMP), terephthalic acid, and adipic acid, bisphenol A ethylene oxide 2 mol adduct, bisphenol A propylene oxide 3 mol adduct, trimethylolpropane, molar ratio (bisphenol A ethylene oxide 2 mol The adduct/3 mol of bisphenol A propylene oxide adduct/trimethylolpropane) is 38.6/57.9/3.5, and the molar ratio (terephthalic acid/adipic acid) of terephthalic acid and adipic acid is 85. /15, and charged so that the molar ratio of hydroxyl groups to carboxyl groups, OH/COOH, is 1.12. Then, after reacting for 4 hours at a reduced pressure of 10 mmHg to 15 mmHg, trimellitic anhydride was added to the reaction vessel so as to be 1 mol% of the total resin components, and reacted at 180 ° C. and normal pressure for 3 hours to obtain a polyester resin D-. got 1.

<Synthesis of polyester resins D-2 to D-3>
[Polyester Resin D-2] to [Polyester Resin D-3] were obtained in the same manner as the synthesis of [Polyester Resin D-1], except that the acid component and the alcohol component were changed as shown in Table 1. .

<Preparation of masterbatch (MB)>
1,200 parts of water, 500 parts of carbon black (manufactured by Printex 35 Dexa) [DBP oil absorption = 42 mL/100 mg, pH = 9.5], and 500 parts of the polyester resin D-1 were added, and a Henschel mixer (manufactured by Mitsui Mining Co., Ltd.) was added. ), the mixture was kneaded at 150° C. for 30 minutes using two rolls, rolled, cooled, and pulverized with a pulperizer to obtain [Masterbatch 1].

<Preparation of WAX dispersion>
50 parts of paraffin wax (manufactured by Nippon Seiro Co., Ltd., HNP-9, hydrocarbon wax, melting point 75 ° C., SP value 8.8) as release agent 1 in a container set with a stirring rod and a thermometer, and acetic acid After 450 parts of ethyl was charged, the temperature was raised to 80°C while stirring, and the temperature was maintained at 80°C for 5 hours. [WAX Dispersion 1] was obtained by dispersing under the conditions of a liquid velocity of 1 kg/hr, a disk peripheral velocity of 6 m/sec, a filling of 80% by volume of zirconia beads with a diameter of 0.5 mm, and three passes.

<Preparation of crystalline polyester resin dispersion>
50 parts of the crystalline polyester resin C and 450 parts of ethyl acetate were charged into a vessel equipped with a stirring rod and a thermometer, heated to 80° C. while stirring, maintained at 80° C. for 5 hours, and then cooled for 1 hour. Cooled to 30° C., using a bead mill (Ultravisco Mill, manufactured by Aimex Co., Ltd.), a liquid feed rate of 1 kg/hr, a disk peripheral speed of 6 m/sec, 80% by volume of zirconia beads with a diameter of 0.5 mm, and 3 passes. to obtain [Crystalline Polyester Resin Dispersion 1].

(Example 1)
<Preparation of oil phase>
[WAX dispersion 1] 500 parts, [prepolymer A] 300 parts, [prepolymer B] 900 parts, [crystalline polyester resin dispersion 1] 350 parts, [polyester resin D-1] 7500 parts, [masterbatch 1] 100 parts and [ketimine compound 1] 2 parts as a curing agent were placed in a container and mixed at 5,000 rpm for 60 minutes with a TK homomixer (manufactured by Tokushu Kika) to obtain [oil phase 1].

<Synthesis of organic fine particle emulsion (fine particle dispersion)>
In a reaction vessel equipped with a stirring rod and a thermometer, 683 parts of water, sodium salt of methacrylic acid ethylene oxide adduct sulfate ester (eleminol RS-30: manufactured by Sanyo Chemical Industries, Ltd.) 11 parts, styrene 138 parts, methacrylic acid 138 parts and 1 part of ammonium persulfate were added and stirred at 400 rpm for 15 minutes to give a white emulsion. The system temperature was raised to 75° C. by heating, and the reaction was carried out for 5 hours. Further, 30 parts of a 1% aqueous ammonium persulfate solution is added, and the mixture is aged at 75° C. for 5 hours to give an aqueous dispersion of vinyl resin (copolymer of sodium salt of styrene-methacrylic acid-ethylene oxide methacrylic acid ethylene oxide adduct sulfate ester) [fine particles]. Dispersion 1] was obtained.
The volume average particle diameter of [fine particle dispersion 1] measured by LA-920 (manufactured by HORIBA) was 0.14 μm. A portion of [fine particle dispersion liquid 1] was dried to isolate the resin component.

<Preparation of aqueous phase>
990 parts of water, 83 parts of [fine particle dispersion 1], 37 parts of a 48.5% aqueous solution of sodium dodecyl diphenyl ether disulfonate (eleminol MON-7: manufactured by Sanyo Chemical Industries, Ltd.), and 90 parts of ethyl acetate are mixed and stirred, A milky liquid was obtained. This was designated as [aqueous phase 1].

<Emulsification/Solvent removal>
1,200 parts of [aqueous phase 1] was added to the vessel containing [oil phase 1], and mixed with a TK homomixer at a rotation speed of 13,000 rpm for 20 minutes to obtain [emulsified slurry 1].
[Emulsified slurry 1] was put into a container equipped with a stirrer and a thermometer, and the solvent was removed at 30° C. for 8 hours, followed by aging at 45° C. for 4 hours to obtain [dispersed slurry 1].

<Washing/Drying>
After filtering 100 parts of [dispersion slurry 1] under reduced pressure,
(1): 100 parts of ion-exchanged water was added to the filter cake, mixed with a TK homomixer (12,000 rpm for 10 minutes) and then filtered.
(2): 100 parts of a 10% sodium hydroxide aqueous solution was added to the filter cake of (1), mixed with a TK homomixer (at 12,000 rpm for 30 minutes), and filtered under reduced pressure.
(3): 100 parts of 10% hydrochloric acid was added to the filter cake of (2), mixed with a TK homomixer (12,000 rpm for 10 minutes) and then filtered.
(4): Add 300 parts of ion-exchanged water to the filter cake of (3), mix with a TK homomixer (12,000 rpm for 10 minutes), and then filter. was performed twice to obtain a [filter cake].
[Filtration cake] was dried at 45° C. for 48 hours in a circulating air dryer and sieved with a mesh having an opening of 75 μm to obtain [Toner base particles 1].

<External addition processing>
Based on 100 parts by mass of toner base particles 1, 0.6 parts by mass of hydrophobic silica with an average particle size of 100 nm, 1.0 parts by mass of titanium oxide with an average particle size of 20 nm, and hydrophobic silica fine powder with an average particle size of 15 nm. Toner 1 was obtained by mixing 0.8 part of the toner with a Henschel mixer.

<Production of carrier>
To 100 parts by mass of toluene, 100 parts by mass of a silicone resin (organo straight silicone), 5 parts by mass of γ-(2-aminoethyl)aminopropyltrimethoxysilane, and 10 parts by mass of carbon black are added and dispersed for 20 minutes with a homomixer. Then, a resin layer coating liquid was prepared. Using a fluidized bed coating apparatus, the surface of 1,000 parts by mass of spherical magnetite having an average particle diameter of 50 μm was coated with the resin layer coating liquid to prepare a carrier.

<Production of developer>
Using a ball mill, 5 parts by mass of the toner 1 and 95 parts by mass of the carrier were mixed to prepare a developer. Next, using each developed developer, various characteristics were evaluated as follows. Table 1 shows the evaluation results.

<Low temperature fixability>
A copy test was performed on type 6200 paper (manufactured by Ricoh Co., Ltd.) using an imageo MP C5002 (manufactured by Ricoh Co., Ltd.) with a modified fixing unit.
Specifically, the cold offset temperature (minimum fixing temperature) and the high temperature offset temperature (maximum fixing temperature) were obtained by changing the fixing temperature.
The evaluation conditions for the lowest fixing temperature were a paper feed linear velocity of 200 mm/sec, a surface pressure of 1.0 kgf/cm ² , and a nip width of 7 mm.
The upper limit fixing temperature was evaluated under the following conditions: a paper feed linear velocity of 100 mm/sec, a surface pressure of 1.0 kgf/cm ² , and a nip width of 7 mm.
If the minimum fixing temperature is less than 140° C., the effect of the low-temperature fixability obtained by the present invention is sufficient.
〔Evaluation criteria〕
○: less than 130 ° C. △: 130 ° C. or higher and less than 140 ° C. ×: 140 ° C. or higher

<Heat-resistant storage stability>
10 g of toner was filled in a 50 ml glass container, left in a constant temperature bath at 50° C. for 24 hours, cooled to 24° C., and the penetration was measured by a penetration test (JIS K2235-1991). The heat-resistant storage stability was evaluated by It should be noted that the higher the penetration, the better the heat-resistant storage stability.
〔Evaluation criteria〕
○: Penetration of 30 mm or more △: Penetration of 15 mm or more and less than 30 mm ×: Penetration of less than 15 mm

<Image gloss>
A copying test was performed on POD gloss coat 128 g/m ² (manufactured by Oji Paper Co., Ltd.) using an apparatus obtained by modifying the fixing unit of imagioMP C5002 (manufactured by Ricoh Co., Ltd.).
Specifically, the glossiness of the image was obtained by passing the paper at a fixing temperature of 140°C. The 60 degree gloss of the image after the copying test was measured with a gloss meter VG-7000 (manufactured by Nippon Denshoku Co., Ltd.).
Fixing evaluation conditions were a paper feed linear velocity of 100 mm/sec, a surface pressure of 1.0 kgf/cm ² , and a nip width of 7 mm.
An image gloss of 20% or more is sufficient for the high gloss and high image quality obtained by the present invention.
〔Evaluation criteria〕
○: 25% or more and less than 50%
△: 20% or more and less than 25% and 50% or more and less than 60% ×: less than 20% and 60% or more

The [Tg1st (toner)] and T1/2 of the toner were also measured, and the results are shown in Table 1.

(Example 2)
In Example 1, [Toner base particles 2] were obtained in the same manner as in Example 1, except that [Prepolymer B] was changed from 900 parts to 300 parts. Toner 2] was evaluated in the same manner as in Example 1. Table 1 shows the results.

(Example 3)
In Example 1, [Toner base particles 3] were obtained in the same manner as in Example 1, except that [Prepolymer B] was changed from 900 parts to 1500 parts. Toner 3] was evaluated in the same manner as in Example 1. Table 1 shows the results.

(Example 4)
[Toner base particles 4] were obtained in the same manner as in Example 1, except that [polyester resin D-1] was replaced with [polyester resin D-2]. was evaluated in the same manner as in Example 1 for [Toner 4] using Table 1 shows the results.

(Example 5)
[Toner base particles 5] were obtained in the same manner as in Example 1, except that [polyester resin D-1] was replaced with [polyester resin D-3]. was evaluated in the same manner as in Example 1 for [Toner 5] using Table 1 shows the results.

(Comparative example 1)
In Example 1, [Toner base particles 6] were obtained in the same manner as in Example 1, except that [Prepolymer B] was changed to 0 parts. On the other hand, evaluation was performed in the same manner as in Example 1. Table 1 shows the results.

(Comparative example 2)
[Toner Base Particles 7] were obtained in the same manner as in Example 1, except that [Prepolymer A] was changed to 1500 parts and [Prepolymer B] was changed to 0 parts. was evaluated in the same manner as in Example 1 for [Toner 7] using Table 1 shows the results.

(Comparative Example 3)
In Example 1, [Toner base particles 8] were obtained in the same manner as in Example 1, except that [Prepolymer A] was changed to 0 parts. On the other hand, evaluation was performed in the same manner as in Example 1. Table 1 shows the results.

(Comparative Example 4)
(Production Example A-2)
<Synthesis of polyester resin A-2>
-Synthesis of prepolymer A-2-
3-Methyl-1,5-pentanediol, terephthalic acid, adipic acid, and trimethylolpropane were added in a reaction vessel equipped with a condenser, stirrer, and nitrogen inlet tube at a hydroxyl to carboxyl molar ratio. OH/COOH is 1.5, the composition of the diol component is 100 mol% of 3-methyl-1,5-pentanediol, the composition of the dicarboxylic acid component is 60 mol% of terephthalic acid and 40 mol% of adipic acid, and all the monomers It was added together with titanium tetraisopropoxide (1,000 ppm with respect to the resin component) so that the amount of trimethylolpropane in the inside was 1 mol %.
After that, the temperature was raised to 200° C. over about 4 hours, then to 230° C. over 2 hours, and the reaction was carried out until no water flowed out.
After that, the mixture was further reacted under a reduced pressure of 10 mmHg to 15 mmHg for 5 hours to obtain an intermediate polyester A-2.
The resulting intermediate polyester A-2 had a Tg of −30° C., an Mw of 10,000 and an Mw/Mn of 2.5.
Next, intermediate polyester A-2 and isophorone diisocyanate (IPDI) were mixed in a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen inlet tube at a molar ratio (isocyanate group of IPDI/hydroxyl group of intermediate polyester) of 1. 8, diluted with ethyl acetate to give a 50% ethyl acetate solution, and reacted at 100° C. for 5 hours to obtain prepolymer A-2.

-Synthesis of polyester resin A-2-
The obtained prepolymer A-2 was stirred in a reaction vessel equipped with a heating device, a stirrer and a nitrogen inlet tube, and the amount of amine in [ketimine compound 1] was determined relative to the amount of isocyanate in prepolymer A-2. An equimolar amount of [ketimine compound 1] was added dropwise to the reaction vessel, and after stirring at 45°C for 10 hours, the prepolymer extension product was taken out.
The resulting prepolymer stretched product was dried under reduced pressure at 50° C. until the residual ethyl acetate amount was 100 ppm or less, to obtain an amorphous polyester resin A-2.
The Tg of the amorphous polyester resin A-2 was -20°C.
Amorphous polyester resin A-2 does not contain an isocyanurate skeleton.

(Comparative Example 4)
[Toner base particles 9] were obtained in the same manner as in Example 1, except that [polyester resin A-1] was replaced with [polyester resin A-2]. was evaluated in the same manner as in Example 1 for [Toner 9] using Table 1 shows the results.

(Manufacturing Example B-2)
<Synthesis of polyester resin B-2>
-Synthesis of Amorphous Polyester Resin B-2-
[Polyester resin B-2] was obtained in the same manner as in the synthesis of [polyester resin B-1], except that trimellitic anhydride was changed to pyromellitic anhydride.
The Tg of the amorphous polyester resin B-2 was 48°C.

(Comparative Example 5)
[Toner base particles 10] were obtained in the same manner as in Example 1, except that [polyester resin B-1] was replaced with [polyester resin B-2]. [Toner 10] was evaluated in the same manner as in Example 1. Table 1 shows the results.

From the results in Table 1, a crystalline polyester resin and an amorphous polyester resin are included as binder resins, and the amorphous polyester resin is an amorphous polyester having an isocyanurate skeleton and a urethane and/or urea bond. The toners of Examples 1 to 5 containing resin A and amorphous polyester resin B having a trimellitic acid skeleton and urethane and/or urea bonds exhibit excellent low-temperature fixability, glossiness, and heat-resistant storage properties. It was confirmed that the
On the other hand, Comparative Examples 1 and 2, which are toners containing no amorphous polyester resin B, deteriorated in image gloss or heat-resistant storage stability.
Since Comparative Example 3 is a toner containing no amorphous polyester resin A, the low-temperature fixability was deteriorated.
In Comparative Example 4, since the amorphous polyester resin A-2 did not contain an isocyanurate skeleton, the low-temperature fixability was deteriorated.
In Comparative Example 5, since the amorphous polyester resin B-2 did not contain a trimellitic acid skeleton, the low-temperature fixability was deteriorated.

10 electrostatic latent image carrier (photosensitive drum)
10K electrostatic latent image carrier 10Y for black electrostatic latent image carrier 10M for yellow electrostatic latent image carrier 10C electrostatic latent image carrier for magenta 10C electrostatic latent image carrier for cyan 14 support roller 15 support roller 16 support roller 17 cleaning device 18 Image Forming Means 20 Charging Roller 21 Exposure Device 22 Secondary Transfer Device 23 Roller 24 Secondary Transfer Belt 25 Fixing Device 26 Fixing Belt 27 Pressure Roller 28 Sheet Reversing Device 32 Contact Glass 33 First Traveling Body 34 Second Traveling Body 35 Image Formation Lens 36 Reading sensor 40 Developing device 41 Developing belt 42K Developer containing portion 42Y Developer containing portion 42M Developer containing portion 42C Developer containing portion 43K Developer supply roller 43Y Developer supply roller 43M Developer supply roller 43C Developer supply roller 44K Developing roller 44Y Developing roller 44M Developing roller 44C Developing roller 45K Black developing unit 45Y Yellow developing unit 45M Magenta developing unit 45C Cyan developing unit 49 Registration roller 50 Intermediate transfer member 51 Roller 52 Separation roller 53 Manual feed path 54 Manual feed tray 55 Switching Claw 56 Discharge roller 57 Discharge tray 58 Corona charger 60 Cleaning device 61 Developing device 62 Transfer charger 63 Cleaning device 64 Eliminating lamp 70 Eliminating lamp 80 Transfer roller 90 Cleaning device 95 Transfer paper 100A, 100B, 100C Image forming device 110 Process cartridge 120 tandem type developer 130 document table 142 paper feed roller 143 paper bank 144 paper feed cassette 145 separation roller 146 paper feed path 147 transport roller 148 paper feed path 150 copying apparatus main body 160 charging device 200 paper feed table 300 scanner 400 automatic document transport Device (ADF)

JP-A-11-133665 JP-A-2002-287400 JP-A-2002-351143 Japanese Patent No. 2579150 Japanese Patent Application Laid-Open No. 2001-158819 JP-A-2004-46095 JP 2007-271789 A Japanese Patent No. 5408210 JP 2013-145369 A

Claims (8)

A toner containing at least a colorant, a release agent, and a binder resin,
including a crystalline polyester resin and an amorphous polyester resin as the binder resin,
The amorphous polyester resin includes an amorphous polyester resin A having an isocyanurate skeleton and urethane and/or urea bonds, and an amorphous polyester resin having a trimellitic acid skeleton and urethane and/or urea bonds. A toner characterized by containing B. 2. The toner according to claim 1, wherein the amorphous polyester resin A has a structure represented by any one of structural formulas 1) to 3) below.
1) R1-(NHCONH-R2)n-
2) R1-(NHCOO-R2)n-
3) R1-(OCONH-R2)n-
(In the above formula, n = 3, R1 represents an isocyanurate skeleton, and R2 represents a group derived from either a polyester containing a polycarboxylic acid and a polyol, or a modified polyester in which the polyester is isocyanate-modified. .) 3. The toner according to claim 1, wherein the toner has a T1/2 of 105[deg.] C. or higher and 125[deg.] C. or lower as measured by a flow tester heating method. (1) to (1), wherein the toner has a glass transition temperature [Tg1st (toner)] of 50° C. or more and 65° C. or less in the endothermic curve measured with a differential scanning calorimeter. 4. The toner according to any one of 3. A toner containing unit containing the toner according to any one of claims 1 to 4. An electrostatic latent image carrier, electrostatic latent image forming means for forming an electrostatic latent image on the electrostatic latent image carrier, and development of the electrostatic latent image formed on the electrostatic latent image carrier. a developing means comprising toner for forming a visible image;
An image forming apparatus, wherein the toner is the toner according to any one of claims 1 to 4. a charging step of charging an electrostatic latent image carrier by charging means; an exposure step of forming an electrostatic latent image on the charged electrostatic latent image carrier by exposing means; a developing step of forming a toner image on the electrostatic latent image carrier by developing means containing toner; and a primary transfer means transferring the toner image formed on the electrostatic latent image carrier onto an intermediate transfer member. a primary transfer step; a secondary transfer step of transferring the toner image transferred on the intermediate transfer member onto a recording medium by a secondary transfer means; a fixing step of fixing the toner image onto a recording medium by a fixing means including a cleaning means for cleaning residual toner adhering to the surface of the electrostatic latent image carrier after the toner image is transferred onto the intermediate transfer member by the primary transfer means; and a cleaning step for cleaning, wherein the toner in the developing step is the toner according to any one of claims 1 to 4. In the secondary transfer step, the linear velocity for transferring the toner image onto the recording material is 100 to 1000 mm/sec, and the transfer time at the nip portion of the secondary transfer means is 0.5 to 60 msec. 8. The image forming method according to claim 7.

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