JP2019174673A - Toner for electrostatic charge image development - Google Patents

Abstract

To provide a toner for electrostatic charge image development excellent in low-temperature fixability and stability with time of low-temperature fixability, and a method for manufacturing the same.SOLUTION: (1) A toner for electrostatic charge image development contains an amorphous resin having an acidic group, a compound B having a polyolefin skeleton, and at least one basic nitrogen-containing group selected from the group consisting of an amino group, an imino group, a cyano group, an azo group, a diazo group, and an azide group, and a crystalline polyester resin. (2) A method for manufacturing a toner for electrostatic charge image development includes a step of performing heat treatment under coexistence of an amorphous resin having an acidic group, a compound B having a polyolefin skeleton, and at least one basic nitrogen-containing group selected from the group consisting of an amino group, an imino group, a cyano group, an azo group, a diazo group, and an azide group, and a crystalline polyester resin, wherein the highest temperature in the step of performing the heat treatment is equal to or higher than a temperature lower by 10°C than the melting point of the compound B and is equal to or lower than a temperature higher by 100°C than the melting point of the compound B.SELECTED DRAWING: None

Description

  The present invention relates to an electrostatic image developing toner used for developing a latent image formed in an electrophotographic method, an electrostatic recording method, an electrostatic printing method, and the like, a method for producing the electrostatic image developing toner, and the like.

  In the field of electrophotography, with development of an electrophotographic system, development of toner for electrophotography corresponding to high image quality and high speed is demanded. In particular, as a method for obtaining a toner having excellent fixability at a low temperature, it is known to use a crystalline resin in addition to an amorphous resin conventionally used as a binder resin.

In Patent Document 1, a binder resin composition for toner containing an amorphous polyester and a crystalline polyester, wherein the amorphous polyester is an alcohol component and a carboxylic acid in the presence of a hydrocarbon wax having a hydroxyl group. A resin obtained by polycondensing a raw material monomer containing a component, the hydrocarbon wax has a melting point of 60 ° C. or more and 110 ° C. or less, a number average molecular weight of 600 or more, and the amount of the hydrocarbon wax is A binder resin composition for toner is described that is 0.5 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the total amount of the alcohol component and the carboxylic acid component. It is described that the resin composition is excellent in low-temperature fixability, storage stability, durability, and gloss.
Patent Document 2 describes an electrostatic charge image developing toner having toner particles and an external additive externally added to the surface of the toner particles, and an organic material having a nitrogen atom weight fraction of 5% to 50%. It describes that the compound has a compound on the surface of the toner particles and that the organic compound is polyethyleneimine. It is described that the toner does not easily cause a decrease in image density and in-plane unevenness of an image without generating fog even in a high temperature and high humidity environment.
In Patent Document 3, an electrostatic charge image development comprising a toner particle containing a binder resin and having at least one compound selected from an alkylated polyalkylene biguanide, an alkylated polyalkylene guanidine, and an alkylated polyalkyleneimine on the surface. Toner is described. Thus, it is described that a toner for developing an electrostatic charge image that suppresses occurrence of unevenness in image density can be obtained.

JP, 2006-4072, A JP 2014-134681 A JP-A-2015-184474

According to the toner of Patent Document 1, since it contains a crystalline resin, it is excellent in low-temperature fixability, but the problem that the low-temperature fixability gradually decreases by storing the toner for a long time under high-temperature and high-humidity conditions. Had. In Patent Documents 2 and 3, since the toner does not contain a crystalline resin, there is room for improvement from the viewpoint of low-temperature fixability.
The present invention relates to a toner for developing an electrostatic image having excellent low-temperature fixability and low-temperature fixability over time, and a method for producing the same.

The present invention relates to the following [1] to [2].
[1] An amorphous resin having an acidic group, a polyolefin skeleton, and at least one basic nitrogen-containing group selected from the group consisting of an amino group, an imino group, a cyano group, an azo group, a diazo group, and an azide group A toner for developing an electrostatic charge image, comprising a compound B having the formula (I) and a crystalline polyester resin.
[2] An amorphous resin having an acidic group, a polyolefin skeleton, and at least one basic nitrogen-containing group selected from the group consisting of an amino group, an imino group, a cyano group, an azo group, a diazo group, and an adi group Including a step of heat-treating in the coexistence of Compound B having a crystalline polyester resin,
A method for producing a toner for developing an electrostatic charge image, wherein a maximum temperature in the heat treatment step is not less than a temperature 10 ° C. lower than the melting point of the compound B and not more than 100 ° C. higher than the melting point of the compound B.

  According to the present invention, there are provided a toner for developing an electrostatic image having excellent low-temperature fixability and low-temperature fixability over time, and a method for producing the same.

[Toner for electrostatic image development]
An electrostatic charge image developing toner according to the present invention (hereinafter also simply referred to as “toner”) includes an amorphous resin having an acidic group (hereinafter also simply referred to as “amorphous resin A”), a polyolefin skeleton, A compound B (hereinafter also simply referred to as “compound B”) having at least one basic nitrogen-containing group selected from the group consisting of an amino group, an imino group, a cyano group, an azo group, a diazo group, and an azide group; A crystalline polyester resin (hereinafter also referred to as “crystalline polyester resin C”).
According to the above configuration, a toner having excellent low-temperature fixability and low-temperature fixability over time and a method for producing the same are provided.

Definitions of various terms and the like in this specification are shown below.
Whether the resin is crystalline or amorphous is determined by the crystallinity index. The crystallinity index is defined by the ratio between the softening point of the resin and the maximum endothermic peak temperature (softening point (° C.) / Maximum endothermic peak temperature (° C.)) in the measurement methods described in the examples described later. The crystalline resin is a resin having a crystallinity index of 0.6 or more and 1.4 or less. An amorphous resin is a resin having a crystallinity index of less than 0.6 or greater than 1.4. 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.
In the present specification, the “binder resin” means a resin component contained in the toner including the amorphous resin A and the crystalline polyester resin C.
In the specification, the carboxylic acid component of the polyester resin includes not only the exemplified compounds but also anhydrides that decompose to generate an acid during the reaction, and alkyl esters of each carboxylic acid (alkyl group having 1 to 3 carbon atoms). The following) are also included.
“Alkyl (meth) acrylate” refers to alkyl acrylate or alkyl methacrylate. In addition, “(iso)” with respect to the alkyl moiety means normal alkyl or isoalkyl.

<Amorphous resin A>
The amorphous resin A has an acidic group from the viewpoint of obtaining a toner having excellent low-temperature fixability and low-temperature fixability over time.
Examples of the acidic group include a carboxy group, a sulfo group, and a phosphoric acid group. Among these, a carboxy group is preferable.
The amorphous resin A is not particularly limited as long as it has an acidic group, and examples thereof include polyester resins and polystyrene resins. Of these, polyester resins are preferred. In the case of a polyester resin, the carboxy group at the end of the polymer chain of the resin corresponds to at least the aforementioned acidic group.
Examples of the polyester resin include polyester resins and modified polyester resins. Examples of the modified polyester resin include a urethane-modified polyester resin in which the polyester resin is modified with a urethane bond, an epoxy-modified polyester resin in which the polyester resin is modified with an epoxy bond, a polyester resin segment, and a vinyl resin segment. The composite resin containing is mentioned.

[Polyester resin]
The polyester resin is, for example, a condensate of an alcohol component and a carboxylic acid component.
Examples of the alcohol component include aromatic diols, linear or branched aliphatic diols, alicyclic diols, and trihydric or higher polyhydric alcohols. Among these, aromatic diols are preferable.
The aromatic diol is preferably an alkylene oxide adduct of bisphenol A, more preferably of formula (I):
(Wherein, OR ¹ and R ² O are oxyalkylene groups, R ¹ and R ² are each independently an ethylene group or a propylene group, x and y are the average number of moles of alkylene oxide added, And 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) alkylene of bisphenol A It is an oxide adduct.
Examples of the alkylene oxide adduct of bisphenol A include a propylene oxide adduct of bisphenol A [2,2-bis (4-hydroxyphenyl) propane] and an ethylene oxide adduct of bisphenol A. These may use 1 type (s) or 2 or more types.
The content of the alkylene oxide adduct of bisphenol A is preferably 70 mol% or more, more preferably 90 mol% or more, still more preferably 95 mol% or more, and 100 mol% or less in the alcohol component. More preferably, it is 100 mol%.

Examples of the linear or branched aliphatic diol include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, and 1,4-butanediol. 2,3-butanediol, 2,2-dimethyl-1,3-propanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, , 12-dodecanediol.
Examples of the alicyclic diol include hydrogenated bisphenol A [2,2-bis (4-hydroxycyclohexyl) propane] and hydrogenated bisphenol A alkylene oxide adduct having 2 to 4 carbon atoms (average added mole number 2 12 or less).
Examples of the trihydric or higher polyhydric alcohol include glycerin, pentaerythritol, trimethylolpropane, and sorbitol.
These alcohol components may be used alone or in combination of two or more.

Examples of the carboxylic acid component include dicarboxylic acids and trivalent or higher polyvalent carboxylic acids.
Examples of the dicarboxylic acid include aromatic dicarboxylic acid, linear or branched aliphatic dicarboxylic acid, and alicyclic dicarboxylic acid. Among these, at least one selected from the group consisting of aromatic dicarboxylic acids and linear or branched aliphatic dicarboxylic acids is preferable.
Examples of the aromatic dicarboxylic acid include phthalic acid, isophthalic acid, and terephthalic acid. Among these, isophthalic acid and terephthalic acid are preferable, and terephthalic acid is more preferable.
The amount of the aromatic dicarboxylic acid in the carboxylic acid component is preferably 20 mol% or more, more preferably 30 mol% or more, still more preferably 40 mol% or more, and preferably 90 mol% or less, more preferably It is 80 mol% or less, More preferably, it is 75 mol% or less.

The carbon number of the linear or branched aliphatic dicarboxylic acid is preferably 2 or more, more preferably 3 or more, and preferably 30 or less, more preferably 20 or less.
Examples of linear or branched aliphatic dicarboxylic acids include oxalic acid, malonic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, succinic acid, adipic acid, sebacic acid, dodecanedioic acid, azelaic acid And succinic acid substituted with an aliphatic hydrocarbon group having 1 to 20 carbon atoms. Examples of succinic acid substituted with an aliphatic hydrocarbon group having 1 to 20 carbon atoms include dodecyl succinic acid, dodecenyl succinic acid, and octenyl succinic acid. Among these, fumaric acid, adipic acid, sebacic acid, and succinic acid substituted with an aliphatic hydrocarbon group having 1 to 20 carbon atoms are preferable, and fumaric acid and sebacic acid are more preferable.
The amount of the linear or branched aliphatic dicarboxylic acid in the carboxylic acid component is preferably 1 mol% or more, more preferably 5 mol% or more, still more preferably 10 mol% or more, and preferably 40 mol%. Hereinafter, it is more preferably 30 mol% or less, and still more preferably 20 mol% or less.

The trivalent or higher polyvalent carboxylic acid is preferably a trivalent carboxylic acid, and examples thereof include trimellitic acid.
In the case of containing a trivalent or higher polyvalent carboxylic acid, the amount of the trivalent or higher polyvalent carboxylic acid is preferably 3 mol% or more, more preferably 5 mol% or more, still more preferably 10 mol% in the carboxylic acid component. And more preferably 40 mol% or less, more preferably 35 mol% or less, still more preferably 30 mol% or less.
These carboxylic acid components may be used alone or in combination of two or more.

  The equivalent ratio [COOH group / OH group] of the carboxylic acid component to the hydroxyl group of the alcohol component is preferably 0.7 or more, more preferably 0.8 or more, and preferably 1.3 or less, more Preferably it is 1.2 or less.

[Composite resin]
The composite resin includes a polyester resin segment and a vinyl resin segment. It is preferable that a polyester resin segment consists of the above-mentioned polyester resin.
The vinyl resin segment is preferably an addition polymer of a raw material monomer containing a styrene compound, and more preferably contains a styrene compound and a vinyl monomer having an aliphatic hydrocarbon group having 3 to 22 carbon atoms. It is an addition polymerization product of the raw material monomer.

Examples of the styrene compound include substituted or unsubstituted styrene. Examples of the substituent include an alkyl group having 1 to 5 carbon atoms, a halogen atom, an alkoxy group having 1 to 5 carbon atoms, a sulfo group, and a salt thereof.
Examples of the styrene compound include styrene, methyl styrene, α-methyl styrene, β-methyl styrene, tert-butyl styrene, chlorostyrene, chloromethyl styrene, methoxy styrene, styrene sulfonic acid or a salt thereof. Among these, styrene is preferable.
The amount of the styrene compound is preferably 50% by mass or more, more preferably 65% by mass or more, still more preferably 70% by mass or more, and 100% by mass or less in the raw material monomer of the vinyl resin segment. Preferably it is 95 mass% or less, More preferably, it is 90 mass% or less, More preferably, it is 85 mass% or less.

  The carbon number of the hydrocarbon group of the vinyl monomer having an aliphatic hydrocarbon group is preferably 3 or more, more preferably 4 or more, still more preferably 6 or more, and preferably 22 or less, more preferably 20 or less. More preferably, it is 18 or less.

Examples of the aliphatic hydrocarbon group include an alkyl group, an alkynyl group, and an alkenyl group. Among these, an alkyl group or an alkenyl group is preferable, and an alkyl group is preferable. The aliphatic hydrocarbon group may be branched or linear.
The vinyl monomer having an aliphatic hydrocarbon group is preferably an alkyl ester of (meth) acrylic acid. In the case of an alkyl ester of (meth) acrylic acid, the hydrocarbon group is the alcohol side residue of the ester.
Examples of alkyl esters of (meth) acrylic acid include (iso) propyl (meth) acrylate, (iso) butyl (meth) acrylate, (iso) hexyl (meth) acrylate, cyclohexyl (meth) acrylate, (Meth) acrylic acid 2-ethylhexyl (meth) acrylic acid (iso) octyl, (meth) acrylic acid (iso) decyl, (meth) acrylic acid (iso) dodecyl (hereinafter referred to as (meth) acrylic acid (iso) Lauryl), (meth) acrylic acid (iso) palmityl, (meth) acrylic acid (iso) stearyl, and (meth) acrylic acid (iso) behenyl. Among these, 2-ethylhexyl (meth) acrylate is preferable.

  The amount of the vinyl monomer having an aliphatic hydrocarbon group having 3 to 22 carbon atoms is preferably 5% by mass or more, more preferably 10% by mass or more, and further preferably 15% by mass in the raw material monomer of the vinyl resin segment. %, And preferably 50% by mass or less, more preferably 35% by mass or less, and still more preferably 25% by mass or less.

  Examples of other raw material monomers include ethylenically unsaturated monoolefins such as ethylene and propylene; conjugated dienes such as butadiene; halovinyls such as vinyl chloride; vinyl esters such as vinyl acetate and vinyl propionate; ) (Meth) acrylic acid aminoalkyl esters such as dimethylaminoethyl acrylate; vinyl ethers such as methyl vinyl ether; vinylidene halides such as vinylidene chloride; N-vinyl compounds such as N-vinylpyrrolidone.

  The total amount of the styrene compound and the vinyl monomer having an aliphatic hydrocarbon group having 3 to 22 carbon atoms in the raw material monomer in the vinyl resin segment is preferably 80% by mass or more, more preferably 90% by mass or more. More preferably, it is 95% by mass or more, and 100% by mass or less, preferably 100% by mass.

(Constituent units derived from amphoteric monomers)
In order to connect the polyester resin segment and the vinyl resin segment, the composite resin may have a structural unit derived from an amphoteric monomer that is bonded to the polyester resin segment and the vinyl resin segment via a covalent bond.
The “structural unit derived from both reactive monomers” means a unit in which the functional group and vinyl moiety of both reactive monomers are reacted.
Examples of the both reactive monomers include vinyl monomers having at least one functional group selected from the group consisting of a hydroxyl group, a carboxy group, an epoxy group, a primary amino group, and a secondary amino group in the molecule. Is mentioned. Among these, from the viewpoint of reactivity, a vinyl monomer having a hydroxyl group or a carboxy group is preferable, and a vinyl monomer having a carboxy group is more preferable.
Examples of the both reactive monomers include acrylic acid, methacrylic acid, fumaric acid, and maleic acid. Among these, acrylic acid or methacrylic acid is preferable, and acrylic acid is more preferable from the viewpoints of both the polycondensation reaction and the addition polymerization reaction.
The amount of the structural unit derived from the both reactive monomers is preferably 1 mol part or more, more preferably 3 mol part or more, still more preferably 5 mol part or more with respect to 100 mol part of the alcohol component of the polyester resin segment of the composite resin. And preferably 30 mol parts or less, more preferably 25 mol parts or less, still more preferably 20 mol parts or less.

The amount of the polyester resin segment in the composite resin is preferably 40% by mass or more, more preferably 50% by mass or more, still more preferably 60% by mass or more, still more preferably 70% by mass or more, and further preferably 75% by mass or more. Yes, and preferably 95% by mass or less, more preferably 90% by mass or less, and still more preferably 85% by mass or less.
The amount of the vinyl resin segment in the composite resin is preferably 5% by mass or more, more preferably 10% by mass or more, still more preferably 15% by mass or more, and preferably 60% by mass or less, more preferably 50% by mass. It is not more than mass%, more preferably not more than 40 mass%, still more preferably not more than 30 mass%.
The amount of the structural unit derived from the both reactive monomers is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, still more preferably 0.8% by mass or more in the composite resin, and preferably Is 10% by mass or less, more preferably 5% by mass or less, and still more preferably 3% by mass or less.
The total amount of the structural units derived from the polyester resin segment, the vinyl resin segment, and both reactive monomers in the composite resin is preferably 80% by mass or more, more preferably 90% by mass or more, still more preferably 93% by mass or more, More preferably, it is 95 mass% or more, and is 100 mass% or less, Preferably it is 99 mass% or less.

  The above amount is calculated based on the ratio of the amounts of the raw material monomer, the bireactive monomer, and the polymerization initiator of the polyester resin segment, vinyl resin segment, and does not consider the amount of dehydration due to polycondensation in the polyester resin segment. When a polymerization initiator is used, the mass of the polymerization initiator is calculated by including it in the vinyl resin segment.

[Method for producing amorphous resin A]
When the amorphous resin A is a polyester resin, it can be obtained, for example, by polycondensation of an alcohol component and a carboxylic acid component.
If necessary, an esterification catalyst such as di (2-ethylhexanoic acid) tin (II), dibutyltin oxide, titanium diisopropylate bistriethanolamate is added to 100 parts by mass of the total amount of the alcohol component and the carboxylic acid component. 0.01 parts by mass or more and 5 parts by mass or less; 0% of an esterification cocatalyst such as gallic acid (same as 3,4,5-trihydroxybenzoic acid) is 100 parts by mass with respect to 100 parts by mass of the alcohol component and the carboxylic acid component. Polycondensation may be performed using 0.001 part by mass or more and 0.5 part by mass or less.
The temperature of the polycondensation reaction is preferably 120 ° C. or higher, more preferably 160 ° C. or higher, still more preferably 180 ° C. or higher, and preferably 250 ° C. or lower, more preferably 240 ° C. or lower. The polycondensation may be performed in an inert gas atmosphere.

When the amorphous resin A is a composite resin, for example, a step A of performing a polycondensation reaction with an alcohol component and a carboxylic acid component, and a step of performing an addition polymerization reaction with a raw material monomer of the vinyl-based resin segment and an amphoteric monomer. And B.
Step B may be performed after step A, step A may be performed after step B, or step A and step B may be performed simultaneously.
In Step A, a part of the carboxylic acid component is subjected to a polycondensation reaction, and then Step B is performed. Then, the remainder of the carboxylic acid component is added to the polymerization system, and the polycondensation reaction in Step A and both reactions as necessary. A method of further promoting the reaction with the functional monomer is preferred.
The conditions of the process A are the same as the manufacturing method of the above-mentioned polyester resin.

Examples of the polymerization initiator for the addition polymerization reaction include peroxides such as dibutyl peroxide, persulfates such as sodium persulfate, and azo compounds such as 2,2′-azobis (2,4-dimethylvaleronitrile). Can be mentioned.
The amount of the polymerization initiator used is preferably 1 part by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the raw material monomer of the vinyl resin segment.
The temperature of the addition polymerization reaction is preferably 110 ° C. or higher, more preferably 130 ° C. or higher, and preferably 220 ° C. or lower, more preferably 210 ° C. or lower.

[Physical properties of amorphous resin A]
The softening point of the amorphous resin A is preferably 70 ° C. or higher, more preferably 90 ° C. or higher, further preferably 100 ° C. or higher, and preferably 140 ° C. or lower, from the viewpoint of further improving the heat resistant storage stability. More preferably, it is 130 degrees C or less, More preferably, it is 125 degrees C or less.
The glass transition temperature of the amorphous resin A is preferably 30 ° C. or higher, more preferably 35 ° C. or higher, and still more preferably 40 ° C. or higher, from the viewpoint of further improving the heat resistant storage stability. From the viewpoint of improving, it is preferably 80 ° C. or lower, more preferably 75 ° C. or lower, and further preferably 70 ° C. or lower.

The acid value of the amorphous resin A is preferably 5 mgKOH / g or more, more preferably 10 mgKOH / g or more, still more preferably 15 mgKOH / g or more, from the viewpoint of further improving the heat resistant storage stability and low-temperature fixability. , Preferably 40 mgKOH / g or less, more preferably 35 mgKOH / g or less, and still more preferably 30 mgKOH / g or less.
The softening point, glass transition temperature, and acid value of the amorphous resin A can be appropriately adjusted depending on the type of raw material monomer and the amount used, and the production conditions such as reaction temperature, reaction time, and cooling rate. These values are determined by the method described in the examples.
In addition, when using 2 or more types of amorphous resin A in combination, it is preferable that the value of the softening point, glass transition temperature, and acid value which were obtained as those mixtures is in the above-mentioned range, respectively.

  In the toner binder resin, the content of the amorphous resin A is preferably 50% by mass or more, more preferably 60% by mass or more, still more preferably 70% by mass or more, and 100% by mass or less. Preferably, it is 99 mass% or less, More preferably, it is 95 mass% or less, More preferably, it is 90 mass% or less, More preferably, it is 88 mass% or less.

<Compound B>
Compound B has a polyolefin skeleton and a basic nitrogen-containing group from the viewpoint of obtaining a toner having excellent low-temperature fixability and low-temperature fixability over time. Compound B is preferably dispersed in amorphous resin A. That is, it is preferable that the compound B is dispersed inside the toner particles.

Basic nitrogen-containing groups include amino groups, imino groups (═NH), cyano groups (—CN), azo groups (—N═N—), diazo groups (═N ₂ ), and azido groups (—N ₃ ). Is at least one selected from the group consisting of
The amino group may be a primary amino group, a secondary amino group, or a tertiary amino group.
From the viewpoint of the affinity of compound B for binder resin A, an amino group is preferred.

  Examples of the functional group other than the basic nitrogen-containing group include a hydroxy group, a formyl group, an acetal group, an oxime group, and a thiol group.

Compound B has a polyolefin skeleton from the viewpoint of obtaining a toner having excellent low-temperature fixability and low-temperature fixability over time.
Examples of the polyolefin that forms the polyolefin skeleton include polyethylene, polypropylene, polybutylene, polymethylpentene, polytetradecene, polyhexadecene, polyoctadecene, polyeicosene, polydocosene, and copolymers of these monomers.
The polyolefin skeleton is preferably a polypropylene skeleton, a polyethylene skeleton, or a propylene / polyethylene copolymer skeleton, more preferably a polyethylene skeleton or a polypropylene skeleton, and still more preferably a polypropylene skeleton.

Compound B is, for example, a reaction product of a basic nitrogen-containing group material and a polyolefin skeleton material.
Examples of basic nitrogen-containing group raw materials include polyamine compounds.
Examples of the polyamine compound include polyalkyleneamine, polyallylamine, and polyaminoalkyl methacrylate.
The polyamine compound is preferably a polyalkyleneamine having at least one amino group selected from the group consisting of primary and secondary from the viewpoint of adsorptivity to the binder resin having an acidic group.
Examples of the polyalkylene amine include polyethylene amine, polypropylene amine, and polybutylene amine.
Examples of the polyethyleneamine include diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, and polyethyleneimine having a number average molecular weight of 300 to 15,000. Among these, tetraethylenepentamine, pentaethylenehexamine, and polyethyleneimine having a number average molecular weight of 300 to 3,000 are more preferable, and polyethyleneimine having a number average molecular weight of 300 to 2,000 is more preferable.

The polyethyleneimine preferably contains, for example, a primary amino group, a secondary amino group, and a tertiary amino group and has a branched structure.
Examples of the commercially available polyethyleneimine include “SP-003”, “SP-006”, “SP-012”, and “SP-018” (manufactured by Junsei Chemical Co., Ltd.) of the “Epomin” series. .
Examples of the polyaminoalkyl methacrylate include polydimethylaminoethyl methacrylate.

The amine value of the basic nitrogen-containing group raw material is preferably 1 mmol / g or more, more preferably 3 mmol / g or more, still more preferably 5 mmol / g or more, and preferably 50 mmol / g or less, more preferably 40 mmol / g. g or less, more preferably 30 mmol / g or less, still more preferably 25 mmol / g or less.
The amine value of the basic nitrogen-containing group material can be measured by the method described later.

The number average molecular weight of the basic nitrogen-containing group raw material is preferably 100 or more, more preferably 300 or more, still more preferably 500 or more, and still more preferably 1,000 or more, from the viewpoint of adsorptivity to the resin having an acidic group. And preferably 15,000 or less, more preferably 10,000 or less, still more preferably 5,000 or less, still more preferably 3,000 or less, and still more preferably 2,000 or less.
Among these, polyethyleneimine is preferable from the viewpoint of improving low-temperature fixability and low-temperature fixability over time.

Examples of the polyolefin skeleton raw material include polyolefin having a reactive functional group. Examples of the reactive functional group include a carboxy group, a halogeno group, an epoxy group, a formyl group, and an isocyanate group. The carboxy group may be its anhydride. Examples of the halogeno group include a chloro group, a bromo group, and an iodo group. Among these, from the viewpoints of safety and reactivity, a carboxy group or an anhydride thereof and a halogeno group are preferable, and a carboxy group or an anhydride thereof is more preferable.
Examples of the polyolefin skeleton raw material include maleic anhydride-modified polyolefin such as maleic anhydride-modified polypropylene, maleic anhydride-modified polyethylene, maleic anhydride-modified ethylene / propylene copolymer, maleic anhydride-modified ethylene / hexene copolymer. It is done.
The acid-modified polyolefin is preferably a single-terminal acid-modified polyolefin, and more preferably a single-terminal maleic anhydride-modified polyolefin.

  The content of the polyolefin having a reactive functional group in the polyolefin skeleton raw material is preferably 70% by mass or more, more preferably 80% by mass or more, still more preferably 90% by mass or more, and 100% by mass or less. More preferably, it is 100 mass%.

  The melting point of the polyolefin skeleton raw material is preferably 60 ° C. or higher, more preferably 70 ° C. or higher, still more preferably 80 ° C. or higher, and preferably 160 ° C. or lower, more preferably 150 ° C. or lower, still more preferably 140 ° C. or lower. It is.

The number average molecular weight of the polyolefin skeleton raw material is preferably 100 or more, more preferably 200 or more, still more preferably 300 or more, and preferably 5,000 or less, more preferably 3,000 or less, still more preferably 2, 000 or less.
The number average molecular weight of the polyolefin skeleton raw material can be determined by, for example, a gel permeation chromatography (GPC) method.

  Examples of the polypropylene skeleton material having a polypropylene skeleton include “100Ts”, “110Ts”, “1001”, “1010” (manufactured by Sanyo Chemical Industries, Ltd.) of “Yumex” series, “13” of “Hardlen” series. -LP "," 13-LLP "," 14-LWP "," 15-LP "," 15-LLP "," 16-LP "," DX-526P "," CY-9122P "," CY-9124P " ”,“ HM-21P ”,“ M-28P ”,“ F-2P ”,“ F-6P ”(above, manufactured by Toyobo Co., Ltd.),“ M-100 ”,“ M-300 ”of“ Toyo Tack ”series "," M-312 "," PMA H1000P "," PMA-F2 "(above, manufactured by Toyobo Co., Ltd.)," C "," L-206 "," 81 " A ”,“ 803M ”,“ 803MW ”,“ 803LT ”,“ 1026 ”,“ 803L ”,“ 814H ”,“ 390S ”,“ 814B ”,“ 360T ”,“ 370M ”,“ 2027MB ”,“ 822 ” , “892L”, “930”, “842LM”, “851L” (above, manufactured by Nippon Paper Industries Co., Ltd.), “X-10065”, “X-10088”, “X-10082”, “X-10087”, “X-10053”, “X-10052” (manufactured by Baker Hughes) may be mentioned.

[Method for Producing Compound B]
Compound B is obtained by a reaction between a basic nitrogen-containing group material and a polyolefin skeleton material.
The reaction temperature is preferably 100 ° C. or higher, more preferably 120 ° C. or higher, further preferably 150 ° C. or higher, and preferably 200 ° C. or lower, more preferably 180 ° C. or lower, still more preferably 170 ° C. or lower.

  The ratio (A / N) of the number of moles (A) of reactive functional groups of the polyolefin skeleton raw material to the number of moles of basic nitrogen (N) of the basic nitrogen-containing group raw material is preferably 0.1 or more, more preferably Is 0.2 or more, more preferably 0.3 or more, and preferably 0.8 or less, more preferably 0.7 or less, and still more preferably 0.6 or less.

In the case of a reaction between a polyamine compound and maleic anhydride-modified polyolefin, it is preferable that an imide bond is formed by the reaction. Formation of an imide bond can be confirmed by observing a peak (1700 cm ⁻¹ ) derived from an imide bond by infrared spectroscopy (hereinafter, also simply referred to as “IR”).

[Physical properties of compound B]
The melting point of Compound B is preferably 34 ° C. or higher, more preferably 50 ° C. or higher, still more preferably 65 ° C. or higher, more preferably 80 ° C. or higher, from the viewpoint of improving low temperature fixability and stability over time of low temperature fixability. Yes, and preferably 150 ° C. or lower, more preferably 140 ° C. or lower, and still more preferably 130 ° C. or lower.
The measuring method of melting | fusing point is based on the method as described in an Example.

  The number average molecular weight of the compound B is preferably 500 or more, more preferably 800 or more, still more preferably 1,000 or more, and preferably from the viewpoint of improving low-temperature fixability and low-temperature fixability over time. It is 10,000 or less, more preferably 7,000 or less, and still more preferably 5,000 or less.

The amine value of Compound B is preferably 1 mmol / g or more, more preferably 3 mmol / g or more, still more preferably 5 mmol / g or more, from the viewpoint of improving low temperature fixability and stability over time of low temperature fixability. , Preferably 50 mmol / g or less, more preferably 40 mmol / g or less, still more preferably 30 mmol / g or less, still more preferably 25 mmol / g or less, still more preferably 15 mmol / g or less.
The amine value of Compound B can be measured by the method described later.

  The content of the compound B is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, further preferably 1 part by mass or more, and further preferably 3 parts by mass with respect to 100 parts by mass of the binder resin. From the viewpoint of chargeability of the toner particles, preferably 40 parts by mass or less, more preferably 30 parts by mass or less, and still more preferably 20 parts by mass. Or less.

<Crystalline polyester resin C>
The toner contains a crystalline polyester resin C from the viewpoint of obtaining a toner having excellent low-temperature fixability and low-temperature fixability over time.
The crystalline polyester resin C is, for example, a polycondensate of an alcohol component and a carboxylic acid component, and preferably a polycondensation of an alcohol component containing an α, ω-aliphatic diol and a carboxylic acid component containing an aliphatic dicarboxylic acid. It is a thing.
The carbon number of the α, ω-aliphatic diol is preferably 2 or more, more preferably 4 or more, still more preferably 6 or more, and preferably 16 or less, more preferably 14 or less, still more preferably 12 or less. is there.
Examples of the α, ω-aliphatic diol 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, 1,11-undecanediol, 1,12-dodecanediol, 1,13-tridecanediol, 1,14-tetradecanediol Can be mentioned. Among these, ethylene glycol, 1,4-butanediol, 1,6-hexanediol and 1,10-decanediol are preferable from the viewpoint of further improving the low-temperature fixability, and 1,4-butanediol, 1,10 -Decanediol is more preferred, and 1,10-decanediol is still more preferred.
The amount of α, ω-aliphatic diol is preferably 80 mol% or more, more preferably 85 mol% or more, still more preferably 90 mol% or more, still more preferably 95 mol% or more in the alcohol component, and 100 mol%. It is less than mol%, more preferably 100 mol%.

  The alcohol component may contain another alcohol component different from the α, ω-aliphatic diol. Examples of other alcohol components include aliphatic diols other than α, ω-aliphatic diols such as 1,2-propylene glycol and neopentyl glycol; aromatic diols such as alkylene oxide adducts of bisphenol A; glycerin and penta Examples thereof include trihydric or higher alcohols such as erythritol and trimethylolpropane. These alcohol components may be used alone or in combination of two or more.

Examples of the carboxylic acid component include aliphatic dicarboxylic acids.
The carbon number of the aliphatic dicarboxylic acid is preferably 4 or more, more preferably 8 or more, still more preferably 10 or more, and preferably 14 or less, more preferably 12 or less.
Examples of the aliphatic dicarboxylic acid include fumaric acid, sebacic acid, dodecanedioic acid, and tetradecanedioic acid. Among these, from the viewpoint of further improving the low-temperature fixability, sebacic acid, dodecanedioic acid, and tetradecanedioic acid are preferable, sebacic acid and tetradecanedioic acid are more preferable, and sebacic acid is more preferable. These carboxylic acid components may be used alone or in combination of two or more.
The amount of the aliphatic dicarboxylic acid in the carboxylic acid component is preferably 80 mol% or more, more preferably 85 mol% or more, still more preferably 90 mol% or more, still more preferably 95 mol% or more, and 100 mol%. % Or less, more preferably 100 mol%.

  The carboxylic acid component may contain another carboxylic acid component different from the aliphatic dicarboxylic acid. Examples of other carboxylic acid components include aromatic dicarboxylic acids such as terephthalic acid and isophthalic acid; and trivalent or higher polyvalent carboxylic acids. These carboxylic acid components may be used alone or in combination of two or more.

  The equivalent ratio of the carboxyl group of the carboxylic acid component to the hydroxyl group of the alcohol component (COOH group / OH group) is preferably 0.7 or more, more preferably 0.8 or more, and preferably 1.3 or less, more Preferably it is 1.2 or less.

  The crystalline polyester resin C is obtained, for example, by polycondensation of an alcohol component and a carboxylic acid component. As the conditions for the polycondensation, for example, the conditions shown for the polycondensation in the polyester resin of the amorphous resin A can be applied.

[Physical properties of crystalline polyester resin C]
The softening point of the crystalline polyester resin C is preferably 60 ° C. or higher, more preferably 70 ° C. or higher, and still more preferably 80 ° C. or higher, from the viewpoint of further improving the temporal stability of the low-temperature fixability. From the viewpoint of further improving the properties, it is preferably 150 ° C. or lower, more preferably 120 ° C. or lower, and still more preferably 100 ° C. or lower.

  The melting point of the crystalline polyester resin C is preferably 50 ° C. or higher, more preferably 60 ° C. or higher, and still more preferably 70 ° C. or higher, from the viewpoint of further improving the temporal stability of the low temperature fixability. From the viewpoint of further improving the temperature, it is preferably 100 ° C. or lower, more preferably 90 ° C. or lower.

  The acid value of the crystalline polyester resin C is preferably 5 mgKOH / g or more, more preferably 10 mgKOH / g or more, and preferably 35 mgKOH from the viewpoint of further improving the low-temperature fixability and the stability over time of the low-temperature fixability. / G or less, more preferably 30 mgKOH / g or less, still more preferably 25 mgKOH / g or less.

  The softening point, melting point, and acid value of the crystalline polyester resin C can be appropriately adjusted according to the type and ratio of the raw material monomers and the production conditions such as reaction temperature, reaction time, and cooling rate. These values are determined by the method described in the examples below. In addition, when using 2 or more types of crystalline polyester resin C combining, it is preferable that the value of the softening point, melting | fusing point, acid value, and hydroxyl value which were obtained as those mixtures is in the said range, respectively.

  In the toner binder resin, the content of the crystalline polyester resin C is preferably 1% by mass or more, more preferably 5% by mass or more, still more preferably 10% by mass or more, and further preferably 12% by mass or more. And preferably it is 50 mass% or less, More preferably, it is 40 mass% or less, More preferably, it is 30 mass% or less.

  The mass ratio [A / C] of the amorphous resin A and the crystalline polyester resin C is preferably 50/50 or more, more preferably from the viewpoint of further improving the low-temperature fixability and the temporal stability of the low-temperature fixability. 60/40 or more, more preferably 70/30 or more, and preferably 99/1 or less, more preferably 95/5 or less, still more preferably 90/10 or less, and still more preferably 88/12 or less.

  In the binder resin of toner particles, the content of the amorphous resin A and the crystalline polyester resin C is preferably 80% by mass or more, more preferably 90% by mass or more, still more preferably 95% by mass or more, and , 100% by mass or less, and preferably 100% by mass.

<Wax>
The toner may contain a wax.
Examples of the wax include polypropylene wax, polyethylene wax, polypropylene polyethylene copolymer wax; hydrocarbon wax such as microcrystalline wax, paraffin wax, Fischer-Tropsch wax, sazol wax, or oxides thereof; carnauba wax, montan wax or Examples thereof include ester waxes such as deoxidized wax and fatty acid ester wax; fatty acid amides, fatty acids, higher alcohols, and fatty acid metal salts. These may use 1 type (s) or 2 or more types.

The melting point of the wax is preferably 60 ° C. or higher, more preferably 70 ° C. or higher, and preferably 160 ° C. or lower, more preferably 150 ° C. or lower, and still more preferably 140 ° C. or lower.
The wax content is preferably 0.1 parts by mass or more, more preferably 1 part by mass or more, still more preferably 2 parts by mass or more, and preferably 20 parts by mass with respect to 100 parts by mass of the binder resin. Hereinafter, it is more preferably 10 parts by mass or less, and still more preferably 5 parts by mass or less.

<Charge control agent>
The toner may contain a charge control agent.
The charge control agent may contain either a positive charge control agent or a negative charge control agent.
Examples of positively chargeable charge control agents include nigrosine dyes such as “Nigrosine Base EX”, “Oil Black BS”, “Oil Black SO”, “Bontron N-01”, “Bontron N-04”, “Bontron N-07”. ”,“ Bontron N-09 ”,“ Bontron N-11 ”(manufactured by Orient Chemical Co., Ltd.) and the like; triphenylmethane dyes containing tertiary amines as side chains, quaternary ammonium salt compounds such as“ Bontron P-51 "(manufactured by Orient Chemical Co., Ltd.), cetyltrimethylammonium bromide," COPY CHARGE PX VP435 "(manufactured by Clariant), etc .; polyamine resin such as" AFP-B "(manufactured by Orient Chemical Industry Co., Ltd.), etc. Imidazole derivatives such as “PLZ-2001”, “PLZ-800”; "(Above, manufactured by Shikoku Chemicals Corporation) and the like; 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 “Varifirst Black 3804”, “Bontron S-31”, “Bontron S-32”, “Bontron S-34”, “Bontron S-36” ( As described above, manufactured by Orient Chemical Co., Ltd.), “Eisenspiron Black TRH”, “T-77” (manufactured by Hodogaya Chemical Co., Ltd.), etc .; metal compounds of benzylic acid compounds such as “LR-147”, “ LR-297 "(manufactured by Nippon Carlit Co., Ltd.), etc .; metal compounds of salicylic acid compounds such as" Bontron E-81 "," Bontron E-84 "," Bontron E-88 "," Bontron E-304 " (Above, made by Orient Chemical Co., Ltd.), “TN-105” (made by Hodogaya Chemical Co., Ltd.), etc .; copper phthalocyanine dye; quaternary ammonium salt Examples thereof include “COPY CHARGE NX VP434” (manufactured by Clariant), nitroimidazole derivatives, and the like; and organometallic compounds.
Among charge control agents, negatively chargeable charge control agents are preferable, and metal compounds of salicylic acid compounds are more preferable.

  The content of the charge control agent is preferably 0.01 parts by mass or more, more preferably 0.1 parts by mass or more, and preferably 10 parts by mass or less, more preferably 100 parts by mass of the binder resin. Is 5 parts by mass or less, more preferably 1 part by mass or less.

<Colorant>
The toner may contain a colorant.
As the colorant, all of dyes and pigments used as colorants for toners can be used. For example, 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. The toner of the present invention may be either black toner or color toner other than black.

  From the viewpoint of improving the image density of the 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. Part or less, more preferably 20 parts by weight or less, still more preferably 10 parts by weight or less.

  In addition, the toner may contain additives such as magnetic powder, fluidity improver, conductivity adjuster, reinforcing filler such as fibrous substance, antioxidant, anti-aging agent, and cleanability improver.

The toner includes, for example, toner particles. The toner particles preferably contain amorphous resin A, compound B, and crystalline polyester resin C. Wax, charge control agent, colorant, and other additives are preferably contained in the toner particles.
Although the toner particles can be used as the toner as they are, it is preferable to use a toner obtained by adding an external additive described later to the surface of the toner particles.
The toner is preferably used as a dry toner.

[Toner Production Method]
The toner may be a toner obtained by any known method such as melt kneading method, emulsion phase inversion method, emulsion polymerization method, emulsion aggregation method, etc., but from the viewpoint of productivity and dispersibility of the colorant, A pulverized toner obtained by a melt kneading method is preferred.
The toner production method of the present invention is preferably selected from the group consisting of an amorphous resin A having an acidic group, a polyolefin skeleton, and an amino group, imino group, cyano group, azo group, diazo group, and azide group. A step of heat-treating in the presence of the compound B having at least one basic nitrogen-containing group and the crystalline polyester resin C.
Here, the maximum temperature of the heat treatment step is not less than a temperature 10 ° C. lower than the melting point of the compound B and not more than 100 ° C. higher than the melting point of the compound B.
By such a manufacturing method, the low-temperature fixability and low-temperature fixability of the toner over time are further improved. Although it is not certain, heat treatment at a temperature of 10 ° C. or lower than the melting point of Compound B in the presence of Amorphous Resin A, Compound B and Crystalline Polyester Resin C gives amorphous resin A and Compound B Compound B can be finely dispersed in non-crystalline resin A while exerting chemical interaction, and compound B can be finely dispersed in amorphous resin A, and the dispersibility of crystalline polyester resin C is enhanced by the polyolefin skeleton of compound B. It is considered that the low-temperature fixability of the toner and the stability over time of the low-temperature fixability are further improved.

The heat treatment step is a step of treating at the highest temperature in the coexistence of the amorphous resin A, the compound B, and the crystalline polyester resin C in the toner production process.
For example, in the melt-kneading method, the melt-kneading process described later corresponds to the heat treatment process. In the emulsion aggregation method, the fusion step after aggregation corresponds to the heat treatment step.

  The maximum temperature of the heat treatment step is preferably at least 10 ° C. lower than the melting point of Compound C, more preferably 5 ° C. lower than the melting point of Compound C, from the viewpoint of further improving low temperature fixability and stability over time of low temperature fixability. More than temperature, more preferably more than the melting point of Compound B, more preferably more than 5 ° C higher than the melting point of Compound B, more preferably more than 10 ° C higher than the melting point of Compound B, more preferably more than 15 ° C than the melting point of Compound B. The temperature is higher than the high temperature, and preferably 100 ° C. or lower than the melting point, more preferably 60 ° C. or lower, more preferably 30 ° C. or lower than the melting point.

In the case of pulverized toner, the toner production method is, for example,
Step 1: Melting and kneading a mixture containing amorphous resin A, compound B, and crystalline polyester resin C, and Step 2: grinding and classifying the melt-kneaded product obtained in Step 1 to obtain toner particles Process.
It is preferable that the maximum temperature in the said process 1 is the range of the maximum temperature of the process to heat-treat.

In step 1, the mixture may contain additives such as a wax, a charge control agent, and a colorant. These toner materials are preferably mixed in advance with a mixer such as a Henschel mixer or a ball mill and then supplied to the kneader.
The melt kneading in Step 1 can be performed using a known kneader such as a closed kneader, a single screw extruder, a twin screw extruder, or an open roll kneader. Among these, a twin screw extruder capable of setting the kneading temperature widely is preferable.
The temperature for melt kneading is preferably 80 ° C. or higher and 160 ° C. or lower.
The melt-kneaded product obtained in step 1 is cooled to such an extent that it can be crushed, and then subjected to subsequent step 2.

The pulverization in step 2 may be performed in multiple stages. For example, the melt-kneaded material may be coarsely pulverized to 1 mm or more and 5 mm or less, and further pulverized to a desired particle size.
Examples of the pulverizer suitably used for coarse pulverization include a hammer mill, an atomizer, and a rotoxplex. Examples of the pulverizer suitably used for fine pulverization include a fluidized bed jet mill, a collision plate jet mill, and a rotary mechanical mill. Among these, from the viewpoint of grinding efficiency, a fluidized bed jet mill and a collision plate jet mill are preferable, and a collision plate jet mill is more preferable.

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

The volume median particle size (D ₅₀ ) of the toner particles is preferably 2 μm or more, more preferably 3 μm or more, still more preferably 4 μm or more, and preferably 10 μm or less, from the viewpoint of obtaining a high-quality image. Preferably it is 8 micrometers or less.
The CV value of the toner particles is preferably 12% or more, more preferably 14% or more, still more preferably 16% or more, and preferably 45% or less, more preferably 40%, from the viewpoint of obtaining a high-quality image. % Or less.

The toner is preferably added to the surface of the toner particles using a fluidizing agent or the like as an external additive.
Examples of the external additive include fine particles of inorganic material such as hydrophobic silica, titanium oxide, alumina, cerium oxide, and carbon black, and fine polymer particles such as polycarbonate, polymethyl methacrylate, and silicone resin. Among these, hydrophobic silica is preferable.
When the external additive is used, the amount of the external additive added is preferably 1 part by mass or more, more preferably 2 parts by mass or more, and further preferably 3 parts by mass or more with respect to 100 parts by mass of the toner particles. The amount is preferably 5 parts by mass or less, more preferably 4.5 parts by mass or less, and still more preferably 4 parts by mass or less.

  The toner is used for developing a latent image formed in electrophotography, electrostatic recording method, electrostatic printing method or the like. The toner can be used as a one-component developer or a two-component developer mixed with a carrier.

  Each property value was measured and evaluated by the following method.

[Measurement]
[Acid value of the resin]
The acid value of the resin was measured according to the neutralization titration method described in JIS K 0070-1992. However, the measurement solvent was chloroform.

[Resin softening point, crystallinity index, endothermic peak temperature and glass transition temperature]
(1) Softening point Using a flow tester “CFT-500D” (manufactured by Shimadzu Corporation), a 1 g sample was heated at a heating rate of 6 ° C./min, and a load of 1.96 MPa was applied by a plunger. The nozzle was extruded from a nozzle having a length 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) Crystallinity index, maximum peak temperature of endotherm Using a differential scanning calorimeter “Q100” (manufactured by TA Instruments Japan Co., Ltd.), 0.02 g of a sample is weighed into an aluminum pan and room temperature (20 ° C.). Then, it was cooled to 0 ° C. at a temperature lowering rate of 10 ° C./min. Next, the sample was kept as it was for 1 minute, and then the temperature was raised to 180 ° C. at a temperature rising rate of 10 ° C./min, and the amount of heat was measured. Of the observed endothermic peaks, the temperature of the peak with the largest peak area is defined as the maximum endothermic peak temperature (1), and (softening point (° C)) / (maximum endothermic peak temperature (1) (° C)), The crystallinity index was determined.
(3) Glass transition temperature Using a differential scanning calorimeter “Q100” (manufactured by TA Instruments Japan Co., Ltd.), 0.02 g of a sample is weighed into an aluminum pan, heated to 200 ° C., and the temperature is lowered from that temperature. Cooled to 0 ° C. at a rate of 10 ° C./min. Next, the sample was heated at a temperature rising rate of 10 ° C./min, and the amount of heat was measured. Among the observed endothermic peaks, the temperature of the peak having the maximum peak area was defined as the maximum endothermic temperature (2). In the case of a crystalline resin, the peak temperature was taken as the melting point.
In the case of an amorphous resin, when the peak is observed, the temperature of the peak is measured. When the step is observed without the peak being observed, the tangent indicating the maximum slope of the curve of the step and the step The glass transition temperature was defined as the temperature at the intersection with the base line extension on the low temperature side.

[Melting point of wax and polyolefin skeleton raw material]
Using a differential scanning calorimeter “Q100” (manufactured by TA Instruments Japan Co., Ltd.), 0.02 g of a sample was weighed into an aluminum pan, heated to 200 ° C., and then cooled down from 200 ° C. to 10 ° C./min. At 0 ° C. Next, the sample was heated at a temperature rising rate of 10 ° C./min, the amount of heat was measured, and the maximum peak temperature of endotherm was taken as the melting point.

[Basic nitrogen-containing group raw material and amine value of Compound B]
The amine value of the basic nitrogen-containing group raw material and compound B is measured based on the method of JIS K2501: 2003. However, only the measurement solvent is changed from chlorobenzene defined in JIS K2501: 2003 to chloroform.

[Number average molecular weight of basic nitrogen-containing base material]
The number average molecular weight was determined by the gel permeation chromatography (GPC) method shown below.
(1) Preparation of sample solution The raw material is dissolved in a 1 mass% acetic acid aqueous solution containing 0.15 mol / L Na ₂ SO ₄ so that the sample concentration is 0.2 g / 100 mL. Subsequently, this solution was filtered using a fluororesin filter “FP-200” (manufactured by Sumitomo Electric Industries, Ltd.) having a pore size of 0.2 μm to remove insoluble components to obtain a sample solution.
(2) Molecular weight measurement Using the following measuring apparatus and analytical column, a 1 mass% acetic acid aqueous solution containing 0.15 mol / L Na ₂ SO ₄ as an eluent was flowed at a flow rate of 1 mL / min, and a constant temperature of 40 ° C. Stabilize the column in the bath. 100 μL of the sample solution was injected therein and the molecular weight was measured. The molecular weight (number average molecular weight Mn) of the sample is several standard pullulans (type name (Mw): “P-5” (5.9 × 10 ³ ), “P-50” (4.73 × 10 ⁴ ), “P-200” (2.12 × 10 ⁵ ), “P-800” (7.08 × 10 ⁵ ); all manufactured by Showa Denko KK) were used as standard samples and calculated based on a calibration curve prepared in advance. .
Measuring device: “HLC-8320GPC” (manufactured by Tosoh Corporation)
Analysis column: “α” + “α-M” + “α-M” (both manufactured by Tosoh Corporation)

[Volume Median Particle Size (D ₅₀ ) and CV Value of Toner Particles]
The volume median particle size (D ₅₀ ) of the toner particles was measured as follows.
Measuring instrument: “Coulter Multisizer (registered trademark) III” (manufactured by Beckman Coulter, Inc.)
・ Aperture diameter: 50μm
Analysis software: “Multisizer (registered trademark) III version 3.51” (manufactured by Beckman Coulter, Inc.)
Electrolyte: “Isoton (registered trademark) II” (Beckman Coulter, Inc.)
Dispersion: Polyoxyethylene lauryl ether “Emalgen (registered trademark) 109P” (manufactured by Kao Corporation, HLB (Hydrophile-Lipophile Balance) = 13.6) was dissolved in the electrolyte solution, and the dispersion solution had a concentration of 5% by mass. Got.
Dispersion condition: 10 mg of a measurement sample of toner particles after drying is added to 5 mL of the dispersion, and dispersed for 1 minute with an ultrasonic disperser, and then 25 mL of electrolyte is added, and further with an ultrasonic disperser. A sample dispersion was prepared by dispersing for 1 minute.
Measurement conditions: After adding the sample dispersion to 100 mL of the electrolyte solution, the particle size of 30,000 particles is adjusted to a concentration that can be measured in 20 seconds, and then 30,000 particles are measured. The volume-median particle size (D ₅₀ ) and the volume average particle size were determined from the distribution.
The CV value (%) was calculated according to the following formula.
CV value (%) = (standard deviation of particle size distribution / volume average particle size) × 100

[Evaluation]
[Low-temperature fixability (minimum fixing temperature T ₁ )]
Using a commercially available printer “Microline (registered trademark) 5400” (manufactured by Oki Data Co., Ltd.) on high-quality paper “J paper A4 size” (manufactured by Fuji Xerox Co., Ltd.), the toner adhesion amount on the paper is 1.49-1. A solid image of .51 mg / cm ² was output without being fixed at a length of 50 mm, leaving a margin of 5 mm from the top edge of the A4 paper.
Next, the same printer with a variable temperature fixing device was prepared. The temperature of the fixing device was set to 110 ° C., and the toner was fixed at a speed of 1.5 seconds per sheet in the A4 longitudinal direction to obtain a printed matter.
In the same manner, the temperature of the fixing device was increased by 5 ° C. to fix the toner, and a printed matter was obtained.
From the margin at the top edge of the printed image to the solid image, lightly paste a 50 mm long mending tape “Scotch (registered trademark) mending tape 810” (manufactured by Sumitomo 3M Limited, width 18 mm). After that, a 500 g weight (contact area 1963 mm ² ) was placed and pressed once back and forth at a speed of 10 mm / s. Thereafter, the affixed tape was peeled off from the lower end side at a peeling angle of 180 ° and a speed of 10 mm / s to obtain a printed matter after peeling off the tape. 30 sheets of high quality paper “Excellent White Paper A4 Size” (made by Oki Data Co., Ltd.) is laid under the printed material before and after the tape is applied, and the reflected image density of the fixed image portion before and after the tape is applied to each printed material. , Using a colorimeter “SpectroEye” (manufactured by GretagMacbeth, light conditions; standard light source D50, observation field of view 2 °, density standard DINNB, absolute white standard), and fixing rate from each reflected image density according to the following formula Was calculated.
Fixing rate (%) = (Reflected image density after peeling tape / Reflected image density before applying tape) × 100
The lowest temperature at which the fixing ratio of 90% or more was the lowest fixing temperature T _1. The lower the minimum fixing temperature, the better the low temperature fixing property.

[Stability of low-temperature fixability over time (minimum fixing temperature T ₂ after storage at high temperature and high humidity)]
The toner was held in a constant temperature bath at a temperature of 45 ° C. and a relative humidity of 50% for 150 hours, and then the minimum fixing temperature T ₂ after high temperature and high humidity storage was evaluated in the same manner as the evaluation of the low temperature fixing property. The lower the minimum fixing temperature, the better the low temperature fixing property after high temperature storage.

[Production of resin]
Production Example A1 (Production of Resin A-1 (Amorphous Resin))
The inside of a 10 L four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple was purged with nitrogen, and 4289 g of propylene oxide (2.2) adduct of bisphenol A, 1322 g of terephthalic acid, (2-ethylhexanoic acid) tin (II) 25 g, 3,4,5-trihydroxybenzoic acid 2.5 g was added, and the temperature was raised to 235 ° C. with stirring in a nitrogen atmosphere and held at 235 ° C. for 8 hours. After that, the pressure in the flask was lowered and held at 8 kPa for 1 hour. Thereafter, after returning to atmospheric pressure, the mixture was cooled to 160 ° C. and maintained at 160 ° C., and a mixture of 1041 g of styrene, 260 g of 2-ethylhexyl acrylate, 71 g of acrylic acid, and 160 g of dibutyl peroxide was added dropwise over 1 hour. did. Then, after maintaining at 160 ° C. for 30 minutes, the temperature was raised to 200 ° C., and the pressure in the flask was further lowered and maintained at 8 kPa for 1 hour. Then, after returning to atmospheric pressure, it is cooled to 190 ° C., and 171 g of fumaric acid, 124 g of sebacic acid, 282 g of trimellitic anhydride, and 2.5 g of 4-tert-butylcatechol are added, and 10 ° C./hr up to 210 ° C. Then, the reaction was carried out at 4 kPa to the desired softening point to obtain Resin A-1. The physical properties are shown in Table 1.

[Production of Compound B]
Production Example B1 (Production of Compound B-1)
A 2L four-necked flask equipped with a cooling tube, nitrogen introduction tube, stirrer, dehydration tube, and thermocouple. 331 g of modified polypropylene (PPSA1000) and 366 g of xylene (manufactured by Wako Pure Chemical Industries, Ltd.) were added, and the inside of the reaction vessel was replaced with nitrogen gas. The reaction vessel is heated to 150 ° C. and held for 1 hour, then heated to 160 ° C. and held for 1 hour, and the pressure in the flask is further reduced to 8.3 kPa to distill off the solvent. The reaction was carried out. From the IR analysis, it was confirmed that the PPSA-derived acid anhydride peak (1780 cm ⁻¹ ) disappeared and the imide bond-derived peak (1700 cm ⁻¹ ) was produced, and thus Compound B-1 was obtained. The physical properties are shown in Table 2.

Production Example B2 (Production of Compound B-2)
Compound B-2 was obtained in the same manner as in Production Example B1, except that the amounts of the basic nitrogen-containing group raw material, polyolefin skeleton raw material, and xylene were changed as shown in Table 2. The physical properties are shown in Table 2.

Production Example C1 (Production of Resin C-1 (Crystalline Polyester Resin))
The inside of a 10 L four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple was purged with nitrogen, and 3416 g of 1,10-decandiol and 4084 g of sebacic acid were added and stirred. The temperature was raised to 135C, held at 135 ° C for 3 hours, and then heated from 135 ° C to 200 ° C over 10 hours. Thereafter, 23 g of di (2-ethylhexanoic acid) tin (II) was added, and further maintained at 200 ° C. for 1 hour, and then the pressure in the flask was lowered and maintained at 8.3 kPa under reduced pressure for 1 hour. C-1 was obtained. Table 3 shows the physical properties.

Production Example C2 (Production of Resin C-2 (Crystalline Polyester Resin))
Except having changed the raw material composition as shown in Table 3, it carried out similarly to manufacture example C1, and obtained resin C-2. Table 3 shows the physical properties.

[Production of toner]
Example 1 (Production of Toner 1)
In a Henschel mixer, 85 parts by mass of resin A-1, 5 parts by mass of compound B-1, 15 parts by mass of resin C-1, negatively chargeable charge control agent “Bontron E-81” (manufactured by Orient Chemical Co., Ltd.) ) 0.2 parts by mass, copper phthalocyanine pigment “ECB-301” (manufactured by Dainichi Seika Kogyo Co., Ltd.), and wax “ester wax WEP-8” (manufactured by NOF Corporation, melting point: 78 ° C.) 2 After adding a mass part and mixing, it melt-kneaded using the same direction rotation twin-screw extruder "PCM-30" (Ikegai Co., Ltd. make, shaft diameter 2.9cm, shaft cross-sectional area 7.06cm < ² >). Operating conditions are barrel set temperature 110 ° C., shaft rotation speed 200 r / min (shaft rotation peripheral speed 0.30 m / sec), mixture supply speed 10 kg / h (mixture supply amount per unit cross-sectional area of shaft 1.42 kg) / H · cm ² ). The obtained melt-kneaded product was cooled, coarsely pulverized with a rotoplex, then pulverized with a jet mill, classified with an airflow classifier, and volume-median particle size (D ₅₀ ) 7.0 μm, CV value 30% Toner particles were obtained.
100 parts by mass of the toner particles, 2.5 parts by mass of hydrophobic silica “RY50” (manufactured by Nippon Aerosil Co., Ltd., number average particle size; 0.04 μm), and hydrophobic silica “Cabosil (registered trademark) TS720” (Cabot Japan) 1.0 part by mass (manufactured by Co., Ltd., number average particle size; 0.012 μm) was placed in a Henschel mixer and stirred, and passed through a 150-mesh sieve to obtain toner 1. Table 4 shows the evaluation results of the obtained toner.

Examples 2 to 8 and Comparative Examples 1 to 5 (Production of Toners 2 to 8, 51 to 55)
As shown in Table 4, toners 2 to 8, 51 to 55 were obtained in the same manner as in Example 1 except that the types and amounts of the resin and compound B were changed. Table 4 shows the evaluation results of the obtained toner.

  As described above, from the results of Examples and Comparative Examples, a toner having excellent low-temperature fixability and low-temperature fixability over time by containing an amorphous resin having an acidic group, a crystalline polyester resin, and Compound B is obtained. It turns out that it is obtained.

Claims (8)

  An amorphous resin having an acidic group, a polyolefin skeleton, and a compound having at least one basic nitrogen-containing group selected from the group consisting of an amino group, an imino group, a cyano group, an azo group, a diazo group, and an azide group An electrostatic charge image developing toner containing B and a crystalline polyester resin.   The electrostatic image developing toner according to claim 1, wherein the compound B is dispersed in the amorphous resin.   The electrostatic image developing toner according to claim 1, wherein the crystalline polyester resin is a polycondensate of an alcohol component containing an α, ω-aliphatic diol and a carboxylic acid component containing an aliphatic dicarboxylic acid. .   The electrostatic image developing toner according to claim 1, wherein the polyolefin skeleton is a polyethylene skeleton or a polypropylene skeleton.   The electrostatic image developing toner according to claim 1, wherein the compound B is a reaction product of a basic nitrogen-containing group raw material and a polyolefin skeleton raw material.   The electrostatic charge image developing according to claim 5, wherein the compound B has a basic nitrogen-containing group raw material of polyethyleneimine, a polyolefin skeleton raw material of maleic anhydride-modified polyolefin, and an imide bond formed by reaction. toner.   The electrostatic image developing toner according to claim 5, wherein the polyolefin skeleton raw material is maleic anhydride-modified polypropylene. An amorphous resin having an acidic group, a polyolefin skeleton, and a compound having at least one basic nitrogen-containing group selected from the group consisting of an amino group, an imino group, a cyano group, an azo group, a diazo group, and an azide group Including a step of heat treatment in the presence of B and the crystalline polyester resin,
A method for producing a toner for developing an electrostatic charge image, wherein a maximum temperature in the heat treatment step is not less than a temperature 10 ° C. lower than the melting point of the compound B and not more than 100 ° C. higher than the melting point of the compound B.