JP2018013600A - toner - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a toner that exhibits good fine line reproducibility and minute dot reproducibility without impairing performance of low-temperature fixability and wax dispersibility.SOLUTION: A toner contains a binder resin and a mold release agent, and the binder resin contains a binder resin A and a binder resin B. The binder resin A is a hybrid resin obtained by chemically bonding a vinyl polymer unit and a polyester unit; the mass ratio of the vinyl polymer and polyester polymer is 10/90 to 50/50; the viny polymer unit is a polymer of styrene and the formula (1): CH=CRCOOR(Ris H or a methyl group, and Ris an alkyl group or a hydroxyalkyl group having 12 carbon atoms or less); the ratio of the formula (1) to the total number of moles of the vinyl monomer is 20 mol% or more and 90 mol% or less. The binder resin B is a polyester resin in which aliphatic monocarboxylic acid having 25 to 102 carbon atoms, inclusive and aliphatic monoalcohol having 25 to 102 carbon atoms, inclusive are condensed in a terminal.SELECTED DRAWING: None

Description

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

In recent years, as image forming apparatuses such as copiers and printers are widely used, the performance required of image forming apparatuses is required to be higher in image quality in addition to higher speed and energy saving.
Various means for improving the low-temperature fixability of toner have been studied as one of means for achieving high speed and energy saving of an image forming apparatus.

For example, in Patent Document 1, in order to improve low-temperature fixability, durability stability, and wax dispersibility, aliphatic compounds having different melting points are condensed at the ends of the polyester units of the binder resin A and the binder resin B, A toner in which binder resin A and binder resin B having different softening points are mixed has been proposed.
Patent Document 2 proposes a toner containing a vinyl copolymer unit having a soft segment rich in an acrylic component as a toner excellent in storage stability, fixing property, and durability stability.

JP 2015-28622 A Japanese Patent No. 4307367

In recent years, with the spread of more delicate images such as security images, further improvements in fine line reproducibility and fine dot reproducibility are indispensable.
However, the toners disclosed in Patent Documents 1 and 2 have room for improvement in terms of further improvement of fine line reproducibility and fine dot reproducibility in a high temperature and high humidity environment.
The present invention has been made in view of the above problems, and an object of the present invention is to provide a toner having good fine line reproducibility and fine dot reproducibility without impairing the performance of low-temperature fixability, storage stability and wax dispersibility. .

In order to achieve the above object, according to the present invention, in a toner having toner particles containing a binder resin and a release agent,
The binder resin contains a binder resin A and a binder resin B,
The binder resin A is
A hybrid resin in which a vinyl polymer unit and a polyester unit are chemically bonded.
The mass ratio of the vinyl polymer unit and the polyester unit (vinyl polymer unit / polyester unit) is 10/90 to 50/50,
The vinyl polymer unit is a polymer obtained by polymerizing at least styrene and a compound represented by the formula (1),
CH ₂ = CR ¹ COOR ² formula (1)
(R ^{1 represents} H or a methyl group, R ² represents an alkyl group having 12 or less carbon atoms or a hydroxyalkyl group)
The ratio of the compound represented by the formula (1) is 20 mol% or more and 90 mol% or less with respect to the total number of moles of the vinyl monomer used for the polymerization of the vinyl polymer unit,
The binder resin B is a polyester in which at least one aliphatic compound selected from the group consisting of an aliphatic monocarboxylic acid having 25 to 102 carbon atoms and an aliphatic monoalcohol having 25 to 102 carbon atoms is condensed at the terminal. A toner that is a resin is provided.

  According to the present invention, a toner having good fine line reproducibility and fine dot reproducibility can be provided without impairing the low-temperature fixability, storage stability, and wax dispersibility.

Embodiments of the present invention will be described below.
Since the toner using a polyester resin condensed with an aliphatic compound at the terminal has good low-temperature fixability, storage stability and wax dispersibility, the fine line reproducibility while taking advantage of these performances. In addition, in order to improve the reproducibility of minute dots, intensive studies were conducted.

As a result, the inventors have found that the following toners are excellent in fine line reproducibility and fine dot reproducibility without impairing the low-temperature fixability, storage stability, and wax dispersibility.
Specifically, the toner of the present invention is a toner having toner particles containing a binder resin and a release agent (hereinafter sometimes referred to as wax), and the binder resin is a binder resin A. And binder resin B.

The binder resin A is a hybrid resin in which a vinyl polymer unit and a polyester unit are chemically bonded.
The mass ratio of the vinyl polymer unit and the polyester unit (vinyl polymer unit / polyester unit) is 10/90 to 50/50,
The vinyl polymer unit is a polymer obtained by polymerizing at least styrene and a compound represented by the formula (1),
CH ₂ = CR ¹ COOR ² formula (1)
(R ^{1 represents} H or a methyl group, R ² represents an alkyl group having 12 or less carbon atoms or a hydroxyalkyl group)
The compound represented by the formula (1) is contained in an amount of 20 mol% or more and 90 mol% or less with respect to the total number of moles of the vinyl monomer used for the polymerization of the vinyl polymer unit.

  The binder resin B is a polyester resin in which at least one aliphatic compound selected from the group consisting of an aliphatic monocarboxylic acid having 25 to 102 carbon atoms and an aliphatic monoalcohol having 25 to 102 carbon atoms is condensed at the terminal. It is.

The reason why the toner of the present invention has an excellent effect that the conventional toner does not have is not clear, but is presumed as follows.
In order to improve the fine line reproducibility and the fine dot reproducibility, it is necessary to develop a necessary and sufficient amount of toner for the electrostatic latent image of the fine lines and fine dots formed on the photoreceptor. For this purpose, it is important to control the toner charge amount distribution.

However, particularly in a high temperature and high humidity environment, it has been difficult to further improve the fine line reproducibility and the fine dot reproducibility even if the toner charge amount distribution is controlled.
Therefore, the present inventors have the effect that the non-electrostatic adhesion force, which is one of the cohesive force of the toner, affects the fine line reproducibility and the fine dot reproducibility because the charge amount of the toner becomes low in a high temperature and high humidity environment. Thought that would grow.

By uniformly controlling the non-electrostatic adhesion force, the cohesive force of the toner becomes uniform and the fluidity of the toner improves, so that the toner is uniformly coated on the developing sleeve. It was considered that the toner is uniformly coated on the developing sleeve, thereby improving the toner developability and improving the fine line reproducibility and the fine dot reproducibility.
The present inventors considered that it is important for the material constituting the toner particles to be uniformly present in the toner particles in order to control the non-electrostatic adhesion force. Since the material constituting the toner particles is uniformly present in the toner particles, a specific material is not localized on the surface or inside of the toner particles, so that the non-electrostatic adhesion force of the toner can be controlled uniformly. In particular, when two or more polymer materials such as a binder resin are combined, it is important to improve the dispersibility or compatibility between the binder resins in order to control the non-electrostatic adhesion force of the toner. is there.

That is, in the present invention, by using the binder resin A and the binder resin B in combination, the compatibility between the binder resins is improved, and the uniformity of the non-electrostatic adhesion force of the toner is improved. It is considered that excellent fine line reproducibility and fine dot reproducibility that the toner does not have could be achieved.
In the present invention, the reason why the compatibility between the binder resin A and the binder resin B is improved is considered as follows.

  The present inventors paid attention to the structure of the acrylic ester and / or methacrylic ester of the vinyl polymer unit of the binder resin A and the structure of the aliphatic compound condensed at the terminal of the binder resin B. These two are similar in structure. Therefore, if the length of these two alkyl groups can be made the same, it was thought that the affinity between the binder resins could be increased and the compatibility could be improved.

However, if the number of carbon atoms of the alkyl group (R ^{2 in the} formula (1)) of the acrylic acid ester and / or methacrylic acid ester part of the vinyl polymer unit of the binder resin A is greater than 12, the storage stability of the toner is impaired. I understood it. It was also found that when the aliphatic compound condensed at the terminal of the binder resin B has less than 25 carbon atoms, the low-temperature fixability and wax dispersibility of the toner are impaired. It was found that if the aliphatic compound condensed at the terminal of the binder resin B has a carbon number greater than 102, the storage stability of the toner is impaired.

  Therefore, the present inventors paid attention to the content of the acrylic ester and / or methacrylic ester portion of the vinyl polymer unit of the binder resin A. As a result, the ratio of the compound represented by the formula (1) is set to 20 mol% or more and 90 mol% or less with respect to the total number of moles of the vinyl monomer used for the polymerization of the vinyl polymer unit of the binder resin A. Thus, it was found that the compatibility between the binder resin A and the binder resin B is improved. Here, the vinyl polymer unit includes a compound capable of reacting with both a vinyl monomer and a polyester monomer (hereinafter referred to as “both reactive compounds”).

  By using the binder resin A and the binder resin B in the present invention in combination, the low-temperature fixability, storage stability and wax dispersibility are good, and fine line reproducibility and fine dot reproducibility are better than before. A good toner could be obtained.

  The binder resin A used in the present invention is characterized in that it is a hybrid resin in which a vinyl polymer unit and a polyester unit are chemically bonded. By using the hybrid resin, the wax dispersibility is improved and the effect of the wax can be sufficiently exhibited, so that fog is hardly generated in a low temperature and low humidity environment.

  Moreover, it is preferable that the mass ratio (vinyl polymer unit / polyester unit) of the vinyl polymer unit and the polyester unit of the binder resin A is 10/90 to 50/50, and 20/80 to 40/60. It is more preferable. By setting the ratio of the vinyl polymer unit within the above range, sufficient compatibility with the binder resin B can be obtained due to the effect of increasing the affinity between the binder resin A and the binder resin B. . As a result, since the non-electrostatic adhesion force of the toner is made uniform, it is possible to provide a toner with good fine line reproducibility and fine dot reproducibility without impairing the low temperature fixability, storage stability and wax dispersibility. it can.

The vinyl polymer unit of the binder resin A is a polymer obtained by polymerizing at least styrene and the compound represented by the formula (1).
It is preferable that the ratio of the compound represented by Formula (1) is 20 mol% or more and 90 mol% or less with respect to the total number of moles of the vinyl monomer used for the polymerization of the vinyl polymer unit. The ratio of the compound represented by the formula (1) to the total number of moles of the vinyl monomer used for the polymerization of the vinyl polymer unit is more preferably 30 mol% or more and 80 mol% or less, and 40 mol%. More preferably, it is 60 mol% or less. In the vinyl polymer unit of the binder resin A, sufficient compatibility with the binder resin B is achieved by setting the ratio of the compound represented by the formula (1) to the above range with respect to the total number of moles of the vinyl monomer. Can be obtained. As a result, a toner having good fine line reproducibility and fine dot reproducibility can be provided without impairing the low-temperature fixability, storage stability, and wax dispersibility.

The binder resin B is a polyester resin in which at least one aliphatic compound selected from the group consisting of an aliphatic monocarboxylic acid having 25 to 102 carbon atoms and an aliphatic monoalcohol having 25 to 102 carbon atoms is condensed at the terminal. It is a feature.
When the carbon number of the aliphatic compound condensed at the terminal is 25 or more and 102 or less, the balance between the molecular motion of the aliphatic compound condensed at the terminal and the affinity between the binder resin and the wax is improved, and the binder resin A And the binder resin B have good compatibility. As a result, a toner with good fine line reproducibility and fine dot reproducibility can be provided without impairing the low-temperature fixability, storage stability and wax dispersibility of the toner.

  “The aliphatic compound is condensed at the terminal of the binder resin” means, for example, a state in which a carboxy group of a resin having a carboxy group at the terminal and a hydroxy group of the aliphatic compound are condensed. Moreover, the state which the hydroxy group of resin which has a hydroxyl group at the terminal and the carboxy group which an aliphatic compound has may be sufficient. Here, the “terminal” includes the branched terminal when the binder resin B has a branched structure.

  It is important that the aliphatic compound has a monovalent functional group. By being monovalent, the aliphatic compound is condensed at the terminal of the binder resin. The end is a part that particularly affects other components. Condensation of an aliphatic compound similar to the structure of acrylic acid and / or methacrylic acid ester of the vinyl polymer unit of the binder resin A at the end of the binder resin B improves molecular mobility. The compatibility between the binder resin A and the binder resin B is improved.

In the present invention, the ratio of the carbon number of R ² of the monomer represented by the formula (1) to the carbon number of the aliphatic compound condensed at the terminal of the binder resin B is 1: 4 to 1:12. It is preferable that the ratio is 1: 4 to 1:10. The binder resin A and the binder can be bound by setting the ratio of the carbon number of R ² of the monomer represented by the formula (1) and the carbon number of the aliphatic compound condensed at the terminal of the binder resin B within the above range. The compatibility of the resin B is further improved. As a result, a toner with better fine line reproducibility and fine dot reproducibility can be provided without impairing the low-temperature fixability, storage stability, and wax dispersibility.

  In the toner of the present invention, the mixing ratio of the binder resin A and the binder resin B is preferably 10/90 to 90/10 by mass ratio (binder resin A: binder resin B), more preferably. It is 20 / 80-80 / 20, More preferably, it is 40 / 60-80 / 20. When the mass ratio of the binder resin A and the binder resin B is within this range, the low-temperature fixability, storage stability and wax dispersibility are further improved, and the compatibility between the binder resin A and the binder resin B is further improved. And fine line reproducibility and fine dot reproducibility are improved.

Moreover, in this invention, binder resin can contain other resin to the extent which does not impair the effect of this invention other than binder resin A and binder resin B. FIG. The other resin is not particularly limited as long as it is a binder resin for toner, and examples thereof include vinyl resins, polyurethane resins, epoxy resins, and phenol resins.
The components constituting the binder resin A will be described. In addition, the following components can use 1 type, or 2 or more types according to a kind and a use.

  Examples of the divalent acid component constituting the polyester unit of the binder resin A and the binder resin B include the following dicarboxylic acids or derivatives thereof. Benzene dicarboxylic acids such as phthalic acid, terephthalic acid, isophthalic acid, and phthalic anhydride, or anhydrides thereof or lower alkyl esters thereof; alkyl dicarboxylic acids such as succinic acid, adipic acid, sebacic acid, azelaic acid, or anhydrides thereof or lower thereof Alkyl ester; alkenyl succinic acid or alkyl succinic acid having 1 to 50 carbon atoms, or an anhydride thereof, or a lower alkyl ester thereof; unsaturated dicarboxylic acid such as fumaric acid, maleic acid, citraconic acid, itaconic acid, or an anhydride thereof, or the like Lower alkyl ester.

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

(In the formula (2), R is an ethylene or propylene group, x and y are each an integer of 0 or more, and the average value of x + y is 0 to 10.)

The constituent components of the polyester unit of the binder resin A and the binder resin B used in the present invention are a trivalent or higher carboxylic acid compound, in addition to the above divalent carboxylic acid compound and divalent alcohol compound. You may contain the alcohol compound more than a valence as a structural component.
Although it does not restrict | limit especially as a trivalent or more carboxylic acid compound, A trimellitic acid, trimellitic anhydride, pyromellitic acid, etc. are mentioned. Examples of the trivalent or higher alcohol compound include trimethylolpropane, pentaerythritol, and glycerin.

The binder resin B in the present invention preferably contains 1 mol% or more and 40 mol% or less of aliphatic polyhydric alcohol with respect to the total number of moles of the divalent and trivalent or higher alcohol components. More preferably, it is contained in mol% or less. By containing an aliphatic polyhydric alcohol within the above range, wax dispersibility, low-temperature fixability, and storage stability are improved.
The aliphatic polyhydric alcohol is more preferably ethylene glycol. Since ethylene glycol has a small molecular weight, the mobility of the binder resin molecules is improved, and the compatibility of the binder resin A and the binder resin B is improved.

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

Specific examples of the titanium-based catalyst include the following. Titanium diisopropylate bistriethanolamate [Ti (C ₆ H ₁₄ O ₃ N) ₂ (C ₃ H ₇ O) ₂ ], Titanium diisopropylate bisdiethanolamate [Ti (C ₄ H ₁₀ O ₂ N) ₂ ( C ₃ H ₇ O) ₂ ], titanium dipentylate bistriethanolaminate [Ti (C ₆ H ₁₄ O ₃ N) ₂ (C ₅ H ₁₁ O) ₂ ], titanium diethylate bistriethanolamate [Ti ( C ₆ H ₁₄ O ₃ N) ₂ (C ₂ H ₅ O) ₂ ], titanium dihydroxyoctylate bistriethanolaminate [Ti (C ₆ H ₁₄ O ₃ N) ₂ (OHC ₈ H ₁₆ O) ₂ ], titanium distearate bis triethanolaminate _{[Ti (C 6 H 14 O 3} N) 2 (C 18 H 37 O) 2 ], Chitanto Isopropylate triethanolaminate _{[Ti (C 6 H 14 O 3} N) 1 (C 3 H 7 O) 3 ], titanium monopropylate tris (triethanolaminate) _{[Ti (C 6 H 14 O 3} N) ₃ (C ₃ H ₇ O) ₁ ] and the like. Of these, titanium diisopropylate bistriethanolamate, titanium diisopropylate bisdiethanolamate and titanium dipentylate bistriethanolamate are preferred.

Specific examples of other titanium catalysts include tetra-n-butyl titanate [Ti (C ₄ H ₉ O) ₄ ], tetrapropyl titanate [Ti (C ₃ H ₇ O) ₄ ], tetrastearyl titanate [Ti (C ₁₈ H ₃₇ O) ₄ ], tetramyristyl titanate [Ti (C ₁₄ H ₂₉ O) ₄ ], tetraoctyl titanate [Ti (C ₈ H ₁₇ O) ₄ ], dioctyl dihydroxyoctyl titanate [Ti (C ₈ H) ₁₇ O) ₂ (OHC ₈ H ₁₆ O) ₂ ], dimyristyl dioctyl titanate [Ti (C ₁₄ H ₂₉ O) ₂ (C ₈ H ₁₇ O) ₂ ] and the like. Among these, tetrastearyl titanate, Tetramyristyl titanate, tetraoctyl titanate and dioctyl dihydroxy octyl titanate are preferred. Arbitrariness. These can be obtained, for example, by reacting titanium halide with the corresponding alcohol.

  Moreover, it is more preferable that the titanium-based catalyst contains an aromatic carboxylic acid titanium compound. The aromatic carboxylic acid titanium compound is preferably obtained by reacting an aromatic carboxylic acid and a titanium alkoxide. The aromatic carboxylic acid is preferably a divalent or higher valent aromatic carboxylic acid (that is, an aromatic carboxylic acid having two or more carboxy groups) and / or an aromatic oxycarboxylic acid.

  Examples of the divalent or higher aromatic carboxylic acid include dicarboxylic acids such as phthalic acid, isophthalic acid, and terephthalic acid or anhydrides thereof, trimellitic acid, benzophenone dicarboxylic acid, benzophenone tetracarboxylic acid, naphthalene dicarboxylic acid, and naphthalene tetracarboxylic acid. Examples thereof include polyvalent carboxylic acids such as acids, anhydrides thereof, esterified products, and the like. Examples of the aromatic oxycarboxylic acid include salicylic acid, m-oxybenzoic acid, p-oxycarboxylic acid, gallic acid, mandelic acid, and tropic acid. Among these, as the aromatic carboxylic acid, it is more preferable to use a divalent or higher carboxylic acid, and it is particularly preferable to use isophthalic acid, terephthalic acid, trimellitic acid, or naphthalenedicarboxylic acid.

Examples of vinyl monomers for producing vinyl polymer units other than styrene include the following styrene monomers and acrylic monomers.
Examples of styrenic monomers include o-methyl styrene, m-methyl styrene, p-methyl styrene, p-phenyl styrene, p-ethyl styrene, 2,4-dimethyl styrene, pn-butyl styrene. , P-tert-butyl styrene, pn-hexyl styrene, pn-octyl styrene, pn-nonyl styrene, pn-decyl styrene, pn-dodecyl styrene, p-methoxy styrene, p- Styrene derivatives such as chlorostyrene, 3,4-dichlorostyrene, m-nitrostyrene, o-nitrostyrene, p-nitrostyrene.

The following are mentioned as an acrylic acid type monomer. Acrylic acid, methyl acrylate, ethyl acrylate, propyl acrylate, acrylate-n-butyl, acrylate isobutyl, acrylate-n-octyl, dodecyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, acrylic acid Acrylic acid and acrylic acid esters such as -2-chloroethyl and phenyl acrylate; methacrylic acid, methyl methacrylate, ethyl methacrylate, propyl methacrylate, -n-butyl methacrylate, isobutyl methacrylate, -n-octyl methacrylate Α-methylene aliphatic monocarboxylic acids such as dodecyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, phenyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate and the like Esters thereof; acrylonitrile, methacrylonitrile, acrylic acid or methacrylic acid derivatives such as acrylamide.
As the acrylic acid monomer, acrylic acid, n-butyl acrylate, and 2-ethylhexyl acrylate are preferable in terms of improving the compatibility of the binder resin A and the binder resin B, and -2-ethylhexyl acrylate is more preferable. preferable.

  Furthermore, the following are mentioned as a monomer of a vinyl-type polymer unit. Acrylic acid or methacrylic acid ester such as 2-hydroxylethyl acrylate, 2-hydroxylethyl methacrylate, 2-hydroxylpropyl methacrylate; 4- (1-hydroxy-1-methylbutyl) styrene, 4- (1-hydroxy-1-methyl) (Hexyl) Monomers having a hydroxy group such as styrene.

  Various monomers capable of vinyl polymerization can be used in combination with the vinyl polymer unit as necessary. Examples of such monomers include the following. Ethylenically unsaturated monoolefins such as ethylene, propylene, butylene and isobutylene; unsaturated polyenes such as butadiene and isoprene; vinyl halides such as vinyl chloride, vinylidene chloride, vinyl bromide and vinyl fluoride; vinyl acetate, Vinyl esters such as vinyl propionate and vinyl benzoate; Vinyl ethers such as vinyl methyl ether, vinyl ethyl ether and vinyl isobutyl ether: Vinyl vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone and methyl isopropenyl ketone; N-vinyl N-vinyl compounds such as pyrrole, N-vinylcarbazole, N-vinylindole, N-vinylpyrrolidone; vinyl naphthalenes; maleic acid, citraconic acid, itaconic acid, alkenyl succinic acid, fumaric acid Unsaturated dibasic acids such as mesaconic acid; unsaturated dibasic acid anhydrides such as maleic anhydride, citraconic anhydride, itaconic anhydride, alkenyl succinic anhydride; methyl maleate half ester, ethyl half maleate Esters, butyl maleate half ester, citraconic acid methyl half ester, citraconic acid ethyl half ester, citraconic acid butyl half ester, itaconic acid methyl half ester, alkenyl succinic acid methyl half ester, fumaric acid methyl half ester, mesaconic acid methyl half ester Half esters of unsaturated basic acids such as; unsaturated basic acid esters such as dimethylmaleic acid and dimethylfumaric acid; acid anhydrides of α, β-unsaturated acids such as acrylic acid, methacrylic acid, crotonic acid and cinnamic acid; The α, β-unsaturated acid Monomers having a carboxy group such as alkenyl malonic acid, alkenyl glutaric acid, alkenyl adipic acid, acid anhydrides thereof and monoesters thereof.

The vinyl polymer unit may be a polymer crosslinked with a crosslinkable monomer as exemplified below if necessary. Examples of the crosslinkable monomer include the following. Aromatic divinyl compounds, diacrylate compounds linked by alkyl chains, diacrylate compounds linked by alkyl chains containing ether bonds, diacrylate compounds linked by chains containing aromatic groups and ether bonds, polyesters Type diacrylates and polyfunctional crosslinking agents.
Examples of the aromatic divinyl compound include divinylbenzene and divinylnaphthalene.

  Examples of the diacrylate compounds linked by the alkyl chain include the following. Ethylene glycol diacrylate, 1,3-butylene glycol diacrylate, 1,4-butanediol diacrylate, 1,5-pentanediol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, and more A compound in which acrylate is replaced with methacrylate.

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

  Examples of the diacrylate compounds connected by a chain containing an aromatic group and an ether bond include the following. Polyoxyethylene (2) -2,2-bis (4-hydroxyphenyl) propane diacrylate, polyoxyethylene (4) -2,2-bis (4-hydroxyphenyl) propane diacrylate, and acrylates of the above compounds Is replaced with methacrylate. Examples of polyester diacrylates include trade name MANDA (Nippon Kayaku Co., Ltd.).

  Examples of the polyfunctional crosslinking agent include the following. Pentaerythritol triacrylate, trimethylol ethane triacrylate, trimethylol propane triacrylate, tetramethylol methane tetraacrylate, oligoester acrylate, and acrylates of the above compounds replaced with methacrylate; triallyl cyanurate, triallyl trimellitate .

The vinyl polymer unit may be a resin produced using a polymerization initiator. These polymerization initiators are preferably used in an amount of 0.05 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the monomer from the viewpoint of efficiency.
Examples of such a polymerization initiator include the following. 2,2′-azobisisobutyronitrile, 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), 2, 2′-azobis (2-methylbutyronitrile), dimethyl-2,2′-azobisisobutyrate, 1,1′-azobis (1-cyclohexanecarbonitrile), 2-carbamoylazoisobutyronitrile, 2,2′-azobis (2,4,4-trimethylpentane), 2-phenylazo-2,4-dimethyl-4-methoxyvaleronitrile, 2,2′-azobis (2-methylpropane), methyl ethyl ketone peroxide, Ketone peroxides such as acetylacetone peroxide and cyclohexanone peroxide, 2,2-bis (t-butylperoxy) butane t-butyl hydroperoxide, cumene hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, di-t-butyl peroxide, t-butylcumyl peroxide, dicumyl peroxide, α, α '-Bis (t-butylperoxyisopropyl) benzene, isobutyl peroxide, octanoyl peroxide, decanoyl peroxide, lauroyl peroxide, 3,5,5-trimethylhexanoyl peroxide, benzoyl peroxide, m-tri Oil peroxide, diisopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, di-n-propyl peroxydicarbonate, di-2-ethoxyethyl peroxycarbonate, dimethoxyi Propyl peroxydicarbonate, di (3-methyl-3-methoxybutyl) peroxycarbonate, acetylcyclohexylsulfonyl peroxide, t-butylperoxyacetate, t-butylperoxyisobutyrate, t-butylperoxyneodeca Noate, t-butylperoxy-2-ethylhexanoate, t-butylperoxylaurate, t-butylperoxybenzoate, t-butylperoxyisopropyl carbonate, di-t-butylperoxyisophthalate, t-butylperoxyallyl carbonate, t-amylperoxy-2-ethylhexanoate, di-t-butylperoxyhexahydroterephthalate, di-t-butylperoxyazelate.

As described above, the binder resin A is a hybrid resin in which a vinyl polymer unit and a polyester unit are chemically bonded.
Therefore, it is preferable to carry out the polymerization using a compound capable of reacting with both monomers of the resin (hereinafter referred to as “both reactive compounds”). Examples of such a bireactive compound include compounds such as fumaric acid, acrylic acid, methacrylic acid, citraconic acid, maleic acid, and dimethyl fumarate in the monomers of the above condensation polymerization resins and addition polymerization resins. Is mentioned. Of these, fumaric acid, acrylic acid, and methacrylic acid are preferably used.
In the present invention, both reactive compounds are used as vinyl monomers used for the polymerization of vinyl polymer units.

  The hybrid resin can be obtained by reacting the raw material monomer of the vinyl polymer unit and the raw material monomer of the polyester unit simultaneously or sequentially. For example, when the raw material monomer of the vinyl polymer unit is subjected to an addition polymerization reaction and then the raw material monomer of the polyester unit is subjected to a condensation polymerization reaction, it is easy to control the molecular weight.

In the present invention, the binder resin B is terminated with at least one aliphatic compound selected from the group consisting of an aliphatic monocarboxylic acid having 25 to 102 carbon atoms and an aliphatic monoalcohol having 25 to 102 carbon atoms. It is important that the polyester resin is condensed.
The aliphatic compound used in the binder resin B of the present invention is not particularly limited as long as it is an aliphatic monocarboxylic acid or aliphatic monoalcohol having a specific carbon number. For example, any of grade 1, 2 and 3 can be used.

Specifically, examples of the aliphatic monocarboxylic acid include serotic acid, heptacosanoic acid, montanic acid, melissic acid, laccellic acid, tetracontanoic acid, and pentacontanoic acid.
Examples of the aliphatic monoalcohol include ceryl alcohol, melyl alcohol, and tetracontanol.

  Moreover, the aliphatic compound used for the binder resin B of this invention can be used if it is the aliphatic monocarboxylic acid or aliphatic monoalcohol which has carbon number prescribed | regulated by this invention. A modified wax produced through a modification step of producing a wax having a hydroxy group or a carboxy group from an aliphatic hydrocarbon wax can also be used. Such modified waxes include, for example, acid-modified aliphatic hydrocarbon waxes and alcohol-modified aliphatic hydrocarbon waxes.

If these modified waxes contain 40% by mass or more of a monovalent acid-modified wax or alcohol-modified wax, the effects of the present invention may be impaired even in a mixture containing unmodified or polyvalent components. Absent.
Specific examples of the acid-modified aliphatic hydrocarbon wax and the alcohol-modified aliphatic hydrocarbon wax include the following.

The acid-modified aliphatic hydrocarbon wax in the present invention is preferably one in which polyethylene or polypropylene is modified with a monovalent unsaturated carboxylic acid such as acrylic acid. The melting point of the acid-modified wax can be controlled by the molecular weight.
Among the alcohol-modified aliphatic hydrocarbon waxes in the present invention, examples of a method for obtaining a primary alcohol-modified aliphatic hydrocarbon wax include the following. A technique in which ethylene is polymerized using a Ziegler catalyst, and after completion of polymerization, is oxidized to produce an alkoxide of a catalytic metal and polyethylene, followed by hydrolysis.

  In addition, as a process for producing a secondary alcohol-modified aliphatic hydrocarbon wax, for example, an aliphatic hydrocarbon wax is preferably used in a liquid phase with a molecular oxygen-containing gas in the presence of boric acid and boric anhydride. Obtained by oxidation. The obtained hydrocarbon wax may be further subjected to purification by a press sweat method, purification using a solvent, hydrogenation treatment, and treatment with activated clay after washing with sulfuric acid. A mixture of boric acid and boric anhydride can be used as the catalyst. The mixing ratio of boric acid and boric anhydride (boric acid / boric anhydride) is in the range of 1 to 2, preferably 1.2 to 1.7 in terms of molar ratio.

The amount of boric acid and boric anhydride to be used is 0.001 to 10 mol, particularly 0.1 to 1 mol, based on 1 mol of the aliphatic hydrocarbon as a raw material, when the mixture is converted into boric acid. Is preferred.
In addition to boric acid / boric anhydride, metaboric acid and pyroboric acid can also be used. Examples of those that form esters with alcohols include boron oxyacids, phosphorus oxyacids, and sulfur oxyacids. Specific examples include boric acid, nitric acid, phosphoric acid, and sulfuric acid.

As the molecular oxygen-containing gas blown into the reaction system, oxygen, air, or a wide range of those diluted with an inert gas can be used. The gas preferably has an oxygen concentration of 1 to 30% by volume, more preferably 3 to 20% by volume.
The liquid phase oxidation reaction is usually carried out in the molten state of the starting aliphatic hydrocarbon without using a solvent. The reaction temperature is 120 to 280 ° C, preferably 150 to 250 ° C. The reaction time is preferably 1 to 15 hours.

Boric acid and boric anhydride are preferably mixed in advance and added to the reaction system. The addition temperature of the mixed catalyst of boric acid and boric anhydride is preferably 100 to 180 ° C, more preferably 110 to 160 ° C.
After completion of the reaction, water is added to the reaction mixture, and the resulting aliphatic hydrocarbon wax borate ester is hydrolyzed and purified to obtain an alcohol-modified aliphatic hydrocarbon wax having a desired functional group. .

Among the above-mentioned aliphatic compounds, aliphatic monoalcohols are preferable, and alcohol-modified aliphatic hydrocarbon waxes are more preferable.
The aliphatic compound condensed at the terminal of the binder resin B is more preferably a primary alcohol-modified aliphatic hydrocarbon wax. As the primary alcohol-modified aliphatic hydrocarbon wax, for example, a wax in which one end of polyethylene is modified with a hydroxy group is preferable because the compatibility between the binder resin A and the binder resin B is improved.
The method for condensing the aliphatic compound to the terminal of the binder resin B is not particularly limited. When the binder resin B is produced, it is preferable to simultaneously add an aliphatic compound to the monomer constituting the polyester unit of the binder resin B and perform condensation polymerization.

  The amount of the aliphatic compound added is preferably 1 part by mass or more and 10 parts by mass or less, and preferably 3 parts by mass or more and 7 parts by mass or less with respect to 100 parts by mass of the total mass of monomers constituting the polyester. More preferred. By setting the amount of the aliphatic compound to be in the above range, the fog is improved. In the present invention, the aliphatic compound is not included in 100 parts by mass of the total mass of monomers constituting the polyester.

In the present invention, a release agent (wax) is contained in order to impart releasability to the toner.
The following are mentioned as an example of the wax used for this invention. Low molecular weight polyethylene, low molecular weight polypropylene, olefin copolymer, aliphatic hydrocarbon wax such as microcrystalline wax, paraffin wax, Fischer-Tropsch wax; oxidized wax of aliphatic hydrocarbon wax such as oxidized polyethylene wax; carnauba wax And waxes mainly composed of fatty acid esters such as behenic acid behenate and montanic acid ester wax; and fatty acid esters such as deoxidized carnauba wax that have been partially or fully deoxidized. In addition, saturated linear fatty acids such as palmitic acid, stearic acid, and montanic acid; unsaturated fatty acids such as brandic acid, eleostearic acid, and parinalic acid; stearyl alcohol, aralkyl alcohol, behenyl alcohol, carnauvir alcohol, and seryl alcohol , Saturated alcohols such as melyl alcohol; polyhydric alcohols such as sorbitol; fatty acid amides such as linoleic acid amide, oleic acid amide, lauric acid amide; methylene bis stearic acid amide, ethylene biscapric acid amide, ethylene bis laurin Saturated fatty acid bisamides such as acid amide and hexamethylenebisstearic acid amide; ethylene bisoleic acid amide, hexamethylene bisoleic acid amide, N, N′-dioleyl adipic acid amide, N, N′— Unsaturated fatty acid amides such as oleyl sebacic acid amide; aromatic bisamides such as m-xylene bis-stearic acid amide, N, N′-distearylisophthalic acid amide; calcium stearate, calcium laurate, zinc stearate, stearic acid Aliphatic metal salts such as magnesium (generally referred to as metal soap); waxes grafted to aliphatic hydrocarbon waxes using vinyl copolymer monomers such as styrene and acrylic acid; behenic acid Examples include partially esterified products of fatty acids such as monoglycerides and polyhydric alcohols; methyl ester compounds having hydroxyl groups obtained by hydrogenation of vegetable oils and the like.

In the present invention, the viewpoint of the ease of dispersion in the toner, the high releasability, and the affinity with the unit derived from the aliphatic compound condensed at the terminal of the binder resin B, which is a feature of the present invention Therefore, hydrocarbon waxes are particularly preferable.
For example, low molecular weight hydrocarbons obtained by radical polymerization of alkylene under high pressure or Ziegler catalyst or metallocene catalyst under low pressure; Fischer-Tropsch wax synthesized from coal or natural gas; obtained by pyrolyzing high molecular weight olefin polymer An olefin polymer to be obtained; a synthetic hydrocarbon wax obtained from a distillation residue of hydrocarbons obtained from a synthesis gas containing carbon monoxide and hydrogen by the age method, or a synthetic hydrocarbon wax obtained by hydrogenating them. Among these, Fischer-Tropsch wax is preferable from the viewpoint of easy dispersion in the toner, high releasability, and affinity with a unit derived from an aliphatic compound condensed at the terminal of the binder resin B.

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

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

When the toner of the present invention is used as a magnetic toner, magnetic iron oxide particles can be used. Specific examples include magnetic iron oxide particles such as magnetite, maghemite, and ferrite, and magnetic iron oxide particles containing other metal oxide particles. Conventionally, the following are known as magnetic iron oxide particles. Iron trioxide (Fe ₃ O ₄ ), iron sesquioxide (γ-Fe ₂ O ₃ ), zinc iron oxide (ZnFe ₂ O ₄ ), iron yttrium oxide (Y ₃ Fe ₅ O ₁₂ ), iron cadmium oxide (Cd ₃ Fe ₂ O ₄ ), iron gadolinium oxide (Gd ₃ Fe ₅ O ₁₂ ), copper iron oxide (CuFe ₂ O ₄ ), lead iron oxide (PbFe ₁₂ O ₁₉ ), nickel iron oxide (NiFe ₂ O ₄ ), oxidation Iron neodymium (NdFe ₂ O ₃ ), iron barium oxide (BaFe ₁₂ O ₁₉ ), magnesium iron oxide (MgFe ₂ O ₄ ), iron manganese oxide (MnFe ₂ O ₄ ), iron lanthanum oxide (LaFeO ₃ ), iron powder ( Fe) etc. Particularly preferred magnetic iron oxide particles are fine powders of iron tetroxide or iron sesquioxide. Moreover, the magnetic iron oxide particles described above can be selected and used alone or in combination of two or more.
The shape of the magnetic iron oxide particles used in the toner of the present invention is more preferably an octahedron with better dispersibility in the toner.
The content of the magnetic iron oxide particles is preferably 30 parts by mass or more and 100 parts by mass or less with respect to 100 parts by mass of the binder resin.

  In the toner of the present invention, a charge control agent can be used in order to stabilize the charging characteristics. Although the charge control agent varies depending on the type and physical properties of other toner particle constituent materials, it is generally preferable that the charge control agent is contained in an amount of 0.1 to 10 parts by mass per 100 parts by mass of the binder resin. More preferably, it is contained in an amount of 0.1 to 5 parts by mass. As such a charge control agent, one kind or two or more kinds can be used depending on the kind and use of the toner.

  Examples of the charge control agent that control the toner to be negatively charged include the following. Organometallic complexes (monoazo metal complexes; acetylacetone metal complexes); metal complexes or metal salts of aromatic hydroxycarboxylic acids or aromatic dicarboxylic acids. In addition, examples of toners that are negatively charged include aromatic mono- and polycarboxylic acids and metal salts and anhydrides thereof; phenol derivatives such as esters and bisphenol. Among these, an aromatic hydroxycalcarboxylic acid or an aromatic dicarboxylic acid metal complex or metal salt that can provide stable charging characteristics is particularly preferable.

In addition, a charge control resin can also be preferably used. As the charge control resin, a polymer or copolymer having a sulfonic acid group, a sulfonic acid group, or a sulfonic acid ester group can be used. Examples of the polymer having a sulfonic acid group, a sulfonic acid group or a sulfonic acid ester group include a polymer containing a sulfonic acid group-containing acrylamide monomer or a sulfonic acid group-containing methacrylamide monomer in a copolymerization ratio of 2% by mass or more. preferable. More preferably, it is a polymer containing 5% by mass or more.
The charge control resin is preferably used in combination with the above-described charge control agent.

  On the other hand, examples of the charge control agent that controls the toner to be positively charged include the following. Modified products with nigrosine and fatty acid metal salts; quaternary ammonium salts such as tributylbenzylammonium-1-hydroxy-4-naphthosulfonate, tetrabutylammonium tetrafluoroborate, and analogs thereof; onium salts such as phosphonium salts and These lake pigments: triphenylmethane dyes and these lake pigments (as rake agents, phosphotungstic acid, phosphomolybdic acid, phosphotungsten molybdic acid, tannic acid, lauric acid, gallic acid, ferricyanic acid, ferrocyanic compound Etc.); metal salts of higher fatty acids. In the present invention, these can be used alone or in combination. Among these, charge control agents such as nigrosine compounds and quaternary ammonium salts are preferable.

  The toner of the present invention may be mixed with a carrier and used as a two-component developer. As the carrier, a normal carrier such as ferrite or magnetite or a resin-coated carrier can be used. A binder type carrier core in which magnetic powder is dispersed in a resin can also be used.

  The resin-coated carrier is composed of carrier core particles and a coating material that is a resin that coats (coats) the surface of the carrier core particles. The following are mentioned as resin used for a coating | covering material. Styrene-acrylic resins such as styrene-acrylic acid ester copolymer and styrene-methacrylic acid ester copolymer; Acrylic resins such as acrylic acid ester copolymer and methacrylic acid ester copolymer; polytetrafluoroethylene, monochloro Fluorine-containing resins such as trifluoroethylene polymer and polyvinylidene fluoride; silicone resins; polyester resins; polyamide resins; polyvinyl butyral; Other examples include ionomer resins and polyphenylene sulfide resins. These resins can be used alone or in combination.

In the toner of the present invention, it is preferable to use a fluidity improver that has a high ability to impart fluidity to the toner surface and has a smaller number average particle size of primary particles. As the fluidity improver, any agent can be used as long as the fluidity after the addition can be increased by adding it externally to the toner. For example, the following are mentioned. Fluorine resin powders such as vinylidene fluoride fine powder and polytetrafluoroethylene fine powder; silica fine powder by wet production method, silica fine powder such as silica fine powder by dry production method, these silica fine powders as silane coupling agent, titanium cup Treated silica fine powder surface-treated with a treating agent such as a ring agent or silicone oil; titanium oxide fine powder; alumina fine powder, treated titanium oxide fine powder, treated alumina oxide fine powder. The fluidity improver preferably has a specific surface area measured by a BET method by nitrogen adsorption of 30 m ² / g or more, more preferably 50 m ² / g or more and 300 m ² / g or less. The addition amount of the fluidity improver is preferably 0.01 parts by mass or more and 8 parts by mass or less, and more preferably 0.1 parts by mass or more and 4 parts by mass or less with respect to 100 parts by mass of the toner.

Other external additives may be added to the toner of the present invention as necessary. For example, a charging aid, a conductivity imparting agent, an anti-caking agent, a release agent at the time of fixing with a heat roller, and resin fine particles and inorganic fine particles functioning as an abrasive.
For example, examples of the abrasive include cerium oxide powder, silicon carbide powder, and strontium titanate powder. These external additives can be sufficiently mixed using a mixer such as a Henschel mixer to obtain the toner of the present invention.
The pulverization method will be described below as an example of the method for producing the toner of the present invention, but the method for producing the toner of the present invention is not limited thereto.

  For example, binder resin A, binder resin B and release agent, and if necessary, other additives are sufficiently mixed by a mixer such as a Henschel mixer or a ball mill, and then heated rolls, kneaders and extruders. Melt and knead using a heat kneader such as. Then, after cooling and solidifying, pulverization and classification are performed to obtain a toner. Furthermore, if necessary, the toner can be obtained by sufficiently mixing silica fine particles and the like with a mixer such as a Henschel mixer to add a fluidity improver.

  The following are mentioned as a mixer. Henschel mixer (manufactured by Nihon Coke Kogyo Co., Ltd.); Super mixer (manufactured by Kawata Co., Ltd.); Ribocorn (manufactured by Okawara Seisakusho Co., Ltd.); Spiral pin mixer (manufactured by Taiheiyo Kiko Co., Ltd.); Redige mixer (manufactured by Matsubo Co., Ltd.).

  Examples of the kneader include the following. KRC Kneader (manufactured by Kurimoto Iron Works); Bus Co Kneader (manufactured by Buss); TEM type extruder (manufactured by Toshiba Machine Co., Ltd.); TEX twin-screw kneader (manufactured by Nippon Steel Works) PCM kneading machine (manufactured by Ikegai Co., Ltd.); triple roll mill, mixing roll mill, kneader (manufactured by Inoue Seisakusho Co., Ltd.); kneedex (manufactured by Nippon Coke Industries Co., Ltd.); MS pressure kneader, nider ruder ( (Manufactured by Moriyama Seisakusho); Banbury mixer (manufactured by Kobe Steel).

  Examples of the pulverizer include the following. Counter jet mill, micron jet, inomizer (manufactured by Hosokawa Micron Corporation); IDS type mill, PJM jet crusher (manufactured by Nippon Pneumatic Industry Co., Ltd.); cross jet mill (manufactured by Kurimoto Iron Works Co., Ltd.); (Manufactured by Nisso Engineering Co., Ltd.); SK Jet O Mill (manufactured by Seishin Enterprise Co., Ltd.); Kryptron (manufactured by Kawasaki Heavy Industries, Ltd.); turbo mill (manufactured by Freund Turbo Inc.); Nissin Engineering Co., Ltd.).

  Examples of the classifier include the following. Classifier, Micron Classifier, Spedick Classifier (manufactured by Seishin Corporation); Turbo Classifier (manufactured by Nissin Engineering Co., Ltd.); Micron Separator, Turboplex (ATP), TSP Separator, TTSP Separator (Hosokawa Micron ( Elbow Jet (manufactured by Nippon Steel & Mining Co., Ltd.), Dispersion Separator (manufactured by Nippon Pneumatic Engineering Co., Ltd.); YM Microcut (manufactured by Eurus Techno Co., Ltd.).

Examples of the sieving apparatus used for sieving coarse particles include the following. Ultrasonic (manufactured by Koei Sangyo Co., Ltd.); Resonator Sheave, Gyroshifter (manufactured by Tokuju Kogakusho Co., Ltd.); Vibrasonic System (manufactured by Dalton Co., Ltd.); Soniclean (manufactured by Shinto Kogyo Co., Ltd.); Screener (manufactured by Freund Turbo); Micro shifter (manufactured by Hadano Sangyo Co., Ltd.); circular vibrating sieve.
Next, it describes about the measuring method of each physical property which concerns on this invention.

  The volume average particle diameter (D4) of the toner in the present invention is preferably in the range of 4 to 10 μm, more preferably in the range of 5 to 9 μm, and still more preferably in the range of 6 to 9 μm. The particle size distribution can be measured by various methods. In the present invention, the particle size distribution was performed using a multisizer of a Coulter counter.

  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 provided with a 100 μm aperture tube is used. For setting of measurement conditions and analysis of measurement data, 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 special grade sodium chloride is dissolved in ion-exchanged water so as to have a concentration of about 1% by mass, for example, “ISOTON II” (manufactured by Beckman Coulter, Inc.) can be used. .
Prior to measurement and analysis, the dedicated software was 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 The value obtained using (made by Co., Ltd.) is set. 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) About 200 mL of the electrolytic solution is placed in a glass 250 mL round-bottom beaker dedicated to Multisizer 3, set on a sample stand, and the stirrer rod is stirred 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) About 30 mL of the electrolytic solution is placed in a glass 100 mL flat bottom beaker. As a dispersant, “Contaminone N” (a nonionic surfactant, an anionic surfactant, a 10% by weight aqueous solution of a neutral detergent for washing a pH 7 precision measuring instrument comprising an organic builder, Wako Pure Chemical Industries, Ltd. About 0.3 mL of a diluted solution obtained by diluting (made in ()) with ion-exchanged water about 3 times by mass.

(3) Two oscillators with an oscillation frequency of 50 kHz are incorporated with the phase shifted by 180 degrees, and an ultrasonic disperser “Ultrasonic Dissipation System Tetora150” (manufactured by Nikki Bios Co., Ltd.) with an electrical output of 120 W is prepared. . About 3.3 liters of ion-exchanged water is placed in the water tank of the ultrasonic disperser, and about 2 mL of Contaminone N is added to the water tank.
(4) The beaker of (2) is set in the beaker fixing hole of the ultrasonic disperser, and the ultrasonic disperser is operated. 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, about 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 of (1) installed in the sample stand, the electrolyte solution of (5) in which the toner is dispersed is dropped using a pipette, and the measurement concentration is adjusted to about 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 by the dedicated software is the weight average particle diameter (D4). The “average diameter” in the “analysis / number statistics (arithmetic average)” screen when the graph / number% is set in the dedicated software is the number average particle diameter (D1).

  Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto. In addition, all the parts and% of an Example and a comparative example are mass references | standards unless there is particular notice.

<Example of production of binder resin A-1>
(Polyester unit prescription)
Bisphenol A propylene oxide (2.2 mol adduct): 100.0 mol parts Terephthalic acid: 63.0 mol parts Trimellitic anhydride: 37.0 mol parts

70 parts by mass of the monomer mixture constituting the polyester unit was charged into a four-necked flask and equipped with a decompression device, a water separation device, a nitrogen gas introduction device, a temperature measurement device, and a stirring device, and stirred at 160 ° C. in a nitrogen atmosphere. did.
Then, the following materials were dropped from the dropping funnel over 4 hours and reacted at 160 ° C. for 5 hours.
・ Vinyl monomer constituting vinyl polymer unit (35.0 mol parts of styrene and 2-ethylhexyl acrylate: 60.0 mol parts and 5.0 mol parts of acrylic acid as both reactive compounds) 30 parts by mass As benzoyl peroxide 1 part by mass

  Then, it heated up at 210 degreeC, 0.2 mass part titanium tetrabutoxide was added with respect to the total amount of the monomer component which comprises a polyester unit, and the polymerization reaction was performed. After completion of the reaction, the product was taken out from the container, cooled and pulverized to obtain a binder resin A-1.

<Example of production of binder resins A-2 to A-17>
Binder resins A-2 to A-17 were obtained according to the production example of binder resin A-1, except that the ratio of the vinyl monomer and vinyl polymer unit to the polyester unit was changed as shown in Table 1.
In the table, StAc is described as a vinyl polymer unit and PES is described as a polyester unit.

<Example of production of binder resin B-1>
Bisphenol A ethylene oxide (2.2 mol adduct): 33.0 mol parts Bisphenol A propylene oxide (2.2 mol adduct): 40.0 mol parts Ethylene glycol: 27.0 mol parts Terephthalic acid: 100 .0 mol part

100 parts by mass of the monomer constituting the polyester unit and 5 parts by mass of a primary alcohol-modified wax (wax having an average carbon number of 50, in which one end of polyethylene was modified with a hydroxy group) were mixed in a 5-liter autoclave together with 500 ppm of titanium tetrabutoxide. . A reflux condenser, a water separator, an N ₂ gas introduction tube, a thermometer, and a stirring device were attached thereto, and a polycondensation reaction was performed at 230 ° C. while introducing N ₂ gas into the autoclave. After completion of the reaction, it was taken out from the container, cooled and pulverized to obtain a binder resin B-1.
The ratio of the carbon number of R ² of the monomer represented by the formula (1) used in the binder resin A-1 to the carbon number of the aliphatic compound used in the binder resin B-1 was 1: 6.

<Example of production of binder resins B-2 to B-15>
Table 2 shows bisphenol A ethylene oxide (2.2 mol adduct), bisphenol A propylene oxide (2.2 mol adduct), and ethylene glycol as the carbon number, content, and type of aliphatic compounds, and alcohol components. Changed to
In the table, bisphenol A ethylene oxide (2.2 mol adduct) is BPA-EO, bisphenol A propylene oxide (2.2 mol adduct) is BPA-PO, and ethylene glycol is EG.
Except these, according to the manufacture example of binder resin B-1, binder resin B-2-B-15 was obtained.
The primary alcohol-modified wax uses a wax having one end of a polyethylene having a carbon number shown in Table 2 modified with a hydroxy group, and the acid-modified wax is a polyethylene having a carbon number shown in Table 2. A wax obtained by modifying the wax with acrylic acid was used.

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

The above materials were premixed with a Henschel mixer and then melt kneaded with a biaxial kneading extruder. At this time, the residence time was controlled so that the temperature of the kneaded resin was 150 ° C. The obtained kneaded product is cooled, coarsely pulverized with a hammer mill, then pulverized with a turbo mill, and the finely pulverized powder obtained is a multi-division classifier using the Coanda effect (elbow jet classification manufactured by Nittetsu Mining Co., Ltd.) And a toner having a weight average particle diameter (D4) of 7 μm was obtained. The following materials were externally added and mixed with 100 parts by mass of the toner, and sieved with a mesh having an opening of 150 μm. 1 was obtained.
• Hydrophobic silica fine powder (specific surface area by nitrogen adsorption measured by BET method is 140 m ² / g, hexamethyldisilazane treatment as a hydrophobization treatment) 1.0 part by mass • Strontium titanate (volume average particle size 1.6 μm ) 3.0 parts by mass Toner No. 1 was evaluated as follows.

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

<Evaluation of image density and fog in normal temperature and humidity>
10,000 images were output in an environment of normal temperature and humidity (temperature 23 ° C., relative humidity 50%). After outputting 10,000 sheets, an original image in which five solid 20 mm square patches were arranged in the development area was output, and the average of the five points was defined as the image density.
The image density was measured using an X-Rite color reflection densitometer (manufactured by X-rite, X-rite 500Series).
A: The image density is 1.45 or more.
B: The image density is 1.40 or more and less than 1.45.
C: Image density of 1.35 or more and less than 1.40.
D: Image density is less than 1.35.

Next, a solid white image was output and fog was evaluated according to the following criteria. The measurement is performed using a reflectometer (reflectometer model TC-6DS manufactured by Tokyo Denshoku Co., Ltd.). The worst value of the white background reflection density after image formation is Ds, and the average reflection density of the transfer material before image formation is calculated. The fog was evaluated using Dr as the amount of fog and Dr-Ds as the fog amount. Therefore, the smaller the value is, the more fog is suppressed.
(Evaluation criteria)
A: The fog amount is less than 1.0.
B: The fog amount is 1.0 or more and less than 2.0.
C: The fog amount is 2.0 or more and less than 3.0.
D: The fog amount is 3.0 or more.

<Evaluation of image density and fog in high temperature and high humidity environment>
10,000 images were output under high temperature and high humidity (temperature 30 ° C., relative humidity 80%) environment. After outputting 10,000 sheets, an original image in which five solid 20 mm square patches were arranged in the development area was output, and the average of the five points was defined as the image density.
The image density was measured using an X-Rite color reflection densitometer (manufactured by X-rite, X-rite 500Series).
The image density was measured using an X-Rite color reflection densitometer (manufactured by X-rite, X-rite 500Series).
A: Image density is 1.40 or more.
B: The image density is 1.35 or more and less than 1.40.
C: The image density is 1.30 or more and less than 1.35.
D: Image density is less than 1.30.

Next, a solid white image was output and fog was evaluated according to the following criteria. The measurement is performed using a reflectometer (reflectometer model TC-6DS manufactured by Tokyo Denshoku Co., Ltd.). The worst value of the white background reflection density after image formation is Ds, and the average reflection density of the transfer material before image formation is calculated. The fog was evaluated using Dr as the amount of fog and Dr-Ds as the fog amount. Therefore, the smaller the value is, the more fog is suppressed.
(Evaluation criteria)
A: The fog amount is less than 1.0.
B: The fog amount is 1.0 or more and less than 2.0.
C: The fog amount is 2.0 or more and less than 3.0.
D: The fog amount is 3.0 or more and less than 4.0.

<Reproducibility of minute dots>
Micro dot reproducibility is evaluated by outputting 10,000 images in a high temperature and high humidity (temperature 30 ° C, relative humidity 80%) environment, and then standing still in a high temperature and high humidity environment for 48 hours or more to absorb moisture sufficiently. Printing was performed using the evaluated paper. The image was determined according to the following criteria using an isolated 1-dot halftone chart.

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

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

(Evaluation criteria)
A: L is 0 μm or more and less than 10 μm.
B: L is 10 μm or more and less than 15 μm.
C: L is 15 μm or more and less than 20 μm.
D: L is 20 μm or more.

<Evaluation of image density and fog at low temperature and low humidity>
10,000 images were output in a low-temperature and low-humidity environment (temperature 15 ° C., relative humidity 10%). After outputting 10,000 sheets, an original image in which five solid 20 mm square patches were arranged in the development area was output, and the average of the five points was defined as the image density.
The image density was measured using an X-Rite color reflection densitometer (manufactured by X-rite, X-rite 500Series).
The image density was measured using an X-Rite color reflection densitometer (manufactured by X-rite, X-rite 500Series).
A: The image density is 1.45 or more.
B: The image density is 1.40 or more and less than 1.45.
C: Image density of 1.35 or more and less than 1.40.
D: Image density is less than 1.35.

Next, a solid white image was output and fog was evaluated according to the following criteria. The measurement is performed using a reflectometer (reflectometer model TC-6DS manufactured by Tokyo Denshoku Co., Ltd.). The worst value of the white background reflection density after image formation is Ds, and the average reflection density of the transfer material before image formation is calculated. The fog was evaluated using Dr as the amount of fog and Dr-Ds as the fog amount. Therefore, the smaller the value is, the more fog is suppressed.
(Evaluation criteria)
A: The fog amount is less than 1.0.
B: The fog amount is 1.0 or more and less than 2.0.
C: The fog amount is 2.0 or more and less than 3.0.
D: The fog amount is 3.0 or more and less than 4.0.

<Low temperature fixability>
Evaluation of low-temperature fixability is made by changing the process speed of a commercially available digital copying machine (image RUNNER 4051 Canon Inc.) to 311 mm / second in an environment of normal temperature and humidity (temperature 23 ° C., relative humidity 50%). went. As the evaluation paper, OCE RED LABEL (80 g / m ² paper, A3) was used. Nine points of 20 mm × 20 mm halftone patches were evenly written on A3 paper, and the development bias was set so that the image density was 0.6. Subsequently, after cooling until the temperature of the pressure roller of the fixing device became 23 ° C. or lower, 20 sheets were continuously fed on one side.

As a sample for low-temperature fixability evaluation, the first, third, fifth, tenth, and twentieth samples were sampled, and a load of 4.9 kPa was applied to the obtained fixed images, The fixed image was rubbed 5 times. Among the five samples, the worst value of the average value of the nine image density reduction rates before and after rubbing was defined as the image density reduction rate at each temperature. The fixing temperature was changed from 170 ° C. to 210 ° C. every 5 ° C., and the image density reduction rate was measured sequentially. The fixing temperature at which the image density reduction rate became 20% or less for the first time was set as the fixing start temperature, and this was the low temperature. Fixability was evaluated. For example, when the image density reduction rate is more than 20% at a fixing temperature of 170 ° C., but the image density reduction rate becomes 20% or less at a fixing temperature of 175 ° C., 175 ° C. is set as the fixing start temperature.
The image density was measured with a Macbeth densitometer (RD-914; manufactured by Macbeth) using an SPI auxiliary filter.

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

<Preservability>
For the evaluation of storage stability, 5 g of toner was placed in a 50 cc resin cup and allowed to stand for 3 days at a temperature of 50 ° C./relative humidity of 10%, and the presence or absence of aggregates was examined and evaluated.
(Evaluation criteria)
A: Agglomerates are not generated.
B: Minor agglomerates are generated and can be solved by light shaking.
C: A slight agglomerate is generated and can be released by lightly pushing with a finger.
D: Agglomerates are generated and do not collapse even when lightly pressed with a finger.
In the above evaluation items, all of the toners of Example 1 were A rank.

<Examples 2 to 22>
(Production example of toner Nos. 2 to 22)
In Example 1, except that the type of the binder resin was changed as shown in Table 3 in the toner formulation, the toner no. 2-22 were produced. The toner No. About 2-22, it evaluated by the method similar to Example 1. FIG. The evaluation results are shown in Table 4.

<Comparative Examples 1-7>
In Example 1, except that the type of the binder resin was changed as shown in Table 6 in the toner formulation, toner No. 23-29 were produced. The toner No. 23 to 29 were evaluated in the same manner as in Example 1. The evaluation results are shown in Table 6.

Claims (4)

In a toner having toner particles containing a binder resin and a release agent,
The binder resin contains a binder resin A and a binder resin B,
The binder resin A is
A hybrid resin in which a vinyl polymer unit and a polyester unit are chemically bonded.
The mass ratio (vinyl polymer unit / polyester unit) between the vinyl polymer unit and the polyester unit is 10/90 to 50/50,
The vinyl polymer unit is a polymer obtained by polymerizing at least styrene and a compound represented by the formula (1),
CH ₂ = CR ¹ COOR ² formula (1)
(R ^{1 represents} H or a methyl group, R ² represents an alkyl group having 12 or less carbon atoms or a hydroxyalkyl group)
The ratio of the compound represented by the formula (1) is 20 mol% or more and 90 mol% or less with respect to the total number of moles of the vinyl monomer used for the polymerization of the vinyl polymer unit,
The binder resin B is a polyester in which at least one aliphatic compound selected from the group consisting of an aliphatic monocarboxylic acid having 25 to 102 carbon atoms and an aliphatic monoalcohol having 25 to 102 carbon atoms is condensed at the terminal. A toner characterized by being a resin. R ² carbon number of the compound represented by the formula (1),
The toner according to claim 1, wherein the ratio of the aliphatic compound condensed at the terminal of the binder resin B to the carbon number is 1: 4 to 1:12.   The binder resin B is a polyester resin obtained by condensation polymerization of at least a polyhydric alcohol, a polyvalent carboxylic acid, and the aliphatic compound. The polyhydric alcohol contains an aliphatic polyhydric alcohol, and The toner according to claim 1, wherein the aliphatic polyhydric alcohol is contained in an amount of 1 mol% to 40 mol% with respect to the total number of moles of the monohydric alcohol. The binder resin B is a polyester resin obtained by polycondensation of at least a polyhydric alcohol, a polyvalent carboxylic acid and the aliphatic compound, and the total mass of the polyhydric alcohol and the polyvalent carboxylic acid is 100 parts by mass. The toner according to claim 1, further comprising 1 to 10 parts by mass of the aliphatic compound.