JP2017068233A - toner - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a toner that is excellent in low-temperature fixability, is less likely to contaminate a fixing member, and prevents the occurrence of unevenness in halftone even after a long-term use in a high-temperature and high-humidity environment.SOLUTION: A toner contains a binder resin, a colorant, and a compound represented by a specific formula. In the formula, X represents a group selected from an oxygen atom, sulfur atom, carbonyl group, and -CRR-.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, with the development of image forming apparatuses such as copiers and printers, there is a demand for toners that can cope with higher speed, higher image quality, longer life, and energy saving than ever before. In order to achieve energy saving in copying machines and printers, it is effective to lower the fixing temperature of the toner, and a toner that melts at a lower temperature is required. Furthermore, the usage environment of toner is diversified, and there is a demand for a toner that can provide a stable image even when used in various environments.
As a technique for melting toner at a lower temperature, it is known to control the melt viscosity of a binder resin, which is the main component of the toner, to be low. However, when the melt viscosity of the binder resin itself is controlled to be low, the durability of the toner is lowered. As a result, after long-term use in a high-temperature and high-humidity environment, the variation in charge amount due to toner deterioration increases, and halftone image density unevenness (hereinafter referred to as halftone unevenness) may occur. . In view of this, various methods for melting the toner at a lower temperature by adding a plasticizer have been studied, rather than a method for lowering the melt viscosity of the binder resin itself.

Patent Document 1 proposes a method for controlling the melting characteristics of a toner by using a low melting point wax.
Patent Document 2 proposes a toner that can accommodate a wide fixing temperature range by containing bisphenoxyethanol fluorene in the toner in an amount of 6% by mass to 17% by mass.
On the other hand, Patent Document 3 discloses a binder resin using bisphenoxyethanol fluorene as one of the monomers constituting the binder resin used in the toner.

JP 2001-13714 A Japanese Unexamined Patent Publication No. 2015-175858 JP 2008-165005 A

As described above, a device for lowering the fixing temperature of the toner by examining the additive has been studied. However, when the toner described in Patent Document 1 is used, the low melting point wax exists as a domain in the toner, and therefore minute dispersion unevenness is likely to occur. As a result, after a long period of use in a high-temperature and high-humidity environment, the charge amount may decrease, and halftone unevenness may easily occur. Further, after a long period of use, a part of the wax domain existing in the vicinity of the toner surface may be gradually transferred to the fixing member to contaminate the fixing member.
In addition, when the toner described in Patent Document 2 was used, an effect on the fixing property was obtained. However, when used in a high-temperature and high-humidity environment, the charge amount decreased and halftone unevenness was likely to occur. There was a case.
Furthermore, the toner described in Patent Document 3 uses bisphenoxyethanol fluorene as one of the monomers as an alternative to the bisphenol A derivative conventionally used in binder resins. Although the same compound as that of Patent Document 2 is used, since it is not present in the toner as an additive, no effect was obtained with respect to improvement in low-temperature fixability and chargeability.

  The present invention has been made in order to solve the above-described problems, and the object thereof is to improve the low-temperature fixability than before, the fixing member is less likely to be contaminated, and halftone even after long-term use in a high-temperature and high-humidity environment. To provide a toner that is less likely to cause unevenness.

  As a result of intensive studies, the inventors of the present invention have excellent low-temperature fixability compared to the prior art by containing a binder resin, a colorant, and a compound represented by the following general formula [1] in the toner. It has been found that it is possible to provide a toner in which the fixing member is not easily contaminated and half-tone unevenness does not occur even after long-term use in a high-temperature and high-humidity environment.

Wherein R ^{1 to} R ⁸ are each independently a hydrogen atom, a fluorine atom, a bromine atom, an iodine atom, a hydroxy group, an acetyl group, an aldehyde group, a hydrocarbon group having 1 to 6 carbon atoms, and an amino group. X represents a group selected from an oxygen atom, a sulfur atom, a carbonyl group, and —CR ⁹ R ¹⁰ —, and R ⁹ and R ¹⁰ each independently represent a hydrogen atom or a bromine atom. Represents a group selected from a hydroxyalkyl group having 1 to 3 carbon atoms, a hydroxyl group, a phenyl group, and a hydrocarbon group having 1 to 6 carbon atoms.)

  According to the present invention, it is possible to obtain a toner that is excellent in low-temperature fixability compared to the prior art, the fixing member is less likely to be contaminated, and halftone unevenness is less likely to occur after long-term use in a high-temperature and high-humidity environment.

In the present invention, the description of “XX or more and XX or less” or “XX to XX” representing a numerical range means a numerical range including a lower limit and an upper limit as endpoints unless otherwise specified.
Hereinafter, the present invention will be described in detail.
The present invention relates to a toner comprising a binder resin, a colorant, and a compound represented by the general formula [1].
According to the study by the present inventors, the use of the toner described above is superior in low temperature fixability than before, the fixing member is less likely to be contaminated, and halftone unevenness occurs even after long-term use in a high temperature and high humidity environment. It has been found that it is possible to provide a toner that is difficult to do.

The reason why an excellent effect that has not been obtained by the above-described configuration can be obtained is considered as follows.
As a result of intensive studies by the present inventors, the compound represented by the general formula [1] is compatible with binder resins (for example, vinyl resins, polyester resins, polyurethane resins, etc.) generally used for toners. It was found that the solubility was very high. Since the compound represented by the general formula [1] is uniformly compatible with the binder resin used in the toner, it is not unevenly distributed in the toner or free from the toner. Therefore, the toner containing the compound represented by the general formula [1] does not contaminate the fixing member and can maintain the charge amount distribution sharply, so that halftone unevenness is hardly generated. .
In addition, the present inventors have found that the compound represented by the general formula [1] has a very high plasticizing effect on a binder resin (for example, vinyl resin, polyester resin, polyurethane resin, etc.) used in the toner. I also found out. Therefore, since the compound represented by the general formula [1] can effectively lower the melt viscosity of the toner, it has become possible to achieve a low-temperature fixability superior to the conventional one. The effects as described above are considered to be derived from the structure of the compound represented by the general formula [1].

From the above, by using the toner containing the compound represented by the general formula [1], the fixing member is excellent in low temperature fixing property, the fixing member is hardly contaminated, and is used for a long time in a high temperature and high humidity environment. It is possible to provide a toner that hardly causes halftone unevenness later.
The compound represented by the general formula [1] used in the present invention will be described.
A feature of the present invention is that the toner contains a compound represented by the following general formula [1].

(In the formula, R ^{1 to} R ⁸ are each independently a hydrogen atom, a fluorine atom, a bromine atom, an iodine atom, a hydroxy group, an acetyl group, an aldehyde group, 1 to 6 carbon atoms (preferably 1 to 4 carbon atoms). And a group selected from an amino group, X represents an oxygen atom, a sulfur atom, a carbonyl group, and a group selected from —CR ⁹ R ¹⁰ —, and R ⁹ and R ¹⁰ are And each independently represents a group selected from a hydrogen atom, a bromine atom, a hydroxyalkyl group having 1 to 3 carbon atoms, a hydroxyl group, a phenyl group, and a hydrocarbon group having 1 to 6 carbon atoms.)
The hydrocarbon group having 1 to 6 carbon atoms is more preferably a tertiary butyl group. The hydroxyalkyl group having 1 to 3 carbon atoms is preferably a methylol group.
In the general formula [1], X being —CR ⁹ R ¹⁰ — indicates a compound represented by the following general formula [2].

(In the formula, R ^{1 to} R ⁸ are each independently a hydrogen atom, a fluorine atom, a bromine atom, an iodine atom, a hydroxy group, an acetyl group, an aldehyde group, 1 to 6 carbon atoms (preferably 1 to 4 carbon atoms). And a group selected from the group consisting of an amino group, R ⁹ and R ¹⁰ are:
Each independently represents a group selected from a hydrogen atom, a bromine atom, a hydroxyalkyl group having 1 to 3 carbon atoms, a hydroxyl group, a phenyl group, and a hydrocarbon group having 1 to 6 carbon atoms. )
The hydrocarbon group having 1 to 6 carbon atoms is more preferably a tertiary butyl group. The hydroxyalkyl group having 1 to 3 carbon atoms is preferably a methylol group.

Examples of the compound represented by the general formula [1] include the following.
Fluorene, 9,9-dimethylfluorene, 2-amino-9,9-dimethylfluorene, 2-iodo-9,9-dimethylfluorene, 2-bromo-9,9-dimethylfluorene, 2-aminofluorene, 9-bromo Fluorene, 2-bromofluorene, 2,7-dibromo-9,9-dihexylfluorene, 2-iodofluorene, 2-fluorofluorene, 2-fluorenecarboxaldehyde, 9-fluorenol, 9-phenyl-9-fluorenol, 2- Fluorene derivatives such as acetylfluorene, 2,7-di-tert-butylfluorene, 9-fluorenylmethanol, 9-fluorenone, 2-bromo-9-fluorenone, fluorenone derivatives such as 2-amino-9-fluorenone , Dibenzothiophene, 2-bromodiben Thiophene, 4-bromodibenzothiophene, 4-iododibenzothiophene, dibenzothiophene-4-carboxaldehyde, dibenzothiophene derivatives such as 2,8-dimethyldibenzothiophene, dibenzofuran, 2-bromodibenzofuran, 4-bromodibenzofuran, dibenzofuran- Dibenzofuran derivatives such as 2-carboxaldehyde.

Among these, a fluorene derivative or a fluorenone derivative is more preferable, and a fluorenone derivative in which X in the general formula [1] is a carbonyl group is more preferable.
By using a fluorenone derivative in which X is a carbonyl group, the plasticizing effect on the toner becomes better, so that the low-temperature fixability becomes better.
The content of the compound represented by the general formula [1] is preferably 0.1 parts by mass or more and 20 parts by mass or less, and 0.2 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the binder resin. Is more preferable, and 1 mass part or more and 5 mass parts or less are still more preferable. By controlling the content of the compound represented by the general formula [1] within the above-mentioned range, the plastic effect and compatibility with the toner become better, and the low-temperature fixability and the contamination with the fixing member become better. Furthermore, an image with little halftone unevenness can be obtained even after long-term use in a high temperature and high humidity environment. Whether or not the compound represented by the formula [1] is contained in the toner can be examined using a pyrolysis gas chromatography mass spectrometer, a nuclear magnetic resonance apparatus ( ¹ H-NMR) or the like. .

The compound represented by the general formula [1] preferably has a melting point of 55 ° C. or higher and 180 ° C. or lower, more preferably 65 ° C. or higher and 160 ° C. or lower, and more preferably 70 ° C. or higher and 100 ° C. or lower. preferable. When the melting point of the compound represented by the general formula [1] is in the above range, it is easy to handle when producing the toner, and it is possible to make it compatible with the binder resin in the toner. As a result, since the plastic effect and compatibility with the toner are more appropriately maintained, an image having excellent low-temperature fixability and less halftone unevenness can be obtained.
The compound represented by the general formula [1] preferably has a boiling point of 290 ° C or higher. When the boiling point is 290 ° C. or higher, the compound is hardly volatilized even by heat during fixing, and contamination of the fixing member can be suppressed. The upper limit is not particularly limited, but is preferably 600 ° C. or lower, more preferably 500 ° C. or lower.

Examples of the binder resin used in the toner of the present invention include the following. Styrene resin, styrene copolymer resin, polyester resin, polyol resin, polyvinyl chloride resin, phenol resin, natural modified phenol resin, natural resin modified maleic acid resin, acrylic resin, methacrylic resin, polyvinyl acetate, silicone resin, polyurethane Resin, polyamide resin, furan resin, epoxy resin, xylene resin, polyvinyl butyral, terpene resin, coumarone indene resin, petroleum resin. Among them, preferred resins include styrene copolymer resins, polyester resins, and hybrid resins in which polyester resins and styrene copolymer resins are mixed or partially reacted.

The component which comprises the said polyester resin is explained in full detail. 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 resin include the following dicarboxylic acids or derivatives thereof. Benzene dicarboxylic acids such as phthalic acid, terephthalic acid, isophthalic acid, 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; The lower alkyl ester; an alkenyl succinic acid or alkyl succinic acid having an average carbon number of 1 to 50 or an anhydride or a lower alkyl ester thereof; unsaturated such as fumaric acid, maleic acid, citraconic acid, itaconic acid Dicarboxylic acids or anhydrides or lower alkyl esters thereof.

  On the other hand, the following are mentioned as a bivalent alcohol component which comprises a polyester resin. 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 (I-1) and its derivatives: and diols represented by formula (I-2).

(In the formula, 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 or more and 10 or less.)

(In the formula, 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 or more and 10 or less.)

The constituent component of the polyester resin used in the present invention contains a trivalent or higher carboxylic acid compound and a trivalent or higher alcohol compound as a constituent component in addition to the above divalent carboxylic acid compound and divalent alcohol compound. May be.
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.

In the present invention, the method for producing the polyester resin is not particularly limited, and a known method can be used. For example, the above-described divalent carboxylic acid compound and divalent alcohol compound are polymerized through an esterification reaction or a transesterification reaction and a condensation reaction to produce a polyester resin. The polymerization temperature is not particularly limited, but a range of 180 ° C. or higher and 290 ° C. or lower is preferable. In the polymerization of the polyester resin, 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 the present invention, it is preferable that at least styrene is used as the vinyl monomer for producing the styrene copolymer resin. Since styrene has a large proportion of aromatic rings in the molecular structure, durability stability is more advantageous. The content of styrene is preferably 70% by mass or more, and more preferably 85% by mass or more in the vinyl monomer. The upper limit is not particularly limited, but is usually 100% by mass or less.
Examples of vinyl monomers for producing styrene copolymer resins other than styrene include the following styrene monomers and acrylic monomers.

  Styrene 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-chloro styrene, 3,4 -Styrene derivatives such as dichlorostyrene, m-nitrostyrene, o-nitrostyrene, p-nitrostyrene.

Examples of acrylic monomers include acrylic acid, methyl acrylate, ethyl acrylate, propyl acrylate, acrylate-n-butyl, acrylate isobutyl, acrylate-n-octyl, dodecyl acrylate, and 2-ethylhexyl acrylate. , Acrylic acid and acrylic esters such as stearyl acrylate, 2-chloroethyl acrylate, phenyl acrylate; methacrylic acid, methyl methacrylate, ethyl methacrylate, propyl methacrylate, methacrylic acid-n-butyl, methacrylic acid Such as isobutyl, methacrylate-n-octyl, dodecyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, phenyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate - methylene aliphatic monocarboxylic acids and their esters; acrylonitrile, methacrylonitrile, acrylic acid or methacrylic acid derivatives such as acrylamide.
Furthermore, as a monomer constituting the styrene copolymer resin, acrylic acid or methacrylic acid esters such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 4- (1-hydroxy-1- And a monomer having a hydroxy group such as methylbutyl) styrene and 4- (1-hydroxy-1-methylhexyl) styrene.

In the styrene copolymer resin, various monomers capable of vinyl polymerization can be used in combination as required. Examples of such monomers include ethylenically unsaturated monoolefins such as ethylene, propylene, butylene and isobutylene; unsaturated polyenes such as butadiene and isoprene; vinyl chloride, vinylidene chloride, vinyl bromide and vinyl fluoride. Vinyl halides such as; vinyl esters such as vinyl acetate, vinyl propionate, vinyl benzoate; vinyl ethers such as vinyl methyl ether, vinyl ethyl ether, vinyl isobutyl ether: vinyl vinyl ketone, vinyl hexyl ketone, Vinyl ketones such as methyl isopropenyl ketone; N-vinyl compounds such as N-vinyl pyrrole, N-vinyl carbazole, N-vinyl indole and N-vinyl pyrrolidone; vinyl naphthalenes; further maleic acid, citraconic acid Unsaturated dibasic acids such as itaconic acid, alkenyl succinic acid, fumaric acid, mesaconic acid; unsaturated dibasic acid anhydrides such as maleic acid anhydride, citraconic acid anhydride, itaconic acid anhydride, alkenyl succinic acid anhydride Products: maleic acid methyl half ester, maleic acid ethyl half ester, maleic acid butyl 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 Unsaturated basic acid half ester such as methyl fumarate half ester and methyl mesaconic acid half ester; Unsaturated basic acid ester such as dimethyl maleic acid and dimethyl fumaric acid; Acrylic acid, methacrylic acid, crotonic acid Α, β-unsaturated acid anhydrides such as: anhydrides of the α, β-unsaturated acids and lower fatty acids; alkenylmalonic acid, alkenylglutaric acid, alkenyladipic acid, their acid anhydrides and these And a monomer having a carboxy group, such as

The styrene copolymer resin may be a polymer cross-linked with a cross-linkable monomer as exemplified below if necessary. Crosslinkable monomers include, for example, aromatic divinyl compounds, diacrylate compounds linked by alkyl chains, diacrylate compounds linked by alkyl chains containing ether bonds, and chains containing aromatic groups and ether bonds. And diacrylate compounds, polyester-type diacrylates, and polyfunctional crosslinking agents.
Examples of the aromatic divinyl compound include divinylbenzene and divinylnaphthalene.

Examples of diacrylate compounds linked by the alkyl chain include ethylene glycol diacrylate, 1,3-butylene glycol diacrylate, 1,4-butanediol diacrylate, 1,5-pentanediol diacrylate, 1, Examples include 6-hexanediol diacrylate, neopentyl glycol diacrylate, and those obtained by replacing the acrylate of the above compound with methacrylate.
Examples of diacrylate compounds linked by an alkyl chain containing an ether bond include, for example, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol # 400 diacrylate, polyethylene glycol # 600 diacrylate, Examples include dipropylene glycol diacrylate and those obtained by replacing acrylate of the above compound with methacrylate.

Examples of the diacrylate compounds connected by a chain containing an aromatic group and an ether bond include polyoxyethylene (2) -2,2-bis (4-hydroxyphenyl) propane diacrylate, polyoxyethylene (4 ) -2,2-bis (4-hydroxyphenyl) propane diacrylate, and those obtained by replacing the acrylate of the above compound with methacrylate. Examples of polyester diacrylates include trade name MANDA (Nippon Kayaku).
Examples of the polyfunctional crosslinking agent include pentaerythritol triacrylate, trimethylol ethane triacrylate, trimethylol propane triacrylate, tetramethylol methane tetraacrylate, oligoester acrylate, and those obtained by replacing acrylates of the above compounds with methacrylate. Triallyl cyanurate, triallyl trimellitate; and the like.

The styrene copolymer resin may be a resin produced using a polymerization initiator. These polymerization initiators are preferably used in an amount of 0.05 to 10 parts by mass with respect to 100 parts by mass of the monomer from the viewpoint of efficiency.
Examples of such a polymerization initiator include 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 Ketone peroxides such as (2-methylpropane), methyl ethyl ketone peroxide, acetylacetone peroxide, cyclohexanone peroxide, 2 2-bis (t-butylperoxy) butane, t-butyl hydroperoxide, cumene hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, di-t-butyl peroxide, t-butyl Cumyl peroxide, dicumyl peroxide, α, α'-bis (t-butylperoxyisopropyl) benzene, isobutyl peroxide, octanoyl peroxide, decanoyl peroxide, lauroyl peroxide, 3,5,5-trimethyl Hexanoyl peroxide, benzoyl peroxide, m-trioyl peroxide, diisopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, di-n-propyl peroxydicarbonate, di-2-ethoxye Ruperoxycarbonate, dimethoxyisopropylperoxydicarbonate, di (3-methyl-3-methoxybutyl) peroxycarbonate, acetylcyclohexylsulfonyl peroxide, t-butylperoxyacetate, t-butylperoxyisobutyrate, t- Butyl peroxyneodecanoate, t-butyl peroxy-2-ethylhexanoate, t-butyl peroxylaurate, t-butyl peroxybenzoate, t-butyl peroxyisopropyl carbonate, di-t-butyl Peroxyisophthalate, t-butylperoxyallyl carbonate, t-amylperoxy-2-ethylhexanoate, di-t-butylperoxyhexahydroterephthalate, di-t-butylperoxyazelate And the like.

As described above, the hybrid resin is a resin in which a polyester resin and a styrene copolymer resin are mixed or partially reacted.
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 polyester resin monomer and the styrene copolymer resin monomer. Can be mentioned. Of these, fumaric acid, acrylic acid, and methacrylic acid are preferably used.

The hybrid resin can be obtained by reacting the raw material monomer of the polyester resin and the raw material monomer of the styrene copolymer resin simultaneously or sequentially. For example, when the raw material monomer of the polyester resin is subjected to a condensation polymerization reaction after the addition polymerization reaction of the styrene copolymer resin monomer, the molecular weight can be easily controlled.
In the hybrid resin, the mixing ratio (mass ratio) of the polyester resin and the styrene copolymer resin is 50/50 to 90/10 for the polyester resin / styrene copolymer resin, from the viewpoint of controlling the crosslinked structure at the molecular level. And preferably 50/50 to 80/20.

The binder resin of the present invention may contain two or more binder resins.
When two or more kinds of binder resins are contained, the high softening point resin preferably has a softening point of 120 ° C. or higher and 170 ° C. or lower. Further, the low softening point resin preferably has a softening point of 70 ° C or higher and lower than 120 ° C.
By containing two or more binder resins having different softening points, the molecular weight distribution of the toner can be designed relatively easily and a wide fixing region can be provided, which is preferable.
When one kind of binder resin is used alone, the softening point is preferably 95 ° C or higher and 170 ° C or lower.
More preferably, it is 120 degreeC or more and 160 degrees C or less. When the softening point is within the above range, high-temperature offset resistance and low-temperature fixability are good.

The softening point is measured as follows. The softening point of the resin is measured by using a constant load extrusion type capillary rheometer “flow characteristic evaluation device Flow Tester CFT-500D” (manufactured by Shimadzu Corporation) according to the manual attached to the device. In this device, while applying a constant load from the top of the measurement sample with the piston, the measurement sample filled in the cylinder is heated and melted, and the melted measurement sample is pushed out from the die at the bottom of the cylinder, and the piston drop amount at this time A flow curve showing the relationship between temperature and temperature can be obtained.
In the present invention, the “melting temperature in the 1/2 method” described in the manual attached to the “flow characteristic evaluation apparatus Flow Tester CFT-500D” is the softening point. The melting temperature in the 1/2 method is calculated as follows. First, ½ of the difference between the piston lowering amount Smax at the time when the outflow ends and the piston lowering amount Smin at the time when the outflow starts is obtained (this is X. X = (Smax−Smin) / 2). And the temperature of the flow curve when the amount of piston descent in the flow curve is the sum of X and Smin is the melting temperature Tm in the 1/2 method.

As a measurement sample, about 1.3 g of a sample is compression-molded at about 10 MPa using a tablet molding compressor (for example, NT-100H, manufactured by NP System Co., Ltd.) in an environment of 25 ° C. for about 60 seconds. A cylindrical shape having a diameter of about 8 mm is used.
The measurement conditions of CFT-500D are as follows.
Test mode: Temperature rising start temperature: 50 ° C
Achieving temperature: 200 ° C
Measurement interval: 1.0 ° C
Temperature increase rate: 4.0 ° C./min
Piston cross-sectional area: 1.000 cm ²
Test load (piston load): 10.0 kgf (0.9807 MPa)
Preheating time: 300 seconds Die hole diameter: 1.0 mm
Die length: 1.0mm

The glass transition temperature (Tg) of the binder resin is preferably 45 ° C. or higher from the viewpoint of storage stability. Further, from the viewpoint of low-temperature fixability, Tg is preferably 75 ° C. or lower, and more preferably 70 ° C. or lower.
The glass transition temperature (Tg) of the binder resin for toner is measured under normal temperature and humidity according to ASTM D3418-82 using a differential scanning calorimeter (DSC) and MDSC-2920 (manufactured by TA Instruments). To do. As a measurement sample, a precisely weighed about 3 mg of binder resin is used. This is put in an aluminum pan and an empty aluminum pan is used as a reference. The measurement temperature range is 30 ° C. or more and 200 ° C. or less, once the temperature is increased from 30 ° C. to 200 ° C. at a temperature increase rate of 10 ° C./min, then the temperature is decreased from 200 ° C. to 30 ° C. at a temperature decrease rate of 10 ° C./min. The temperature is raised to 200 ° C. at a temperature rising rate of 10 ° C./min. In the DSC curve obtained in the second temperature raising process, the intersection point between the baseline intermediate line before and after the specific heat change and the differential heat curve is defined as the glass transition temperature Tg of the resin.

The toner of the present invention can be used as any one of magnetic one-component toner, non-magnetic one-component toner, and non-magnetic two-component toner.
When used as a magnetic one-component toner, magnetic iron oxide particles are preferably used as the colorant. Magnetic iron oxide particles contained in the magnetic one-component toner include magnetic iron oxides such as magnetite, maghemite and ferrite, and magnetic iron oxides containing other metal oxides; Fe, C
o, metals such as Ni, or these metals and Al, Co, Cu, Pb, Mg, Ni, Sn, Zn, Sb, Be, Bi, Cd, Ca, Mn, Se, Ti, W, V And alloys with such metals, and mixtures thereof.
The content of the magnetic iron oxide particles is preferably 30 parts by mass or more and 150 parts by mass or less with respect to 100 parts by mass of the binder resin.

Examples of the colorant used as the nonmagnetic one-component toner and the nonmagnetic two-component toner include the following.
As the black pigment, carbon black such as furnace black, channel black, acetylene black, thermal black and lamp black is used, and magnetic powder such as magnetite and ferrite is also used.
As a colorant suitable for the yellow color, a pigment or a dye can be used. Examples of the pigment include C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 7, 10, 11, 12, 13, 14, 15, 17, 23, 62, 65, 73, 74, 81, 83, 93, 94, 95, 97, 98, 109, 110, 111, 117, 120, 127, 128, 129, 137, 138, 139, 147, 151, 154, 155, 167, 168, 173, 174, 176, 180, 181, 183, 191, C.I. I. Butt yellow 1,3,20 is mentioned. Examples of the dye include C.I. I. Solvent yellow 19, 44, 77, 79, 81, 82, 93, 98, 103, 104, 112, 162 etc. are mentioned. These are used alone or in combination of two or more.

As a colorant suitable for cyan, a pigment or a dye can be used. Examples of the pigment include C.I. I. Pigment Blue 1, 7, 15, 15; 1, 15; 2, 15; 3, 15; 4, 16, 17, 60, 62, 66, etc., C.I. I. Bat Blue 6, C.I. I. Acid Blue 45 is exemplified. Examples of the dye include C.I. I. Solvent Blue 25, 36, 60, 70, 93, 95 etc. are mentioned. These are used alone or in combination of two or more.
A pigment or dye can be used as a colorant suitable for magenta. Examples of the pigment include C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 39, 40, 41, 48, 48; 2, 48; 3, 48; 4, 49, 50, 51, 52, 53, 54, 55, 57, 57; 1, 58, 60, 63, 64, 68, 81, 81; 1, 83, 87, 88, 89, 90, 112, 114, 122, 123, 144, 146, 150, 163, 166, 169, 177, 184, 185, 202, 206, 207, 209, 220, 221, 238, 254, etc., C.I. I. Pigment violet 19; C.I. I. Buttred 1, 2, 10, 13, 15, 23, 29, 35 may be mentioned. Examples of the magenta dye include C.I. I. Solvent Red 1, 3, 8, 23, 24, 25, 27, 30, 49, 52, 58, 63, 81, 82, 83, 84, 100, 109, 111, 121, 122, etc. I. Disper thread 9, C.I. I. Solvent Violet 8, 13, 14, 21, 27 etc., C.I. I. Oil-soluble dyes such as disperse violet 1, C.I. I. Basic Red 1, 2, 9, 12, 13, 14, 15, 17, 18, 22, 23, 24, 27, 29, 32, 34, 35, 36, 37, 38, 39, 40, etc. I. Basic violet 1,3,7,10,14,15,21,25,26,27,28 etc. basic dyes etc. are mentioned. These are used alone or in combination of two or more.
The content of the colorant is preferably 1 part by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the binder resin.

In order to give the toner releasability, a release agent (wax) may be used. As the wax, aliphatic hydrocarbon waxes such as low molecular weight polyethylene, low molecular weight polypropylene, Fischer-Tropsch wax, microcrystalline wax, and paraffin wax are preferable because of easy dispersion in the toner and high releasability. Used. If necessary, one kind or two or more kinds of waxes may be used in a small amount.
Examples of the hydrocarbon that is the base of the aliphatic hydrocarbon wax include the following. Specifically, those synthesized by the reaction of carbon monoxide and hydrogen using a metal oxide catalyst (often a multi-component system of two or more types) (for example, the Gintor method, Hydrocol method (using a fluidized catalyst bed) ) Synthesized hydrocarbons)); hydrocarbons with up to several hundred carbon atoms obtained by the age method (using identified catalyst bed) that can produce a large amount of waxy hydrocarbons; polymerization of ethylene and other alkylenes with Ziegler catalysts And the like.

  More specifically, the following are mentioned. That is, Biscol (registered trademark) 330-P, 550-P, 660-P, TS-200 (Sanyo Chemical Industry Co., Ltd.); High wax 400P, 200P, 100P, 410P, 420P, 320P, 220P, 210P, 110P ( Mitsui Chemicals, Inc.); Sazol H1, H2, C80, C105, C77 (Sazol); HNP-1, HNP-3, HNP-9, HNP-10, HNP-11, HNP-12 (Nippon Seiwa Co., Ltd.) ), Unilin (registered trademark) 350, 425, 550, 700, Unicid (registered trademark) 350, 425, 550, 700 (Toyo Petrolite); wood wax, beeswax, rice wax, candelilla wax, carnauba wax ( Celarica NODA).

Also, oxides of aliphatic hydrocarbon waxes such as oxidized polyethylene wax, or block copolymers thereof; waxes containing fatty acid esters such as montanic acid ester wax as the main component; fatty acid esters such as deoxidized carnauba wax What deoxidized one part or all part can also be used as a mold release agent. Furthermore, the following are mentioned as what can be used as a mold release agent.
Saturated linear fatty acids such as palmitic acid, stearic acid, and montanic acid; unsaturated fatty acids such as brassic acid, eleostearic acid, and parinaric acid; stearyl alcohol, aralkyl alcohol, behenyl alcohol, carnauvyl alcohol, seryl alcohol, Saturated alcohols such as sil alcohol; Long chain alkyl alcohols; 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 Saturated bisamides such as ethylene bislauric acid amide and hexamethylene bis stearic acid amide; ethylene bis oleic acid amide, hexamethylene bis oleic acid amide, N, N′-dioleyl adipic acid amide, N, Unsaturated fatty acid amides such as N-dioleyl sebacic acid amide; m-xylene bis stearic acid amide, aromatic bisamides such as N, N-distearylisophthalic acid amide; calcium stearate, calcium laurate, zinc stearate, Fatty acid metal salts such as magnesium stearate (generally called metal soap); waxes grafted with aliphatic hydrocarbon waxes using vinyl monomers such as styrene and acrylic acid; behenic acid monoglycerides, etc. Examples include partially esterified products obtained by reacting fatty acids with polyhydric alcohols; methyl ester compounds having hydroxyl groups obtained by hydrogenation of vegetable oils and the like.
The timing of adding the release agent may be added at the time of manufacturing the toner or may be added at the time of manufacturing the binder resin. Moreover, these mold release agents may be used individually by 1 type, and may be used in combination of 2 or more types. The release agent is preferably added in an amount of 1 to 20 parts by mass with respect to 100 parts by mass of the binder resin.

In the toner of the present invention, a known charge control agent can be used as the charge control agent. Known charge control agents include azo-based iron compounds, azo-based chromium compounds, azo-based manganese compounds, azo-based cobalt compounds, azo-based zirconium compounds, carboxylic acid derivative chromium compounds, carboxylic acid derivative zinc compounds, and carboxylic acid derivatives. And aluminum compounds of carboxylic acids and zirconium compounds of carboxylic acid derivatives. The carboxylic acid derivative is preferably an aromatic hydroxycarboxylic acid. A charge control resin can also be used. If necessary, one type or two or more types of charge control agents may be used in combination. The charge control agent is preferably added in an amount of 0.1 to 10 parts by mass with respect to 100 parts by mass of the binder resin.

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. Examples of the resin used for the coating material include styrene-acrylic resins such as styrene-acrylic acid ester copolymers and styrene-methacrylic acid ester copolymers; acrylic resins such as acrylic acid ester copolymers and methacrylic acid ester copolymers. Fluorine-containing resins such as polytetrafluoroethylene, monochlorotrifluoroethylene polymer and polyvinylidene fluoride; silicone resins; polyester resins; polyamide resins; polyvinyl butyral; aminoacrylate resins. 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, silica fine powder is preferably externally added to the toner particles in order to improve charging stability, developability, fluidity, and durability. The silica fine powder preferably has a specific surface area of 30 m ² / g or more and 500 m ² / g or less, more preferably 50 m ² / g or more and 400 m ² / g or less by the BET method by nitrogen adsorption. The silica fine powder is preferably used in an amount of 0.01 to 8.00 parts by mass, and more preferably 0.10 to 5.00 parts by mass with respect to 100 parts by mass of the toner particles.
The BET specific surface area of the silica fine powder is, for example, a silica fine powder using a specific surface area measuring device Autosorb 1 (manufactured by Yuasa Ionics), GEMINI 2360/2375 (manufactured by Micrometric), Tristar 3000 (manufactured by Micrometric). Nitrogen gas is adsorbed on the surface of the body and can be calculated using the BET multipoint method.

Silica fine powder has unmodified silicone varnish, various modified silicone varnishes, unmodified silicone oil, various modified silicone oils, silane coupling agents, and functional groups as necessary for the purpose of hydrophobization and triboelectric charge control. It is also preferable that it is treated with a treating agent such as a silane compound or other organosilicon compound or in combination with various treating agents.
Furthermore, you may add another external additive to the toner of this invention as needed. Examples of such external additives include charging aids, conductivity imparting agents, fluidity imparting agents, anti-caking agents, release agents at the time of heat roller fixing, lubricants, abrasives, and the like. An inorganic fine powder is mentioned. Examples of the charging aid include metal oxides such as titanium oxide, zinc oxide, and alumina. Examples of the lubricant include polyfluorinated ethylene powder, zinc stearate powder, and polyvinylidene fluoride powder. Examples of the abrasive include cerium oxide powder, silicon carbide powder, and strontium titanate powder. Of these, strontium titanate powder is preferable.

Examples of the method for producing toner particles include a pulverization method, an emulsion aggregation method, a suspension polymerization method, and a dissolution suspension method.
The toner particles produced by the pulverization method are produced, for example, as follows. The binder resin, the colorant, the compound represented by the general formula [1], and other additives as necessary are sufficiently mixed by a mixer such as a Henschel mixer or a ball mill. The mixture is melt kneaded using a thermal kneader such as a twin-screw kneading extruder, a heating roll, a kneader, or an extruder. At that time, wax, magnetic iron oxide particles, and a metal-containing compound may be added. The melt-kneaded product is cooled and solidified, and then pulverized and classified to obtain toner particles. Further, if necessary, the toner particles and the external additive can be mixed with a mixer such as a Henschel mixer to obtain a toner.

The following are mentioned as a mixer. Henschel mixer (made by Mitsui Mining); Super mixer (made by Kawata); Ribocorn (made by Okawara Seisakusho); Nauta mixer, turbulizer, cyclomix (made by Hosokawa Micron); Spiral pin mixer (made by Taiheiyo Kiko) A Ladige mixer (manufactured by Matsubo).
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); TEX twin-screw kneader (manufactured by Nippon Steel); PCM kneader (Ikegai Steel mill); three roll mill, mixing roll mill, kneader (manufactured by Inoue Seisakusho); kneedex (manufactured by Mitsui Mining); MS-type pressure kneader, nider ruder (manufactured by Moriyama Seisakusho); Banbury mixer (Kobe Steel) (Made by the company).
Examples of the pulverizer include the following. Counter jet mill, micron jet, inomizer (manufactured by Hosokawa Micron); IDS type mill, PJM jet crusher (manufactured by Nippon Pneumatic Industrial Co., Ltd.); cross jet mill (manufactured by Kurimoto Iron Works Co., Ltd.); SK; jet mill (manufactured by Seishin Enterprise Co., Ltd.); kryptron (manufactured by Kawasaki Heavy Industries, Ltd.); turbo mill (manufactured by Turboe Corporation); super rotor (manufactured by Nisshin Engineering Co., Ltd.).

Examples of the classifier include the following. Classifier, Micron Classifier, Spedic Classifier (manufactured by Seishin Enterprise); Turbo Classifier (manufactured by Nissin Engineering); Micron Separator, Turboplex (ATP), TSP Separator (manufactured by Hosokawa Micron); Elbow Jet (Japan) Iron Mining Co., Ltd.), Dispersion Separator (manufactured by Nippon Pneumatic Engineering Co., Ltd.); YM Microcut (manufactured by Yaskawa Corporation).
Examples of the sieving apparatus used for sieving coarse particles include the following. Ultrasonic (manufactured by Sakae Sangyo Co., Ltd.); Resonator Sheave, Gyroshifter (Tokusu Kosakusha Co., Ltd.); Vibrasonic System (manufactured by Dalton Co.); Soniclean (manufactured by Shinto Kogyo Co., Ltd.); Micro shifter (manufactured by Hadano Sangyo Co., Ltd.); circular vibrating sieve.

The toner particles produced by the emulsion aggregation method are produced, for example, as follows.
A method for producing toner particles by an emulsion aggregation method is a method for producing toner including a step of aggregating resin fine particles and colorant fine particles, wherein the resin fine particles contain the compound represented by the general formula [1]. It is preferable that it is a manufacturing method to do.
Specifically, toner particles are produced through an aggregation step, a fusion step, a cooling step, and a washing step of the resin fine particles containing the compound represented by the general formula [1] and the colorant fine particles. If necessary, fine particles of the compound represented by the formula [1] may be prepared and used separately from the resin fine particles. Further, if necessary, a shelling step can be added after the cooling step to form core-shell toner particles.

<Emulsification process of resin fine particles>
The resin fine particles containing the binder resin can be prepared by a known method. For example, the binder resin is dissolved in an organic solvent and added to an aqueous medium, and the particles are dispersed in the aqueous medium together with a surfactant or polymer electrolyte by a disperser such as a homogenizer, and then the solvent is removed by heating or decompressing. Thus, a resin particle dispersion can be produced. Any organic solvent can be used as long as it dissolves the binder resin, but tetrahydrofuran, ethyl acetate, chloroform and the like are preferable from the viewpoint of solubility.
As a method of adding the compound represented by the general formula [1], the compound represented by the general formula [1] is dissolved in an organic solvent together with the binder resin. Binder resin fine particles containing the compound to be prepared may be prepared.

In addition, the binder resin, surfactant, base, etc. are added to the aqueous medium, and emulsified and dispersed in an aqueous medium substantially free of an organic solvent by a disperser that applies high-speed shearing force such as CLEARMIX, Homomixer, and Homogenizer. You can also
In the emulsification step, the pH in the aqueous medium is preferably 8 or more. By setting the pH to 8 or more, the monomer component generated during emulsification can be easily removed into the aqueous medium. Any base can be used to adjust the pH, but sodium hydroxide or potassium hydroxide is preferred.
The surfactant used at the time of emulsification is not particularly limited, and examples thereof include anionic surfactants such as sulfate ester, sulfonate, carboxylate, phosphate, and soap; Examples thereof include cationic surfactants such as amine salt type and quaternary ammonium salt type; nonionic surfactants such as polyethylene glycol type, alkylphenol ethylene oxide adduct type, and polyhydric alcohol type. The said surfactant may be used individually by 1 type, and may use 2 or more types together.
The volume-based median diameter of the resin fine particles is preferably from 0.05 μm to 1.0 μm, and more preferably from 0.05 μm to 0.4 μm. When it is 1.0 μm or less, it becomes easy to obtain toner particles having a volume-based median diameter of 4.0 μm or more and 7.0 μm or less that are suitable as toner particles.

<Colorant fine particles>
The colorant fine particles are obtained by dispersing a colorant in an aqueous medium. The colorant is dispersed by a known method, and for example, a media-type disperser such as a rotary shearing homogenizer, a ball mill, a sand mill, or an attritor, or a high-pressure opposed collision disperser is preferably used. Further, a surfactant or a polymer dispersant that imparts dispersion stability can be added as necessary. The colorant mentioned above can be used as the colorant.

<Fine particles of the compound represented by the general formula [1]>
In the emulsion aggregation method, fine particles of the compound represented by the formula [1] may be used. The fine particles of the compound represented by the general formula [1] are obtained by dispersing the compound represented by the general formula [1] in an aqueous medium. The compound represented by the general formula [1] is dispersed by a publicly known method. For example, a rotary shear type homogenizer, a ball mill, a sand mill, an attritor or other media type disperser, a high pressure opposed collision type disperser, etc. Preferably used. Further, a surfactant or a polymer dispersant that imparts dispersion stability can be added as necessary.
Analysis of the particle size distribution of resin fine particles, colorant fine particles, and fine particles of the compound represented by the general formula [1] is performed using a laser diffraction / scattering particle size distribution measuring apparatus (LA-950, manufactured by Horiba, Ltd.). Measure according to the instrument's operating manual. After dropping the surfactant aqueous solution into the circulating water, each fine particle dispersion is dropped to the optimum concentration of the equipment and dispersed for 30 seconds with ultrasonic waves, and measurement is started. 50% cumulative particle size value (D50) and 90% The cumulative particle size value (D90) is determined.

<Aggregation process>
The agglomeration step is to mix the above-mentioned resin fine particles, colorant fine particles and the like according to a necessary amount to prepare a mixed solution, and then aggregate the particles contained in the prepared mixed solution to form an aggregate. It is a process. As a method for forming the agglomerates, for example, a method in which a flocculant is added and mixed in the above mixed solution, and a temperature, mechanical power, and the like are appropriately added can be preferably exemplified.
Examples of the flocculant include metal salts of monovalent metals such as sodium and potassium; metal salts of divalent metals such as calcium and magnesium; metal salts of trivalent metals such as iron and aluminum.

The addition and mixing of the flocculant is performed by the glass transition temperature (Tg) of the resin fine particles contained in the mixture
It is preferable to carry out at the following temperature. When the above mixing is performed under this temperature condition, aggregation proceeds in a stable state. The said mixing can be performed using a well-known mixing apparatus, a homogenizer, a mixer, etc.
The average particle size of the aggregate formed here is not particularly limited, but it is usually preferable to control the average particle size to 4.0 μm or more and 9.0 μm or less so as to be the same as the average particle size of the toner particles to be obtained. . Control can be easily performed, for example, by appropriately setting and changing the temperature at the time of addition / mixing of the flocculant and the like and the conditions of the stirring and mixing. The particle size distribution of the toner particles can be measured with a particle size distribution analyzer (Coulter Multisizer III: manufactured by Coulter, Inc.) using a Coulter method.
Moreover, it is preferable to make pH in an aqueous medium into 8 or more from a viewpoint of dissolving and removing the monomer which generate | occur | produces by hydrolysis of a polyester resin in an aqueous medium similarly to an emulsification process. When the pH is 8 or more, the monomer that has flowed into the aqueous medium in the emulsification step is unlikely to be precipitated, so that the possibility of being taken into the toner is reduced.

<Fusion process>
The fusing step is a step of producing particles in which the agglomerate surface is smoothed by heating and fusing the agglomerates above the glass transition point (Tg) of the resin. Before entering the primary fusing step, a chelating agent, a pH adjusting agent, a surfactant and the like can be appropriately added in order to prevent fusion between toner particles.
Examples of chelating agents include alkali metal salts such as ethylenediaminetetraacetic acid (EDTA) and its Na salt, sodium gluconate, sodium tartrate, potassium citrate and sodium citrate, both nitrotriacetate (NTA) salts, COOH and OH There are many water-soluble polymers (polyelectrolytes) that contain the following functionalities.

  The heating temperature may be between the glass transition temperature (Tg) of the resin contained in the aggregate and the temperature at which the resin is thermally decomposed. The binder resin and the compound represented by the general formula [1] It is preferable that the temperature be equal to or higher than the melting point. When the temperature is equal to or higher than the melting point of the binder resin and the compound represented by the general formula [1], the compatibility between the binder resin and the compound represented by the general formula [1] is improved and the coagulation is performed. The surface of the aggregate can be smoothed more efficiently. As the heating / fusion time, a short time is sufficient if the heating temperature is high, and a long time is required if the heating temperature is low. That is, the heating / fusion time depends on the temperature of heating and cannot be generally defined, but is generally 10 minutes or more and 10 hours or less.

<Cooling process>
The cooling step is a step of cooling the temperature of the aqueous medium containing the particles to a temperature lower than the glass transition point (Tg) of the binder resin. By performing cooling to a temperature lower than the Tg, generation of coarse particles can be suppressed. The specific cooling rate is preferably 0.1 ° C./min or more and 50 ° C./min or less.

<Shelling process>
In the present invention, if necessary, a shelling step can be added before the following washing and drying step. The shelling step is a step of newly adding resin fine particles to the particles produced in the previous steps and attaching them to form a shell.
The resin fine particles added here may have the same structure as the resin fine particles used for the core, or may be resin fine particles having a different structure.

The resin constituting such a shell layer is not particularly limited, and known resins used for toners, for example, vinyl polymers such as polyester resins and styrene-acrylic copolymers, epoxy resins, polycarbonate resins, and polyurethane resins. Etc. can be used. Among these, a polyester resin or a styrene-acrylic copolymer is preferable, and a polyester resin is more preferable from the viewpoints of fixability and durability. A polyester resin has a lower molecular weight than a vinyl polymer because it has flexibility compared to a vinyl polymer such as a styrene-acrylic copolymer when it has a rigid aromatic ring in the main chain. Can provide equivalent mechanical strength. Therefore, a polyester resin is preferable as a resin suitable for low-temperature fixability.
In the present invention, the binder resin constituting the shell layer may be used alone or in combination of two or more.

<Washing and drying process>
Toner particles can be obtained by washing, filtering, drying and the like of the particles produced through the above steps. It is preferable to carry out washing filtration with ion-exchanged water whose pH is adjusted with sodium hydroxide or potassium hydroxide, and then washing and filtering with ion-exchanged water a plurality of times. By performing washing by this method, the monomer component generated by hydrolysis can be efficiently removed.
Through the above steps, toner particles can be obtained by an emulsion aggregation method, and if necessary, the toner particles and external additives can be mixed with a mixer such as a Henschel mixer to obtain a toner.

Toner particles by the suspension polymerization method are produced, for example, as follows.
The method for producing toner particles by the suspension polymerization method is to form particles of a polymerizable monomer composition containing a polymerizable monomer that produces a binder resin and a colorant in an aqueous medium and is contained in the particles. It is a method for producing toner particles obtained by polymerizing the polymerizable monomer, and the polymerizable monomer composition is preferably a production method containing the compound represented by the general formula [1].
The particles obtained by polymerizing the particles of the polymerizable monomer composition are preferably filtered, washed, and dried to obtain toner particles. If necessary, distillation may be performed after polymerization to remove the remaining polymerizable monomer.

As a polymerizable monomer, the vinyl-type monomer used for superposition | polymerization of said styrene-type copolymer resin is mentioned, A styrene-type monomer and an acrylic acid-type monomer are used preferably especially. Furthermore, you may use combining the crosslinkable monomer used for superposition | polymerization of said styrene-type copolymer resin.
The polymerization initiator that can be used for polymerizing the polymerizable monomer may be added simultaneously with the addition of the other additives in the polymerizable monomer, or the particles of the polymerizable monomer composition in the aqueous medium. You may add just before forming. Further, a polymerization initiator dissolved in the polymerizable monomer or solvent may be added immediately after the formation of the polymerizable monomer composition particles and before the polymerization reaction is started.

As the polymerization initiator, a polymerization initiator used for the polymerization of the styrene copolymer resin can be used. The type of the polymerization initiator is selected with reference to the 10 hour half-life temperature. 1 type may be used for a polymerization initiator and 2 or more types may be used for it.
It is preferable that the usage-amount of these polymerization initiators is 3.0 to 20.0 mass parts with respect to 100.0 mass parts of polymerizable monomers.

Examples of the dispersant for dispersing the polymerizable monomer composition in the aqueous medium include inorganic dispersion stabilizers and organic dispersion stabilizers.
Examples of inorganic dispersion stabilizers include tricalcium phosphate, magnesium phosphate, aluminum phosphate, zinc phosphate, magnesium carbonate, calcium carbonate, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, calcium metasilicate, Examples thereof include calcium sulfate, barium sulfate, bentonite, silica, and alumina.
Examples of the organic dispersion stabilizer include polyvinyl alcohol, gelatin, methyl cellulose, methyl hydroxypropyl cellulose, ethyl cellulose, carboxymethyl cellulose sodium salt, starch and the like.

Further, nonionic, anionic and cationic surfactants can be used as the dispersion stabilizer.
Examples of the surfactant include sodium dodecyl sulfate, sodium tetradecyl sulfate, sodium pentadecyl sulfate, sodium octyl sulfate, sodium oleate, sodium laurate, potassium stearate, calcium oleate and the like.
Among these dispersion stabilizers, inorganic, poorly water-soluble dispersion stabilizers are preferable. Further, a poorly water-soluble inorganic dispersion stabilizer that is soluble in an acid is more preferable.
Moreover, it is preferable that the usage-amount of a dispersion stabilizer is 0.2 to 2.0 mass parts with respect to 100.0 mass parts of polymerizable monomers.
Moreover, the usage-amount of an aqueous medium has preferable what was prepared using 300 mass parts or more and 3000 mass parts or less of water with respect to 100 mass parts of polymerizable monomer compositions.

  When preparing an aqueous medium in which a hardly water-soluble inorganic dispersion stabilizer is dispersed, the dispersion stabilizer may be dispersed as it is in a liquid medium such as water. In addition, in order to obtain particles of a dispersion stabilizer having a fine uniform particle size, a raw material of a poorly water-soluble inorganic dispersion stabilizer is added to a liquid medium such as water under high-speed stirring, and the poorly water-soluble inorganic dispersion stabilizer is added. To form an aqueous medium. For example, when using tricalcium phosphate, which is a kind of poorly water-soluble inorganic dispersion stabilizer, as a dispersion stabilizer, a sodium phosphate aqueous solution and a calcium chloride aqueous solution are mixed under high-speed stirring to form fine particles of tricalcium phosphate. Can be formed.

A shell layer may be formed on the surface of the toner particles in the present invention. Examples of the method for fixing the resin particles for forming the shell layer include a method in which toner particles and resin particles are mixed by a dry method and fixed by mechanical treatment. Another example is a method in which toner particles and resin particles are dispersed in an aqueous medium and heated or a flocculant is added. In order to uniformly fix the resin particles on the surface of the toner particles and to suppress variations among the toner particles, it is preferable to fix the resin particles on the surface of the toner base particles by heating in an aqueous medium.
Through the above steps, toner particles can be obtained by suspension polymerization, and if necessary, the toner particles and external additives can be mixed with a mixer such as a Henschel mixer to obtain a toner.

Toner particles by the dissolution suspension method are produced, for example, as follows.
A method for producing toner particles by a dissolution suspension method is a mixed resin in which a toner particle composition containing a binder resin, a colorant, and a compound represented by the general formula [1] is dissolved or dispersed in an organic solvent. A granulation step of dispersing the solution in an aqueous medium to form particles of the mixed resin solution; and a solvent removal step of obtaining toner particles by removing the organic solvent present in the particles of the mixed resin solution. A method for producing toner particles.

<Making process of mixed resin solution>
As a method for preparing a mixed resin solution in which a toner particle composition containing a binder resin, a colorant, and the compound represented by the general formula [1] is dissolved or dispersed in an organic solvent, The binder resin, the colorant, the compound represented by the general formula [1] and the like may be gradually added while being stirred, and dissolved or dispersed.
By dissolving the binder resin and the compound represented by the general formula [1] in an organic solvent, the binder resin and the compound represented by the general formula [1] are uniformly compatible. On the other hand, when using a pigment as a colorant or adding a release agent or charge control agent that is difficult to dissolve in an organic solvent, the particles are made smaller prior to addition to the organic solvent. It is preferable. For dispersion, a known disperser such as a bead mill or a disk mill can be used.

<Granulation process>
The mixed resin solution obtained in the above-mentioned step is dispersed in an aqueous medium containing at least a surfactant or an inorganic dispersion stabilizer to prepare an aqueous dispersion of the toner particle composition. When a modified resin having a site capable of reacting with the active hydrogen group-containing compound is added to the toner particle composition, the active hydrogen group-containing compound is added, and the active hydrogen group-containing compound is added to the toner particle composition in an aqueous medium. An aqueous dispersion of the toner particle composition may be formed while producing a binder resin by reacting with a modified resin.

Examples of the active hydrogen group of the active hydrogen group-containing compound include a hydroxyl group (alcoholic hydroxyl group or phenolic hydroxyl group), an amino group, a carboxyl group, or a mercapto group. An active hydrogen group containing compound may be used individually by 1 type, and may use 2 or more types together.
As an apparatus used in the granulation step, for example, a vertical stirring tank equipped with a stirrer having a high shearing force can be used. As a stirrer having a high shearing force, a high shear mixer (manufactured by IKA), T.A. K. Homo mixer (manufactured by Special Machine Industries Co., Ltd.) K. Commercially available products such as Philmix (manufactured by Special Machine Engineering Co., Ltd.) and Claremix (manufactured by M Technique Co., Ltd.) can be used.

Surfactants include anionic surfactants such as alkylbenzene sulfonates, α-olefin sulfonates and phosphate esters; amine salt types such as alkylamine salts, amino alcohol fatty acid derivatives, polyamine fatty acid derivatives and imidazoline, Quaternary ammonium salt type cationic surfactants such as alkyltrimethylammonium salts, dialkyldimethylammonium salts, alkyldimethylbenzylammonium salts, pyridinium salts, alkylisoquinolinium salts and benzethonium chloride; fatty acid amide derivatives and polyhydric alcohols Nonionic surfactants such as derivatives; amphoteric interfaces such as alanine, dodecyl di (aminoethyl) glycine, di (octylaminoethyl) glycine and N-alkyl-N, N-dimethylammonium betaine Sex agents. These can be used alone or in combination of two or more.
Examples of the inorganic dispersion stabilizer used for the production of toner particles by the dissolution suspension method include those similar to the suspension polymerization method, and can be used alone or in combination of two or more.

<Solvent removal step>
In the solvent removal step, the organic solvent is removed from the aqueous dispersion of the obtained toner particle composition. In order to remove the organic solvent, it is possible to employ a method in which the temperature of the entire system is gradually raised while stirring to completely evaporate and remove the organic solvent in the droplets. Alternatively, the aqueous dispersion of the toner particle composition may be depressurized while stirring, and the organic solvent may be removed by evaporation.

<Aging process>
In the case where a modified resin having a site capable of reacting with an active hydrogen group-containing compound such as an isocyanate group is added at the terminal, an aging step may be performed in order to advance the elongation / crosslinking reaction of the isocyanate. The aging time is usually 10 minutes to 40 hours, preferably 2 to 24 hours. The reaction temperature is usually 0 to 65 ° C., preferably 35 to 50 ° C.
Through the above steps, toner particles can be obtained by the dissolution suspension method, and if necessary, the toner particles and external additives can be mixed with a mixer such as a Henschel mixer to obtain a toner.

Next, a method for measuring the particle size distribution of the toner according to the present invention will be described.
<Measurement of toner weight average particle diameter (D4)>
The weight average particle diameter (D4) of the toner is a precision particle size distribution measuring apparatus “Coulter Counter Multisizer by pore electrical resistance method equipped with an aperture tube of 100 μm.
3 ”(registered trademark, manufactured by Beckman Coulter) and attached dedicated software“ Beckman Coulter Multisizer 3 Version 3.51 ”(manufactured by Beckman Coulter, Inc.) for measurement condition setting and measurement data analysis, Measure with 25,000 effective measurement channels, analyze and calculate the measurement data.
As the electrolytic aqueous solution used for the measurement, 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 is set as follows.
In the “Standard Measurement Method (SOM) Change Screen” of the dedicated software, set the total count in the control mode to 50000 particles, set the number of measurements once, and set the Kd value to “standard particles 10.0 μm” (Beckman Coulter, Inc.) Set the value obtained using The threshold and noise level are automatically set by pressing the threshold / noise level measurement button. Also, the current is set to 1600 μA, the gain is set to 2, the electrolyte is set to ISOTON II, and the aperture tube flash 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 exclusively for 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 aqueous solution is put in a glass 100 ml flat bottom beaker, and "Contaminone N" (nonionic surfactant, anionic surfactant, organic builder pH 7 precision measurement is used as a dispersant therein. About 0.3 ml of a diluted solution obtained by diluting a 10% by weight aqueous solution of a neutral detergent for washing a vessel (made by Wako Pure Chemical Industries, Ltd.) 3 times with ion-exchanged water is added.
(3) Two oscillators with an oscillation frequency of 50 kHz are incorporated in a state where the phase is shifted by 180 degrees, and is placed in a water tank of an ultrasonic disperser “Ultrasonic Dispersion System Tetora 150” (manufactured by Nikka Ki Bios) with an electrical output of 120 W. A predetermined amount of ion-exchanged water is put, and about 2 ml of the above-mentioned Contaminone N is added to 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, 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 (1) round bottom beaker installed in the sample stand, the (5) electrolytic aqueous solution in which the toner is dispersed is dropped using a pipette, and the measured 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) is calculated. The “average diameter” on the analysis / volume statistics (arithmetic average) screen when the graph / volume% is set with the dedicated software is the weight average particle diameter (D4).

Next, the verification method of the plastic effect and compatibility of the compound represented by the general formula [1] and other additives to the binder resin will be described.
1) Method for Verifying Plastic Effect The plastic effect is verified by measuring the glass transition temperature Tg of the toner containing the compound represented by the general formula [1] or other additive and the toner not containing it. The glass transition temperature Tg 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, about 3 mg of each sample is precisely weighed, put in an aluminum pan, an empty aluminum pan is used as a reference, and a temperature increase rate of 10 ° C. is measured between 20 ° C. and 200 ° C. Measure at / min. The measurement temperature range is 20 ° C. to 200 ° C., and the temperature is once increased from 20 ° C. to 200 ° C. at a temperature increase rate of 10 ° C./min. The temperature is raised to 200 ° C. at a rate of temperature increase of 10 ° C./min.
In the DSC curve obtained in the second temperature raising process, the intersection of the baseline intermediate line before and after the specific heat change and the differential heat curve is defined as the glass transition temperature Tg of each toner. At this time, the difference in glass transition temperature Tg between the toner containing the compound represented by the general formula [1] or other additive and the toner not containing it is measured, and the plastic effect is verified using the difference. . The greater the difference between the glass transition temperatures Tg of the toners, the greater the plastic effect.

2) Compatibility verification method The compatibility is determined by the compatibility of the toner represented by the general formula [1] or the toner containing the compound represented by the general formula [1] or the other additive. This is verified by measuring the endotherm. The endothermic amount 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, about 3 mg of each sample is precisely weighed and placed in an aluminum pan, and an empty aluminum pan is used as a reference. Measure in min. The measurement temperature range is 20 ° C. to 200 ° C., and the temperature is once increased from 20 ° C. to 200 ° C. at a temperature increase rate of 10 ° C./min. The temperature is raised to 200 ° C. at a rate of temperature increase of 10 ° C./min.
In the compound represented by the general formula [1] or other additive, the general formula [1] contained in the toner in the temperature range of 20 ° C. to 200 ° C. in the second temperature raising process. The endothermic amount derived from the compound is measured and the compatibility is verified. The smaller the endothermic amount derived from the compound represented by the general formula [1] or other additives, the higher the compatibility.
In the present invention, the endothermic amount derived from the compound represented by the general formula [1] contained in the toner is preferably 1.0 J / g or less, and more preferably 0.5 J / g or less. .

  Although the basic configuration and features of the present invention have been described above, the present invention will be specifically described below based on examples. However, the present invention is not limited to this. Unless otherwise specified, parts and% are based on mass.

<Example of production of binder resin 1>
117 parts of propylene oxide adduct of bisphenol A (average number of moles added: 2.2 moles)
-62 parts of bisphenol A ethylene oxide adduct (average number of moles added: 2.2 moles)
・ Isophthalic acid 390 parts ・ n-dodecenyl succinic acid 360 parts ・ trimellitic anhydride 19 parts 2 parts of dibutyltin oxide is added to 100 parts of the total acid component and stirred for 6 hours at 220 ° C. in a nitrogen stream. The binder resin 1 was obtained by reacting with this. Softening point 135 ° C, Tg6
It was 5 ° C.

<Example of production of binder resin 2>
-70 parts of styrene-24 parts of n-butyl acrylate-6 parts of monobutyl maleate-1 part of di-t-butyl peroxide The monomer was added dropwise to 200 parts of xylene over 4 hours. Furthermore, the polymerization was completed under xylene reflux. Thereafter, the temperature was raised to distill off the organic solvent, and the mixture was cooled to room temperature and pulverized to obtain a binder resin 2. The softening point was 125 ° C and Tg was 60 ° C.

<Example A-1>
(Production Example of Toner A-1)
Binder resin 1 100 parts Compound represented by general formula [1] (9-fluorenone, melting point: 84 ° C.) 3 parts C.I. I. Pigment Blue 15: 3 4 parts · 3,5-di-tert-butylsalicylic acid aluminum compound 0.5 parts The above materials were premixed with a Henschel mixer and then melt-kneaded with a twin-screw kneading extruder.
The obtained kneaded product is cooled, coarsely pulverized with a hammer mill, then pulverized with a jet mill, and the obtained finely pulverized powder is classified using a multi-division classifier utilizing the Coanda effect, and the weight average particle diameter (D4) 6.8 μm negative triboelectrically chargeable toner particles were obtained. To 100 parts of the toner particles, 1.0 part of hydrophobic silica fine powder (specific surface area by nitrogen adsorption measured by BET method is 140 m ^{2 /} g) and strontium titanate (volume average particle diameter 1.6 μm) 3.0 Parts were externally mixed and sieved with a mesh having an opening of 150 μm to obtain toner A-1.

For Toner A-1, the plastic effect and compatibility were verified. As a comparative toner, a toner to which the compound represented by the general formula [1] (9-fluorenone, melting point: 84 ° C.) was not added was prepared. This toner is referred to as toner a-1.
First, as verification of the plastic effect, the glass transition temperatures Tg of the toner A-1 and the toner a-1 were measured using a differential scanning calorimeter “Q1000”. The glass transition temperature Tg of the toner A-1 was 53 ° C., and the glass transition temperature Tg of the toner a-1 was 61 ° C. From this result, it was found that by adding 3 parts of 9-fluorenone, a Tg plasticity effect of 8 ° C. was obtained.
Next, as verification of compatibility, endothermic peaks of 9-fluorenone and toner A-1 were measured using a differential scanning calorimeter “Q1000”. 9-fluorenone observed a sharp endothermic peak at 84 ° C. On the other hand, in the toner A-1, no endothermic peak was observed within the measurement temperature range, and it was determined that all 9-fluorenone was compatible.
From the above, it was confirmed that 9-fluorenone has a high plastic effect and compatibility with the binder resin 1.

<Example of manufacturing magnetic carrier>
Water was added to 100 parts of Fe ₂ O ₃ and pulverized with a ball mill for 15 minutes to produce a magnetic core having an average particle size of 55 μm.
Next, a mixed solution of 1.0 part of a straight silicone resin (manufactured by Shin-Etsu Chemical Co., Ltd .: KR271), 0.5 part of γ-aminopropyltriethoxysilane, and 98.5 parts of toluene is added to 100 parts of the magnetic core, Further, the mixture was dried under reduced pressure at 70 ° C. for 5 hours while stirring and mixing with a solution vacuum kneader to remove the solvent. Then, it baked at 140 degreeC for 2 hours, and sieved with the sieve shaker (300MM-2 type | mold, Tsutsui physics and chemistry machine: 75 micrometers opening), and the magnetic carrier was obtained.

<Preparation of developer A-1>
A V-type mixer (V-10 type: Tokuju Seisakusho Co., Ltd.) is used so that the toner A-1 and the magnetic carrier are 10.0 parts by mass with respect to 1.0 part by mass of the carrier. The developer A-1 was prepared by mixing under conditions of 0.5 s ⁻¹ and a rotation time of 5 min.
Evaluation is a Canon full-color copier imageRUNNER as an image forming device.
ADVANCE C5255 was used. As the evaluation paper, A4 size laser beam printer paper CS-814 (81.4 g / m ² ) was used.
The image density was measured with a color reflection densitometer (X-Rite 504 manufactured by X-Rite).

<Image density under normal temperature and humidity>
The test was conducted under a room temperature and humidity environment (temperature: 23 ° C./humidity: 50% RH). Concentration was measured.

<Evaluation of contamination of fixing member>
The test was conducted under a low-temperature and low-humidity environment (temperature 10 ° C./humidity 15% RH) after conducting a continuous paper feed test of 500,000 sheets using an original chart with a printing ratio of 50%, and then the image density of a solid black image In addition, the contamination around the fixing unit was visually evaluated according to the following criteria.
A: No contamination is seen around the fixing device.
B: A small amount of contamination is observed around the fixing device.
C: Contamination is observed around the fixing device.
D: The spread of contamination is observed around the fixing device.

<Evaluation of halftone unevenness>
In a high-temperature and high-humidity (32 ° C., 80% RH) environment, 300,000 continuous sheet passing tests were performed using a test chart with a printing ratio of 5%. Thereafter, the image density of the solid black image was measured, and a halftone image (development shading unevenness) of 2 dots and 3 spaces at a resolution of 600 dpi was visually evaluated.
A: No shading unevenness is felt.
B: Slight unevenness is slightly seen, but it is hardly a concern.
C: Some shading unevenness is observed.
D: Light and shade unevenness is conspicuous.

<Evaluation of low-temperature fixability>
Canon full color copier imageRUNNER ADVA as an image forming device
NCE C5255 was modified and evaluated. The modification was made to work with only cyan toner. In addition, the fuser was modified so that it could be changed to any temperature.
Evaluation of low-temperature fixability was performed in a low-temperature and low-humidity (5 ° C., 5% RH) environment. 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 5 ° 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 160 ° C. to 175 ° C. every 5 ° C., and the fixing temperature at which the image density reduction rate was 10% or less was set as the fixing start temperature.
(Evaluation criteria)
A: The fixing start temperature is 160 ° C.
B: Fixing start temperature is 165 ° C.
C: Fixing start temperature is 170 ° C.
D: Fixing start temperature is 175 ° C.
In each of the above evaluation items, all the developers of Example A-1 were A determinations.

(Production Example of Toner A-2)
-Binder resin 2 100 parts-Compound represented by the general formula [1] (2-amino-9-fluorenone, melting point: 156 ° C)
5 parts I. Pigment Blue 15: 3 4 parts · 3,5-di-tert-butylsalicylic acid aluminum compound 0.5 parts The above materials were premixed with a Henschel mixer and then melt-kneaded with a twin-screw kneading extruder.
The obtained kneaded product is cooled, coarsely pulverized with a hammer mill, then pulverized with a jet mill, and the obtained finely pulverized powder is classified using a multi-division classifier utilizing the Coanda effect, and the weight average particle diameter (D4) 6.8 μm negative triboelectrically chargeable toner particles were obtained. To 100 parts of the toner particles, 1.0 part of hydrophobic silica fine powder (specific surface area by nitrogen adsorption measured by BET method is 140 m ^{2 /} g) and strontium titanate (volume average particle diameter 1.6 μm) 3.0 Parts were externally added and sieved with a mesh having an opening of 150 μm to obtain toner A-2. The glass transition temperature Tg of the toner A-2 was 50 ° C., and no endothermic peak was observed within the measurement temperature range, and it was determined that all 2-amino-9-fluorenone was compatible.

(Production Example of Toners A-3 to A-20)
Toners A-3 to A-20 were obtained in the same manner as in the production example of the toner A-1, except that the type and addition amount of the compound represented by the general formula [1] were changed as shown in Table 1. Table 1 shows the glass transition temperatures Tg of Toners A-3 to A-20. Since the Tg of toners A-3 to A-20 are all lower than 61 ° C., which is the Tg of toner a-1, it was confirmed that the compounds shown in Table 1 have a plasticizing effect. Further, in the toners A-3 to A-20, no endothermic peak was observed within the measurement temperature range, and it was determined that all the compounds represented by the general formula [1] were compatible.

(Production Examples of Developers A-2 to A-20)
As shown in Table 1, Developers A-2 to A-20 were obtained in the same manner as Developer A-1, except that the toner was changed to A-2 to A-20.

<Examples A-2 to A-20>
Developers A-2 to A-20 were evaluated in the same manner as in Example 1. The evaluation results are shown in Table 2.

(Production Examples of Developers A-21 to A-27)
Toners A-21 to A-27 were obtained in the same manner as in the production example of the toner A-1, except that the compounds shown in Table 3 were added instead of the compounds represented by the general formula [1]. Further, as shown in Table 3, Developers A-21 to A-27 were obtained in the same manner as Developer A-1, except that the toner was changed to A-21 to A-27.

<Comparative Examples A-1 to A-7>
Developers A-21 to A-27 were evaluated in the same manner as in Example A-1. The evaluation results are shown in Table 4.

<Example B-1>
(Preparation of resin fine particle dispersion 1)
Binder resin 1 1200 parts 9-fluorenone 36 parts Anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen SC-A) 0.5 parts Tetrahydrofuran 2400 parts The above ingredients were added and stirred for 10 minutes. . Thereafter, 3600 parts of ion-exchanged water was added dropwise with stirring at a rotational speed of 5000 rpm using a homogenizer (manufactured by IKA: Ultra Tarrax T50). The obtained mixture was treated at 50 ° C. under reduced pressure (50 mmHg) to remove THF and obtain resin fine particle dispersion 1. D50 of the obtained resin fine particles was 0.12 μm, and D90 was 0.16 μm.

(Preparation of colorant fine particle dispersion)
・ C. I. Pigment Blue 15: 3 100 parts ・ Anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen RK) 15 parts ・ Ion-exchanged water 885 parts Was used for 1 hour to prepare an aqueous dispersion of colorant fine particles obtained by dispersing a colorant. D50 of the colorant fine particles was 0.19 μm, and D90 was 0.26 μm.

(Production example of toner B-1)
・ Resin fine particle dispersion 1 600 parts ・ Colorant fine particle dispersion 60 parts ・ 1 mass% magnesium sulfate aqueous solution 150 parts ・ Ion-exchanged water 515 parts Each of the above components was put into a round stainless steel flask and homogenizer (IKA). (Made by Ultra Turrax T50) at 5000 rpm for 10 minutes, and then dispersed using a stirring blade in an oil bath for heating. Until heated. Holding at 43 ° C. for 1 hour formed aggregated particles.
Thereafter, an aqueous solution in which 15 parts of trisodium citrate was dissolved was added to 285 parts of ion-exchanged water, and then heated to 90 ° C. while maintaining stirring, and maintained for 3 hours. Then, after cooling to room temperature, it filtered, and the filtrate was fully wash | cleaned with ion-exchange water, and the toner particle was obtained by making it dry using a vacuum dryer. The weight average particle diameter of the toner particles was 6.0 μm.
To 100 parts of the toner particles, 1.0 part of hydrophobic silica fine powder (specific surface area by nitrogen adsorption measured by BET method is 140 m ^{2 /} g) and strontium titanate (volume average particle diameter 1.6 μm) 3.0 Parts were externally mixed and sieved with a mesh having an opening of 150 μm to obtain toner B-1. The glass transition temperature Tg of the toner B-1 was 52 ° C., and no endothermic peak was observed within the measurement temperature range, and it was determined that all 9-fluorenone was compatible.

(Example of production of developer B-1)
Using a V-type mixer (V-10 type: Tokuju Seisakusho Co., Ltd.) so that toner B-1 and magnetic carrier are 10.0 parts of toner B-1 with respect to 1.0 part of carrier. , 0.5 s ⁻¹ , and a rotation time of 5 minutes were mixed to prepare developer B-1. The obtained developer B-1 was evaluated.
Regarding the evaluation of the fouling property, halftone unevenness and low-temperature fixability of the fixing member, the evaluation was performed in the same manner as in Example A-1. Developer B-1 was all A grade.

<Example C-1>
<Production Example of Toner C-1>
To 1300.0 parts of ion-exchanged water heated to a temperature of 60 ° C., 9.0 parts of tricalcium phosphate is added, and the stirring speed is 15,000 rpm using a TK homomixer (manufactured by Special Machine Industries). Stir to prepare an aqueous medium. Further, the following materials were mixed with a propeller type stirring device at a stirring speed of 100 rpm to prepare a mixed solution.
-Styrene 50.0 parts-n-Butyl acrylate 30.0 parts-Binder resin 1 5.0 parts
-Styrene 20.0 parts-C.I. I. Pigment Blue 15: 3 7.0 parts · 3,5-di-tert-butylsalicylic acid aluminum compound 0.5 parts · Compound represented by the general formula [1] (9-fluorenone, melting point: 84 ° C.) 3.0 After that, the mixture was heated to a temperature of 65 ° C., and then stirred with a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) at a stirring speed of 10,000 rpm to dissolve and disperse the polymerizable monomer composition. I adjusted things.

Subsequently, the polymerizable monomer composition was charged into the aqueous medium, and 6.0 parts of perbutyl PV (10-hour half-life temperature 54.6 ° C. (manufactured by NOF Corporation)) was added as a polymerization initiator, and the temperature was 70 ° C. The mixture was stirred for 10 minutes at a stirring speed of 12,000 rpm using a TK homomixer and granulated.
The mixture was transferred to a propeller-type stirring device and stirred at a stirring speed of 200 rpm, and the styrene and n-butyl acrylate, which are polymerizable monomers in the polymerizable monomer composition, were subjected to a polymerization reaction at a temperature of 85 ° C. for 5 hours. A slurry containing was produced. After completion of the polymerization reaction, the slurry was cooled. Hydrochloric acid was added to the cooled slurry to adjust the pH to 1.4, and the mixture was stirred for 1 hour to dissolve the calcium phosphate salt. Thereafter, the toner particles were washed with 10 times the amount of water of the slurry, filtered and dried, and classified using a multi-division classifier utilizing the Coanda effect, and a negative frictional charging property with a weight average particle diameter (D4) of 6.8 μm. Toner particles were obtained.
To 100 parts of the toner particles, 1.0 part of hydrophobic silica fine powder (specific surface area by nitrogen adsorption measured by BET method is 140 m ^{2 /} g) and strontium titanate (volume average particle diameter 1.6 μm) 3.0 Parts were externally mixed and sieved with a mesh having an opening of 150 μm to obtain toner C-1. The glass transition temperature Tg of the toner C-1 was 54 ° C., and no endothermic peak was observed within the measurement temperature range, and it was determined that all 9-fluorenone was compatible.

(Example of production of developer C-1)
Using a V-type mixer (V-10 type: Tokuju Seisakusho Co., Ltd.) so that toner C-1 and magnetic carrier are 10.0 parts of toner C-1 with respect to 1.0 part of carrier. , 0.5 s ⁻¹ , and a rotation time of 5 minutes were mixed to prepare developer C-1. The obtained developer C-1 was evaluated for the fouling property, halftone unevenness and low temperature fixability of the fixing member in the same manner as in Example A-1. The developer C-1 was all judged as A.

<Example D-1>
(Production example of toner D-1)
(Preparation of aqueous medium)
To 330 parts of ion-exchanged water, 5.0 parts of Na ₃ PO ₄ : 2.0 parts of 10% hydrochloric acid was added and stirred using a high shear mixer (manufactured by IKA) at 3,000 r / min. Warmed to 60 ° C. To this, an aqueous solution in which 3.0 parts of CaCl ₂ was dissolved in 20 parts of ion-exchanged water was added, and after 30 minutes, a 48.5% by mass aqueous solution of sodium dodecyl diphenyl ether disulfonate (Eleminol MON-7, Sanyo Chemical Industries) 15 parts and 30 parts of ethyl acetate were added, and the liquid temperature was cooled to 30 ° C. to prepare an aqueous medium.

(Production of master batch)
・ C. I. Pigment Blue 15: 3 40 parts and binder resin 1 60 parts were kneaded at 150 ° C. for 30 minutes using two rolls, rolled and cooled, and pulverized with a pulverizer to obtain a master batch.

(Synthesis of intermediate polyester and prepolymer)
-Bisphenol A ethylene oxide adduct 682 parts (average number of moles added: 2.2 moles)
-Bisphenol A propylene oxide 81 parts (average addition mole number: 2.2 mol)
-283 parts of terephthalic acid-22 parts of trimellitic anhydride-2 parts of dibutyltin oxide were put in a reaction vessel and reacted at 230 ° C for 8 hours under normal pressure. Next, an intermediate polyester was synthesized by reacting at a reduced pressure of 10 to 15 mmHg for 5 hours.
Then
-410 parts of intermediate polyester-89 parts of isophorone diisocyanate-500 parts of ethyl acetate were reacted at 100 ° C for 5 hours to synthesize a prepolymer.

(Synthesis of ketimine)
In a reaction vessel, 170 parts of isophoronediamine and 75 parts of methyl ethyl ketone are charged.
Reaction was performed at 0 ° C. for 5 hours to synthesize a ketimine compound.
(Preparation of toner particle composition)
In a container in which a stir bar and a thermometer are set, 150 parts of a master batch, 1: 700 parts of a binder resin, 23 parts of a compound represented by the general formula [1] (9-fluorenone, melting point: 84 ° C.),
850 parts of ethyl acetate was added and mixed with a TK homomixer (manufactured by Tokushu Kika Co., Ltd.) at a rotation speed of 9,000 rpm for 10 minutes.
Thereafter, while cooling the container, the number of revolutions of the TK homomixer was set to 1,000 rpm, and the mixture was stirred until the liquid temperature became 30 ° C. After the liquid temperature reached 30 ° C., 194 parts of a prepolymer and 6 parts of a ketimine compound were further added and stirred at a rotational speed of 5,000 rpm for 30 seconds to obtain a toner particle composition.

(Granulation)
The amount of the material used was adjusted at the following ratio so that the total amount of the granulated slurry was 600 kg. Aqueous medium: 60 parts of the toner particle composition is placed in a container containing 140 parts, and mixed for 10 minutes at 3,000 r / min using a high shear mixer (manufactured by IKA) to obtain a dispersion of the toner particle composition. Obtained.
(Solvent removal / aging)
After completion of the granulation step, the dispersion of the toner particle composition was transferred to a container maintained at 30 ° C., and stirring was started at 50 r / min, and the solvent was removed for 10 hours. Subsequently, the temperature in the jacket was set to 80 ° C., the temperature in the container was raised to 55 ° C., and aging was further performed at 55 ° C. for 5 hours to obtain toner particles.
The obtained toner particles were classified using a multi-division classifier utilizing the Coanda effect to obtain negative triboelectrically chargeable toner particles having a weight average particle diameter (D4) of 6.8 μm.
To 100 parts of the toner particles, 1.0 part of hydrophobic silica fine powder (specific surface area by nitrogen adsorption measured by BET method is 140 m ^{2 /} g) and strontium titanate (volume average particle diameter 1.6 μm) 3.0 Parts were externally mixed and sieved with a mesh having an opening of 150 μm to obtain toner D-1. The glass transition temperature Tg of the toner D-1 was 52 ° C., and no endothermic peak was observed within the measurement temperature range, and it was determined that all 9-fluorenone was compatible.

(Example of production of developer D-1)
Using a V-type mixer (V-10 type: Tokuju Seisakusho Co., Ltd.) so that toner D-1 and magnetic carrier are 10.0 parts of toner D-1 with respect to 1.0 part of carrier. , 0.5 s ⁻¹ , and a rotation time of 5 min, to prepare developer D-1. Evaluation of the fouling property, halftone unevenness and low-temperature fixability of the fixing member was performed on the obtained developer D-1 in the same manner as in Example A-1. The developer D-1 was all judged as A.

Claims (4)

A toner comprising a binder resin, a colorant, and a compound represented by the following general formula [1].

Wherein R ^{1 to} R ⁸ are each independently a hydrogen atom, a fluorine atom, a bromine atom, an iodine atom, a hydroxy group, an acetyl group, an aldehyde group, a hydrocarbon group having 1 to 6 carbon atoms, and an amino group. X represents a group selected from an oxygen atom, a sulfur atom, a carbonyl group, and —CR ⁹ R ¹⁰ —, and R ⁹ and R ¹⁰ each independently represent a hydrogen atom or a bromine atom. Represents a group selected from a hydroxyalkyl group having 1 to 3 carbon atoms, a hydroxyl group, a phenyl group, and a hydrocarbon group having 1 to 6 carbon atoms.)   2. The toner according to claim 1, wherein the content of the compound represented by the general formula [1] is 0.1 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 according to claim 1, wherein a boiling point of the compound represented by the general formula [1] is 290 ° C. or higher.   The toner according to claim 1, wherein X in the general formula [1] is a carbonyl group.