JP2016045357A - Toner binder resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a toner binder resin composition that can give an electrophotographic toner excellent in low-temperature fixability, durability, and glossiness of printed matter, and an electrophotographic toner containing the toner binder resin composition.SOLUTION: Provided is a toner binder resin composition containing an amorphous polyester (AH) having a softening point of 120°C or more and 170°C or less, an amorphous polyester (AL) having a softening point of 80°C or more and less than 120°C, and a crystalline polyester (C). The amorphous polyester (AH) is a polyester obtained by polycondensation of an alcohol component (AH-al) containing an alkylene oxide adduct (AH-bp) of bisphenol A with a carboxylic acid component (AH-ac). The alcohol component (AH-al) contains 3 mol% or more and less than 20 mol% of a propylene oxide adduct of bisphenol A, having an addition molar number of propylene oxide of 3 or more. The amorphous polyester (AL) is a polyester obtained by polycondensation of an alcohol component (AL-al) containing an alkylene oxide adduct (AL-bp) of bisphenol A with a carboxylic acid component (AL-ac). The alcohol component (AL-al) contains 20 mol% or more and 70 mol% or less of a propylene oxide adduct of bisphenol A, having an addition molar number of propylene oxide of 3 or more.SELECTED DRAWING: None

Description

  The present invention relates to a binder resin composition for toner used for developing a latent image formed in an electrophotographic method, an electrostatic recording method, an electrostatic printing method, and the like, and an electron containing the binder resin composition for toner. The present invention relates to a photographic toner.

In recent years, toners having excellent low-temperature fixability have been developed from the viewpoint of energy saving.
For example, Patent Document 1 contains a polyester obtained by polycondensation of an alcohol component containing 30 mol% or more of a propylene oxide adduct of bisphenol A and a carboxylic acid component, and has a softening point of 70 ° C. or higher and 120 ° C. The content of a propylene oxide adduct of bisphenol A, which is a binder resin for toner having a glass transition point of 45 to 70 ° C., and having 3 mol or more of propylene oxide added in the propylene oxide adduct of bisphenol A Is disclosed as a binder resin for toners having a toner content of 40 mol% or more.
Patent Document 2 discloses an electrophotographic toner comprising a crystalline polyester and an amorphous polyester as a binder resin, wherein the amorphous polyester contains an alkylene oxide adduct of bisphenol A. Is an alcohol component in which the content of the alkylene oxide adduct of bisphenol A in which 3 mol or more of alkylene oxide is added in the alkylene oxide adduct of bisphenol A is 15% by weight or less, and a carboxylic acid component; An electrophotographic toner comprising a resin obtained by polycondensation of is disclosed.

JP 2006-301128 A JP 2006-337872 A

In Patent Document 1, the propylene oxide adduct of specific bisphenol A is used as a raw material for polyester to improve the fixability in a low pressure state. However, low temperature fixability, durability, and gloss of printed matter Further improvement was desired for sex.
Patent Document 2 attempts to improve thermal characteristics and image fixability when a crystalline polyester and an amorphous polyester are used in combination by using an amorphous polyester derived from a specific raw material. Fixability, durability, and gloss of printed matter are still not sufficient, and improvements have been desired.
The present invention relates to a binder resin composition for toner capable of obtaining an electrophotographic toner excellent in low-temperature fixability, durability, and gloss of printed matter, and for electrophotography containing the binder resin composition for toner. It is an object to provide a toner.

  The inventors of the present invention considered that the factors affecting the low-temperature fixability, durability, and gloss of printed matter are the composition and dispersion state of the binder resin in the toner. As a result, it has been found that low-temperature fixability, durability, and gloss of printed matter can be improved by using two types of amorphous polyester derived from a specific raw material and a crystalline polyester in combination.

That is, the present invention provides the following binder resin composition for toner and electrophotographic toner.
[1] An amorphous polyester (AH) having a softening point of 120 ° C. or higher and 170 ° C. or lower, an amorphous polyester (AL) having a softening point of 80 ° C. or higher and lower than 120 ° C., and a crystalline polyester (C) A binder resin composition for toner, wherein the amorphous polyester (AH) comprises an alcohol component (AH-al) containing an alkylene oxide adduct (AH-bp) of bisphenol A, and a carboxylic acid component (AH). -Ac) is a polyester obtained by polycondensation with a propylene oxide adduct of bisphenol A in which the alcohol component (AH-al) is 3 mol or more and 6 mol or less of propylene oxide. The amorphous polyester (AL) is contained in an alkylene oxide adduct of bisphenol A (AL-b). ) -Containing alcohol component (AL-al) and a carboxylic acid component (AL-ac) are polyesters obtained by polycondensation, wherein the alcohol component (AL-al) has an added mole number of propylene oxide. A binder resin composition for toner, comprising a propylene oxide adduct of bisphenol A that is 3 mol to 6 mol in an amount of 20 mol% to 70 mol%.
[2] A toner for electrophotography containing the binder resin composition for toner according to [1] above.

  According to the present invention, a binder resin composition for toner capable of obtaining an electrophotographic toner excellent in low-temperature fixability, durability, and gloss of printed matter, and an electron containing the binder resin composition for toner Photographic toner can be provided.

[Binder resin composition for toner]
The binder resin composition for toner of the present invention includes an amorphous polyester (AH) having a softening point of 120 ° C. or higher and 170 ° C. or lower, an amorphous polyester (AL) having a softening point of 80 ° C. or higher and lower than 120 ° C., and A binder resin composition for toner containing a crystalline polyester (C), wherein the amorphous polyester (AH) is an alcohol component (AH-) containing an alkylene oxide adduct (AH-bp) of bisphenol A. al) and a polyester obtained by polycondensation of a carboxylic acid component (AH-ac), wherein the alcohol component (AH-al) has a propylene oxide addition mole number of 3 mol or more and 6 mol or less. A propylene oxide adduct of bisphenol A is contained in an amount of 3 mol% to less than 20 mol%, and the amorphous polyester (AL) A polyester obtained by polycondensation of an alcohol component (AL-al) containing an oxide adduct (AL-bp) and a carboxylic acid component (AL-ac), wherein the alcohol component (AL-al) is A propylene oxide adduct of bisphenol A having an addition mole number of propylene oxide of 3 mol or more and 6 mol or less is contained in an amount of 20 mol% or more and 70 mol% or less.

The toner binder resin composition of the present invention (hereinafter also simply referred to as “binder resin composition”) is an electrophotographic toner (hereinafter simply referred to as “toner”) having excellent low-temperature fixability, durability, and gloss of printed matter. The reason why it can also be obtained is not clear, but is considered as follows.
The amorphous polyester (AL) contained in the binder resin composition of the present invention is a bisphenol in which the number of moles of propylene oxide added is 3 mol or more and 6 mol or less in the alcohol component (AL-al) as the raw material. The propylene oxide adduct of A (hereinafter also referred to as “3 to 6 mol adduct”) is contained in an amount of 20 mol% to 70 mol%. The structure of the 3-6 mol adduct is highly flexible, and the polyester obtained by using the adduct in an amount of 20 mol% to 70 mol% is the same as the polyester having less 3-6 mol adduct. A large amount of monomer is required to reach the softening point. Thus, the molecular weight of the resulting polyester is estimated to be higher at the same softening point than the polyester with less 3-6 mole adduct.
In addition, the amorphous polyester (AH) contained in the binder resin composition of the present invention contains 3 to 20 mol% of an adduct of 3 to 6 mol in the alcohol component (AH-al) as the raw material. Contains less. Thus, the resulting polyester is less flexible and requires less monomer to reach the same softening point compared to a polyester with more 3-6 mole adduct. Thereby, it is estimated that the molecular weight of the obtained polyester is small at the same softening point as compared with the polyester having more 3 to 6 mol adduct.
Therefore, in the present invention, the molecular weight difference between the amorphous polyester (AH) and the amorphous polyester (AL) can be reduced, and the conventional low softening point resin and high softening point resin can be used during melt-kneading. It is possible to suppress a non-uniform state of the binder resin and the like due to the difference in viscosity. As a result, the amorphous polyester (AH) and the amorphous polyester (AL) form a more uniform matrix phase. As a result, the polyester is excellent in gloss and the crystalline polyester (C) is more uniformly dispersed in the matrix phase. It is thought that it is excellent in low-temperature fixability and durability.
Thus, in the toner obtained from the binder resin composition of the present invention, the crystalline polyester (C) contained as the binder resin component is finely dispersed in the amorphous polyester, and the amorphous polyester ( By uniformly mixing AH) and amorphous polyester (AL), it is considered that the low-temperature fixability, durability, and gloss of printed matter are excellent.

<Amorphous polyester (AH)>
The amorphous polyester (AH) is obtained by polycondensing an alcohol component (AH-al) containing an alkylene oxide adduct (AH-bp) of bisphenol A and a carboxylic acid component (AH-ac). A propylene oxide adduct of bisphenol A, which is an amorphous polyester having a softening point of 120 ° C. or higher and 170 ° C. or lower, wherein the alcohol component (AH-al) is 3 mol or more and 6 mol or less of propylene oxide. 3 mol% or more and less than 20 mol%.

In the present invention, the amorphous polyester is defined by the ratio of the softening point and the maximum endothermic peak temperature (softening point (° C.) / Maximum endothermic peak temperature (° C.)) in the measurement method described in the examples described later. The crystallinity index is greater than 1.4 or less than 0.6.
The crystallinity index of the amorphous polyester (AH) is preferably 1.5 or more and 4.0 or less, more preferably 2.0 or more and 3.0, from the viewpoints of low-temperature fixability, durability, and gloss of printed matter. It is as follows.
The crystallinity index can be appropriately adjusted according to the production conditions such as the type and ratio of the raw material monomers, the reaction temperature, the reaction time, and the cooling rate.

(Softening point)
The softening point of the amorphous polyester (AH) is 120 ° C. or higher and 170 ° C. or lower from the viewpoints of low-temperature fixability, durability, and printed gloss. From the same viewpoint, it is preferably 125 ° C. or higher, more preferably 130 ° C. or higher, and preferably 160 ° C. or lower, more preferably 150 ° C. or lower, and further preferably 140 ° C. or lower.
(Glass-transition temperature)
The glass transition temperature of the amorphous polyester (AH) is preferably 40 ° C. or higher, more preferably 45 ° C. or higher, and still more preferably 50 ° C. or higher, from the viewpoints of low-temperature fixability, durability, and printed gloss. And, it is preferably 80 ° C. or less, more preferably 70 ° C. or less, and further preferably 60 ° C. or less.
(Acid value)
The acid value of the amorphous polyester (AH) is preferably 2 mgKOH / g or more, more preferably 5 mgKOH / g or more, still more preferably 10 mgKOH / g or more, from the viewpoints of low-temperature fixability, durability, and gloss of printed matter. And preferably 30 mg KOH / g or less, more preferably 25 mg KOH / g or less.
The softening point, glass transition temperature, and acid value of the amorphous polyester (AH) can be appropriately adjusted according to the production conditions such as the type and ratio of the raw material monomers, the reaction temperature, the reaction time, and the cooling rate. A softening point, a glass transition temperature, and an acid value are calculated | required by the method as described in an Example.

(Method for producing amorphous polyester (AH))
The amorphous polyester (AH) can be produced by polycondensation of an alcohol component (AH-al) and a carboxylic acid component (AH-ac).

[Alcohol component (AH-al)]
The alcohol component (AH-al) contains an alkylene oxide adduct (AH-bp) of bisphenol A.
In the alcohol component (AH-al), the content of the alkylene oxide adduct (AH-bp) of bisphenol A is preferably 80% by mass or more, more preferably 90% by mass from the viewpoints of durability and gloss of printed matter. % Or more, more preferably 95% by mass or more, and still more preferably 100% by mass.
The average addition mole number of the bisphenol A alkylene oxide adduct (AH-bp) is preferably 2.1 mol or more, more preferably 2.15 mol, from the viewpoints of low-temperature fixability, durability, and gloss of printed matter. The amount is preferably 2.3 mol or less, more preferably 2.25 mol or less.

In addition, the alcohol component (AH-al) is a propylene oxide adduct of bisphenol A in which the number of moles of propylene oxide added is 3 mol or more and 6 mol or less from the viewpoint of low-temperature fixability, durability, and gloss of printed matter. 3 mol% or more and less than 20 mol%.
In addition, the propylene oxide adduct of bisphenol A in the present invention is represented by the following general formula (1).

  In general formula (1), m and n represent positive numbers. The sum of m and n means the number of moles of propylene oxide added to one molecule of bisphenol A. That is, the added mole number of propylene oxide in this specification represents the sum of m and n.

  In the alcohol component (AH-al), the content of propylene oxide adduct of bisphenol A having a propylene oxide addition mole number of 3 mol or more and 6 mol or less is low temperature fixability, durability, and gloss of printed matter. From 3 mol% to less than 20 mol%, preferably 5 mol% or more, more preferably 7 mol% or more, still more preferably 10 mol% or more, and preferably 18 mol% or less, more preferably It is 16 mol% or less.

As the alkylene oxide adduct (AH-bp) of bisphenol A other than the propylene oxide adduct of bisphenol A having an addition mol number of propylene oxide of 3 mol or more and 6 mol or less, for example, the addition mol number of propylene oxide is 3 mol. Preferred are propylene oxide adducts of bisphenol A, propylene oxide adducts of more than 6 mol of propylene oxide, adducts of ethylene oxide of bisphenol A (average addition mol number of 1 to 16). Can be mentioned.
Propylene oxide adduct of bisphenol A in which the number of moles of propylene oxide in the alcohol component (AH-al) is 3 to 6 moles, and propylene in bisphenol A in which the number of moles of propylene oxide is less than 3 moles The total content of the oxide adduct and the propylene oxide adduct of bisphenol A in which the number of moles of propylene oxide exceeds 6 mol, that is, the content of the propylene oxide adduct of all bisphenol A is low temperature fixability, durability, And from the viewpoint of gloss of printed matter, it is preferably 70 mol% or more, more preferably 80 mol% or more, still more preferably 85 mol% or more, and preferably 100 mol% or less, more preferably 98 mol% or less. More preferably, it is 95 mol% or less.

The alcohol component (AH-al) may contain an alcohol component other than the alkylene oxide adduct of bisphenol A.
Examples of other alcohols include alcohols that can be used as an alcohol component (C-al) described later.
In the alcohol component (AH-al), the total content of the propylene oxide adduct of bisphenol A and the ethylene oxide (average addition mole number 1 to 16) adduct of bisphenol A is low temperature fixability, durability, and From the viewpoint of gloss of printed matter, it is preferably 80% by mass or more, more preferably 90% by mass or more, still more preferably 95% by mass or more, and still more preferably 100% by mass.

[Carboxylic acid component (AH-ac)]
Examples of the carboxylic acid component (AH-ac) include dicarboxylic acid compounds and trivalent or higher polyvalent carboxylic acid compounds.
In the present invention, the carboxylic acid component includes not only dicarboxylic acid compounds and trivalent or higher polyvalent carboxylic acid compounds, but also anhydrides thereof and alkyl esters having 1 to 3 carbon atoms.
Examples of the dicarboxylic acid compound include aliphatic dicarboxylic acid compounds, aromatic dicarboxylic acid compounds, and alicyclic dicarboxylic acid compounds.
Specific examples of the aliphatic dicarboxylic acid compound include oxalic acid, malonic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, succinic acid, adipic acid, sebacic acid, 1,8-octanedicarboxylic acid, 1 , 12-dodecanedioic acid, azelaic acid, succinic acid having an alkyl group having 1 to 14 carbon atoms, succinic acid having an alkenyl group having 2 to 14 carbon atoms, and the like.
Specific examples of the aromatic dicarboxylic acid compound include phthalic acid, isophthalic acid, terephthalic acid and the like.
Specific examples of the alicyclic dicarboxylic acid compound include cyclohexane dicarboxylic acid.
Specific examples of the trivalent or higher polyvalent carboxylic acid compound include trimellitic acid, 2,5,7-naphthalene tricarboxylic acid, pyromellitic acid and the like.
Among these, adipic acid, terephthalic acid, and trimellitic anhydride are preferable from the viewpoint of low-temperature fixability, durability, and gloss of printed matter, and adipic acid, terephthalic acid, and trimellitic anhydride may be used in combination. More preferred.
A carboxylic acid component (AH-ac) can be used individually or in combination of 2 or more types.

[Reaction conditions]
An amorphous polyester (AH) is formed by a polycondensation reaction between the alcohol component (AH-al) and the carboxylic acid component (AH-ac).
From the viewpoint of reactivity, the polycondensation reaction temperature is preferably 160 ° C. or higher, more preferably 200 ° C. or higher, still more preferably 220 ° C. or higher, and preferably 260 ° C. or lower, more preferably 250 ° C. or lower. More preferably, it is 240 degrees C or less.
The molar ratio of the carboxylic acid component (AH-ac) to the alcohol component (AH-al) [(AH-ac) / (AH-al)]) is from the viewpoint of low-temperature fixability, durability, and gloss of printed matter. , Preferably 0.70 or more, more preferably 0.80 or more, further preferably 0.85 or more, and preferably 1.20 or less, more preferably 1.10 or less, still more preferably 1.00 or less. It is.
The polycondensation reaction may be performed in an inert gas atmosphere in the presence of an esterification catalyst, an esterification cocatalyst, a polymerization inhibitor, or the like, if necessary.

≪Esterification catalyst≫
Examples of the esterification catalyst suitably used for the polycondensation reaction include a titanium compound and a tin (II) compound having no Sn—C bond, and these may be used alone or in combination of two or more. it can.
As the titanium compound, a titanium compound having a Ti—O bond is preferable, and a compound having an alkoxy group, an alkenyloxy group or an acyloxy group having 1 to 28 carbon atoms in total is more preferable.
Examples of the tin (II) compound having no Sn—C bond include a tin (II) compound having a Sn—O bond, a tin (II) compound having a Sn—X (X represents a halogen atom) bond, and the like. Preferred is a tin (II) compound having a Sn-O bond, and among them, tin 2-ethylhexanoate is still more preferable from the viewpoints of reactivity, molecular weight adjustment, and physical property adjustment of amorphous polyester.
The amount of the esterification catalyst used is preferably based on 100 parts by mass of the total amount of the alcohol component (AH-al) and the carboxylic acid component (AH-ac) from the viewpoints of reactivity, molecular weight adjustment, and resin physical property adjustment. Is 0.01 parts by mass or more, more preferably 0.1 parts by mass or more, still more preferably 0.4 parts by mass or more, and preferably 1.5 parts by mass or less, more preferably 1.0 parts by mass or less. More preferably, it is 0.6 parts by mass or less.

≪Esterification cocatalyst≫
Examples of esterification promoters include pyrogallol compounds such as pyrogallol, gallic acid, and gallic acid esters; benzophenone derivatives such as 2,3,4-trihydroxybenzophenone and 2,2 ′, 3,4-tetrahydroxybenzophenone; epigallocatechin And catechin derivatives such as epigallocatechin gallate, and gallic acid is preferred from the viewpoint of reactivity.
The use amount of the esterification co-catalyst is preferably based on 100 parts by mass of the total amount of the alcohol component (AH-al) and the carboxylic acid component (AH-ac) from the viewpoints of reactivity, molecular weight adjustment, and resin physical property adjustment. Is 0.001 part by mass or more, more preferably 0.01 part by mass or more, further preferably 0.04 part by mass or more, and preferably 0.15 part by mass or less, more preferably 0.10 part by mass or less. More preferably, it is 0.06 parts by mass or less.
≪Polymerization inhibitor≫
The polymerization inhibitor is not particularly limited, but 4-t-butylcatechol is preferable.

<Amorphous polyester (AL)>
The amorphous polyester (AL) is obtained by polycondensing an alcohol component (AL-al) containing an alkylene oxide adduct (AL-bp) of bisphenol A and a carboxylic acid component (AL-ac). A propylene oxide adduct of bisphenol A, which is an amorphous polyester having a softening point of 80 ° C. or higher and lower than 120 ° C., wherein the alcohol component (AL-al) is 3 mol or more and 6 mol or less of propylene oxide. It contains 20 mol% or more and 70 mol% or less.
The crystallinity index of the amorphous polyester (AL) is preferably 1.5 or more and 4.0 or less, more preferably 1.55 or more and 3.0, from the viewpoints of low-temperature fixability, durability, and gloss of printed matter. Hereinafter, it is more preferably 1.6 or more and 2.0 or less.
The crystallinity index can be appropriately adjusted according to the production conditions such as the type and ratio of the raw material monomers, the reaction temperature, the reaction time, and the cooling rate.

(Softening point)
The softening point of the amorphous polyester (AL) is 80 ° C. or more and less than 120 ° C. from the viewpoints of low-temperature fixability, durability, and gloss of the printed matter, and low-temperature fixability and glossy viewpoint of the printed matter. Therefore, it is preferably 83 ° C. or higher, more preferably 85 ° C. or higher, and preferably 110 ° C. or lower, more preferably 100 ° C. or lower, still more preferably 95 ° C. or lower.
The difference between the softening point of the amorphous polyester (AL) and the softening point of the amorphous polyester (AH) is preferably 10 ° C. or higher from the viewpoint of low-temperature fixability, durability, and gloss of printed matter, and is 20 ° C. The above is more preferable, 30 ° C. or higher is further preferable, 40 ° C. or higher is more preferable, and from the same viewpoint, 70 ° C. or lower is preferable, and 60 ° C. or lower is more preferable.
(Glass-transition temperature)
The glass transition temperature of the amorphous polyester (AL) is preferably 40 ° C. or higher, more preferably 45 ° C. or higher, and further preferably 50 ° C. or higher, from the viewpoints of low-temperature fixability, durability, and gloss of printed matter. And, it is preferably 80 ° C. or less, more preferably 70 ° C. or less, and further preferably 60 ° C. or less.
(Acid value)
The acid value of the amorphous polyester (AL) is preferably 2 mgKOH / g or more, more preferably 5 mgKOH / g or more, still more preferably 8 mgKOH / g or more, from the viewpoints of low-temperature fixability, durability, and gloss of printed matter. And preferably 30 mgKOH / g or less, more preferably 25 mgKOH / g or less, and still more preferably 20 mgKOH / g or less.
The softening point, glass transition temperature, and acid value of the amorphous polyester (AL) can be appropriately adjusted according to the production conditions such as the type and ratio of the raw material monomers, the reaction temperature, the reaction time, and the cooling rate. A softening point, a glass transition temperature, and an acid value are calculated | required by the method as described in an Example.

(Method for producing amorphous polyester (AL))
The amorphous polyester (AL) can be produced by polycondensation of an alcohol component (AL-al) and a carboxylic acid component (AL-ac).

[Alcohol component (AL-al)]
The alcohol component (AL-al) contains an alkylene oxide adduct (AL-bp) of bisphenol A.
In the alcohol component (AL-al), the content of the alkylene oxide adduct (AL-bp) of bisphenol A is preferably 80% by mass or more, more preferably 90% by mass from the viewpoints of durability and gloss of printed matter. % Or more, more preferably 95% by mass or more, and still more preferably 100% by mass.
The average number of moles of alkylene oxide adduct (AL-bp) of bisphenol A is preferably 2.3 moles or more, more preferably 2.4 moles or more, even more preferably from the viewpoints of low-temperature fixability and durability. From the viewpoint of low-temperature fixability and gloss of printed matter, it is preferably 3.0 moles or less, more preferably 2.9 moles or less, and even more preferably 2.8 moles or less. .

In addition, the alcohol component (AL-al) is a propylene oxide adduct of bisphenol A in which the number of moles of propylene oxide added is 3 mol or more and 6 mol or less from the viewpoint of low-temperature fixability, durability, and gloss of printed matter. It contains 20 mol% or more and 70 mol% or less.
In the alcohol component (AL-al), the content of propylene oxide adduct of bisphenol A having a propylene oxide addition mole number of 3 mol or more and 6 mol or less is preferably 25 from the viewpoint of low-temperature fixability and durability. From the viewpoint of low-temperature fixability and gloss of printed matter, it is preferably 60 mol% or less, more preferably 50 mol%, more preferably mol% or more, more preferably 30 mol% or more, and even more preferably 35 mol% or more. Hereinafter, it is more preferably 45 mol% or less.

As the alkylene oxide adduct (AL-bp) of bisphenol A other than the propylene oxide adduct of bisphenol A having an addition mol number of propylene oxide of 3 mol or more and 6 mol or less, for example, the addition mol number of propylene oxide is 3 mol. Preferred are propylene oxide adducts of bisphenol A, propylene oxide adducts of more than 6 mol of propylene oxide, adducts of ethylene oxide of bisphenol A (average addition mol number of 1 to 16). Can be mentioned.
Propylene oxide adduct of bisphenol A in which the number of moles of propylene oxide in the alcohol component (AL-al) is 3 to 6 moles, and propylene in bisphenol A in which the number of moles of propylene oxide added is less than 3 moles The total content of the oxide adduct and the propylene oxide adduct of bisphenol A in which the number of moles of propylene oxide exceeds 6 mol, that is, the content of the propylene oxide adduct of all bisphenol A is low temperature fixability, durability, And from the viewpoint of gloss of printed matter, it is preferably 70 mol% or more, more preferably 80 mol% or more, still more preferably 85 mol% or more, and preferably 100 mol% or less, more preferably 98 mol% or less. More preferably, it is 95 mol% or less.

The alcohol component (AL-al) may contain an alcohol component other than the propylene oxide adduct of bisphenol A.
Examples of other alcohols include alcohols that can be used as an alcohol component (C-al) described later.
The total content of the propylene oxide adduct of bisphenol A and the ethylene oxide (average addition mole number of 1 to 16) adducts of bisphenol A in the alcohol component (AL-al) is low temperature fixability, durability, and From the viewpoint of gloss of printed matter, it is preferably 80% by mass or more, more preferably 90% by mass or more, still more preferably 95% by mass or more, and still more preferably 100% by mass.

[Carboxylic acid component (AL-ac)]
Examples of the carboxylic acid component (AL-ac) include the same carboxylic acid compounds as the carboxylic acid component (AH-ac), and preferred embodiments thereof are also the same.

[Reaction conditions]
An amorphous polyester (AL) is formed by a polycondensation reaction between the alcohol component (AL-al) and the carboxylic acid component (AL-ac).
The temperature of the polycondensation reaction is the same as the temperature of the polycondensation reaction in the production of the amorphous polyester (AH), and the preferred embodiment is also the same.
The molar ratio of the carboxylic acid component (AL-ac) to the alcohol component (AL-al) [(AL-al) / (AL-ac)]) is from the viewpoint of low-temperature fixability, durability, and gloss of printed matter. , Preferably 0.70 or more, more preferably 0.80 or more, further preferably 0.85 or more, and preferably 1.20 or less, more preferably 1.10 or less, still more preferably 1.00 or less. It is.
The polycondensation reaction may be performed in an inert gas atmosphere in the presence of an esterification catalyst, an esterification cocatalyst, a polymerization inhibitor, or the like, if necessary.
Examples of the esterification catalyst, esterification co-catalyst, and polymerization inhibitor include those similar to the esterification catalyst, esterification co-catalyst, and polymerization inhibitor that can be used in the production of the amorphous polyester (AH), and are preferable. The aspect is also the same.

<Crystalline polyester (C)>
In the present invention, the crystalline polyester means a polyester having a crystallinity index of 0.6 or more and 1.4 or less, preferably 0.8 or more and 1.2 or less, more preferably 0.9 or more and 1.1 or less. It is. In crystalline polyester, the melting point is the maximum endothermic peak temperature.
The crystallinity index can be appropriately adjusted according to the production conditions such as the type and ratio of the raw material monomers, the reaction temperature, the reaction time, and the cooling rate.

(Softening point)
The softening point of the crystalline polyester (C) is preferably 55 ° C. or higher, more preferably 60 ° C. or higher, more preferably 65 ° C. or higher, from the viewpoint of low-temperature fixability, durability, and gloss of printed matter. The temperature is preferably 120 ° C. or lower, more preferably 100 ° C. or lower, and still more preferably 80 ° C. or lower.
(Melting point)
The melting point of the crystalline polyester (C) is preferably 40 ° C. or higher, more preferably 50 ° C. or higher, more preferably 65 ° C. or higher, from the viewpoint of low-temperature fixability, durability, and gloss of printed matter. Preferably it is 120 degrees C or less, More preferably, it is 100 degrees C or less, More preferably, it is 80 degrees C or less.
The softening point and melting point of the crystalline polyester (C) can be appropriately adjusted depending on the type and ratio of the raw material monomers, and the production conditions such as reaction temperature, reaction time, and cooling rate. The softening point and melting point are determined by the method described in the examples.

(Method for producing crystalline polyester (C))
The crystalline polyester (C) can be produced by polycondensation of an alcohol component (C-al) and a carboxylic acid component (C-ac).

[Alcohol component (C-al)]
Examples of the alcohol component (C-al) include aliphatic diols, aromatic diols, hydrogenated products of bisphenol A, and trivalent or higher alcohols. Among these, aliphatic diols are preferable from the viewpoint of promoting crystallization of polyester and improving low-temperature fixability of the toner.

The carbon number of the aliphatic diol is preferably 2 or more, more preferably 4 or more, still more preferably 6 or more, and preferably 14 or less, from the viewpoints of low-temperature fixability, durability, and gloss of printed matter. More preferably, it is 12 or less, More preferably, it is 10 or less, More preferably, it is 8 or less, More preferably, it is 6 or less.
The aliphatic diol preferably has a hydroxyl group at the end of the carbon chain, more preferably α, ω-linear alkanediol, from the viewpoints of low-temperature fixability, durability, and gloss of printed matter.
Aliphatic diols include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol 1,9-nonanediol, 1,10-decanediol, 1,12-dodecanediol and the like. Among these, 1,6-hexanediol, 1,10-decanediol, and 1,12-dodecanediol, more preferably 1,6, are preferred from the viewpoint of low-temperature fixability, durability, and gloss of printed matter. -Hexanediol.

Examples of the aromatic diol include adducts of bisphenol A alkylene (2 to 3 carbon atoms) oxide (average number of added moles of 1 to 16).
Examples of trihydric or higher alcohols include sorbitol, pentaerythritol, glycerin, trimethylolpropane, and the like.
An alcohol component (C-al) can be used individually or in combination of 2 or more types.

[Carboxylic acid component (C-ac)]
Examples of the carboxylic acid component (C-ac) include dicarboxylic acid compounds and trivalent or higher polyvalent carboxylic acid compounds.
Examples of the dicarboxylic acid compound include aliphatic dicarboxylic acid compounds, aromatic dicarboxylic acid compounds, and alicyclic dicarboxylic acid compounds.
Among these, from the viewpoint of low-temperature fixability, durability, and gloss of printed matter, an aliphatic dicarboxylic acid compound is preferable, and a saturated aliphatic dicarboxylic acid compound is more preferable.
The number of carbon atoms of the aliphatic dicarboxylic acid compound is preferably 4 or more, more preferably 8 or more, still more preferably 10 or more, still more preferably 12 or more, from the viewpoint of durability, and from the viewpoint of low-temperature fixability. , Preferably 14 or less, more preferably 12 or less.
In addition, the carbon number of the aliphatic dicarboxylic acid compound includes the carbon number of the carboxy group in the carbon number of the linear or branched hydrocarbon group, and does not include the carbon number of the alkyl ester.
Specific examples of the aliphatic dicarboxylic acid compound include oxalic acid, malonic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, succinic acid, adipic acid, sebacic acid, 1,8-octanedicarboxylic acid, 1 , 10-decanedicarboxylic acid, 1,12-dodecanedicarboxylic acid, azelaic acid, succinic acid having an alkyl group having 1 to 14 carbon atoms, and succinic acid having an alkenyl group having 2 to 14 carbon atoms.
Among these, from the viewpoint of low-temperature fixability, durability, and gloss of printed matter, fumaric acid, succinic acid, sebacic acid, and 1,10-decanedicarboxylic acid, more preferably 1,10-decanedicarboxylic acid are preferable. It is.

Examples of the alicyclic dicarboxylic acid compound include cyclohexane dicarboxylic acid.
Specific examples of the aromatic dicarboxylic acid compound include phthalic acid, isophthalic acid, terephthalic acid and the like.
Specific examples of the trivalent or higher polyvalent carboxylic acid compound include trimellitic acid, 2,5,7-naphthalene tricarboxylic acid, pyromellitic acid and the like.
A carboxylic acid component (C-ac) can be used individually or in combination of 2 or more types.

The raw material monomer of the crystalline polyester (C) may contain at least one of a monovalent carboxylic acid compound or a monovalent alcohol from the viewpoints of low-temperature fixability and gloss of printed matter. That is, the alcohol component (C-al) may contain a monovalent alcohol, and the carboxylic acid component (C-ac) may contain a monovalent carboxylic acid compound as appropriate.
The monovalent alcohol and the monovalent carboxylic acid compound are preferably aliphatic and more preferably have an alkyl group from the viewpoint of low-temperature fixability and gloss of printed matter.
From the same viewpoint, the carbon number of the alkyl group of the monohydric alcohol having an alkyl group is preferably 12 or more, more preferably 14 or more, still more preferably 16 or more, and preferably 18 or less.
From the same viewpoint, the carbon number of the alkyl group of the monovalent carboxylic acid compound having an alkyl group is preferably 12 or more, more preferably 14 or more, still more preferably 16 or more, and preferably 18 or less. .
Examples of the monovalent aliphatic monoalcohol having 12 to 18 carbon atoms include aliphatic alcohols such as palmityl alcohol, stearyl alcohol, and behenyl alcohol. Among these, stearyl alcohol is preferable.
Examples of the monovalent aliphatic monocarboxylic acid compound having 12 to 18 carbon atoms include aliphatic carboxylic acid compounds such as palmitic acid, stearic acid, and behenic acid. Among these, stearic acid is preferable.
The total content of the monohydric alcohol having 12 to 18 carbon atoms and the monovalent carboxylic acid compound having 12 to 18 carbon atoms is the raw material monomer of the crystalline polyester (C), that is, the alcohol component (C-al ) And the carboxylic acid component (C-ac) are preferably 2 mol% or more, more preferably 4 mol% or more, and preferably 10 mol in terms of low-temperature fixability and gloss of printed matter. % Or less, more preferably 8 mol% or less, still more preferably 6 mol% or less.

[Reaction conditions]
Crystalline polyester (C) is formed by the polycondensation reaction of the alcohol component (C-al) and the carboxylic acid component (C-ac).
From the viewpoint of reactivity, the polycondensation reaction temperature is preferably 140 ° C. or higher, more preferably 160 ° C. or higher, still more preferably 180 ° C. or higher, and preferably 250 ° C. or lower, more preferably 230 ° C. or lower, More preferably, it is 220 degrees C or less.
The molar ratio [(C-ac) / (C-al)] of the carboxylic acid component (C-ac) to the alcohol component (C-al) is determined from the viewpoints of low-temperature fixability, durability, and gloss of printed matter. Preferably it is 0.70 or more, More preferably, it is 0.80 or more, More preferably, it is 0.90 or more, Preferably it is 1.20 or less, More preferably, it is 1.15 or less, More preferably, it is 1.10 or less. is there.

The polycondensation reaction may be performed in an inert gas atmosphere in the presence of an esterification catalyst, an esterification cocatalyst, a polymerization inhibitor, or the like, if necessary.
Examples of the esterification catalyst, esterification co-catalyst, and polymerization inhibitor include those similar to the esterification catalyst, esterification co-catalyst, and polymerization inhibitor that can be used in the production of the amorphous polyester (AH), and are preferable. The aspect is also the same.
The amount of the esterification catalyst used is preferably 100 parts by mass with respect to the total amount of the alcohol component (C-al) and the carboxylic acid component (C-ac) from the viewpoints of reactivity, molecular weight adjustment, and resin physical property adjustment. 0.01 parts by mass or more, more preferably 0.10 parts by mass or more, further preferably 0.15 parts by mass or more, and preferably 1.00 parts by mass or less, more preferably 0.50 parts by mass or less, More preferably, it is 0.30 mass part or less.
The use amount of the esterification co-catalyst is preferably based on 100 parts by mass of the total amount of the alcohol component (C-al) and the carboxylic acid component (C-ac) from the viewpoints of reactivity, molecular weight adjustment, and resin physical property adjustment. Is 0.001 part by mass or more, more preferably 0.005 part by mass or more, further preferably 0.01 part by mass or more, and preferably 0.15 part by mass or less, more preferably 0.08 part by mass or less. More preferably, it is 0.04 parts by mass or less.

<Content of each resin>
The total content of the amorphous polyester (AH), the amorphous polyester (AL), and the crystalline polyester (C) in all the binder resin components contained in the binder resin composition of the present invention is low temperature fixability. From the viewpoint of durability, and gloss of printed matter, it is preferably 80% by mass or more, more preferably 90% by mass or more, still more preferably 98% by mass or more, and still more preferably 100% by mass.
The mass ratio [(AL) / (AH)] of the amorphous polyester (AL) and the amorphous polyester (AH) contained in the binder resin composition of the present invention is preferably 0 from the viewpoint of durability. .6 or more, more preferably 0.8 or more, still more preferably 0.9 or more, and preferably 4.0 or less, more preferably 3.0 from the viewpoint of low-temperature fixability and gloss of printed matter. Hereinafter, it is further preferably 2.0 or less, more preferably 1.5 or less, and still more preferably 1.2 or less.
Mass ratio of total amount of amorphous polyester (AH) and amorphous polyester (AL) contained in the binder resin composition of the present invention to crystalline polyester (C) [(AH + AL) / (C)] Is preferably 65/35 or more, more preferably 70/30 or more, still more preferably 80/20 or more from the viewpoint of durability and gloss of printed matter, and preferably from the viewpoint of low-temperature fixability. It is 97/3 or less, More preferably, it is 95/5 or less, More preferably, it is 92/8 or less.

<Optional component>
For the binder resin composition of the present invention, known resins used for toner, such as polyester, styrene-acrylic copolymer, epoxy, polycarbonate, polyurethane and the like can be used.
The binder resin composition of the present invention further comprises a colorant, a release agent, a charge control agent, a magnetic powder, a fluidity improver, a conductivity modifier, an extender pigment, a reinforcing filler such as a fibrous substance, and an antioxidant. Additives such as an agent, an anti-aging agent, and a cleaning property improver may be appropriately contained.

[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 of the present invention may be either black toner or color toner.
The content of the colorant is preferably 0.1% by mass with respect to 100 parts by mass of the binder resin component from the viewpoint of improving the image density of the toner and from the viewpoint of low-temperature fixability, durability, and gloss of printed matter. Part or more, more preferably 0.5 part by weight or more, further preferably 1.0 part by weight or more, and preferably 40 parts by weight or less, more preferably 20 parts by weight or less, still more preferably 10 parts by weight or less. is there.

〔Release agent〕
As the release agent, low molecular weight polypropylene, low molecular weight polyethylene, low molecular weight polypropylene polyethylene copolymer, aliphatic hydrocarbon wax such as microcrystalline wax, paraffin wax, Fischer-Tropsch wax and oxides thereof, carnauba wax, Examples include ester waxes such as montan wax, sazol wax and their deoxidized waxes, fatty acid ester waxes, fatty acid amides, fatty acids, higher alcohols, fatty acid metal salts, and the like. It can be used by mixing.
The melting point of the release agent is preferably 50 ° C. or higher, more preferably 70 ° C. or higher, further preferably 100 ° C. or higher, and preferably 170 ° C. from the viewpoints of low-temperature fixability, durability, and printed gloss. ° C or lower, more preferably 160 ° C or lower, still more preferably 150 ° C or lower.
The content of the release agent is preferably 0.5 with respect to 100 parts by mass of the binder resin component from the viewpoint of dispersibility in the resin, low-temperature fixability, durability, and gloss of the printed matter. Part by mass or more, more preferably 1.0 part by mass or more, further preferably 1.5 parts by mass or more, and preferably 10 parts by mass or less, more preferably 5 parts by mass or less, still more preferably 3 parts by mass or less. It is.

[Charge control agent]
The charge control agent is not particularly limited, and 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 (registered trademark) N-01”, “Bontron N-04”, “ Bontron N-07 "," Bontron N-09 "," Bontron N-11 "(manufactured by Orient Chemical Industry Co., Ltd.), etc .; triphenylmethane dyes containing quaternary amines as side chains, quaternary ammonium salts Compounds such as “Bontron P-51” (manufactured by Orient Chemical Co., Ltd.), cetyltrimethylammonium bromide, “COPY CHARGE PX VP435” (manufactured by Clariant), etc .; polyamine resins such as “AFP-B” (Orient Chemical Industries Ltd.) Imidazole derivatives such as “PLZ-2001”, “P Z-8001 "(all, made by Shikoku Kasei Co., Ltd.); styrene - acrylic resin, for example," FCA-701PT "(manufactured by Fujikura Kasei), and the like.
Examples of the negatively chargeable charge control agent include metal-containing azo dyes such as “Varifast Black 3804”, “Bontron S-31”, “Bontron S-32”, “Bontron S-34”, “Bontron S-”. 36 ”(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.) and the like; metal compounds of salicylic acid compounds such as“ Bontron E-81 ”,“ Bontron E-84 ”,“ Bontron E-88 ”,“ E- ” 304 "(above, manufactured by Orient Chemical Co., Ltd.)," TN-105 "(manufactured by Hodogaya Chemical Co., Ltd.), etc .; copper phthalocyanine dye; quaternary ammonia Salts, for example, "COPY CHARGE NX VP434" (manufactured by Clariant), nitroimidazole derivatives; organometallic compounds such as "TN105" (manufactured by Hodogaya Chemical Co., Ltd.).
The content of the charge control agent is preferably 0.01 parts by mass or more, more preferably 0.1 parts by mass or more, and still more preferably from 100 parts by mass of the binder resin component, from the viewpoint of toner charging stability. 0.5 parts by mass or more, and preferably 3.0 parts by mass or less, more preferably 2.0 parts by mass or less, and further preferably 1.5 parts by mass or less.

<Method for producing binder resin composition for toner>
The binder resin composition of the present invention can be produced by mixing the amorphous polyester (AH), the amorphous polyester (AL), the crystalline polyester (C), and, if necessary, the optional components. it can.
Although there is no restriction | limiting in particular as the method of mixing, The method of mixing in a solution, the method of melt-kneading, the method of mixing in a solid state, etc. are mentioned.
Among these, the method of melt kneading is preferable from the viewpoint of improving the dispersibility of the crystalline polyester (C). In melt kneading, the constituent components of the binder resin composition are uniformly mixed with a mixer such as a Henschel mixer, and then the obtained mixture is mixed with a closed kneader, a single or twin screw extruder, an open roll kneading machine. It can be performed using a machine or the like.
From the viewpoint of improving the dispersibility of the crystalline polyester (C), the melt kneading temperature is preferably 100 ° C. or higher, more preferably 110 ° C. or higher, still more preferably 115 ° C. or higher, and preferably 150 ° C. or lower. More preferably, it is 140 degrees C or less, More preferably, it is 130 degrees C or less.

[Electrophotographic toner]
The toner for electrophotography of the present invention contains the binder resin composition of the present invention.
In addition to the binder resin composition of the present invention, the toner of the present invention further includes a colorant, a release agent, a charge control agent, a magnetic powder, a fluidity improver, a conductivity modifier, an extender pigment, and a fibrous substance. Additives such as reinforcing fillers such as antioxidants, antioxidants, cleaning improvers and the like are appropriately contained as necessary.
Examples of the colorant, release agent, and charge control agent include the same colorants, release agents, and charge control agents that can be contained in the binder resin composition of the present invention, and preferred embodiments are also the same. is there.
In the case where the binder resin composition used in the production of the toner of the present invention does not contain a colorant, a release agent, and a charge control agent, in the toner production process described later, the colorant, the release agent, and It is preferable to add a charge control agent.
The content of the binder resin composition of the present invention in the toner of the present invention is the binder resin component constituting the binder resin composition of the present invention from the viewpoint of low-temperature fixability, durability, and gloss of printed matter. Is preferably 80% by mass or more, more preferably 85% by mass or more, still more preferably 90% by mass or more, and preferably 99% by mass or less, more preferably 97% by mass or less. The amount is more preferably 95% by mass or less.

The volume median particle size (D ₅₀ ) of the toner of the present invention is preferably 3 μm or more, more preferably 4 μm or more, still more preferably 5 μm or more, and preferably 15 μm or less, more preferably 10 μm or less, even more preferably. Is 8 μm or less.
In the present specification, the volume-median particle size (D ₅₀ ) means a particle size at which the cumulative volume frequency calculated by the volume fraction is 50% when calculated from the smaller particle size. Also, when processing a toner external additive, the volume median particle size of the toner particles prior to treatment with an external additive (D ₅₀₎ a toner having a volume-median particle size (D ₅₀₎ .

(External additive)
In the toner of the present invention, the toner particles containing the above-described components can be used as they are, but it is preferable to use a toner obtained by adding a fluidizing agent or the like to the toner particle surface as an external additive.
Examples of the external additive include hydrophobic silica, titanium oxide fine particles, alumina fine particles, cerium oxide fine particles, inorganic fine particles such as carbon black, and polymer fine particles such as polycarbonate, polymethyl methacrylate, and silicone resin. Among these, hydrophobic Silica is preferred. You may use an external additive individually or in combination of 2 or more types.
When the surface treatment of the toner particles is performed using an external additive, the amount of the external additive added is preferably 0.5 parts by mass or more, more preferably 100 parts by mass of the toner particles before the treatment with the external additive. Is 1.0 part by mass or more, more preferably 1.5 parts by mass or more, and preferably 5.0 parts by mass or less, more preferably 4.0 parts by mass or less, still more preferably 3.0 parts by mass or less. It is.

<Method for producing electrophotographic toner>
The toner of the present invention can be produced by a conventionally known method such as a melt-kneading method, an emulsion phase inversion method, or a polymerization method. Among these, the melt kneading method is preferable from the viewpoint of improving the dispersibility of the crystalline polyester (C).
In the melt-kneading method, the binder resin composition of the present invention and the optional component added as necessary are uniformly mixed with a mixer such as a Henschel mixer, and then a closed kneader, a single-screw or a twin-screw extrusion is used. A method of melt-kneading with a machine, an open roll kneader or the like, cooling, pulverizing, and classifying is preferable.
From the viewpoint of improving the dispersibility of the crystalline polyester (C), the melt kneading temperature is preferably 100 ° C. or higher, more preferably 110 ° C. or higher, still more preferably 115 ° C. or higher, and preferably 150 ° C. or lower. More preferably, it is 140 degrees C or less, More preferably, it is 130 degrees C or less.
When the binder resin composition used in the toner of the present invention is already melt-kneaded, the melt-kneading step in the toner production method is omitted, and the binder resin composition after melt-kneading is pulverized. The toner of the present invention can also be produced by classification.

  Each property such as resin and toner was measured and evaluated by the following method.

[Acid value of resin]
The acid value of the resin was measured based on the method of JIS K 0070. However, only the measurement solvent was changed from the mixed solvent of ethanol and ether specified in JIS K 0070 to a mixed solvent of acetone and toluene (acetone: toluene = 1: 1 (volume ratio)).

[Resin softening point, endothermic maximum peak temperature, melting point, crystallinity index, and glass transition temperature]
(1) Softening point of resin Using a flow tester (manufactured by Shimadzu Corporation, trade name: “CFT-500D”), 1.96 MPa by a plunger while heating a 1 g sample at a heating rate of 6 ° C./min. And was extruded from a nozzle having a diameter of 1 mm and a length of 1 mm. 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 and melting point of the resin Using a differential scanning calorimeter (manufactured by TA Instruments Japan, trade name: “Q-100”), the rate of temperature decrease from room temperature (20 ° C.) The sample cooled to 0 ° C. at 10 ° C./min was allowed to stand still for 1 minute, and then measured while raising the temperature to 180 ° C. at a rate of temperature increase of 10 ° C./min. Among the observed endothermic peaks, the temperature of the peak on the highest temperature side is defined as the maximum peak temperature of the endotherm, and if the maximum peak temperature is within 20 ° C. from the softening point, it is defined as the melting point of the crystalline polyester.
(3) Crystallinity index The ratio between the softening point measured as described above and the maximum endothermic peak temperature, that is, “softening point (° C.) / Maximum endothermic peak temperature (° C.)” was calculated, and the crystallinity It was an index.
(4) Glass transition temperature of amorphous resin Using a differential scanning calorimeter (trade name: “Q-100”, manufactured by TA Instruments Japan Co., Ltd.), a sample was 0.01 to 0.02 g. Was measured in an aluminum pan, heated to 200 ° C., and cooled to 0 ° C. from the temperature 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 indicating the maximum slope from the peak rising portion to the peak apex.
[Volume Median Particle Size (D ₅₀ ) of Toner and Toner Particles]
The volume median particle size (D ₅₀ ) of the toner and toner particles was measured as follows.
・ Measuring machine: "Coulter Multisizer III" (Beckman Coulter, Inc.)
・ Aperture diameter: 50μm
・ Analysis software: “Multisizer III version 3.51” (manufactured by Beckman Coulter)
・ Electrolyte: “Isoton II” (Beckman Coulter, Inc.)
-Dispersion: Polyoxyethylene lauryl ether "Emulgen (registered trademark) 109P" (manufactured by Kao Corporation, HLB: 13.6) was dissolved in the electrolytic solution to obtain a dispersion having a concentration of 5% by mass.
Dispersion condition: 10 mg of sample (converted to solid content) is added to 5 mL of the dispersion, and dispersed for 1 minute with an ultrasonic disperser, then 25 mL of electrolyte is added, and further for 1 minute with an ultrasonic disperser. A sample dispersion was prepared by dispersing.
Measurement conditions: The sample dispersion is added to 100 mL of the electrolytic solution to adjust the particle size of 30,000 particles to a concentration that can be measured in 20 seconds, and then 30,000 particles are measured and the particle size distribution thereof. From this, the volume median particle size (D ₅₀ ) was determined.

[Minimum fixing temperature]
The toner obtained in Examples and Comparative Examples 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 200 mm / sec) improved so that the fixing machine of the copying machine “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 the rub is measured by a reflection densitometer “RD-915” ( The temperature of the fixing roller in which the ratio between the two (after rubbing / before rubbing) first exceeded 70% was defined as the minimum fixing temperature. The lower the minimum fixing temperature, the better the low-temperature fixing property.

[Glossiness of printed matter]
A toner was mounted on a copying machine “AR-505” (manufactured by Sharp Corporation), and an image was printed without fixing (printing area: 2 cm × 12 cm, adhesion amount: 0.5 mg / cm ² ). The unfixed image was fixed on the print medium at 160 ° C. and 400 mm / sec with the fixing machine of the copying machine. Note that J paper (trade name, manufactured by Fuji Xerox Co., Ltd.) was used as the print medium.
A cardboard was laid under the image, and the glossiness of the printed matter was measured using a gloss meter (trade name: “IG-330”, manufactured by Horiba, Ltd.) under light irradiation conditions at an incident angle of 60 °. The higher the glossiness obtained, the better the glossiness.

[durability]
A toner was mounted on a non-magnetic one-component developing device “OKI MICROLINE 5400” (manufactured by Oki Data Co., Ltd.), and an endurance test was performed at a printing rate of 5% under an environment of a temperature of 32 ° C. and a humidity of 85%. On the way, a black solid image was printed every 500 sheets, and the presence or absence of streaks on the image was confirmed. Printing was stopped when streaks occurred on the image, and printing was performed up to 9000 sheets. The number of prints until the time when the streaks were visually observed on the image was defined as the number of streaks due to the fusion and fixing of the toner on the developing roll. The greater the number of printed sheets, the better the durability of the toner.

[Synthesis of propylene oxide adduct of bisphenol A]
Synthesis example 1
In an autoclave equipped with stirring and temperature control functions, 228 g (1 mol) of bisphenol A and 2 g of potassium hydroxide were added, and 139 g (2.2 mol) of propylene oxide was added at 135 ° C. under a pressure in the range of 0.1 to 0.4 MPa. And then added for 3 hours.
16 g of an adsorbent “KYOWARD 600” (manufactured by Kyowa Chemical Industry Co., Ltd., 2MgO.6SiO ₂ .XH ₂ O) was added to the reaction product, and the mixture was aged by stirring at 90 ° C. for 30 minutes. Thereafter, filtration was performed to obtain a propylene oxide adduct of bisphenol A (BPA-PO-C).

Synthesis example 2
In the same manner as in Synthesis Example 1 except that 139 g (2.2 mol) of propylene oxide was changed to 174 g (3 mol) of propylene oxide in Synthesis Example 1, a propylene oxide adduct (BPA-PO-A) of bisphenol A was used. )

Synthesis example 3
In the same manner as in Synthesis Example 1 except that 139 g (2.2 mol) of propylene oxide was changed to 232 g (4 mol) of propylene oxide in Synthesis Example 1, the propylene oxide adduct (BPA-PO-B) of bisphenol A was used. )

Synthesis example 4
In the same manner as in Synthesis Example 1 except that 139 g (2.2 mol) of propylene oxide was changed to 116 g (2 mol) of propylene oxide in Synthesis Example 1, a propylene oxide adduct (BPA-PO-D) of bisphenol A was used. )

[Synthesis of ethylene oxide adduct of bisphenol A]
Synthesis example 5
Except that 139 g (2.2 mol) of propylene oxide was changed to 97 g (2.2 mol) of ethylene oxide in Synthesis Example 1, an ethylene oxide adduct of bisphenol A (BPA-EO) was obtained in the same manner as in Synthesis Example 1. -C) was obtained.

  Table 1 shows the compositions of the propylene oxide adduct of bisphenol A and the ethylene oxide adduct of bisphenol A obtained in each synthesis example. For the composition, the mass ratio was calculated from the peak area ratio of gas chromatography, and the mass ratio was converted to the molecular weight to obtain mol%.

[Production of amorphous polyester]
Production Examples 1-11
(Amorphous polyester a-1 to a-3, A-1 to A-8)
A 10-liter four-necked flask equipped with a thermometer, a stainless stir bar, a flow-down condenser, and a nitrogen introduction tube is mixed with raw material monomers for polyester resin other than trimellitic anhydride and adipic acid shown in Table 2, 2-ethylhexane 45 g of tin (II) acid and 5 g of gallic acid were added and subjected to polycondensation 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, the reaction was continued until the softening point reached the softening point shown in Table 2, and amorphous polyester a-1 To a-3 and A-1 to A-8 were obtained. Table 2 shows the physical properties of the obtained amorphous polyester.

[Production of crystalline polyester (C)]
Production Examples 12-18
(Crystalline polyester C-1 to C-7)
The raw material monomers shown in Table 3 were placed in a 10-liter four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple, and held at 140 ° C. for 6 hours. Then, after heating up to 200 ° C. over 6 hours, 20 g of tin (II) 2-ethylhexanoate and 2 g of gallic acid were added and reacted at 200 ° C. for 1 hour. Furthermore, it was made to react at 8.3 kPa for 1 hour, and crystalline polyester C-1 to C-7 was obtained. Table 3 shows the physical properties of the obtained crystalline polyester.

Production Example 19
(Crystalline polyester C-8)
The raw material monomers shown in Table 3 and 2 g of tert-butylcatechol were placed in a 10 L four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer and a thermocouple, and held at 140 ° C. for 6 hours. Then, after heating up to 200 ° C. over 6 hours, 20 g of tin (II) 2-ethylhexanoate and 2 g of gallic acid were added and reacted at 200 ° C. for 1 hour. Furthermore, it was made to react at 8.3 kPa for 1 hour, and crystalline polyester C-8 was obtained. Table 3 shows the physical properties of the obtained crystalline polyester.

[Manufacture of toner for developing electrostatic image]
Examples 1-13, Comparative Examples 1-7
100 parts by mass of a binder resin in which the resins shown in Tables 4 and 5 are mixed, 5 parts by mass of a 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.) 1 part by mass and mold release agent “NP-105” (manufactured by Mitsui Chemicals, polypropylene wax, melting point: 140 ° C.) 2 parts by mass using a Henschel mixer After stirring, 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 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 with a cooling roller, and then pulverized with a jet mill to obtain toner particles having a volume-median particle size (D ₅₀ ) of 6.5 μm.

To 100 parts by mass of the toner particles obtained above, 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, manufactured by Nippon Aerosil Co., Ltd. (average particle size: 40 nm) is added in an amount of 1.0 part by mass and mixed with a Henschel mixer for 3,600 r / min for 5 minutes to perform external additive treatment. A toner having a unit particle size (D ₅₀ ) of 6.5 μm was obtained. The evaluation results of the obtained toner are shown in Tables 4 and 5.

  As is clear from Tables 4 and 5, the toners of Examples 1 to 13 obtained from the binder resin composition of the present invention were excellent in low-temperature fixability, durability, and gloss of printed matter.

Claims (9)

For toner containing amorphous polyester (AH) having a softening point of 120 ° C. or higher and 170 ° C. or lower, amorphous polyester (AL) having a softening point of 80 ° C. or higher and lower than 120 ° C., and crystalline polyester (C) A binder resin composition comprising:
The amorphous polyester (AH) is a polyester obtained by polycondensing an alcohol component (AH-al) containing an alkylene oxide adduct (AH-bp) of bisphenol A and a carboxylic acid component (AH-ac). Because
The alcohol component (AH-al) contains 3 mol% or more and less than 20 mol% of a propylene oxide adduct of bisphenol A having an addition mole number of propylene oxide of 3 mol or more and 6 mol or less,
The amorphous polyester (AL) is a polyester obtained by polycondensing an alcohol component (AL-al) containing an alkylene oxide adduct (AL-bp) of bisphenol A and a carboxylic acid component (AL-ac). Because
The binder resin composition for toner, wherein the alcohol component (AL-al) contains a propylene oxide adduct of bisphenol A having a propylene oxide addition mole number of 3 mol or more and 6 mol or less and 20 mol% or more and 70 mol% or less. .   The binder resin composition for toner according to claim 1, wherein the carboxylic acid component (C-ac), which is a raw material monomer of the crystalline polyester (C), contains an aliphatic dicarboxylic acid compound having 4 to 14 carbon atoms. .   The toner according to claim 1, wherein a mass ratio [(AL) / (AH)] of the amorphous polyester (AL) to the amorphous polyester (AH) is 0.6 or more and 4.0 or less. Binder resin composition.   The mass ratio [(AH + AL) / (C)] of the total amount of the amorphous polyester (AH) and the amorphous polyester (AL) to the crystalline polyester (C) is 65/35 to 97/3. The binder resin composition for toner according to any one of claims 1 to 3.   The average addition mole number of the alkylene oxide adduct (AH-bp) of bisphenol A contained in the alcohol component (AH-al) is 2.1 or more and 2.3 or less. Binder resin composition for toner.   The average addition mole number of the alkylene oxide adduct (AL-bp) of bisphenol A contained in the alcohol component (AL-al) is 2.3 or more and 3.0 or less. Binder resin composition for toner.   The binder resin for toner according to claim 1, wherein the alcohol component (C-al) which is a raw material monomer of the crystalline polyester (C) contains an aliphatic alcohol having 2 to 14 carbon atoms. Composition.   The toner for electrophotography containing the binder resin composition for toners in any one of Claims 1-7.   An electrophotographic toner obtained by melt-kneading the binder resin composition for toner according to claim 1.