JP2017032681A - toner - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a toner that is excellent in charge rising property where the amount of electrical charge is instantaneously held, has the optimal amount of electrical charge, and maintains stable image density even after a large number of printouts from the beginning, in various environments from a low-temperature and low-humidity environment to a high-temperature and high-humidity environment.SOLUTION: There is provided a toner comprising toner particles containing a resin, polyester resin A, and a polymer having a specific monomer unit, wherein the polyester resin A contains an isosorbide unit, and the content of the polyester resin A is 1.00 parts by mass or more and 40.00 parts by mass or less based on 100.00 parts by mass of the resin.SELECTED DRAWING: None

Description

  The present invention relates to a toner used in an electrophotographic method, an electrostatic recording method, a magnetic recording method, and a toner jet method.

Conventionally, in image forming methods such as electrophotography and electrostatic printing, charged toner particles are configured to develop an electrostatic latent image on a drum by an electrostatic force corresponding to a potential difference on the photosensitive drum. Yes. At this time, the charging of the toner is specifically generated by friction between the toner and the toner, or between the toner and the carrier, and further between the toner and the regulating blade. For this reason, it is essential to control the chargeability of the toner.
On the other hand, in the recent market, LED and laser beam printers are the mainstream printer devices, and the direction of technology is higher resolution, that is, the conventional 300, 400 dpi has become 600, 1200 dpi. Accordingly, with this development, higher definition is required. Therefore, there is a demand for a toner that can maintain good chargeability.
From the background as described above, studies for improving the chargeability of the toner have been actively conducted. In order to control the chargeability of the toner, the triboelectric charge characteristic of the binder resin itself can be used, but generally a charge control agent that imparts chargeability is added. .
Conventional charge control agents include metal complexes of monoazo dyes, nitrohumic acid and its salts, salicylic acid, alkylsalicylic acid, dialkylsalicylic acid, naphthoic acid, dicarboxylic acid and other metal compounds, boron compounds, urea compounds, silicon compounds, calix There are arenes, sulfonated copper phthalocyanine pigments, chlorinated paraffins and the like.
Among the charge control agents including these dyes and pigments, metal compounds such as salicylic acid, alkylsalicylic acid, dialkylsalicylic acid, naphthoic acid, and dicarboxylic acid can give sufficient chargeability to the toner. Furthermore, since the rising of the charge is good, high performance as a charge control agent can be exhibited.
However, most of these charge control agents cause thermal degradation of the charge control agent itself during the production of the toner, decomposition due to the influence of other materials, and the like, resulting in a decrease in chargeability. In addition, in a high-humidity environment, the toner tends to absorb moisture, so the chargeability of the toner tends to decrease, and some of the functions cannot be sufficiently exhibited.
On the other hand, a charge control agent using a copolymer of vinyl aromatic hydrocarbon, (meth) acrylate and sulfonic acid group-containing (meth) acrylamide has been disclosed (Patent Document 1).
Since this charge control agent is a polymer, it is chemically stable. Furthermore, since the charge generation capability is high, it is excellent in the rise of charge that the amount of charge can be held instantaneously when friction charging is performed. However, the actual situation is that the charge amount becomes too high and it is difficult to maintain a constant charge amount.
In addition, a technique for improving the chargeability of the toner by improving the resin component used in the toner has been proposed. A toner having excellent electrical characteristics has been proposed by using a polyester resin obtained by polycondensation of a carboxylic acid component and a polyhydric alcohol component derived from a sugar alcohol (Patent Document 2).
As one of the polyhydric alcohol components, an isosorbide unit is used, and fogging can be improved. However, as a result of intensive studies, the present inventors have found that the image density is reduced due to a decrease in chargeability of the toner in a high humidity environment. This is considered to be a decrease in the charge amount due to the moisture absorption characteristic peculiar to isosorbide.
Further, a toner that improves the fixability, storage stability, and durability of the toner by using a polyester resin having an isosorbide unit has been proposed (Patent Documents 3 and 4).
Also, a toner using a polyester resin having an isosorbide unit has been proposed from the viewpoint of environmental friendliness (Patent Document 5).
Certainly, these toners have excellent fixability and storage stability. However, since the toner has an isosorbide unit as the main resin as described above, the moisture absorption characteristics of the toner are increased, and the toner The charge amount tends to decrease.
For the above reasons, there is an urgent need for a toner having excellent image quality with excellent chargeability and stable image density in various environments ranging from low temperature and low humidity to high temperature and high humidity. .

Japanese Patent No. 3724539 JP 2012-145600 A JP 2012-233037 A JP 2012-255083 A Special table 2012-521567 gazette

  The present invention has an excellent charge start-up property in which the charge amount is instantaneously maintained in various environments ranging from a low temperature and low humidity to a high temperature and high humidity environment, and has an optimum charge amount. The present invention provides a toner having a stable image density even if it is out.

The present invention
A toner having toner particles containing a resin, a polyester resin A, and a polymer having a monomer unit represented by the following formula (1):
The polyester resin A contains an isosorbide unit represented by the following formula (2),
A toner wherein the content of the polyester resin A is 1.00 parts by mass or more and 40.00 parts by mass or less with respect to 100.00 parts by mass of the resin.

［前記式（１）中、Ｘは置換基を有していてもよい２価の脂肪族基又は置換基を有していてもよいフェニレン基を示し、Ｒ_１は水素原子、アルカリ金属、炭素数１以上４以下のアルキル基、又はフェニル基を示し、Ｒ_２は水素原子又はメチル基を示す。］

[In the formula (1), X represents a divalent aliphatic group which may have a substituent or a phenylene group which may have a substituent, and R ₁ represents a hydrogen atom, an alkali metal, carbon. An alkyl group having a number of 1 or more and 4 or less, or a phenyl group is shown, and R ₂ is a hydrogen atom or a methyl group. ]

  According to the present invention, in various environments ranging from low temperature and low humidity to high temperature and high humidity environment, the charge amount can be instantaneously maintained, and it has an optimum charge amount. Thus, a toner having a stable image density can be provided even when the printout is performed.

Enlarged view of the developing section of an electrophotographic apparatus Cross section of electrophotographic device

The toner of the present invention is
A toner having toner particles containing a resin, a polyester resin A, and a polymer having a monomer unit represented by the following formula (1):
The polyester resin A contains an isosorbide unit represented by the following formula (2),
The content of the polyester resin A is 1.00 parts by mass or more and 40.00 parts by mass or less with respect to 100.00 parts by mass of the resin.

［前記式（１）中、Ｘは置換基を有していてもよい２価の脂肪族基又は置換基を有していてもよいフェニレン基を示し、Ｒ_１は水素原子、アルカリ金属、炭素数１以上４以下のアルキル基、又はフェニル基を示し、Ｒ_２は水素原子又はメチル基を示す。］

[In the formula (1), X represents a divalent aliphatic group which may have a substituent or a phenylene group which may have a substituent, and R ₁ represents a hydrogen atom, an alkali metal, carbon. An alkyl group having a number of 1 or more and 4 or less, or a phenyl group is shown, and R ₂ is a hydrogen atom or a methyl group. ]

In the present invention, the toner particles contain a resin, a polymer having a monomer unit represented by the above formula (1), and a polyester resin A having an isosorbide unit represented by the above formula (2). Here, the monomer unit refers to a form in which the monomer substance in the polymer has reacted.
Moreover, content of this polyester resin A is 1.00 mass part or more and 40.00 mass parts or less with respect to 100.00 mass parts of resin. By setting the content of the polyester resin A in the above range, the chargeability of the toner can be improved.
Specifically, the rising property of charging of the toner is improved and the charge amount of the toner can be optimized. As a result, it is possible to stably provide a high image density even when printing is performed on a large number of sheets from the beginning using the toner of the present invention.
In the present invention, the portion having a sulfonic acid group and an amide bond in the monomer unit represented by the formula (1) and the oxygen atom portion of the isosorbide unit represented by the formula (2) interact with each other at the molecular level. Therefore, when the toner is triboelectrically charged, an amount of charge can be instantaneously obtained at the monomer unit site represented by the formula (1), and an appropriate charge leakage action can be performed at the isosorbide unit site represented by the formula (2). Is called. As a result, the present inventors consider that the charge amount in the toner can be optimized.

In the present invention, the toner particles contain a polymer having a monomer unit represented by the above formula (1) (hereinafter also simply referred to as a polymer).
By including the polymer in the toner particles, the rising property of charging of the toner is improved. This is because, as described above, since the monomer unit represented by the formula (1) contains a sulfonic acid group, frictional charging can be instantaneously performed at the sulfonic acid group site.
On the other hand, since sulfonic acid groups tend to retain a high charge amount, it is difficult to control the charge amount. However, in the present invention, the charge amount of the toner can be maintained at an appropriate value by coexisting the polyester resin A having the isosorbide unit represented by the formula (2).
The content ratio of the monomer unit represented by the formula (1) in the polymer used in the present invention is preferably 0.50 mol% or more and 20.00 mol% or less based on the total monomer units constituting the polymer. More preferably, it is 0.50 mol% or more and 10.00 mol% or less.
When the content ratio of the monomer unit represented by the formula (1) is less than 0.50 mol%, the charge rising property tends to be lowered, and the image density at the initial stage of development tends to be lowered.
On the other hand, when the content ratio exceeds 20.00 mol%, the moisture absorption property of the toner becomes high, and the charge amount tends to decrease under high temperature and high humidity, and the image density tends to decrease.

In the present invention, the content of the polymer is preferably 0.10 parts by mass or more and 10.00 parts by mass or less, and 0.50 parts by mass or more and 10.00 parts by mass with respect to 100.00 parts by mass of the resin. It is more preferable that the amount is not more than parts.
When the content of the polymer is less than 0.10 parts by mass, the charge rising property of the toner tends to be lowered. On the other hand, when the content exceeds 10.00 parts by mass, the polarity of the resin increases and the compatibility with the polyester resin A tends to decrease.
As a feature of the monomer unit represented by the formula (1), a sulfonic acid group and an amide group are adjacent to each other at a relatively short distance in the unit. Therefore, it is easy to interact with oxygen atoms in the isosorbide unit contained in the polyester resin A. Therefore, it is possible to improve the rising property of charging of the toner and maintain an appropriate charge amount over a long period of time.
In this invention, it is preferable that the glass transition temperature (Tg) of this polymer is 40 degreeC or more and 90 degrees C or less. The peak average molecular weight of the polymer is preferably 10,000 or more and 30,000 or less, and the weight average molecular weight of the polymer is preferably 25,000 or more and 40,000 or less.
When the polymer is used, preferred charging characteristics can be enjoyed without affecting the thermal characteristics required of the toner particles.
Further, since the polymer contains a sulfonic acid group, the dispersibility of the polymer in the resin, and the dispersibility of the colorant used as necessary, improve the coloring power, transparency, And the chargeability is remarkably improved.

In the present invention, in the above formula (1), X represents a divalent aliphatic group which may have a substituent or a phenylene group which may have a substituent.
The divalent aliphatic group which may have a substituent is preferably an alkanediyl group having 2 or more and 6 or less carbon atoms which may have a substituent. An unsubstituted alkanediyl group having 2 to 6 carbon atoms is more preferable.
The phenylene group which may have a substituent is preferably a p-phenylene group.
R ₁ represents a hydrogen atom, an alkali metal, an alkyl group having 1 to 4 carbon atoms, or a phenyl group. On the other hand, R ₂ represents a hydrogen atom or a methyl group.
Monomers that give rise to the monomer unit represented by the above formula (1) include 2- (meth) acrylamide propanesulfonic acid, 2- (meth) acrylamide-n-butanesulfonic acid, 2- (meth) acrylamide-n-hexane. Sulfonic acid, 2- (meth) acrylamide-n-octanesulfonic acid, 2- (meth) acrylamide-n-dodecanesulfonic acid, 2- (meth) acrylamide-n-tetradecanesulfonic acid, 2- (meth) acrylamide-2 -Methylpropanesulfonic acid, 2- (meth) acrylamide-2-phenylpropanesulfonic acid, 2- (meth) acrylamide-2,2,4-trimethylpentanesulfonic acid, 2- (meth) acrylamide-2-methylphenylethane Sulfonic acid, 2- (meth) acrylamide-2- (4- Rolophenyl) propanesulfonic acid, 2- (meth) acrylamide-2-carboxymethylpropanesulfonic acid, 2- (meth) acrylamide-2- (2-pyridyl) propanesulfonic acid, 2- (meth) acrylamide-1-methylpropane Examples thereof include sulfonic acid and 3- (meth) acrylamide-3-methylbutanesulfonic acid.
Of these, 2-acrylamido-2-methylpropanesulfonic acid and 2-methacrylamido-2-methylpropanesulfonic acid can be preferably exemplified from the standpoint of rising of charge.

The polymer preferably contains a monomer unit represented by the formula (1) and a monomer unit other than the monomer unit as a constituent component of the polymer.
The monomer that generates monomer units other than the monomer unit represented by the formula (1) is not particularly limited, and examples thereof include known monofunctional monomers and polyfunctional monomers.
The following can be illustrated as a monofunctional monomer.
Styrene; α-methylstyrene, β-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, pn-butylstyrene, p-tert-butylstyrene, p- Styrenic monomers such as n-hexyl styrene, pn-octyl styrene, pn-nonyl styrene, pn-decyl styrene, pn-dodecyl styrene, p-methoxy styrene, p-phenyl styrene; methyl Acrylate, ethyl acrylate, n-propyl acrylate, iso-propyl acrylate, n-butyl acrylate, iso-butyl acrylate, tert-butyl acrylate, n-amyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate , Acrylic monomers such as n-nonyl acrylate, cyclohexyl acrylate, benzyl acrylate, dimethyl phosphate ethyl acrylate, diethyl phosphate ethyl acrylate, dibutyl phosphate ethyl acrylate, 2-benzoyloxyethyl acrylate; methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, iso-propyl methacrylate, n-butyl methacrylate, iso-butyl methacrylate, tert-butyl methacrylate, n-amyl methacrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate, n-octyl methacrylate, n-nonyl methacrylate, Diethyl phosphate ethyl methacrylate, dibutyl phosphate Methacrylic monomers such as toethyl methacrylate; methylene aliphatic monocarboxylic acid esters; vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate, vinyl formate; vinyl methyl ether, vinyl ethyl ether, vinyl isobutyl Vinyl ethers such as ethers; vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone and vinyl isopropyl ketone.
The following can be illustrated as a polyfunctional monomer.
Diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, tripropylene glycol diacrylate, polypropylene glycol diacrylate, 2,2 '-Bis (4- (acryloxy-diethoxy) phenyl) propane, trimethylolpropane triacrylate, tetramethylolmethane tetraacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, polyethylene glycol Dimethacrylate, 1,3-buty Lenglycol dimethacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol dimethacrylate, polypropylene glycol dimethacrylate, 2,2′-bis (4- (methacryloxy-diethoxy) phenyl) propane, 2,2′-bis ( 4-methacryloxy-polyethoxy) phenyl) propane, trimethylolpropane trimethacrylate, tetramethylolmethane tetramethacrylate, divinylbenzene, divinylnaphthalene, divinyl ether.

In the present invention, the polyester resin A contains an isosorbide unit represented by the formula (2) (hereinafter also simply referred to as an isosorbide unit).
Since the isosorbide unit has a cyclic structure having a plurality of ether groups in the unit, it can cause an appropriate charge leak action by coexisting with the polymer. In the present invention, the charge amount of the toner can be maintained at an appropriate value by utilizing the charge leakage action of the isosorbide unit.
In this invention, content of the polyester resin A is 1.00 mass part or more and 40.00 mass parts with respect to 100.00 mass parts of resin, and is 1.00 mass part or more and 6.00 mass parts or less. It is preferable.
By setting the content of the polyester resin A in the above range, the interaction with the polymer works well, and the charge rising property of the toner and the optimization of the charge amount are greatly improved.
Therefore, even when a large number of printouts are performed in various environments ranging from a low temperature and low humidity environment to a high temperature and high humidity environment, a high image density can be stably maintained from the beginning.

In the present invention, the content ratio of the isosorbide unit represented by the above formula (2) is preferably 0.10 mol% or more and 30.00 mol% or less based on the total monomer units constituting the polyester resin A. More preferably, it is 1.00 mol% or more and 30.00 mol% or less.
By setting the content ratio of the isosorbide unit in the above range, the interaction with the polymer works most effectively, and the charge rising property of the toner and the optimization of the charge amount are improved.
When the content rate of an isosorbide unit is less than 0.10 mol%, the presence rate of the isosorbide unit in the polymer chain of the polyester resin A is small, and the characteristics contributing to the charging property of the polyester resin A tend to be lowered. Specifically, the characteristics for controlling the charge amount generated by the polymer tend to be reduced, and the charge amount of the toner tends to be high. If the charge amount of the toner becomes too high, the image density tends to decrease.
On the other hand, when the content ratio of the isosorbide unit exceeds 30.00 mol%, the charge leakage action tends to work strongly, so that the charge amount of the toner tends to be low. If the charge amount of the toner is too low, the image density tends to decrease.

In the present invention, the acid value of the polyester resin A is preferably from 0.50 mgKOH / g to 25.00 mgKOH / g, and more preferably from 1.50 mgKOH / g to 20.00 mgKOH / g.
By setting the acid value of the polyester resin A in the above range, the compatibility with the polymer is good, and the interaction with the polymer can be sufficiently expressed.
The acid value (mgKOH / g) of the polyester resin A can be controlled by the monomer composition ratio during polymerization.

In the present invention, the polyester resin A containing the isosorbide unit represented by the above formula (2) as a constituent component includes a dibasic acid or an anhydride thereof (monomer), an isosorbide represented by the following formula (3), and a divalent The alcohol (monomer) can be prepared by a dehydration condensation method at a reaction temperature of 180 to 260 ° C. in a nitrogen atmosphere at a composition ratio in which carboxyl groups remain. Further, a trifunctional or higher polybasic acid or an anhydride thereof, a monobasic acid, a trihydric or higher alcohol, a monohydric alcohol, or the like can be used as necessary.
Examples of the divalent alcohol include polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene (3.3) -2,2-bis (4-hydroxy). Phenyl) propane, polyoxyethylene (2.0) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene (2.0) -polyoxyethylene (2.0) -2,2-bis ( Alkylene oxide adducts of bisphenol A such as 4-hydroxyphenyl) propane, polyoxypropylene (6) -2,2-bis (4-hydroxyphenyl) propane; ethylene glycol, diethylene glycol, triethylene glycol, 1,2- Propylene glycol, 1,3-propylene glycol, 1,4-butanediol, neo Such as enthyl glycol, 1,4-butenediol, 1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol Aliphatic diols; bisphenol A such as bisphenol A and hydrogenated bisphenol A.
Examples of the trivalent or higher alcohol include sorbitol, 1,2,3,6-hexanetetrol, 1,4-sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol, 1,2,4-butanetriol, 1,2,5-pentanetriol, glycerol, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane, 1,3,5-trihydroxymethylbenzene It is done.
On the other hand, examples of the acid component such as the dibasic acid include the following.
Aromatic polyvalent carboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid and pyromellitic acid; 1 to C carbon atoms such as fumaric acid, maleic acid, adipic acid, succinic acid, dodecenyl succinic acid, octenyl succinic acid Aliphatic polycarboxylic acids such as succinic acid substituted by 20 alkyl groups or alkenyl groups having 2 to 20 carbon atoms; anhydrides of these acids and alkyl (1-8 carbon atoms) esters of these acids.
Among them, in particular, a polyester resin obtained by polycondensation using a bisphenol derivative as an alcohol component and a divalent or higher carboxylic acid or acid anhydride thereof or a lower alkyl ester thereof as an acid component can be preferably used. .

In the present invention, the resin contained in the toner particles is not particularly limited, and examples thereof include conventionally known styrene resins, acrylic resins, or polyester resins other than the polyester resin A.
Specific examples include commonly used styrene acrylic copolymers, styrene methacryl copolymers, epoxy resins, styrene butadiene copolymers, and the like.
It does not specifically limit as a monomer which comprises this copolymer, The following monomers can be illustrated.
Styrene; Styrenic monomers such as o- (m-, p-) methylstyrene, m- (p-) ethylstyrene; methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, methacryl Propyl acrylate, butyl acrylate, butyl methacrylate, octyl acrylate, octyl methacrylate, dodecyl acrylate, dodecyl methacrylate, stearyl acrylate, stearyl methacrylate, behenyl acrylate, behenyl methacrylate, 2-ethylhexyl acrylate, methacryl Acrylic acid ester monomers such as 2-ethylhexyl acid, dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl acrylate, diethylaminoethyl methacrylate, or methacrylate Le ester monomer; butadiene, isoprene, cyclohexene, acrylonitrile, methacrylonitrile, acrylic acid amide, ene-based monomers such as methacrylic acid amide.
These are used singly or generally with appropriate mixing of monomers with reference to the theoretical glass transition temperature (Tg) described in the publication Polymer Handbook 2nd edition III-p139 to 192 (manufactured by John Wiley & Sons). .

In the present invention, a low molecular weight polymer may be added to make the toner particles have a preferable molecular weight distribution. The low molecular weight polymer can be added when melt-kneading a resin or the like when the toner particles are produced by a pulverization method, and the monomer composition when the toner particles are produced by a suspension polymerization method. Can be added inside.
The low molecular weight polymer preferably has a weight average molecular weight (Mw) of 2,000 or more and 5,000 or less as measured by gel permeation chromatography (GPC), and a weight average molecular weight (Mw) / The number average molecular weight (Mn) is preferably less than 4.5, more preferably less than 3.0.
Examples of the low molecular weight polymer include low molecular weight polystyrene, low molecular weight styrene-acrylic acid ester copolymer, and low molecular weight styrene-acrylic copolymer.
In this invention, resin may contain polyester resins other than the said polyester resin A, polycarbonate resin, etc. as polar resin.
In the present invention, a crosslinking agent may be used when synthesizing the resin in order to increase the mechanical strength of the toner particles and to control the molecular weight of the resin contained in the toner particles.
As the crosslinking agent, difunctional linking agents such as divinylbenzene, bis (4-acryloxypolyethoxyphenyl) propane, ethylene glycol diacrylate, 1,3-butylene glycol diacrylate, 1,4-butanediol diacrylate 1,5-pentanediol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol # 200, # 400, # 600 diacrylates, dipropylene glycol diacrylate, polypropylene glycol diacrylate, polyester diacrylate (MANDA Nippon Kayaku), and above It includes those substituted for diacrylate dimethacrylate.
On the other hand, as the polyfunctional crosslinking agent, pentaerythritol triacrylate, trimethylolethane triacrylate, trimethylolpropane triacrylate, tetramethylolmethane tetraacrylate, oligoester acrylate and its methacrylate, 2,2-bis (4-methacryloxy) Polyethoxyphenyl) propane, diallyl phthalate, triallyl cyanurate, triallyl isocyanurate and triallyl trimellitate.
The addition amount of these crosslinking agents is preferably 0.05 parts by mass or more and 100.00 parts by mass or less, more preferably 0.10 parts by mass or more and 5 parts by mass or less with respect to 100.00 parts by mass of the monomer constituting the resin. 0.000 part by mass or less.

In the present invention, the toner particles may contain a charge control agent other than the polymer as necessary.
By adding a charge control agent other than the above polymer, it becomes possible to further stabilize the charging characteristics and to control the optimum charge amount according to the development system.
As the charge control agent, known ones can be used, and a charge control agent that has a high charging speed and can stably maintain a constant charge amount is particularly preferable.
As specific examples, organic metal compounds and chelate compounds are effective for controlling toner particles to be negatively chargeable, and monoazo metal compounds, acetylacetone metal compounds, aromatic oxycarboxylic acids, aromatic dicarboxylic acids, oxycarboxylic acids. Examples thereof include acid and dicarboxylic acid metal compounds. Moreover, aromatic oxycarboxylic acids, aromatic mono- and polycarboxylic acids, metal salts thereof, anhydrides thereof, esters thereof, phenol derivatives such as bisphenol, and the like can also be exemplified. Further examples include urea derivatives, metal-containing salicylic acid compounds, metal-containing naphthoic acid compounds, boron compounds, quaternary ammonium salts, calixarene, and the like.
On the other hand, the toner particles are controlled to be positively charged. Nigrosine-modified products such as nigrosine and fatty acid metal salts; guanidine compounds; imidazole compounds; tributylbenzylammonium-1-hydroxy-4-naphthosulfonate, tetrabutylammonium Quaternary ammonium salts such as tetrafluoroborate, and onium salts such as phosphonium salts and analogs thereof and lake pigments thereof; triphenylmethane dyes and lake lake pigments (the rake agents include phosphotungstic acid, phosphorus Molybdic acid, phosphotungstic molybdic acid, tannic acid, lauric acid, gallic acid, ferricyanide, ferrocyanide, etc.); metal salts of higher fatty acids; dibutyltin oxide, dioctyltin oxide, dicyclohexyltin Diorganotin oxides such as Kisaido; dibutyl tin borate, dioctyl tin borate, and the like diorgano tin borate such as dicyclohexyl tin borate.
The toner particles may contain these charge control agents alone or in combination of two or more.
The content of the charge control agent is preferably 0.01 parts by mass or more and 20.00 parts by mass or less, more preferably 0.50 parts by mass or more and 10.00 parts by mass with respect to 100.00 parts by mass of the resin. Or less. However, it is not essential to add a charge control agent to the toner of the present invention.

The toner particles may contain a colorant. As the colorant, known ones can be used.
Examples of the black colorant include carbon black, a magnetic material, and those that are toned in black using yellow, magenta, and cyan colorants described below.
Examples of the yellow colorant include compounds typified by condensed azo compounds, isoindolinone compounds, anthraquinone compounds, azo metal complexes, methine compounds, and allylamide compounds. Specifically, the following C.I. I. Pigment Yellow 12, 13, 14, 15, 17, 62, 73, 74, 83, 93, 94, 95, 97, 109, 110, 111, 120, 128, 129, 138, 147, 150, 151, 154, Examples include 155, 168, 180, 185, 214 and the like.
Examples of the magenta colorant include condensed azo compounds, diketopyrrolopyrrole compounds, anthraquinone compounds, quinacridone compounds, basic dye lake compounds, naphthol compounds, benzimidazolone compounds, thioindigo compounds, and perylene compounds. Specifically, the following C.I. I. Pigment Red 2, 3, 5, 6, 7, 23, 48: 2, 48: 3, 48: 4, 57: 1, 81: 1, 122, 146, 150, 166, 169, 177, 184, 185, 202, 206, 220, 221, 238, 254, 269, C.I. I. Examples thereof include CI Pigment Bio Red 19.
Examples of cyan colorants include copper phthalocyanine compounds and derivatives thereof, anthraquinone compounds, basic dye lake compounds, and the like. Specifically, C.I. I. Pigment blue 1, 7, 15, 15: 1, 15: 2, 15: 3, 15: 4, 60, 62, 66, and the like.
These colorants can be used alone or in combination, and further in a solid solution state. The colorant is selected from the viewpoints of hue angle, saturation, lightness, light resistance, OHP transparency, and dispersibility in toner particles. The content of the colorant is preferably 1 part by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the resin.

In the present invention, it is also possible to obtain a magnetic toner containing a magnetic material. In that case, the magnetic material can also serve as a colorant.
Examples of the magnetic material include iron oxides such as magnetite, hematite, and ferrite; metals such as iron, cobalt, and nickel; and these metals and aluminum, cobalt, copper, lead, magnesium, tin, zinc, antimony, Examples include alloys with metals such as beryllium, bismuth, cadmium, calcium, manganese, selenium, titanium, tungsten, and vanadium, and mixtures thereof.
The magnetic material is preferably surface-modified. When the magnetic toner is prepared by the suspension polymerization method, it is preferable that the toner is subjected to a hydrophobic treatment with a surface modifier which is a substance that does not inhibit polymerization. Examples of such surface modifiers include silane coupling agents and titanium coupling agents.
The magnetic material preferably has a number average particle diameter of 2 μm or less, more preferably 0.1 μm or more and 0.5 μm or less. The content of the magnetic material in the toner particles is preferably 20 parts by mass or more and 200 parts by mass or less, and more preferably 40 parts by mass or more and 150 parts by mass or less with respect to 100 parts by mass of the resin.

In the present invention, the toner particles may contain a wax. Examples of the wax include the following.
Petroleum wax such as paraffin wax, microcrystalline wax, petrolactam and derivatives thereof; montan wax and derivatives thereof; hydrocarbon wax and derivatives thereof according to Fischer-Tropsch method; polyolefin wax such as polyethylene wax and polypropylene wax and derivatives thereof, carnauba Natural wax such as wax, candelilla wax and derivatives thereof. Examples of the derivatives include oxides, block copolymers with vinyl monomers, and graft modified products. Furthermore, the following are mentioned. Higher fatty alcohols; fatty acids such as stearic acid and palmitic acid; acid amide waxes; ester waxes; hardened castor oil and its derivatives; plant waxes; Among these, ester wax and hydrocarbon wax are preferable from the viewpoint of excellent releasability. In addition, a compound in which a compound having the same total carbon number is contained in a wax of 50% by mass or more and 95% by mass or less is preferable from the viewpoint of high wax purity and developability.
The content of the wax is preferably 1 part by mass or more and 40 parts by mass or less, and more preferably 3 parts by mass or more and 25 parts by mass or less with respect to 100 parts by mass of the resin.
When the content of the wax is 1 part by mass or more and 40 parts by mass or less, winding resistance at a high temperature is improved by having an appropriate wax bleeding property when the toner is heated and pressurized. Further, even when subjected to stress on the toner during development or transfer, the exposure of the wax to the toner surface is small, and uniform chargeability of each toner can be obtained.

The toner of the present invention preferably has an aspect in which inorganic fine particles are externally added to the toner particles for the purpose of improving fluidity.
The inorganic fine particles to be externally added to the toner particles preferably contain at least silica fine particles. The number average particle diameter of primary particles of the silica fine particles is preferably 4 nm or more and 80 nm or less. When the number average particle diameter of the primary particles of the silica fine particles is in the above range, the fluidity of the toner is improved and the storage stability of the toner is also improved.
The number average particle size of the primary particles of the inorganic fine particles is obtained by observing with a scanning electron microscope, measuring the particle sizes of 100 primary particles of the inorganic fine particles in the visual field, and calculating the arithmetic average thereof.
As the inorganic fine particles, silica fine particles and fine particles of titanium oxide, alumina, or a double oxide thereof can be used in combination. As the inorganic fine particles used in combination, titanium oxide is preferable.
The silica fine particles include fine particles of both dry silica produced by vapor phase oxidation of silicon halides, called dry silica or fumed silica, and wet silica produced from water glass. As the silica, dry silica is preferred because it has few silanol groups on the surface and inside of the silica, and few production residues of Na ₂ O and SO ₃ ²⁻ . In addition, dry silica can also be used to obtain composite fine particles of silica and other metal oxides by using other metal halogen compounds such as aluminum chloride and titanium chloride together with silicon halogen compounds in the production process. Silica also includes them.
The inorganic fine particles may be added to make the triboelectric charge property of the toner uniform. Hydrophobic treatment of inorganic fine particles can provide functions such as adjustment of triboelectric charge amount of toner, improvement of environmental stability, and improvement of properties under high humidity environment. It is preferable to use fine particles. When the inorganic fine particles externally added to the toner particles absorb moisture, the triboelectric charge amount as the toner tends to decrease, and the developability and transferability tend to decrease.
Examples of the treatment agent for the hydrophobic treatment of the inorganic fine particles include the following.
Unmodified silicone varnish, various modified silicone varnishes, unmodified silicone oil, various modified silicone oils, silane compounds, silane coupling agents, other organosilicon compounds, and organotitanium compounds. These treatment agents may be used alone or in combination of two or more.
Among these, inorganic fine particles treated with silicone oil are preferable. More preferably, when the inorganic fine particles are hydrophobized with a coupling agent, or after the hydrophobizing treatment with a coupling agent, the hydrophobized inorganic fine particles treated with silicone oil are triboelectrically charged to the toner particles even in a high humidity environment. Can be maintained high and the selective developability can be reduced.
The addition amount of the inorganic fine particles is usually 0.01 parts by mass or more and 10 parts by mass or less, and preferably 0.05 parts by mass or more and 5 parts by mass or less with respect to 100 parts by mass of the toner particles.

In the present invention, the method for producing toner particles is not particularly limited, and the toner particles can be produced by a conventionally known production method such as a suspension polymerization method, a dissolution suspension method, an emulsion aggregation method, or a pulverization method. Among them, the suspension polymerization method can easily control the presence state of the polymer and the polyester resin A in the vicinity of the surface of the toner particles by utilizing the balance of the polarities of water and the toner material. Therefore, the suspension polymerization method is a more preferable form for improving the chargeability of the toner.
A method for producing toner particles using the suspension polymerization method will be described below.
First, a water-based monomer composition containing the polyester resin A, a polymer having a monomer unit represented by the above formula (1), a monomer constituting the resin, and other components such as a colorant as required. Disperse in a medium, form particles of the monomer composition in the aqueous medium, and polymerize the monomer contained in the particles. The particles obtained by the polymerization may be converted into toner particles through filtration, washing, and drying processes.
A dispersant may be added to the aqueous medium in order to uniformly disperse the monomer composition and form particles of the monomer composition.
In the case of producing by the suspension polymerization method, a polymerization initiator may be used, or may be added at the same time when other additives are added to the monomer, or particles of the monomer composition may be added in an aqueous medium. You may mix immediately before forming. Further, immediately after the formation of the particles, a polymerization initiator dissolved in a monomer or a solvent may be added before starting the polymerization reaction.
Examples of the polymerization initiator include the following.
2,2′-azobis- (2,4-dimethylvaleronitrile), 2,2′-azobisisobutyronitrile, 1,1′-azobis (cyclohexane-1-carbonitrile), 2,2
Azo or diazo polymerization initiators such as' -azobis-4-methoxy-2,4-dimethylvaleronitrile, azobisisobutyronitrile; benzoyl peroxide, methyl ethyl ketone peroxide, diisopropyl peroxycarbonate, cumene hydroperoxide, 2, Peroxide-based polymerization initiators such as 4-dichlorobenzoyl peroxide, lauroyl peroxide, tert-butyl-peroxypivalate.
Although the usage-amount of these polymerization initiators changes with the target degree of polymerization, generally it is preferable that they are 3 mass parts or more and 20 mass parts or less with respect to 100 mass parts of said monomers. The kind of the polymerization initiator is slightly different depending on the polymerization method, but is selected with reference to the 10-hour half-life temperature and used alone or in combination.

As the dispersant for dispersing the monomer composition in the aqueous medium, known inorganic and organic dispersants can be used.
Examples of the inorganic dispersant include the following.
Tricalcium phosphate, magnesium phosphate, aluminum phosphate, zinc phosphate, magnesium carbonate, calcium carbonate, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, calcium metasilicate, calcium sulfate, barium sulfate, bentonite, silica, alumina .
On the other hand, examples of the organic dispersant include the following.
Polyvinyl alcohol, gelatin, methyl cellulose, methyl hydroxypropyl cellulose, ethyl cellulose, carboxymethyl cellulose sodium salt, starch.
Also, commercially available nonionic, anionic, and cationic surfactants can be used as a dispersant for dispersing the monomer composition in the aqueous medium. Examples of such surfactants include the following.
Sodium dodecyl sulfate, sodium tetradecyl sulfate, sodium pentadecyl sulfate, sodium octyl sulfate, sodium oleate, sodium laurate, potassium stearate, calcium oleate.
Among these dispersants, inorganic, poorly water-soluble dispersants are preferable, and it is more preferable to use poorly water-soluble inorganic dispersants that are soluble in acids.
The amount of the dispersant used is preferably 0.2 parts by mass or more and 2.0 parts by mass or less with respect to 100 parts by mass of the monomer. Moreover, it is preferable that an aqueous medium is prepared using 300 mass parts or more and 3000 mass parts or less of water with respect to 100 mass parts of monomer compositions.
In the present invention, when preparing an aqueous medium in which the poorly water-soluble inorganic dispersant as described above is prepared, a commercially available dispersant may be used as it is. Moreover, in order to obtain the particle | grains of the dispersing agent which has a fine uniform particle size, you may produce a slightly water-soluble inorganic dispersing agent in an aqueous medium under high speed stirring. For example, when tricalcium phosphate is used as a dispersant, it is possible to form a tricalcium phosphate microparticle by mixing a sodium phosphate aqueous solution and a calcium chloride aqueous solution under high-speed stirring.

Next, the image forming method used in the present invention will be described with reference to FIGS.
FIG. 2 shows the configuration of the image forming apparatus including the image forming method used in the present embodiment. The image forming apparatus shown in FIG. 2 is a laser beam printer using a transfer type electrophotographic process. In particular, FIG. 2 shows a cross-sectional view of a tandem color LBP (color laser printer).
In FIG. 2, reference numeral 101 (101a to 101d) denotes a drum-type electrophotographic photosensitive member (hereinafter referred to as a photosensitive drum) as a latent image carrier that rotates in a direction indicated by an arrow (counterclockwise) at a predetermined process speed. . The photosensitive drums 101a, 101b, 101c, and 101d sequentially share the yellow (Y) component, magenta (M) component, cyan (C) component, and black (Bk) component of the color image.
Hereinafter, the image forming apparatuses Y, M, C, and Bk are referred to as a unit a, a unit b, a unit c, and a unit d, respectively.
These photosensitive drums 101a to 101d are rotationally driven by a drum motor (DC servo motor) (not shown), but independent driving sources may be provided for the respective photosensitive drums 101a to 101d. The rotational drive of the drum motor is controlled by a DSP (digital signal processor) (not shown), and other control is performed by a CPU (not shown).
The electrostatic adsorption conveyance belt 109a is stretched around a driving roller 109b, fixed rollers 109c and 109e, and a tension roller 109d. The electrostatic adsorption conveyance belt 109a is rotationally driven by the driving roller 109b in the direction of the arrow in the figure, and adsorbs and conveys the recording medium S. To do.
Hereinafter, unit a (yellow) of the four colors will be described as an example.
The photosensitive drum 101a is uniformly charged to a predetermined polarity and potential by the primary charging means 102a during its rotation. The photosensitive drum 101a is exposed to a light image by a laser beam exposure means (hereinafter referred to as a scanner) 103a, and an electrostatic latent image of image information is formed on the photosensitive drum 101a.
Next, a toner image is formed on the photosensitive drum 101a by the developing unit 104a, and the electrostatic latent image is visualized. Similar steps are performed for the other three colors (magenta (B), cyan (C), and black (Bk)).
Thus, the four-color toner images are synchronized with the photosensitive drums 101a to 101d by the registration rollers 108c that stop and re-transport the recording medium S conveyed by the paper feed roller 108b at a predetermined timing. The toner images are sequentially transferred onto the recording medium S at the nip portion with the belt 109a. At the same time, the photosensitive drums 101a to 101d after the transfer of the toner image to the recording medium S are subjected to repeated image formation by removing residual deposits such as transfer residual toner by the cleaning means 106a, 106b, 106c and 106d. .
The recording medium S on which the toner images are transferred from the four photosensitive drums 101a to 101d is separated from the surface of the electrostatic attraction / conveyance belt 109a by the driving roller 109b and sent to the fixing device 110, and the toner image is fixed by the fixing device 110. Then, the sheet is discharged to the discharge tray 113 by the discharge roller 110c.

Next, a specific example of an image forming method using a non-magnetic one-component contact developing method that can be applied to the present invention will be described with reference to an enlarged view of the developing portion (FIG. 1). In FIG. 1, the developing unit 13 is located in a developer container 23 containing a non-magnetic toner 17 as a one-component developer, and an opening extending in the longitudinal direction in the developer container 23, and a latent image carrier. A (photosensitive drum) 10 and a toner carrier 14 disposed opposite to each other are provided, and the electrostatic latent image on the latent image carrier 10 is developed and visualized. The latent image carrier contact charging member 11 is in contact with the latent image carrier 10. The bias of the latent image carrier contact charging member 11 is applied by a power source 12.
The toner carrier 14 is horizontally provided with the substantially right half-periphery surface shown in the drawing through the opening into the developer container 23 and the left substantially half-periphery surface exposed outside the developer container 23. The surface exposed to the outside of the developer container 23 is in contact with the latent image carrier 10 located on the left side of the developing unit 13 as shown in FIG.
The toner carrier 14 is rotationally driven in the direction of arrow B, the peripheral speed of the latent image carrier 10 is 50 to 170 mm / s, and the peripheral speed of the toner carrier 14 is 1 to 2 with respect to the peripheral speed of the latent image carrier 10. It is rotating at twice the peripheral speed.

At a position above the toner carrier 14, a metal plate such as SUS, a rubber material such as urethane or silicone, a metal thin plate of SUS or phosphor bronze having spring elasticity is used as a base, and a contact surface side to the toner carrier 14 A restricting member 16 made of a rubber material and the like is supported by a restricting member support metal plate 24 and is provided so that the vicinity of the free end side is in contact with the outer peripheral surface of the toner carrier 14 by surface contact. The contact direction is a so-called counter direction in which the tip side with respect to the contact portion is located upstream of the rotation direction of the toner carrier 14. As an example of the regulating member 16, a plate-like urethane rubber having a thickness of 1.0 mm is bonded to the regulating member support sheet metal 24, and the contact pressure (linear pressure) with respect to the toner carrier 14 is appropriately set. is there. The contact pressure is preferably 20 to 300 N / m. The measurement of the contact pressure is converted from a value obtained by inserting three metal thin plates with known friction coefficients into the contact portion and pulling out the central one with only a spring. The regulating member 16 having a rubber material or the like bonded to the abutting surface is desirable in terms of adhesion to the toner, and can suppress the fusion and fixing of the toner to the regulating member in long-term use. Further, the restricting member 16 can be in contact with the toner carrier 14 by edge contact with which the tip is in contact. In the case of edge contact, it is more desirable in terms of toner layer regulation to set the contact angle of the regulating member with respect to the tangent of the toner carrying body at the contact point with the toner carrying body to be 40 degrees or less.
The toner supply roller 15 is in contact with the contact portion of the regulating member 16 with the surface of the toner carrier 14 on the upstream side in the rotation direction of the toner carrier 14 and is rotatably supported. The contact width of the toner supply roller 15 with respect to the toner carrier 14 is preferably 1 to 8 mm, and it is preferable that the toner carrier 14 has a relative speed at the contact portion.
The charging roller 29 is not essential for the image forming method of the present invention, but is preferably installed. The charging roller 29 is an elastic body such as NBR or silicone rubber, and is attached to the suppression member 30. The contact load of the charging member 29 on the toner carrier 14 by the suppressing member 30 is set to 0.49 to 4.9N. Due to the contact of the charging roller 29, the toner layer on the toner carrier 14 is finely filled and uniformly coated. The longitudinal positional relationship between the regulating member 16 and the charging roller 29 is preferably arranged so that the charging roller 29 can reliably cover the entire contact area of the regulating member 16 on the toner carrier 14.
Further, for the driving of the charging roller 29, a driven or the same peripheral speed is indispensable between the charging roller 29 and the toner carrier 14, and if a peripheral speed difference occurs between the charging roller 29 and the toner carrier 14, the toner coat becomes uneven. This is not preferable because unevenness occurs on the image.
The bias of the charging roller 29 is applied by a power source 27 between the toner carrier 14 and the latent image carrier 10 in a direct current (27 in FIG. 1), and the nonmagnetic toner 17 on the toner carrier 14 is charged by the charging roller. From 29, charge is applied by discharge.
The bias of the charging roller 29 is a bias equal to or higher than the discharge start voltage having the same polarity as that of the nonmagnetic toner, and is set so that a potential difference of 1000 to 2000 V is generated with respect to the toner carrier 14.
After being charged by the charging roller 29, the toner layer formed as a thin layer on the toner carrier 14 is uniformly conveyed to a developing unit that is a portion facing the latent image carrier 10.
In this developing unit, the toner layer formed as a thin layer on the toner carrier 14 is transferred to the latent image by a DC bias applied between the toner carrier 14 and the latent image carrier 10 by the power source 27 shown in FIG. The electrostatic latent image on the carrier 10 is developed as a toner image.

Hereinafter, a method for measuring physical properties of the toner of the present invention will be described.
<Measurement of molecular weight distribution of resin, etc.>
The weight average molecular weight (Mw), number average molecular weight (Mn), and peak molecular weight (Mp) of the resin and the like are measured under the following conditions using gel permeation chromatography (GPC).
The column is stabilized in a heat chamber at 40 ° C., and tetrahydrofuran (THF) as a solvent is allowed to flow through the column at this temperature at a flow rate of 1 ml / min. As the column, a plurality of commercially available polystyrene gel columns are combined in order to accurately measure a molecular weight region of 1 × 10 ³ to 2 × 10 ⁶ . A combination of shodex GPC KF-801, 802, 803, 804, 805, 806, 807, 800P manufactured by Showa Denko KK, or TSKgel G1000H (HXL), G2000H (HXL), G3000H (HXL), G4000H manufactured by Tosoh Corporation A combination of (HXL), G5000H (HXL), G6000H (HXL), G7000H (HXL) and TSKguard column is used. In this application, a combination of seven columns of shodex KF-801, 802, 803, 804, 805, 806, 807 manufactured by Showa Denko Co., Ltd. was used.
On the other hand, after dispersing and dissolving the resin in THF and allowing to stand overnight, a sample processing filter (pore size 0.2 to 0.5 μm, Mysori Disc H-25-2 (manufactured by Tosoh Corporation) is used. ) And use the filtrate as a sample. Measurement is performed by injecting 50 to 200 μl of a THF solution of the resin adjusted so that the resin concentration is 0.5 to 5 mg / ml as a sample concentration. An RI (refractive index) detector is used as the detector.
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, Pressure Chemical Co. Made by Tosoh Corporation or having a molecular weight of 6 × 10 ² , 2.1 × 10 ³ , 4 × 10 ³ , 1.75 × 10 ⁴ , 5.1 × 10 ⁴ , 1.1 × 10 ⁵ , 3. 9 × 10 ⁵ , 8.6 × 10 ⁵ , 2 × 10 ⁶ , 4.48 × 10 ⁶ are used, and at least about 10 standard polystyrene samples are used.

<Measurement of acid value of polyester resin A>
The acid value of the polyester resin A is determined by the following operation. The acid value is the number of mg of potassium hydroxide necessary for neutralizing the acid contained in 1 g of the sample. Although basic operation is measured according to JIS K0070-1992, specifically, it measures according to the following procedures.
(1) Preparation of Reagent 1.0 g of phenolphthalein is dissolved in 90 ml of ethyl alcohol (95 vol%), and ion exchanged water is added to make 100 ml to obtain a phenolphthalein solution.
7 g of special grade potassium hydroxide is dissolved in 5 ml of water, and ethyl alcohol (95 vol%) is added to make 1 L. In order to avoid contact with carbon dioxide, etc., it is placed in an alkali-resistant container and allowed to stand for 3 days, followed by filtration to obtain a potassium hydroxide solution. The obtained potassium hydroxide solution is stored in an alkali-resistant container. The factor of the potassium hydroxide solution was as follows: 25 ml of 0.1 mol / L hydrochloric acid was placed in an Erlenmeyer flask, a few drops of the phenolphthalein solution were added, titrated with the potassium hydroxide solution, and the hydroxylation required for neutralization. Determined from the amount of potassium solution. As the 0.1 mol / L hydrochloric acid, one prepared according to JIS K 8001-1998 is used. (2) Operation (A) Main test 2.0 g of the pulverized polyester resin A is precisely weighed in a 200 ml Erlenmeyer flask, and 100 ml of a mixed solution of toluene: ethanol (2: 1) is added and dissolved over 5 hours. Subsequently, several drops of the phenolphthalein solution is added as an indicator, and titration is performed using the potassium hydroxide solution. The end point of titration is when the light red color of the indicator lasts for about 30 seconds. (B) Blank test Titration is performed in the same manner as described above, except that no sample is used (that is, only a mixed solution of toluene: ethanol (2: 1) is used).
(3) The acid value is calculated by substituting the obtained result into the following formula.
A = [(C−B) × f × 5.61] / S
Here, A: acid value (mgKOH / g), B: addition amount (ml) of a potassium hydroxide solution in a blank test, C: addition amount (ml) of a potassium hydroxide solution in this test, f: potassium hydroxide Solution factor, S: sample (g).

<Calculation method of the content of the polyester resin A and the content of the polymer having the monomer unit represented by the formula (1) with respect to the resin in the toner particles, and the content ratio of the isosorbide unit in the polyester resin A and the polymer Method for calculating content ratio of monomer unit represented by formula (1) in
For the analysis, a pyrolysis gas chromatography mass spectrometer (hereinafter, pyrolysis GC / MS) and NMR are used. In the present invention, components having a molecular weight of 1500 or more are measured. This is because the region having a molecular weight of less than 1500 is considered to be a region having a high wax ratio and almost no resin component.
In pyrolysis GC / MS, the constituent monomer of the total amount of resin in the toner can be determined and the peak area of each monomer can be determined. Necessary. On the other hand, in NMR, it is possible to determine and quantify constituent monomers without using a sample having a known concentration. Therefore, depending on the situation, the constituent monomer is determined by comparing the spectra of both NMR and pyrolysis GC / MS.
Specifically, when the resin component insoluble in deuterated chloroform, which is an extraction solvent at the time of NMR measurement, is less than 5.0% by mass, quantification is performed by NMR measurement.
On the other hand, when the resin component insoluble in deuterated chloroform, which is an extraction solvent at the time of NMR measurement, is present in an amount of 5.0% by mass or more, NMR and pyrolysis GC / Both MS measurements are performed, and pyrolysis GC / MS is measured for deuterated chloroform insoluble matter. In this case, first, NMR measurement of deuterated chloroform solubles is performed, and the constituent monomers are determined and quantified (quantitative result 1). Next, pyrolysis GC / MS measurement is performed on the deuterated chloroform solubles to determine the peak area of the peak attributed to each constituent monomer. Using the quantitative result 1 obtained by NMR measurement, the relationship between the amount of each constituent monomer and the peak area of pyrolysis GC / MS is determined. Subsequently, pyrolysis GC / MS measurement of a deuterated chloroform insoluble content is performed, and the peak area attributed to each constituent monomer is determined. Based on the relationship between the amount of each constituent monomer obtained by measurement of deuterated chloroform solubles and the peak area of pyrolysis GC / MS, the constituent monomers in the deuterated chloroform insoluble matter are quantified (quantitative result 2). . Then, the quantitative result 1 and the quantitative result 2 are combined to obtain the final quantitative result of each constituent monomer.
Specifically, the following operation is performed.
(1) Weigh accurately 500 mg of toner into a 30 mL glass sample bottle, add 10 mL of deuterated chloroform, cap, disperse and dissolve for 1 hour with an ultrasonic disperser. Subsequently, it filters with a 0.4 micrometer diameter membrane filter, and collect | recovers filtrate. At this time, the deuterated chloroform insoluble matter remains on the membrane filter.
(2) Using a preparative high-efficiency liquid chromatography (HPLC), 3 mL of the filtrate is recovered with a fraction collector except a molecular weight of less than 1500 and a resin solution from which components having a molecular weight of less than 1500 have been removed. Chloroform is removed from the collected solution using a rotary evaporator to obtain a resin. The molecular weight of less than 1500 is determined by measuring a polystyrene resin having a known molecular weight in advance and obtaining the elution time.
(3) Dissolve 20 mg of the obtained resin in 1 mL of deuterated chloroform, perform ¹ H-NMR measurement, assign a spectrum to each constituent monomer used in the polymer and the polyester resin, and obtain a quantitative value. .
(4) If analysis of deuterium chloroform insolubles is required, analysis is performed by pyrolysis GC / MS. If necessary, derivatization treatment such as methylation is performed.
<NMR measurement conditions>
Bruker AVANCE 500 manufactured by Bruker BioSpin Corporation
Measurement nucleus: ¹ H
Measurement frequency: 500.1 MHz
Integration count: 16 times Measurement temperature: Room temperature <Measurement conditions for pyrolysis GC / MS>
Thermal decomposition apparatus: TPS-700 manufactured by Nippon Analytical Industrial Co., Ltd.
Thermal decomposition temperature: Appropriate value between 400 ° C and 600 ° C, in this case 590 ° C
GC / MS device: ISQ manufactured by Thermo Fisher Scientific Co., Ltd.
Column: “HP5-MS” (Agilent / 19091S-433), length 30 m, inner diameter 0.25 mm, film thickness 0.25 μm
GC / MS condition Inlet condition:
InletTemp: 250 ° C.
SplitFlow: 50ml / min
GC temperature rising condition: 40 ° C. (5 min) → 10 ° C./min (300 ° C.) → 300 ° C. (20 min)
Mass range: m / z = 10-550

  The present invention will be specifically described with reference to the following examples and comparative examples, but the present invention is not limited to the examples and comparative examples. In the examples and comparative examples, “part” and “%” are based on mass unless otherwise specified.

<Polymer having monomer unit represented by formula (1)>
Polymers (1) to (6) shown in Table 1 below were used.

<Production Example 1 of Polyester Resin A>
100 parts by mass of a mixture prepared by mixing raw material monomers other than trimellitic anhydride in the amounts shown in Table 2, and 0.52 parts by mass of di (2-ethylhexanoic acid) tin as a catalyst, a nitrogen introduction tube, a dehydration tube, The mixture was placed in a 6-liter four-necked flask equipped with a stirrer and a thermocouple, and reacted at 200 ° C. for 6 hours under a nitrogen atmosphere. Further, trimellitic anhydride was added at 210 ° C., and the reaction was carried out under reduced pressure of 40 kPa, and the reaction was continued until the weight average molecular weight (Mw) became 12,000. Let the obtained polyester resin A be resin (1). Table 2 shows the amount of charge of the resin (1) and the results of the composition analysis. Table 2 also shows the acid value (mgKOH / g) of the obtained resin.
The composition analysis of the polyester resin A was performed by ¹ H-NMR. The specific measurement method is as follows.
Measuring apparatus: FT NMR apparatus JNM-EX400 (manufactured by JEOL Ltd.)
Measurement frequency: 400MHz
Pulse condition: 5.0μs
Frequency range: 10500Hz
Integration count: 64 times Measurement temperature: 30 ° C
A sample of 50 mg was put into a sample tube having an inner diameter of 5 mm, deuterated chloroform (CDCl 3) was added as a solvent, and this was dissolved in a constant temperature bath at 40 ° C. to prepare a measurement sample. It measured on the said conditions using the said measurement sample.

<Production Examples 2 to 8 of polyester resin A>
A polyester resin A was produced in the same manner as in Production Example 1 except that the charged amounts of the acid component and the alcohol component were changed as shown in Table 2. Let the obtained polyester resin A be resin (2)-(8). The acid values of the obtained resins (2) to (8) are also shown in Table 2.

※モノマー組成の表記はアルコールの総モル数を１００とした時のモル比を示す。
ＴＰＡ：テレフタル酸
ＩＰＡ：イソフタル酸
ＴＭＡ：トリメリット酸
ＢＰＡ（ＰＯ）：ビスフェノールＡのプロピレンオキサイド３モル付加物

* The notation of the monomer composition indicates the molar ratio when the total number of moles of alcohol is 100.
TPA: terephthalic acid IPA: isophthalic acid TMA: trimellitic acid BPA (PO): propylene oxide 3 mol adduct of bisphenol A

<Toner Production Example 1>
Toner (A) was produced by the following procedure.
850 parts by mass of 0.1 mol / L-Na ₃ PO ₄ aqueous solution was added to a container equipped with a high-speed stirrer CLEARMIX (M Technique Co., Ltd.), the rotation speed was adjusted to 15000 rpm, and the mixture was heated to 60 ° C. . Here was added 1.0mol / L-CaCl ₂ aqueous solution 68 parts by mass, to prepare an aqueous medium containing a fine sparingly water-soluble dispersing agent _Ca 3 _{(PO 4) 2.} Moreover, the following material was melt | dissolved at 100 r / min with the propeller-type stirring apparatus, and the solution was prepared.
-Styrene 75.00 parts by mass-n-butyl acrylate 25.00 parts by mass-Polymer (1) 0.70 parts by mass-Resin (1) 4.00 parts by mass Next, the following materials were added to the solution. .
・ C. I. Pigment Blue 15: 3 6.50 parts by mass / hydrocarbon wax 9.00 parts by mass (the peak temperature of the maximum endothermic peak is 77 ° C., HNP-51, manufactured by Nippon Seiwa Co., Ltd.)
Thereafter, the mixture was heated to a temperature of 60 ° C. and then stirred and dissolved and dispersed at 9000 r / min with a TK homomixer (manufactured by Tokushu Kika Kogyo).
In this, 10.00 parts by mass of a polymerization initiator 2,2′-azobis (2,4-dimethylvaleronitrile) was dissolved to prepare a monomer composition. The monomer composition was put into the aqueous medium and granulated at a temperature of 60 ° C. for 15 minutes while rotating the CLEARMIX at 15000 rpm.
Thereafter, the mixture was transferred to a propeller type stirring device and reacted at a temperature of 70 ° C. for 5 hours while stirring at 100 r / min. Then, the temperature was raised to 80 ° C. and the reaction was further performed for 5 hours to produce toner particles. After completion of the polymerization reaction, the slurry containing the particles was cooled, washed with 10 times the amount of water as the slurry, filtered and dried, and then the particle size was adjusted by classification to obtain toner particles.
Hydrophobic silica fine particles (primary primary) treated with dimethyl silicone oil (20% by mass) as a fluidity improver and frictionally charged to the same polarity (negative polarity) as the toner particles with respect to 100.0 parts by mass of the toner particles. Toner (A) was obtained by mixing 2.0 parts by mass of the number average particle diameter of the particles: 10 nm, BET specific surface area: 170 m ^{2 /} g) with a Henschel mixer (manufactured by Mitsui Miike) at 3000 r / min for 15 minutes.

<Toner Production Examples 2 to 22>
As shown in Table 3, the procedure was the same as in Toner Production Example 1 except that the type and content of the polymer having the monomer unit represented by formula (1) and the type and content of polyester resin A were changed. Manufactured.

<Toner Production Example 23>
A toner was produced by the dissolution suspension method according to the following procedure.
First, an aqueous medium and a solution were prepared according to the following procedure to prepare a toner.
660 parts by weight of water and 25 parts by weight of 48.5% by weight aqueous sodium dodecyl diphenyl ether disulfonate solution were mixed and stirred, and then stirred at 10000 r / min using a TK homomixer (made by Tokushu Kika Kogyo Co., Ltd.). Prepared.
Moreover, the following material was thrown into 500 mass parts of ethyl acetate, and it melt | dissolved at 100 r / min with the propeller-type stirring apparatus, and prepared the solution.
Copolymer of styrene and n-butyl acrylate 100.00 parts by mass (copolymerization mass ratio: styrene / n-butyl acrylate = 75/25, Mp = 17000) Polymer (1) 0.70 parts by mass Resin (1) 4.00 parts by mass. I. Pigment Blue 15: 3 6.50 parts by mass / hydrocarbon wax 9.00 parts by mass (the peak temperature of the maximum endothermic peak is 77 ° C., HNP-51, manufactured by Nippon Seiwa Co., Ltd.)
Next, 150 parts by mass of an aqueous medium is placed in a container, and stirred using a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) at a rotational speed of 12000 rpm. To this, 100 parts by mass of the solution is added and mixed for 10 minutes. Thus, an emulsified slurry was prepared.
Thereafter, 100 parts by mass of the emulsified slurry was charged into a flask equipped with a deaeration pipe, a stirrer and a thermometer, and the solvent was removed at 45 ° C. under reduced pressure at 30 ° C. for 12 hours while stirring at a stirring peripheral speed of 20 m / min. Aged for 4 hours to obtain a solvent-free slurry. After the solvent-removed slurry was filtered under reduced pressure, 300 parts by mass of ion-exchanged water was added to the obtained filter cake, mixed and redispersed (at 12,000 rpm for 10 minutes) with a TK homomixer, and then filtered. The obtained filter cake was dried with a dryer at 45 ° C. for 48 hours, and sieved toner particles were obtained with a mesh opening of 75 μm.
Hydrophobic silica fine particles (primary primary) treated with dimethyl silicone oil (20% by mass) as a fluidity improver and frictionally charged to the same polarity (negative polarity) as the toner particles with respect to 100.0 parts by mass of the toner particles. Toner (W) was obtained by mixing 2.0 parts by mass of particles with a number average particle diameter of 10 nm and a BET specific surface area of 170 m ^{2 /} g with a Henschel mixer (manufactured by Mitsui Miike) at 3000 r / min for 15 minutes.

<Toner Production Example 24>
A toner was produced by an emulsion aggregation method according to the following procedure.
[Preparation of resin particle dispersion]
Copolymer of styrene and n-butyl acrylate 100.00 parts by mass (copolymerization mass ratio: styrene / n-butyl acrylate = 75/25, Mp = 17000) Polymer (1) 0.70 parts by mass Resin (1) 4.00 parts by mass was dissolved in 250 parts by mass of tetrahydrofuran. While stirring this tetrahydrofuran solution at room temperature, 1000 parts by mass of ion-exchanged water was added dropwise. The mixed solution was heated to about 75 ° C. to remove tetrahydrofuran to obtain a resin particle dispersion having an average particle size of 0.09 μm.
[Preparation of wax particle dispersion]
Hydrocarbon wax 9.00 parts by mass (peak temperature of the maximum endothermic peak is 77 ° C., HNP-51, manufactured by Nippon Seiwa Co., Ltd.)
・ Ion-exchanged water 50.00 parts by mass or more was heated to 95 ° C. and dispersed using a homogenizer (manufactured by IKA: Ultra Tarrax T50), and then dispersed with a pressure discharge type homogenizer. A wax particle dispersion was prepared by dispersing a wax having a diameter of .51 μm.
[Preparation of colorant particle dispersion]
・ C. I. Pigment Blue 15: 3 6.50 parts by mass, anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen SC) 2.00 parts by mass, ion-exchanged water 78.00 parts by mass or more were mixed, and a sand grinder Dispersed using a mill. When the particle size distribution in the colorant particle dispersion was measured using a particle size measuring device (LA-700, manufactured by Horiba, Ltd.), the average particle size of the colorant particles contained was 0.21 μm, and 1 μm No larger coarse particles were observed.
[Preparation of mixture]
All of the resin particle dispersion, the colorant particle dispersion, and the wax particle dispersion were mixed and charged into a 5 liter separable flask equipped with a stirrer, a condenser, and a thermometer. The mixture was adjusted to pH = 5.2 using 1N potassium hydroxide.
[Formation of aggregated particles]
As a flocculant, 2 parts by mass of a 10% sodium chloride aqueous solution was added dropwise to the obtained mixed solution, and the flask was heated to 50 ° C. while stirring the inside of the flask.
[Fusion process]
Thereafter, 70 parts by mass of a 15% aqueous solution of dodecylbenzenesulfonate was slowly added thereto, and the liquid temperature was raised to 80 ° C. and held for 5 hours. After cooling, it was filtered, sufficiently washed with ion exchange water, and dried to obtain toner particles.
Hydrophobic silica fine particles (primary primary) treated with dimethyl silicone oil (20% by mass) as a fluidity improver and frictionally charged to the same polarity (negative polarity) as the toner particles with respect to 100.0 parts by mass of the toner particles. Toner (X) was obtained by mixing 2.0 parts by mass of particle number average particle diameter: 10 nm, BET specific surface area: 170 m ^{2 /} g) with a Henschel mixer (manufactured by Mitsui Miike) at 3000 r / min for 15 minutes.

<Toner Production Example 25>
A toner was produced by a pulverization method according to the following procedure.
Copolymer of styrene and n-butyl acrylate 100.00 parts by mass (copolymerization mass ratio: styrene / n-butyl acrylate = 75/25, Mp = 17000) Polymer (1) 0.70 parts by mass Resin (1) 4.00 parts by mass. I. Pigment Blue 15: 3 6.50 parts by mass / hydrocarbon wax 9.00 parts by mass (the peak temperature of the maximum endothermic peak is 77 ° C., HNP-51, manufactured by Nippon Seiwa Co., Ltd.)
The above was melt-kneaded and then pulverized to obtain toner particles. Hydrophobic silica fine particles (primary primary) treated with dimethyl silicone oil (20% by mass) as a fluidity improver and frictionally charged to the same polarity (negative polarity) as the toner particles with respect to 100.0 parts by mass of the toner particles. Toner (Y) was obtained by mixing 2.0 parts by mass of particle number average particle diameter: 10 nm, BET specific surface area: 170 m ^{2 /} g) with a Henschel mixer (manufactured by Mitsui Miike) at 300 r / min for 15 minutes.

<Production Examples 1 to 4 for Comparative Toner>
As shown in Table 3, the procedure was the same as in Toner Production Example 1 except that the type and content of the polymer having the monomer unit represented by formula (1) and the type and content of polyester resin A were changed. Manufactured.

  Table 3 shows the types and contents of the polymer having the monomer unit represented by the formula (1) and the types and contents of the polyester resin A for the toners (A) to (Y) and the toners (a) to (d). Show.

<Examples 1 to 25 and Comparative Examples 1 to 4>
The toners (A) to (Y) and the toners (a) to (d) were evaluated for image density in three environments, respectively. The results are shown in Table 4. In the table, LL, NN, and HH are low temperature and low humidity (temperature 10 ° C., humidity 15% RH), normal temperature and normal humidity (temperature 23 ° C., humidity 60% RH), and high temperature and high humidity (temperature 30 ° C., humidity 85%). RH). In addition, the numerical values described in the table are those of the 1st sheet / 5th sheet / 10th sheet / 1000th sheet.

<Evaluation method>
In the developing device (Satera LBP5300; manufactured by Canon Inc.) of the one-component contact developing system shown in FIG. In addition, Xerox 4200 (Xerox Co., Ltd., 75 g / m ² paper) was used as the transfer paper.
・ Low temperature and low humidity (Temperature 10 ℃, Humidity 15% RH)
・ Normal temperature and humidity (temperature 23 ℃, humidity 60% RH)
・ High temperature and high humidity (temperature 30 ℃, humidity 85% RH)
In each of the three environments, the developing device shown in FIG. 1 was mounted on the unit 104a shown in FIG. The process speed was set to 150 mm / s in the cyan monochrome mode. A solid image (image printing rate of 4%) was continuously printed on the transfer paper so that the toner loading amount was 0.40 mg / cm ^2, and the solid image density was measured.

<Image density measurement method and evaluation>
Evaluation was made based on the image density of the solid portion. For measurement of the image density, a “Macbeth reflection densitometer RD918” (manufactured by Macbeth) was used to measure a relative density with respect to a printout image of a white background portion having a document density of 0.00.
For the evaluation of image density, first, first, fifth and tenth printout images were measured to confirm the rising property of toner charging.
Next, the 1000th printout image was measured to confirm the stability of the image density after printing out a large number of sheets.
Table 4 shows the evaluation results of the image density in the three environments of toners (A) to (Y) and toners (a) to (d).

DESCRIPTION OF SYMBOLS 10 Latent image carrier (photosensitive drum), 11 Contact charging member, 12 Power supply, 13 Developing unit, 14 Toner carrier, 15 Toner supply roller, 15a Toner supply roller shaft, 16 Control member, 17 Nonmagnetic toner, 23 Developer Container, 24 regulating member support sheet metal, 25
Toner stirring member, 26 Toner blowing prevention sheet, 27 Power source, 29 Charging roller, 30 Suppressing member, 101a to d Photosensitive drum, 102a to d Primary charging means, 103a to d Scanner, 104a to d Developing section, 106a to d Cleaning means , 108b Paper feed roller, 108c Registration roller, 109a Electrostatic attracting and conveying belt, 109b Drive roller, 109c Fixed roller, 109d Tension roller, 109e Fixed roller, 110 Fixing device, 110c Discharge roller, 110d Static elimination sheet, 111 Fixing device frame , 111a Paper passage guide, 112 Fixing device maintenance door, 112a Fixing device fixing member, 113 Discharge tray, 115, 116 Discharge roller, 117 Paper passage guide, S recording medium

Claims (5)

A toner having toner particles containing a resin, a polyester resin A, and a polymer having a monomer unit represented by the following formula (1):
The polyester resin A contains an isosorbide unit represented by the following formula (2),
A toner wherein the content of the polyester resin A is 1.00 parts by mass or more and 40.00 parts by mass or less with respect to 100.00 parts by mass of the resin.

[In the formula (1), X represents a divalent aliphatic group which may have a substituent or a phenylene group which may have a substituent, and R ₁ represents a hydrogen atom, an alkali metal, carbon. An alkyl group having a number of 1 or more and 4 or less, or a phenyl group is shown, and R ₂ is a hydrogen atom or a methyl group. ]

  The toner according to claim 1, wherein a content ratio of the isosorbide unit represented by the formula (2) is 0.10 mol% or more and 30.00 mol% or less based on all monomer units constituting the polyester resin A.   The toner according to claim 1, wherein the acid value of the polyester resin A is 0.50 mgKOH / g or more and 25.00 mgKOH / g or less.   The content rate of the monomer unit shown by the said Formula (1) is 0.50 mol% or more and 20.00 mol% or less on the basis of all the monomer units which comprise the said polymer, The any one of Claims 1-3 The toner according to item.   Content of the polymer which has a monomer unit shown by the said Formula (1) is 0.10 mass part or more and 10.00 mass parts or less with respect to 100.00 mass parts of said resin. The toner according to any one of the above.

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