JP2018059963A - Electrophotographic toner - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an electrophotographic toner that has excellent low-temperature fixability and excellent developability, a binder resin composition from which the electrophotographic toner can be obtained, and a method for manufacturing the electrophotographic toner.SOLUTION: An electrophotographic toner contains a composition containing a resin having at least a polyester part, and the composition is obtained with a method including a step of obtaining the polyester part through polycondensation of an alcohol component and a carboxylic acid component. In the polycondensation, from the time point when a reaction ratio of the alcohol component is 70% or more, 0.001 parts by mass or more and 5 parts by mass or less of a polyhydroxyamine compound represented by the following formula (1) is added to total 100 parts by mass of the entire monomer component.SELECTED DRAWING: None

Description

  The present invention relates to an electrophotographic toner, a binder resin composition from which the electrophotographic toner is obtained, and a method for producing the electrophotographic toner.

In recent years, with the increase in speed and energy saving of printers and copiers, toners that can meet these demands are increasingly required.
Patent Document 1 describes a method for producing a binder component of an electrophotographic toner. This document satisfies the requirements such as fixing at a lower temperature, no offset even at a higher temperature, being able to form a stable image even when environmental conditions such as humidity fluctuate greatly, and being excellent in the rise of charging. Is an issue. Patent Document 1 describes a method for producing a carbodiimide-modified polyester resin characterized by reacting a polyester resin (A) with a carbodiimide group-containing compound (B).

JP 2000-336163 A

Along with energy saving of printers and copiers, low temperature fixability that allows toner to be fixed on a print medium is required even at low temperatures. However, the electrophotographic toner described in Patent Document 1 is desired to be further improved from the viewpoint of developability in which filming occurs in the developing roller when an electrophotographic toner having excellent low-temperature fixability is obtained. It is rare.
In the present invention, it is an object to provide an electrophotographic toner having excellent low-temperature fixability and excellent developability, a binder resin composition from which the electrophotographic toner is obtained, and a method for producing the electrophotographic toner. And

  By adding a predetermined amount of a specific polyhydroxyamine compound from the time when a predetermined reaction rate is obtained during polycondensation of an alcohol component and a carboxylic acid component, the low-temperature fixability and developability of the electrophotographic toner can be improved. I found it to increase.

The present invention relates to the following [1] to [3].
[1] containing a composition containing a resin having at least a polyester moiety;
The composition is obtained by a method including a step of obtaining a polyester site by polycondensation of an alcohol component and a carboxylic acid component,
From the time when the reaction rate of the alcohol component in the polycondensation is 70% or more, the polyhydroxy compound represented by the following formula (1) of 0.001 to 5 parts by mass with respect to 100 parts by mass in total of all monomer components An electrophotographic toner to which an amine compound is added.

[Wherein, R ¹ represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a hydroxyalkyl group having 1 to 5 carbon atoms, and R ² represents a hydrogen atom, an alkyl having 1 to 6 carbon atoms. Group or a hydroxyalkyl group having 1 to 5 carbon atoms, and R ³ and R ⁴ represent an alkanediyl group having 1 to 5 carbon atoms. R ³ and R ⁴ may be the same or different. ]
[2] containing a composition containing a resin having at least a polyester moiety;
The composition is obtained by a method including a step of obtaining a polyester site by polycondensation of an alcohol component and a carboxylic acid component,
From the time when the reaction rate of the alcohol component is 70% or more in the polycondensation, 0.001 part by mass or more and 5 parts by mass or less of the polyhydroxyamine represented by the formula (1) with respect to a total of 100 parts by mass of all monomer components A binder resin composition for electrophotographic toner, to which a compound is added.
[3] including a step of obtaining a polyester moiety by polycondensation of an alcohol component and a carboxylic acid component,
From the time when the reaction rate of the alcohol component is 70% or more in the polycondensation, 0.001 part by mass or more and 5 parts by mass or less of the polyhydroxyamine represented by the formula (1) with respect to a total of 100 parts by mass of all monomer components A method for producing an electrophotographic toner, comprising adding a compound.

  According to the present invention, it is possible to provide an electrophotographic toner having excellent low-temperature fixability and excellent developability, a binder resin composition from which the electrophotographic toner is obtained, and a method for producing the electrophotographic toner. it can.

[Electrophotographic toner]
The electrophotographic toner of the present invention (hereinafter also simply referred to as “toner”) is a composition (hereinafter also referred to as “composition A”) containing a resin having at least a polyester moiety (hereinafter also referred to as “resin A”). Containing.
The composition is obtained by a method including a step of obtaining a polyester site by polycondensation of an alcohol component and a carboxylic acid component. From the time when the reaction rate of the alcohol component is 70% or more by the polycondensation, A polyhydroxyamine compound represented by the following formula (1) of 0.001 to 5 parts by mass is added to 100 parts by mass in total.

[Wherein, R ¹ represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a hydroxyalkyl group having 1 to 5 carbon atoms, and R ² represents a hydrogen atom, an alkyl having 1 to 6 carbon atoms. Group or a hydroxyalkyl group having 1 to 5 carbon atoms, and R ³ and R ⁴ represent an alkanediyl group having 1 to 5 carbon atoms. R ³ and R ⁴ may be the same or different. ]

According to the present invention, a toner having excellent low-temperature fixability and excellent developability can be obtained.
The reason is not clear, but it is thought as follows.
The toner of the present invention is obtained by adding a predetermined amount of a polyhydroxyamine compound having a predetermined structure from the time when the reaction rate of the alcohol component is 70% or more due to resin polycondensation. The polyhydroxyamine compound is highly polar and preferentially hydrogen bonds with a low molecular weight component in the polyester resin, resulting in a decrease in mobility of the low molecular weight component, resulting in the low molecular weight component of the polyester resin. It is considered that the filming on the fixing roller was improved and the developability was improved. Since the polycondensation of the polyester proceeds and the reaction rate of the alcohol component is 70% or more, the polyhydroxyamine compound remains in a highly dispersed state by adding the polyhydroxyamine compound, so that it remains after the completion of the reaction. It is considered that the low molecular weight component can be easily captured by hydrogen bonding, and the above effect is remarkably obtained.

[Binder resin]
<Composition A containing resin A>
The toner of the present invention contains a composition A containing a resin A having at least a polyester moiety as a binder resin.
Composition A is obtained by a method including a step of obtaining a polyester moiety by polycondensation of an alcohol component and a carboxylic acid component from the viewpoint of obtaining a toner having excellent low-temperature fixability and excellent developability. From the time when the reaction rate of the alcohol component is 70% or more, the polyhydroxyamine compound represented by the formula (1) of 0.001 part by mass or more and 5 parts by mass or less is added with respect to a total of 100 parts by mass of all the monomer components. That is, the addition of the polyhydroxyamine compound is started at a time when the reaction rate is 70% or more.

The “reaction rate of the alcohol component” means the conversion rate of the alcohol component consumed by the polycondensation of the alcohol component and the carboxylic acid component. The “reaction rate of the alcohol component” is determined by the following calculation formula (A).
[Reaction rate of alcohol component (%)] = [Amount of water removed from polycondensation system] / [Theoretical dehydration amount calculated from the amount of alcohol component used as raw material] × 100 (A)

  When the polyhydroxyamine compound is added, the reaction rate of the alcohol component is preferably 75% or more, more preferably 80% or more, from the viewpoint of obtaining a toner having excellent low-temperature fixability and excellent developability. Preferably it is 85% or more, more preferably 90% or more, and 100% or less, preferably 95% or less.

  The addition amount of the polyhydroxyamine compound is 0.001 part by mass or more and 5 parts by mass or less with respect to a total of 100 parts by mass of all monomer components, from the viewpoint of obtaining a toner having excellent low-temperature fixability and excellent developability. From the viewpoint of improving the developability of the toner, it is preferably 0.01 parts by mass or more, more preferably 0.03 parts by mass or more, more preferably 0.1 parts by mass or more, more preferably 0.3 parts by mass or more. From the viewpoint of improving, it is preferably 4 parts by mass or less, more preferably 3 parts by mass or less, and still more preferably 1 part by mass or less.

The polyhydroxyamine compound may be added as a solution. In that case, as a solvent used, well-known solvents, such as water, alcohol, and methyl ethyl ketone, can be used.
The addition rate of the polyhydroxyamine compound is preferably 0.05 parts by mass / min or more, more preferably 0.1 parts by mass / min or more, further preferably 0.2 parts by mass / min or more, with respect to 100 parts by mass of all monomer components. Yes, and preferably 1.0 parts by mass / min or less, more preferably 0.5 parts by mass / min or less, and still more preferably 0.3 parts by mass / min or less.

The temperature at which the polyhydroxyamine compound is added is preferably 130 ° C. or higher, more preferably 150 ° C. or higher, more preferably 180 ° C. or higher, from the viewpoint of improving the low-temperature fixability and developability of the toner. The temperature is preferably 20 ° C. or lower, more preferably 30 ° C. or lower, and further preferably 35 ° C. lower or lower than the boiling point of the amine compound.
In addition, the temperature to add means the temperature in a polycondensation reaction system. The boiling point of the polyhydroxyamine compound means the boiling point at normal pressure (0.1 MPa) of the polyhydroxyamine compound to be added.

After adding the whole amount of the polyhydroxyamine compound, the temperature is preferably maintained at 130 ° C or higher and 20 ° C or lower than the boiling point of the polyhydroxyamine compound.
From the viewpoint of improving the low-temperature fixability and developability of the toner, the holding temperature is preferably 150 ° C. or higher, preferably 180 ° C. or higher, and preferably 20 ° C. or lower than the boiling point of the polyhydroxyamine compound. More preferably, the temperature is lower by 30 ° C. or lower, and further preferably lower by 35 ° C. or lower.
The holding time is preferably 0.5 hours or more, more preferably 0.75 hours or more, further preferably 1 hour or more, and preferably 3 hours or less, more preferably from the viewpoint of improving the low-temperature fixability and developability of the toner. Is 2.5 hours or less, more preferably 2 hours or less.

[Polyhydroxyamine compound]
The polyhydroxyamine compound is a compound represented by the following formula (1) from the viewpoint of obtaining a toner having excellent low-temperature fixability and excellent developability.

[Wherein, R ¹ represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a hydroxyalkyl group having 1 to 5 carbon atoms, and R ² represents a hydrogen atom, an alkyl having 1 to 6 carbon atoms. Group or a hydroxyalkyl group having 1 to 5 carbon atoms, and R ³ and R ⁴ represent an alkanediyl group having 1 to 5 carbon atoms. R ³ and R ⁴ may be the same or different. ]

The number of carbon atoms of the alkyl group of R ¹ is preferably 4 or less, more preferably 3 or less, still more preferably 2 or less, and still more preferably 1 from the viewpoint of improving the low-temperature fixability and developability of the toner.
The alkyl group for R ¹ may be either linear or branched, and examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, various butyl groups, and various pentyl groups, preferably methyl. And at least one selected from a group and an ethyl group, more preferably a methyl group.

The number of carbon atoms of the hydroxyalkyl group of R ¹ is preferably 4 or less, more preferably 3 or less, still more preferably 2 or less, and still more preferably 1 from the viewpoint of improving the low-temperature fixability and developability of the toner.
Examples of the hydroxyalkyl group of R ¹ include hydroxymethyl group, 2-hydroxyethyl group, 2-hydroxypropyl group, 3-hydroxypropyl group, 2-hydroxybutyl group, 3-hydroxybutyl group, 4-hydroxybutyl group, and the like. Preferably, it is at least one selected from a hydroxymethyl group and a 2-hydroxyethyl group, and more preferably a hydroxymethyl group.

Among these, R ¹ is preferably an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group having 1 to 3 carbon atoms, and more preferably a methyl group, an ethyl group, a hydroxymethyl group, and a hydroxyethyl group. At least one selected from a group, more preferably a hydroxymethyl group.

The carbon number of the alkyl group represented by R ² is preferably 3 or less, more preferably 2 or less, and preferably 1 or more.
The alkyl group for R ² may be linear, branched or cyclic, and examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, various butyl groups, various pentyl groups, and various hexyl groups. Group, cyclopentyl group, cyclohexyl group and the like.
The carbon number of the hydroxyalkyl group of R ² is preferably 3 or less, more preferably 2 or less, and preferably 1 or more. Examples of the hydroxyalkyl group for R ² include the same as those for R ¹ described above.
Among these, R ² is preferably a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or a hydroxyalkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom.

The carbon number of the alkanediyl group of R ³ and R ⁴ is preferably 4 or less, more preferably 3 or less, more preferably 2 or less, and more preferably 1.
Examples of the alkanediyl group of R ³ and R ⁴ include a methylene group, an ethylene group, a trimethylene group, a propane-1,2-diyl group, a tetramethylene group, and the like, and a methylene group is preferable.

Specific examples of the polyhydroxyamine compound include, for example, 2-amino-1,3-propanediol, 2-amino-2-methyl-1,3-propanediol, 2-amino-2-ethyl-1,3- Propanediol, 2-amino-2-hydroxymethyl-1,3-propanediol, 2-amino-2-hydroxyethyl-1,3-propanediol, 4-amino-4-hydroxypropyl-1,7-heptanediol 2- (N-ethyl) amino-1,3-propanediol, 2- (N-ethyl) amino-2-hydroxymethyl-1,3-propanediol, 2- (N-decyl) amino-1,3 -Propanediol, 2- (N-decyl) amino-2-hydroxymethyl-1,3-propanediol, and the like.
Among these, from the viewpoint of improving low-temperature fixability and developability of the toner, 2-amino-2-hydroxymethyl-1,3-propanediol, 2-amino-2-hydroxyethyl-1,3 are preferable. At least one selected from -propanediol, 2-amino-1,3-propanediol, 2-amino-2-methyl-1,3-propanediol, and 2-amino-2-ethyl-1,3-propanediol Species, more preferably 2-amino-2-hydroxymethyl-1,3-propanediol, 2-amino-2-hydroxyethyl-1,3-propanediol, and 2-amino-2-methyl-1,3- At least one selected from propanediol, more preferably 2-amino-2-hydroxymethyl-1,3-propanediol.
1 type (s) or 2 or more types can be used for said polyhydroxyamine compound. In addition, a polyhydroxyamine compound can be manufactured by a conventional method.

  The resin A is, for example, at least one selected from polyester and a composite resin having a polyester segment, and at least one selected from polyester and a composite resin having a polyester segment and a styrene resin segment is preferable.

〔polyester〕
The polyester is obtained by polycondensation of an alcohol component and a carboxylic acid component.
(Alcohol component)
The alcohol component may be an aromatic polyol compound or an aliphatic polyol compound.
The aromatic polyol compound is preferably an alkylene oxide adduct of bisphenol A from the viewpoint of improving the low-temperature fixability and developability of the toner, more preferably the formula (I):

[Wherein, RO and OR are oxyalkylene groups, R is at least one selected from an ethylene group and a propylene group, and x and y represent the average number of moles of alkylene oxide added, each being a positive number. The value of the sum of x and y is 1 or more, preferably 1.5 or more, and 16 or less, preferably 8 or less, more preferably 4 or less. An alkylene oxide adduct of bisphenol A represented by the formula:

  Examples of the alkylene oxide adduct of bisphenol A represented by the formula (I) include 2,2-bis (4-hydroxyphenyl) propane propylene oxide adduct, 2,2-bis (4-hydroxyphenyl) propane ethylene. And oxide adducts. It is preferable to use one or more of these.

  The content of the alkylene oxide adduct of bisphenol A represented by the formula (I) is preferably 70 mol% or more, more preferably 90 mol% or more, still more preferably 95 mol% or more, more preferably in the alcohol component. 100 mol%.

Examples of the aliphatic polyol compound include aliphatic diols having 2 to 20 carbon atoms, and trihydric or higher aliphatic alcohols such as glycerin. Among these, aliphatic diols are preferable.
Aliphatic diols include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,4-butenediol 1,3-butanediol, neopentyl glycol, 1,10-decanediol, 1,12-dodecanediol and the like.

  When the aliphatic diol is contained as the alcohol component, the content of the aliphatic diol in the alcohol component is preferably 70 mol% or more, more preferably 90 mol% or more, still more preferably 95 mol% or more, and still more preferably 100 mol%. Mol%.

(Carboxylic acid component)
On the other hand, in the carboxylic acid component, the divalent carboxylic acid is preferably an aromatic dicarboxylic acid from the viewpoint of storage stability. From the viewpoint of improving the low-temperature fixability of the toner, an aliphatic dicarboxylic acid is preferable.

  Aromatic dicarboxylic acids include phthalic acid, isophthalic acid, terephthalic acid; anhydrides of these acids or alkyl (C1-3) esters of these acids, among which terephthalic acid or isophthalic acid Acid is preferred, and terephthalic acid is more preferred. These can be used alone or in combination of two or more. In the present invention, the carboxylic acid component includes not only a free acid but also an anhydride that decomposes during the reaction to produce an acid, and an alkyl ester having an alkyl group with 1 to 3 carbon atoms.

  The content of the aromatic dicarboxylic acid in the carboxylic acid component is preferably 10 mol% or more, more preferably 30 mol% or more, still more preferably 50 mol% or more, and 100 mol% or less, preferably 95 mol% or less.

  Examples of the aliphatic dicarboxylic acids include alkyl groups having 1 to 20 carbon atoms such as oxalic acid, malonic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, succinic acid, adipic acid, dodecenyl succinic acid, octyl succinic acid, etc. Or aliphatic dicarboxylic acids such as succinic acid substituted with an alkenyl group having 2 to 20 carbon atoms; anhydrides of these acids or alkyl (C1 to C3) esters of these acids. These can be used alone or in combination of two or more. Among these, adipic acid is preferable.

  The content of the aliphatic dicarboxylic acid is preferably 5 mol% or more, more preferably 8 mol% or more in the carboxylic acid component from the viewpoint of improving the low-temperature fixability of the toner, and improves the developability of the toner. In view of the above, it is preferably 90 mol% or less, more preferably 50 mol% or less, still more preferably 30 mol% or less, still more preferably 15 mol% or less.

  The carboxylic acid component preferably contains a trivalent or higher carboxylic acid from the viewpoint of productivity.

  As the trivalent or higher carboxylic acid, trivalent carboxylic acid is preferable, 1,2,4-benzenetricarboxylic acid (trimellitic acid), 2,5,7-naphthalenetricarboxylic acid, pyromellitic acid or acid anhydrides thereof. Products, lower alkyl (1 to 3 carbon atoms) esters, and the like. Among these, trimellitic acid or its acid anhydride is preferable.

  The content of trivalent or higher carboxylic acid, preferably trimellitic acid, is preferably 3 mol% or more, more preferably 5 mol% or more, and still more preferably 8 mol% in the carboxylic acid component from the viewpoint of productivity. From the viewpoint of improving the low-temperature fixability of the toner, it is preferably 50 mol% or less, more preferably 40 mol% or less, more preferably 30 mol% or less, and still more preferably 20 mol% or less. is there.

  In addition, the alcohol component may contain a monovalent alcohol, and the carboxylic acid component may contain a monovalent carboxylic acid compound as appropriate from the viewpoint of molecular weight adjustment.

  The equivalent ratio of the carboxylic acid component and the alcohol component (COOH group / OH group) is preferably 0.7 or more, more preferably 0.8 or more, and preferably 1.3 or less, more preferably from the viewpoint of adjusting the terminal group. 1.2 or less, more preferably 1 or less.

In the polycondensation of the alcohol component and the carboxylic acid component, a polyhydroxyamine compound is added. The conditions for addition are as described above.
The polycondensation of the alcohol component and the carboxylic acid component is carried out, for example, in the presence of an esterification catalyst, a polymerization inhibitor, etc. It can be carried out at a temperature 20 ° C. lower than the boiling point. Examples of the esterification catalyst include tin compounds such as dibutyltin oxide and tin (II) 2-ethylhexanoate, and titanium compounds such as titanium diisopropylate bistriethanolamate. Examples of the esterification cocatalyst that can be used together with the esterification catalyst include gallic acid and the like. The amount of the esterification catalyst used is preferably 0.01 parts by weight or more, more preferably 0.1 parts by weight or more, and preferably 1 part by weight with respect to 100 parts by weight of the total amount of the polyhydroxyamine compound, the alcohol component, and the carboxylic acid component. It is not more than part by mass, more preferably not more than 0.6 part by mass. The amount of the esterification cocatalyst used is preferably 0.001 part by mass or more, more preferably 0.01 part by mass or more, and preferably 100 parts by mass or more with respect to 100 parts by mass of the total amount of the polyhydroxyamine compound, the alcohol component, and the carboxylic acid component. 0.5 parts by mass or less, more preferably 0.1 parts by mass or less.

[Composite resin]
The composite resin preferably has a polyester segment and a styrene resin segment.
The polyester segment is made of polyester, and preferred examples of the polyester are the same as those described above.

(Styrene resin segment)
The styrene resin segment is made of a styrene resin, and the styrene resin is preferably obtained by addition polymerization of a raw material monomer containing a styrene compound.
As the styrene compound, at least styrene, or styrene derivatives such as α-methylstyrene and vinyltoluene (hereinafter, styrene and styrene derivatives are collectively referred to as “styrene compound”) is used.

  The content of the styrene compound is preferably 50% by mass or more, more preferably 60% by mass or more, and still more preferably 65% by mass or more from the viewpoint of durability in the raw material monomer of the styrenic resin. From the viewpoint of improving low-temperature fixability, it is preferably 95% by mass or less, more preferably 90% by mass or less, and still more preferably 80% by mass or less.

  As raw material monomers for styrene resins used in addition to styrene compounds, (meth) acrylic acid alkyl esters; ethylenically unsaturated monoolefins such as ethylene and propylene; diolefins such as butadiene; halovinyls such as vinyl chloride; Vinyl esters such as vinyl acetate and vinyl propionate; Ethylene monocarboxylic acid esters such as dimethylaminoethyl (meth) acrylate; Vinyl ethers such as vinyl methyl ether; Vinylidene halides such as vinylidene chloride; N-vinyl pyrrolidone, etc. And N-vinyl compounds.

  Two or more kinds of raw material monomers for the styrene resin used in addition to the styrene compound can be used. In the present specification, “(meth) acrylic acid” means at least one selected from acrylic acid and methacrylic acid.

  Among the raw material monomers of the styrenic resin used in addition to the styrene compound, (meth) acrylic acid alkyl ester is preferable from the viewpoint of improving the low-temperature fixability of the toner. In view of the above, the carbon number of the alkyl group in the (meth) acrylic acid alkyl ester is preferably 1 or more, more preferably 2 or more, more preferably 3 or more, more preferably 5 or more, more preferably 7 or more, And it is preferably 22 or less, more preferably 18 or less, still more preferably 12 or less, and still more preferably 8 or less. In addition, carbon number of this alkyl ester means carbon number derived from the alcohol component which comprises ester.

  Specific examples of (meth) acrylic acid alkyl esters include methyl (meth) acrylate, ethyl (meth) acrylate, (iso) propyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, (iso or tertiary ) Butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, (iso) octyl (meth) acrylate, (iso) decyl (meth) acrylate, (iso) stearyl (meth) acrylate, and the like. Here, `` (iso or tertiary) '', `` (iso) '' means to include both the presence and absence of these prefixes, and the presence of these prefixes. If not, it indicates normal. Further, “(meth) acrylate” indicates that both acrylate and methacrylate are included.

  The content of the (meth) acrylic acid alkyl ester is preferably 5% by mass or more, more preferably 10% by mass or more, and still more preferably from the viewpoint of improving the low-temperature fixability of the toner in the raw material monomer of the styrene resin segment. From the same viewpoint, it is preferably 50% by mass or less, more preferably 40% by mass or less, and still more preferably 35% by mass or less.

  A resin obtained by addition polymerization of a raw material monomer containing a styrene compound and a (meth) acrylic acid alkyl ester is also referred to as a styrene- (meth) acrylic resin.

  The addition polymerization reaction of the raw material monomer of the styrenic resin can be carried out in a conventional manner, for example, in the presence of a polymerization initiator such as dicumyl peroxide, a crosslinking agent, etc., in the presence of an organic solvent, or in the absence of a solvent. The temperature condition is preferably 110 ° C or higher, more preferably 120 ° C or higher, more preferably 130 ° C or higher, and preferably 250 ° C or lower, more preferably 200 ° C or lower, more preferably 170 ° C or lower. .

  When an organic solvent is used in the addition polymerization reaction, xylene, toluene, methyl ethyl ketone, acetone or the like can be used. The amount of the organic solvent used is preferably about 10 parts by mass or more and 50 parts by mass or less with respect to 100 parts by mass of the raw material monomer of the styrene resin.

(Amotropic monomer)
From the viewpoint of improving the low-temperature fixability and developability of the toner, the composite resin is used in addition to the polyester segment raw material monomer and the styrene resin segment raw material monomer, as well as the polyester segment raw material monomer and the styrene resin segment raw material monomer. It is preferably a composite resin obtained by using a bireactive monomer that can react with both. Accordingly, when the raw material monomer for the polyester segment and the raw material monomer for the styrene resin segment are polymerized to obtain a composite resin, the polycondensation reaction or the addition polymerization reaction is preferably performed in the presence of both reactive monomers. As a result, the composite resin becomes a composite resin in which the polyester segment and the styrene resin segment are bonded via the structural unit derived from the both reactive monomers, and the polyester segment and the styrene resin segment are more finely and uniformly dispersed. Will be.

  That is, the composite resin comprises (i) an alcohol component containing an alkylene oxide adduct of bisphenol A represented by the formula (I) and an aromatic dicarboxylic acid from the viewpoint of improving low-temperature fixability and developability of the toner. A polyester segment raw material monomer containing a carboxylic acid component, (ii) a styrene resin segment raw material monomer, and (iii) a polyester segment raw material monomer and a styrene resin segment raw material monomer. A resin obtained by polymerizing a reactive monomer is preferred.

  As the both reactive monomers, at least one functional group selected from a hydroxyl group, a carboxy group, an epoxy group, a primary amino group and a secondary amino group in the molecule, preferably at least selected from a hydroxyl group and a carboxy group. A compound having one kind of functional group, more preferably a carboxy group and an ethylenically unsaturated bond is preferred, and by using such a bireactive monomer, the dispersibility of the resin as the dispersed phase can be further improved. it can. The both reactive monomers are preferably at least one selected from acrylic acid, methacrylic acid, fumaric acid, maleic acid and maleic anhydride. From the viewpoint of the reactivity of polycondensation reaction and addition polymerization reaction, acrylic acid is preferred. Methacrylic acid or fumaric acid is more preferable, and acrylic acid or methacrylic acid is still more preferable. However, when used together with a polymerization inhibitor, a polyvalent carboxylic acid having an ethylenically unsaturated bond such as fumaric acid functions as a raw material monomer for the polyester segment. In this case, fumaric acid or the like is not a bireactive monomer but a raw material monomer for the polyester segment.

  From the viewpoint of improving the low-temperature fixability of the toner, the amount of both reactive monomers is preferably 1 mol or more, more preferably 2 mol or more, and still more preferably 3 mol with respect to 100 mol of the total alcohol component of the polyester segment. From the viewpoint of improving the developability of the toner, it is preferably 20 moles or less, more preferably 10 moles or less, and even more preferably 7 moles or less.

The mass ratio of the polyester segment to the styrene resin segment (polyester segment / styrene resin segment) in the composite resin is preferably 60/40 or more, more preferably 70/30 or more, from the viewpoint of improving the low-temperature fixability of the toner. Further, it is preferably 75/25 or more, and preferably 95/5 or less, more preferably 90/10 or less, and still more preferably 85/15 or less, from the viewpoint of improving the developability of the toner. In the above calculation, the mass of the polyester segment is the amount obtained by subtracting the amount (calculated value) of the reaction water dehydrated by the polycondensation reaction from the mass of the raw material monomer of the polycondensation resin used. The amount of the monomer is included in the amount of the raw material monomer of the polyester segment. The amount of the styrene resin segment is the amount of the raw material monomer of the styrene resin segment, but the amount of the polymerization initiator is included in the amount of the raw material monomer of the styrene resin segment.
In the case where the resin A is a composite resin, a polyhydroxyamine compound is added in the polycondensation of the alcohol component and the carboxylic acid component, as shown in the above conditions, from the viewpoint of improving the low-temperature fixability and developability of the toner. Is done.

  The softening point of the resin A is preferably 90 ° C. or higher, more preferably 95 ° C. or higher, further preferably 100 ° C. or higher, from the viewpoint of improving the low-temperature fixability and developability of the toner. From the viewpoint of improving the temperature, it is preferably 150 ° C. or lower, more preferably 145 ° C. or lower, and further preferably 140 ° C. or lower.

  The glass transition temperature of the resin A is preferably 45 ° C. or higher, more preferably 50 ° C. or higher, and further preferably 55 ° C. or higher, from the viewpoint of improving the low-temperature fixability and developability of the toner. From the viewpoint of improving the properties, it is preferably 80 ° C. or lower, more preferably 75 ° C. or lower, more preferably 70 ° C. or lower, and further preferably 65 ° C. or lower.

  The acid value of the resin A is preferably 40 mgKOH / g or less, more preferably 30 mgKOH / g or less, still more preferably 20 mgKOH / g or less, and preferably from the viewpoint of improving the low-temperature fixability and developability of the toner. 1 mgKOH / g or more, more preferably 5 mgKOH / g or more, more preferably 10 mgKOH / g or more.

  The hydroxyl value of Resin A is preferably 50 mgKOH / g or less, more preferably 40 mgKOH / g or less, still more preferably 25 mgKOH / g or less, and preferably from the viewpoint of improving the low-temperature fixability and developability of the toner. 1 mgKOH / g or more, more preferably 8 mgKOH / g or more, more preferably 15 mgKOH / g or more.

The number average molecular weight of the resin A is preferably 1,000 or more, more preferably 1,500 or more, further preferably 2,000 or more, and preferably 7,000 or less, more preferably, from the viewpoint of improving the low-temperature fixability and developability of the toner. Is 6,000 or less, more preferably 5,000 or less.
The measuring method of a softening point, a glass transition temperature, an acid value, a hydroxyl value, and a number average molecular weight is based on the method described in Examples. When two or more kinds of resins are contained, the weighted average values of the softening point, glass transition temperature, acid value, hydroxyl value, and number average molecular weight are preferably in the above ranges.

The binder resin contained in the toner preferably contains other polyester.
Examples of other polyesters include polyesters obtained by polycondensation of alcohol components and carboxylic acid components exemplified in the above polyester.

  The total content of the resin A in the binder resin is preferably 3% by mass or more, more preferably 10% by mass or more, still more preferably 20% by mass or more, and 100% by mass or less, preferably 90% or less. It is not more than mass%, more preferably not more than 80 mass%, still more preferably not more than 70 mass%.

The toner binder resin may contain a plurality of types of resins having different softening points and crystallinity.
Specifically, the following resin H and resin L may be contained, or the following resin H, resin L, and resin C may be contained.

<Resin H, L>
Among the above-described resins, the toner preferably contains a binder resin including two types of resins having different softening points of 20 ° C. or more from the viewpoint of improving high-temperature offset resistance and low-temperature fixability.

  The softening point of the resin H having the higher softening point is preferably 170 ° C. or less, more preferably 160 ° C. or less, from the viewpoint of improving the low-temperature fixability of the toner, and from the viewpoint of high-temperature offset resistance, Is 110 ° C or higher, more preferably 120 ° C or higher, more preferably 130 ° C or higher.

  The softening point of the resin L having the lower softening point is preferably 80 ° C. or higher, more preferably 95 ° C. or higher from the viewpoint of durability, and preferably 125 ° C. from the viewpoint of improving the low-temperature fixability of the toner. C. or lower, more preferably 115.degree. C. or lower.

  The difference in softening point between the resin H and the resin L is preferably 10 ° C. or higher, more preferably 20 ° C. or higher, more preferably 25 ° C. or higher, from the viewpoint of improving high temperature offset resistance and low temperature fixability. Preferably it is 60 degrees C or less, More preferably, it is 50 degrees C or less, More preferably, it is 40 degrees C or less.

  The mass ratio of resin H to resin L (resin H / resin L) is preferably 20/80 or more, more preferably 40/60 or more, more preferably 50/50 or more, from the viewpoint of durability and productivity. From the viewpoint of improving the low-temperature fixability of the toner, it is preferably 90/10 or less, more preferably 80/20 or less, and even more preferably 75/25 or less.

The resin H and the resin L are preferably amorphous resins.
In the present invention, the “amorphous resin” means the ratio of the softening point (° C.) to the maximum endothermic peak temperature (° C.) measured by a differential scanning calorimeter (DSC), that is, [(softening point) / (high endotherm peak). Temperature)] is a resin having a crystallinity index value of 1.4 or more or less than 0.6. The maximum peak temperature of endotherm refers to the temperature of the peak on the highest temperature side among the endothermic peaks observed under the conditions of the measurement methods described in the examples.
When the resin H and the resin L are amorphous resins, among the above-described resins, a resin containing an aromatic polyol compound is preferable as the alcohol component. In addition, the preferable example of an aromatic polyol compound and another preferable example are the same as that of the above-mentioned illustration.

<Resin C>
Among the above-described resins, the toner preferably further contains a crystalline resin C (hereinafter also simply referred to as “resin C”).
The “crystalline resin” refers to a resin having a crystallinity index value of 0.6 or more and less than 1.4, preferably 0.8 or more and 1.2 or less.
Among the above-mentioned resins, the crystalline resin C is preferably a resin containing an aliphatic polyol compound as an alcohol component. In addition, the preferable example of an aliphatic polyol compound and another preferable example are the same as that of the above-mentioned illustration.

The softening point of the resin C is preferably 100 ° C. or lower, more preferably 90 ° C. or lower from the viewpoint of improving the low-temperature fixability of the toner, and preferably 60 ° C. or higher from the viewpoint of improving the developability of the toner. More preferably, it is 70 ° C or higher, more preferably 80 ° C or higher.
The melting point of the resin C is preferably 100 ° C. or less, more preferably 90 ° C. or less from the viewpoint of improving the low-temperature fixability of the toner, and preferably 60 ° C. or more from the viewpoint of improving the developability of the toner. More preferably, it is 70 ° C. or higher, more preferably 80 ° C. or higher.

  The content of the resin C in the binder resin is preferably 1% by mass or more, more preferably 2% by mass or more, still more preferably 3% by mass or more, and preferably 20% by mass or less, more preferably 15% by mass. It is at most 8% by mass, more preferably at most 8% by mass.

Among these, the binder resin is
Preferably, (i) an amorphous resin and a crystalline resin, and at least one selected from the amorphous resin and the crystalline resin is the resin A,
More preferably, (ii) at least one selected from amorphous resin H, amorphous resin L, and crystalline resin C, including amorphous resin H, amorphous resin L, and crystalline resin C Is the resin A,
More preferably, (iii) the amorphous resin H, the amorphous resin L, and the crystalline resin C are included, and the amorphous resin H is the resin A.

  The total content of the resin having at least a polyester moiety in the binder resin is preferably 80% by mass or more, more preferably 90% by mass or more, still more preferably 95% by mass or more, and preferably 100% by mass or less. .

<Charge control agent>
The toner preferably contains a charge control agent.
The charge control agent may contain either a positively chargeable charge control agent or a negatively chargeable charge control agent.
Examples of positively chargeable charge control agents include nigrosine dyes such as “Nigrosine Base EX”, “Oil Black BS”, “Oil Black SO”, “Bontron N-01”, “Bontron N-04”, “Bontron N-07 ”,“ Bontron N-09 ”,“ Bontron N-11 ”(manufactured by Orient Chemical Co., Ltd.) and the like; triphenylmethane dyes containing tertiary amines as side chains, quaternary ammonium salt compounds such as“ Bontron P-51 "(manufactured by Orient Chemical Industry Co., Ltd.), cetyltrimethylammonium bromide," COPY CHARGE PX VP435 "(manufactured by Clariant), etc .; polyamine resin such as" AFP-B "(manufactured by Orient Chemical Industry Co., Ltd.), etc. Imidazole derivatives such as “PLZ-2001” and “PLZ-8001” (manufactured by Shikoku Kasei Kogyo Co., Ltd.); styrene-acrylic resins such as “FCA-701PT” (Fujikura Chemical) Etc., Ltd.) Co., Ltd., and the like.

Examples of negatively chargeable charge control agents include metal-containing azo dyes such as “Varifirst Black 3804”, “Bontron S-31”, “Bontron S-32”, “Bontron S-34”, “Bontron S-36” ( As described above, manufactured by Orient Chemical Co., Ltd.), “Eisenspiron Black TRH”, “T-77” (manufactured by Hodogaya Chemical Co., Ltd.), etc .; metal compounds of benzylic acid compounds such as “LR-147”, “ LR-297 "(manufactured by Nippon Carlit Co., Ltd.), etc .; metal compounds of salicylic acid compounds, such as" Bontron E-81 "," Bontron E-84 "," Bontron E-88 "," Bontron E-304 " (Above, manufactured by Orient Chemical Co., Ltd.), “TN-105” (manufactured by Hodogaya Chemical Co., Ltd.), etc .; copper phthalocyanine dyes; quaternary ammonium salts such as “COPY CHARGE NX VP434” (manufactured by Clariant), nitro Imidazole derivatives, etc. Machine metal compounds and the like.
Among charge control agents, negatively chargeable charge control agents are preferable, and metal compounds of salicylic acid compounds are more preferable.

  The content of the charge control agent is preferably 0.01 parts by mass or more, more preferably 0.2 parts by mass or more with respect to 100 parts by mass of the binder resin, from the viewpoint of suppressing fogging of the toner, and from the same viewpoint. The amount is preferably 10 parts by mass or less, more preferably 5 parts by mass or less, still more preferably 3 parts by mass or less, and still more preferably 2 parts by mass or less.

<Colorant>
The toner may contain a colorant.
As the colorant, all of dyes and pigments used as toner colorants can be used, such as carbon black, phthalocyanine blue, permanent brown FG, brilliant first scarlet, pigment green B, rhodamine-B base, Solvent Red 49, Solvent Red 146, Solvent Blue 35, Quinacridone, Carmine 6B, Disazo Yellow and the like can be used, and the toner may be either black toner or color toner.

  The content of the colorant is preferably 1 part by mass or more, more preferably 2 parts by mass or more, and preferably 40 parts by mass with respect to 100 parts by mass of the binder resin from the viewpoint of improving the image density of the toner. Part or less, more preferably 20 parts by weight or less, still more preferably 10 parts by weight or less.

<Release agent>
The toner may contain a release agent.
Examples of mold release agents include polypropylene wax, polyethylene wax, polypropylene polyethylene copolymer wax; hydrocarbon wax such as microcrystalline wax, paraffin wax, Fischer-Tropsch wax, sazol wax, or oxides thereof; carnauba wax, montan Examples thereof include waxes or ester waxes such as deoxidized waxes and fatty acid ester waxes; fatty acid amides, fatty acids, higher alcohols, fatty acid metal salts and the like, and these can be used alone or in combination.

  The melting point of the release agent is preferably 60 ° C. or higher, more preferably 70 ° C. or higher, from the viewpoint of toner transferability, and preferably 160 ° C. or lower, from the viewpoint of improving the low-temperature fixability of the toner. Preferably it is 150 degrees C or less, More preferably, it is 140 degrees C or less.

  The content of the release agent is preferably 0.5 parts by mass or more, more preferably 1.0 part by mass or more, and further preferably 100 parts by mass with respect to 100 parts by mass of the binder resin, from the viewpoint of improvement in low-temperature fixability of the toner and offset resistance. Is 1.5 parts by mass or more, and from the viewpoint of dispersibility in the binder resin, it is preferably 10 parts by mass or less, more preferably 8 parts by mass or less, and still more preferably 7 parts by mass or less.

  In addition, additives such as magnetic powder, fluidity improvers, conductivity modifiers, reinforcing fillers such as fibrous substances, antioxidants, anti-aging agents, and cleanability improvers are appropriately used as toner raw materials. It may be.

The volume median particle size (D ₅₀ ) of the toner is preferably 2 μm or more, more preferably 3 μm or more, more preferably 4 μm or more, and preferably 20 μm or less, more preferably 15 μm or less, more preferably 10 μm or less. It is.

[Method for producing toner for electrophotography]
As a toner production method,
(1) A method of producing a toner by melt-kneading a toner raw material mixture containing a binder resin containing the composition A, and pulverizing the obtained melt-kneaded product,
(2) Toner by obtaining toner particles by aggregating and fusing the binder resin particles in a toner raw material mixture containing a dispersion in which the binder resin containing the composition A is dispersed in an aqueous medium. How to manufacture,
(3) A method for producing a toner by, for example, obtaining toner particles by stirring a dispersion liquid in which a binder resin containing the composition A is dispersed in an aqueous medium and a toner raw material at high speed.
From the viewpoint of improving the productivity of the toner and the viewpoint of improving the fixing property of the toner, the melt kneading method (1) is preferable. Further, the toner may be obtained by the aggregation and fusion method (2). In addition, as long as it is in the range which does not impair the effect of this invention, in any process, you may further add a polyhydroxyamine compound.

  In the case of producing the toner by any of the above methods, the amount of the binder resin used in the toner is preferably 5% by mass or more, more preferably 30% by mass or more, more preferably 50% by mass or more, and more preferably. Is 70% by mass or more, more preferably 80% by mass or more, more preferably 90% by mass or more, and 100% by mass or less, preferably 99% by mass or less.

(1) A method for producing a toner by melt kneading a toner raw material mixture containing the composition A, and pulverizing the obtained melt kneaded product (melt kneading method)
The method (1) preferably includes the following step 1 and step 2.
Step 1: Step of melt-kneading a toner raw material mixture containing a binder resin containing the composition A Step 2: Step of pulverizing and classifying the melt-kneaded product obtained in Step 1

  In step 1, it is more preferable to melt knead the colorant, and it is preferable to melt and knead other additives such as other resins, release agents, and charge control agents. In addition, as long as it does not impair the effect of this invention, you may further add a polyhydroxyamine compound in the case of melt-kneading.

  The melt-kneading can be performed using a known kneader such as a closed kneader, a single- or twin-screw extruder, and an open roll kneader. From the viewpoint of efficiently and highly dispersing additives such as a colorant, a charge control agent, and a release agent in a toner without repeating kneading or using a dispersion aid, an open roll kneader is used. The open roll type kneader is preferably provided with a supply port and a kneaded product discharge port along the axial direction of the roll.

  The toner raw materials such as the binder resin, the colorant, the charge control agent, and the release agent are preferably mixed in advance with a mixer such as a Henschel mixer or a ball mill and then supplied to the kneader.

  The open roll type kneader refers to a kneading section that is not sealed and released, and can easily dissipate the kneading heat generated during kneading. The continuous open roll type kneader is preferably a kneader equipped with at least two rolls, and the continuous open roll type kneader used in the present invention comprises two rolls having different peripheral speeds, That is, it is a kneader equipped with two rolls, a high rotation side roll with a high peripheral speed and a low rotation side roll with a low peripheral speed. In the present invention, the viewpoint of improving the dispersibility in the toner of additives such as a colorant, a charge control agent, and a release agent, a viewpoint of reducing mechanical force during melt-kneading and suppressing heat generation, and melt-kneading. From the viewpoint of reducing the temperature at the time, the high rotation side roll is preferably a heating roll, and the low rotation side roll is preferably a cooling roll.

The temperature of the roll can be adjusted by, for example, the temperature of the heat medium passed through the roll.
The heating temperature in the roll is preferably 20 ° C. or higher, more preferably 30 ° C. or higher, and preferably 150 ° C. or lower, more preferably 130 ° C. or lower, from the viewpoint of the dispersibility of the additive.

  The roll rotation peripheral speed is the same from the viewpoint of improving the dispersibility of additives such as colorants, charge control agents, and release agents in the toner, reducing the mechanical force during melt-kneading, and suppressing heat generation. In the case of a directional rotating twin screw extruder, it is preferably 5 m / min or more, more preferably 10 m / min or more, more preferably 20 m / min or more, and preferably 50 m / min or less, more preferably 40 m / min or less. More preferably, it is 30 m / min or less.

  Peripheral speed of the high rotation side roll is to improve the dispersibility in the toner of additives such as a release agent, a colorant, and a charge control agent, to reduce mechanical force during melt kneading, and to suppress heat generation From the viewpoint of improving the durability and low-temperature fixability of the toner, it is preferably 2 m / min or more, more preferably 10 m / min or more, still more preferably 25 m / min or more, and preferably 100 m / min or less. More preferably, it is 75 m / min or less, More preferably, it is 50 m / min or less.

  From the same viewpoint, the peripheral speed of the low-rotation side roll is preferably 1 m / min or more, more preferably 5 m / min or more, still more preferably 15 m / min or more, and preferably 90 m / min or less, more preferably Is 60 m / min or less, more preferably 30 m / min or less. Further, the ratio of the peripheral speeds of the two rolls (low rotation side roll / high rotation side roll) is preferably 1/10 to 9/10, and more preferably 3/10 to 8/10.

  The structure, size, material, etc. of the roll are not particularly limited, and the roll surface may be any of smooth, corrugated, uneven, etc., but the kneading share is increased, and the colorant, charge control agent, mold release From the viewpoint of improving the dispersibility of the additive such as an agent in the toner, reducing the mechanical force during melt-kneading, and suppressing heat generation, it is preferable to have a plurality of spiral grooves on the surface of each roll. .

  The melt-kneaded product obtained in step 1 is cooled to such an extent that it can be crushed, and then subjected to subsequent step 2.

  In step 2, the melt-kneaded product obtained in step 1 is pulverized and classified.

  The pulverization process may be performed in multiple stages. For example, a resin kneaded product obtained by curing a melt-kneaded product may be coarsely pulverized to about 1 to 5 mm and further pulverized to a desired particle size.

  The pulverizer used in the pulverization step is not particularly limited, and examples of the pulverizer suitably used for coarse pulverization include a hammer mill, an atomizer, and a rotplex. Further, examples of the pulverizer suitably used for fine pulverization include a fluidized bed jet mill, a collision plate jet mill, and a rotary mechanical mill. From the viewpoint of pulverization efficiency, it is preferable to use a fluidized bed jet mill and a collision plate jet mill, and more preferably a fluidized bed jet mill.

  Examples of the classifier used in the classification process include a rotor classifier, an airflow classifier, an inertia classifier, and a sieve classifier. In the classification step, the pulverized product that has been removed due to insufficient pulverization may be subjected to the pulverization step again, and the pulverization step and the classification step may be repeated as necessary.

The method (1) may further include the following step 3.
Step 3: Step of mixing powder obtained by classification and external additive As external additive, hydrophobic silica, titanium oxide fine particles, alumina fine particles, cerium oxide fine particles, inorganic fine particles such as carbon black, polycarbonate, polymethacryl Examples thereof include polymer fine particles such as methyl acid and silicone resin, and among these, hydrophobic silica is preferable.
When the toner particles are subjected to surface treatment using an external additive, the amount of the external additive added is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, and still more preferably 100 parts by mass of the toner particles. 1.0 part by mass or more, and preferably 5 parts by mass or less, more preferably 4 parts by mass or less, and further preferably 3 parts by mass or less.

  About each physical-property value of resin etc., it measured and evaluated by the following method.

[Acid value and hydroxyl value of resin]
The acid value and hydroxyl value of the resin were measured based on the method of JIS K0070. However, only the measurement solvent was changed from the mixed solvent of ethanol and ether specified in JIS K0070 to the mixed solvent of acetone and toluene (acetone: toluene = 1: 1 (volume ratio)).

[Softening point and glass transition temperature of resin]
(1) Softening point Using a flow tester “CFT-500D” (manufactured by Shimadzu Corporation), a 1 g sample was heated at a heating rate of 6 ° C./min. Extruded from a 1 mm long nozzle. The amount of plunger drop of the flow tester was plotted against the temperature, and the temperature at which half of the sample flowed out was taken as the softening point.
(2) Maximum endothermic peak temperature Using a differential scanning calorimeter “Q-100” (manufactured by TA Instruments Japan Co., Ltd.), it was cooled from room temperature (20 ° C.) to 0 ° C. at a rate of temperature decrease of 10 ° C./min. The sample was maintained at the same temperature for 1 minute, and then measured while raising the temperature to 180 ° C. at a rate of temperature increase of 10 ° C./min. Of the endothermic peaks observed, the peak temperature on the highest temperature side was defined as the highest endothermic peak temperature.
(3) Glass transition temperature Using a differential scanning calorimeter “Q-100” (manufactured by TA Instruments Japan Co., Ltd.), 0.01 to 0.02 g of a sample is weighed into an aluminum pan and heated to 200 ° C. The temperature was cooled to 0 ° C. at a rate of temperature decrease of 10 ° C./min. Next, the measurement was performed while increasing the temperature to 150 ° C. at a temperature increase rate of 10 ° C./min. The glass transition temperature was defined as the temperature at the intersection of the base line extension below the maximum peak temperature of endotherm and the tangent line indicating the maximum slope from the peak rising portion to the peak apex.

[Number average molecular weight, weight average molecular weight of resin]
The molecular weight distribution was measured by the gel permeation chromatography (GPC) method according to the following method, and the number average molecular weight Mn and the weight average molecular weight Mw of the resin were determined.
(1) Preparation of sample solution The resin was dissolved in chloroform so that the concentration was 0.5 g / 100 mL. Next, this solution was filtered using a fluororesin filter having a pore size of 2 μm (trade name “FP-200”, manufactured by Sumitomo Electric Industries, Ltd.) to remove insoluble components to obtain a sample solution.
(2) Molecular weight measurement Using the following apparatus, chloroform was flowed as an eluent at a flow rate of 1 mL per minute, and the column was stabilized in a constant temperature bath at 40 ° C. Measurement was performed by injecting 100 μL of the sample solution. The molecular weight of the sample was calculated based on a calibration curve prepared in advance. In the calibration curve at this time, several types of monodispersed polystyrenes with known molecular weights (manufactured by Tosoh Corporation; 2.63 × 10 ³ , 2.06 × 10 ⁴ , 1.02 × 10 ⁵ , GL Sciences Corporation; 2.10 × 10 ³ , 7.00) × 10 ³ , 5.04 × 10 ⁴ ) prepared as standard samples were used.
Measuring device: "CO-8010" (manufactured by Tosoh Corporation)
Analytical column: “GMH _XL ” + “G3000H _XL ” (both manufactured by Tosoh Corporation)

[Volume-Medium Particle Size of Toner (D ₅₀ )]
The volume median particle size (D ₅₀ ) of the toner was measured by the following method.
Measuring machine: Coulter Multisizer II (Beckman Coulter, Inc.)
Aperture diameter: 50μm
Analysis software: Coulter Multisizer AccuComp version 1.19 (Beckman Coulter)
Electrolyte: Isoton II (Beckman Coulter, Inc.)
Dispersion: Emulgen 109P (manufactured by Kao Corporation, polyoxyethylene lauryl ether, HLB: 13.6) 5% electrolyte Dispersion condition: Add 10 mg of measurement sample to 5 ml of dispersion, and disperse for 1 minute with an ultrasonic disperser. Thereafter, 25 ml of an electrolytic solution is added, and further dispersed with an ultrasonic disperser for 1 minute.
Measurement conditions: Add 100 ml of electrolyte and dispersion in a beaker, measure 30,000 particles at a concentration that can measure the particle size of 30,000 particles in 20 seconds, and determine the volume-median particle size ( determine the D _50).

[Low temperature fixability]
The obtained toner was mounted on a copying machine “AR-505” (manufactured by Sharp Corporation), and an unfixed image (2 cm × 12 cm) having a toner adhesion amount of 0.7 mg / cm ² was obtained. Using a fixing machine (fixing speed 200mm / sec) that has been improved so that the fixing machine of the copier "AR-505" (manufactured by Sharp Corporation) can be fixed off-line, the fixing temperature is changed from 90 ° C to 240 ° C to 5 ° C. The fixing test was performed at each fixing temperature while gradually increasing. “CopyBond SF-70NA” (manufactured by Sharp Corporation, 75 g / m ² ) was used as the fixing paper.
The minimum fixing temperature is a sand eraser with a bottom of 15 mm x 7.5 mm with a load of 500 g. The image fixed through the fixing machine is rubbed 5 times, and the optical reflection density before and after rubbing is measured by the reflection densitometer “RD-915” (Macbeth The temperature of the fixing roller in which the ratio between the two (after rubbing / before rubbing) first exceeds 70% is defined as the minimum fixing temperature. The lower the minimum fixing temperature, the better the low-temperature fixing property.

[Developability]
70r / min (equivalent to 36 sheets / min) under the condition of temperature 30 ° C and relative humidity 65% by mounting toner on the ID cartridge of the non-magnetic one-component developer “OKI MICROLINE 5400” (Oki Data Co., Ltd.) The test was carried out by rotating and developing the surface of the developing roll to visually observe the occurrence of uneven stripes, and the time until the occurrence of uneven stripes was measured. The longer the time until streaks occur, the better the developability. The uneven stripe means a state in which the amount of toner adhering to the developing roll varies, and the occurrence of uneven stripe causes the image density to vary during printing.
(Evaluation criteria)
A: Time until the occurrence of streak is 1 week or more B: Time until the occurrence of streak is 3 days or more, less than 1 week C: Time until the streak occurs is 1 day or more, less than 3 days D: Time to occur is 12 hours or more, less than 1 day E: Time to cause streak is less than 12 hours

[Production of resin]
Production Examples 1-8, 10-12 [Resin H-1 to H-8, H-10 to H-12]
The raw material monomer of polyester resin other than adipic acid and trimellitic anhydride shown in Table 1 and titanium diisopropylate bistriethanolamate are placed, and equipped with a thermometer, a stainless steel stirring rod, a flow-down condenser, a dehydration tube, and a nitrogen introduction tube In the 10 liter four-necked flask, polycondensation was performed at 235 ° C. for 6 hours in a mantle heater in a nitrogen atmosphere, and then cooled to 200 ° C. Then, after adding adipic acid and trimellitic anhydride, the temperature was raised to 210 ° C., a polycondensation reaction was performed, and the reaction was continued until the reaction rate reached the value shown in the table. Amine compound (2-amino-2-hydroxymethyl-1,3-propanediol, boiling point 219 ° C. (0.1 MPa)) was added and maintained for the temperature and time shown in the table. Amorphous polyester (resin H-1 To H-8, H-10 to H-12).

Production Example 9 [H-9]
Raw materials other than adipic acid and trimellitic anhydride shown in Table 1 are put into a 10-liter four-necked flask equipped with a dehydration tube equipped with a nitrogen introduction tube, a stirrer and a thermocouple, and are heated at 160 ° C. in a nitrogen atmosphere. The temperature was raised to. Thereafter, a mixture of acrylic acid (both reactive monomers), a raw material monomer of vinyl resin, and a polymerization initiator was added dropwise over 1 hour using a dropping funnel. After the dropwise addition, after aging the addition polymerization reaction for 1 hour while maintaining at 160 ° C, the temperature was raised to 200 ° C, and after adding 2 g of the catalyst and gallic acid shown in the table, a polycondensation reaction was performed at 235 ° C for 6 hours, Furthermore, reaction was performed at 235 degreeC and 8.0 kPa for 1 hour. After cooling to 180 ° C, adipic acid and trimellitic anhydride are added, the temperature is raised from 180 ° C to 210 ° C at 10 ° C / hour, and the reaction is carried out at 210 ° C and 10 kPa to the reaction rate shown in the table The polyhydroxyamine compound was charged at the addition temperature shown in the table, and the temperature and time shown in the table were maintained for an amorphous composite resin.

In Table 1, each annotation has the following meaning:
* 1 Indicates the number of moles when the total amount of alcohol components is 100 moles.
* 2 Indicates parts by mass when the total amount of styrene resin segment raw material monomers is 100 parts by mass.
* 3 Indicates mass% relative to the total amount of styrene resin segment raw material monomer.
* 4 Indicates the amount of polyester resin added to 100 parts by mass of the raw material monomers.
* 5 Indicates parts by mass relative to 100 parts by mass of the total amount of raw material monomers for the polyester resin.
* 6 BPA-PO: Polyoxypropylene (2.2) adduct of 2,2-bis (4-hydroxyphenyl) propane
* 7 BPA-EO: 2,2-bis (4-hydroxyphenyl) propane polyoxyethylene (2.2) adduct

[Manufacture of toner for electrophotography]
Examples and Comparative Examples 100 parts by weight of binder resin mixed with the resins shown in Table 2, 5 parts by weight of coloring agent “ECB-301” (manufactured by Dainichi Seika Kogyo Co., Ltd., CI Pigment Blue 15: 3), negative chargeability Charge control agent “LR-147” (manufactured by Nippon Carlit Co., Ltd.) and 1 part by weight of release agent “NP-105” (manufactured by Mitsui Chemicals, polypropylene wax, melting point: 140 ° C.) in a Henschel mixer After stirring well, the mixture was melt kneaded using a co-rotating twin screw extruder having a total length of 1560 mm, a screw diameter of 42 mm, and a barrel inner diameter of 43 mm. The rotation speed of the roll was 200 r / min, the heating temperature in the roll was 120 ° C., the feed rate of the mixture was 10 kg / hr, and the average residence time was about 18 seconds. The obtained kneaded product was rolled and cooled with a cooling roller, and then a powder with a volume-median particle size (D ₅₀ ) of 6.5 μm was obtained with a jet mill.

To 100 parts by mass of the obtained powder, 1.0 part by mass of external additive “Aerosil R-972” (hydrophobic silica, manufactured by Nippon Aerosil Co., Ltd., average particle size: 16 nm) and “SI-Y” (hydrophobic silica, Nippon Aerosil Co., Ltd., average particle size: 40 nm) 1.0 part by mass was added and mixed with a Henschel mixer at 3600 r / min for 5 minutes to perform external additive treatment, and the volume-median particle size (D ₅₀ ) 6.5 A μm toner was obtained. Evaluation was performed by the above-described method, and the results are shown in the table.

Claims (8)

Containing a composition comprising a resin having at least a polyester moiety;
The composition is obtained by a method including a step of obtaining a polyester site by polycondensation of an alcohol component and a carboxylic acid component,
From the time when the reaction rate of the alcohol component in the polycondensation is 70% or more, the polyhydroxy compound represented by the following formula (1) of 0.001 to 5 parts by mass with respect to 100 parts by mass in total of all monomer components An electrophotographic toner to which an amine compound is added.

[Wherein, R ¹ represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a hydroxyalkyl group having 1 to 5 carbon atoms, and R ² represents a hydrogen atom, an alkyl having 1 to 6 carbon atoms. Group or a hydroxyalkyl group having 1 to 5 carbon atoms, and R ³ and R ⁴ represent an alkanediyl group having 1 to 5 carbon atoms. R ³ and R ⁴ may be the same or different. ]   The polyhydroxyamine compound is 2-amino-1,3-propanediol, 2-amino-2-methyl-1,3-propanediol, 2-amino-2-ethyl-1,3-propanediol, 2- 2. The electrophotographic toner according to claim 1, wherein the toner is one or more selected from amino-2-hydroxymethyl-1,3-propanediol and 2-amino-2-hydroxyethyl-1,3-propanediol.   The toner for electrophotography according to claim 1 or 2, wherein the polyhydroxyamine compound is 2-amino-2-hydroxymethyl-1,3-propanediol.   The toner for electrophotography according to any one of claims 1 to 3, wherein a temperature at which the polyhydroxyamine compound is added is 130 ° C or higher and 20 ° C or lower than a boiling point of the polyhydroxyamine compound.   5. The temperature is maintained at 130 ° C. or higher and 20 ° C. or lower than the boiling point of the polyhydroxyamine compound for 0.5 hour to 3.0 hour after the total amount of the polyhydroxyamine compound is added. The toner for electrophotography described in 1.   The electrophotographic toner according to claim 1, wherein a reaction rate of the alcohol component is 85% or more. Containing a composition comprising a resin having at least a polyester moiety;
The composition is obtained by a method including a step of obtaining a polyester site by polycondensation of an alcohol component and a carboxylic acid component,
From the time when the reaction rate of the alcohol component in the polycondensation is 70% or more, the polyhydroxy compound represented by the following formula (1) of 0.001 to 5 parts by mass with respect to 100 parts by mass in total of all monomer components A binder resin composition for electrophotographic toner, to which an amine compound is added.

[Wherein, R ¹ represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a hydroxyalkyl group having 1 to 5 carbon atoms, and R ² represents a hydrogen atom, an alkyl having 1 to 6 carbon atoms. Group or a hydroxyalkyl group having 1 to 5 carbon atoms, and R ³ and R ⁴ represent an alkanediyl group having 1 to 5 carbon atoms. R ³ and R ⁴ may be the same or different. ] Including a step of obtaining a polyester moiety by polycondensation of an alcohol component and a carboxylic acid component,
From the time when the reaction rate of the alcohol component in the polycondensation is 70% or more, the polyhydroxy compound represented by the following formula (1) of 0.001 to 5 parts by mass with respect to 100 parts by mass in total of all monomer components A method for producing an electrophotographic toner, comprising adding an amine compound.

[Wherein, R ¹ represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a hydroxyalkyl group having 1 to 5 carbon atoms, and R ² represents a hydrogen atom, an alkyl having 1 to 6 carbon atoms. Group or a hydroxyalkyl group having 1 to 5 carbon atoms, and R ³ and R ⁴ represent an alkanediyl group having 1 to 5 carbon atoms. R ³ and R ⁴ may be the same or different. ]