JP6786285B2 - toner - Google Patents

Description

The present invention relates to a toner for developing an electrostatic charge image used in an electrophotographic method, an electrostatic recording method, and the like.

In recent years, as image forming devices such as copiers and printers have become widespread, the performance required for the image forming devices is required to be higher in speed, energy saving, and higher image quality.
Various improvements in the low temperature fixability of toner have been studied as one of the means for achieving high speed and energy saving of the image forming apparatus.

In Patent Document 1, in order to improve low temperature fixability, durability stability, and fog, aliphatic compounds having different melting points are condensed at the ends of the polyester units of the binder resin A and the binder resin B, and the softening point is obtained. A toner obtained by mixing a binder resin A and a binder resin B having different values has been proposed. Fog is an image defect in which toner is slightly developed in a non-image area (unexposed area), which is an area where toner is not originally developed.

Further, Patent Document 2 discloses a toner having excellent low-temperature fixability and high-temperature offset resistance, regardless of the type of paper, even when image formation is performed at high speed. Then, Patent Document 2 proposes a method of controlling the storage elastic modulus and activation energy of the toner by controlling the crosslinked structure of the THF insoluble component of the binder resin.

By using the above-mentioned toner, the fixability of the toner is improved, and the speed and energy saving of the image forming apparatus can be achieved.
On the other hand, with the spread of more delicate images such as security images, further improvement of fine line reproducibility and fine dot reproducibility has been indispensable.

JP-A-2015-28622 Japanese Patent No. 4914349

An object of the present invention is to provide a toner having good fine line reproducibility and fine dot reproducibility without impairing low temperature fixability, high temperature offset resistance, storage stability, and fog performance.

The present invention
A toner having toner particles containing a binder resin and a mold release agent.
The binding resin contains a binding resin A and a binding resin B.
The binder resin A is
It is a hybrid resin in which a vinyl polymer unit and a polyester unit are chemically bonded.
Containing THF insoluble X, which is not extracted by 16 hours Soxhlet extraction with tetrahydrofuran (THF),
The content of the THF insoluble content X is 25% by mass or more and 45% by mass or less based on the mass of the binder resin A.
The THF insoluble component X contains a TOR insoluble component Y that is not extracted by Soxhlet extraction using toluene (TOR) for 16 hours.
The content (mass%) of the TOR insoluble matter Y based on the mass of the binder resin A and the content (mass%) of the THF insoluble content X based on the mass of the binder resin A. The ratio (content of TOR insoluble matter Y / content of THF insoluble matter X) is 0.10 or more and 0.60 or less.
The binder resin B is softened by condensing at least one aliphatic compound selected from the group consisting of an aliphatic monocarboxylic acid having 25 or more and 102 or less carbon atoms and an aliphatic monoalcohol having 25 or more and 102 or less carbon atoms at the terminal. The present invention relates to a toner, which is a polyester resin having a point of 80 ° C. or higher and 110 ° C. or lower .

According to the present invention, it is possible to provide a toner having good fine line reproducibility and fine dot reproducibility without impairing low temperature fixability, high temperature offset resistance, storage stability, and fog performance.

The present inventors have good low-temperature fixability, storage stability, and fog performance in a toner using a polyester resin in which an aliphatic compound is condensed at the terminal. Therefore, the present inventors make use of these performances while maintaining fine line reproducibility and fineness. Diligent studies were conducted to further improve the dot reproducibility.
As a result, the toner containing the following binder resin A and the following binder resin B reproduces fine lines and fine dots without impairing low temperature fixability, high temperature offset resistance, storage stability, and fog performance. It was found that the sex was improved.

Specifically, the toner of the present invention is a toner having toner particles containing a binder resin and a mold release agent, and the binder resin contains a binder resin A and a binder resin B.
The binder resin A is
It is a hybrid resin in which a vinyl polymer unit and a polyester unit are chemically bonded.
Containing THF insoluble X, which is not extracted by 16 hours Soxhlet extraction with tetrahydrofuran (THF),
The content of the THF-insoluble matter X is referenced to the weight of the binder resin A, and 45 wt% or less than 25 wt%,
The THF insoluble component X contains a TOR insoluble component Y that is not extracted by Soxhlet extraction using toluene (TOR) for 16 hours.
The content (mass%) of the TOR insoluble matter Y based on the mass of the binder resin A and the content (mass%) of the THF insoluble content X based on the mass of the binder resin A. The ratio ( content of TOR insoluble matter Y / content of THF insoluble matter X ) is 0.10 or more and 0.60 or less.

The binder resin B is softened by condensing at least one aliphatic compound selected from the group consisting of an aliphatic monocarboxylic acid having 25 or more and 102 or less carbon atoms and an aliphatic monoalcohol having 25 or more and 102 or less carbon atoms at the terminal. It is a polyester resin having a point of 80 ° C. or higher and 110 ° C. or lower .
Although it is not clear why the configuration of the present invention provides an unprecedentedly superior effect, it is probably as follows.

In the present invention, it is necessary to use a polyester resin in which an aliphatic compound is condensed at the terminal in order to obtain a toner having good low temperature fixability, fog, and storage stability. Since the aliphatic compound condensed at the terminal has an action of softening the resin, the low temperature fixability is improved. Further, since it is condensed at the terminal and exists as a part of the polyester resin, it is possible to maintain a good storage state. Further, since the aliphatic compound has a structure similar to that of wax, the wax dispersibility is improved. Wax dispersibility is one of the important factors in controlling the charge distribution of the toner, and a toner having good wax dispersibility has good fog.

On the other hand, in order to improve the fine line reproducibility and the fine dot reproducibility, it is necessary to develop a necessary and sufficient amount of toner for the electrostatic latent image of the fine lines and fine dots formed on the photoconductor. For that purpose, it is important to control the charge amount distribution of the toner and the cohesive force between the toners.
However, it has been difficult to further improve the fine line reproducibility and the fine dot reproducibility even if the charge amount distribution of the toner is controlled, particularly in a high temperature and high humidity environment.

Therefore, the present inventors reduce the charge amount of the toner in a high temperature and high humidity environment, so that the non-electrostatic adhesive force, which is one of the cohesive forces between the toners, improves the fine line reproducibility and the fine dot reproducibility. I thought that the impact would be greater.
In order to control the non-electrostatic adhesive force between toners more uniformly, it is important to make the materials constituting the toner, particularly the binder resin, uniformly present, and the configuration of the present invention has been found. It was.
That is, in the present invention, by using the binder resin A and the binder resin B in combination, the compatibility between the resins is improved and the uniformity of the non-electrostatic adhesive force between the toners is improved. Conceivable. As a result, it is considered that low-temperature fixability, storage stability, fog are good, and excellent fine line reproducibility and fine dot reproducibility, which have not been achieved in the past, can be achieved.

In order to explain the compatibility between the resins, the characteristics of the binder resin A and the binder resin B in the present invention will be described.
(Content of THF insoluble X)
The binder resin A contains 25% by mass or more and 45% by mass or less of a THF insoluble content in order to maintain high temperature offset resistance. The THF insoluble component in the present invention is an ultra-high molecular weight component, a so-called gel, which is not extracted by Soxhlet extraction for 16 hours. Gel is a necessary component to maintain high temperature offset resistance, but it can also interfere with low temperature fixability.

Therefore, the present inventors considered that it is necessary to design the gel so as not to impair the low temperature fixability. Specifically, the THF insoluble component X of the binder resin A in the present invention needs to contain a TOR insoluble component Y that is not extracted by Soxhlet extraction for 16 hours using toluene (TOR). Then, it is necessary to control the ratio (Y / X) of the TOR insoluble content Y (mass%) to the THF insoluble content X (mass%) to be 0.10 or more and 0.60 or less. I found it.

(Ratio of TOR insoluble matter Y and THF insoluble matter X (Y / X))
The ratio (Y / X) of the TOR insoluble matter Y (mass%) to the THF insoluble matter X (mass%) is less than 1.0, which means that it dissolves in the TOR in the THF insoluble matter X. It means that there is a soluble component to be extracted.
The solubility parameters of THF and TOR are almost the same, and it is considered that the difference in the solubility due to solvation is negligible. Therefore, the reason why the soluble component is extracted from the THF insoluble component X by Soxhlet extraction using TOR is due to the difference in extraction temperature when both solvents are used.

The boiling point of THF is 66 ° C. and the boiling point of TOR is 110.6 ° C. In Soxhlet extraction, the extraction temperature depends on the boiling points of both solvents, so TOL is extracted at a higher temperature than THF.
The THF insoluble content X contained in the binder resin A of the present invention contains both a gel component having a chemically bonded cross-linking point and a gel component having a pseudo-cross-linking point formed by entanglement of molecular chains. It has been. When this THF insoluble component X is extracted with a higher temperature TOR, the molecular chains forming the pseudo-crosslink point are untangled and become a soluble component, and only the gel component having the chemically bonded cross-linking point is regarded as the TOR insoluble component. Remain.

That is, the ratio (Y / X) of the TOR insoluble content Y (mass%) to the THF insoluble content X (mass%) in the present invention is the ratio of chemically bonded cross-linking points in the gel content. It becomes an index to represent.
The ratio (Y / X) of the TOR insoluble matter Y to the THF insoluble matter X is 0.10 or more, which means that the gel has a pseudo-crosslink point as well as a chemically bonded cross-linking point. Indicates that it has a gel content. On the other hand, when the ratio (Y / X) of the TOR insoluble matter Y to the THF insoluble matter X is 0.60 or less, it is shown that the pseudo-crosslink point is sufficiently provided.

The gel component having a chemically bonded cross-linking point gives elasticity to the toner and improves high temperature offset resistance. Further, the presence of the gel component having a pseudo-crosslink point causes the gel component to be entangled with the chemically bonded gel component, and the high temperature offset resistance is improved.
On the other hand, the gel component having a pseudo-crosslink point has a level of freedom of molecular motion at a level where it is unentangled and becomes a soluble component in Soxhlet extraction. Therefore, the low-temperature fixability derived from the binder resin B is not impaired when the toner is fixed. Further, the compatibility between the binder resin A and the binder resin B is improved due to the degree of freedom of the molecular motion.

The reason why the gel having the pseudo-crosslink point improves the compatibility with the binder resin B is considered as follows. In general, it is known that the compatibility between the binder resins when two or more kinds of binder resins are mixed is inversely proportional to the degree of polymerization of the binder resins. The reason for this is that as the degree of polymerization increases, the mobility of the molecule is limited to chemical bonds. That is, the gel component, which is an ultra-high molecular weight substance, is difficult to be compatible with other resin components and tends to exist as a domain in the toner. However, since the gel content of the binder resin A in the present invention contains a large amount of gel having pseudo-crosslink points due to entanglement, the actual degree of polymerization is not high. Therefore, it is considered that the gel content of the binder resin A used in the present invention is in a state of high compatibility with other resin components.

On the other hand, the binder resin B in the present invention is a polyester resin in which an aliphatic compound having 25 or more and 102 or less carbon atoms is condensed at the terminal. By condensing an aliphatic compound at the terminal, the mobility of the molecule at the end of the polyester resin is improved as compared with a normal polyester resin. The mobility of the molecules at the ends of the binder resin B acts to separate from the components that are likely to exist as domains, such as chemically bonded gels, but like gels with pseudo-crosslink points. In addition, it becomes easy to be compatible with components that do not have a high degree of polymerization.

In the present invention, a binder resin A having a quasi-crosslink point and having a gel component that is easily compatible with each other and a binder resin B which is a polyester resin in which an aliphatic compound is condensed at the terminal are used in combination. By doing so, the ease of mutual compatibility can be maximized, and the non-electrostatic adhesive force between the toners can be made uniform, so that good fine line reproducibility and fine dot reproducibility can be obtained. It is presumed that it was possible. Further, the gel having a pseudo-crosslinked point did not hinder the low-temperature fixability of the binder resin B at the time of fixing, the high-temperature offset resistance was improved, and good levels of fog and storage stability could be achieved. ..

The binder resin A is characterized in that it is a hybrid resin in which a vinyl-based polymer unit and a polyester unit are chemically bonded. By using the hybrid resin, it becomes easy to control the gel content having the pseudo-crosslink point.
Further, the binder resin A has a content of THF insoluble content X of 25% by mass or more and 45% by mass or less with respect to the binder resin A, and the TOR insoluble content Y and the THF insoluble content X The ratio (Y / X) of is 0.10 or more and 0.60 or less.

When the ratio (Y / X) of the TOR insoluble matter Y to the THF insoluble matter X is 0.10 or more and 0.60 or less, the gel having a chemically bonded cross-linking point and the pseudo-crosslinking point can be separated. The balance of the abundance ratio of the gel content is good. Therefore, low temperature fixability and high temperature offset resistance are good, fog and storage stability are excellent, compatibility with the binder resin B is better, and fine line reproducibility and fine dot reproducibility are good.
The ratio (Y / X) of the TOR insoluble matter Y to the THF insoluble matter X is more preferably 0.15 or more and 0.55 or less.

When the binder resin A contains THF insoluble content X in an amount of 25% by mass or more and 45% by mass or less with respect to the binder resin A, it becomes possible to sufficiently maintain the elasticity of the toner and to withstand high temperature offset. Becomes good.
The content of the THF insoluble content X is more preferably 30% by mass or more and 40% by mass or less.
The binder resin B is a polyester obtained by condensing at the terminal with at least one aliphatic compound selected from the group consisting of an aliphatic monocarboxylic acid having 25 or more and 102 or less carbon atoms and an aliphatic monoalcohol having 25 or more and 102 or less carbon atoms. It is characterized by being a resin.

When the carbon number of the aliphatic compound condensed at the terminal is 25 or more and 102 or less, the balance between the molecular motion of the aliphatic compound condensed at the terminal and the affinity between the binder resin and the wax becomes good, and the binder resin Good compatibility with A. As a result, the low temperature fixability and fog of the toner are improved.
"The aliphatic compound is condensed at the end of the binder resin" is, for example, a state in which the carboxy group of the resin having a carboxy group at the end and the hydroxy group of the aliphatic compound are condensed. Further, the hydroxy group of the resin having a hydroxy group at the terminal and the carboxy group of the aliphatic compound may be condensed. Here, the "terminal" also includes the branched end when the binder resin B has a branched structure.

It is important that the above aliphatic compound has a monovalent functional group. By being monovalent, the aliphatic compound will be condensed at the end of the binder resin. Since the end is a part that has a particularly large effect on other components, the wax-like aliphatic compound is condensed at the end, so that the wax dispersibility is improved and the mobility of the molecule is improved. , The compatibility with the binder resin A is improved.

In the present invention, the binder resin B preferably has a softening point of 80 ° C. or higher and 110 ° C. or lower, and more preferably 85 ° C. or higher and 105 ° C. or lower. By setting the softening point of the binder resin B within the above range, low temperature fixability and storage stability are improved.
In the toner of the present invention, the mixing ratio of the binder resin A and the binder resin B is preferably 10:90 to 90:10 in terms of mass ratio (bonding resin A: binding resin B), more preferably. It is 20:80 to 80:20, more preferably 40:60 to 80:20. When the mass ratio of the binder resin A and the binder resin B is in this range, the low temperature fixability, the high temperature offset resistance, the storage stability, and the fog are further improved, and the binder resin A and the binder resin B are further improved. Compatibility is improved, and fine line reproducibility and fine dot reproducibility are improved.

Further, the toner of the present invention may contain other resins other than the binder resin A and the binder resin B to the extent that the effects of the present invention are not impaired. The other resin is not particularly limited as long as it is a binder resin for toner, and can be used, and examples thereof include vinyl-based resin, polyurethane resin, epoxy resin, and phenol resin.

(Polyester unit)
The polyester unit of the binder resin A and the components constituting the binder resin B will be described in detail. The following components may be used alone or in combination of two or more depending on the type and use.
Examples of the divalent acid component constituting the polyester unit of the binder resin A and the binder resin B include the following dicarboxylic acids or derivatives thereof. Benzenedicarboxylic acids such as phthalic acid, terephthalic acid, isophthalic acid, phthalic anhydride or its anhydrides or lower alkyl esters thereof; alkyldicarboxylic acids such as succinic acid, adipic acid, sebacic acid, azelaic acid or their anhydrides or their lower grades. Alkyl ester; Alkenyl succinic acid or alkyl succinic acid having 1 to 50 carbon atoms, or anhydride thereof or lower alkyl ester thereof; Unsaturated dicarboxylic acid such as fumaric acid, maleic acid, citraconic acid, itaconic acid or anhydride thereof or its anhydride Lower alkyl ester.

On the other hand, examples of the divalent alcohol component constituting the polyester unit of the binder resin A and the binder resin B include the following. Ethylene glycol, polyethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, diethylene glycol, triethylene glycol, 1,5 -Pentanediol, 1,6-hexanediol, neopentyl glycol, 2-methyl-1,3-propanediol, 2-ethyl-1,3-hexanediol, 1,4-cyclohexanedimethanol (CHDM), hydrogenation Bisphenol A, bisphenol represented by the formula (1) and derivatives thereof: and diols represented by the formula (2).

（式中、Ｒはエチレンまたはプロピレン基であり、ｘ、ｙはそれぞれ０以上の整数であり、かつ、ｘ＋ｙの平均値は０〜１０である。）

(In the formula, R is an ethylene or propylene group, x and y are integers of 0 or more, respectively, and the average value of x + y is 0 to 10.)

In the binder resin B in the present invention, the ratio of the unit derived from the aliphatic polyhydric alcohol is preferably 1 mol% or more and 40 mol% or less, and 5 mol% or more, based on the total number of moles of the polyhydric alcohol component. It is more preferable to contain 35 mol% or less. Since the aliphatic polyhydric alcohol acts as a soft segment in the polyester unit, the low temperature fixability is improved by containing 1 mol% or more. By containing 40 mol% or less, the fixing strength of the fixed toner can be maintained, and the low temperature fixability becomes good.

Further, the aliphatic polyhydric alcohol is more preferably ethylene glycol. Since ethylene glycol has a small molecular weight, it is preferable for adjusting the physical properties of the binder resin B.
In addition to the above-mentioned divalent carboxylic acid compound and divalent alcohol compound, the constituent components of the polyester unit of the binder resin A and the binder resin B used in the present invention are trivalent or higher carboxylic acid compounds, 3 It is preferable to contain an alcohol compound having a value or higher as a constituent component.

Examples of the trivalent or higher carboxylic acid compound include trimellitic acid, trimellitic anhydride, pyromellitic acid and the like. Examples of the trihydric or higher alcohol compound include trimethylolpropane, pentaerythritol, and glycerin.
In the binder resin A in the present invention, the proportion of the unit derived from trimellitic acid is preferably 30 mol% or more and 60 mol% or less with respect to the total number of moles of the acid component constituting the polyester unit. When the ratio of the unit derived from trimellitic acid is within the above range, it is possible to obtain a gel having a higher degree of freedom of molecular motion in the gel having a pseudo-crosslink point, so that the gel with the binding resin B can be obtained. The compatibility becomes better, and the fine dot reproducibility, fine line reproducibility, and high temperature offset resistance become good. Trimellitic acid can be obtained by using trimellitic acid or trimellitic anhydride as a carboxylic acid compound.

In the present invention, the method for producing the polyester unit of the binder resin A is not particularly limited, and a known method can be used. For example, the above-mentioned polyvalent carboxylic acid compound and polyhydric alcohol compound are mixed and polymerized through an esterification reaction, a transesterification reaction, and a condensation reaction to produce a polyester unit.
The method for producing the binder resin B is not particularly limited, and a known method can be used. For example, a polyvalent carboxylic acid compound and a polyhydric alcohol compound are simultaneously mixed with an aliphatic monocarboxylic acid or an aliphatic monoalcohol, and polymerized through an esterification reaction, a transesterification reaction, and a condensation reaction to form a binder resin B. To manufacture.
The polymerization temperature is not particularly limited, but is preferably in the range of 180 ° C. or higher and 290 ° C. or lower. When polymerizing the polyester unit, for example, a polymerization catalyst such as a titanium-based catalyst, a tin-based catalyst, zinc acetate, antimony trioxide, or germanium dioxide can be used. In particular, the binder resin in the present invention more preferably contains a polyester unit polymerized using a titanium-based catalyst.

Specific examples of the titanium-based catalyst include the following. Titanium Diisopropirate Bistriethanol Aminate [Ti (C ₆ H ₁₄ O ₃ N) ₂ (C ₃ H ₇ O) ₂ ], Titanium Diisopropirate Bisdiethanol Aminate [Ti (C ₄ H ₁₀ O ₂ N) ₂ ( C ₃ H ₇ O) ₂ ], Titanium Dipentylate Bistriethanol Aminate [Ti (C ₆ H ₁₄ O ₃ N) ₂ (C ₅ H ₁₁ O) ₂ ], Titanium Diethylate Bistriethanol Aminate [Ti (C ₆ H ₁₄ O ₃ N) ₂ ] C ₆ H ₁₄ O ₃ N) ₂ (C ₂ H ₅ O) ₂ ], Titanium Dihydroxyoctylate bistriethanolamineate [Ti (C ₆ H ₁₄ O ₃ N) ₂ (OHC ₈ H ₁₆ O) ₂ ], Titanium Distearate Bistriethanol Aminate [Ti (C ₆ H ₁₄ O ₃ N) ₂ (C ₁₈ H ₃₇ O) ₂ ], Titanium Triisopropirate Triethanol Aminate [Ti (C ₆ H ₁₄ O ₃ N) ₁ ( C ₃ H ₇ O) ₃ ], Titanium Monopropyrate Tris (Triethanol Aminate) [Ti (C ₆ H ₁₄ O ₃ N) ₃ (C ₃ H ₇ O) ₁ ], etc. Of these, titanium diisopropirate bistriethanolamate, titanium diisopropirate bisdiethanolamate and titanium dipentylate bistriethanolamate are preferred.

Specific examples of other titanium-based catalysts include tetra-n-butyl titanate [Ti (C ₄ H ₉ O) ₄ ], tetrapropyl titanate [Ti (C ₃ H ₇ O) ₄ ], and tetrastearyl titanate [Ti. (C ₁₈ H ₃₇ O) ₄ ], Tetramyristyl titanate [Ti (C ₁₄ H ₂₉ O) ₄ ], Tetraoctyl titanate [Ti (C ₈ H ₁₇ O) ₄ ], Dioctyl dihydroxyoctyl titanate [Ti (C ₈ H) ₁₇ O) ₂ (OHC ₈ H ₁₆ O) ₂ ], dimyristyl dioctyl titanate [Ti (C ₁₄ H ₂₉ O) ₂ (C ₈ H ₁₇ O) ₂ ], etc., among which tetrastearyl titanate, Tetramyristyl titanate, tetraoctyl titanate and dioctyl dihydroxyoctyl titanate are preferred. These can be obtained, for example, by reacting titanium halide with the corresponding alcohol. Further, it is more preferable that the titanium-based catalyst contains an aromatic titanium carboxylate compound. The titanium aromatic carboxylic acid compound is preferably obtained by reacting the aromatic carboxylic acid with the titanium alkoxide.

Further, the aromatic carboxylic acid is preferably a divalent or higher aromatic carboxylic acid (that is, an aromatic carboxylic acid having two or more carboxy groups) and / or an aromatic oxycarboxylic acid. Examples of the above divalent or higher aromatic carboxylic acids include dicarboxylic acids such as phthalic acid, isophthalic acid, and terephthalic acid or their anhydrides, trimellitic acid, benzophenone dicarboxylic acid, benzophenone tetracarboxylic acid, naphthalenedicarboxylic acid, and naphthalene tetracarboxylic acid. Examples thereof include polyvalent carboxylic acids such as acids, anhydrides thereof, and esterified products. Examples of the aromatic oxycarboxylic acid include salicylic acid, m-oxybenzoic acid, p-oxycarboxylic acid, gallic acid, mandelic acid, tropic acid and the like. Among these, it is more preferable to use a divalent or higher carboxylic acid as the aromatic carboxylic acid, and it is particularly preferable to use isophthalic acid, terephthalic acid, trimellitic acid, and naphthalenedicarboxylic acid.

(Vinyl polymer unit)
In the present invention, as the vinyl-based monomer for producing the vinyl-based polymer unit of the binder resin A, at least styrene and the monomer represented by the formula (3) are preferably used.
CH ₂ = CR ¹ COOR ² ... Equation (3)
(R ¹ : H or methyl group, R ² : represents an alkyl group or hydroxyalkyl group having 12 or less carbon atoms)

Further, it is preferable that the unit derived from the monomer represented by the formula (3) is contained in an amount of 20 mol% or more and 90 mol% or less based on the total number of moles of the vinyl-based monomer unit.
When the unit derived from the monomer represented by the formula (3) is contained within the above range, the compatibility with the binder resin B is improved, and the fine line reproducibility and the fine dot reproducibility are improved.

Examples of the vinyl-based monomer for producing a vinyl-based copolymerization unit other than styrene include the following styrene-based monomers and acrylic acid-based monomers.
Examples of styrene-based monomers include o-methylstyrene, m-methylstyrene, p-methylstyrene, p-phenylstyrene, p-ethylstyrene, 2,4-dimethylstyrene, pn-butylstyrene, and p-tert-butyl. Styrene, pn-hexyl styrene, pn-octyl styrene, pn-nonyl styrene, pn-decyl styrene, pn-dodecyl styrene, p-methoxy styrene, p-chloro styrene, 3,4 Examples include styrene derivatives such as −dichlorostyrene, m-nitrostyrene, o-nitrostyrene and p-nitrostyrene.

Examples of the acrylic acid-based monomer include acrylic acid, -2-chloroethyl acrylate, phenylacrylic acid, methacrylic acid, phenyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, acrylonitrile, methacrylic acid, and acrylamide. ..

Further, examples of the monomer constituting the vinyl polymer unit include monomers having a hydroxyl group such as 4- (1-hydroxy-1-methylbutyl) styrene and 4- (1-hydroxy-1-methylhexyl) styrene.

Various monomers capable of vinyl polymerization can be used in combination with the vinyl polymer unit, if necessary. Such monomers include ethylene-based unsaturated monoolefins such as ethylene, propylene, butylene and isobutylene; unsaturated polyenes such as butadiene and isoprene; halogens such as vinyl chloride, vinylidene chloride, vinyl bromide and vinyl fluoride. Vinyl chemicals; vinyl esters such as vinyl acetate, vinyl propionate, vinyl citrate; vinyl ethers such as vinyl methyl ether, vinyl ethyl ether, vinyl isobutyl ether :; vinyl methyl ketone, vinyl hexyl ketone, methyl isopropenyl ketone Vinyl ketones such as: N-vinylpyrrole, N-vinylcarbazole, N-vinylindole, N-vinylpyrrolidone and other N-vinyl compounds; vinylnaphthalins; Unsaturated dibasic acids such as acids, mesaconic acid; unsaturated dibasic acids such as maleic acid anhydride, citraconic acid anhydride, itaconic acid anhydride, alkenyl succinic acid anhydride; maleic acid methyl half ester, maleic acid Ethyl half ester, butyl maleic acid half ester, methyl citraconic acid half ester, ethyl citraconic acid half ester, butyl citraconic acid half ester, methyl itaconic acid half ester, methyl alkenyl succinate half ester, methyl fumaric acid half ester, methyl mesaconic acid Half esters of unsaturated basic acids such as half esters; unsaturated basic acid esters such as dimethylmaleic acid and dimethylfumaric acid; acid anhydrides of α, β-unsaturated acids such as acrylic acid, methacrylic acid, crotonic acid and citraconic acid Stuff; anhydrides of the α, β-unsaturated acid and lower fatty acids; alkenylmalonic acid, alkenylglutaric acid, alkenyladipic acid, these acid anhydrides and monomers having a carboxy group such as monoesters thereof. ..

Further, the vinyl-based polymer unit may be a polymer crosslinked with a crosslinkable monomer as exemplified below, if necessary. Examples of the crosslinkable monomer include the following. Aromatic divinyl compounds, diacrylate compounds linked by an alkyl chain, and diacrylate compounds linked by an alkyl chain containing an ether bond. Diacrylate compounds linked by chains containing aromatic groups and ether bonds, polyester-type diacrylates, polyfunctional cross-linking agents and the like.

Examples of the aromatic divinyl compound include divinylbenzene and divinylnaphthalene. Examples of the diacrylate compounds linked by the above alkyl chains include the following. Ethylene glycol diacrylate, 1,3-butylene glycol diacrylate, 1,4-butanediol diacrylate, 1,5-pentanediol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, and above. Acrylate of a compound replaced with methacrylate, etc.

Examples of the diacrylate compounds linked by the alkyl chain containing the ether bond include the following. Diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol # 400 diacrylate, polyethylene glycol # 600 diacrylate, dipropylene glycol diacrylate, and acrylates of the above compounds replaced with methacrylate.

Examples of the diacrylate compounds linked by the chain containing the aromatic group and the ether bond include the following. Polyoxyethylene (2) -2,2-bis (4-hydroxyphenyl) propandiacrylate, polyoxyethylene (4) -2,2-bis (4-hydroxyphenyl) propandiacrylate, and acrylates of the above compounds. Is replaced with methacrylate, etc. Examples of polyester-type diacrylates include the trade name MANDA (Nippon Kayaku).

Examples of the polyfunctional cross-linking agent include the following. Pentaerythritol triacrylate, trimethylolethane triacrylate, trimethylolpropane triacrylate, tetramethylolmethanetetraacrylate, oligoester acrylate, and acrylates of the above compounds replaced with methacrylate; triallyl cyanurate, triallyl trimerite. ;etc.

The vinyl-based polymer unit may be a resin produced by using a polymerization initiator. From the viewpoint of efficiency, these polymerization initiators are preferably used in an amount of 0.05 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the monomer.
Examples of such a polymerization initiator include the following. 2,2'-azobisisobutyronitrile, 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), 2, 2'-azobis (2-methylbutyronitrile), dimethyl-2,2'-azobisisobutyrate, 1,1'-azobis (1-cyclohexanecarbonitrile), 2-carbamoylazoisobutyronitrile, 2,2'-azobis (2,4,4-trimethylpentane), 2-phenylazo-2,4-dimethyl-4-methoxyvaleronitrile, 2,2'-azobis (2-methylpropane), methylethylketone peroxide, Ketone peroxides such as acetylacetone peroxide and cyclohexanone peroxide, 2,2-bis (t-butylperoxy) butane, t-butylhydroperoxide, cumenehydroperoxide, 1,1,3,3-tetramethyl Butylhydroperoxide, di-t-butyl peroxide, t-butylcumyl peroxide, dicumyl peroxide, α, α'-bis (t-butylperoxyisopropyl) benzene, isobutyl peroxide, octanoyl peroxide, Decanoyl peroxide, lauroyl peroxide, 3,5,5-trimethylhexanoyl peroxide, benzoyl peroxide, m-trioil peroxide, diisopropylperoxydicarbonate, di-2-ethylhexylperoxydicarbonate, di- n-Provir peroxydicarbonate, di-2-ethoxyethylperoxycarbonate, dimethoxyisopropylperoxydicarbonate, di (3-methyl-3-methoxybutyl) peroxycarbonate, acetylcyclohexylsulfonyl peroxide, t-butyl Peroxyacetate, t-butylperoxyisobutyrate, t-butylperoxyneodecanoate, t-butylperoxy-2-ethylhexanoate, t-butylperoxylaurate, t-butylperoxybenzo Eight, t-butylperoxyisopropyl carbonate, di-t-butylperoxyisophthalate, t-butylperoxyallyl carbonate, t-amylperoxy-2-ethylhexanoate, di-t-butylperoxyhexahydro Telephthalate, di-t-butylperoxyaselate.
As described above, the binder resin A is a hybrid resin in which a vinyl-based polymer unit and a polyester unit are chemically bonded.

Therefore, it is necessary to carry out the polymerization using a compound that can react with any of the monomers of both resins (hereinafter referred to as “bireactive compound”). Examples of such a bireactive compound include compounds such as fumaric acid, acrylic acid, methacrylic acid, citraconic acid, maleic acid, and dimethyl fumarate in the monomer of the polycondensation resin and the monomer of the addition polymerization resin. Can be mentioned. Of these, fumaric acid, acrylic acid, and methacrylic acid are preferably used.

The amount of the bireactive compound added is preferably 5.0 parts by mass or more and 15.0 parts by mass or less, and 7.5 parts by mass or more and 12.0 by mass, based on 100 parts by mass of the total mass of the vinyl-based monomer. It is more preferably less than or equal to parts by mass.
In particular, when the proportion of the unit derived from the trimellitic acid is 30 mol% or more and 60 mol% or less and the addition amount of the bireactive compound is within the above range, the gel having a pseudo-crosslink point Further, since a gel component having a high degree of freedom in molecular motion can be obtained, the compatibility with the binder resin B becomes better, and the fine dot reproducibility, fine line reproducibility and high temperature offset resistance become good.

As a method for obtaining the hybrid resin, it can be obtained by reacting the raw material monomer of the vinyl polymer unit and the raw material monomer of the polyester unit at the same time or sequentially. For example, when the raw material monomer of the vinyl polymer unit is subjected to the polycondensation reaction and then the raw material monomer of the polyester unit is subjected to the polycondensation reaction, the molecular weight can be easily controlled.

In the binder resin A, the mass ratio of the vinyl polymer unit and the polyester unit (vinyl polymer unit / polyester unit) is 10/90 to 50/50, that is, the TOR insoluble matter Y and the THF insoluble matter X. It is preferable in controlling the ratio (Y / X), and 20/80 to 50/50 is more preferable.
In the present invention, the binder resin B is at least one aliphatic compound selected from the group consisting of an aliphatic monocarboxylic acid having 25 or more and 102 or less carbon atoms and an aliphatic monoalcohol having 25 or more and 102 or less carbon atoms at the terminal. It is important that the polyester resin is condensed.

The aliphatic compound used in the binder resin B is not particularly limited as long as it is an aliphatic monocarboxylic acid or an aliphatic monoalcohol having a specific carbon number. For example, any of the first grade, the second grade, and the third grade can be used.
Specific examples of the aliphatic monocarboxylic acid include palmitic acid, stearic acid, arachidic acid, behenic acid, and the like, as well as cerotic acid, heptacosanoic acid, montanic acid, melissic acid, laxelic acid, and tetracontane acid. Examples include pentacontane acid.
Examples of the aliphatic monoalcohol include behenyl alcohol, ceryl alcohol, melicyl alcohol, and tetracontanol.

Further, the aliphatic compound used in the binder resin B of the present invention can be any aliphatic monocarboxylic acid or aliphatic monoalcohol having the carbon number specified in the present invention. A modified wax produced through a modification step of producing a wax having a hydroxy group or a carboxy group from an aliphatic hydrocarbon-based wax (for example, an acid-modified aliphatic hydrocarbon-based wax or an alcohol-modified aliphatic hydrocarbon). System wax) can also be used.

If 40% by mass or more of the monovalent acid-modified wax or the alcohol-modified wax is contained in these modified waxes, the effect of the present invention may be impaired even if the mixture contains unmodified or polyvalent components. There is no.
Specific examples of the acid-modified aliphatic hydrocarbon wax and the alcohol-modified aliphatic hydrocarbon wax include the following.

As the acid-modified aliphatic hydrocarbon-based wax in the present invention, polyethylene or polypropylene modified with a monovalent unsaturated carboxylic acid such as acrylic acid is preferable. The melting point of the acid-modified wax can be controlled by the molecular weight.

Among the alcohol-modified aliphatic hydrocarbon-based waxes in the present invention, the primary alcohol-modified aliphatic hydrocarbon-based wax can be obtained, for example, by the following method. A method in which ethylene is polymerized using a Ziegler catalyst, and after the polymerization is completed, it is oxidized to form an alkoxide of a catalyst metal and polyethylene, and then hydrolyzed.
Further, the secondary alcohol-modified aliphatic hydrocarbon wax is obtained by, for example, liquid phase oxidation of the aliphatic hydrocarbon wax with a molecular oxygen-containing gas in the presence of boric acid and boric anhydride. can get.

Among the above-mentioned aliphatic compounds, the aliphatic compound condensed at the terminal of the binder resin B is an aliphatic monoalcohol, and a primary alcohol-modified aliphatic hydrocarbon-based wax is more preferable.
The method for condensing the aliphatic compound at the end of the binder resin B is not particularly limited. In a preferred embodiment, when the binder resin B is produced, it is preferable to simultaneously add an aliphatic compound to the monomer constituting the polyester unit of the binder resin B to carry out polycondensation.

The amount of the aliphatic compound added is preferably 1 part by mass or more and 10 parts by mass or less, and 3 parts by mass or more and 7 parts by mass or less, based on 100 parts by mass of the total mass of the monomers constituting the polyester. More preferred. By keeping the addition amount of the aliphatic compound within the above range, fog becomes good.

In the present invention, a mold release agent (wax) is contained in order to impart mold releasability to the toner.
Examples of the wax used in the present invention include the following. Fatty acid hydrocarbon waxes such as low molecular weight polyethylene, low molecular weight polypropylene, olefin copolymers, microcrystallin wax, paraffin wax, Fishertroph wax; oxidized wax of aliphatic hydrocarbon wax such as polyethylene oxide wax; carnauba wax , Waxes mainly composed of fatty acid esters such as behenyl behenate and montanic acid ester wax; and waxes obtained by deoxidizing a part or all of fatty acid esters such as deoxidized carnauba wax. In addition, saturated linear fatty acids such as palmitic acid, stearic acid and montanic acid; unsaturated fatty acids such as brandic acid, eleostearic acid and parinalic acid; stearyl alcohol, aralkyl alcohol, behenyl alcohol, carnaubil alcohol and ceryl alcohol. , Saturated alcohols such as melisyl alcohol; polyhydric alcohols such as sorbitol; fatty acid amides such as linoleic acid amide, oleic acid amide, lauric acid amide; methylene bisstearic acid amide, ethylene biscapric acid amide, ethylene bislaurin Saturated fatty acid bisamides such as acid amides and hexamethylene bisstearic acid amides; ethylene bisoleic acid amides, hexamethylene bisoleic acid amides, N, N'-diorail adipate amides, N, N'-diorail sebasic acid amides. Unsaturated fatty acid amides such as; aromatic bisamides such as m-xylene bisstearic acid amide, N, N'-distearylisophthalic acid amide; fats such as calcium stearate, calcium laurate, zinc stearate, magnesium stearate Group metal salts (generally called metal soaps); waxes obtained by grafting aliphatic hydrocarbon waxes with vinyl copolymer monomers such as styrene and acrylic acid; fatty acids such as behenic acid monoglyceride. And a partial esterified product of polyhydric alcohol; a methyl ester compound having a hydroxyl group obtained by hydrogenation of vegetable fats and oils and the like can be mentioned.

In the present invention, the viewpoint of ease of dispersion in the toner, high releasability, and affinity with the unit derived from the aliphatic compound condensed at the end of the binder resin B, which is a feature of the present invention. Therefore, hydrocarbon wax is particularly preferable.
For example, low molecular weight hydrocarbons obtained by radical polymerization of alkylene under high pressure or polymerized with Cheegler catalyst or metallocene catalyst under low pressure; Fischer-Tropsch wax synthesized from coal or natural gas; obtained by thermal decomposition of high molecular weight olefin polymer. Olefin polymer to be obtained; synthetic hydrocarbon wax obtained from the distillation residue of hydrocarbon obtained by the Age method from synthetic gas containing carbon monoxide and hydrogen, or synthetic hydrocarbon wax obtained by hydrogenating these is preferable. Further, those obtained by separating the hydrocarbon wax by the press sweating method, the solvent method, the use of vacuum distillation or the fractional crystallization method are more preferably used. In particular, a wax synthesized by a method not based on alkylene polymerization is preferable from the viewpoint of its molecular weight distribution.

The timing of adding the wax may be added at the time of manufacturing the toner or at the time of manufacturing the binder resin. In addition, one type of these waxes may be used alone, or two or more types may be used in combination. The wax is preferably added in an amount of 1 part by mass or more and 20 parts by mass or less, more preferably 1 part by mass or more and 10 parts by mass or less, based on 100 parts by mass of the binder resin. By adding 1 part by mass or more and 20 parts by mass or less, the mold release effect of the wax is effectively obtained, and the fog is also improved.
The melting point of the wax is preferably 60 ° C. or higher and 150 ° C. or lower, and more preferably 70 ° C. or higher and 140 ° C. or lower in order to further improve the dispersibility in the binder resin of the present invention.

The toner of the present invention may be a magnetic toner or a non-magnetic toner.
When the toner of the present invention is used as a non-magnetic toner, one or more of carbon black and any other conventionally known pigments and dyes can be used as a colorant, if necessary. The amount of the colorant added is preferably 0.1 part by mass or more and 60 parts by mass or less, and more preferably 0.5 parts by mass or more and 50 parts by mass or less with respect to 100 parts by mass of the binder resin.

When the toner of the present invention is used as a magnetic toner, magnetic iron oxide particles can be used. Specific examples thereof include magnetic iron oxide particles such as magnetite, maghemite and ferrite, and magnetic iron oxide particles containing other metal oxide particles. Conventionally, the following materials are known as materials for magnetic iron oxide particles. Iron tetraoxide (Fe ₃ O ₄ ), iron sesquioxide (γ-Fe ₂ O ₃ ), zinc iron oxide (ZnFe ₂ O ₄ ), iron oxide yttrium (Y ₃ Fe ₅ O ₁₂ ), iron cadmium oxide (Cd) ₃ Fe ₂ O ₄ ), iron gadrinium oxide (Gd ₃ Fe ₅ O ₁₂ ), iron copper oxide (CuFe ₂ O ₄ ), lead iron oxide (PbFe ₁₂ O ₁₉ ), nickel iron oxide (NiFe ₂ O ₄ ), oxidation Iron neodymium (NdFe ₂ O ₃ ), iron barium oxide (BaFe ₁₂ O ₁₉ ), iron magnesium oxide (MgFe ₂ O ₄ ), iron manganese oxide (MnFe ₂ O ₄ ), iron lantern oxide (LaFeO ₃ ), iron powder ( Fe) etc. Particularly suitable magnetic iron oxide particles are fine powders of iron tetraoxide or γ iron sesquioxide. Further, the above-mentioned magnetic iron oxide particles can be selectively used alone or in combination of two or more kinds.

The shape of the magnetic iron oxide particles used in the toner of the present invention is more preferably an octahedron having better dispersibility in the toner.
A charge control agent can be used in the toner of the present invention in order to stabilize its charge characteristics. The charge control agent varies depending on the type and the physical properties of other toner particle constituent materials, but in general, it is preferable that the toner contains 0.1 parts by mass or more and 10 parts by mass or less per 100 parts by mass of the binder resin. , 0.1 part by mass or more and 5 parts by mass or less is more preferable. As such a charge control agent, one or two or more kinds can be used depending on the type and application of the toner.

Examples of the charge control agent that controls the toner to be negatively charged include the following. Organic metal complex (monoazo metal complex; acetylacetone metal complex); metal complex or metal salt of aromatic hydroxycarboxylic acid or aromatic dicarboxylic acid. In addition, examples of those that control the toner to be negatively charged include aromatic mono and polycarboxylic acids and their metal salts and anhydrides; phenol derivatives such as esters and bisphenols. Of these, a metal complex or metal salt of an aromatic hydroxycarboxylic acid or an aromatic dicarboxylic acid that can obtain stable charging characteristics is particularly preferable.

A charge control resin can also be used. As the charge control resin, a polymer or copolymer having a sulfonic acid group, a sulfonic acid base or a sulfonic acid ester group can be used. As the polymer having a sulfonic acid group or the like, a polymer containing a sulfonic acid group-containing acrylamide-based monomer or a sulfonic acid group-containing methacrylamide-based monomer in a copolymerization ratio of 2% by mass or more is particularly preferable, and more preferably 5% by mass. It is a polymer containing the above. The polymer having a sulfonic acid group and the like includes a polymer having a sulfonic acid group, a sulfonic acid base or a sulfonic acid ester group.
The charge control resin is preferably used in combination with the above-mentioned charge control agent.

On the other hand, examples of the charge control agent for controlling the toner to be positively charged include the following. Modified products with niglosin and fatty acid metal salts; quaternary ammonium salts such as tributylbenzylammonium-1-hydroxy-4-naphthosulfonate, tetrabutylammoniumtetrafluoroborate, and analogs thereof; onium salts such as phosphonium salt and These lake pigments; triphenylmethane dyes and their lake pigments (as lake agents, phosphotung acid, phosphomolybdic acid, phosphotungene molybdic acid, tannic acid, lauric acid, gallic acid, ferricyanic acid, ferrocyanic compounds Etc.); Metal salts of higher fatty acids. In the present invention, one of these or a combination of two or more thereof can be used. Among these, charge control agents such as niglosin compounds and quaternary ammonium salts are preferable.

In the toner of the present invention, it is preferable to use a fluidity improver having a high ability to impart fluidity to the toner surface and having a smaller number average particle size of primary particles. As the fluidity improver, any agent can be used as long as the fluidity can be increased by externally adding to the toner when the fluidity can be increased before and after the addition. For example, the following can be mentioned. Fluorine-based resin powder such as vinylidene fluoride fine powder and polytetrafluoroethylene fine powder. Silica fine powder produced by a wet method, silica fine powder such as silica fine powder produced by a dry method, and treated silica fine powder obtained by surface-treating the silica fine powder with a treatment agent such as a silane coupling agent, a titanium coupling agent, or silicone oil. .. Titanium oxide fine powder; alumina fine powder, treated titanium oxide fine powder, treated alumina fine powder. The fluidity improver preferably has a specific surface area of 30 m ² / g or more, more preferably 50 m ² / g or more and 300 m ² / g or less, as measured by the BET method by nitrogen adsorption. The fluidity improver is preferably added in an amount of 0.01 parts by mass or more and 8.0 parts by mass or less, and more preferably 0.1 parts by mass or more and 4.0 parts by mass or less with respect to 100 parts by mass of the toner. ..

Other external additives may be added to the toner of the present invention, if necessary. For example, it is a resin fine particle or an inorganic fine particle that acts as a charge auxiliary agent, a conductivity imparting agent, an anti-caking agent, a mold release agent at the time of fixing a thermal roller, and an abrasive.
For example, examples of the abrasive include cerium oxide powder, silicon carbide powder, and strontium titanate powder. These external additives can be sufficiently mixed using a mixer such as a Henschel mixer to obtain the toner of the present invention.

(Toner manufacturing method)
The method for producing the toner (pulverization method) of the present invention is described below, but the method is not limited thereto.
For example, the binder resin A, the binder resin B and the mold release agent, and if necessary, other additives are sufficiently mixed with a mixer such as a Henschel mixer or a ball mill, and then a heating roll, a kneader, and an extruder are used. Melt and knead using a heat kneader such as. Then, after cooling and solidifying, pulverization and classification are performed to obtain toner. Further, if necessary, silica fine particles and the like can be sufficiently mixed with the toner by a mixer such as a Henschel mixer to obtain a toner to which a fluidity improver has been added.

Examples of the mixer include the following. Henschel Mixer (manufactured by Nippon Coke Industries Co., Ltd.); Super Mixer (manufactured by Kawata Co., Ltd.); Ribocorn (manufactured by Okawara Seisakusho Co., Ltd.); Nowter Mixer, Turbulizer, Cyclomix (manufactured by Hosokawa Micron Co., Ltd.); Spiral pin mixer (manufactured by Pacific Kiko Co., Ltd.); Ladyge mixer (manufactured by Matsubo Co., Ltd.).

Examples of the kneading machine include the following. KRC Kneader (manufactured by Kurimoto Iron Works Co., Ltd.); Bus Co Kneader (manufactured by Buss); TEM type extruder (manufactured by Toshiba Machine Co., Ltd.); TEX twin-screw kneader (manufactured by Japan Steel Works, Ltd.) PCM kneader (manufactured by Ikekai Co., Ltd.); three roll mill, mixing roll mill, kneader (manufactured by Inoue Seisakusho Co., Ltd.); Kneadex (manufactured by Japan Steel Works, Ltd.); MS type pressurized kneader, nidar ruder Moriyama Seisakusho Co., Ltd.); Banbury Mixer (Kobe Steel Works, Ltd.).

Examples of the crusher include the following. Counter jet mill, micron jet, innomizer (manufactured by Hosokawa Micron Co., Ltd.); IDS type mill, PJM jet crusher (manufactured by Nippon Pneumatic Industries Co., Ltd.); cross jet mill (manufactured by Kurimoto Iron Works Co., Ltd.); (Manufactured by Nisso Engineering Co., Ltd.); SK Jet O Mill (manufactured by Seishin Co., Ltd.); Cryptron (manufactured by Kawasaki Heavy Industries, Ltd.); Turbo Mill (manufactured by Turboe Co., Ltd.); Super Rotor (manufactured by Nisshin Engineering Co., Ltd.) Made by Co., Ltd.).

Examples of the classifier include the following. Classy, Micron Classifier, Spedic Classifier (manufactured by Seishin Co., Ltd.); Turbo Classy Fire (manufactured by Nisshin Engineering Co., Ltd.); Micron Separator, Turboplex (ATP), TSP Separator, TTSP Separator (Hosokawa Micron (Hosokawa Micron) Co., Ltd.); Elbow Jet (manufactured by Nittetsu Mining Co., Ltd.), Dispersion Separator (manufactured by Nippon Pneumatic Co., Ltd.); YM Microcut (manufactured by Yasukawa Shoji Co., Ltd.).

Examples of the sieving device used for sieving the coarse particles include the following. Ultrasonic (manufactured by Koei Sangyo Co., Ltd.); Resonase sieve, gyro shifter (manufactured by Tokuju Kosakusho Co., Ltd.); Vibrasonic System (manufactured by Dalton Co., Ltd.); Soniclean (manufactured by Shinto Kogyo Co., Ltd.); Turbo Screener (manufactured by Turboe Co., Ltd.); Microshifter (manufactured by Makino Sangyo Co., Ltd.); Circular vibrating sieve.
Next, a method for measuring each physical property according to the present invention will be described.

(1) Measurement of THF insoluble content Weigh 1.0 g of the binder resin (W1 g), put it in a cylindrical filter paper (for example, No. 86R size 28 x 100 mm manufactured by Toyo Filter Paper Co., Ltd.), put it in a Soxhlet extractor, and 200 mL of THF as a solvent. Is extracted for 16 hours. At this time, the extraction is performed at a reflux rate such that the extraction cycle of the solvent is once every about 4 to 5 minutes. After the extraction is completed, the cylindrical filter paper is taken out, vacuum dried at 40 ° C. for 8 hours, and the extraction residue is weighed (W2 g).
Then, the THF insoluble content X (mass%) is obtained from the following formula.
THF insoluble content X (mass%) = (W2 / W1) × 100

(2) Measurement of TOR insoluble matter The amount of insoluble matter by re-extracting THF insoluble matter X is measured as follows. First, using a cylindrical filter paper containing the extraction residue (W2 g) in THF, Soxhlet extraction is performed again with 200 mL of toluene for 16 hours. At this time, the extraction is performed at a reflux rate such that the extraction cycle of the solvent is once every about 4 to 5 minutes. After the extraction is completed, the cylindrical filter paper is taken out, vacuum dried at 40 ° C. for 8 hours, and the toluene extraction residue is weighed (W3 g).
The TOR insoluble matter Y (mass%) is calculated from the following formula.
TOR insoluble matter Y (mass%) = (W3 / W1) × 100
The ratio (Y / X) of the TOR insoluble content Y (mass%) and the THF insoluble content X (mass%) is calculated from the value obtained by the above method.

(3) Softening point of the binding resin The softening point of the binding resin is attached to the device using a constant load extrusion type thin tube rheometer "Flow Tester CFT-500D" (manufactured by Shimadzu Corporation). Measure according to the manual.
In this device, while applying a constant load from the top of the measurement sample with a piston, the temperature of the measurement sample filled in the cylinder is raised and melted, and the melted measurement sample is pushed out from the die at the bottom of the cylinder, and the amount of piston drop at this time. Obtain a flow curve showing the relationship between and temperature.

In the present invention, the softening point is the "melting temperature in the 1/2 method" described in the manual attached to the "flow characteristic evaluation device flow tester CFT-500D". The melting temperature in the 1/2 method is calculated as follows. First, 1/2 of the difference between the piston descent amount Smax at the time when the outflow ends and the piston descent amount Smin at the time when the outflow starts is obtained (this is defined as X. X = (Smax-Smin) / 2). Then, the temperature of the flow curve when the amount of descent of the piston is the sum of X and Smin in the flow curve is the melting temperature in the 1/2 method.

For the measurement sample, 1.0 g of the binder resin was compression-molded in an environment of 25 ° C. using a tablet molding compressor (NT-100H, manufactured by NPA System Co., Ltd.) at about 10 MPa for about 60 seconds. , A columnar one having a diameter of about 8 mm is used.
The measurement conditions for the CFT-500D are as follows.
Test mode: Hot compress start temperature: 30 ° C
Achieved temperature: 200 ° C
Measurement interval: 1.0 ° C
Temperature rise rate: 4.0 ° C / min Piston cross-sectional area: 1.000 cm ²
Test load (piston load): 10.0 kgf (0.9807 MPa)
Preheating time: 300 seconds Die hole diameter: 1.0 mm
Die length: 1.0 mm

(4) Measurement of Toner Weight Average Particle Size (D4) Toner weight average particle size (D4) can be measured with 25,000 effective measurement channels using the following precision particle size distribution measuring device and the following dedicated software. Measure on the channel, analyze the measurement data, and calculate.
-Precise particle size distribution measuring device "Coulter Counter Multisizer 3" by pore electrical resistance method equipped with a 100 μm aperture tube (registered trademark, manufactured by Beckman Coulter Co., Ltd.)
-Attached dedicated software for setting measurement conditions and analyzing measurement data "Beckman Coulter Multisizer 3 Version 3.51" (manufactured by Beckman Coulter Co., Ltd.)
The electrolytic aqueous solution used for the measurement should be one in which special grade sodium chloride is dissolved in ion-exchanged water so that the concentration becomes about 1% by mass, for example, "ISOTON II" (manufactured by Beckman Coulter, Inc.). Can be done.

Before performing measurement and analysis, set the dedicated software as follows.
In the dedicated software "Change standard measurement method (SOM) screen", set the total count number in the control mode to 50,000 particles, measure once, and set the Kd value to "standard particles 10.0 μm" (Beckman Coulter (Beckman Coulter) The value obtained by using (manufactured by Co., Ltd.) is set. By pressing the threshold / noise level measurement button, the threshold and noise level are automatically set. Also, set the current to 1600 μA, the gain to 2, and the electrolyte to ISOTON II, and check the flash of the aperture tube after measurement.
On the "pulse to particle size conversion setting screen" of the dedicated software, the bin spacing is set to logarithmic particle size, the particle size bin is set to 256 particle size bins, and the particle size range is set from 2 μm to 60 μm.
The specific measurement method is as follows.

(1) Put about 200 mL of the electrolytic aqueous solution in a glass 250 mL round bottom beaker dedicated to Multisizer 3, set it on a sample stand, and stir the stirrer rod counterclockwise at 24 rpm. Then, the dirt and air bubbles in the aperture tube are removed by the "aperture flash" function of the analysis software.
(2) About 30 mL of the electrolytic aqueous solution is placed in a 100 mL flat-bottomed beaker made of glass, and about 0.3 mL of the following diluent is added as a dispersant.
-Diluted solution: "Contaminone N" (10% by mass aqueous solution of neutral detergent for cleaning pH 7 precision measuring instruments consisting of nonionic surfactant, anionic surfactant, and organic builder, manufactured by Wako Pure Chemical Industries, Ltd. ) Was diluted 3 times by mass with ion-exchanged water.

(3) Two oscillators with an oscillation frequency of 50 kHz are built in with the phase shifted by 180 degrees, and the water tank of the ultrasonic disperser "Ultrasonic Dispersion System Tetora 150" (manufactured by Nikkaki Bios Co., Ltd.) with an electrical output of 120 W. A predetermined amount of ion-exchanged water is put therein, and about 2 mL of the contaminanton N is added into the water tank.
(4) The beaker of (2) is set in the beaker fixing hole of the ultrasonic disperser, and the ultrasonic disperser is operated. Then, the height position of the beaker is adjusted so that the resonance state of the liquid level of the electrolytic aqueous solution in the beaker is maximized.

(5) With the electrolytic aqueous solution in the beaker of (4) irradiated with ultrasonic waves, about 10 mg of toner is added little by little to the electrolytic aqueous solution and dispersed. Then, the ultrasonic dispersion processing is continued for another 60 seconds. In ultrasonic dispersion, the water temperature in the water tank is appropriately adjusted to be 10 ° C. or higher and 40 ° C. or lower.
(6) The electrolytic aqueous solution (5) in which toner is dispersed is dropped onto the (1) round bottom beaker installed in the sample stand using a pipette, and the measured concentration is adjusted to about 5%. Then, the measurement is performed until the number of measurement particles reaches 50,000.
(7) The measurement data is analyzed by the dedicated software attached to the device, and the weight average particle size (D4) is calculated. The "average diameter" of the analysis / volume statistical value (arithmetic mean) screen when the graph / volume% is set by the dedicated software is the weight average particle diameter (D4).

Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto. Unless otherwise specified, the number of copies and% of Examples and Comparative Examples are all based on mass.

<Production example of binder resin A-1>
(Prescription of polyester unit)
-Bisphenol A ethylene oxide (2.2 mol adduct): 100.0 mol parts-Terephthalic acid: 63.0 mol parts-Trimellitic anhydride: 37.0 mol parts 60 parts by mass of the monomer mixture constituting the polyester unit The parts were mixed in a 4-port flask, and a decompression device, a water separator, a nitrogen gas introduction device, a temperature measuring device, and a stirring device were attached and stirred at 160 ° C. in a nitrogen atmosphere.

The following materials were added dropwise thereto from the dropping funnel over 4 hours, and the vinyl-based monomer was reacted at 160 ° C. for 5 hours.
Vinyl-based monomers constituting the vinyl-based polymer unit (40.0 parts by mass of styrene and 60.0 parts by mass of 2-ethylhexyl acrylate) 40 parts by mass Acrylic acid as a bireactive compound 4.0 parts by mass Bencoyl peroxide as a polymerization initiator 1 part by mass

Then, the temperature is raised to 210 ° C., 0.2 parts by mass of titanium tetrabutoxide is added to the total amount of the monomer components constituting the polyester unit, and a polycondensation reaction is carried out until a desired THF insoluble component X is obtained. It was. After completion of the reaction, the mixture was taken out from the container, cooled and pulverized to obtain a binder resin A-1.
The THF insoluble content X of the binder resin A-1 was 35% by mass, the TOR insoluble content Y was 10% by mass, and Y / X was 0.29.

<Production examples of binder resins A-2 to A-10 and A-12 >
Bending resins A-2 to A-10 and A-12 were obtained according to the production examples of the binder resin A-1, except that the acid component and the bireactive compound were changed as shown in Table 1.

<Production example of binder resin B-1>
-Bisphenol A ethylene oxide (2.2 mol adduct): 33.0 mol parts-Bisphenol A propylene oxide (2.2 mol adduct): 40.0 mol parts-Ethylene glycol: 27.0 mol parts-terephthalic acid : 100.0 mol parts

100 parts by mass of the monomer and 5 parts by mass of the primary alcohol-modified wax constituting the polyester unit were mixed in a 5 liter autoclave together with 500 ppm of titanium tetrabutoxide. The primary alcohol-modified wax is a wax having an average carbon number of 50 in which one end of polyethylene is modified with a hydroxy group.
A reflux condenser, a moisture separator, an N ₂ gas introduction tube, a thermometer and a stirrer were attached thereto, and a polycondensation reaction was carried out at 230 ° C. while introducing N ₂ gas into the autoclave. The reaction time was adjusted so as to reach a desired softening point, and after the reaction was completed, the mixture was taken out of the container, cooled and pulverized to obtain a binder resin B-1.

<Production example of binder resins B-2 to B-12>
The carbon number of the aliphatic compound, the content of the aliphatic compound, and the desired softening point were changed as shown in Table 2. Further, as alcohol components, bisphenol A ethylene oxide (2.2 mol adduct) (described as BPA-EO in the table) and bisphenol A propylene oxide (2.2 mol adduct) (in the table, described as BPA-PO). ) And ethylene glycol (denoted as EG in the table) were changed as shown in Table 2. Except for these changes, binder resins B-2 to B-12 were obtained according to the production example of binder resin B-1.
The primary alcohol-modified wax used was a wax obtained by modifying one end of polyethylene having the carbon number shown in Table 2 with a hydroxy group, and the acid-modified wax was a polyethylene having the carbon number shown in Table 2. A wax obtained by modifying the wax with acrylic acid was used.

<Example 1>
(Manufacturing example of toner No. 1)
-Bundling resin A-1: 70 parts by mass-Bundling resin B-1: 30 parts by mass-Fishertro push wax (melting point 105 ° C): 5 parts by mass-Magnetic iron oxide particles a: 90 parts by mass (number average grains) Diameter 0.20 μm, Hc (coercive force) = 10 kA / m, σs (saturation magnetization) = 83 Am ² / kg, σr (residual magnetization) = 13 Am ² / kg)
-Aluminum compound of 3,5-di-tert-butylsalicylic acid: 1 part by mass

The above materials were premixed with a Henschel mixer and then melt-kneaded with a twin-screw kneading extruder. At this time, the residence time was controlled so that the temperature of the kneaded resin became 150 ° C. The obtained kneaded product is cooled, roughly crushed with a hammer mill, and then crushed with a turbo mill, and the obtained finely crushed powder is classified by a multi-division classifier (Nittetsu Mining Co., Ltd. elbow jet classification) using the Coanda effect. The toner was classified using a machine) to obtain a toner having a weight average particle diameter (D4) of 7 μm. With respect to 100 parts by mass of the toner, 1.0 part by mass of hydrophobic silica fine powder (specific surface area measured by nitrogen adsorption by BET method is 140 m ² / g, hexamethyldisilazane treatment as hydrophobic treatment) and strontium titanate (strontium titanate) Volume average particle size 1.6 μm) 3.0 parts by mass was externally mixed. Then, the toner No. is sieved with a mesh having an opening of 150 μm. I got 1. Toner No. Regarding 1, the following evaluation was performed. The evaluation results are shown in Table 4.

The image quality was evaluated by modifying the process speed of a commercially available digital copying machine (imageRUNNER 4051, manufactured by Canon Inc.) to 311 mm / sec. As the evaluation paper, CS-680 (68.0 g / m ² paper, A4) (sold by Canon Marketing Japan Inc.) was used. Further, as the output image in the repeated use test, an image having a printing rate of 5% was used.

<Evaluation of minute dot reproducibility>
To evaluate the reproducibility of minute dots, after outputting 10,000 images in a high temperature and high humidity (temperature 30 ° C, relative humidity 80%) environment, leave it to stand for 48 hours or more in a high temperature and high humidity environment to sufficiently absorb moisture. Printing was performed using the evaluation paper. The image was judged by the following criteria using an isolated 1-dot halftone chart.

(Evaluation criteria)
A: The dots are faithfully reproduced.
B: A slight change in dot size can be visually confirmed.
C: The change in dot size can be visually confirmed, but it is a slight level.
D: The change in dot size can be clearly confirmed visually.

<Thin line reproducibility>
The fine line reproducibility was evaluated by outputting 10,000 images in a high temperature and high humidity (temperature 30 ° C, relative humidity 80%) environment, and then printing a grid pattern with a line width of 3 pixels on the entire surface of A4 paper ( (Print area ratio 4%) was printed and evaluated according to the following evaluation criteria. The line width of 3 pixels is theoretically 127 μm. The line width of the image was measured with a microscope VK-8500 (manufactured by KEYENCE CORPORATION). When 5 points were randomly selected and the line width was measured and the average value of 3 points excluding the minimum value and the maximum value was d (μm), the following L was defined as the fine line reproducibility index.
L (μm) = | 127-d |
L defines the difference between the theoretical line width of 127 μm and the line width d on the output image. Since d may be larger than 127 or smaller than 127, it is defined as the absolute value of the difference. The smaller L is, the better the fine line reproducibility is shown.

(Evaluation criteria)
A: L is 5 μm or more and less than 10 μm.
B: L is 10 μm or more and less than 15 μm.
C: L is 15 μm or more and less than 20 μm.
D: L is 20 μm or more.

<Fog>
For fog, a solid white image was evaluated according to the following criteria after enduring 10,000 sheets in a low temperature and low humidity (temperature 15 ° C., relative humidity 10%) environment. The measurement was performed using a reflectance meter (Reflectometer model TC-6DS (with Tokyo Denshoku)), and the worst value of the reflection density on the white background after image formation was Ds, and the reflection average of the transfer material before image formation. The fog was evaluated by using Dr as the concentration and Dr-Ds as the amount of fog. Therefore, the smaller the value, the more the fog is suppressed.

(Evaluation criteria)
A: Fog amount is less than 1.0 B: Fog amount is 1.0 or more and less than 1.5 C: Fog amount is 1.5 or more and less than 2.0 D: Fog amount is 2.0 or more

<High temperature offset resistance>
The fuser of a commercially available digital copier (imageRUNNER 4051, manufactured by Canon Inc.) was taken out and modified so that it could operate outside the copier and the fixing temperature and process speed could be set arbitrarily. Using this external fuser, the high temperature offset resistance was evaluated in an environment of normal temperature and humidity (N / N: temperature 23.5 ° C., relative humidity 60%). As the evaluation paper, CS-680 (68.0 g / m ² paper, A4) (sold by Canon Marketing Japan Inc.) was used. As the evaluation image, an unfixed image was prepared in which the entire area 5 cm from the tip was placed horizontally and the halftone image density was 0.6, and the other areas were solid white. The unfixed image was obtained by modifying the imageRUNNER 4051 so that an unfixed image could be obtained. The temperature of the external fuser was adjusted every 10 ° C. in the temperature range of 220 to 240 ° C., the process speed was set to 100 mm / sec, the nip width was set to 13 mm, and the unfixed image was passed. The level of offset appearing on the white background at this time was visually confirmed.

(Evaluation criteria)
A: No offset occurs.
B: At a fixing temperature of 240 ° C., a thin offset was generated at the end.
C: At a fixing temperature of 230 ° C., a thin offset was generated at the end.
D: At a fixing temperature of 220 ° C., a thin offset was generated at the end.

<Low temperature fixability evaluation>
For the evaluation of low temperature fixability, the process speed of a commercially available digital copier (imageRUNNER 4051 Canon Inc.) was modified to 311 mm / sec, and the temperature was 23 ° C and the relative humidity was 50%. went. As the evaluation paper, OCE RED LABEL (80 g / m ² paper, A3) was used. Nine points of 20 mm × 20 mm size halftone patches were evenly written on A3 paper, and the development bias was set so that the image density was 0.6. Next, the temperature control of the fuser was changed to a desired temperature control, and after cooling until the temperature of the pressurizing roller of the fuser became 23 ° C. or lower, 20 sheets were continuously passed on one side. As a sample for low temperature fixability evaluation, the first, third, fifth, tenth, and twentieth sheets were sampled, and a load of 4.9 kPa was applied to the obtained fixed image, and the result was made of Sylbon paper. The fixed image was rubbed back and forth 5 times. Of the 5 samples, the worst value of the average value of the image density reduction rates at the 9 points before and after rubbing was defined as the image density reduction rate at each temperature. The fixing temperature is changed from 170 ° C. to 210 ° C. every 5 ° C., and the image density reduction rate is sequentially measured. The fixing temperature at which the image density reduction rate becomes 20% or less for the first time is set as the fixing start temperature, and the temperature is low based on this. The fixability was evaluated. For example, when the fixing temperature was 170 ° C. and the image density reduction rate was more than 20%, but the fixing temperature was 175 ° C. and the image density reduction rate was 20% or less, 175 ° C. was set as the fixing start temperature.
The image density was measured with a Macbeth densitometer (RD-914; manufactured by Macbeth) using an SPI auxiliary filter.

(Evaluation criteria)
A: The fixing start temperature is less than 180 ° C.
B: The fixing start temperature is 180 ° C. or higher and lower than 190 ° C.
C: The fixing start temperature is 190 ° C. or higher and lower than 200 ° C.
D: The fixing start temperature is 200 ° C. or higher.

<Preservation>
For the evaluation of storage stability, 5 g of toner was placed in a 50 cc resin cup and allowed to stand at a temperature of 50 ° C. and a relative humidity of 50% for 3 days, and the presence or absence of agglomerates was examined and evaluated.

(Evaluation criteria)
A: No agglutination
B: A slight agglutination is generated and can be dissolved by light shaking.
C: A slight agglutination is generated and can be loosened by pressing it lightly with a finger.
D: Aggregates are generated and do not collapse even when lightly pressed with a finger. In each of the above evaluation items, all the toners of Example 1 were ranked A.

<Examples 2 to 13>
(Manufacturing example of toner Nos. 2 to 13)
In Example 1, the toner No. 1 was obtained in the same manner as in Example 1 except that the type of the binder resin was changed as shown in Table 3. 2 to 13 were manufactured. Then, the toner No. 2 to 13 were evaluated in the same manner as in Example 1. The evaluation results are shown in Table 4.

All of Examples 1 to 7 were ranked A or B, and good results were obtained.
Examples 8 and 9 were ranked C in low temperature fixability and storage stability. It is considered that the ethylene glycol acting as a soft segment lowered the fixing strength and the storage stability of the toner by using a large amount of ethylene glycol in the alcohol component of the binder resin B.
In Examples 10 and 11, fog was C rank. In the binder resin B, the amount of the aliphatic compound condensed at the terminal is appropriate, and it is considered that the effect of wax dispersibility cannot be obtained if the amount is too large or too small.
In Examples 12 and 13, the fine dot reproducibility and the fine line reproducibility were C rank. The values of Y / X representing the crosslinked structure of the THF insoluble component of the binder resin A are 0.60 and 0.11. Therefore, it is considered that the compatibility with the binder resin B is slightly deteriorated, which affects the fine dot reproducibility and the fine line reproducibility.

<Comparative Examples 1 to 5>
In Example 1, the toner No. 1 was obtained in the same manner as in Example 1 except that the type of the binder resin was changed as shown in Table 5. 14-18 were manufactured. Then, the toner No. 14 to 18 were evaluated in the same manner as in Example 1. The evaluation results are shown in Table 6.

In Comparative Example 1, since the polyester resin in which the aliphatic compound was condensed at the end was not used as the binder resin B, the dot reproducibility and the fine line reproducibility were ranked D. It is considered that this is because the compatibility between the binder resin A and the binder resin B has decreased.
On the other hand, in Comparative Example 2, a polyester resin in which an aliphatic compound is condensed at the terminal is used as the binder resin B, but the Y / X of the binder resin A is 0.65, and the crosslinks are chemically bonded. Since the binder resin has many points, the fine dot reproducibility and the fine line reproducibility were D rank. It is considered that this is because the compatibility between the binder resin A and the binder resin B has decreased.

Claims (2)

A toner having toner particles containing a binder resin and a mold release agent.
The binding resin contains a binding resin A and a binding resin B.
The binder resin A is
It is a hybrid resin in which a vinyl polymer unit and a polyester unit are chemically bonded.
Containing THF insoluble X, which is not extracted by 16 hours Soxhlet extraction with tetrahydrofuran (THF),
The content of the THF insoluble content X is 25% by mass or more and 45% by mass or less based on the mass of the binder resin A.
The THF insoluble component X contains a TOR insoluble component Y that is not extracted by Soxhlet extraction using toluene (TOR) for 16 hours.
The content (mass%) of the TOR insoluble matter Y based on the mass of the binder resin A and the content (mass%) of the THF insoluble content X based on the mass of the binder resin A. The ratio (content of TOR insoluble matter Y / content of THF insoluble matter X) is 0.10 or more and 0.60 or less.
The binder resin B is softened by condensing at least one aliphatic compound selected from the group consisting of an aliphatic monocarboxylic acid having 25 or more and 102 or less carbon atoms and an aliphatic monoalcohol having 25 or more and 102 or less carbon atoms at the terminal. A toner characterized by being a polyester resin having a point of 80 ° C. or higher and 110 ° C. or lower . The toner according to claim 1, wherein the binder resin A has a ratio of the unit derived from trimellitic acid of 30 mol% or more and 60 mol% or less with respect to the total number of moles of the acid component constituting the polyester unit.