JP6471047B2 - Toner for electrophotography - Google Patents

Description

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

From the viewpoint of increasing the speed and energy saving of a printing apparatus, a toner having excellent low-temperature fixability is required.
In addition, as the print-on-demand market has grown in recent years, the demand for higher image quality for electrophotographic technology is increasing.

  For example, Patent Document 1 is a toner having toner particles containing at least a binder resin, a colorant and a crystalline polyester, and the toner contains 3 to 50% by mass of tetrahydrofuran-insoluble matter derived from the binder resin. The tetrahydrofuran-insoluble component contains a hybrid resin, the tetrahydrofuran-insoluble component is hydrolyzed, and then the tetrahydrofuran-soluble component of the component that is filtered and filtered is measured by molecular weight distribution measured by GPC. The crystalline polyester has a main peak in the range of 10,000 to 1,000,000, and has a maximum endothermic peak at 50 ° C. or higher and 130 ° C. or lower in a DSC curve measured by a differential scanning calorimeter (DSC). Toner is disclosed.

  On the other hand, in Patent Document 2, the problem is an electrophotographic toner whose charge amount and image quality are not influenced by the environment. In the electrophotographic toner containing at least a binder resin and a colorant, the binder resin forms a continuous phase. An electrophotographic toner comprising a polycondensation resin and an addition polymerization resin forming a dispersed phase, wherein the dispersed phase having a diameter of 2 μm or less in the resin cross section occupies 90% or more of the entire cross-sectional area of the dispersed phase Is disclosed.

JP 2008-102390 A JP-A-7-98518

However, even with the techniques of Patent Documents 1 and 2, the low-temperature fixability, charging stability, and document offset resistance of printed matter obtained are not sufficient, and further improvements have been desired.
It is an object of the present invention to provide an electrophotographic toner that is excellent in low-temperature fixability, charging stability, and document offset resistance of printed matter.

The present inventors, as a binder resin constituting the electrophotographic toner, have a core portion containing a crystalline resin (C) obtained from a specific raw material, and an amorphous composite resin (AH) obtained from a specific raw material. It has been found that a toner having excellent low-temperature fixing property, charging stability and document offset resistance of printed matter (hereinafter also simply referred to as “document offset resistance”) can be obtained by using core-shell particles having a shell portion containing It was.
That is, the present invention provides the following electrophotographic toner.
An electrophotographic toner containing core-shell particles as a binder resin,
A polycondensation resin component (CH-1) obtained by polycondensation of an alcohol component and a carboxylic acid component containing 80 to 100 mol% of a dicarboxylic acid compound having 12 to 16 carbon atoms in the core portion; A crystalline composite resin (CH) having a styrenic resin component (CH-2), an alcohol component, and a carboxylic acid component containing 80 to 100 mol% of a dicarboxylic acid compound having 12 to 16 carbon atoms. Containing one or more crystalline resins (C) selected from crystalline polyester resins (CP) obtained by condensation,
The shell part is a polycondensation of an alcohol component containing an alkylene oxide adduct of bisphenol A represented by the following general formula (I) and a carboxylic acid component containing 70 to 98 mol% of an isophthalic acid compound. An electrophotographic toner containing an amorphous composite resin (AH) having a polycondensation resin component (AH-1) and a styrene resin component (AH-2) obtained in this manner.

(Wherein R ¹ O and OR ¹ are oxyalkylene groups, x and y represent the average number of added moles of alkylene oxide, each being a positive number, and the sum of x and y is 1 or more and 16 It is the following.)

  According to the present invention, it is possible to provide an electrophotographic toner that is excellent in low-temperature fixability, charging stability, and document offset resistance of printed matter.

The electrophotographic toner of the present invention (hereinafter also simply referred to as “toner”) is an electrophotographic toner containing core-shell particles as a binder resin,
A polycondensation resin component (CH-1) obtained by polycondensation of an alcohol component and a carboxylic acid component containing 80 to 100 mol% of a dicarboxylic acid compound having 12 to 16 carbon atoms in the core portion; A crystalline composite resin (CH) having a styrenic resin component (CH-2), an alcohol component, and a carboxylic acid component containing 80 to 100 mol% of a dicarboxylic acid compound having 12 to 16 carbon atoms. Containing one or more crystalline resins (C) selected from crystalline polyester resins (CP) obtained by condensation,
The shell portion polycondenses an alcohol component containing an alkylene oxide adduct of bisphenol A represented by the general formula (I) and a carboxylic acid component containing 70 to 98 mol% of an isophthalic acid compound. And an amorphous composite resin (AH) having a polycondensation-based resin component (AH-1) and a styrene-based resin component (AH-2).

The reason why the toner of the present invention is excellent in low-temperature fixability, charging stability, and document offset resistance is not clear, but can be considered as follows.
In the present invention, an alcohol component containing an alkylene oxide adduct of bisphenol A represented by the above general formula (I) and a carboxylic acid component containing 70 to 98 mol% of isophthalic acid in the shell portion. An amorphous composite resin (AH) having a polycondensation resin component (AH-1) and a styrene resin component (AH-2) obtained by polycondensation is used.
The amorphous composite resin (AH) obtained using an isophthalic acid compound as a raw material monomer of the polycondensation resin component (AH-1) has a polymer chain as compared with the case where a terephthalic acid compound or the like is used as a raw material monomer. The viscosity at the time of melting tends to be low because of the small amount of entanglement. Further, since the core portion contains the crystalline resin (C), the melting viscosity at the time of fixing tends to decrease above the melting point. Accordingly, the toner of the present invention is considered to be excellent in low-temperature fixability.
Further, since the amorphous composite resin (AH) of the shell portion has a low viscosity at the time of melting, the highly hydrophobic styrene resin component (AH-2) is placed inside, and the polycondensation resin component (AH-1). Is a crystalline resin (C) obtained by using, as a raw material monomer, a carboxylic acid component containing 80 mol% or more and 100 mol% or less of a highly hydrophobic dicarboxylic acid compound having 12 to 16 carbon atoms. It is thought that it is easy to encapsulate and is excellent in charging stability.
In addition, after printing, a crystalline resin obtained by polycondensation of a carboxylic acid component containing 80 to 100 mol% of a highly hydrophobic dicarboxylic acid compound having 12 to 16 carbon atoms and an alcohol component. It is considered that C) is easily exposed on the printing surface and works like a wax, or is excellent in document offset resistance.

[Crystalline resin (C)]
The crystalline resin (C) is selected from a crystalline composite resin (CH) having a polycondensation resin component (CH-1) and a styrene resin component (CH-2) and a crystalline polyester resin (CP). More than seed resin. Among these, from the viewpoint of low-temperature fixability, charging stability, and document offset resistance, a crystalline composite resin (CH) having a polycondensation resin component (CH-1) and a styrene resin component (CH-2) Is preferred.

In the present invention, the crystallinity of the resin is represented by the crystallinity index defined by the ratio between the softening point and the maximum endothermic peak temperature measured by a differential scanning calorimeter, that is, the value of [softening point / maximum endothermic peak temperature]. The
The crystalline resin is a resin having a crystallinity index of 0.6 or more and 1.4 or less, preferably 0.7 or more and 1.2 or less, more preferably 0.9 or more and 1.2 or less.
The crystallinity of the resin can be adjusted by the types and ratios of the raw material monomers, production conditions (for example, reaction temperature, reaction time, cooling rate) and the like. The maximum endothermic peak temperature refers to the temperature of the peak on the highest temperature side among the observed endothermic peaks. In crystalline resins, the maximum endothermic peak temperature is the melting point. The crystallinity index can be measured by the method described in the examples.
Hereinafter, the crystalline composite resin (CH) and the crystalline polyester resin (CP) will be described.

[Crystalline composite resin (CH)]
The crystalline composite resin (CH) includes a polycondensation resin component (CH-1) and a styrene resin component (CH-2). The polycondensation resin component (CH-1) and the styrene resin Component (CH-2) and a component derived from a bireactive monomer capable of reacting with both the polycondensation resin component (CH-1) and the styrene resin component (CH-2) preferable. Moreover, within the range which does not inhibit the objective of this invention, you may include structural parts other than these three structural parts, but it is preferable not to include structural parts other than three structural parts.
The crystalline composite resin (CH) is composed of 80 mol% or more and 100 mol of (i) an alcohol component and a dicarboxylic acid compound having 12 to 16 carbon atoms from the viewpoint of low-temperature fixability, charging stability and document offset resistance. % Of the raw material monomer of the polycondensation resin component (CH-1), (b) the raw material monomer of the styrene resin component (CH-2), and (c) the polycondensation resin component. It is more preferable that the resin is obtained by polymerizing both reactive monomers capable of reacting with both the raw material monomer of (CH-1) and the raw material monomer of the styrene resin component (CH-2).

  The total content of the polycondensation resin component (CH-1), the styrene resin component (CH-2), and the components derived from both reactive monomers in the crystalline composite resin (CH) is low temperature fixability. From the viewpoint of charging stability and document offset resistance, it is preferably 90 mol% or more, more preferably 95 mol% or more, still more preferably 99 mol% or more, and preferably 100 mol% or less, more preferably 100 mol%.

<Polycondensation resin component (CH-1)>
The polycondensation resin component (CH-1) includes an alcohol component (hereinafter also referred to as “alcohol component (CH-al)”), a carbon number of 12 from the viewpoint of low-temperature fixability, charging stability, and document offset resistance. It is a resin component obtained by polycondensation with a carboxylic acid component (hereinafter also referred to as “carboxylic acid component (CH-ac)”) containing 80 to 100 mol% of the above 16 or less dicarboxylic acid compound.
As the resin constituting such a polycondensation resin component (CH-1), a polyester resin is preferable.

(Alcohol component (CH-al))
Examples of the alcohol component (CH-al) include aliphatic diols, aromatic diols, trihydric or higher polyhydric alcohols, and the like, and aliphatic diols from the viewpoint of low-temperature fixability, charge stability, and document offset resistance. Is preferred.
The number of carbon atoms of the alcohol component (CH-al) is preferably 2 or more, more preferably 4 or more, still more preferably 6 or more, from the viewpoints of low-temperature fixability, charge stability, and document offset resistance. In view of the above, it is preferably 12 or less, more preferably 10 or less, still more preferably 8 or less, and still more preferably 6.
As the aliphatic diol having 2 to 12 carbon atoms, α, ω-aliphatic diols are preferable from the viewpoint of improving crystallinity and improving low-temperature fixability. For example, ethylene glycol, 1,3-propanediol, 1 , 4-butanediol, 1,4-butenediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,12-dodecanediol, etc. It is done. Among these, ethylene glycol, 1,4-butanediol, 1,6-hexanediol, and more preferably 1,6-hexanediol are preferred from the viewpoints of low-temperature fixability, charge stability, and document offset resistance. .
The content of the aliphatic diol, preferably the aliphatic diol having 2 to 12 carbon atoms, more preferably the aliphatic diol having 4 to 8 carbon atoms in the alcohol component (CH-al) is low-temperature fixability, charged From the viewpoint of stability and document offset resistance, it is preferably 80 mol% or more, more preferably 90 mol% or more, still more preferably 95 mol% or more, and preferably 100 mol% or less, more preferably 100 mol%. %.

The alcohol component (CH-al) may contain an alcohol other than the aliphatic diol.
Other alcohol components that can be contained in the alcohol component (CH-al) include aromatic diols, alicyclic diols, trihydric or higher polyhydric alcohols, or alkylene oxides having 2 to 4 carbon atoms (average addition moles). (1 to 16)) adducts.
Specific examples of other alcohols that can be contained in the alcohol component (CH-al) include aromatic diols such as bisphenol A or their alkylene oxide (average added mole number of 1 to 16) adducts, hydrogenated bisphenol A, and the like. Tricyclic or higher polyhydric alcohols such as alicyclic diols or alkylene oxides having 2 to 4 carbon atoms (average added mole number of 2 to 12), glycerin, pentaerythritol, trimethylolpropane, sorbitol, or the like And an adduct of an alkylene oxide having 2 to 4 carbon atoms (average added mole number of 1 to 16).

  These alcohol components (CH-al) can be used alone or in combination of two or more.

(Carboxylic acid component (CH-ac))
The carboxylic acid component (CH-ac) contains from 80 mol% to 100 mol% of a dicarboxylic acid compound having 12 to 16 carbon atoms from the viewpoint of low-temperature fixability, charging stability and document offset resistance.
Examples of the dicarboxylic acid compound having 12 to 16 carbon atoms include aromatic dicarboxylic acid compounds, aliphatic dicarboxylic acid compounds, alicyclic dicarboxylic acid compounds having 12 to 16 carbon atoms, and among these, low-temperature fixability. From the viewpoint of charging stability and document offset resistance, an aliphatic dicarboxylic acid compound is preferred.
The aliphatic dicarboxylic acid compound having 12 to 16 carbon atoms is preferably an α, ω-linear aliphatic dicarboxylic acid compound from the viewpoint of enhancing crystallinity and improving low-temperature fixability. For example, dodecanedioic acid (carbon 12), tridecanedioic acid (13 carbon atoms), tetradecanedioic acid (14 carbon atoms), pentadecanedioic acid (15 carbon atoms), hexadecanedioic acid (16 carbon atoms) or alkyl having 1 to 3 carbon atoms. Examples include esters. Among these, tetradecanedioic acid is preferable from the viewpoint of low-temperature fixability, charging stability, and document offset resistance.

The carbon number of the dicarboxylic acid compound is 12 or more, preferably 14 or more from the viewpoint of charge stability and document offset resistance, and 16 or less, preferably 14 from the viewpoint of low-temperature fixability.
In addition, the carbon number of the 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.
The content of the dicarboxylic acid compound having 12 to 16 carbon atoms in the carboxylic acid component (CH-ac) is 80 mol% or more, preferably 90 from the viewpoint of low-temperature fixability, charging stability and document offset resistance. From the same viewpoint, it is 100 mol% or less, preferably 100 mol%.

The carboxylic acid component (CH-ac) may contain other carboxylic acid components other than the dicarboxylic acid compound having 12 to 16 carbon atoms.
Other carboxylic acid components that may be contained in the carboxylic acid component (CH-ac) include dicarboxylic acid compounds other than dicarboxylic acid compounds having 12 to 16 carbon atoms, trivalent or higher polyvalent carboxylic acid compounds, and anhydrides thereof. And alkyl esters having 1 to 3 carbon atoms thereof.
Examples of the dicarboxylic acid compound include aromatic dicarboxylic acid compounds, aliphatic dicarboxylic acid compounds, and alicyclic dicarboxylic acid compounds other than dicarboxylic acid compounds having 12 to 16 carbon atoms.
Examples of the aromatic dicarboxylic acid compound include phthalic acid, isophthalic acid, and terephthalic acid.
Examples of the aliphatic dicarboxylic acid compound other than the dicarboxylic acid compound having 12 to 16 carbon atoms include malonic acid (carbon number 3), maleic acid (carbon number 4), fumaric acid (carbon number 4), citraconic acid (carbon 5), itaconic acid (5 carbon atoms), glutaconic acid (5 carbon atoms), succinic acid (4 carbon atoms), adipic acid (6 carbon atoms), azelaic acid (9 carbon atoms), sebacic acid (10 carbon atoms) ), Undecanedioic acid (11 carbon atoms), heptadecanedioic acid (17 carbon atoms), octadecanedioic acid (18 carbon atoms), nonadecanedioic acid (19 carbon atoms), eicosanedioic acid (20 carbon atoms), docosanedioic acid (C22) and the like.
Examples of the trivalent or higher polyvalent carboxylic acid compound include trimellitic acid, 2,5,7-naphthalene tricarboxylic acid, pyromellitic acid and the like.

  These carboxylic acid components (CH-ac) can be used alone or in combination of two or more.

  The equivalent ratio (COOH group / OH group) of the carboxylic acid component (CH-ac) to the alcohol component (CH-al) is preferably 0.7 or more from the viewpoint of low-temperature fixability, charging stability and document offset resistance. More preferably, it is 0.8 or more, more preferably 0.9 or more, and preferably 1.3 or less, more preferably 1.2 or less, and still more preferably 1.1 or less.

  From the viewpoint of adjusting the physical properties, the alcohol component (CH-al) may optionally contain a monovalent alcohol, and the carboxylic acid component (CH-ac) suitably contains a monovalent carboxylic acid compound. It may be.

<Styrene resin component (CH-2)>
The styrene resin component (CH-2) is a segment made of a styrene resin.
The content of the styrene resin component (CH-2) in the crystalline composite resin (CH) is preferably 5% by mass or more, more preferably 8%, from the viewpoints of low-temperature fixability, charging stability and document offset resistance. From the same viewpoint, it is preferably 30% by mass or less, more preferably 25% by mass or less, still more preferably 20% by mass or less, and still more preferably 15% by mass or less.
In the calculation of the content of the styrene resin component (CH-2), the mass of the polycondensation resin component (CH-1) is calculated from the total amount of raw material monomers of the polycondensation resin component (CH-1): The value obtained by removing the amount of dehydration during the condensation reaction is used, and the total amount of the styrene resin component (CH-2) raw material monomer and polymerization initiator is used as the mass of the styrene resin component (CH-2). Moreover, the amphoteric monomer used if necessary is calculated as the mass of the polycondensation resin component (CH-1). The same applies to the amorphous composite resin (AH) described later.

  Examples of styrenic resins include polystyrene, styrene derivative polymers, styrene-acrylic copolymers, and the like. From the viewpoint of low-temperature fixability, charge stability, and document offset resistance, polystyrene, styrene derivative polymers, and styrene. -One or more types selected from acrylic copolymers are preferable, one or more types selected from polystyrene and styrene-acrylic copolymers are more preferable, and styrene-acrylic copolymers are still more preferable.

The raw material monomer for the styrene resin component (CH-2) is preferably at least one selected from styrene and styrene derivatives from the viewpoints of low-temperature fixability, charge stability, and document offset resistance. Styrene is more preferable from the viewpoint of raw material price and storage stability.
The styrene derivative is preferably at least one selected from methyl styrene, α-methyl styrene, β-methyl styrene, t-butyl styrene, chlorostyrene, chloromethyl styrene, methoxy styrene, styrene sulfonic acid and salts thereof.
In the present specification, one or more selected from styrene and styrene derivatives are referred to as “styrene compound”.

  In the raw material monomer of the styrene resin component (CH-2), the content of the styrene compound is preferably 50% by mass or more, more preferably 60% by mass from the viewpoints of low-temperature fixability, charging stability and document offset resistance. Or more, more preferably 65% by mass or more, still more preferably 70% by mass or more, and from the same viewpoint, preferably 100% by mass or less, more preferably 95% by mass or less, still more preferably 90% by mass or less. More preferably, it is 85 mass% or less.

Examples of the raw material monomer for the styrene resin component (CH-2) used in addition to the styrene compound include alkyl (meth) acrylates; ethylenically unsaturated monoolefins such as ethylene and propylene; diolefins such as butadiene; vinyl chloride and the like Halovinyls; vinyl esters such as vinyl acetate and vinyl propionate; ethylenic monocarboxylic acid esters such as dimethylaminoethyl (meth) acrylate; vinyl ethers such as vinyl methyl ether; vinylidene halides such as vinylidene chloride; N -N-vinyl compounds, such as vinylpyrrolidone, etc. are mentioned.
“Alkyl (meth) acrylate” means both alkyl acrylate and alkyl methacrylate. The same applies to the following.

Among the raw material monomers for the styrene resin component (CH-2) used in addition to these styrene compounds, alkyl (meth) acrylates are preferred from the viewpoints of low-temperature fixability, charge stability, and document offset resistance.
From the above viewpoint, the carbon number of the alkyl group in the alkyl (meth) acrylate is preferably 1 or more, more preferably 2 or more, still more preferably 4 or more, and preferably 22 or less, more preferably 18 or less, More preferably, it is 12 or less. In addition, carbon number of this alkyl ester means carbon number derived from the alcohol component which comprises ester.
Specific examples of the alkyl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, (iso) propyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, and (iso or tertiary) butyl. (Meth) acrylate, 2-ethylhexyl (meth) acrylate, (iso) octyl (meth) acrylate, (iso) decyl (meth) acrylate, (iso) stearyl (meth) acrylate, and the like.
Here, “(iso or tertiary)” and “(iso)” mean that both of these groups are present and not present, and these groups are not present. Indicates normal. In addition, “(meth) acrylate” indicates that both acrylate and methacrylate are included.

  In the raw material monomer of the styrene-based resin component (CH-2), the content of the alkyl (meth) acrylate is preferably 5% by mass or more, more preferably from the viewpoint of low-temperature fixability, charging stability and document offset resistance. From the same viewpoint, it is preferably 50% by mass or less, more preferably 40% by mass or less, still more preferably 30% by mass or less, and still more preferably 25% by mass. It is below mass%.

  The mass ratio of alkyl (meth) acrylate to styrene compound (alkyl (meth) acrylate / styrene compound) in the raw material monomer of the styrene resin component (CH-2) is low temperature fixability, charging stability and document offset resistance. In view of the above, it is preferably 0/100 or more, more preferably 10/90 or more, and from the viewpoint of low-temperature fixability and charging stability, preferably 80/20 or less, more preferably 50/50 or less, and further Preferably it is 40/60 or less, More preferably, it is 30/70 or less.

<Amotropic monomer>
It is preferable that the crystalline composite resin (CH) further contains a structural unit derived from the both reactive monomers.
When an amphoteric monomer is used as a raw material monomer for the crystalline composite resin (CH), the amphoteric monomer reacts with both the polycondensation resin component (CH-1) and the styrene resin component (CH-2). By doing so, the crystalline composite resin (CH) can be produced satisfactorily.
As a result, the polycondensation resin (CH) is bonded to the polycondensation resin component (CH-1) and the styrene resin component (CH-2) via a structural unit derived from both reactive monomers. The resin component (CH-1) and the styrene resin component (CH-2) are uniformly dispersed, and the low-temperature fixing property, charging stability, and document offset resistance are good.

As the both reactive monomers, one or more functional groups selected from a hydroxyl group, a carboxy group, an epoxy group, a primary amino group and a secondary amino group, preferably a hydroxyl group and / or a carboxy group, in the molecule Preferably, it is a compound having a carboxy group and an ethylenically unsaturated bond, and by using such a reactive monomer, the low-temperature fixability, charging stability and document offset resistance can be further improved.
The both reactive monomers are preferably at least one selected from acrylic acid, methacrylic acid, fumaric acid, maleic acid and maleic anhydride from the viewpoints of low-temperature fixability, charge stability and document offset resistance. One or more selected from acids and fumaric acids are more preferable, and one or more selected from acrylic acid and methacrylic acid are more preferable from the viewpoints of low-temperature fixability, charge stability, and document offset resistance.
However, when used together with a polymerization inhibitor, a carboxylic acid compound having an ethylenically unsaturated bond such as fumaric acid functions as a raw material monomer for the polycondensation resin component (CH-1). In this case, fumaric acid or the like is not a bireactive monomer but a raw material monomer for the polycondensation resin component (CH-1).

  The amount of both reactive monomers used is 100 mol parts of the alcohol component (CH-al), which is a raw material monomer of the polycondensation resin component (CH-1), from the viewpoints of low-temperature fixability, charging stability and document offset resistance. Is preferably 1 mol part or more, more preferably 3 mol part or more, and from the viewpoint of low-temperature fixability, preferably 30 mol part or less, more preferably 25 mol part or less, still more preferably 20 mol. Part or less, more preferably 15 parts by mole or less, still more preferably 10 parts by mole or less.

<Method for producing crystalline composite resin (CH)>
The crystalline composite resin (CH) can be produced, for example, by any of the following methods (1) to (3). In addition, it is preferable that both reactive monomers are supplied to a reaction system with the raw material monomer of a styrene resin component (CH-2) from a reactive viewpoint. From the same viewpoint, a catalyst such as an esterification catalyst or an esterification cocatalyst may be used, and a polymerization initiator and a polymerization inhibitor may be further used.

(1) After the step (X) of the polycondensation reaction with the alcohol component (CH-al) and the carboxylic acid component (CH-ac), the raw material monomer of the styrene-based resin component (CH-2) and, if necessary, both reactions A step (Y) of an addition polymerization reaction with a functional monomer.
In the step (X), a part of the carboxylic acid component (CH-ac) is subjected to a polycondensation reaction, and then the step (Y) is performed. Then, the reaction temperature is increased again, and the carboxylic acid component (CH-ac) More preferred is a method in which the remainder of) is added to the polymerization system to further proceed with the polycondensation reaction in step (X) and, if necessary, the reaction with both reactive monomers.

(2) After the step (Y) of the addition polymerization reaction with the raw material monomer of the styrene resin component (CH-2) and the both reactive monomers, the polycondensation reaction with the raw material monomer of the polycondensation resin component (CH-1) A method of performing step (X).
The alcohol component (CH-al) and the carboxylic acid component (CH-ac) are present in the reaction system during the addition polymerization reaction, and are esterified at a temperature suitable for the polycondensation reaction and, if necessary, an ester. The polycondensation reaction can be started by adding a co-catalyst, and the alcohol component (CH-al) and the carboxylic acid component (CH-ac) are later introduced into the reaction system under temperature conditions suitable for the polycondensation reaction. ) Can be added to start the polycondensation reaction. In the former case, the molecular weight and molecular weight distribution can be adjusted by adding an esterification catalyst and, if necessary, an esterification co-catalyst at a temperature suitable for the polycondensation reaction.

(3) Step (X) of the polycondensation reaction with the alcohol component (CH-al) and the carboxylic acid component (CH-ac), and addition polymerization with the raw material monomer and the both reactive monomers of the styrene resin component (CH-2) A method in which the reaction is carried out under conditions in which the reaction step (Y) proceeds in parallel.
In this method, the step (X) and the step (Y) are performed under a reaction temperature condition suitable for the addition polymerization reaction, the reaction temperature is increased, and under a temperature condition suitable for the polycondensation reaction, if necessary, It is preferable to add a trivalent or higher valence raw material monomer of the polycondensation resin component (CH-1) to the polymerization system as a crosslinking agent, and further perform the polycondensation reaction in the step (X). At that time, under a temperature condition suitable for the polycondensation reaction, a radical polymerization inhibitor can be added to advance only the polycondensation reaction. Both reactive monomers are involved in the polycondensation reaction as well as the addition polymerization reaction.

Of the above methods (1) to (3), the crystalline composite resin (CH) is preferably produced by the method according to (1), and more preferably produced by the method having the following steps I to III. .
Step I: Step of polycondensing a part of the raw material monomer of the polycondensation resin component (CH-1) Step II: In the presence of the polycondensate obtained in Step I, the styrene resin component (CH-2) Step of addition polymerization of raw material monomer Step III: Step of polycondensing the raw material monomer of the remaining polycondensation resin component (CH-1) in the presence of the reaction product obtained in Step II. From the viewpoint of low-temperature fixability, it is preferably used together with a raw material monomer for the styrene resin component (CH-2).
By performing the above steps I to III, the polycondensation resin component (CH-1) and the styrene resin component (CH-2) in the crystalline composite resin (CH) are appropriately dispersed, and the polycondensation system The dispersibility of the resin component (CH-1) is enhanced, and the low-temperature fixability, charging stability, and document offset resistance can be improved.

(Process I)
Step I is a step of polycondensing a part of the raw material monomer of the polycondensation resin component (CH-1).
In the raw material monomer used in Step I, the amount of the carboxylic acid component (CH-ac) is preferably 10% by mass or more of the total amount of the carboxylic acid component (CH-ac) used for the production of the crystalline composite resin (CH). Preferably it is 20% by mass or more, more preferably 30% by mass or more, still more preferably 40% by mass or more, and preferably 90% by mass or less, more preferably 80% by mass or less, still more preferably 70% by mass or less. More preferably, it is 60 mass% or less.
Moreover, in the raw material monomer to be used in Step I, the amount of the alcohol component (CH-al) is preferably not less than the number of moles of the carboxylic acid component (CH-ac), and is used for the production of the crystalline composite resin (CH). The total amount of the alcohol component (CH-al) is more preferable because the unreacted alcohol component (CH-al) serves as a solvent when performing Step II.
The temperature of the polycondensation reaction in Step I is preferably 120 ° C. or higher, more preferably 130 ° C. or higher, and preferably 230 ° C. or lower, more preferably 200 ° C. or lower, and still more preferably 180 ° C. from the viewpoint of reactivity. It is below ℃. The pressure during the polycondensation reaction may be a normal pressure.
The completion of the polycondensation reaction in Step I is preferably performed when the raw material monomer subjected to Step I reacts preferably at 95 mol% or more, more preferably 98 mol% or more.

(Step II)
Step II is a step of subjecting the raw material monomer of the styrene resin component (CH-2) to addition polymerization in the presence of the polycondensate obtained in Step I.
From the viewpoint of reactivity, the temperature of the addition polymerization reaction in Step II is preferably 120 ° C. or higher, more preferably 130 ° C. or higher, and preferably 200 ° C. or lower, more preferably 180 ° C. or lower.
In addition, the raw material monomer of the styrene resin component (CH-2) to be subjected to the addition polymerization reaction in Step II may be added to the reaction system in Step I in advance, and in that case, a polymerization initiator may be added in Step II. .
At the end of the reaction in Step II, the residual raw material monomer of the styrene-based resin component (CH-2) is preferably 1000 ppm (wt / wt) or less with respect to the resin obtained in Step 2.

(Step III)
Step III is a step of polycondensing the remaining raw material monomers of the polycondensation resin component (CH-1) in the presence of the reaction product obtained in Step II.
The temperature of the polycondensation reaction in Step III is preferably 120 ° C. or higher, more preferably 130 ° C. or higher, still more preferably 150 ° C. or higher, and preferably 230 ° C. or lower, more preferably 220 ° C., from the viewpoint of reactivity. It is below ℃. The pressure during the polycondensation reaction in Step III may be a normal pressure.

  After Step III, it is preferable to carry out Step IV in which a polycondensation reaction is further performed under reduced pressure from the viewpoint of causing the polycondensation reaction to proceed and reducing the acid value of the crystalline composite resin (CH) to a preferred range.

(Process IV)
The temperature of the polycondensation reaction in Step IV is preferably 120 ° C. or higher, more preferably 130 ° C. or higher, still more preferably 150 ° C. or higher, and preferably 230 ° C. or lower, more preferably 220 ° C. or lower.
Here, the reduced pressure is a pressure less than normal pressure (101.3 kPa), preferably 80 kPa or less, more preferably 50 kPa or less, and still more preferably 20 kPa or less.
Step IV is preferably performed until the produced crystalline composite resin (CH) has a preferable acid value described below. Step IV is preferably performed in the presence of the esterification catalyst.

  It is preferable to perform process I-III or process I-IV in the same container.

(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 in particular, di (2-ethylhexanoic acid) from the viewpoint of reactivity, molecular weight adjustment, and physical property adjustment of the crystalline composite resin (CH). Tin (II) is more preferred.
The amount of the esterification catalyst used is a total amount of alcohol component (CH-al) and carboxylic acid component (CH-ac) of 100 from the viewpoints of reactivity, molecular weight adjustment, and physical property adjustment of the crystalline composite resin (CH). The amount is preferably 0.01 parts by mass or more, more preferably 0.1 parts by mass or more, still more preferably 0.2 parts by mass or more, and preferably 1.5 parts by mass or less, more preferably 0.1 parts by mass or more. Is 1.0 part by mass or less, more preferably 0.5 part by mass or less.

(Esterification promoter)
As the esterification cocatalyst, a pyrogallol compound is preferred. This pyrogallol compound has a benzene ring in which three hydrogen atoms adjacent to each other are substituted with hydroxyl groups, and pyrogallol, gallic acid, gallic acid ester, 2,3,4-trihydroxybenzophenone, 2,2 ′ Benzophenone derivatives such as 3,3,4-tetrahydroxybenzophenone, catechin derivatives such as epigallocatechin and epigallocatechin gallate, and the like, and gallic acid is preferred from the viewpoint of reactivity.
(Polymerization inhibitor)
Examples of the polymerization inhibitor include 4-t-butylcatechol.

(Softening point)
The softening point of the crystalline composite resin (CH) is preferably 60 ° C. or higher, more preferably 70 ° C. or higher, and still more preferably 80 ° C. or higher, from the viewpoint of low-temperature fixability, charging stability and document offset resistance. And from a viewpoint of low temperature fixability, Preferably it is 120 degrees C or less, More preferably, it is 100 degrees C or less, More preferably, it is 90 degrees C or less.
(Melting point)
The melting point of the crystalline composite resin (CH) is preferably 50 ° C. or higher, more preferably 60 ° C. or higher, more preferably 70 ° C. or higher, from the viewpoint of low-temperature fixability, charging stability and document offset resistance. From the viewpoint of low-temperature fixability, it is preferably 110 ° C. or lower, more preferably 90 ° C. or lower, and still more preferably 80 ° C. or lower.
(Acid value)
The acid value of the crystalline composite resin (CH) is preferably 3 mgKOH / g or more, more preferably 10 mgKOH / g or more, still more preferably 15 mgKOH / g or more, from the viewpoints of low-temperature fixability and charge stability. From the viewpoint of low-temperature fixability, charging stability, and document offset resistance, it is preferably 40 mgKOH / g or less, more preferably 35 mgKOH / g or less, and further preferably 30 mgKOH / g or less.
The hydroxyl value of the crystalline composite resin (CH) is preferably 1 mgKOH / g or more, more preferably 3 mgKOH / g or more, still more preferably 5 mgKOH / g or more, from the viewpoints of low-temperature fixability, charging stability and document offset resistance. From the same viewpoint, it is preferably 30 mgKOH / g or less, more preferably 20 mgKOH / g or less, still more preferably 10 mgKOH / g or less.
The softening point, melting point, acid value and hydroxyl value of the crystalline composite resin (CH) can be appropriately adjusted according to the production conditions such as the type and ratio of the raw material monomers, reaction temperature, reaction time, and cooling rate. The softening point, melting point, acid value, and hydroxyl value are determined by the methods described in the examples.

[Crystalline polyester resin (CP)]
The crystalline polyester resin (CP) contains 80 mol% to 100 mol% of an alcohol component (hereinafter also referred to as “alcohol component (CP-al)”) and a dicarboxylic acid compound having 12 to 16 carbon atoms. It is a resin obtained by polycondensation with an acid component (hereinafter also referred to as “carboxylic acid component (CP-ac)”).
Examples of the alcohol component (CP-al) and the carboxylic acid component (CP-ac) include those similar to the alcohol component (CH-al) and the carboxylic acid component (CH-ac), and preferred types and equivalents thereof. The ratio and reaction conditions are similar.
The type and amount of esterification catalyst and esterification cocatalyst used in the polycondensation reaction of the alcohol component (CP-al) and the carboxylic acid component (CP-ac) are the same as the polycondensation of the crystalline composite resin (CH). It is the same as that of the kind and usage-amount of the esterification catalyst in the polycondensation reaction of a system resin part (CH-1), and an esterification co-catalyst, and its preferable aspect is also the same.
The preferred range of the softening point, melting point, acid value and hydroxyl value of the crystalline polyester resin (CP) is the same as that of the crystalline composite resin (CH).

[Amorphous composite resin (AH)]
The amorphous composite resin (AH) includes a polycondensation resin component (AH-1) and a styrene resin component (AH-2). The polycondensation resin component (AH-1) and the styrene resin It consists of a resin component (AH-2) and a component derived from an amphoteric monomer capable of reacting with both the polycondensation resin component (AH-1) and the styrene resin component (AH-2). Is preferred. Moreover, within the range which does not inhibit the objective of this invention, you may include structural parts other than these three structural parts, but it is preferable not to include structural parts other than three structural parts.
In addition, the amorphous composite resin (AH) is obtained from (b) an alkylene oxide adduct of bisphenol A represented by the general formula (I) from the viewpoint of low-temperature fixability, charging stability, and document offset resistance. A raw material monomer of a polycondensation resin component (AH-1), comprising an alcohol component containing from mol% to 100 mol% and a carboxylic acid component containing from 70 mol% to 95 mol% of isophthalic acid, (b) Both can react with the raw material monomer of the styrene resin component (AH-2), and (c) the raw material monomer of the polycondensation resin component (AH-1) and the raw material monomer of the styrene resin component (AH-2). A resin obtained by polymerizing a reactive monomer is more preferable.

  The amorphous composite resin (AH) is a resin having a crystallinity index exceeding 1.4 or less than 0.6, preferably exceeding 1.5, or 0.5 or less, more preferably 1 .6 or more or 0.5 or less.

  The total content of the polycondensation resin component (AH-1), the styrene resin component (AH-2), and the components derived from both reactive monomers in the amorphous composite resin (AH) is low temperature fixing. From the viewpoint of stability, charge stability and document offset resistance, it is preferably 90 mol% or more, more preferably 95 mol% or more, still more preferably 99 mol% or more, and preferably 100 mol% or less, more preferably Is 100 mol%.

<Polycondensation resin component (AH-1)>
The polycondensation resin component (AH-1) is an alcohol component containing an alkylene oxide adduct of bisphenol A represented by the following general formula (I) from the viewpoint of low-temperature fixability, charging stability, and document offset resistance. (Hereinafter also referred to as “alcohol component (AH-al)”) and a carboxylic acid component containing 70 to 98 mol% of isophthalic acid compound (hereinafter also referred to as “carboxylic acid component (AH-ac)”) And obtained by polycondensation.

(Alcohol component (AH-al))
The alcohol component (AH-al) contains an alkylene oxide adduct of bisphenol A represented by the following general formula (I) from the viewpoint of low-temperature fixability, charge stability, and document offset resistance.

In the formula, R ¹ O and OR ¹ are oxyalkylene groups, x and y represent the average number of added moles of alkylene oxide, each is a positive number, and the sum of x and y is 1 or more and 16 or less. It is.

Examples of the alkylene oxide adduct of bisphenol A represented by the general formula (I) include a propylene oxide adduct of bisphenol A, an ethylene oxide adduct of bisphenol A, and the like. Low temperature fixability, charge stability and document resistance From the viewpoint of offset property, a propylene oxide adduct of bisphenol A is preferred.
These alcohol components (AH-al) can be used alone or in combination of two or more.
The content of the alkylene oxide adduct of bisphenol A represented by the general formula (I) in the alcohol component (AH-al) is preferably 60 mol% or more from the viewpoint of charge stability and document offset resistance. More preferably, it is 70 mol% or more, more preferably 80 mol% or more, still more preferably 90 mol% or more, and preferably 100 mol% or less, more preferably 100 mol%.
The average number of moles of propylene oxide added to the propylene oxide adduct of bisphenol A is preferably 1 or more, more preferably 1.2 or more, and still more preferably 1 from the viewpoints of low-temperature fixability, charging stability, and document offset resistance. 0.5 or more, and preferably 16 or less, more preferably 12 or less, still more preferably 8 or less, and still more preferably 4 or less.

The alcohol component (AH-al) may contain other alcohol components other than the alkylene oxide adduct of bisphenol A represented by the general formula (I).
Examples of other alcohol components that can be contained in the alcohol component (AH-al) include the same alcohols listed as the alcohol component (CH-al).

(Carboxylic acid component (AH-ac))
The carboxylic acid component (AH-ac) contains an isophthalic acid compound in an amount of 70 mol% to 98 mol% from the viewpoint of low-temperature fixability, charging stability, and document offset resistance.
The content of the isophthalic acid compound in the carboxylic acid component (AH-ac) is 70 mol% or more, preferably 75 mol% or more, more preferably 80 from the viewpoints of low-temperature fixability, charging stability and document offset resistance. From the same viewpoint, it is 98 mol% or less, preferably 96 mol% or less.

The carboxylic acid component (AH-ac) may contain a carboxylic acid component other than the isophthalic acid compound.
Examples of the other carboxylic acid that can be contained in the carboxylic acid component (AH-ac) include the same carboxylic acids as those mentioned as the carboxylic acid component (CH-ac).
Among these, from the viewpoint of low-temperature fixability and charge stability, an aliphatic carboxylic acid compound is preferable, an aliphatic dicarboxylic acid compound is more preferable, an aliphatic saturated dicarboxylic acid compound is further preferable, and succinic acid is still more preferable.
The number of carbon atoms of the aliphatic dicarboxylic acid compound is preferably 2 or more, more preferably 3 or more, and preferably 8 or less, more preferably 6 from the viewpoints of low-temperature fixability, charging stability and document offset resistance. Hereinafter, it is more preferably 4 or less.
The content of the aliphatic dicarboxylic acid compound in the carboxylic acid component (AH-ac), preferably the aliphatic dicarboxylic acid compound having 2 to 8 carbon atoms, is from the viewpoint of low-temperature fixability, charging stability and document offset resistance. From the same viewpoint, it is preferably 30 mol% or less, more preferably 25 mol% or less, still more preferably 20 mol% or less, and still more preferably 2 mol% or more, more preferably 4 mol% or more. Preferably it is 15 mol% or less, More preferably, it is 10 mol% or less.

  The equivalent ratio (COOH group / OH group) of the carboxylic acid component (AH-ac) to the alcohol component (AH-al) is preferably 0.6 or more from the viewpoint of low-temperature fixability, charging stability, and document offset resistance. More preferably, it is 0.7 or more, more preferably 0.8 or more, and preferably 1.2 or less, more preferably 1.0 or less, still more preferably 0.9 or less.

  From the viewpoint of adjusting the physical properties, the alcohol component (AH-al) may optionally contain a monovalent alcohol, and the carboxylic acid component (AH-ac) suitably contains a monovalent carboxylic acid compound. It may be.

<Styrene resin component (AH-2)>
The styrene resin component (AH-2) is a segment made of a styrene resin.
The content of the styrenic resin component (AH-2) in the amorphous composite resin (AH) is preferably 5 mol% or more, more preferably from the viewpoint of low-temperature fixability, charging stability, and document offset resistance. 10 mol% or more, more preferably 15 mol% or more, still more preferably 20 mol% or more, and from the same viewpoint, it is preferably 50 mol% or less, more preferably 40 mol% or less, still more preferably 30 mol%. It is less than mol%.

  Examples of styrenic resins include polystyrene, styrene derivative polymers, styrene-acrylic copolymers, and the like. From the viewpoint of low-temperature fixability, charge stability, and document offset resistance, polystyrene, styrene derivative polymers, and styrene. -One or more types selected from acrylic copolymers are preferable, one or more types selected from polystyrene and styrene-acrylic copolymers are more preferable, and styrene-acrylic copolymers are still more preferable.

  Examples of the raw material monomer for the styrenic resin component (AH-2) include the same as those mentioned as the raw material monomer for the styrene resin component (CH-2). Among these, the low-temperature fixability and the charge stability From the viewpoints of properties and document offset resistance, styrene compounds are preferable, and styrene is more preferable from the viewpoints of monomer raw material prices and storage stability.

  In the raw material monomer of the styrene-based resin component (AH-2), the content of the styrene compound is preferably 50% by mass or more, more preferably 60% by mass from the viewpoints of low-temperature fixability, charging stability and document offset resistance. Or more, more preferably 65% by mass or more, still more preferably 70% by mass or more, and from the same viewpoint, preferably 100% by mass or less, more preferably 95% by mass or less, still more preferably 90% by mass or less. More preferably, it is 85 mass% or less.

  Examples of the raw material monomer for the styrene resin component (AH-2) used in addition to the styrene compound include those similar to the raw material monomer for the styrene resin component (CH-2), and preferred embodiments are also the same.

  In the raw material monomer of the styrenic resin component (AH-2), the content of the alkyl (meth) acrylate is preferably 5% by mass or more, more preferably from the viewpoint of low-temperature fixability, charging stability, and document offset resistance. From the same viewpoint, it is preferably 50% by mass or less, more preferably 40% by mass or less, still more preferably 30% by mass or less, and still more preferably 25% by mass. It is below mass%.

  The mass ratio of alkyl (meth) acrylate to styrene compound (alkyl (meth) acrylate / styrene compound) in the raw material monomer of the styrene resin component (AH-2) is low temperature fixability, charging stability and document offset resistance. In view of the above, it is preferably 0/100 or more, more preferably 10/90 or more, and from the viewpoint of low-temperature fixability and charging stability, preferably 80/20 or less, more preferably 50/50 or less, and further Preferably it is 40/60 or less, More preferably, it is 30/70 or less.

<Amotropic monomer>
It is preferable that the amorphous composite resin (AH) further includes a structural unit derived from the both reactive monomers from the same viewpoint as the crystalline composite resin (CH).
Examples of the both-reactive monomers include those similar to the both-reactive monomers listed as the raw material monomers for the crystalline composite resin (CH). Among these, low-temperature fixability, charging stability, and document offset resistance From the viewpoint, acrylic acid is preferable.

  From the viewpoint of low-temperature fixability, the amount of both reactive monomers used is preferably 1 mol part with respect to 100 mol parts of the alcohol component (AH-al) which is a raw material monomer of the polycondensation resin component (AH-1). Or more, more preferably 3 parts by mole or more, still more preferably 5 parts by mole or more, and from the viewpoint of low-temperature fixability, charging stability and document offset resistance, preferably 30 parts by mole or less, more preferably 25 moles. Part or less, more preferably 20 parts by mole or less, still more preferably 15 parts by mole or less, and still more preferably 10 parts by mole or less.

  The amorphous composite resin (AH) can be produced by the same method as the production methods (1) to (3) of the crystalline composite resin (CH), and the preferred embodiments are also the same.

(Softening point)
The softening point of the amorphous composite resin (AH) is preferably 80 ° C. or higher, more preferably 100 ° C. or higher, and still more preferably 110 ° C. or higher, from the viewpoints of low-temperature fixability, charging stability, and document offset resistance. And, it is preferably 150 ° C. or lower, more preferably 140 ° C. or lower, and further preferably 130 ° C. or lower.
(Glass-transition temperature)
The glass transition temperature of the amorphous composite resin (AH) is preferably 30 ° C. or higher, more preferably 40 ° C. or higher, and still more preferably 50 ° C. or higher, from the viewpoints of low-temperature fixability, charging stability, and document offset resistance. Yes, and preferably 90 ° C. or lower, more preferably 80 ° C. or lower, and still more preferably 70 ° C. or lower.
(Acid value)
The acid value of the amorphous composite resin (AH) is preferably 3 mgKOH / g or more, more preferably 5 mgKOH / g or more, still more preferably 8 mgKOH / g, from the viewpoints of low-temperature fixability, charging stability and document offset resistance. More preferably, it is 10 mgKOH / g or more, and preferably 40 mgKOH / g or less, more preferably 30 mgKOH / g or less, still more preferably 20 mgKOH from the viewpoint of low-temperature fixability, charging stability and document offset resistance. / G or less.
The softening point, glass transition temperature, and acid value of the amorphous composite resin (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.

  In addition to the crystalline resin (C) and the amorphous composite resin (AH), the toner of the present invention is a known resin used for the toner, for example, the crystalline resin (C) and the amorphous composite resin (AH). Other polyesters, styrene-acrylic copolymers, epoxies, polycarbonates, polyurethanes and the like may be contained.

In the toner of the present invention, the content of the amorphous composite resin (AH) constituting the shell portion is preferably 2% by mass or more, more preferably 5% by mass or more, from the viewpoint of low-temperature fixability and charging stability. More preferably, it is 10% by mass or more, and from the viewpoint of low-temperature fixability and document offset resistance, it is preferably 50% by mass or less, more preferably 30% by mass or less, and still more preferably 20% by mass or less.
In the toner of the present invention, the content of the crystalline resin (C) constituting the core part is preferably 2% by mass or more, more preferably 5% by mass or more, from the viewpoint of low-temperature fixability and document offset resistance. Preferably, it is 10% by mass or more, and from the viewpoint of charging stability, it is preferably 50% by mass or less, more preferably 30% by mass or less, and still more preferably 20% by mass or less.

  The toner of the present invention is one kind selected from an amorphous styrenic resin (AS) and an amorphous polyester resin (AP) in the core part from the viewpoint of low-temperature fixability, charging stability, and document offset resistance. It is preferable to contain the above amorphous resin (AA), and it is more preferable to contain the amorphous polyester resin (AP).

[Amorphous styrene resin (AS)]
Examples of the amorphous styrenic resin (AS) include polystyrene, a polymer of a styrene derivative, a styrene-acrylic copolymer, and the like, from the viewpoint of low-temperature fixability, charging stability, and document offset resistance, One or more selected from a polymer of a derivative and a styrene-acrylic copolymer is preferable, one or more selected from polystyrene and a styrene-acrylic copolymer is more preferable, and a styrene-acrylic copolymer is still more preferable.

Examples of the raw material monomer for the amorphous styrenic resin (AS) include the same materials as those cited as the raw material monomer for the styrene resin component (CH-2). Among these, it is preferable to use styrene and alkyl (meth) acrylate together.
The content of styrene in the raw material monomer of the amorphous styrenic resin (AS) is preferably 50% by mass or more, more preferably 60% by mass or more, from the viewpoints of low-temperature fixability, charging stability and document offset resistance. More preferably, it is 70% by mass or more, more preferably 75% by mass or more, and from the same viewpoint, preferably 95% by mass or less, more preferably 90% by mass or less, still more preferably 85% by mass or less. is there. A polymerization initiator is not contained in the raw material monomer of the amorphous styrenic resin (AS).

Examples of the alkyl (meth) acrylate include the same as those exemplified as the raw material monomer of the styrene resin component (CH-2). Among these, n-butyl acrylate is preferable.
The number of carbon atoms of the alkyl group of the alkyl (meth) acrylate used as a raw material monomer for the amorphous styrenic resin (AS) is preferably 2 or more from the viewpoint of low-temperature fixability, charging stability and document offset resistance, More preferably, it is 3 or more, and preferably 12 or less, more preferably 10 or less, still more preferably 8 or less, and still more preferably 6 or less.
When using an alkyl (meth) acrylate, the content of the alkyl (meth) acrylate in the raw material monomer of the amorphous styrenic resin (AS) is preferably from the viewpoint of low-temperature fixability, charging stability and document offset resistance. Is 5% by mass or more, more preferably 10% by mass or more, still more preferably 15% by mass or more, and preferably 30% by mass or less, more preferably 25% by mass or less.

The amorphous styrenic resin (AS) can be produced by subjecting the raw material monomer to an addition polymerization reaction.
From the viewpoint of reactivity, the temperature of the addition polymerization reaction is preferably 120 ° C. or higher, more preferably 130 ° C. or higher, still more preferably 150 ° C. or higher, and preferably 230 ° C. or lower, more preferably 220 ° C. or lower. is there.
Moreover, it is preferable to accelerate the reaction by reducing the pressure of the reaction system in the latter half of the polymerization.

(Softening point)
The softening point of the amorphous styrenic resin (AS) is preferably 90 ° C. or higher, more preferably 105 ° C. or higher, and still more preferably 115 ° C. or higher, from the viewpoints of low-temperature fixability, charging stability and document offset resistance. From the viewpoint of low-temperature fixability, it is preferably 150 ° C. or lower, more preferably 140 ° C. or lower, and further preferably 130 ° C. or lower.
〔Glass-transition temperature〕
The glass transition temperature of the amorphous styrenic resin (AS) is preferably 30 ° C. or higher, more preferably 40 ° C. or higher, more preferably 50 ° C. or higher, from the viewpoints of low-temperature fixability, charging stability and document offset resistance. From the viewpoint of low-temperature fixability, it is preferably 90 ° C. or lower, more preferably 70 ° C. or lower, and further preferably 60 ° C. or lower.
(Acid value)
The acid value of the amorphous styrenic resin (AS) is preferably 0 mgKOH / g or more, and preferably 30 mgKOH / g or less, more preferably from the viewpoints of low-temperature fixability, charging stability and document offset resistance. Is 25 mgKOH / g or less, more preferably 10 mgKOH / g or less.
The softening point, glass transition temperature, and acid value of the amorphous styrenic resin (AS) can be appropriately adjusted according to the production conditions such as the type and ratio of the raw material monomers, reaction temperature, reaction time, and cooling rate.

[Amorphous polyester resin (AP)]
The amorphous polyester resin (AP) comprises an alcohol component (hereinafter also referred to as “alcohol component (AP-al)”) and a carboxylic acid component (hereinafter also referred to as “carboxylic acid component (AP-ac)”). It can be obtained by polycondensation reaction.

(Alcohol component (AP-al))
As an alcohol component (AP-al), the thing similar to the said alcohol component (CH-al) is mentioned.
Among these, aromatic diols such as bisphenol A or their alkylene oxides (average added mole number of 1 to 16) are preferable from the viewpoint of low-temperature fixability, charging stability, and document offset resistance. A propylene oxide adduct is more preferable.
In the alcohol component (AP-al), the content of the propylene oxide adduct of bisphenol A is preferably 80 mol% or more, more preferably 90 mol%, from the viewpoints of low-temperature fixability, charge stability, and document offset resistance. More preferably, it is 95 mol% or more, more preferably 98 mol% or more, and preferably 100 mol% or less, more preferably 100 mol%.
The average number of moles of propylene oxide added to the propylene oxide adduct of bisphenol A is preferably 1 or more, more preferably 1.2 or more, and still more preferably 1 from the viewpoints of low-temperature fixability, charging stability, and document offset resistance. 0.5 or more, and preferably 16 or less, more preferably 12 or less, still more preferably 8 or less, and still more preferably 4 or less.
These alcohol components (AP-al) can be used alone or in combination of two or more.

(Carboxylic acid component (AP-ac))
Examples of the carboxylic acid component (AP-ac) include those similar to those exemplified as the carboxylic acid component (CH-ac).
Among these, from the viewpoint of low-temperature fixability, charging stability and document offset resistance, aliphatic dicarboxylic acid compounds and aromatic dicarboxylic acid compounds are preferable, and aliphatic dicarboxylic acid compounds and aromatic dicarboxylic acid compounds are used in combination. Is more preferable.
As the aliphatic dicarboxylic acid compound, adipic acid is preferable. The number of carbon atoms of the aliphatic dicarboxylic acid compound is preferably 2 or more, more preferably 4 or more, and preferably 10 or less, more preferably 8 from the viewpoints of low-temperature fixability, charging stability and document offset resistance. It is as follows.
As the aromatic dicarboxylic acid compound, terephthalic acid is preferred. The content of the aromatic dicarboxylic acid compound, preferably terephthalic acid, in the carboxylic acid component (AP-ac) is preferably 30 mol% or more, more preferably from the viewpoint of low-temperature fixability, charge stability and document offset resistance. Is at least 40 mol%, more preferably at least 50 mol%, and preferably at most 80 mol%, more preferably at most 70 mol%, still more preferably at most 60 mol%.
These alcohol components (AP-ac) can be used alone or in combination of two or more.

  The equivalent ratio (COOH group / OH group) of the carboxylic acid component (AP-ac) to the alcohol component (AP-al) is preferably 0.6 or more from the viewpoint of low-temperature fixability, charging stability and document offset resistance. More preferably, it is 0.7 or more, more preferably 0.8 or more, and preferably 1.2 or less, more preferably 1.0 or less, still more preferably 0.95 or less.

  From the viewpoint of adjusting the physical properties, the alcohol component (AP-al) may appropriately contain a monovalent alcohol, and the carboxylic acid component (AP-ac) appropriately contains a monovalent carboxylic acid compound. It may be.

Amorphous polyester resin (AP) consists of an alcohol component (AP-al) and a carboxylic acid component (AP-ac) in an inert gas atmosphere. It can be produced by polycondensation using an agent or the like.
The conditions for the polycondensation reaction are the same as the conditions for the polycondensation reaction between the alcohol component (AH-al) and the carboxylic acid component (AH-ac).

Examples of the esterification catalyst, esterification co-catalyst, and polymerization inhibitor that are suitably used for the polycondensation reaction include the same ones as those used for the production of the crystalline composite resin (CH).
The amount of the esterification catalyst used is the total amount of alcohol component (AP-al) and carboxylic acid component (AP-ac) from the viewpoints of reactivity, molecular weight adjustment, and physical property adjustment of the amorphous polyester resin (AP). Preferably, it is 0.01 parts by mass or more, more preferably 0.1 parts by mass or more, further preferably 0.3 parts by mass or more, and preferably 2.0 parts by mass or less, more preferably 100 parts by mass or more. Preferably it is 1.5 mass parts or less, More preferably, it is 1.0 mass part or less.
The amount of the esterification cocatalyst used is 100 in terms of the total amount of alcohol component (AP-al) and carboxylic acid component (AP-ac) from the viewpoint of reactivity, molecular weight adjustment, and physical property adjustment of the amorphous polyester resin (AP). Preferably it is 0.001 mass part or more with respect to a mass part, More preferably, it is 0.01 mass part or more, More preferably, it is 0.03 mass part or more, Preferably it is 0.2 mass part or less, More preferably Is 0.15 parts by mass or less, more preferably 0.1 parts by mass or less.
From the viewpoint of reactivity, the mass ratio of the esterification cocatalyst to the esterification catalyst [esterification cocatalyst / esterification catalyst] is preferably 0.001 or more, more preferably 0.01 or more, and still more preferably 0.00. It is 05 or more, and preferably 0.5 or less, more preferably 0.3 or less, and still more preferably 0.15 or less.

[Softening point]
The softening point of the amorphous polyester resin (AP) is preferably 50 ° C. or higher, more preferably 70 ° C. or higher, and still more preferably 85 ° C. or higher, from the viewpoints of low-temperature fixability, charging stability and document offset resistance. From the viewpoint of low-temperature fixability, it is preferably 130 ° C. or lower, more preferably 110 ° C. or lower, and still more preferably 95 ° C. or lower.
〔Glass-transition temperature〕
The glass transition temperature of the amorphous polyester resin (AP) is preferably 30 ° C. or higher, more preferably 35 ° C. or higher, from the viewpoints of low-temperature fixability, charging stability and document offset resistance, and low-temperature fixability. From this viewpoint, it is preferably 90 ° C. or lower, more preferably 70 ° C. or lower, and further preferably 60 ° C. or lower.
[Acid value]
The acid value of the amorphous polyester resin (AP) is preferably 0 mgKOH / g or more, more preferably 10 mgKOH / g or more, still more preferably 15 mgKOH / g, from the viewpoints of low-temperature fixability, charging stability, and document offset resistance. From the viewpoint of low temperature fixability, it is preferably 40 mgKOH / g or less, more preferably 30 mgKOH / g or less, and further preferably 25 mgKOH / g or less.
The softening point, glass transition temperature and acid value of the amorphous polyester resin (AP) can be appropriately adjusted according to the production conditions such as the type and ratio of the raw material monomers, reaction temperature, reaction time and cooling rate.

In the toner of the present invention, the content of the amorphous resin (AA) constituting the core part is preferably 30% by mass or more, more preferably 50%, from the viewpoints of low-temperature fixability, charging stability and document offset resistance. From the same viewpoint, it is preferably 90% by mass or less, more preferably 85% by mass or less, and still more preferably 80% by mass or less.
The mass ratio of the crystalline resin (C) constituting the core portion of the toner of the present invention to the amorphous composite resin (AH) constituting the shell portion and the amorphous resin (AA) constituting the core portion [Crystal Resin (C) / [amorphous composite resin (AH) + amorphous resin (AA)]] is preferably 1/99 or more, more preferably 3 from the viewpoint of low-temperature fixability and document offset resistance. / 97 or more, more preferably 5/95 or more, still more preferably 10/90 or more, and from the viewpoint of charging stability, preferably 50/50 or less, more preferably 40/60 or less, and still more preferably. 30/70 or less, more preferably 20/80 or less.

In addition to the crystalline resin (C), the amorphous composite resin (AH), and the amorphous resin (AA), the toner of the present invention includes a known resin used for the toner, such as a crystalline resin (C). In addition, polyester other than amorphous composite resin (AH) and amorphous resin (AA), styrene-acrylic copolymer, epoxy, polycarbonate, polyurethane and the like may be contained.
In the binder resin constituting the toner of the present invention, the content of the crystalline resin (C), the amorphous composite resin (AH) and the amorphous resin (AA) is preferably 80% by mass or more, more preferably It is 90% by mass or more, more preferably 95% by mass or more, and preferably 100% by mass or less, more preferably 100% by mass.

[Toner Production Method]
The toner of the present invention is preferably produced by a method including the following steps 1 to 5.
Step 1: Step of mixing a crystalline resin (C) and a neutralizing agent to obtain a mixture Step 2: A resin containing the crystalline resin (C) by mixing at least water with the mixture obtained in Step 1 Step of obtaining aqueous dispersion of particles (X) Step 3: Step of agglomerating resin particles (X) obtained in Step 2 in an aqueous medium to obtain aggregated particles (1) Step 4: Obtained in Step 3 Step of aggregating resin particles (Z) containing amorphous composite resin (AH) to the obtained aggregated particles (1) to obtain aggregated particles (2) Step 5: Aggregated particles obtained in Step 4 ( 2) Fusion process

<Step 1>
Step 1 is a step of mixing the crystalline resin (C) and the neutralizing agent to obtain a mixture.
In this step, it is preferable to use an organic solvent from the viewpoints of low-temperature fixability, charging stability, and document offset resistance.

(Organic solvent)
As an organic solvent, from the viewpoint of solubility, alcohol solvents such as isopropanol and isobutanol; ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone and diethyl ketone; ether solvents such as dibutyl ether and dioxane; ethyl acetate and isopropyl acetate An acetic acid ester solvent such as Among these, from the viewpoint of low-temperature fixability, charge stability, and document offset resistance, a ketone solvent is more preferable, and methyl ethyl ketone is more preferable.
The mass ratio [organic solvent / crystalline resin (C)] between the organic solvent and the crystalline resin (C) in step 1 is preferably from the viewpoint of low-temperature fixability, charging stability, and document offset resistance. It is 3 or more, more preferably 0.5 or more, still more preferably 0.7 or more, and preferably 2.0 or less, more preferably 1.5 or less, still more preferably 1.3 or less.

(Neutralizer)
Examples of the neutralizing agent used in Step 1 include metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide; ammonia; organic bases such as trimethylamine, ethylamine, diethylamine, triethylamine, triethanolamine, and tributylamine. Can be mentioned. Among these, metal hydroxide and ammonia are preferable, metal hydroxide is more preferable, alkali metal hydroxide is more preferable, one or more selected from sodium hydroxide and potassium hydroxide is still more preferable, Sodium oxide is even more preferred.
The degree of neutralization of the crystalline resin (C) with the neutralizing agent is adjusted by adjusting the volume-median particle size (D ₅₀ ) of the resin particles (X) obtained in Step 3, and low-temperature fixability, charging stability, and document resistance From the viewpoint of improving the offset property, it is preferably 30 mol% or more, more preferably 50 mol% or more, further preferably 60 mol% or more, and from the same viewpoint, preferably 150 mol% or less, more preferably It is 120 mol% or less, more preferably 100 mol% or less, still more preferably 80 mol% or less.
In addition, the neutralization degree (mol%) of resin can be calculated | required by a following formula.
Degree of neutralization = {[mass of neutralizer (g) / equivalent of neutralizer] / [[acid value of resin (mgKOH / g) × mass of resin (g)] / (56 × 1000)]} × 100

(Surfactant)
In Step 1, a surfactant is preferably used from the viewpoint of low-temperature fixability, charge stability, and document offset resistance of the obtained toner.
Surfactants include nonionic surfactants, anionic surfactants and cationic surfactants. Among these, nonionic surfactants and / or anionic surfactants are preferable from the viewpoint of emulsion stability of the resin, and anionic surfactants are more preferable.
Nonionic surfactants include polyoxyethylene nonyl phenyl ether, polyoxyethylene oleyl ether, polyoxyethylene alkyl aryl ethers such as polyoxyethylene lauryl ether or polyoxyethylene alkyl ethers, polyethylene glycol monolaurate, Examples include polyoxyethylene fatty acid esters such as polyethylene glycol monostearate and polyethylene glycol monooleate, and oxyethylene / oxypropylene block copolymers. Among these, from the viewpoint of emulsion stability of the resin, polyoxyethylene alkyl ethers Is preferred.
Examples of the anionic surfactant include alkylbenzene sulfonates such as sodium alkylbenzene sulfonate, alkyl sulfates such as sodium alkyl sulfate, and alkyl ether sulfates such as sodium polyoxyethylene lauryl ether sulfate. From the viewpoint of emulsion stability, sodium alkylbenzene sulfonate and alkyl ether sulfate are preferable, and alkyl ether sulfate is more preferable.
Examples of the cationic surfactant include alkyltrimethylammonium chloride and dialkyldimethylammonium chloride.
Among these, from the viewpoint of emulsion stability of the binder resin, polyoxyethylene alkyl ethers and alkyl ether sulfates are preferable, and polyoxyethylene alkyl ether sulfates are more preferable. The polyoxyethylene alkyl ether sulfate is preferably a sodium salt from the same viewpoint.

The polyoxyethylene alkyl ether sulfate preferably contains polyoxyethylene alkyl ether sulfate (EO2) having an addition mole number of ethylene oxide of 2 mol.
In the anionic surfactant, the content of polyoxyethylene alkyl ether sulfate is preferably 80% by mass or more, more preferably 85% by mass or more, from the viewpoints of low-temperature fixability, charging stability, and document offset resistance. Further, it is preferably 90% by mass or more, more preferably 95% by mass or more, and preferably 100% by mass or less, more preferably 100% by mass.

The amount of the surfactant used is preferably 1 part by mass or more, more preferably as a solid content, from the viewpoint of low-temperature fixability, charging stability and document offset resistance with respect to 100 parts by mass of the crystalline resin (C). Is 2.5 parts by mass or more, more preferably 3 parts by mass or more, and preferably 10 parts by mass or less, more preferably 8 parts by mass or less, still more preferably 6 parts by mass or less, and even more preferably 5.5. It is 5 parts by mass or less, more preferably 5 parts by mass or less.
The addition amount of the surfactant in the step 1 is preferably 70% by mass or more, more preferably 80% by mass or more, further preferably 90% by mass or more, in the total addition amount of the surfactants in the steps 1 to 5. And preferably 100% by mass or less, more preferably 100% by mass.

(Optional component)
Also, in this step, optional components such as coloring agents, charge control agents, mold release agents, surfactants, conductivity modifiers, reinforcing fillers such as fibrous substances, antioxidants and anti-aging agents are added. Also good.
Additives such as a colorant and a charge control agent may be mixed with the binder resin in advance, and in that case, it is preferable to melt-knead the binder resin and the additive.
For melt kneading, it is preferable to use an open roll type biaxial kneader. An open roll type biaxial kneader is a kneader in which two rolls are arranged close to each other in parallel, and a heating function or a cooling function can be imparted by passing a heat medium through each roll. Therefore, the open roll type biaxial kneader is an open type part to be melt kneaded, and is provided with a heating roll and a cooling roll. The kneading heat can be easily dissipated.

[Colorant]
There is no restriction | limiting in particular as a coloring agent, A well-known coloring agent is mentioned, According to the objective, it can select suitably. Specifically, carbon black, inorganic composite oxide, chrome yellow, hansa yellow, benzidine yellow, selenium yellow, quinoline yellow, permanent orange GTR, pyrazolone orange, vulcan orange, watch young red, permanent red, brilliantamine 3B, Brilliantamine 6B, Dupont Oil Red, Pyrazolone Red, Resol Red, Rhodamine B Lake, Lake Red C, Bengal, Aniline Blue, Ultramarine Blue, Calco Oil Blue, Methylene Blue Chloride, Phthalocyanine Blue, Phthalocyanine Green, Malachite Green Oxalate, etc. Various pigments: acridine, xanthene, azo, benzoquinone, azine, anthraquinone, indico, thioy Zico type, phthalocyanine type, aniline black, polymethine, triphenylmethane dyes, diphenylmethane dyes, thiazine, include various dyes of thiazole, and the like. These can be used alone or in combination of two or more.
The amount of the colorant used is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, and still more preferably from the viewpoint of improving the image density of the toner with respect to 100 parts by mass of the total amount of the binder resin. Is 1.0 part by mass or more, and preferably 40 parts by mass or less, more preferably 20 parts by mass or less, and still more preferably 10 parts by mass or less.

[Charge control agent]
Examples of the charge control agent include chromium azo dyes, iron azo dyes, aluminum azo dyes, and salicylic acid metal complexes. You may use these individually or in combination of 2 or more types.
The amount of the charge control agent used 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 total amount of the binder resin, from the viewpoint of charging stability of the toner. Is 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 still more preferably 1.5 parts by mass or less.

〔Release agent〕
Release agents include polyolefin wax, paraffin wax, silicones; fatty acid amides such as oleic acid amide, erucic acid amide, ricinoleic acid amide, stearic acid amide; carnauba wax, rice wax, candelilla wax, wood wax, jojoba Plant waxes such as oil; animal waxes such as beeswax; waxes such as mineral and petroleum waxes such as montan wax, ozokerite, ceresin, microcrystalline wax, and Fischer-Tropsch wax, which are used alone or in combination of two or more Can be mixed and used.
The amount of the release agent used is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, and further preferably 2 parts by mass with respect to the total amount of the binder resin, from the viewpoint of resin dispersibility. The amount is preferably 20 parts by mass or less, more preferably 15 parts by mass or less, and still more preferably 10 parts by mass or less.

<Process 2>
Step 2 is a step of obtaining an aqueous dispersion of resin particles (X) containing the crystalline resin (C) by mixing at least water with the mixture obtained in Step 1.
Methods for obtaining an aqueous dispersion of resin particles (X) include a method in which a resin or the like is added to an aqueous medium and dispersed using a disperser, a method in which an aqueous medium is gradually added to a resin or the like and a phase inversion emulsification is performed. From the viewpoint of improving the low-temperature fixability of the obtained toner, a method using phase inversion emulsification is preferable.
Hereinafter, a method for preparing an aqueous dispersion of resin particles (X) by a phase inversion emulsification method will be described.

In the phase inversion emulsification method, by adding an aqueous medium to the mixture, first, a W / O phase is formed, and then the phase is inverted to the O / W phase. Whether or not phase inversion has occurred can be confirmed, for example, by visual observation or electrical conductivity.
The phase inversion step can be adjusted by the addition rate and amount of the aqueous medium as described later.

As the aqueous medium, those mainly containing water are preferable. The water content is preferably 80% by mass or more, more preferably 90% by mass or more, still more preferably 95% by mass or more, and preferably from the viewpoint of improving the emulsion stability of the resin in the aqueous medium. It is 100 mass% or less, More preferably, it is 100 mass%. The water is preferably deionized water or distilled water.
Examples of components other than water include organic solvents that dissolve in water, such as methanol, ethanol, acetone; and cyclic ethers such as tetrahydrofuran.

  The temperature at which the aqueous medium is added is preferably 20 ° C. or higher, more preferably 40 ° C. or higher, further preferably 50 ° C. or higher, and preferably 90 ° C. or lower, from the viewpoint of improving the emulsion stability of the resin. More preferably, it is 85 degrees C or less, More preferably, it is 80 degrees C or less.

  From the viewpoint of obtaining resin particles having a small particle size, the addition rate of the aqueous medium is preferably 0.1 parts by mass / min or more with respect to 100 parts by mass of the crystalline resin (C) until the phase inversion is completed. More preferably 1 part by mass / min or more, further preferably 3 parts by mass / min or more, still more preferably 4 parts by mass / min or more, and preferably 50 parts by mass / min or less, more preferably 30 parts by mass. / Min or less, more preferably 20 parts by mass / min or less, still more preferably 10 parts by mass / min or less. There is no restriction | limiting in the addition rate of the aqueous medium after phase inversion.

  The amount of the aqueous medium used is preferably 100 parts by mass or more, more preferably 200 parts by mass or more, more preferably 100 parts by mass or more with respect to 100 parts by mass of the crystalline resin (C) from the viewpoint of obtaining uniform aggregated particles in the subsequent aggregation process. Preferably it is 400 parts by mass or more, more preferably 600 parts by mass or more, and preferably 2000 parts by mass or less, more preferably 1500 parts by mass or less, still more preferably 1000 parts by mass or less, and even more preferably 800 parts by mass. It is as follows.

When an organic solvent is used in step 1, it is preferable to remove the organic solvent from the dispersion obtained by phase inversion emulsification in this step.
The method for removing the organic solvent is not particularly limited, and any method can be used. However, since it is dissolved in water, it is preferably distilled. Further, the organic solvent may not be completely removed and may remain in the aqueous dispersion. In this case, the residual amount of the organic solvent is preferably 1% by mass or less, more preferably 0.5% by mass or less, and still more preferably 0% in the aqueous dispersion.
When removing the organic solvent by distillation, it is preferable to raise the temperature to a temperature equal to or higher than the boiling point of the organic solvent to be used while stirring. Further, from the viewpoint of maintaining the dispersion stability of the resin particles (X), it is more preferable to raise the temperature to a temperature equal to or higher than the boiling point of the organic solvent to be used under reduced pressure and to distill it off. Note that the temperature may be increased after the pressure is reduced, or the pressure may be decreased after the temperature is increased. From the viewpoint of maintaining the dispersion stability of the resin particles (X), it is preferable to distill off at a constant temperature and pressure.
Further, after step 2, a step of mixing a surfactant with the obtained aqueous dispersion may be performed.

  The solid content concentration of the aqueous dispersion of the resin particles (X) is preferably 3% by mass or more, more preferably 5% by mass, by appropriately adding water from the viewpoint of stability of the aqueous dispersion and ease of handling. More preferably, the content is 15% by mass or more, and preferably 40% by mass or less, more preferably 30% by mass or less, and still more preferably 25% by mass or less.

The volume median particle size (D ₅₀ ) of the resin particles (X) obtained in this step is preferably 30 nm or more, more preferably 50 nm or more, more preferably from the viewpoint of low-temperature fixability, charging stability and document offset resistance. The thickness is preferably 70 nm or more, and preferably 250 nm or less, more preferably 200 nm or less, still more preferably 150 nm or less, and still more preferably 130 nm 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% calculated from the smaller particle size.

<Step 3>
Step 3 is a step in which the resin particles (X) obtained in Step 2 are aggregated in an aqueous medium to obtain aggregated particles (1).
Step 3 includes resin particles (X) obtained in Step 2 and resin particles containing amorphous resin (AA) (from the viewpoint of low-temperature fixability, charge stability, and document offset resistance of the obtained toner ( Y) is preferably aggregated to obtain aggregated particles (1).

The resin particles (Y) are preferably obtained as an aqueous dispersion of the resin particles (Y). By using an amorphous resin (AA) as the binder resin, the resin particles (Y) are similar to the aqueous dispersion of the resin particles (X). It can manufacture by the method of.
The volume median particle size (D ₅₀ ) of the resin particles (Y) is preferably 70 nm or more, more preferably 90 nm or more, and preferably 200 nm or less, more preferably 150 nm or less, from the viewpoint of toner productivity. More preferably, it is 120 nm or less.
The solid content concentration of the aqueous dispersion of the resin particles (Y) is preferably 3% by mass or more, more preferably 5% by mass or more, by appropriately adding water from the viewpoint of stability of the dispersion and ease of handling. More preferably, it is 15% by mass or more, and preferably 40% by mass or less, more preferably 30% by mass or less, and still more preferably 25% by mass or less.

  In step 3, it is preferable to mix the aqueous dispersion of resin particles (X) and the aqueous dispersion of resin particles (Y) to aggregate the resin particles (X) and the resin particles (Y). In Step 3, it is preferable to add a flocculant in order to efficiently perform the aggregation.

As the flocculant, a quaternary salt cationic surfactant, an organic flocculant such as polyethyleneimine; and an inorganic flocculant such as inorganic metal salt and inorganic ammonium salt are used. From the viewpoint of toner particle size distribution and heat-resistant storage stability, inorganic flocculants are preferable, and inorganic metal salts are particularly preferable.
Examples of the inorganic metal salt include sodium sulfate, sodium chloride, calcium chloride, calcium nitrate, barium chloride, magnesium chloride, zinc chloride, and aluminum chloride. The valence of the central metal of the inorganic metal salt is preferably 2 or more from the viewpoint of the particle size distribution of the toner and heat resistant storage stability.
When adding a flocculant, the addition amount is preferably 0.001 parts by mass or more, more preferably 0.01 parts by mass or more, with respect to 100 parts by mass in total of the resin particles (X) and the resin particles (Y). More preferably, it is 0.1 parts by mass or more, and preferably 10 parts by mass or less, more preferably 5 parts by mass or less, and still more preferably 1 part by mass or less.
The flocculant is preferably added after being dissolved in an aqueous medium, and it is preferable that the flocculant is sufficiently stirred at the time of addition of the flocculant and after completion of the addition.

In the aggregation step, the solid content concentration in the system is preferably 5% by mass or more, more preferably 10% by mass or more, and preferably 50% by mass or less, more preferably, in order to cause uniform aggregation. It is 40 mass% or less, More preferably, it is 30 mass% or less.
In the coagulation step, from the viewpoint of uniformly dispersing the coagulant and causing uniform coagulation, the temperature during addition of the coagulant is preferably 10 ° C or higher, more preferably 15 ° C or higher, and further preferably 18 ° C or higher. Yes, and preferably 40 ° C. or lower, more preferably 35 ° C. or lower, still more preferably 30 ° C. or lower.
The holding temperature after adding the flocculant is preferably 40 ° C or higher, more preferably 45 ° C or higher, still more preferably 47 ° C or higher, and preferably 65 ° C or lower, more preferably 60 ° C or lower, still more preferably. Is 55 ° C. or lower.

In step 3, the colorant, the charge control agent, the release agent, the conductivity adjusting agent, the reinforcing filler such as a fibrous substance, the antioxidant, the anti-aging agent and the like are added and then aggregated. May be.
Additives such as a colorant, a charge control agent, and a release agent may be premixed in the binder resin, or a dispersion in which each additive is separately dispersed in a dispersion medium such as water, that is, colorant fine particles. You may prepare the coloring agent dispersion containing, the charge control agent dispersion containing charge control agent microparticles | fine-particles, and the mold release agent dispersion containing release agent microparticles | fine-particles, and may use for an aggregation process.
The volume median particle size (D ₅₀ ) of the colorant fine particles is preferably 50 nm or more, more preferably 100 nm or more, and preferably 200 nm or less, more preferably 150 nm or less.
The volume median particle size (D ₅₀ ) of the charge control agent fine particles is preferably 100 nm or more, more preferably 300 nm or more, and preferably 800 nm or less, more preferably 500 nm or less.
The volume median particle size (D ₅₀ ) of the release agent fine particles is preferably 100 nm or more, more preferably 300 nm or more, and preferably 1000 nm or less, more preferably 700 nm or less.

<Step 4>
Step 4 is a step in which the aggregated particles (1) obtained in Step 3 are aggregated with the resin particles (Z) containing the amorphous composite resin (AH) to obtain aggregated particles (2).

The resin particles (Z) are preferably obtained as an aqueous dispersion of the resin particles (Z). By using an amorphous composite resin (AH) as a binder resin, the resin particles (Z) and the aqueous dispersion of the resin particles (X) It can be manufactured by a similar method.
The volume median particle size (D ₅₀ ) of the resin particles (Z) is preferably 60 nm or more, more preferably 70 nm or more, still more preferably 80 nm or more, and preferably 200 nm or less from the viewpoint of toner productivity. More preferably, it is 150 nm or less, More preferably, it is 130 nm or less.
The solid content concentration of the aqueous dispersion of the resin particles (Z) is preferably 3% by mass or more, more preferably 5% by mass or more, by appropriately adding water from the viewpoint of stability of the dispersion and ease of handling. More preferably, it is 15% by mass or more, and preferably 40% by mass or less, more preferably 30% by mass or less, and still more preferably 25% by mass or less.

In step 4, the resin particles (Z) are further adhered to the aggregated particles (1) by adding an aqueous dispersion of the resin particles (Z) to the dispersion of the aggregated particles (1) described above. It is preferable to obtain the dispersion liquid 2).
Before adding the aqueous dispersion of resin particles (Z) to the dispersion of aggregated particles (1), an aqueous medium may be added to the dispersion of aggregated particles (1) for dilution. Further, when the aqueous dispersion of the resin particles (Z) is added to the dispersion of the aggregated particles (1), the coagulant is added in order to efficiently attach the resin particles (Z) to the aggregated particles (1). It may be used in the process.

  The temperature at which the aqueous dispersion of the resin particles (Z) is added is preferably 40 ° C. or higher, more preferably 45 ° C. or higher, from the viewpoint of low-temperature fixability, charge stability and document offset resistance of the obtained toner. More preferably, it is 50 degreeC or more, Preferably it is 80 degreeC or less, More preferably, it is 70 degreeC or less, More preferably, it is 65 degreeC or less.

The volume-median particle size (D ₅₀ ) of the obtained aggregated particles (2) is determined from the viewpoint of obtaining a toner from which a high-quality image can be obtained, and from the viewpoint of low-temperature fixability, charging stability, and document offset resistance of the obtained toner. Therefore, it 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, more preferably 9 μm or less, still more preferably 8 μm or less.

The total amount of the resin particles (Z) may be added, and aggregation may be stopped when the toner particles have grown to an appropriate particle size.
Examples of the method for stopping the aggregation include a method of cooling the dispersion, a method of adding an aggregation stopper, and a method of diluting the dispersion. From the viewpoint of reliably preventing unnecessary aggregation, a method of stopping aggregation by adding an aggregation stopper is preferable.
A surfactant is preferably used as the aggregation terminator, and an anionic surfactant is more preferably used. Of the anionic surfactants, it is more preferable to use one or more selected from alkyl ether sulfates, alkyl sulfates, and linear alkylbenzene sulfonates, and it is more preferable to use alkyl ether sulfates.

<Step 5>
Step 5 is a step of obtaining core-shell particles by fusing the aggregated particles (2) obtained in Step 4.
The temperature in the system in Step 5 is amorphous from the viewpoint of the target toner particle size, particle size distribution, shape control and particle fusing property, as well as low temperature fixing property, charging stability and document offset resistance. The composite resin (AH) preferably has a softening point of −55 ° C. or higher, more preferably a softening point of −50 ° C. or higher, still more preferably a softening point of −45 ° C. or higher, and a softening point of + 10 ° C. or lower is preferable. More preferably, the softening point is −10 ° C. or lower, the softening point −20 ° C. or lower is still more preferable, and the softening point −30 ° C. or lower is still more preferable.
Specifically, it is preferably 70 ° C or higher, more preferably 75 ° C or higher, and preferably 100 ° C or lower, more preferably 90 ° C or lower.

By appropriately subjecting the core-shell particles obtained in step 5 to a solid-liquid separation step such as filtration, a washing step, and a drying step, the electrophotographic toner of the present invention can be suitably obtained.
In the washing step, it is preferable to completely remove the added nonionic surfactant by washing, and washing with an aqueous solution below the cloud point of the nonionic surfactant is preferred. The washing is preferably performed a plurality of times.
In the drying step, any method such as a vibration type fluidized drying method, a spray drying method, a freeze drying method, a flash jet method, or the like can be employed. The water content after drying of the toner is preferably adjusted to 1.5% by mass or less, more preferably 1.0% by mass or less from the viewpoint of chargeability.

The toner particles can be used as the toner 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.
The average particle diameter of the external additive is preferably 10 nm or more, more preferably 15 nm or more, and preferably 250 nm or less, more preferably 200 nm or less, from the viewpoints of chargeability, fluidity and transferability of the toner. Preferably it is 100 nm or less, More preferably, it is 50 nm or less.
The content of the external additive is preferably 0.05 parts by mass or more, more preferably 0.1 parts by mass or more, and still more preferably 0.3 parts by mass with respect to 100 parts by mass of the toner before processing with the external additive. And preferably 5 parts by mass or less, more preferably 4 parts by mass or less, and still more preferably 3 parts by mass or less.

The volume median particle size (D ₅₀ ) of the toner of the present invention is preferably 3.0 μm or more, more preferably 3.5 μm or more, and still more preferably, from the viewpoints of low-temperature fixability, charging stability and document offset resistance. 4.0 μm or more, more preferably 4.5 μm or more, and preferably 9.0 μm or less, more preferably 8.5 μm or less, still more preferably 8.0 μm or less, and even more preferably 7.5 μm or less. is there.

  The electrophotographic toner of the present invention can be used as a one-component developing toner or as a two-component developer mixed with a carrier.

  Each property such as resin, resin particles, 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 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) Maximum endothermic peak temperature and melting point Using a differential scanning calorimeter “Q-100” (manufactured by TA Instruments Japan Co., Ltd.), the temperature drop rate is 10 ° C./min from room temperature (20 ° C.). The sample cooled to 0 ° C. was allowed to stand still for 1 minute, and then measured while raising the temperature to 180 ° C. at a temperature rising rate of 10 ° C./min. Of the endothermic peaks observed, the peak temperature on the highest temperature side was defined as the maximum endothermic peak temperature. The maximum peak temperature of the heat of fusion is the melting point.

(3) Glass transition temperature Using a differential scanning calorimeter “Q-100” (manufactured by TA Instruments Japan Co., Ltd.), 0.01 to 0.02 g of a sample is weighed into an aluminum pan, and 200 ° C. The temperature was raised to 0 ° C. from the temperature at a temperature drop rate 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 of Aggregated Particles (D ₅₀ )]
The volume median particle size of the aggregated 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 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. The volume-median particle diameter (D ₅₀ ) and the number% of the particle diameter of 2 μm or less were determined.

[Volume Median Particle Size (D ₅₀ ) of Resin Particles, Colorant Fine Particles, Charge Control Agent Fine Particles, Release Agent Particles]
(1) Measuring apparatus: Laser diffraction type particle size measuring instrument “LA-920” (manufactured by Horiba, Ltd.)
(2) Measurement conditions: Distilled water was added to the measurement cell, and the volume-median particle size (D ₅₀ ) was measured at a concentration at which the absorbance was in an appropriate range.

[Solid content concentration of colorant dispersion, charge control agent dispersion, release agent particle dispersion, aqueous dispersion]
Using an infrared moisture meter “FD-230” (manufactured by Kett Science Laboratory Co., Ltd.), 5 g of the sample was subjected to a drying temperature of 150 ° C. and a measurement mode of 96 (monitoring time 2.5 minutes / variation width 0.05%). The sample was dried and the moisture content (% by mass) of the sample was measured. The solid content was calculated according to the following formula.
Solid content concentration (% by mass) = 100-M
M: moisture of the sample (% by mass)

[Toner charging stability]
Under conditions of a temperature of 25 ° C. and a relative humidity of 50%, 0.6 g of toner and 19.4 g of a silicone ferrite carrier (manufactured by Kanto Denka Kogyo Co., Ltd., average particle size 90 μm) are placed in a 50 ml polybin, and a ball mill is used. The toner charge amount was measured by the following method using a Q / M meter (manufactured by EPPING).
After mixing for a predetermined time, a specified amount of toner and carrier mixture is put into a cell attached to the Q / M meter, and only the toner is passed through a sieve having a mesh size of 32 μm (stainless steel, twill, wire diameter: 0.0035 mm). Suctioned for 2 seconds. The change in voltage on the carrier generated at that time was monitored, and the value of X = [total amount of electricity after 90 seconds (μC) / amount of attracted toner (g)] was defined as the charge amount (μC / g). The ratio of the charge amount after 60 seconds mixing time and the charge amount after 600 seconds mixing time (charge amount after 60 seconds mixing time / charge amount after 600 seconds mixing time) was calculated, and the charging stability was evaluated as follows. Evaluated according to. The larger the value, the better the charging stability.
(Evaluation criteria)
A: X is 0.90 or more B: X is 0.85 or more and less than 0.90 C: X is 0.80 or more and less than 0.85 D: X is 0.70 or more and less than 0.80 E: X is 0.00. Less than 70

[Minimum fixing temperature of toner]
The toner was mounted on an apparatus in which the fixing machine of the copying machine “AR-505” (manufactured by Sharp Corporation) was improved so that fixing outside the apparatus was possible, and a printed matter was obtained in an unfixed state (printing area: 2 cm). × 12 cm, adhesion amount: 0.5 mg / cm ² ). After that, using a fixing machine (fixing speed 150 mm / sec) adjusted so that the total fixing pressure becomes 40 kgf, the fixing roll temperature is increased from 80 ° C. to 240 ° C. by 5 ° C., and unfixed at each temperature. A fixing test of the printed matter in the state was performed. A cellophane adhesive tape “UNICEF Cellophane” (Mitsubishi Pencil Co., Ltd., width: 18 mm, JIS Z1522) was attached to the image portion of the obtained printed matter, passed through a fixing roller set at 30 ° C., and then the tape was peeled off. . The optical reflection density before and after the tape was peeled was measured using a reflection densitometer “RD-915” (manufactured by Gretag Macbeth Co.), and the ratio between the two (after peeling / before sticking × 100) was initially 90%. The temperature of the fixing roller that exceeded the minimum fixing temperature. The lower the minimum fixing temperature, the better the low-temperature fixing property.

[Document offset resistance of printed matter]
A toner was mounted on a copying machine “AR-505” (trade name, 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. When the fixed image and the unprinted J paper are overlaid, left under a condition of a temperature of 80 ° C. and a humidity of 50% under a load of 80 g / cm ² for 5 days, and then peeled off after 5 days. The presence or absence of document offset was confirmed visually. The obtained results were evaluated according to the following criteria.
A: The document offset cannot be confirmed.
B: White spots cannot be confirmed on the fixed image side, but a shift to the unprinted J paper side is observed.
C: Slight white spots can be confirmed on the fixed image side, but the actual usable level.
D: White spots can be clearly confirmed on the fixed image side.
E: Significant white spots can be confirmed on the fixed image side.
F: The papers are fixed to each other, and the paper is damaged when peeled off.

[Manufacture of amorphous resin for shell]
Synthesis Examples A-1 to A-2, A-4 to A-13
(Production of amorphous composite resins A-1 to A-2, A-4 to A-13)
BPA-PO, isophthalic acid, terephthalic acid, esterification catalyst and esterification co-catalyst shown in Table 1 were added to a 10 liter four-necked flask equipped with a thermometer, a stainless stir bar, a flow-down condenser and a nitrogen inlet tube. And heated up to 235 ° C. in a mantle heater over 2 hours in a nitrogen atmosphere. Thereafter, it was confirmed that the reaction rate reached 95% or higher at 235 ° C., cooled to 160 ° C., and mixed solution of raw material monomer of styrene resin component, both reactive monomers and radical polymerization initiator shown in Table 1 The solution was added dropwise over 1 hour. Then, after maintaining at 160 ° C. for 30 minutes, the temperature was raised to 200 ° C., further reacted for 1 hour under a reduced pressure of 8 kPa, and then cooled to 180 ° C. Thereafter, a radical polymerization inhibitor (4-t-butylcatechol) and the remaining carboxylic acid component were added, and the temperature was raised to 210 ° C. over 2 hours. Then, after reacting at 210 ° C. for 1 hour, the reaction was performed at 40 kPa until the softening point shown in Table 1 was reached. Table 1 shows the physical properties of the resin. In addition, the reaction rate in this invention means the value of production | generation reaction water amount (mol) / theoretical production | generation water amount (mol) x100.

Synthesis Example A-3
(Production of amorphous polyester resin A-3)
BPA-PO, isophthalic acid, esterification catalyst and esterification co-catalyst shown in Table 1 were placed in a 10 liter four-necked flask equipped with a thermometer, a stainless stir bar, a flow-down condenser and a nitrogen inlet tube, and nitrogen was added. The temperature was raised to 235 ° C. over 2 hours in a mantle heater in the atmosphere. Thereafter, it was confirmed that the reaction rate reached 95% or more at 235 ° C. Then, it cooled to 190 degreeC, the remaining carboxylic acid component was added, and it heated up to 210 degreeC over 2 hours. Then, after reacting at 210 ° C. for 1 hour, the reaction was performed at 40 kPa until the softening point shown in Table 1 was reached. Table 1 shows the physical properties of the resin.

[Manufacture of crystalline resin for core]
Synthesis Examples B-1 to B-5, B-7 to B-10
(Production of crystalline composite resins B-1 to B-5, B-7 to B-10)
Among the raw material monomers of the polycondensation resin component shown in Table 2, the total amount of alcohol component, half the amount of carboxylic acid component, esterification catalyst, thermometer, stainless steel stirring rod, flow-down condenser and nitrogen inlet tube were equipped 10 The mixture was placed in a liter four-necked flask, heated in a mantle heater in a nitrogen atmosphere from 135 ° C. to 160 ° C. over 6 hours, and then reacted at 160 ° C. Thereafter, it was confirmed that the reaction rate reached 95% or more, and a mixed solution of the raw material monomer of the styrene resin component, the both reactive monomers and the radical polymerization initiator shown in Table 2 was added dropwise over 1 hour. Then, after maintaining at 160 ° C. for 30 minutes, the remaining carboxylic acid component was added, the temperature was raised from 130 ° C. to 200 ° C. over 8 hours, and further reacted for 2 hours under a reduced pressure of 8 kPa. -1 to B-5 and B-7 to B-10 were obtained. Table 2 shows the physical properties of the resin.

Synthesis Example B-6
(Production of crystalline polyester resin B-6)
Among the raw material monomers of the polycondensation resin component shown in Table 2, the total amount of alcohol component, the total amount of carboxylic acid component, esterification catalyst, 10 equipped with a thermometer, a stainless steel stirring rod, a flow-down condenser, and a nitrogen inlet tube Put in a liter four-necked flask, raise the temperature from 130 ° C to 200 ° C over 8 hours in a mantle heater in a nitrogen atmosphere, and then react at 200 ° C for 2 hours. The reaction rate reaches 95% or more. I confirmed. Furthermore, it was made to react under reduced pressure of 8 kPa for 2 hours, and crystalline polyester resin B-6 was obtained. Table 2 shows the physical properties of the resin.

[Manufacture of amorphous resin for core]
Synthesis Example C-1
(Amorphous styrene resin C-1)
2 liters of xylene was placed in a 10 liter four-necked flask equipped with a thermometer, a stainless stirrer, a falling condenser, a dropping funnel and a nitrogen introducing tube, and the raw material monomers and radical polymerization of the styrenic resin shown in Table 3 The initiator was placed in a dropping funnel equipped with a four-necked flask. Thereafter, xylene in the four-necked flask was heated to 135 ° C. under a nitrogen atmosphere, and a mixture of the raw material monomer and the polymerization initiator was dropped into xylene from the dropping funnel over 1 hour. Furthermore, the temperature was raised to 200 ° C. and held at 200 ° C. for 2 hours. Thereafter, the xylene was removed by holding it under reduced pressure of 8 kPa for 1 hour to obtain an amorphous styrene resin C-1. Table 3 shows the physical properties.

Synthesis Example D-1
(Production of amorphous polyester resin D-1)
BPA-PO, terephthalic acid, esterification catalyst and esterification co-catalyst shown in Table 4 were put into a 10 liter four-necked flask equipped with a thermometer, a stainless stir bar, a flow-down condenser and a nitrogen inlet tube, and nitrogen was added. The temperature was raised to 235 ° C. over 2 hours in a mantle heater in the atmosphere. Thereafter, it was confirmed that the reaction rate reached 95% or more at 235 ° C., and then cooled to 180 ° C. Then, adipic acid was added and it heated up to 210 degreeC over 2 hours. Then, after reacting at 210 ° C. for 1 hour, the reaction was performed at 40 kPa until the softening point shown in Table 4 was reached. Table 4 shows the physical properties of the resin.

[Production of colorant dispersion]
Preparation Example 1
50 g of copper phthalocyanine “ECB-301” (manufactured by Dainichi Seika Kogyo Co., Ltd.), 5 g of nonionic surfactant “Emulgen 150” (polyoxyethylene lauryl ether, manufactured by Kao Corporation) and 200 g of ion-exchanged water are mixed. A colorant dispersion containing fine colorant particles was obtained by dispersing for 10 minutes using a homogenizer. The volume median particle size (D ₅₀ ) of the colorant fine particles was 120 nm, and the solid content concentration was 22% by mass.

[Production of charge control agent dispersion]
Preparation Example 2
50 g of salicylic acid compound “Bontron E-84” (manufactured by Orient Chemical Co., Ltd.) as the charge control agent, 5 g of “Emulgen 150” (manufactured by Kao Corporation) and 200 g of ion-exchanged water as the nonionic surfactant are mixed, Glass beads were used and dispersed for 10 minutes using a sand grinder to obtain a charge control agent dispersion liquid containing charge control agent fine particles. The volume median particle size (D ₅₀ ) of the charge control agent fine particles was 400 nm, and the solid content concentration was 22% by mass.

[Production of release agent particle dispersion]
Preparation Example 3
Paraffin wax “HNP9” (produced by Nippon Seiwa Co., Ltd.) 50 g, cationic surfactant “Sanisol (registered trademark) B50” (produced by Kao Corporation, alkylbenzyldimethylammonium chloride) and ion-exchanged water 200 g at 95 ° C. Disperse the release agent containing release agent particles by heating and dispersing using an ultrasonic homogenizer (trade name: “UP-400S” manufactured by Dr. Heelscher Co., Ltd.) at an output of 350 W for 30 minutes. A liquid was obtained. The volume median particle size (D ₅₀ ) of the paraffin wax (release agent particles) was 550 nm, and the solid content concentration was 22% by mass.

Production Examples a-1 to a-13, b-1 to b-10
(Production of aqueous dispersions a-1 to a-13, b-1 to b-10)
In a 3 L container equipped with a stirrer, reflux condenser, dropping funnel, thermometer and nitrogen inlet tube, 100 g of resin shown in Tables 5 and 6, 100 g of methyl ethyl ketone, anionic surfactant “Emar E27C (polyoxyethylene lauryl) 16.7 g of sodium ether sulfate (solid content: 27% by mass) ”(manufactured by Kao Corporation) (4.5% by mass with respect to 100 g of resin) was added and dissolved at 73 ° C. over 2 hours. To the obtained solution, a 5% by mass aqueous sodium hydroxide solution was added so that the neutralization degree was 70 mol% with respect to the acid value of the resin, and the mixture was stirred for 30 minutes.
While maintaining at 73 ° C., 675 g of ion-exchanged water was added over 77 minutes while stirring at 280 r / min (peripheral speed 88 m / min), and phase inversion emulsification was performed. Methyl ethyl ketone was distilled off under reduced pressure while maintaining at 73 ° C. Thereafter, the aqueous dispersion was cooled to 30 ° C. while stirring at 280 r / min (peripheral speed 88 m / min). Thereafter, the solid content concentration of the dispersion was measured, and ion exchange water was added so as to be 20% by mass to obtain an aqueous dispersion in which resin particles were dispersed in an aqueous medium. Tables 5 and 6 show the volume-median particle diameters of the resin particles in the obtained aqueous dispersion.

[Production of aqueous dispersion of resin particles]
Production Example a-14
(Production of aqueous dispersion a-14)
In a 3 L container equipped with a stirrer, reflux condenser, dropping funnel, thermometer and nitrogen introduction tube, 100 g of amorphous composite resin A-14, anionic surfactant “Emar E27C” (manufactured by Kao Corporation) 16.7 g (4.5% by mass with respect to 100 g of resin) and 5% by mass of sodium hydroxide aqueous solution were added so that the degree of neutralization was 70 mol% with respect to the acid value of the resin, and 98 ° C. For 3 hours.
While maintaining at 98 ° C., 675 g of ion-exchanged water was added over 180 minutes while stirring at 280 r / min (peripheral speed 88 m / min), and phase inversion emulsification was performed. Thereafter, the aqueous dispersion was cooled to 30 ° C. while stirring at 280 r / min (peripheral speed 88 m / min). Thereafter, the solid content concentration of the dispersion was measured, and ion exchange water was added so as to be 20% by mass to obtain an aqueous dispersion in which resin particles were dispersed in an aqueous medium. Table 5 shows the volume median particle size of the resin particles in the obtained aqueous dispersion.

Production Example a-15
(Production of aqueous dispersion a-15)
An aqueous dispersion a-15 was obtained in the same manner as in Production Example a-1, except that methyl ethyl ketone was changed to ethyl acetate. Table 5 shows the volume median particle size of the resin particles in the obtained aqueous dispersion.

Production Example a-16
(Production of aqueous dispersion a-16)
Amorphous composite resin A-1 150 g, ethyl acetate 75 g, anionic surfactant (trade name: “Emal E27C” manufactured by Kao Corporation) 16.7 g was dissolved at 25 ° C., and 73 ° C. for 2 hours. And dissolved. A 5% by mass aqueous sodium hydroxide solution was added to the resulting solution so that the neutralization degree was 70 mol% with respect to the acid value of the resin, and then 600 g of ion-exchanged water was mixed and an ultrasonic homogenizer ( The product was subjected to dispersion treatment at an output of 350 W for 30 minutes using a doctor Heelscher Co., Ltd., trade name: “UP-400S”. Thereafter, ethyl acetate was distilled off under reduced pressure at 73 ° C. to obtain an aqueous dispersion a-16. Table 5 shows the volume median particle size of the resin particles in the obtained aqueous dispersion.

Production Example c-1
(Production of aqueous dispersion c-1)
100 g of amorphous styrene-based resin C-1, 100 g of methyl ethyl ketone, 16.7 g of anionic surfactant “Emar E27C” (manufactured by Kao Corporation) (4.5% by mass with respect to 100 g of resin) at 25 ° C. And dissolved at 73 ° C. for 2 hours. 600 g of ion-exchanged water at 73 ° C. was mixed with the obtained solution, and subjected to a dispersion treatment at an output of 350 W for 30 minutes using an ultrasonic homogenizer (trade name: “UP-400S” manufactured by Dr. Heelscher). Thereafter, methyl ethyl ketone was distilled off under reduced pressure at 70 ° C. to obtain an aqueous dispersion c-1. Table 7 shows the volume median particle size of the resin particles in the obtained aqueous dispersion.

Production Example d-1
(Production of aqueous dispersion d-1)
In Production Example a-1, an aqueous dispersion d-1 was obtained in the same manner as Production Example a-1, except that the type of resin was changed to the resin shown in Table 7. Table 7 shows the volume median particle size of the resin particles in the obtained aqueous dispersion.

[Manufacture of toner for developing electrostatic image]
Example 1
(Manufacture of toner A)
45 g of aqueous dispersion b-1 of crystalline polyester resin B-1, 210 g of aqueous dispersion d-1 of amorphous polyester resin D-1, 8 g of colorant dispersion, 20 g of release agent particle dispersion, charge 2 g of the control agent dispersion and 52 g of deionized water are placed in a 2 L container, and 150 g of a 0.1 mass% calcium chloride aqueous solution at 20 ° C. with stirring of 100 r / min (peripheral speed 31 m / min) with an anchor type stirrer. Was added dropwise over 30 minutes. Then, it heated up to 50 degreeC, stirring and hold | maintained at 50 degreeC.
After confirming that the volume median particle size (D ₅₀ ) reached 6.5 μm, 45 g of the aqueous dispersion a-1 of the amorphous composite resin A-1 was immediately added and dispersed by stirring. Thereafter, a dilute solution obtained by diluting 4.2 g of anionic surfactant “Emar E27C” (manufactured by Kao Corporation) with 37 g of deionized water was added as an aggregation terminator. Next, the temperature was raised to 80 ° C., and after maintaining at 80 ° C. for 1 hour from the time when the temperature reached 80 ° C., the heating was terminated. As a result, fused particles were formed, and then slowly cooled to 20 ° C., filtered through a 150 mesh (mesh 150 μm) wire mesh, suction filtered, and washed and dried to obtain toner particles. .

(External addition process)
Hydrophobic silica “NAX-50” (manufactured by Nippon Aerosil Co., Ltd., number average particle diameter 40 nm) 1.0 part by mass, hydrophobic silica “R972” (manufactured by Nippon Aerosil Co., Ltd.) A 10 L Henschel mixer equipped with ST and A0 stirring blades (number average particle diameter 16 nm) 0.6 parts by mass, titanium oxide “JMT-150IB” (manufactured by Teika Co., Ltd., number average particle diameter 15 nm) Toner A was obtained by stirring at 3000 rpm for 2 minutes. Table 8 shows the evaluation results of the toner.

Examples 2 to 25, Comparative Examples 1 to 5
(Production of toners B to X, Z, AA to AE)
In Example 1, toners B to X, Z, and AA to AE were obtained in the same manner as in Example 1 except that the aqueous dispersion was changed to the types and ratios of the aqueous dispersions shown in Tables 8 and 9. The total amount of the aqueous dispersion used for the core was the same as that in Example 1 (300 g). The evaluation results of the obtained toner are shown in Tables 8 and 9.

Comparative Example 6
(Manufacture of toner Y)
45 g of aqueous dispersion b-1 of crystalline polyester resin B-1, 210 g of aqueous dispersion d-1 of amorphous polyester resin D-1, and aqueous dispersion a-1 of amorphous composite resin A-1 Was added to a 2 L container, and 100 r / min (peripheral speed 31 m / min) with an anchor-type stirrer. Min) was added dropwise at 20 ° C. over a period of 30 minutes. Then, it heated up to 50 degreeC, stirring.
After confirming that the volume median particle size (D ₅₀ ) reached 6.5 μm, 4.2 g of an anionic surfactant “Emar E27C” (manufactured by Kao Corporation) as a coagulation terminator was added with 37 g of deionized water. Diluted diluent was added. Next, the temperature was raised to 80 ° C., and after maintaining at 80 ° C. for 1 hour from the time when the temperature reached 80 ° C., the heating was terminated. As a result, fused particles were formed, and then slowly cooled to 20 ° C., filtered through a 150 mesh (mesh 150 μm) wire mesh, suction filtered, and washed and dried to obtain toner particles. . Thereafter, toner Y was obtained through the same external addition step as described above. Table 9 shows the evaluation results of the obtained toner.

When Example 1 is compared with Example 2, Example 1 in which the carboxylic acid component (AH-ac), which is a raw material monomer of the amorphous composite resin (AH), contains an aliphatic saturated dicarboxylic acid compound having 4 carbon atoms. It can be seen that it is excellent in low-temperature fixability and charging stability.
When Example 1 is compared with Example 9, Example 1 in which the carboxylic acid component (AH-ac), which is a raw material monomer of the amorphous composite resin (AH), contains an aliphatic saturated dicarboxylic acid compound having 4 carbon atoms is obtained. It can be seen that the charging stability and document offset resistance are excellent.
When Examples 1, 3, and 4 are compared, in the styrene resin component (AH-2) of the amorphous composite resin (AH), the mass ratio of 2-ethylhexyl acrylate to styrene (2-ethylhexyl acrylate / styrene) is It can be seen that Example 1 which is 20/80 has an excellent balance of low-temperature fixability, charging stability, and document offset resistance.
When Example 1 is compared with Example 5, the carbon number of the alkyl group of the alkyl (meth) acrylate which is a raw material monomer of the styrene resin component (AH-2) of the amorphous composite resin (AH) is 8. It can be seen that Example 1 is excellent in low-temperature fixability.
A comparison of Example 1 and Example 6 shows that both reactive monomers, which are raw material monomers of the amorphous composite resin (AH), are acrylic acid. Example 1 shows that low-temperature fixability, charging stability, and document resistance It turns out that it is excellent in offset property.
When Examples 1, 7 and 8 are compared, the amount of the both reactive monomers which are the raw material monomers of the amorphous composite resin (AH) is equal to the alcohol component (AH-al) of the polycondensation resin component (AH-1). It can be seen that Example 1 which is 8 mole parts with respect to 100 mole parts in total is excellent in low-temperature fixability, charging stability and document offset resistance.
Comparing Examples 1, 10 and 11, it can be seen that Example 1 in which the acid value of the amorphous composite resin (AH) is 18 mgKOH / g is excellent in low-temperature fixability, charging stability and document offset resistance. .
Comparing Example 1 and Example 12, Example 1 in which an amorphous composite resin (AH) was phase-inverted and emulsified using an organic solvent to obtain an aqueous dispersion of resin particles was obtained at low temperature fixability. It can be seen that the charging stability and document offset resistance are excellent.
When Example 1 is compared with Comparative Example 1, the content of the isophthalic acid compound is 95 mol% in the carboxylic acid component (AH-ac) that is the raw material monomer of the amorphous composite resin (AH). However, it is understood that it is excellent in low-temperature fixing property, charging stability and document offset resistance.
A comparison between Example 1 and Comparative Examples 3 and 4 is obtained by polycondensation of a carboxylic acid component containing 100 mol% of a C14 dicarboxylic acid compound and an alcohol component as a binder resin constituting the core part. It can be seen that Example 1 using the crystalline composite resin (CH) is excellent in low-temperature fixability, charging stability and document offset resistance.
When Example 1 and Comparative Example 5 are compared, as a binder resin constituting the core portion, a dicarboxylic acid compound having 12 to 16 carbon atoms is polycondensed with a carboxylic acid component containing 100 mol% and an alcohol component. It can be seen that Example 1 using the crystalline composite resin (CH) obtained in this way is excellent in low-temperature fixability, charging stability and document offset resistance.
When Example 1 is compared with Example 13, Example 1 using an aliphatic diol having 6 carbon atoms as the alcohol component (CH-al) of the crystalline composite resin (CH) constituting the core portion is low in temperature. It can be seen that the fixing property, charging stability and document offset resistance are excellent.
A comparison of Example 1 and Example 14 shows that Example 1 using a crystalline composite resin (CH) as a binder resin constituting the core portion has low temperature fixability, charging stability, and document offset resistance. It turns out that it is excellent.
When Example 1 is compared with Example 15, the raw material monomer of the styrene resin component (CH-2) of the crystalline composite resin (CH) contains styrene and 2-ethylhexyl acrylate, and the styrene and 2-ethylhexyl. It can be seen that Example 1 having a mass ratio with acrylate (2-ethylhexyl acrylate / styrene) of 20/80 is excellent in low-temperature fixability and charging stability.
When Examples 1, 16 and 17 are compared, Example 1 using a crystalline resin (C) having an acid value of 23 mgKOH / g as the binder resin constituting the core portion has a low-temperature fixability, charge stability and It can be seen that the document offset resistance is excellent.
A comparison between Example 1 and Example 18 shows that Example 1 using a crystalline resin (C) having a hydroxyl value of 6 mgKOH / g as the binder resin constituting the core portion has low-temperature fixability and charge stability. It can also be seen that the document offset resistance is excellent.
When Example 1 and Example 19 are compared, Example 1 in which the core portion further contains an amorphous polyester resin (AP) is excellent in low-temperature fixability, charging stability, and document offset resistance. I understand.
When Example 1 and Comparative Example 6 are compared, it can be seen that Comparative Example 6 is not core-shell particles, and therefore low-temperature fixability, charging stability, and document offset resistance are reduced.
When Examples 1, 20 and 21 are compared, the content of the amorphous composite resin (AH) constituting the shell portion in the toner is 15% by mass, and Example 1 shows that low-temperature fixability, charging stability and It can be seen that the document offset resistance is excellent.
Comparing Examples 1, 22 and 23, the content of the crystalline resin (C) constituting the core portion in the toner is 15% by mass, and Example 1 is low-temperature fixability, charging stability and document offset resistance. It turns out that it is excellent in property.

Claims (7)

Core portion, a polycondensation resin component obtained a carboxylic acid component containing an alcohol component and having 12 or more carbon atoms 16 following aliphatic dicarboxylic acid compound 80 to 100 mol% by polycondensing (CH- 1) Crystalline composite resin (CH) having styrenic resin component (CH-2) and a carbon compound containing 80 to 100 mol% of an alcohol component and an aliphatic dicarboxylic acid compound having 12 to 16 carbon atoms Containing one or more crystalline resins (C) selected from crystalline polyester resins (CP) obtained by polycondensation with an acid component,
The shell part is a polycondensation of an alcohol component containing an alkylene oxide adduct of bisphenol A represented by the following general formula (I) and a carboxylic acid component containing 70 to 98 mol% of an isophthalic acid compound. An electrophotographic toner containing core-shell particles , which contains an amorphous composite resin (AH) having a polycondensation resin component (AH-1) and a styrene resin component (AH-2).

(Wherein R ¹ O and OR ¹ are oxyalkylene groups, x and y represent the average number of added moles of alkylene oxide, each being a positive number, and the sum of x and y is 1 or more and 16 It is the following.)   The carboxylic acid component which is a raw material monomer of the polycondensation resin component (AH-1) contains 2 to 30 mol% of an aliphatic dicarboxylic acid compound having 2 to 8 carbon atoms. Toner for electrophotography.   The amorphous composite resin (AH) comprises (i) an alcohol component containing 60 mol% to 100 mol% of an alkylene oxide adduct of bisphenol A represented by the general formula (I), and 70 mol of isophthalic acid. % Of the raw material monomer of the polycondensation resin component (AH-1), (b) the raw material monomer of the styrene resin component (AH-2), and (c) heavy The resin obtained by polymerizing both reactive monomers capable of reacting with both the raw material monomer of the condensation resin component (AH-1) and the raw material monomer of the styrene resin component (AH-2). 2. The toner for electrophotography according to 2. A crystalline composite resin (CH) is contained as the crystalline resin (C), and the crystalline composite resin (CH) comprises 80 mol% of (a) an alcohol component and an aliphatic dicarboxylic acid compound having 12 to 16 carbon atoms. The raw material monomer of the polycondensation resin component (CH-1), (b) the raw material monomer of the styrene resin component (CH-2), and (c) the polycondensation containing the carboxylic acid component contained in the amount of 100 mol% or less It is resin obtained by polymerizing the both reactive monomer which can react with either the raw material monomer of a styrene resin component (CH-1) and the raw material monomer of a styrene resin component (CH-2). The electrophotographic toner according to any one of the above.   The core part further contains at least one amorphous resin (AA) selected from an amorphous styrenic resin (AS) and an amorphous polyester resin (AP). The toner for electrophotography as described.   In the toner, the content of the amorphous composite resin (AH) constituting the shell part is 2% by mass or more and 50% by mass or less, and the content of the crystalline resin (C) constituting the core part is 2% by mass. The toner for electrophotography according to any one of claims 1 to 5, which is not less than 50% and not more than 50% by mass.   The alcohol component, which is a raw material monomer of the polycondensation resin component (CH-1), and the alcohol component, which is a raw material monomer of the crystalline polyester resin (CP), contain 80 mol% or more of an aliphatic diol having 2 to 12 carbon atoms. The toner for electrophotography according to any one of claims 1 to 6, which is contained in a mol% or less.