JP6777283B2 - Manufacturing method of binder resin composition for toner for electrophotographic - Google Patents

Description

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

In recent years, with the speeding up and energy saving of printers and copiers, there is an increasing need for toner that can meet these demands.
Patent Document 1 describes a method for producing a binder component of an electrophotographic toner. The document satisfies the requirements of fixing at a lower temperature, not offsetting even at a higher temperature, being able to form a stable image even when environmental conditions such as humidity fluctuate greatly, and having an excellent rise in charging. Is an issue. Patent Document 1 describes a method for producing a carbodiimide-modified polyester resin, which comprises reacting a polyester resin (A) with a carbodiimide group-containing compound (B).

Japanese Unexamined Patent Publication No. 2000-336163

With the energy saving of printers and copiers, low temperature fixability is required so that toner can be fixed on print media even at low temperatures. However, with the electrophotographic toner described in Patent Document 1, further improvement is desired from the viewpoint of developability in which filming occurs in the developing roller when trying to obtain an electrophotographic toner having excellent low-temperature fixability. It is rare.
An object of the present invention is to provide an electrophotographic toner having excellent low-temperature fixability and excellent developability, a binder resin composition for obtaining the electrophotographic toner, and a method for producing an electrophotographic toner. And.

By adding a predetermined amount of a specific polyhydroxyamine compound at the time of polycondensation of the alcohol component and the carboxylic acid component from the time when a predetermined reaction rate is reached, 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 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, the polyhydroxy represented by the following formula (1) 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 the monomer components. Electrophotographic toner to which an amine compound is added.

[In the formula, 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 is a hydrogen atom, an alkyl having 1 to 6 carbon atoms. It represents a group or a hydroxyalkyl group having 1 or more and 5 or less carbon atoms, and R ³ and R ⁴ represent an alkanediyl group having 1 or more and 5 or less 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 moiety by polycondensation of an alcohol component and a carboxylic acid component.
Polyhydroxyamine represented by the formula (1) of 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 time when the reaction rate of the alcohol component is 70% or more in the polycondensation. 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.
Polyhydroxyamine represented by the formula (1) of 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 time when the reaction rate of the alcohol component is 70% or more in the polycondensation. A method for producing an electrophotographic toner to which a compound is added.

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 for obtaining the electrophotographic toner, and a method for producing an electrophotographic toner. it can.

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

[In the formula, 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 is a hydrogen atom, an alkyl having 1 to 6 carbon atoms. It represents a group or a hydroxyalkyl group having 1 or more and 5 or less carbon atoms, and R ³ and R ⁴ represent an alkanediyl group having 1 or more and 5 or less 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 can be considered 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 polycondensation of the resin. The polyhydroxyamine compound has a high polarity and preferentially hydrogen-bonds with a particularly low molecular weight component in the polyester resin to reduce the motility of the low molecular weight component, and as a result, it is generated due to the low molecular weight component of the polyester resin. It is probable that the filming on the fixing roller was improved and the developability was improved. By adding the polyhydroxyamine compound from the time when the polycondensation of the polyester progresses and the reaction rate of the alcohol component is 70% or more, the polyhydroxyamine compound remains in a high dispersion and moderately, so that it remains after the reaction is completed. It is considered that the low molecular weight component can be easily supplemented by hydrogen bonding, and the above effect can be remarkably obtained.

[Bundling resin]
<Composition A containing resin A>
The toner of the present invention contains a composition A containing at least a resin A having a polyester moiety as a binder resin.
The 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, and is obtained by the polycondensation. 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 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 certain 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 calculated by the following 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] x 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, and further, from the viewpoint of obtaining a toner having excellent low-temperature fixability and excellent developability. It is preferably 85% or more, more preferably 90% or more, and 100% or less, preferably 95% or less.

The amount of the polyhydroxyamine compound added is 0.001 part by mass or more and 5 part by mass or less with respect to 100 parts by mass in total of all the 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 part by mass or more, more preferably 0.03 part by mass or more, more preferably 0.1 part by mass or more, more preferably 0.3 part by mass or more, and the developability of the toner is improved. From the viewpoint of improvement, it is preferably 4 parts by mass or less, more preferably 3 parts by mass or less, and further preferably 1 part by mass or less.

The polyhydroxyamine compound may be added as a solution. In that case, as the solvent used, a known solvent such as water, alcohol, or 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, still more preferably 0.2 parts by mass / min or more, based on 100 parts by mass of all the monomer components. Yes, and preferably 1.0 part by mass or less, more preferably 0.5 part by mass or less, still more preferably 0.3 part by mass or less.

The temperature at which the polyhydroxyamine compound is added is preferably 130 ° C. or higher, more preferably 150 ° C. or higher, still more preferably 180 ° C. or higher, and polyhydroxyl 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 even more preferably 35 ° C. lower than the boiling point of the amine compound.
The temperature of addition means the temperature in the polycondensation reaction system. The boiling point of the polyhydroxyamine compound means the boiling point of the added polyhydroxyamine compound at normal pressure (0.1 MPa).

After adding the entire amount of the polyhydroxyamine compound, it is preferable to maintain the temperature at 130 ° C. or higher and 20 ° C. or lower than the boiling point of the polyhydroxyamine compound.
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, from the viewpoint of improving the low temperature fixability and developability of the toner. , More preferably 30 ° C. lower temperature or lower, still more preferably 35 ° C. lower temperature 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.

[In the formula, 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 is a hydrogen atom, an alkyl having 1 to 6 carbon atoms. It represents a group or a hydroxyalkyl group having 1 or more and 5 or less carbon atoms, and R ³ and R ⁴ represent an alkanediyl group having 1 or more and 5 or less 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, still more preferably 1 from the viewpoint of improving the low temperature fixability and developability of the toner.
The alkyl group of R ¹ may be either a straight chain or a branched chain, and examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, various butyl groups, and various pentyl groups, and methyl is preferable. It is at least one selected from a group and an ethyl group, and 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, 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 a hydroxymethyl group, a 2-hydroxyethyl group, a 2-hydroxypropyl group, a 3-hydroxypropyl group, a 2-hydroxybutyl group, a 3-hydroxybutyl group, a 4-hydroxybutyl group and the like. It is preferably 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 the groups, more preferably a hydroxymethyl group.

The alkyl group of R ² preferably has 3 or less carbon atoms, more preferably 2 or less carbon atoms, and preferably 1 or more carbon atoms.
The alkyl group of R ² may be linear, branched or cyclic, and may be, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, various butyl groups, various pentyl groups, or various hexyl groups. Examples include a group, a cyclopentyl group, a cyclohexyl group and the like.
The hydroxyalkyl group of R ² preferably has 3 or less carbon atoms, more preferably 2 or less carbon atoms, and preferably 1 or more carbon atoms. Examples of the hydroxyalkyl group of R ² include those similar to R ¹ described above.
Among these, R ² is preferably a hydrogen atom, an alkyl group having 1 or more and 3 or less carbon atoms, or a hydroxyalkyl group having 1 or more and 3 or less carbon atoms, and 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, and 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 can be mentioned.
Among these, 2-amino-2-hydroxymethyl-1,3-propanediol and 2-amino-2-hydroxyethyl-1,3 are preferable from the viewpoint of improving the low-temperature fixability and developability of the toner. -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.
As the above polyhydroxyamine compound, one kind or two or more kinds can be used. The polyhydroxyamine compound can be produced 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 preferably at least one selected from polyester and a composite resin having a polyester segment and a styrene resin segment.

〔polyester〕
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, and more preferably the formula (I) :.

[In the formula, RO and OR are oxyalkylene groups, R is at least one selected from an ethylene group and a propylene group, and x and y indicate the average number of moles of alkylene oxide added, which are positive numbers, respectively. , 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. ] Is an alkylene oxide adduct of bisphenol A.

Examples of the alkylene oxide adduct of bisphenol A represented by the formula (I) include a propylene oxide adduct of 2,2-bis (4-hydroxyphenyl) propane and ethylene of 2,2-bis (4-hydroxyphenyl) propane. Examples include 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, still more preferably 95 mol% or more in the alcohol component. 100 mol%.

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

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

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

Examples of the aromatic dicarboxylic acid include phthalic acid, isophthalic acid, and terephthalic acid; anhydrides of those acids or alkyl (1 to 3 carbon atoms) esters of those acids, and among these, terephthalic acid or isophthalic acid. Acids are preferred, and terephthalic acids are 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 a reaction to generate an acid, and an alkyl ester having an alkyl group having 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, further preferably 50 mol% or more, and 100 mol% or less, preferably 100 mol% or less. It is 95 mol% or less.

Examples of the aliphatic dicarboxylic acid 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, and octyl succinic acid. Alternatively, aliphatic dicarboxylic acids such as succinic acid substituted with an alkenyl group having 2 to 20 carbon atoms; anhydrides of those acids or alkyl (1 to 3 carbon atoms) esters of those acids can be mentioned. These can be used alone or in combination of two or more. Of these, adipic acid is preferred.

The content of the aliphatic dicarboxylic acid is preferably 5 mol% or more, more preferably 8 mol% or more, and improves the developability of the toner in the carboxylic acid component from the viewpoint of improving the low temperature fixability of the toner. From the viewpoint 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.

Further, the carboxylic acid component preferably contains a carboxylic acid having a valence of 3 or more from the viewpoint of productivity.

As the trivalent or higher carboxylic acid, a trivalent carboxylic acid is preferable, and 1,2,4-benzenetricarboxylic acid (trimellitic acid), 2,5,7-naphthalenetricarboxylic acid, pyromellitic acid or their acid anhydrides are preferable. Examples thereof include lower alkyl (1 to 3 carbon atoms) esters, and among these, trimellitic acid or an acid anhydride thereof is preferable.

From the viewpoint of productivity, the content of carboxylic acid having a valence of 3 or more, preferably the content of trimellitic acid, is preferably 3 mol% or more, more preferably 5 mol% or more, still more preferably 8 among the carboxylic acid components. 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, still more preferably 20 mol% or less. is there.

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 adjusting the molecular weight.

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

The polyhydroxyamine compound is added in the polycondensation of the alcohol component and the carboxylic acid component. The conditions for addition are as described above.
The polycondensation of the alcohol component and the carboxylic acid component is carried out in, for example, in an inert gas atmosphere, in the presence of an esterification catalyst, a polymerization inhibitor, etc., as described above, at 130 ° C. or higher. 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 diisopropyrate bistriethanolamite. Examples of the esterification co-catalyst 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 mass or more, more preferably 0.1 parts by mass or more, and preferably 1 with respect to 100 parts by mass of the total amount of the polyhydroxyamine compound, the alcohol component, and the carboxylic acid component. By mass or less, more preferably 0.6 parts by mass or less. The amount of the esterification co-catalyst used is preferably 0.001 part by mass or more, more preferably 0.01 part by mass or more, and preferably 0.01 part by mass or more, based on 100 parts by mass of the total amount of the polyhydroxyamine compound, the alcohol component, and the carboxylic acid component. It is 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 the same polyester as the above-mentioned polyester is preferable as an example.

(Styrene resin segment)
The styrene-based resin segment is made of a styrene-based resin, and the styrene-based resin is preferably obtained by addition polymerization of a raw material monomer containing a styrene compound.
As the styrene compound, at least styrene or a styrene derivative such as α-methylstyrene or vinyltoluene (hereinafter, styrene and the styrene derivative 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, still more preferably 65% by mass or more, and the toner in the raw material monomer of the styrene resin, from the viewpoint of durability. From the viewpoint of improving low-temperature fixability, it is preferably 95% by mass or less, more preferably 90% by mass or less, and further preferably 80% by mass or less.

Examples of the raw material monomer of the styrene resin used other than the styrene compound include (meth) acrylic acid alkyl ester; 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-vinylpyrrolidone and the like N-vinyl compounds and the like.

Two or more kinds of raw material monomers of the styrene resin used other than the styrene compound can be used. In addition, in this specification, "(meth) acrylic acid" means at least one selected from acrylic acid and methacrylic acid.

Among the raw material monomers of the styrene resin used other than the styrene compound, the (meth) acrylic acid alkyl ester is preferable from the viewpoint of improving the low temperature fixability of the toner. From the above viewpoint, the number of carbon atoms 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, and more preferably 7 or more. Then, it is preferably 22 or less, more preferably 18 or less, still more preferably 12 or less, still more preferably 8 or less. The carbon number of the alkyl ester refers to the carbon number derived from the alcohol component constituting the ester.

Specific examples of the (meth) acrylic acid alkyl ester include methyl (meth) acrylate, ethyl (meth) acrylate, (iso) propyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, and (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)" and "(iso)" mean that these prefixes are included both when they are present and when they are not, and these prefixes are present. If not, it indicates normal. Further, "(meth) acrylate" indicates that the case of both acrylate and methacrylate is included.

The content of the (meth) acrylic acid alkyl ester is preferably 5% by mass or more, more preferably 10% by mass or more, still more preferably 10% by mass or more, from the viewpoint of improving the low-temperature fixability of the toner in the raw material monomer of the styrene resin segment. It is 15% by mass or more, more preferably 20% by mass or more, and from the same viewpoint, preferably 50% by mass or less, more preferably 40% by mass or less, 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 styrene resin can be carried out by a conventional method in the presence of, for example, a polymerization initiator such as dicumyl peroxide, a cross-linking agent, etc., in the presence of an organic solvent or in the absence of a solvent. The temperature conditions are 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 and 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.

(Bi-reactive monomer)
From the viewpoint of improving the low-temperature fixability and developability of the toner, the composite resin contains, in addition to the raw material monomer of the polyester segment and the raw material monomer of the styrene resin segment, the raw material monomer of the polyester segment and the raw material monomer of the styrene resin segment. It is preferable that the composite resin is obtained by using a bireactive monomer that can react with any of them. Therefore, when the raw material monomer of the polyester segment and the raw material monomer of the styrene resin segment are polymerized to obtain a composite resin, the polycondensation reaction or the addition polymerization reaction is preferably carried out 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 a structural unit derived from both reactive monomers, and the polyester segment and the styrene resin segment are dispersed more finely and uniformly. It will be the one that was done.

That is, from the viewpoint of improving the low-temperature fixability and developability of the toner, the composite resin contains an alcohol component containing an alkylene oxide adduct of bisphenol A represented by the formula (i) (i) and an aromatic dicarboxylic acid. Both that can react with any of the raw material monomer of the polyester segment, the raw material monomer of the styrene resin segment, and the raw material monomer of the polyester segment and the raw material monomer of the styrene resin segment, which contain the carboxylic acid component contained therein. It is preferably a resin obtained by polymerizing a reactive monomer.

The bireactive monomer includes 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, preferably at least one selected from a hydroxyl group and a carboxy group in the molecule. A compound having one functional group, more preferably a carboxy group and an ethylenically unsaturated bond is preferable, and by using such a bireactive monomer, the dispersibility of the resin as the dispersed phase can be further improved. it can. The bireactive monomer is preferably at least one selected from acrylic acid, methacrylic acid, fumaric acid, maleic acid and maleic anhydride, but from the viewpoint of reactivity of polycondensation reaction and addition polymerization reaction, acrylic acid. , Methacrylic acid or fumaric acid is more preferable, and acrylic acid or methacrylic acid is further 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 and the like are not bireactive monomers but raw material monomers for polyester segments.

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

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. It is more preferably 75/25 or more, and from the viewpoint of improving the developability of the toner, it is preferably 95/5 or less, more preferably 90/10 or less, still more preferably 85/15 or less. In the above calculation, the mass of the polyester segment is the amount obtained by subtracting the amount of reaction water (calculated value) dehydrated by the polycondensation reaction from the mass of the raw material monomer of the polycondensation resin used, and both reactions. The amount of sex monomer is included in the amount of 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.
Even when the resin A is a composite resin, a polyhydroxyamine compound is added in the polycondensation of the alcohol component and the carboxylic acid component from the viewpoint of improving the low temperature fixability and developability of the toner, as shown in the above conditions. Will be done.

The softening point of the resin A is preferably 90 ° C. or higher, more preferably 95 ° C. or higher, still more preferably 100 ° C. or higher, and the low temperature fixability of the toner from the viewpoint of improving the low temperature fixability and developability of the toner. From the viewpoint of improving the temperature, the temperature 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, still more preferably 55 ° C. or higher, and low-temperature fixing of the toner, from the viewpoint of improving the low-temperature fixability and developability of the toner. From the viewpoint of improving the properties, the temperature is preferably 80 ° C. or lower, more preferably 75 ° C. or lower, more preferably 70 ° C. or lower, still more 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 20 mgKOH / g or less, from the viewpoint of improving the low temperature fixability and developability of the toner. It is 1 mgKOH / g or more, more preferably 5 mgKOH / g or more, and more preferably 10 mgKOH / g or more.

The hydroxyl value of the 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 25 mgKOH / g or less, from the viewpoint of improving the low temperature fixability and developability of the toner. It is 1 mgKOH / g or more, more preferably 8 mgKOH / g or more, and 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, still more 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 method for measuring the softening point, the glass transition temperature, the acid value, the hydroxyl value, and the number average molecular weight is as described in Examples. When two or more kinds of resins are contained, it is preferable that the weighted average values of the softening point, the glass transition temperature, the acid value, the hydroxyl value, and the number average molecular weight are in the above ranges.

The binder resin contained in the toner preferably contains other polyester.
Examples of other polyesters include polyesters obtained by polycondensing an alcohol component and a carboxylic acid component exemplified in the above-mentioned 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, further preferably 20% by mass or more, and 100% by mass or less, preferably 90% by mass. It is mass% or less, more preferably 80 mass% or less, still more preferably 70 mass% or less.

The toner binding 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-mentioned resins, the toner preferably contains a binder resin containing two kinds 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 lower, more preferably 160 ° C. or lower from the viewpoint of improving the low temperature fixability of the toner, and is preferably from the viewpoint of high temperature offset resistance. Is 110 ° C. or higher, more preferably 120 ° C. or higher, and 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 ° C or lower.

The difference between the softening points of 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, and from the viewpoint of improving high temperature offset resistance and low temperature fixability. It is preferably 60 ° C. or lower, more preferably 50 ° C. or lower, and more preferably 40 ° C. or lower.

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, and more, from the viewpoint of durability and productivity. It is preferably 60/40 or more, and is preferably 90/10 or less, more preferably 80/20 or less, still more preferably 75/25 or less, from the viewpoint of improving the low temperature fixability of the toner.

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

<Resin C>
Among the above-mentioned resins, the toner preferably further contains 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. Preferred examples of the aliphatic polyol compound and other preferable examples are the same as those described above.

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 70 ° C. or higher, more preferably 80 ° C. or higher.
The melting 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. It is more preferably 70 ° C. or higher, and 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, further preferably 3% by mass or more, and preferably 20% by mass or less, more preferably 15% by mass. It is mass% or less, more preferably 8 mass% or less.

Among the above, the binding resin is
Preferably, (i) the amorphous resin and the crystalline resin are contained, 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 (ii) 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 contained, 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, further 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 positive charge control agent or a negative charge control agent.
Positive charge control agents include niglosin dyes such as "niglosin base EX", "oil black BS", "oil black SO", "bontron N-01", "bontron N-04", and "bontron N-07". , "Bontron N-09", "Bontron N-11" (all manufactured by Orient Chemical Industry Co., Ltd.), etc .; Triphenylmethane dyes containing tertiary amines as side chains, quaternary ammonium salt compounds, for example, " Bontron P-51 "(manufactured by Orient Chemical Industry Co., Ltd.), cetyltrimethylammonium bromide," COPY CHARGE PX VP435 "(manufactured by Clariant), etc .; Imidazole derivatives such as "PLZ-2001" and "PLZ-8001" (manufactured by Shikoku Kasei Kogyo Co., Ltd.); styrene-acrylic resins such as "FCA-701PT" (manufactured by Fujikura Kasei Co., Ltd.) Be done.

Negative charge control agents include metal-containing azo dyes such as "Varifast Black 3804", "Bontron S-31", "Bontron S-32", "Bontron S-34", and "Bontron S-36" ( (Manufactured by Orient Chemical Industry Co., Ltd.), "Eisenspiron Black TRH", "T-77" (manufactured by Hodoya Chemical Industry Co., Ltd.), etc .; Metal compounds of benzylic acid compounds, for example, "LR-147", " LR-297 "(above, manufactured by Nippon Carlit Co., Ltd.); Metal compounds of salicylic acid compounds, for example," Bontron E-81 "," Bontron E-84 "," Bontron E-88 "," Bontron E-304 " (The above is manufactured by Orient Chemical Industry Co., Ltd.), "TN-105" (manufactured by Hodoya Chemical Industry Co., Ltd.), etc .; Copper phthalocyanine dye; Quadruple ammonium salt, for example, "COPY CHARGE NX VP434" (manufactured by Clariant), Nitro Imidazole derivatives and the like; organic metal compounds and the like can be mentioned.
Among the charge control agents, a negative charge control agent is preferable, and a metal compound of a salicylic acid compound is more preferable.

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

<Colorant>
The toner may contain a colorant.
As the colorant, all dyes, pigments, etc. used as colorants for toner can be used, and 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, disazoero, etc. 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. Parts or less, more preferably 20 parts by mass or less, still more preferably 10 parts by mass or less.

<Release agent>
The toner may contain a release agent.
As the release agent, polypropylene wax, polyethylene wax, polypropylene-polyethylene copolymer wax; hydrocarbon waxes such as microcrystallin wax, paraffin wax, Fishertropsh wax, and sazole wax or their oxides; carnauba wax, montane. Ester waxes such as waxes or their deoxidizing waxes and fatty acid ester waxes; fatty acid amides, fatty acids, higher alcohols, fatty acid metal salts and the like can be mentioned, and one or more of these can be used.

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, more preferably from the viewpoint of improving the low temperature fixability of the toner. It is preferably 150 ° C. or lower, more preferably 140 ° C. or lower.

The content of the release agent is preferably 0.5 parts by mass or more, more preferably 1.0 part by mass or more, still more preferably 1.0 part by mass or more, with respect to 100 parts by mass of the binder resin from the viewpoint of improving the low temperature fixability of the toner and the 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 further preferably 7 parts by mass or less.

Further, as the raw material of the toner, additives such as magnetic powder, fluidity improver, conductivity adjusting agent, reinforcing filler such as fibrous substance, antioxidant, antiaging agent, and cleaning property improving agent are appropriately used. 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. Is.

[Manufacturing method of toner for electrophotographic]
As a toner manufacturing method,
(1) A method for producing a toner by melt-kneading a raw material mixture for toner containing a binder resin containing composition A and pulverizing the obtained melt-kneaded product.
(2) Toner by aggregating and fusing the binder resin particles in a raw material mixture for toner containing a dispersion liquid in which the binder resin containing the composition A is dispersed in a water-soluble medium to obtain toner particles. How to manufacture,
(3) Examples thereof include a method of producing toner by obtaining toner particles by stirring a dispersion liquid in which a binder resin containing composition A is dispersed in a water-soluble medium and a raw material for toner at high speed.
The melt-kneading method of (1) is preferable from the viewpoint of improving the productivity of the toner and the fixability of the toner. Further, the toner may be obtained by the aggregation and fusion method of (2). The polyhydroxyamine compound may be further added in any of the steps as long as the effects of the present invention are not impaired.

In any of the above methods for producing the toner, 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 of melt-kneading a raw material mixture for toner containing composition A and pulverizing the obtained melt-kneaded product to produce a toner (melt-kneading method).
The method (1) preferably includes the following steps 1 and 2.
Step 1: Melt-kneading the toner raw material mixture containing the binder resin containing the composition A Step 2: The step of crushing and classifying the melt-kneaded product obtained in Step 1.

Further, in step 1, it is more preferable to melt-knead the colorant as well, and it is preferable to melt-knead the other additives such as the resin, the release agent, and the charge control agent together. In addition, a polyhydroxyamine compound may be further added at the time of melt-kneading as long as the effect of the present invention is not impaired.

The melt kneading can be carried out by using a known kneader such as a closed kneader, a single-screw or twin-screw extruder, or an open roll type kneader. From the viewpoint of efficiently and highly dispersing additives such as colorants, charge control agents, and mold release agents in the toner without repeating kneading and using a dispersion aid, an open roll type kneader is used. It is preferable to use the open roll type kneader, and it is preferable that the open roll type kneader is provided with a supply port and a kneaded product discharge port along the axial direction of the roll.

It is preferable that the toner raw materials such as the binder resin, the colorant, the charge control agent, and the release agent are 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 is one in which the kneading portion is not sealed and is open, and the kneading heat generated during kneading can be easily dissipated. Further, the continuous open roll type kneader is preferably a kneader having at least two rolls, and the continuous open roll type kneader used in the present invention has two rolls having different peripheral speeds. That is, it is a kneading machine provided with two rolls, a high rotation side roll having a high peripheral speed and a low rotation side roll having a low peripheral speed. In the present invention, from the viewpoint of improving the dispersibility of additives such as colorants, charge control agents, and mold release agents in toner, from the viewpoint of reducing mechanical force during melt-kneading and suppressing heat generation, and from the viewpoint of melt-kneading. From the viewpoint of reducing the temperature at the time, it is preferable that the high rotation side roll is a heating roll and the low rotation side roll is a cooling roll.

The temperature of the roll can be adjusted, for example, by the temperature of the heat medium passed through the inside of 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 mold release agents in toner, and reducing the mechanical force during melt-kneading and suppressing heat generation. In the case of a directional rotary 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 30 m / min or less.

The peripheral speed of the roll on the high rotation side is from the viewpoint of improving the dispersibility of additives such as mold release agent, colorant, and charge control agent in the toner, and from the viewpoint of reducing the mechanical force during melt kneading and suppressing 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, further preferably 25 m / min or more, and preferably 100 m / min or less. It is more preferably 75 m / min or less, and even more preferably 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, further 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. 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, 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 smooth, corrugated, uneven, etc., but the kneading share is increased, and the colorant, charge control agent, and mold release are used. From the viewpoint of improving the dispersibility of additives such as agents 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 a extent that it can be pulverized, and then subjected to the subsequent step 2.

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

The crushing step may be divided into a plurality of steps. For example, the resin kneaded product obtained by curing the melt-kneaded product may be roughly pulverized to about 1 to 5 mm and then finely pulverized to a desired particle size.

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

Examples of the classifying machine used in the classification process include a rotor type classifying machine, an air flow type classifying machine, an inertial type classifying machine, and a sieve type classifying machine. In the classification step, the pulverized product removed due to insufficient pulverization may be subjected to the pulverization step again, or 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 the classified powder and the external additive The external additive includes hydrophobic fine particles, titanium oxide fine particles, alumina fine particles, cerium oxide fine particles, carbon black and other inorganic fine particles, and polycarbonate and polymethacryl. Examples thereof include polymer fine particles such as methyl acid and silicone resin, and among these, hydrophobic silica is preferable.
When the surface treatment of the toner particles is performed using an external additive, the amount of the external additive added is preferably 0.1 part by mass or more, more preferably 0.5 part by mass or more, and further preferably 0.5 part by mass or more with respect to 100 parts by mass of the toner particles. It is 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.

Each physical property value of resin and the like was 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)).

[Resin softening point and glass transition temperature]
(1) Softening point Using a flow tester "CFT-500D" (manufactured by Shimadzu Corporation), a 1 g sample is heated at a heating rate of 6 ° C / min, and a load of 1.96 MPa is applied by a plunger to a diameter of 1 mm. , 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 used as the softening point.
(2) Maximum peak temperature of endothermic cooling using a differential scanning calorimeter "Q-100" (manufactured by TA Instruments Japan Co., Ltd.) from room temperature (20 ° C) to 0 ° C at a temperature lowering rate of 10 ° C / min. The sample was maintained at the same temperature for 1 minute, and then the measurement was performed while raising the temperature to 180 ° C. at a heating rate of 10 ° C./min. Among the observed endothermic peaks, the temperature of the peak on the highest temperature side was defined as the maximum endothermic temperature.
(3) Glass transition temperature Using a differential scanning calorimeter "Q-100" (manufactured by TA Instruments Japan Co., Ltd.), weigh 0.01 to 0.02 g of the sample into an aluminum pan, raise the temperature to 200 ° C, and then raise the temperature to 200 ° C. It was cooled from the temperature to 0 ° C at a temperature lowering rate of 10 ° C / min. Next, the measurement was performed while raising the temperature to 150 ° C. at a heating rate of 10 ° C./min. The temperature at the intersection of the extension of the baseline below the maximum endothermic peak temperature and the tangent line indicating the maximum slope from the rising portion of the peak to the peak of the peak was defined as the glass transition temperature.

[Number average molecular weight and weight average molecular weight of resin]
The molecular weight distribution was measured by gel permeation chromatography (GPC) by 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. Then, this solution was filtered using a fluororesin filter having a pore size of 2 μm (manufactured by Sumitomo Electric Industries, Ltd., trade name “FP-200”) to remove insoluble components, and used as a sample solution.
(2) Molecular Weight Measurement Using the following device, chloroform was flowed as an eluent at a flow rate of 1 mL per minute to stabilize the column in a constant temperature bath at 40 ° C. 100 μL of the sample solution was injected therein and the measurement was performed. The molecular weight of the sample was calculated based on a calibration curve prepared in advance. The calibration curve of the several molecular weight known monodisperse polystyrene (Tosoh ^{Corporation; 2.63 × 10 3, 2.06 ×} 10 4, 1.02 × 10 5, GL Science Co., Ltd.; 2.10 × 10 ^3, 7.00 × 10 ³ , 5.04 × 10 ⁴ ) were used as standard samples.
Measuring device: "CO-8010" (manufactured by Tosoh Corporation)
Analytical column: "GMH _XL " + "G3000H _XL " (both manufactured by Tosoh Corporation)

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

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

[Developability]
Toner is mounted on the ID cartridge of the non-magnetic one-component developing device "OKI MICROLINE 5400" (Oki Data Corporation), and under the conditions of temperature 30 ° C and relative humidity 65%, 70r / min (equivalent to 36 sheets / minute). The development roll surface was visually observed for shavings, and the time until shavings were generated was measured. The longer it takes for sujimura to occur, the better the developability. Note that the sizzle refers to a state in which the amount of toner adhering to the developing roll varies, and the occurrence of the sizzle causes shading in the image density during printing.
(Evaluation criteria)
A: Time until Sujimura occurs is 1 week or more B: Time until Sujimura occurs is 3 days or more and less than 1 week C: Time until Sujimura occurs is 1 day or more and less than 3 days D: Sujimura Time to occur is 12 hours or more, less than 1 day E: Time to occur Sujimura is less than 12 hours

[Manufacturing of resin]
Production Examples 1-8, 10-12 [Resin H-1 to H-8, H-10 to H-12]
A polyester resin raw material monomer other than adipic acid and trimellitic anhydride shown in Table 1 and titanium diisopropyrate bistriethanol aminate are put in, and equipped with a thermometer, a stainless stir bar, a flow-down condenser, a dehydration tube and a nitrogen introduction tube. After polycondensation at 235 ° C. for 6 hours in a mantle heater in a nitrogen atmosphere in a 10-liter four-necked flask, the mixture was cooled to 200 ° C. Then, after adding adipic acid and trimellitic anhydride, the temperature is raised to 210 ° C., a polycondensation reaction is carried out, and the reaction is carried out until the reaction rate reaches the value shown in the table, and then polyhydroxyl at the addition temperature shown in the table. Amine compound (2-amino-2-hydroxymethyl-1,3-propanediol, boiling point 219 ° C (0.1 MPa)) was added and held for the temperature and time shown in the table, and amorphous polyester (resin H-1). ~ H-8, H-10 ~ H-12) were obtained.

Production Example 9 [H-9]
Raw materials other than adipic acid and trimellitic anhydride shown in Table 1 were placed in a dehydration tube equipped with a nitrogen introduction tube, a stirrer and a 10-liter four-necked flask equipped with a thermocouple, and placed at 160 ° C. under a nitrogen atmosphere. The temperature was raised to. Then, a mixture of acrylic acid (both reactive monomers), a raw material monomer of a vinyl resin and a polymerization initiator was added dropwise over 1 hour using a dropping funnel. After the dropping, the addition polymerization reaction was aged for 1 hour while being maintained at 160 ° C., the temperature was raised to 200 ° C., the catalyst shown in the table and 2 g of gallic acid were added, and then the polycondensation reaction was carried out at 235 ° C. for 6 hours. Further, the reaction was carried out at 235 ° C. 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 rates shown in the table. , The polyhydroxyamine compound was added at the addition temperature shown in the table and held for the temperature and time shown in the table to obtain an amorphous composite resin.

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

[Manufacturing of toner for electrophotographic]
Examples and Comparative Examples 100 parts by mass of the binder resin mixed with the resins shown in Table 2, 5 parts by mass of the colorant "ECB-301" (manufactured by Dainichiseika Kogyo Co., Ltd., CI Pigment Blue 15: 3), negative chargeability 1 part by mass of charge control agent "LR-147" (manufactured by Nippon Carlit Co., Ltd.) and 2 parts by mass of mold release agent "NP-105" (manufactured by Mitsui Chemicals, Inc., polypropylene wax, melting point: 140 ° C) in a Henschel mixer After stirring well, melt kneading was performed 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 supply speed of the mixture was 10 kg / hr, and the average residence time was about 18 seconds. The obtained kneaded product was rolled and cooled by a cooling roller, and then a powder having a volume medium particle size (D ₅₀ ) of 6.5 μm was obtained by a jet mill.

To 100 parts by mass of the obtained powder, 1.0 part by mass of the external additive "Aerosil R-972" (hydrophobic silica, manufactured by Nippon Aerosil Co., Ltd., average particle size: 16 nm) and "SI-Y" (hydrophobic silica, Made by Nippon Aerosil Co., Ltd., average particle size: 40 nm) 1.0 part by mass is added and mixed with a Henchel mixer at 3600 r / min for 5 minutes to treat with an external additive, and the volume medium particle size (D ₅₀ ) 6.5 A μm toner was obtained. The evaluation was performed by the above method, and the results are shown in the table.

Claims (7)

It looks including the step of obtaining a polyester site by polycondensation of A 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, the polyhydroxy represented by the following formula (1) 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 the monomer components. A method for producing a binder resin composition for an electrophotographic toner, to which an amine compound is added.

[In the formula, R ¹ represents a hydroxyalkyl group having 1 to 5 carbon atoms, and R ² represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a hydroxyalkyl group having 1 to 5 carbon atoms. Shown, R ³ and R ⁴ represent an alkylandyl group having 1 or more and 5 or less carbon atoms. R ³ and R ⁴ may be the same or different. ] Claim that the polyhydroxyamine compound is at least one selected from 2-amino-2-hydroxymethyl-1,3-propanediol and 2-amino-2-hydroxyethyl-1,3-propanediol. The method for producing a binder resin composition for an electrophotographic toner according to 1. The method for producing a binder resin composition for an electrophotographic toner according to claim 1 or 2, wherein the polyhydroxyamine compound is 2-amino-2-hydroxymethyl-1,3-propanediol. The binder resin for an electrophotographic toner according to any one of claims 1 to 3, wherein the temperature at which the polyhydroxyamine compound is added is 130 ° C. or higher and 20 ° C. or lower than the boiling point of the polyhydroxyamine compound. Method for producing the composition . Any of claims 1 to 4, wherein after adding the entire amount of the polyhydroxyamine compound, the temperature is maintained at 130 ° C. or higher and at a temperature 20 ° C. lower than the boiling point of the polyhydroxyamine compound for 0.5 hours or more and 3.0 hours or less. A method for producing a binder resin composition for toner for electrophotographic photography. The method for producing a binder resin composition for an electrophotographic toner according to any one of claims 1 to 5, wherein the reaction rate of the alcohol component is 85% or more. A method for producing an electrophotographic toner, which uses the binder resin composition obtained by the method for producing a binder resin composition for an electrophotographic toner according to any one of claims 1 to 6.