JP2017083665A - Toner and manufacturing method of toner - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a toner that is excellent in low-temperature fixability and storage stability and prevents image defects, such as fogging even after a long-term use.SOLUTION: There is provided a toner containing a colorant, ester wax, resin A, and binder resin, wherein the ester wax contains an ester compound of di- to hexa-valent alcohol and an aliphatic monocarboxylic acid, or an ester compound of di- to hexa-valent carboxylic acid and an aliphatic monoalcohol; the resin A is a polymer having a specific structure; the binder resin has a benzene ring and an ester linkage.SELECTED DRAWING: None

Description

  The present invention relates to a toner used in an electrophotographic method, an electrostatic recording method, a toner jet method or the like and a method for producing the toner.

In recent years, there has been a growing demand to make copiers and printers small and excellent in energy saving.
In response to the above demands, there is a demand for a toner that is superior in low-temperature fixability, has good storage stability, and can maintain excellent image quality over a long period of time.
In response to this requirement, in Patent Document 1, the core particles composed of colored polymer particles containing a polyfunctional ester wax, Fischer-Tropsch wax and a colorant are more than the glass transition temperature of the polymer component constituting the core particles. A core-shell type polymerized toner coated with a shell made of a polymer having a high glass transition temperature, wherein the use ratio of the polyfunctional ester compound and the Fischer-Tropsch wax is 5/5 to 29/1 Structured polymerized toners and manufacturing methods have been proposed.
However, there are still some problems regarding compatibility between low-temperature fixability and storage stability.
In Patent Document 2, a toner containing colored polymer particles containing a binder resin, a colorant, and a bifunctional ester wax, and inorganic fine particles, and a specific displacement curve is obtained in a micro compression test for the toner. And a toner having a specific DSC curve in the measurement of the differential scanning calorimeter of the toner.
However, there are still some problems regarding compatibility between low-temperature fixability and storage stability.

JP 11-218960 A JP 2010-85909 A

  An object of the present invention is to provide a toner which is excellent in low-temperature fixability and storage stability and is free from image defects such as fogging even when used for a long period of time.

The present invention
A toner containing a colorant, ester wax, resin A, and a binder resin,
The ester wax contains an ester compound of a divalent to hexavalent alcohol and an aliphatic monocarboxylic acid, or an ester compound of a divalent to hexavalent carboxylic acid and an aliphatic monoalcohol,
The resin A is a polymer having a structure represented by the following formula (1):
The toner is characterized in that the binder resin has a benzene ring and an ester bond.
The present invention also provides:
A polymerizable monomer composition containing a colorant, ester wax, resin A, and a polymerizable monomer is dispersed in an aqueous medium, and particles of the polymerizable monomer composition are formed in the aqueous medium. Process and
A method for producing a toner comprising a step of polymerizing the polymerizable monomer contained in the particles of the polymerizable monomer composition,
The ester wax contains an ester compound of a divalent to hexavalent alcohol and an aliphatic monocarboxylic acid, or an ester compound of a divalent to hexavalent carboxylic acid and an aliphatic monoalcohol,
The resin A is a polymer having a structure represented by the following formula (1):
In the toner production method, the binder resin has a benzene ring and an ester bond.

［前記式（１）中、Ｒ^１は、それぞれ独立して、炭素数１以上１８以下のアルキル基、又は、炭素数１以上１８以下のアルコキシ基を示し、ｎは０以上３以下の整数を示し、＊は前記樹脂Ａにおける結合部位である。］

[In the formula (1), each R ¹ independently represents an alkyl group having 1 to 18 carbon atoms or an alkoxy group having 1 to 18 carbon atoms, and n represents an integer of 0 to 3 inclusive. * Indicates a binding site in the resin A. ]

  According to the present invention, it is possible to obtain a toner that is excellent in low-temperature fixability and storage stability and is free from image defects such as fogging even when used for a long period of time.

Hereinafter, the present invention will be described in detail.
The toner of the present invention is a toner containing a colorant, ester wax, resin A, and a binder resin,
The ester wax contains an ester compound of a divalent to hexavalent alcohol and an aliphatic monocarboxylic acid, or an ester compound of a divalent to hexavalent carboxylic acid and an aliphatic monoalcohol,
The resin A is a polymer having a structure represented by the following formula (1):
The binder resin has a benzene ring and an ester bond.

［前記式（１）中、Ｒ^１は、それぞれ独立して、炭素数１以上１８以下のアルキル基、又は、炭素数１以上１８以下のアルコキシ基を示し、ｎは０以上３以下の整数を示し、＊は前記樹脂Ａにおける結合部位である。］

[In the formula (1), each R ¹ independently represents an alkyl group having 1 to 18 carbon atoms or an alkoxy group having 1 to 18 carbon atoms, and n represents an integer of 0 to 3 inclusive. * Indicates a binding site in the resin A. ]

The reason why the effect of the present invention is manifested is not necessarily clear, but the present inventors consider as follows.
In the toner, an ester compound of a divalent to hexavalent alcohol and an aliphatic monocarboxylic acid, or an ester compound of a divalent to hexavalent carboxylic acid and an aliphatic monoalcohol (hereinafter referred to as a polyfunctional ester wax). In the case where the resin A having the structure represented by the formula (1) and the binder resin having a benzene ring and an ester bond are contained, first, the resin having the structure represented by the formula (1) The carboxy group and hydroxyl group in the structure of A are coordinated to the carboxy group of the polyfunctional ester wax.
In this state, the resin A having the structure represented by the formula (1) functions as a dispersant in the multifunctional ester wax toner.
This is because the benzene ring in the resin A having the structure represented by the formula (1) and the benzene ring in the binder resin having a benzene ring and an ester bond interact with each other to express affinity. is there.
That is, this is because the resin A having the structure represented by the formula (1) having an affinity for the benzene ring in the binder resin acts so as to mediate the binder resin and the polyfunctional ester wax.
As a result, since the polyfunctional ester wax can be present in the toner in a moderately stable state, it can be distributed with a small dispersed particle size.
For this reason, the polyfunctional ester wax is distributed in the toner with a large specific surface area.
Further, since the binder resin has an ester bond, it exhibits affinity with the polyfunctional ester wax at the time of fixing.
As a result, it is considered that the polyfunctional ester wax and the binder resin are rapidly melted and compatible at the time of fixing, so that the melt viscosity is lowered and the low-temperature fixability is improved.
On the other hand, it has been found that when the ester wax is composed of an ester compound of a monohydric alcohol and an aliphatic monocarboxylic acid, the effects of the present invention are not exhibited.
The reason is that when there is one ester bond in the ester wax, the function of the resin A having the structure represented by the formula (1) as a dispersant is insufficient.

In the present invention, when there are n OH groups or COOH groups in one molecule of alcohol or carboxylic acid, it is expressed as n valence. Moreover, in this invention, when one ester bond exists in 1 molecule of an ester compound, it represents as 1 function, and when n exists, it represents as n function.
In the present invention, the ester wax contains an ester compound of a divalent to hexavalent alcohol and an aliphatic monocarboxylic acid, or an ester compound of a divalent to hexavalent carboxylic acid and an aliphatic monoalcohol. .
Here, the ester wax is an ester compound of a divalent alcohol and an aliphatic monocarboxylic acid, or an ester compound of a divalent carboxylic acid and an aliphatic monoalcohol (hereinafter sometimes referred to as a bifunctional ester wax). ) Is preferably contained.
When the ester wax contains a bifunctional ester wax, the bifunctional ester wax has a long and thin molecular shape in which molecules are extended. Therefore, it can exist in a state where the specific surface area is large.
Further, the resin A having the structure represented by the formula (1) can exhibit the effect as a dispersant more remarkably without being affected by steric hindrance to the bifunctional ester wax.
When the ester wax contains an ester compound of a trivalent to hexavalent alcohol and an aliphatic monocarboxylic acid, or an ester compound of a trivalent to hexavalent carboxylic acid and an aliphatic monoalcohol, the molecular shape As a bifunctional ester wax, since the number of ester groups increases, the specific surface area does not exist in a large state as compared with the bifunctional ester wax. It is believed that the effects of the invention can be obtained.

Specific examples of the aliphatic monocarboxylic acid include myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, lignoceric acid, serotic acid, montanic acid, mellicic acid, oleic acid, vaccenic acid, linoleic acid, Examples include linolenic acid.
Specific examples of the aliphatic monoalcohol include myristyl alcohol, cetanol, stearyl alcohol, arachidyl alcohol, behenyl alcohol, tetracosanol, hexacosanol, octacosanol, triacontanol and the like.
Specific examples of divalent carboxylic acids include butanedioic acid (succinic acid), pentanedioic acid (glutaric acid), hexanedioic acid (adipic acid), heptanedioic acid (pimelic acid), and octanedioic acid (suberic acid). , Nonanedioic acid (azelaic acid), decanedioic acid (sebacic acid), dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, hexadecanedioic acid, octadecanedioic acid, eicosanedioic acid, phthalic acid, isophthalic acid, terephthalic acid, etc. Is mentioned.
Specific examples of the divalent alcohol include ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, and 1,10-decanediol. 1,12-dodecanediol, 1,14-tetradecanediol, 1,16-hexadecanediol, 1,18-octadecanediol, 1,20-eicosanediol, 1,30-triacontanediol, diethylene glycol, diethylene glycol Examples include propylene glycol, 2,2,4-trimethyl-1,3-pentanediol, neopentyl glycol, 1,4-cyclohexanedimethanol, spiroglycol, 1,4-phenylene glycol, bisphenol A, hydrogenated bisphenol A, and the like. It is done.
Specific examples of the trivalent alcohol include 1,2,4-butanetriol, 1,2,5-pentanetriol, 2-methyl-1,2,4-butanetriol, glycerin, 2-methylpropanetriol, tri Examples include methylolethane, triethylolethane, trimethylolpropane, 1,3,5-trihydroxymethylbenzene.
Specific examples of the tetravalent alcohol include 1,2,3,6-hexanetetrol and pentaerythritol. Specific examples of the pentavalent alcohol include glucose. Specific examples of the hexavalent alcohol include dipenta Examples include erythritol.
Specific examples of the trivalent or higher carboxylic acid include trimellitic acid and pyromellitic acid.

  Moreover, in this invention, ester wax may contain ester compounds other than the said ester compound to such an extent that the effect of this invention is not impaired. The toner may contain a known wax in addition to the ester wax to the extent that the effects of the present invention are not impaired. Specific examples of known waxes include aliphatic hydrocarbon waxes such as low molecular weight polyethylene, low molecular weight polypropylene, microcrystalline wax, paraffin wax, and Fischer-Tropsch wax; oxides of aliphatic hydrocarbon waxes such as oxidized polyethylene wax; Those block copolymers are mentioned.

In the present invention, the polyfunctional ester wax is more preferably an ester compound represented by the following formula (2) or formula (3).
Formula (2): R ³ —C (═O) —O— (CH ₂ ) _x —O—C (═O) —R ⁴
Equation _{^{(3): R 5 -O-}} C (= O) - (CH 2) y -C (= O) -O-R 6
[In Formula (2) and Formula (3), R ³ , R ⁴ , R ⁵ , and R ⁶ are each independently an alkyl group having 13 to 26 carbon atoms, and x and y are each Independently, it is an integer of 8 or more and 10 or less. ]
Although the mechanism by which the effect of the present invention is more suitable by using the ester compound is unclear, the toner of the present invention has a better balance between the decrease in melt viscosity during fixing and the storage stability. Are thinking.
In the toner of the present invention, the content of the ester wax is preferably 2.0 parts by mass or more and 20.0 parts by mass or less, and 3.0 parts by mass or more and 10.0 parts by mass with respect to 100 parts by mass of the binder resin. It is more preferable that the amount is not more than part by mass. By setting the content in the above range, the low temperature fixability can be further improved while maintaining the storage stability.

In the present invention, the binder resin has a benzene ring and an ester bond.
The resin having a benzene ring and an ester bond is not particularly limited, but a styrene-acrylic resin, a styrene-methacrylic resin, a polyester resin containing an alcohol compound having a benzene ring and a carboxylic acid compound as constituents, an alcohol compound, and Polyester resin containing a carboxylic acid compound having a benzene ring as a constituent component, an alcohol compound having a benzene ring and a polyester resin containing a carboxylic acid compound having a benzene ring as a constituent component (hereinafter referred to as a polyester resin having a benzene ring and an ester bond) Can also be suitably exemplified.
Among these, the binder resin preferably contains at least one of a styrene acrylic resin and a styrene methacrylic resin, and more preferably contains a styrene acrylic resin.
Further, the content ratio of the monomer unit derived from styrene in the styrene acrylic resin and the styrene methacrylic resin is preferably 60% by mass or more and 90% by mass or less based on the respective resins, and 65% by mass. It is more preferable that the content is not less than 80% and not more than 80% by mass. The monomer unit refers to a reacted form of the monomer substance in the resin.
Moreover, this styrene is the concept also containing the following styrene derivative.
When the content ratio of the monomer unit derived from styrene is 60% by mass or more, π-π mutual due to the benzene ring in the structure represented by the formula (1) in the resin A and the benzene ring derived from styrene in the binder resin. The action becomes sufficient, and the effects of the present invention are more suitably exhibited.

When the binder resin is a styrene acrylic resin or a styrene methacrylic resin, a known resin can be used. In addition, when a toner is obtained using a suspension polymerization method, styrene and an acrylic polymerizable monomer or styrene and a methacrylic polymerizable monomer are copolymerized during the suspension polymerization reaction as a polymerizable monomer. By doing so, a styrene acrylic resin or a styrene methacrylic resin may be produced.
Specific examples of the polymerizable monomer are as follows.
Styrene; α-methylstyrene, β-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, pn-butylstyrene, p-tert-butylstyrene, p- Styrene derivatives 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 polymerizable 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, and the acrylate A methacrylic polymerizable monomer having a methacrylate as an example is exemplified.
When preparing a styrene acrylic resin or a styrene methacrylic resin, various polymerization initiators such as peroxide polymerization initiators and azo polymerization initiators can be used.
Examples of organic peroxide polymerization initiators include peroxyesters, peroxydicarbonates, dialkyl peroxides, peroxyketals, ketone peroxides, hydroperoxides, and diacyl peroxides. Examples of the inorganic system include persulfate and hydrogen peroxide. Specifically, t-butyl peroxyacetate, t-butyl peroxypivalate, t-butyl peroxyisobutyrate, t-hexyl peroxyacetate, t-hexyl peroxypivalate, t-hexyl peroxyiso Peroxyesters such as butyrate, t-butylperoxyisopropyl monocarbonate, t-butylperoxy 2-ethylhexyl monocarbonate; diacyl peroxides such as benzoyl peroxide; peroxydicarbonates such as diisopropyl peroxydicarbonate; 1 , 1-di-t-hexylperoxycyclohexane and other peroxyketals; di-t-butyl peroxide and other dialkyl peroxides; and other t-butyl peroxyallyl monocarbonate and the like It is below.
As the azo polymerization initiator, 2,2′-azobis- (2,4-dimethylvaleronitrile), 2,2′-azobisisobutyronitrile, 1,1′-azobis (cyclohexane-1-carbonitrile) ), 2,2′-azobis-4-methoxy-2,4-dimethylvaleronitrile, azobisisobutyronitrile, dimethyl-2,2′-azobis (2-methylpropionate), and the like.
If necessary, two or more of these polymerization initiators can be used simultaneously. It is preferable that the usage-amount of the polymerization initiator used in this case is 0.1 mass part or more and 20.0 mass parts or less with respect to 100 mass parts of polymerizable monomers.

The alcohol compound having a benzene ring and the carboxylic acid compound having a benzene ring constituting the polyester resin having a benzene ring and an ester bond are not particularly limited, and known compounds can be used. Moreover, this polyester resin can be manufactured using a well-known manufacturing method.
Specific examples of the alcohol compound having a benzene ring are as follows.
Polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene (3.3) -2,2-bis (4-hydroxyphenyl) propane, polyoxyethylene (2. 0) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene (2.0) -polyoxyethylene (2.0) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene (6) Alkylene oxide adduct of bisphenol A such as -2,2-bis (4-hydroxyphenyl) propane; bisphenol A such as bisphenol A and hydrogenated bisphenol A; 1,3,5-trihydroxymethyl Benzene is mentioned.
On the other hand, specific examples of the carboxylic acid compound having a benzene ring are as follows.
And aromatic polycarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid and pyromellitic acid.

The weight average molecular weight (Mw) of the binder resin is not particularly limited, but is preferably 4000 or more and 100,000 or less from the viewpoint of further improving the low-temperature fixability and the storage stability.
The weight average molecular weight (Mw) can be controlled by a known method such as the amount of polymerization initiator added, the reaction temperature during polymerization, and the reaction solvent.

［前記式（１）中、Ｒ^１は、それぞれ独立して、炭素数１以上１８以下（好ましくは炭素数１以上８以下）のアルキル基、又は、炭素数１以上１８以下（好ましくは炭素数１以上８以下）のアルコキシ基を示し、ｎは０以上３以下の整数を示し、＊は前記樹脂Ａにおける結合部位である。］ In the present invention, the resin A is a polymer having a structure represented by the following formula (1).

[In the formula (1), each R ¹ independently represents an alkyl group having 1 to 18 carbon atoms (preferably 1 to 8 carbon atoms), or 1 to 18 carbon atoms (preferably carbon number). 1 represents an alkoxy group of 1 to 8, n represents an integer of 0 to 3, and * represents a binding site in the resin A. ]

The polymer having the structure represented by the formula (1) can be produced by a known method using, for example, a polymerizable monomer having a structure represented by the formula (1).
Specific examples of the polymerizable monomer having a salicylic acid structure that can be used (vinyl-based polymerizable monomer) include the following.
3-vinylsalicylic acid, 4-vinylsalicylic acid, 5-vinylsalicylic acid, 6-vinylsalicylic acid, 3-vinyl-5-isopropylsalicylic acid, 3-vinyl-5-t-butylsalicylic acid, 4-vinyl-6-t- An example is butylsalicylic acid.
The polymer containing the formula (1) may be a single polymer or a copolymer with other polymerizable monomer. Specific examples of the polymerizable monomer that can be used as the copolymer are as follows.
Styrene; α-methylstyrene, β-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, pn-butylstyrene, p-tert-butylstyrene, p- Styrene derivatives 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 polymerizable 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-buty 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 polymerizable monomers such as ethyl methacrylate, vinyl type polymerizable monomers such as are exemplified.
When producing the polymer containing Formula (1), the above-mentioned thing can be used similarly as a polymerization initiator which can be used.
In the present invention, the weight average molecular weight (Mw) of the resin A is not particularly limited, but is preferably 4000 or more and 100,000 or less from the viewpoint of further improving the low-temperature fixability and the storage stability.
The weight average molecular weight (Mw) can be controlled by a known method such as the amount of polymerization initiator added, the reaction temperature during polymerization, and the reaction solvent.
The content of the resin A is preferably 0.05 parts by mass or more and 15.00 parts by mass or less with respect to 100 parts by mass of the binder resin from the viewpoint of more suitably exhibiting the effects of the present invention. More preferably, it is 0.50 parts by mass or more and 10.00 parts by mass or less.

［前記式（４）中、Ｒ^７は、それぞれ独立して、炭素数１以上１８以下（好ましくは炭素数１以上８以下）のアルキル基、又は、炭素数１以上１８以下（好ましくは炭素数１以上８以下）のアルコキシ基を示し、Ｒ^８は、水素原子、ヒドロキシ基、炭素数１以上１８以下（好ましくは炭素数１以上８以下）のアルキル基、又は、炭素数１以上１８以下（好ましくは炭素数１以上８以下）のアルコキシ基を示し、ｇは１以上３以下の整数を示し、ｈは０以上３以下の整数を示し、＊は前記樹脂Ａにおける結合部位である。］ In the present invention, the resin A is preferably a polymer having a structure represented by the following formula (4). By having this structure, the effect of this invention is exhibited more suitably.

[In the formula (4), each R ⁷ independently represents an alkyl group having 1 to 18 carbon atoms (preferably 1 to 8 carbon atoms), or 1 to 18 carbon atoms (preferably carbon number). R ⁸ represents a hydrogen atom, a hydroxy group, an alkyl group having 1 to 18 carbon atoms (preferably 1 to 8 carbon atoms), or 1 to 18 carbon atoms ( Preferably, it represents an alkoxy group having 1 to 8 carbon atoms, g represents an integer of 1 to 3, h represents an integer of 0 to 3, and * represents a binding site in the resin A. ]

When the resin A is a polymer having a structure represented by the above formula (4), the benzene ring of the salicylic acid moiety represented by the formula (4) in the resin A, the salicylic acid moiety, and — (CH ₂ ) _g This is because a benzene ring connected via − interacts with a benzene ring present in the binder resin by π-π to further express affinity.
In this case, since the structure of — (CH ₂ ) _g — becomes an appropriate spacer, steric hindrance does not occur, and interaction with the benzene ring existing in the binder resin is efficiently generated. It is believed that the effects of the invention are more suitably exhibited.

In this invention, it does not specifically limit as a manufacturing method of resin A, It can manufacture by a well-known method.
When the resin A is a polymer having a structure represented by the above formula (4), for example, a polymerizable monomer having a structure represented by the following formula (5), and if necessary, the above-mentioned vinyl-based polymerizable monomer What is necessary is just to superpose | polymerize using a monomer and a polymerization initiator.

［前記式（５）中、Ｒ^９は、それぞれ独立して、炭素数１以上１８以下（好ましくは炭素数１以上８以下）のアルキル基、又は、炭素数１以上１８以下（好ましくは炭素数１以上８以下）のアルコキシ基を表し、Ｒ^１０は、水素原子、ヒドロキシ基、炭素数１以上１８以下（好ましくは炭素数１以上８以下）のアルキル基、又は、炭素数１以上１８以下（好ましくは炭素数１以上８以下）のアルコキシ基を表し、Ｒ^１１は、水素原子、又は、メチル基を表し、ｍは１以上３以下の整数を表し、ｎは０以上３以下の整数を表す。］

[In the formula (5), each R ⁹ independently represents an alkyl group having 1 to 18 carbon atoms (preferably 1 to 8 carbon atoms), or 1 to 18 carbon atoms (preferably carbon number). Represents an alkoxy group having 1 to 8 carbon atoms, and R ¹⁰ represents a hydrogen atom, a hydroxy group, an alkyl group having 1 to 18 carbon atoms (preferably 1 to 8 carbon atoms), or 1 to 18 carbon atoms ( Preferably, it represents an alkoxy group having 1 to 8 carbon atoms, R ¹¹ represents a hydrogen atom or a methyl group, m represents an integer of 1 to 3 and n represents an integer of 0 to 3 . ]

  Specific examples of the polymerizable monomer (formula (5)) include the following. The examples shown here are merely examples, and the present invention is not limited to these examples.

The polymer containing the formula (4) may be a single polymer or a copolymer with another polymerizable monomer. As the polymerizable monomer that can be used as the copolymer, those similar to the polymerizable monomers exemplified for the polymer containing the above formula (1) can be used. Moreover, the same thing as the case where the polymerization initiator which can be used produces the polymer containing the said Formula (1) can be used.
The weight average molecular weight (Mw) of the polymer containing the above formula (4) is not particularly limited, but is preferably 4000 or more and 100,000 or less from the viewpoint of further improving the low-temperature fixability and storage stability.
The weight average molecular weight (Mw) can be controlled by a known method such as the amount of polymerization initiator added, the reaction temperature during polymerization, and the reaction solvent.

In the present invention, the molar content of the structure represented by the formula (1) is preferably 0.10 μmol / g or more and 100.00 μmol / g or less, based on the mass of the toner, and is 1.00 μmol / g or more. More preferably, it is 90.00 μmol / g or less.
When the molar content of the structure represented by the formula (1) is 0.10 μmol / g or more and 100.00 μmol / g or less, the resin A having the structure represented by the formula (1) with respect to the polyfunctional ester wax It is considered that the function sufficiently develops as a dispersant in the toner, and the effects of the present invention are more suitably exhibited.
When the molar content of the structure represented by the formula (1) is less than 0.10 μmol / g, the resin A having the structure represented by the formula (1) functions as a dispersant in the toner for the polyfunctional ester wax. Tend to decrease. On the other hand, when it is more than 100.00 μmol / g, the glass transition temperature (Tg) of the resin A tends to be high, and the low-temperature fixability tends to decrease.
The molar content of the structure represented by the formula (1) can be controlled by adjusting the addition amount of the resin A during toner production from the content of the structure represented by the formula (1) in the resin A.
The molar content of the structure represented by the formula (1) in the resin A can be quantified from the acid value measurement of the resin A.

The toner of the present invention contains a colorant. As the colorant, known colorants such as various conventionally known dyes and pigments can be used.
Examples of the black colorant include carbon black, aniline black, acetylene black, titanium black, and those adjusted to black using the following yellow, magenta, and cyan colorants.
Examples of the pigment-based yellow colorant include compounds typified by condensed azo compounds, isoindolinone compounds, anthraquinone compounds, azo metal complexes, methine compounds, and allylamide compounds. Specifically, C.I. I. Pigment Yellow 3, 7, 10, 12, 13, 14, 15, 17, 23, 24, 60, 62, 74, 75, 83, 93, 94, 95, 99, 100, 101, 104, 108, 109, 110 111, 117, 123, 128, 129, 138, 139, 147, 148, 150, 155, 166, 168, 169, 177, 179, 180, 181, 183, 185, 191: 1, 191, 192, 193 199.
Examples of the dye-based yellow colorant include C.I. I. solvent Yellow 33, 56, 79, 82, 93, 112, 162, 163, C.I. I. Disperse Yellow 42, 64, 201, 211 are listed.
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, 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. And CI Pigment Bio Red 19.
Examples of the cyan colorant include phthalocyanine compounds and derivatives thereof, anthraquinone compounds, and basic dye lake compounds. Specifically, C.I. I. Pigment Blue 1, 7,
15, 15: 1, 15: 2, 15: 3, 15: 4, 60, 62, 66.
The colorants can be used alone or mixed and further used in the form of a solid solution. In the present invention, the colorant is selected from the viewpoints of hue angle, saturation, brightness, weather resistance, OHT transparency, and dispersibility in the toner. The addition amount 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 binder resin.

The toner of the present invention may contain a magnetic material to form a magnetic toner. In that case, the magnetic material can also serve as a colorant.
Examples of the magnetic material include iron oxides such as magnetite, maghemite, and ferrite, or iron oxides including other metal oxides; metals such as Fe, Co, and Ni, or these metals and Al, Co, Cu, Examples include alloys with metals such as Pb, Mg, Ni, Sn, Zn, Sb, Ca, Mn, Se, Ti, and mixtures thereof.
Specifically, triiron tetraoxide _{(Fe 3 O} 4), iron sesquioxide _{(γ-Fe 2 O 3)} , iron oxide, zinc (ZnFe ₂ O _4), oxidized iron-copper (CuFe ₂ O _4), iron oxide Examples thereof include neodymium (NdFe ₂ O ₃ ), iron barium oxide (BaFe ₁₂ O ₁₉ ), iron magnesium oxide (MgFe ₂ O ₄ ), and iron oxide manganese (MnFe ₂ O ₄ ).
These magnetic materials may be used alone or in combination of two or more. A particularly suitable magnetic substance is a fine powder of triiron tetroxide or γ-iron sesquioxide.
The average particle diameter of these magnetic materials is preferably 0.1 μm or more and 2 μm or less, and more preferably 0.1 μm or more and 0.3 μm or less.
The magnetic characteristics when 795.8 kA / m (10 k Oersted) is applied are such that the coercive force (Hc) is 1.6 kA / m to 12 kA / m (20 Oersted to 150 Oersted). Saturation magnetization ([sigma] s) is preferably from ^5am 2 / kg or more 200 Am ² / kg, more preferably not more than 50 Am ² / kg or more 100 Am ² / kg. Residual magnetization (.sigma.r) is, ^2Am 2 / kg or more 20 Am ² / kg or less being preferred.
The content of the magnetic body is preferably 10.0 parts by mass or more and 200.0 parts by mass or less, more preferably 20.0 parts by mass or more and 150.0 parts by mass with respect to 100 parts by mass of the binder resin. It is as follows.

In the present invention, a charge control agent may be blended in order to stabilize the charging characteristics of the toner.
As the charge control agent, known ones can be used, and in particular, a charge control agent that has a high charging speed and can stably maintain a constant charge amount is preferable.
The addition amount of the charge control agent is preferably 0.1 parts by mass or more and 10.0 parts by mass or less, more preferably 0.1 parts by mass or more and 5.0 parts by mass with respect to 100 parts by mass of the binder resin. It is as follows.

The toner of the present invention preferably has a core-shell structure.
In this case, the shell layer preferably contains an amorphous polyester resin.
In the present invention, having a core-shell structure means a structure in which the shell layer covers the surface of the core layer. Here, the coating means that the surface of the core is covered with a shell layer.
It is preferable to use an amorphous polyester resin for the shell layer because the storage stability and durability are further improved.
The amorphous polyester is not particularly limited as long as it is an amorphous polyester resin obtained by polycondensation of a polyhydric alcohol and a polyvalent carboxylic acid.
Examples of the polyhydric alcohol component include ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, diethylene glycol, triethylene glycol, 1,5-pentanediol, 1,6 -Hexanediol, neopentyl glycol, 2-ethyl-1,3-hexanediol, cyclohexanedimethanol, butenediol, octenediol, cyclohexenedimethanol, hydrogenated bisphenol A, ethylene oxide adduct of bisphenol A, propylene of bisphenol A An oxide adduct is mentioned.
As the polyvalent carboxylic acid, benzene dicarboxylic acid such as phthalic acid, terephthalic acid, isophthalic acid, phthalic anhydride or the anhydride thereof: alkyl dicarboxylic acid such as succinic acid, adipic acid, sebacic acid, azelaic acid or the like Anhydrides are mentioned.
In the present invention, the glass transition temperature (Tg) of the amorphous polyester resin is preferably 60 ° C. or higher and 90 ° C. or lower. By setting it as the said range, storage stability and durability improve more and are preferable.
The weight average molecular weight (Mw) of the amorphous polyester is not particularly limited, but is preferably 5000 or more and 30000 or less from the viewpoint of further improving the low-temperature fixability and the storage stability.
The weight average molecular weight (Mw) can be controlled by a known method such as the type of catalyst, the reaction temperature during the condensation polymerization, and the reaction solvent.
In the present invention, the resin used for the core layer of the core-shell structure preferably contains at least one of a styrene acrylic resin and a styrene methacrylic resin, and more preferably contains a styrene acrylic resin.
Examples of the styrene acrylic resin or styrene methacrylic resin used for the core layer include those described above.
In the present invention, when the toner has a core-shell structure, the content of the amorphous polyester resin is preferably 1 part by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the binder resin.

Next, a method for producing the toner of the present invention will be described.
As a method for producing the toner of the present invention, a pulverization method, a suspension polymerization method, a dispersion polymerization method, a solution in which a raw material is dissolved or dispersed in an organic solvent is granulated in an aqueous medium to form a toner. There is a method such as law.
In particular, since the production process is simple and the desired toner can be easily obtained, it is preferable to produce the toner by suspension polymerization. Further, the suspension polymerization method is preferable since exposure of the polyfunctional ester wax to the toner surface is suppressed when compared with the pulverization method, and thus a toner having excellent image quality can be obtained.
For example, the toner production method of the present invention includes:
A polymerizable monomer composition containing a colorant, ester wax, resin A, and a polymerizable monomer is dispersed in an aqueous medium, and particles of the polymerizable monomer composition are formed in the aqueous medium. Process and
A method for producing a toner comprising a step of polymerizing the polymerizable monomer contained in the particles of the polymerizable monomer composition,
The ester wax contains an ester compound of a divalent to hexavalent alcohol and an aliphatic monocarboxylic acid, or an ester compound of a divalent to hexavalent carboxylic acid and an aliphatic monoalcohol,
The resin A has a structure represented by the above formula (1),
The binder resin is a resin having a benzene ring and an ester bond.

The method for producing the toner will be described more specifically, but is not limited thereto.
First, a colorant is uniformly dissolved or dispersed in a polymerizable monomer constituting the binder resin by a stirrer or the like. In particular, when the colorant is a pigment, it is preferable to disperse the pigment in the polymerizable monomer using a disperser to obtain a pigment dispersion (master batch dispersion).
As a method for dispersing the pigment in the polymerizable monomer, a known method can be used. For example, the pigment powder is gradually added to the polymerizable monomer while stirring, and the polymerized monomer is sufficiently blended with the solvent. Further, by applying mechanical shearing force with a dispersing machine such as a ball mill, paint shaker, dissolver, attritor, sand mill, and high speed mill, the pigment can be stably finely dispersed, that is, dispersed into uniform fine particles.
The obtained pigment dispersion is uniformly dissolved by a stirrer or the like together with the polymerizable monomer constituting the binder resin, the resin A and the ester wax, and, if necessary, the polymerization initiator and other additives. Disperse to prepare a polymerizable monomer composition.
The obtained polymerizable monomer composition is added to an aqueous medium containing a dispersant, and finely dispersed to a toner particle size using a stirrer such as a high-speed stirrer or an ultrasonic disperser (granulation). Step), particles of the polymerizable monomer composition are formed in an aqueous medium.
Then, the polymerizable monomer contained in the particles of the polymerizable monomer composition is polymerized by light or heat (polymerization step). The particles obtained by polymerization may be filtered, washed, and dried by a known method, and if necessary, external additives and the like may be mixed and adhered to the surface to form a toner.
In the production method, the polymerization initiator may be added at the same time when other additives are added to the polymerizable monomer as described above, or the particles of the polymerizable monomer composition in an aqueous medium. You may mix immediately before forming. Further, immediately after the formation of the particles, a polymerization initiator dissolved in a polymerizable monomer or a solvent may be added before starting the polymerization reaction. As the polymerization initiator, the above-mentioned polymerization initiators can be used similarly. Moreover, you may add a well-known crosslinking agent.
Furthermore, as the polymerizable monomer that can be suitably used in the suspension polymerization method, the above polymerizable monomers can be similarly used.

In the present invention, examples of the aqueous medium include water; alcohols such as methyl alcohol, ethyl alcohol, modified ethyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, tert-butyl alcohol, sec-butyl alcohol; Examples include ether alcohols such as methyl cellosolve, cellosolve, isopropyl cellosolve, butyl cellosolve, diethylene glycol monobutyl ether, and water-soluble ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; esters such as ethyl acetate; Ethers such as ethyl ether and ethylene glycol; acetals such as methylal and diethyl acetal; acids such as formic acid, acetic acid and propionic acid It is selected. Of these, water or alcohols are preferred. Further, two or more kinds of these solvents can be mixed and used.
The concentration of the polymerizable monomer composition is preferably 1% by mass or more and 80% by mass or less, and more preferably 10% by mass or more and 65% by mass or less with respect to the aqueous medium.

A well-known thing can be used as this dispersing agent. For example, as an inorganic compound, calcium phosphate, magnesium phosphate, aluminum phosphate, zinc phosphate, calcium carbonate, magnesium carbonate, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, calcium metasilicate, calcium sulfate, barium sulfate, bentonite, Examples thereof include silica and alumina. As the organic compound, polyvinyl alcohol, gelatin, methylcellulose, methylhydroxypropylcellulose, ethylcellulose, sodium salt of carboxymethylcellulose, polyacrylic acid and its salt, starch and the like can be dispersed in an aqueous phase.
The concentration of the dispersant is preferably 0.2 parts by mass or more and 20.0 parts by mass or less with respect to 100 parts by mass of the polymerizable monomer composition.

In the present invention, an external additive may be externally added (externally added) to the toner for the purpose of improving the fluidity of the toner.
The external additive may be added to and mixed with the toner in order to improve the fluidity of the toner and to make the charge uniform, and the added external additive may be present in a state of adhering to the surface of the toner.
The external additive preferably has a number average particle diameter (D1) of primary particles of 4 nm to 500 nm.
Examples of the external additive include inorganic fine particles selected from silica fine particles, alumina fine particles, and titania fine particles, or composite oxides thereof. Examples of the composite oxide include silica aluminum fine particles and strontium titanate fine particles. These inorganic fine particles are preferably used after the surface is hydrophobized.
Further, the toner of the present invention may further contain other additives such as a lubricant powder such as Teflon (registered trademark) powder, zinc stearate powder, and polyvinylidene fluoride powder within a range that does not substantially adversely affect the toner. Abrasives such as cerium powder and silicon carbide powder, anti-caking agents, and organic and / or inorganic fine particles having reverse polarity can also be used in small amounts as developability improvers. These additives can also be used after hydrophobizing the surface.
The addition amount of the external additive is preferably 0.010 parts by mass or more and 8.0 parts by mass or less, more preferably 0.10 parts by mass or more and 4.0 parts by mass with respect to 100 parts by mass of the toner particles. It is as follows.

The weight average particle diameter (D4) of the toner of the present invention is preferably 4.0 μm or more and 12.0 μm or less, and more preferably 4.0 μm or more and 9.0 μm or less.
When the weight average particle size is in the above range, the specific surface area of the toner is appropriate, and therefore, durability, heat resistance, toner coloring power, and image resolution can be further improved.
The weight average particle diameter of the toner can be adjusted by the production conditions and classification at the time of toner production.
In the present invention, the glass transition temperature (Tg) of the toner is preferably 40 ° C. or higher and 70 ° C. or lower.
When the glass transition temperature is in the above range, storage stability, prevention of toner deterioration during long-term use, and low-temperature fixability can be further improved.
The glass transition temperature of the toner can be adjusted by the composition of the binder resin and the manufacturing conditions at the time of toner production.
Furthermore, in the molecular weight distribution measured by gel permeation chromatography (GPC) of the tetrahydrofuran soluble content of the toner, it is preferable that the molecular weight has a peak top of the main peak in the range of 8000 to 30000.
When the peak top is in the above range, it is possible to further improve the storage stability of the toner, the prevention of toner deterioration during long-term use, and the low-temperature fixability.

Hereinafter, methods for measuring physical properties of the toner of the present invention will be described.
<Measuring method of weight average particle diameter (D4) and number average particle diameter (D1) of toner>
The weight average particle diameter (D4) and number average particle diameter (D1) of the toner are calculated as follows. As a measuring device, a precise particle size distribution measuring device “Coulter Counter Multisizer 3” (registered trademark, manufactured by Beckman Coulter, Inc.) using a pore electrical resistance method equipped with a 100 μm aperture tube is used. For setting the measurement conditions and analyzing the measurement data, the attached dedicated software “Beckman Coulter Multisizer 3 Version 3.51” (manufactured by Beckman Coulter, Inc.) is used. The measurement is performed with 25,000 effective measurement channels.
As the electrolytic aqueous solution used for the measurement, a solution obtained by dissolving special grade sodium chloride in ion-exchanged water so as to have a concentration of 1% by mass, for example, “ISOTON II” (manufactured by Beckman Coulter, Inc.) can be used.
Prior to measurement and analysis, the dedicated software is set as follows. On the “Change Standard Measurement Method (SOM)” screen of the dedicated software, set the total count in the control mode to 50,000 particles, set the number of measurements once, and set the Kd value to “standard particles 10.0 μm” (Beckman Coulter Set the value obtained using By pressing the “Threshold / Noise Level Measurement Button”, the threshold and noise level are automatically set. In addition, the current is set to 1600 μA, the gain is set to 2, the electrolyte is set to ISOTON II, and the “aperture tube flush after measurement” is checked. In the “Pulse to particle size conversion setting” screen of the dedicated software, the bin interval is set to logarithmic particle size, the particle size bin is set to 256 particle size bin, and the particle size range is set to 2 μm to 60 μm.
The specific measurement method is as follows.
(1) Put 200 mL of the aqueous electrolytic solution into a 250 mL round bottom beaker made exclusively for Multisizer 3, set it on a sample stand, and stir the stirrer rod counterclockwise at 24 rpm. Then, the dirt and bubbles in the aperture tube are removed by the “aperture flush” function of the dedicated software.
(2) Put 30 mL of the electrolytic aqueous solution into a glass 100 mL flat bottom beaker. In this, "Contaminone N" (nonionic surfactant, anionic surfactant, 10% by weight aqueous solution of neutral detergent for pH7 precision measuring instrument cleaning, made by organic builder, manufactured by Wako Pure Chemical Industries, Ltd. 0.3 mL of a diluted solution obtained by diluting 3) with ion-exchanged water.
(3) Two oscillators with an oscillation frequency of 50 kHz are incorporated with the phase shifted by 180 degrees, and an ultrasonic disperser “Ultrasonic Dispersion System Tetora 150” (manufactured by Nikka Ki Bios) having an electrical output of 120 W is prepared. Put 3.3 L of ion exchange water in the water tank of the ultrasonic disperser, and add 2 mL of Contaminone N into this water tank. (4) The beaker of (2) is set in the beaker fixing hole of the ultrasonic disperser, and the ultrasonic disperser is operated. And the height position of a beaker is adjusted so that the resonance state of the liquid level of the electrolyte solution in a beaker may become the maximum.
(5) In a state where the electrolytic aqueous solution in the beaker of (4) is irradiated with ultrasonic waves, 10 mg of toner is added to the electrolytic aqueous solution little by little and dispersed. Then, the ultrasonic dispersion process is continued for another 60 seconds. In ultrasonic dispersion, the temperature of the water tank is appropriately adjusted so as to be 10 ° C. or higher and 40 ° C. or lower.
(6) To the round bottom beaker (1) installed in the sample stand, the electrolytic aqueous solution (5) in which the toner is dispersed is dropped using a pipette, and the measurement concentration is adjusted to 5%. Measurement is performed until the number of measured particles reaches 50,000.
(7) The measurement data is analyzed with the dedicated software attached to the apparatus, and the weight average particle diameter (D4) and the number average particle diameter (D1) are calculated. The “average diameter” on the “analysis / volume statistics (arithmetic average)” screen when the graph / volume% is set in the dedicated software is the weight average particle size (D4), and the graph / volume in the dedicated software is graph / When the number% is set, the “average diameter” on the “analysis / number statistics (arithmetic average)” screen is the number average particle diameter (D1).

<Measurement of molecular weight of resin, etc.>
The molecular weight and molecular weight distribution of the resin and toner are calculated in terms of polystyrene using gel permeation chromatography (GPC).
When measuring the molecular weight of a resin having an acid group, the column elution rate also depends on the amount of the acid group, so a sample with an acid group capped in advance is prepared.
Methyl esterification is preferable for capping, and a commercially available methyl esterifying agent can be used. Specifically, a method of treating with trimethylsilyldiazomethane is used.
The molecular weight is measured by GPC as follows.
A sample is added to THF (tetrahydrofuran), and the solution which is allowed to stand at room temperature for 24 hours is filtered through a solvent-resistant membrane filter “Maysho Disc” (manufactured by Tosoh Corporation) having a pore diameter of 0.2 μm to obtain a sample solution.
The amount of THF in the sample solution is adjusted so that the concentration of the sample is 0.8% by mass. In addition, when the sample is difficult to dissolve in THF, a basic solvent such as N, N-dimethylformamide (DMF) can be used.
Measurement is performed using the sample solution under the following conditions.
Apparatus: HLC8120 GPC (detector: RI) (manufactured by Tosoh Corporation)
Column: Seven series of Shodex KF-801, 802, 803, 804, 805, 806, 807 (manufactured by Showa Denko KK)
Eluent: Tetrahydrofuran (THF)
Flow rate: 1.0 mL / min
Oven temperature: 40.0 ° C
Sample injection volume: 0.10 mL
In calculating the molecular weight of the sample, the molecular weight distribution of the sample is calculated from the relationship between the logarithmic value of the calibration curve created by several monodisperse polystyrene standard samples and the number of counts.
Standard polystyrene samples for preparing calibration curves are trade names “TSK Standard Polystyrene F-850, F-450, F-288, F-128, F-80, F-40, F-20, manufactured by Tosoh Corporation. F-10, F-4, F-2, F-1, A-5000, A-2500, A-1000, A-500 ".

<Measurement of acid value of resin>
The acid value is the number of mg of potassium hydroxide necessary for neutralizing the acid contained in 1 g of the sample. The acid value in the present invention is measured according to JIS K 0070-1992. Specifically, it is measured according to the following procedure.
Titration is performed using a 0.1 mol / L potassium hydroxide ethyl alcohol solution (manufactured by Kishida Chemical Co., Ltd.). The factor of the potassium hydroxide ethyl alcohol solution is determined using a potentiometric titrator (potentiometric titrator AT-510 manufactured by Kyoto Electronics Industry Co., Ltd.).
Specifically, 100 mL of 0.100 mol / L hydrochloric acid is placed in a 250 mL tall beaker, titrated with a potassium hydroxide ethyl alcohol solution, and obtained from the amount of potassium hydroxide ethyl alcohol solution required for neutralization. As 0.100 mol / L hydrochloric acid, one prepared according to JIS K 8001-1998 is used.
The measurement conditions for the acid value measurement are shown below.
Titration device: potentiometric titration device AT-510 (manufactured by Kyoto Electronics Industry Co., Ltd.)
Electrode: Composite glass electrode double junction type (manufactured by Kyoto Electronics Industry Co., Ltd.)
Titrator control software: AT-WIN
Titration analysis software: Tview
The titration parameters and control parameters at the time of titration are as follows.
<Titration parameter>
Titration mode: Blank titration Titration style: Total titration Maximum titration: 20 mL
Waiting time before titration: 30 seconds Titration direction: Automatic <Control parameters>
End point determination potential: 30 dE
End point determination potential value: 50 dE / dmL
End point detection judgment: Not set Control speed mode: Standard gain: 1
Data collection potential: 4 mV
Data collection titration: 0.1 mL
<Main test>
0.100 g of the measurement sample is precisely weighed in a 250 mL tall beaker, and 150 mL of a mixed solution of toluene and ethanol (3: 1) is added and dissolved over 1 hour. Titrate with a potassium hydroxide ethyl alcohol solution using a potentiometric titrator.
<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 and ethanol (3: 1) is used).
The acid value is calculated by substituting the obtained result into the following formula.
A = [(C−B) × f × 5.611] / S
Here, A: acid value (mgKOH / g), B: addition amount of potassium hydroxide ethyl alcohol solution in blank test (mL), C: addition amount of potassium hydroxide ethyl alcohol solution in this test (m
L), f: factor of potassium hydroxide ethyl alcohol solution, S: sample (g).

<Composition analysis of resin A, amorphous polyester, binder resin, and polyfunctional ester wax>
The structures of the resin A, the amorphous polyester, the binder resin, and the polyfunctional ester wax were determined using a nuclear magnetic resonance apparatus ( ¹ H-NMR) [400 MHz, CDCl ₃ , room temperature (25 ° C.)], and the composition ratio Can be calculated.
Measuring apparatus: FT NMR apparatus JNM-EX400 (manufactured by JEOL Ltd.)
Measurement frequency: 400MHz
Pulse condition: 5.0μs
Frequency range: 10500Hz
Number of integrations: 64 times 50 mg of a sample is put in a sample tube having an inner diameter of 5 mm, and deuterated chloroform (CDCl3) is added as a solvent. The sample tube is placed in a constant temperature bath at 40 ° C., and the sample is dissolved to prepare a measurement sample. Measurement is performed under the above conditions using the measurement sample.
The molar ratio of each monomer component is determined from the integral value of the obtained spectrum, and the composition ratio is calculated based on this.
In addition, the molar content of the structure represented by the formula (1) in the resin A can be calculated by the above acid value measurement in addition to the above nuclear magnetic resonance apparatus.
Specifically, the structure of the monomer contained in the resin A is analyzed using a nuclear magnetic resonance apparatus, and the constituent monomer is identified. Next, from the above acid value measurement, it is quantified from the relationship between the structure represented by the formula (1) contained in the resin A and the acid value, and calculated as the molar content.
<Measurement of Glass Transition Temperature (Tg) of Toner and Resin>
The glass transition temperature of the toner and the resin is measured according to ASTM D3418-82 using a differential scanning calorimeter “Q1000” (manufactured by TA Instruments).
The temperature correction of the device detection unit uses the melting points of indium and zinc, and the correction of heat uses the heat of fusion of indium.
Specifically, 3 mg of a measurement sample is precisely weighed, placed in an aluminum pan, an empty aluminum pan is used as a control, equilibrated at 20 ° C. for 5 minutes, and then a measurement range of 20 ° C. to 140 ° C. The measurement is performed at a rate of temperature increase of 1 ° C./min with a modulation of 1.0 ° C./min between the following. The glass transition temperature is a temperature at a point where a straight line equidistant in the vertical axis direction from a straight line extended from each baseline at the time of measurement and a curve of a step-like change portion of the glass transition intersect.

  EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated concretely, this invention is not restrict | limited to these Examples. In the examples and comparative examples, “part” and “%” are based on mass unless otherwise specified.

<Production example of polyfunctional ester wax 1>
To a reactor equipped with a Dimroth, Dean-Stark water separator and thermometer, 300 mol parts of benzene, 200 mol parts of behenyl alcohol, 100 mol parts of sebacic acid, and 10 mol parts of p-toluenesulfonic acid were added and refluxed for 8 hours. The valve of the water separator was opened and azeotropic distillation was performed. After azeotropic distillation, it was washed with sodium carbonate and dried, and then benzene was distilled off. The obtained product was recrystallized, washed and purified to obtain a polyfunctional ester wax 1.

<Production example of polyfunctional ester wax 2-3>
Except having changed raw material alcohol and raw material carboxylic acid into the thing of Table 2, it manufactured similarly to the manufacture example of the polyfunctional ester wax 1, and obtained the polyfunctional ester wax 2-3.

<Manufacture of polyfunctional ester wax 4>
Benzene 3 in reactor equipped with Jim Roth, Dean-Stark water separator, thermometer
00 mol parts, 100 mol parts of 1,10-decanediol, 200 mol parts of behenic acid, and 10 mol parts of p-toluenesulfonic acid were added and refluxed for 8 hours. The valve of the water separator was opened and azeotropic distillation was performed. After azeotropic distillation, it was washed with sodium carbonate and dried, and then benzene was distilled off. The obtained product was recrystallized, washed and purified to obtain a polyfunctional ester wax 4.

<Production of monofunctional ester wax 1>
To a reactor equipped with Dimroth, Dean-Stark water separator and thermometer, 300 mol parts of benzene, 100 mol parts of behenyl alcohol, 100 mol parts of behenic acid and 10 mol parts of p-toluenesulfonic acid were added and refluxed for 8 hours. The valve of the water separator was opened and azeotropic distillation was performed. After azeotropic distillation, it was washed with sodium carbonate and dried, and then benzene was distilled off. The obtained product was recrystallized, washed and purified to obtain monofunctional ester wax 1.

<Manufacture of resin A>
[Production Example of Polymerizable Monomer (Formula (5))]
<Production example of polymerizable monomer B-1>
18 g of 2,4-dihydroxybenzoic acid was dissolved in 150 mL of methanol. To this solution, 36.9 g of potassium carbonate was added and heated to 65 ° C. A solution obtained by mixing and dissolving 18.7 g of 4- (chloromethyl) styrene and 100 mL of methanol was prepared, and this was dropped into a solution containing a salicylic acid intermediate, and reacted at 65 ° C. for 3 hours. The obtained reaction solution was cooled and then filtered, and methanol in the filtrate was distilled off under reduced pressure to obtain a precipitate. The precipitate was dispersed in 1.50 L of water at pH = 2, and extracted by adding ethyl acetate. Then, after washing with water, it was dried with magnesium sulfate, and ethyl acetate was distilled off under reduced pressure to obtain a precipitate. The precipitate was washed with hexane and then recrystallized with toluene / ethyl acetate to obtain 20.1 g of a polymerizable monomer B-1 having a structure represented by the following formula (6).

<Production example of polymerizable monomer B-2>
(Process 1)
100 g of 2,5-dihydroxybenzoic acid and 1441 g of 80% sulfuric acid were mixed while heating to 50 ° C., 144 g of tert-butyl alcohol was added to the mixture, and the mixture was stirred at 50 ° C. for 30 minutes. Next, 144 g of tert-butyl alcohol was added to the mixed solution, and the mixture was stirred at 50 ° C. for 30 minutes three times. The reaction solution was cooled to room temperature and then slowly poured into 1.00 kg of ice water, and the precipitate was filtered. The precipitate was washed with water and further washed with hexane. The precipitate obtained here was dissolved in 200 mL of methanol and reprecipitated in 3.60 L of water. After filtration, it was dried at 80 ° C. to obtain 74.9 g of a salicylic acid intermediate represented by the following formula (7).

(Process 2)
25.0 g of the salicylic acid intermediate was dissolved in 150 mL of methanol. To this solution, 36.9 g of potassium carbonate was added and heated to 65 ° C. A solution obtained by mixing and dissolving 18.7 g of 4- (chloromethyl) styrene and 100 mL of methanol was prepared, and this was dropped into a solution containing a salicylic acid intermediate, and reacted at 65 ° C. for 3 hours. The obtained reaction solution was cooled and then filtered, and methanol in the filtrate was distilled off under reduced pressure to obtain a precipitate. The precipitate was dispersed in 1.50 L of water at pH = 2, and extracted by adding ethyl acetate. Then, after washing with water, it was dried with magnesium sulfate, and ethyl acetate was distilled off under reduced pressure to obtain a precipitate. The precipitate was washed with hexane and then recrystallized with toluene / ethyl acetate to obtain 20.1 g of a polymerizable monomer B-2 having a structure represented by the following formula (8).

<Production example of polymerizable monomer B-3>
100.0 g of 2,5-dihydroxybenzoic acid was dissolved in 2 L of methanol, 88.3 g of potassium carbonate was added, and the mixture was heated to 67 ° C. To this solution, 102.0 g of 4- (chloromethyl) styrene was added dropwise over 22 minutes and reacted at 67 ° C. for 12 hours. The obtained reaction liquid was cooled, methanol was distilled off under reduced pressure, and washed with hexane. The residue was dissolved in methanol, dropped into water, reprecipitated, and the precipitate was filtered. This reprecipitation operation was repeated twice, and the residue was dried at 80 ° C. to obtain a polymerizable monomer B-3 having a structure represented by the following formula (9).

<Production example of polymerizable monomer B-4>
A salicylic acid intermediate was obtained in the same manner as in Production Example (Step 1) of the polymerizable monomer B-2 except that 144 g of tert-butyl alcohol was changed to 253 g of 2-octanol. A polymerizable monomer having a structure represented by the following formula (10) in the same manner as in Production Example (Step 2) of the polymerizable monomer B-2 except that 32 g of the obtained salicylic acid intermediate is used. Body B-4 was obtained.

<Production example of polymerizable monomer B-5>
The polymerizable monomer B-5 is Journal of Polymer Science:
It was produced using the method described in Polymer Chemistry Edition 18, 2755 (1980).

<Production example of resin A>
<Production Example of Resin A-1>
12.00 g of the polymerizable monomer B-1 and 88.00 g of styrene were dissolved in 40.00 ml of N, N-dimethylformamide (DMF), stirred for 1 hour, and then heated to 110 ° C.
Solution obtained by stirring a solution prepared by adding 3.40 g of tert-butylperoxyisopropyl monocarbonate (trade name Perbutyl I, manufactured by Nippon Oil & Fats Co., Ltd.) to 40.00 ml of toluene in this reaction solution for 1 hour. Was dripped.
The reaction was further carried out at 110 ° C. for 4 hours while introducing nitrogen. Then, it cooled and it was dripped at methanol 1.00L, and the deposit was obtained.
The obtained precipitate was dissolved in 120 ml of tetrahydrofuran (THF), and then added dropwise to 1.80 L of methanol to precipitate a white precipitate, which was filtered and dried at 90 ° C. under reduced pressure. Resin A-1 obtained from -1 and styrene was obtained.
The composition analysis of the obtained resin A-1 was performed using ¹ H-NMR as described above, and it was confirmed that the polymerizable monomer B-1 was polymerized.
In addition, the acid value of the resin A-1 is 24.9 mgKOH / g, and it is confirmed from the acid value that the structure represented by the formula (1) derived from the polymerizable monomer B-1 contains 444 μmol / g. did.
Table 3 shows the charged amount and physical properties of Resin A-1.

<Production Examples of Resins A-2 to A-9>
Resins A-2 to A-9 were obtained in the same manner as in the production example of Resin A-1, except that the polymerizable monomer species and blending were changed as shown in Table 3. Table 3 shows the physical properties of the obtained resins A-2 to A-9.

表中、２−ＥＨＡは、２−エチルヘキシルアクリレートを表す。

In the table, 2-EHA represents 2-ethylhexyl acrylate.

[Production Example of Comparative Resin for Resin A]
<Production Example of Resin A-10>
As the polymerizable monomer B-6, 4-vinylbenzoic acid was used, and except that it was changed to the polymerizable monomer and formulation as shown in Table 4, and the production example of the resin A-1 Resin A-10 was obtained in the same manner. Table 4 shows the physical properties of the obtained resin A-10.

<Production Example of Resin A-11>
Except that acrylic acid was used as the polymerizable monomer B-7, and the others were changed to the polymerizable monomers and blends shown in Table 4, the same as in the production example of the resin A-1. Resin A-11 was obtained. Table 4 shows the physical properties of the obtained resin A-11.

<Production Example of Resin A-12>
As the polymerizable monomer B-8, 2-acrylamido-2-methylpropanesulfonic acid was used, and a reaction vessel was prepared with a stirrer, a condenser, a thermometer, and a nitrogen introduction tube. The reaction vessel was charged with 100.0 parts of 2-butanone and 50.0 parts of methanol in a non-light-shielded state and brought to 60 ° C. under a nitrogen stream.
Next, the following monomers and solvent were mixed to prepare a monomer mixture.
(Monomer composition and mixing ratio)
2-acrylamido-2-methylpropanesulfonic acid-containing mixed solution, 2-acrylamido-2-methylpropanesulfonic acid 8.00 parts, styrene 83.00 parts, 2-ethylhexyl acrylate (2-EHA) 9.00 parts, 2 -Butanone 100.00 parts-Methanol 50.00 parts-Dimethyl-2,2'-azobis (2-methylpropionate) 1.00 parts The said monomer liquid mixture was dripped over 60 minutes to reaction container. The mixture was stirred at 60 ° C. for 8 hours and cooled to room temperature. The obtained polymer-containing composition was added dropwise to 1400 parts of methanol to precipitate and crystallize the resin composition. The obtained resin composition was filtered and washed twice with 200 parts of methanol. The obtained resin powder was dried at 60 ° C. under reduced pressure for 10 hours to obtain Resin A-12. Table 4 shows the physical properties of the obtained resin A-12.

表中、２−ＥＨＡは、２−エチルヘキシルアクリレートを表す。

In the table, 2-EHA represents 2-ethylhexyl acrylate.

<Example of production of amorphous polyester resin>
The amorphous polyester resin used for the Example of this invention was manufactured by the following.
(Production example of amorphous polyester resins 1 and 2)
A monomer other than trimellitic anhydride shown in Table 5 was put in a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe in the molar ratio shown in Table 5, and the mixture was placed at 230 ° C. under a nitrogen stream. The reaction was carried out for 10 hours while removing the produced water. At this time, 0.25 part of a titanium-based catalyst (titanium dihydroxybis (triethanolamate)) was added as a catalyst with respect to 100 parts of the total amount of acid and alcohol monomers.
Next, the reaction was carried out under a reduced pressure of 20 mmHg, and when the acid value became 0.5 (mgKOH / g) or less, it was cooled to 180 ° C., and trimellitic anhydride was added at a molar ratio shown in Table 5, The mixture was reacted for 2 hours under sealing, then taken out, cooled to room temperature, and pulverized to obtain amorphous polyester resins 1 and 2. Table 5 shows the physical properties of the obtained amorphous polyester resins 1 and 2.

ＢＰＡ−ＰＯ（２）：ビスフェノールＡのプロピレンオキサイド２モル付加物
ＢＰＡ−ＰＯ（３）：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
ＢＰＡ−ＥＯ（２）：ビスフェノールＡのエチレンオキサイド２モル付加物
ＴＰＡ：テレフタル酸
ＩＰＡ：イソフタル酸
ＴＭＡ：無水トリメリット酸

BPA-PO (2): Propylene oxide 2-mole adduct of bisphenol A BPA-PO (3): Propylene oxide 3-mole adduct of bisphenol A BPA-EO (2): Ethylene oxide 2-mole adduct of bisphenol A TPA: Terephthalic acid IPA: Isophthalic acid TMA: Trimellitic anhydride

<Production Example of Toner 1>
Toner 1 was produced by the following procedure.
(Preparation of aqueous medium)
To 1000 parts by mass of ion-exchanged water, 15.3 parts by mass of sodium phosphate and 4.9 parts by mass of 10% hydrochloric acid were added, and kept at 65 ° C. for 60 minutes while purging with nitrogen. T.A. K. Using a homomixer (made by Tokushu Kika Kogyo Co., Ltd.), while stirring at 12,000 rpm, an aqueous solution of calcium chloride in which 8.5 parts by mass of calcium chloride is dissolved is added to 10 parts by mass of ion-exchanged water, and dispersed. An aqueous medium containing the agent was prepared.
(Preparation of polymerizable monomer composition)
-Styrene (St) 50.0 parts by mass-C.I. I. Pigment Blue 15: 3 6.5 parts by mass The above material was put into an attritor (manufactured by Mitsui Miike Chemical Co., Ltd.), and further dispersed using a zirconia particle having a diameter of 1.7 mm at 220 rpm for 5 hours to disperse the master batch. A liquid was obtained.
In the masterbatch dispersion liquid: 25.0 parts by mass of styrene (St) 25.0 parts by mass of n-butyl acrylate (BA) 1.0 part by mass of resin A-1 Polyfunctional ester wax 1 (wax 1) 6 0.0 part by mass-Amorphous polyester resin 1 3.0 parts by mass was added to obtain a polymerizable monomer-containing composition.
In a separate container, the material is kept at 60 ° C. K. The mixture was stirred, dissolved, and dispersed at 9000 r / min with a homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.). In this, 9 parts by mass of a polymerization initiator t-hexyl peroxypivalate (manufactured by NOF Corporation, trade name “Perhexyl PV”, molecular weight: 202, 10 hour half-life temperature: 53.2 ° C.) is dissolved and polymerized. A monomer composition was prepared.
The polymerizable monomer composition is charged into the aqueous medium, and the T.I. K. The mixture was stirred for 5 minutes at 10,000 rpm with a homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) and granulated at pH 5.5. Then, it was made to react at 65 degreeC for 6 hours, stirring with a paddle stirring blade, and it heated up at 90 degreeC, and was made to react for another 6 hours. After completion of the polymerization reaction, the reaction vessel was cooled. Thereafter, 10% hydrochloric acid was added and the mixture was stirred at pH 2.0 for 2 hours to dissolve the dispersant. Thereafter, the toner particles 1 were obtained by washing with ion-exchanged water, drying and classification.
Hydrophobic silica fine particles (1) which are treated with dimethyl silicone oil (20% by mass) as an external additive 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 1 Toner 1 was obtained by mixing 1.2 parts by mass of the number average particle size of the secondary particles (12 nm) with a Mitsui Henschel mixer (manufactured by Mitsui Miike Chemical Co., Ltd.) at 3000 r / min for 15 minutes. Table 7 shows the physical properties of Toner 1.

<Production Example of Toners 2 to 22>
As shown in Table 6, in the same manner as in the production example of the toner 1 except that the mass part of the monomer, the kind and part of the resin A, the kind and part of the ester wax, and the kind of the amorphous polyester resin are changed. Toners 2 and 2 were obtained. Table 7 shows the physical properties of Toners 2-22.

<Production Example of Toners 23 to 25>
In the production example of the toner 6, C.I. I. Pigment Blue 15: 3 to C.I. I. Pigment yellow 93, C.I. I. Toners 23 to 25 were obtained in the same manner except that they were changed to CI Pigment Red 269 and Carbon Black, respectively.

<Production Example of Toners 26 to 38>
As shown in Table 6, in the same manner as in the production method of the toner 1 except that the mass part of the monomer, the kind and part of the resin A, the kind and part of the ester wax, and the kind of the amorphous polyester resin are changed. Toners 26 to 38 were obtained.
In the production examples of the toners 32 and 33, Bontron E-88 (aluminum compound of 3,5-di-tert-butylsalicylic acid: manufactured by Orient Chemical Co., Ltd.) was used instead of the resin A.

<Physical properties of each toner>
Table 7 shows the particle size and particle size distribution of the obtained toner, the molar content of the structure represented by the formula (1) based on the toner mass, and the glass transition temperature (Tg) of the toner.
The molar content of the structure represented by the formula (1) based on the toner mass was calculated from the charged amount at the time of toner production.

Each toner obtained was evaluated for performance according to the following method.
<Storage stability>
5.0 g of toner was placed in a 100 ml plastic cup and allowed to stand for 10 days in an environment of temperature 55 ° C./humidity 10% RH, and then the sample was further allowed to stand in an environment of temperature 23 ° C./humidity 60% RH for 24 hours. .
As a measuring method, the degree of aggregation of the toner was measured as follows, and evaluation was performed according to the following criteria.
As the measuring apparatus, a “powder tester” (manufactured by Hosokawa Micron Co., Ltd.) having a vibration table side surface portion connected with a digital display vibrometer “Digivibro MODEL 1332A” (manufactured by Showa Keiki Co., Ltd.) was used. Then, a sieve having a mesh size of 38 μm (400 mesh), a sieve having a mesh size of 75 μm (200 mesh), and a sieve having a mesh size of 150 μm (100 mesh) were stacked in this order on the vibrating table of the powder tester. The measurement was performed as follows in a temperature 23 ° C./humidity 60% RH environment.
(1) The vibration width of the vibration table was adjusted in advance so that the displacement value of the digital display vibrometer was 0.60 mm (peak-to-peak).
(2) As described above, 5 g of the toner left for 24 hours in an environment of a temperature of 23 ° C./humidity of 60% RH was precisely weighed and gently placed on a sieve having an opening of 150 μm.
(3) After vibrating the sieve for 15 seconds, the mass of the toner remaining on each sieve was measured, and the degree of aggregation was calculated based on the following equation.
Aggregation degree (%) = {(sample mass (g) on a sieve having an opening of 150 μm) / 5 (g)} × 100
+ {(Sample mass on a sieve having an opening of 75 μm (g)) / 5 (g)} × 100 × 0.6
+ {(Sample mass (g) on a sieve having an opening of 38 μm) / 5 (g)} × 100 × 0.2
(Evaluation criteria)
A: Aggregation degree is less than 20% B: Aggregation degree is 20% or more and less than 30% C: Aggregation degree is 30% or more and less than 40% D: Aggregation degree is 40% or more Evaluation results are shown in Table 8.

<Low temperature fixability>
A color laser printer (HP Color LaserJet 3525dn, manufactured by HP) with the fixing unit removed was prepared, and the toner was taken out from the cyan cartridge and filled with the toner to be evaluated instead. As a recording medium, color laser copier paper (manufactured by Canon, 80 g / m ² ) was used. Next, using the filled toner, an unfixed image having a length of 2.0 cm and a width of 15.0 cm is formed at a portion 1.0 cm from the upper end with respect to the sheet passing direction so that the applied toner amount is 0.20 mg / cm ^2. Formed. Next, the removed fixing unit was remodeled so that the fixing temperature and the process speed could be adjusted, and a fixing test of an unfixed image was performed using this.
First, in a normal temperature and humidity environment (23 ° C., 60% RH), the process speed is set to 230 mm / s, the fixing linear pressure is set to 27.4 kgf, the initial temperature is set to 110 ° C., and the set temperature is gradually increased by 5 ° C. The unfixed image was fixed at each temperature.
Evaluation criteria for low-temperature fixability are as follows. The low temperature side fixing start point is when the surface of the image is rubbed five times at a speed of 0.2 m / sec with Sylbon paper (Dasper K-3) applied with a load of 4.9 kPa (50 g / cm ² ). The minimum temperature at which the density reduction rate of the image density before and after rubbing is 10.0% or less. When the fixing is not performed firmly, the reduction rate of the image density tends to increase.
The evaluation results are shown in Table 8.
(Evaluation criteria)
A: Low temperature side fixing start point is 120 ° C. or less B: Low temperature side fixing start point is 125 ° C. or 130 ° C.
C: The low temperature side fixing start point is 135 ° C. or 140 ° C.
D: The low temperature side fixing start point is 145 ° C. or higher.

<Developability>
Commercially available color laser printer (HP Color LaserJet 3525d
n, manufactured by HP) was evaluated by modifying it so that it can be operated even when only one color process cartridge is installed. The toner contained in the cyan cartridge mounted on the color laser printer was taken out, the interior was cleaned by air blow, and the toner to be evaluated (100 g) was filled instead. Under high temperature and high humidity (30 ° C., 80% RH), Canon office planner (64 g / m ² ) was used as the image receiving paper, and 5000 sheets of a 2% printing rate chart were continuously printed.
(Evaluation of development lines)
After the image was printed, a halftone image was further output, and the presence or absence of image streaks in the halftone image and the presence or absence of a fused product on the developing roller were observed, and developability was evaluated as follows.
The evaluation results are shown in Table 8.
(Evaluation criteria)
A: No vertical streak in the paper discharge direction that appears as a development streak is seen on the image on the developing roller and the halftone part. B: Although there are 1 to 4 thin streaks on the developing roller, (There is no vertical streak in the paper discharge direction that appears as a development streak on the image.
C: Although there are 5 to 9 fine streaks on the developing roller, no vertical streak in the paper discharge direction, which appears as a developing streak, is seen on the halftone image D: 10 streaks on the developing roller There is a visible development streak on the halftone image.

(Evaluation of fog density)
After the evaluation of the development streaks, one image having a white background portion was output. Thereafter, with respect to the image having the white background portion, the fog density is determined from the difference between the whiteness (reflectance Ds (%)) of the white background portion of the image having the white background portion and the whiteness (average reflectance Dr (%)) of the transfer paper. (%) (= Dr (%) − Ds (%)) was calculated. The whiteness is “REFLECTMETER MODEL”.
It was measured by “TC-6DS” (manufactured by Tokyo Denshoku). An amberlite filter was used as the filter. The following evaluation criteria were used for the fog density.
The evaluation results are shown in Table 8.
(Evaluation criteria)
A: The fog density is 0.5% or less B: The fog density exceeds 0.5% and 1.0% or less C: The fog density exceeds 1.0% and is 2.0% or less D: The fog density exceeds 2.0%

Claims (6)

A toner containing a colorant, ester wax, resin A, and a binder resin,
The ester wax contains an ester compound of a divalent to hexavalent alcohol and an aliphatic monocarboxylic acid, or an ester compound of a divalent to hexavalent carboxylic acid and an aliphatic monoalcohol,
The resin A is a polymer having a structure represented by the following formula (1):
A toner wherein the binder resin has a benzene ring and an ester bond.

[In the formula (1), each R ¹ independently represents an alkyl group having 1 to 18 carbon atoms or an alkoxy group having 1 to 18 carbon atoms, and n represents an integer of 0 to 3 inclusive. * Indicates a binding site in the resin A. ] The toner according to claim 1, wherein the ester wax contains an ester compound represented by the following formula (2) or formula (3).
Formula (2): R ³ —C (═O) —O— (CH ₂ ) _x —O—C (═O) —R ⁴
Equation _{^{(3): R 5 -O-}} C (= O) - (CH 2) y -C (= O) -O-R 6
[In Formula (2) and Formula (3), R ³ , R ⁴ , R ⁵ , and R ⁶ are each independently an alkyl group having 13 to 26 carbon atoms, and x and y are each Independently, it is an integer of 8 or more and 10 or less. ] The binder resin contains at least one of a styrene acrylic resin and a styrene methacrylic resin,
The content ratio of the monomer unit derived from styrene in the styrene acrylic resin and the styrene methacrylic resin is 60% by mass or more and 90% by mass or less based on the resin. toner. The toner according to claim 1, wherein the resin A is a polymer having a structure represented by the following formula (4).

[In the formula (4), R ⁷ each independently represents an alkyl group having 1 to 18 carbon atoms or an alkoxy group having 1 to 18 carbon atoms, and R ⁸ represents a hydrogen atom or a hydroxy group. , An alkyl group having 1 to 18 carbon atoms, or an alkoxy group having 1 to 18 carbon atoms, g represents an integer of 1 to 3 and h represents an integer of 0 to 3; It is a binding site in Resin A. ]   The molar content of the structure represented by the formula (1) is 0.10 μmol / g or more and 100.00 μmol / g or less based on the mass of the toner. Toner. A polymerizable monomer composition containing a colorant, ester wax, resin A, and a polymerizable monomer is dispersed in an aqueous medium, and particles of the polymerizable monomer composition are formed in the aqueous medium. Process and
A method for producing a toner comprising a step of polymerizing the polymerizable monomer contained in the particles of the polymerizable monomer composition,
The ester wax contains an ester compound of a divalent to hexavalent alcohol and an aliphatic monocarboxylic acid, or an ester compound of a divalent to hexavalent carboxylic acid and an aliphatic monoalcohol,
The resin A is a polymer having a structure represented by the following formula (1):
A toner production method, wherein the binder resin is a resin having a benzene ring and an ester bond.

[In the formula (1), each R ¹ independently represents an alkyl group having 1 to 18 carbon atoms or an alkoxy group having 1 to 18 carbon atoms, and n represents an integer of 0 to 3 inclusive. * Indicates a binding site in the resin A. ]