JP2018054803A - Toner for electrostatic charge image development - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a toner for electrostatic charge image development that is excellent in low-temperature fixability, exhibits good low-temperature fixability after storage at a high temperature, and is excellent in charge stability, and a method of manufacturing the same.SOLUTION: A toner for electrostatic charge image development that contains a resin composition (D) containing a reaction product obtained by a reaction that chemically bonds at least part of a crystalline resin (A) including a vinyl resin segment and a polyester segment, and an amorphous resin (B).SELECTED DRAWING: None

Description

  The present invention relates to a toner for developing an electrostatic image, a resin composition, and a method for producing the same.

  In the field of electrophotography, with development of an electrophotographic system, development of a toner for developing an electrostatic image corresponding to high image quality and high speed is demanded. In particular, as a method for obtaining a toner having excellent fixability at a low temperature, it is known to use a crystalline resin in addition to an amorphous resin conventionally used as a binder resin. Furthermore, in order to improve the basic characteristics of the toner such as storability, it has been studied to give the resin a specific structure.

For example, Patent Document 1 discloses a toner binder containing an amorphous polyester resin, a crystalline polyester resin composed of only a crystalline part, and a block resin composed of a crystalline part and an amorphous part; A toner composition is disclosed, and it is described that both low-temperature fixability and hot offset resistance are compatible, and that storage stability and charge stability are excellent.
Patent Document 2 discloses a toner containing a crosslinked polyester resin and a block copolymer resin, wherein the crosslinked polyester resin contains a diol component as a constituent component, and the diol component has 3 to 10 carbon atoms. The aliphatic diol is contained in an amount of 50 mol% or more, and further contains a trihydric or higher aliphatic alcohol or acid as a cross-linking component. The block copolymer resin is composed of a crystalline segment and an amorphous segment. An image forming toner is disclosed, characterized in that the glass transition temperature (Tg1st) at the first temperature rise by scanning calorimetry (DSC) is 20 ° C. or more and 50 ° C. or less, and has excellent low-temperature fixability and fixing width. In other words, it is described that the toner has a wide range of heat resistance and excellent heat resistance and has excellent abrasion resistance.
Further, Patent Document 3 includes resin particles containing crystalline polyester having a polyester portion obtained using a monomer having a molar average carbon number of 8 to 12, a polyester segment and an addition polymerization resin segment, An agglomerate X containing an amorphous composite resin containing 3% by mass or more and 15% by mass or less of a component derived from a bireactive monomer in an addition polymerization resin segment is obtained in an aqueous medium. Step I and Step II of fusing the aggregate X, wherein the mass ratio of the crystalline polyester to the amorphous composite resin (crystalline polyester / amorphous composite resin) is 1/99 to 40 / No. 60, a method for producing an electrostatic charge image developing toner is disclosed, and an electrostatic charge image developing toner having both low-temperature fixability and heat-resistant storage stability and excellent bending resistance of the obtained printed matter can be produced. Rukoto have been described.

Japanese Patent Laid-Open No. 2015-42737 JP2015-79240A JP 2014-235409 A

However, it has been found that even when a crystalline resin is mixed with a binder resin to improve the low-temperature fixability of the toner, this low-temperature fixability is lowered during high-temperature storage. In addition, the conventional techniques such as giving a specific structure to the resin that has been studied for improving the basic properties of the toner such as storability are not sufficient for suppressing the low temperature fixability during high temperature storage. I have also understood.
Accordingly, the present invention provides a toner for developing an electrostatic image having excellent low-temperature fixability, good low-temperature fixability after high-temperature storage, and excellent charge stability, a resin composition from which the toner is obtained, and production thereof It is an object to provide a method.

  The present inventors have considered that the factor that affects the characteristics of toner using a crystalline resin is the dispersion state of the crystalline resin in the toner particles. As a result, the toner contains a resin composition including a reaction product obtained by a reaction in which an amorphous resin and a crystalline resin having a vinyl resin segment and a polyester segment are chemically bonded at least partially. Thus, it has been found that a toner for developing an electrostatic image having excellent low-temperature fixability, good low-temperature fixability after high-temperature storage, and excellent charge stability can be obtained.

That is, the present invention relates to the following [1] to [3].
[1] A resin composition comprising a reaction product obtained by a reaction in which a crystalline resin (A) having a vinyl resin segment and a polyester segment and an amorphous resin (B) are chemically bonded at least partially. An electrostatic charge image developing toner containing the product (D).
[2] A resin composition comprising a reaction product obtained by a reaction in which a crystalline resin (A) having a vinyl resin segment and a polyester segment and an amorphous resin (B) are chemically bonded at least partially. object.
[3] A resin composition containing a reaction product obtained by a reaction in which at least a part of the crystalline resin (A) having a vinyl resin segment and a polyester segment and the amorphous resin (B) are chemically bonded. A method for producing a toner for developing an electrostatic charge image, comprising a step of obtaining a product (D).

  According to the present invention, a toner for developing an electrostatic image having excellent low-temperature fixability, good low-temperature fixability after high-temperature storage, and excellent charge stability, a resin composition from which the toner is obtained, and production thereof A method can be provided.

[Toner for electrostatic image development]
The electrostatic image developing toner of the present invention (hereinafter also simply referred to as “toner”) comprises at least one of a crystalline resin (A) having a vinyl resin segment and a polyester segment and an amorphous resin (B). An electrostatic image developing toner containing a resin composition (D) containing a reaction product obtained by a reaction of chemically bonding parts.

The reason why the toner for developing an electrostatic charge image of the present invention is excellent in low-temperature fixability, good in low-temperature fixability after high-temperature storage, and excellent in charge stability is not clear, but is considered as follows.
Since the crystalline resin in the toner does not necessarily have good compatibility with the resin component constituting the other binder resin, even if the crystalline resin is sufficiently finely dispersed in the toner base particles during the production of the toner, the toner The crystal domain size cannot be fixed during storage after production, and the crystal domain size tends to gradually increase as crystallization progresses. As a result, the interface between the crystalline resin and the other binder resin is relatively reduced, and at the time of toner fixing, the surrounding amorphous resin becomes difficult to melt together with the melting of the crystalline resin. It is thought that it declines.

In the resin composition (D), the crystalline resin (A), the amorphous resin (B), the polyester segment end of the crystalline resin (A), and the end of the amorphous resin (B) are chemically formed. It is thought that the block resin (AB) bonded to is included. The block resin (AB) forms a block structure in which the polyester segment and the amorphous resin segment of the crystalline resin (A) are connected.
When the crystalline resin (A) having a vinyl resin segment and a polyester segment is mixed with the amorphous resin (B) to form a microhydrophobic field, in the present invention, the non-crystalline resin (A) is interposed with the block resin (AB) interposed. It is mixed with the crystalline resin (B). Since the block resin (AB) enters both the crystalline resin domain and the matrix of the amorphous resin component, the crystalline resin domain is finely dispersed and then substantially bonded to the amorphous resin component. And is extremely stabilized in the toner. As a result, it is considered that the low temperature fixability is excellent, the expansion of the crystalline resin domain during high temperature storage is suppressed, and the low temperature fixability after storage is improved.
Further, since the finely dispersed crystalline resin domain has a structure encapsulated in the amorphous resin, the highly hydrophobic crystalline resin domain is exposed on the surface of the toner base particle, or is removed from the toner base particle. Since the separation is also suppressed, it is considered that the charge amount distribution of the toner is narrowed and the charging stability is improved.
Hereinafter, the components of the electrostatic image developing toner of the present invention will be described.

<Crystalline resin (A)>
The crystalline resin (A) has a vinyl resin segment and a polyester segment.
Here, in the present invention, whether the resin is crystalline or amorphous is determined by the crystallinity index. The crystallinity index is defined by the ratio between the softening point of the resin and the maximum endothermic peak temperature (softening point (° C.) / Maximum endothermic peak temperature (° C.)) in the measurement method described in the examples described later. The crystalline resin is one having a crystallinity index of 0.6 or more and 1.4 or less.
The crystalline resin (A) has a crystallinity index of 0.6 or more and 1.4 or less, and has excellent low-temperature fixability, good low-temperature fixability after high-temperature storage, and excellent charge stability. From the viewpoint, it is preferably 0.8 or more, more preferably 0.9 or more, and preferably 1.3 or less, more preferably 1.2 or less.
The crystallinity index can be appropriately adjusted according to the production conditions such as the type and ratio of the raw material monomers, the reaction temperature, the reaction time, and the cooling rate.
It is preferable that the crystalline resin (A) has a component derived from a bireactive monomer capable of reacting with both the vinyl resin segment and the polyester segment.

[Vinyl resin segment]
The vinyl resin segment is preferably composed of a vinyl monomer having a hydrocarbon group, from the viewpoint of obtaining a toner having excellent low-temperature fixability, good low-temperature fixability after high-temperature storage, and excellent charge stability. Has units. The vinyl resin segment more preferably further contains a structural unit derived from a styrene compound.

The number of carbon atoms of the hydrocarbon group of the vinyl monomer having a hydrocarbon group is preferably 4 from the viewpoint of obtaining a toner having excellent low-temperature fixability, good low-temperature fixability after high-temperature storage, and excellent charge stability. Or more, more preferably 6 or more, still more preferably 8 or more, still more preferably 10 or more, still more preferably 12 or more, still more preferably 14 or more, and preferably 22 or less, more preferably 20 or less, More preferably, it is 18 or less.
If the vinyl resin segment has a hydrophobic hydrocarbon group, it is considered that a highly hydrophobic crystalline resin is easily dispersed well in the toner.

Examples of the hydrocarbon group include aliphatic hydrocarbon groups such as an alkyl group, an alkynyl group, and an alkenyl group, preferably an alkyl group and an alkenyl group, and more preferably an alkyl group.
The hydrocarbon group may be branched or linear.
The vinyl monomer having a hydrocarbon group is preferably an alkyl ester of (meth) acrylic acid, more preferably an alkyl (meth) acrylate, from the viewpoints of availability and reactivity. In the case of an alkyl ester of (meth) acrylic acid, the hydrocarbon group is the alcohol side residue of the ester. Specifically, (meth) acrylic acid (iso) butyl, (meth) acrylic acid (iso) hexyl, (meth) acrylic acid cyclohexyl, (meth) acrylic acid (iso) octyl (hereinafter, (meth) acrylic acid 2 -(Also called ethylhexyl), (meth) acrylic acid (iso) decyl, (meth) acrylic acid (iso) dodecyl (hereinafter also referred to as (meth) acrylic acid (iso) lauryl), (meth) acrylic acid (iso) palmityl , (Meth) acrylic acid (iso) stearyl, (meth) acrylic acid (iso) behenyl, etc., preferably (meth) acrylic acid 2-ethylhexyl, (meth) acrylic acid (iso) decyl, (meth) acrylic Acid (iso) lauryl, (meth) acrylic acid (iso) stearyl, (meth) acrylic acid (iso) behenyl, more preferably (meth) (Iso) decyl crylate, (meth) acrylic acid (iso) lauryl, (meth) acrylic acid (iso) stearyl, more preferably (meth) acrylic acid (iso) lauryl, (meth) acrylic acid (iso) stearyl, Still more preferred is (meth) acrylic acid (iso) stearyl.
Here, “alkyl (meth) acrylate” refers to alkyl acrylate or alkyl methacrylate. In addition, “(iso)” with respect to the alkyl moiety means normal alkyl or isoalkyl.
The content of the structural unit derived from the vinyl monomer having a hydrocarbon group in the vinyl resin segment is excellent in low-temperature fixability, good in low-temperature fixability after high-temperature storage, and further excellent in charge stability. From the viewpoint of obtaining, it is preferably 5% by mass or more, more preferably 10% by mass or more, further preferably 15% by mass or more, and preferably 50% by mass or less, more preferably 45% by mass or less, and still more preferably 40% by mass. It is below mass%.

Examples of the styrene compound include substituted or unsubstituted styrene. Examples of the substituent include an alkyl group having 1 to 5 carbon atoms, a halogen atom, an alkoxy group having 1 to 5 carbon atoms, a sulfonic acid group, or a salt thereof. Specific examples include styrenes such as styrene, methyl styrene, α-methyl styrene, β-methyl styrene, t-butyl styrene, chlorostyrene, chloromethyl styrene, methoxy styrene, styrene sulfonic acid or a salt thereof, and the like. Contains styrene, more preferably styrene.
In the vinyl resin segment, the content of the structural unit derived from the styrene compound is preferably from the viewpoint of obtaining a toner having excellent low-temperature fixability, good low-temperature fixability after high-temperature storage, and excellent charge stability. Is 50% by mass or more, more preferably 55% by mass or more, further preferably 60% by mass or more, and preferably 95% by mass or less, more preferably 90% by mass or less, still more preferably 85% by mass or less. .
In addition to the above, the starting vinyl monomers that can be used in the vinyl resin segment include ethylenically unsaturated monoolefins such as ethylene and propylene; conjugated dienes such as butadiene; halovinyls such as vinyl chloride; vinyl acetate and vinyl propionate. (Meth) acrylic acid aminoalkyl esters such as dimethylaminoethyl (meth) acrylate; vinyl ethers such as methyl vinyl ether; vinylidene halides such as vinylidene chloride; N-vinyl such as N-vinylpyrrolidone Examples thereof include compounds.

  From the viewpoint of obtaining a toner having excellent low-temperature fixability, good low-temperature fixability after high-temperature storage, and excellent charge stability, the raw material vinyl monomer that is a component derived from the vinyl resin segment has 4 to 22 carbon atoms. A combination of a vinyl monomer having the following hydrocarbon group and a styrene compound is preferable, and a combination of an alkyl ester of (meth) acrylic acid having an alkyl group having 4 to 22 carbon atoms and styrene is more preferable.

  When a vinyl monomer having a hydrocarbon group and a styrene compound are used in combination, the mass ratio of the structural unit derived from the vinyl monomer having a hydrocarbon group and the structural unit derived from the styrene compound in the vinyl resin segment [carbonization The structural unit derived from a vinyl monomer having a hydrogen group / the structural unit derived from a styrenic compound] has an excellent low-temperature fixability, a good low-temperature fixability after high-temperature storage, and a toner having excellent charge stability. Therefore, it is preferably 5/95 or more, more preferably 10/90 or more, still more preferably 15/85 or more, and preferably 50/50 or less, more preferably 45/55 or less, still more preferably 40/60. It is as follows.

  The total content of the structural unit derived from the vinyl monomer having a hydrocarbon group in the vinyl-based resin segment and the structural unit derived from the styrene-based compound is excellent in low-temperature fixability and low-temperature fixability after high-temperature storage, Further, from the viewpoint of obtaining a toner having excellent charge stability, it is preferably 80% by mass or more, more preferably 90% by mass or more, still more preferably 95% by mass or more, and further preferably 100% by mass or less. Is 100% by mass.

[Polyester segment]
The polyester segment is a segment made of polyester obtained by polycondensation of a polyhydric alcohol component (a-al) and a polyvalent carboxylic acid component (a-ac). The polyester segment is preferably a crystalline polyester.

(Polyhydric alcohol component (a-al))
The polyhydric alcohol component (a-al) is preferably α, ω-aliphatic from the viewpoint of obtaining a toner having excellent low-temperature fixability, good low-temperature fixability after high-temperature storage, and excellent charge stability. It contains 80 mol% or more of diol.
The content of α, ω-aliphatic diol is preferably 80 mol% or more, more preferably 85 mol% or more, still more preferably 90 mol% or more, and still more preferably 95 mol% or more in the polyhydric alcohol component. Yes, and it is 100 mol% or less, More preferably, it is 100 mol%.

The number of carbon atoms of the α, ω-aliphatic diol is preferably 2 or more, more preferably from the viewpoint of obtaining a toner having excellent low-temperature fixability, good low-temperature fixability after high-temperature storage, and excellent charge stability. Is 4 or more, more preferably 6 or more, still more preferably 8 or more, and is preferably 16 or less, more preferably 14 or less, still more preferably 12 or less.
Examples of the α, ω-aliphatic diol include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,13-tridecanediol, 1,14-tetradecanediol, etc. Is mentioned. Among these, ethylene glycol, 1,6-hexanediol, and 1,9-nonane are preferred from the viewpoint of obtaining a toner having excellent low-temperature fixability, good low-temperature fixability after high-temperature storage, and excellent charge stability. Diol, 1,10-decanediol and 1,12-dodecanediol are preferred, 1,6-hexanediol, 1,10-decanediol and 1,12-dodecanediol are more preferred, and 1,10-decanediol is further preferred. preferable.

The polyhydric alcohol component (a-al) may contain a polyhydric alcohol component other than the α, ω-aliphatic diol. For example, aliphatic diols other than α, ω-aliphatic diols such as 1,2-propylene glycol and neopentyl glycol; aromatic diols such as alkylene oxide adducts of bisphenol A; glycerin, pentaerythritol, trimethylolpropane, etc. Examples include trivalent or higher alcohols.
These polyhydric alcohol components can be used alone or in combination of two or more.

(Polyvalent carboxylic acid component (a-ac))
The polyvalent carboxylic acid component (a-ac) has an excellent low-temperature fixability, low-temperature fixability after high-temperature storage, and 80 mol of an aliphatic dicarboxylic acid from the viewpoint of obtaining a toner excellent in charge stability. % Or more is preferable. The content of the aliphatic dicarboxylic acid is preferably 80 mol% or more, more preferably 85 mol% or more, still more preferably 90 mol% or more, and still more preferably 95 mol in the polyvalent carboxylic acid component (a-ac). % Or more and 100 mol% or less, more preferably 100 mol%.

The number of carbon atoms of the aliphatic dicarboxylic acid is preferably 2 or more, more preferably 4 or more, from the viewpoint of obtaining a toner having excellent low-temperature fixability, good low-temperature fixability after high-temperature storage, and excellent charge stability. Further, it is preferably 8 or more, more preferably 10 or more, and preferably 14 or less, more preferably 12 or less.
Examples of the aliphatic dicarboxylic acid include fumaric acid, sebacic acid, dodecanedioic acid, and tetradecanedioic acid. Among these, sebacic acid, dodecanedioic acid, and tetradecanedioic acid are preferable, and sebacic acid is more preferable.
The polyvalent carboxylic acid component includes not only a free acid but also an anhydride that decomposes to generate an acid during the reaction, and an alkyl ester having 1 to 3 carbon atoms of each carboxylic acid.
These polyvalent carboxylic acid components can be used alone or in combination of two or more.

  The equivalent ratio of the polycarboxylic acid component to the polyhydric alcohol component (COOH group / OH group) is preferably 0.7 or more, more preferably 0.8 or more, from the viewpoint of obtaining a crystalline resin having desired physical properties. Preferably it is 0.9 or more, and preferably 1.3 or less, more preferably 1.2 or less, and still more preferably 1.1 or less.

(Amotropic monomer)
The crystalline resin (A) preferably has a constituent component derived from both reactive monomers. When an amphoteric monomer is used as a raw material monomer for the crystalline resin (A), the amphoteric monomer reacts with both the polyester segment and the vinyl resin segment to produce the crystalline resin (A). Becomes easier. Therefore, it is preferable to use a bireactive monomer as a raw material monomer for the crystalline resin (A). The structural unit derived from the both reactive monomers is preferably a bonding point between the vinyl resin segment and the polyester segment.
Examples of the both reactive monomers include vinyl monomers having 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 in the molecule. Among these, from the viewpoint of reactivity, a vinyl monomer having a hydroxyl group or a carboxy group is preferable, and a vinyl monomer having a carboxy group is more preferable. Examples of the vinyl monomer having a carboxy group include acrylic acid, methacrylic acid, fumaric acid, maleic acid and the like. Among these, acrylic acid and methacrylic acid are preferable, and acrylic acid is more preferable from the viewpoint of the reactivity of both the polycondensation reaction and the addition polymerization reaction.

  From the viewpoint of improving the dispersibility of the crystalline resin (A) in the amorphous resin (B) and the reaction control of the addition polymerization reaction and the polycondensation reaction, the constituent components derived from both reactive monomers are polyester segments. Preferably, it is 0.5 mol part or more, more preferably 1 mol part or more, still more preferably 3 mol part or more, and preferably 30 mol part with respect to 100 mol parts of the total amount of the polyhydric alcohol component that is a raw material of Hereinafter, it is more preferably 20 parts by mole or less, and still more preferably 15 parts by mole or less. In addition, in the case of using a bireactive monomer and calculating the content of each segment in the crystalline resin (A), the structural unit derived from the bireactive monomer is included in the structural unit of the polyester segment. Calculate as

The content of the polyester segment in the crystalline resin (A) is preferably 60% from the viewpoint of obtaining a toner having excellent low-temperature fixability, good low-temperature fixability after high-temperature storage, and excellent charge stability. % Or more, more preferably 65% by mass or more, still more preferably 70% by mass or more, and preferably 97% by mass or less, more preferably 95% by mass or less, and further preferably 92% by mass or less. From the same viewpoint, the content of the polyester segment in the crystalline resin (A) is preferably 60% by mass or more, more preferably 65% by mass or more, based on the total content of the polyester segment and the vinyl resin segment. More preferably, it is 70 mass% or more, and preferably 97 mass% or less, More preferably, 95 mass% or less, More preferably, it is 92 mass% or less.
In addition, the content of the vinyl resin segment in the crystalline resin (A) is excellent in low-temperature fixability, good in low-temperature fixability after high-temperature storage, and from the viewpoint of obtaining a toner that is also excellent in charging stability. Preferably it is 3 mass% or more, More preferably, it is 5 mass% or more, More preferably, it is 8 mass% or more, Preferably it is 40 mass% or less, More preferably, it is 35 mass% or less, More preferably, it is 30 mass% or less. is there. From the same viewpoint, the content of the vinyl resin segment in the crystalline resin (A) is preferably 3% by mass or more, more preferably 5% by mass, based on the total content of the polyester segment and the vinyl resin segment. More preferably, it is 8% by mass or more, and preferably 40% by mass or less, more preferably 35% by mass or less, and still more preferably 30% by mass or less.
In addition, the total content of the polyester segment and the vinyl resin segment in the crystalline resin (A) is excellent in low-temperature fixability, good in low-temperature fixability after high-temperature storage, and excellent in charge stability. Is preferably 80% by mass or more, more preferably 90% by mass or more, still more preferably 93% by mass or more, still more preferably 95% by mass or more, and preferably 100% by mass or less. It is 99 mass% or less, More preferably, it is 97 mass% or less, More preferably, it is 96 mass% or less.

[Physical properties of crystalline resin (A)]
The softening point of the crystalline resin (A) is preferably 60 ° C. or more, more preferably from the viewpoint of obtaining a toner having excellent low-temperature fixability, good low-temperature fixability after high-temperature storage, and excellent charge stability. Is 70 ° C. or higher, more preferably 80 ° C. or higher, and preferably 150 ° C. or lower, more preferably 120 ° C. or lower, still more preferably 100 ° C. or lower.

  The melting point of the crystalline resin (A) is preferably 50 ° C. or more, more preferably from the viewpoint of obtaining a toner having excellent low-temperature fixability, good low-temperature fixability after high-temperature storage, and excellent charge stability. It is 60 ° C. or higher, more preferably 70 ° C. or higher, and preferably 100 ° C. or lower, more preferably 90 ° C. or lower, still more preferably 80 ° C. or lower.

  The acid value of the crystalline resin (A) is from the viewpoint of producing a block resin (AB), having excellent low-temperature fixability, good low-temperature fixability after high-temperature storage, and excellent charge stability. , Preferably 5 mgKOH / g or more, more preferably 10 mgKOH / g or more, and preferably 35 mgKOH / g or less, more preferably 30 mgKOH / g or less, still more preferably 20 mgKOH / g or less.

  From the viewpoint of obtaining a toner that produces a block resin (AB), has excellent low-temperature fixability, good low-temperature fixability after high-temperature storage, and excellent charge stability. , Preferably 3 mgKOH / g or more, more preferably 5 mgKOH / g or more, and preferably 35 mgKOH / g or less, more preferably 25 mgKOH / g or less, still more preferably 20 mgKOH / g or less.

  The ratio of the acid value to the hydroxyl value (acid value / hydroxyl value) of the crystalline resin (A) produces a block resin (AB), has excellent low-temperature fixability, and good low-temperature fixability after high-temperature storage. Further, from the viewpoint of obtaining a toner having excellent charge stability, it is preferably 1.00 or more, more preferably more than 1.00, still more preferably 1.05 or more, and preferably 5.00 or less, more preferably Is 2.00 or less, more preferably 1.5 or less.

  The softening point, melting point, acid value, and hydroxyl value of the crystalline resin (A) 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. These values are determined by the method described in the examples below. In addition, when using 2 or more types of crystalline resin in combination, it is preferable that the value of the softening point, melting | fusing point, acid value, and hydroxyl value which were obtained as those mixtures is in the said range, respectively.

[Production of crystalline resin (A)]
Although the manufacturing method of crystalline resin (A) is not specifically limited, For example, the method of the following (i)-(iii) is mentioned.
(I) A method of performing an addition polymerization reaction with a raw material monomer and an amphoteric monomer of a vinyl resin segment after a polycondensation reaction with a polyhydric alcohol component and a polyvalent carboxylic acid component From the viewpoint of reactivity, the vinyl resin segment It is preferable that both reactive monomers are supplied to the reaction system together with the raw material monomers. From the viewpoint of reactivity, a catalyst such as an esterification catalyst or an esterification cocatalyst may be used, and a radical polymerization initiator and a radical polymerization inhibitor may be further used.
From the viewpoint of further proceeding with the polycondensation reaction and, if necessary, the reaction with both reactive monomers, the polyvalent carboxylic acid component is partially subjected to the polycondensation reaction and then subjected to the addition polymerization reaction and then the reaction temperature is increased again. It is preferable to add the remainder to the reaction system.

Further, it can be produced by the following method (ii) or (iii).
(Ii) A method of performing a polycondensation reaction with a raw material monomer of a polyester segment after an addition polymerization reaction with a raw material monomer of a vinyl-based resin segment and an amphoteric monomer. Method of performing reaction and addition polymerization reaction of vinyl resin segment raw material monomer and both reactive monomers in parallel The polycondensation reaction and the addition polymerization reaction of the above methods (i) to (iii) are both in the same container. It is preferable to carry out within.
The crystalline resin (A) is preferably produced by the above method (i) from the viewpoint that the reaction temperature of the polycondensation reaction is high.

The temperature of the polycondensation reaction is preferably 120 ° C. or higher, more preferably 140 ° C. or higher, still more preferably 150 ° C. or higher, and preferably 230 ° C. or lower, from the viewpoint of productivity of the crystalline resin (A). More preferably, it is 220 degrees C or less, More preferably, it is 200 degrees C or less.
Examples of the esterification catalyst suitably used for the polycondensation reaction include tin compounds such as dibutyltin oxide and di (2-ethylhexanoic acid) tin (II), and titanium compounds such as titanium diisopropylate bistriethanolamate. Can be mentioned. Among these, a tin compound is preferable, and di (2-ethylhexanoic acid) tin (II) is more preferable.
The amount of esterification catalyst used is preferably 0.01 parts by mass or more, more preferably 0.1 parts by mass with respect to 100 parts by mass of the total amount of the polyhydric alcohol component and the polyvalent carboxylic acid component from the viewpoint of reactivity. Part or more, and preferably 5 parts by mass or less, more preferably 2 parts by mass or less.
Examples of esterification promoters include pyrogallol compounds such as pyrogallol, gallic acid (same as 3,4,5-trihydroxybenzoic acid), gallic acid ester; 2,3,4-trihydroxybenzophenone, 2,2 ′, Examples include benzophenone derivatives such as 3,4-tetrahydroxybenzophenone; catechin derivatives such as epigallocatechin and epigallocatechin gallate, and gallic acid is preferred from the viewpoint of reactivity.
As a radical polymerization inhibitor in the polycondensation reaction, 4-tert-butylcatechol or the like can be used.

Although the temperature of the addition polymerization reaction varies depending on the type of radical polymerization initiator used, etc., from the viewpoint of productivity of the crystalline resin (A), it is preferably 110 ° C. or higher, more preferably 130 ° C. or higher, and Preferably it is 220 degrees C or less, More preferably, it is 200 degrees C or less.
Moreover, it is preferable to accelerate the reaction by reducing the pressure of the reaction system in the latter half of the polymerization.

  Known polymerization initiators for addition polymerization reaction include peroxides such as dibutyl peroxide, persulfates such as sodium persulfate, and azo compounds such as 2,2′-azobis (2,4-dimethylvaleronitrile). These radical polymerization initiators can be used.

  The amount of the radical polymerization initiator used is preferably 1 part by mass or more, more preferably 3 parts by mass or more, and preferably 20 parts by mass or less, based on 100 parts by mass of the raw material monomer of the vinyl resin segment. Preferably it is 15 mass parts or less.

<Amorphous resin (B)>
The amorphous resin (B) is preferably a resin having a functional group at its terminal, and has excellent low-temperature fixability, good low-temperature fixability after high-temperature storage, and further excellent charge stability. From the viewpoint, amorphous polyester is more preferable.
The amorphous resin (B) of the present invention has a crystallinity index greater than 1.4 or less than 0.6.
Amorphous polyester is obtained by polycondensation of a polyhydric alcohol component (b-al) and a polyvalent carboxylic acid component (b-ac).

(Polyhydric alcohol component (b-al))
The polyhydric alcohol component (b-al) is an alkylene oxide adduct of bisphenol A that has excellent low-temperature fixability, good low-temperature fixability after high-temperature storage, and excellent charge stability. What contains 80 mol% or more is preferable. From the same viewpoint, the content of the alkylene oxide adduct of bisphenol A in the polyhydric alcohol component (b-al) is preferably 80 mol% or more, more preferably 90 mol% or more, and still more preferably 95 mol% or more. More preferably, it is 98 mol% or more, and 100 mol% or less, More preferably, it is 100 mol%.

  The alkylene oxide adduct of bisphenol A is preferably an ethylene oxide adduct of bisphenol A (polyoxyethylene-2,2-bis (4-hydroxyphenyl) propane) and a propylene oxide adduct of bisphenol A (polyoxypropylene- 2,2-bis (4-hydroxyphenyl) propane), more preferably a propylene oxide adduct of bisphenol A.

  The average addition mole number of alkylene oxide of the alkylene oxide adduct of bisphenol A is preferably 1 or more, more preferably 1.2 or more, still more preferably 1.5 or more, and preferably 16 or less, more preferably It is 12 or less, more preferably 8 or less, and still more preferably 4 or less.

The polyhydric alcohol component (b-al) may contain other polyhydric alcohols other than the bisphenol A alkylene oxide adduct. Other polyhydric alcohol components that the polyhydric alcohol component (b-al) may contain include aliphatic diols, aromatic diols, alicyclic diols, trivalent or higher polyhydric alcohols, or those having 2 or more carbon atoms. The following alkylene oxide (average addition mole number 1-16) addition products etc. are mentioned. Specific examples thereof include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, and 2,3-butanediol. Neopentyl glycol, 1,4-butenediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,12 Aliphatic diols such as dodecanediol; aromatic diols such as bisphenol A (2,2-bis (4-hydroxyphenyl) propane); hydrogenated bisphenol A (2,2-bis (4-hydroxycyclohexyl) propane), etc. Of these alicyclic diols, or alkylene oxides having 2 or more and 4 or less carbon atoms (average added mole number 2) Top 12 or less) Adducts: Trivalent or higher polyhydric alcohols such as glycerin, pentaerythritol, trimethylolpropane, sorbitol, or their alkylene oxides having 2 to 4 carbon atoms (average added mole number of 1 to 16) Thing etc. are mentioned.
These polyhydric alcohol components can be used alone or in combination of two or more.

(Polyvalent carboxylic acid component (b-ac))
Examples of the polyvalent carboxylic acid component (b-ac) include dicarboxylic acids, trivalent or higher polyvalent carboxylic acids, anhydrides thereof, and alkyl esters having 1 to 3 carbon atoms. Among these, dicarboxylic acids are preferable, and it is more preferable to use dicarboxylic acids and trivalent or higher polyvalent carboxylic acids in combination.

Examples of the dicarboxylic acid include aromatic dicarboxylic acid, aliphatic dicarboxylic acid, and alicyclic dicarboxylic acid. Among these, at least one selected from aromatic dicarboxylic acids and aliphatic dicarboxylic acids is preferable.
The polyvalent carboxylic acid component includes not only a free acid but also an anhydride that decomposes to generate an acid during the reaction, and an alkyl ester having 1 to 3 carbon atoms of each carboxylic acid.
Examples of the aromatic dicarboxylic acid include phthalic acid, isophthalic acid, terephthalic acid and the like. Among these, isophthalic acid and terephthalic acid are preferable, and terephthalic acid is more preferable from the viewpoint of obtaining a toner having excellent low-temperature fixability, good low-temperature fixability after high-temperature storage, and excellent charge stability.
The aliphatic dicarboxylic acid has a carbon number of preferably 2 or more, more preferably 3 or more, and preferably 30 or less, more preferably 20 or less, from the viewpoints of availability and reactivity.

Examples of the aliphatic dicarboxylic acid having 2 to 30 carbon atoms include oxalic acid, malonic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, succinic acid, adipic acid, sebacic acid, dodecanedioic acid, Examples include azelaic acid, succinic acid substituted with an alkyl group having 1 to 20 carbon atoms, or an alkenyl group having 2 to 20 carbon atoms. Among these, fumaric acid and adipic acid are preferable from the viewpoint of obtaining a toner having excellent low-temperature fixability, excellent low-temperature fixability after high-temperature storage, and excellent charge stability. Examples of the succinic acid substituted with an alkyl group having 1 to 20 carbon atoms or an alkenyl group having 2 to 20 carbon atoms include dodecyl succinic acid, dodecenyl succinic acid, octenyl succinic acid, and the like.
Among these, terephthalic acid, adipic acid, and fumaric acid are preferable. From the viewpoint of obtaining a toner that has excellent low-temperature fixability, good low-temperature fixability after high-temperature storage, and excellent charge stability. More preferably it is used.
The content of the dicarboxylic acid in the polyvalent carboxylic acid component (b-ac) is preferably 80 mol% or more, more preferably 85 mol% or more, still more preferably 87 mol% or more, and preferably 97 mol%. % Or less, more preferably 95 mol% or less.

The trivalent or higher polyvalent carboxylic acid is preferably a trivalent carboxylic acid from the viewpoint of reaction control, more preferably trimellitic acid or an anhydride thereof, and further preferably trimellitic anhydride.
In addition, in the case of containing a trivalent or higher polyvalent carboxylic acid, the content thereof is excellent in low-temperature fixability, good low-temperature fixability after high-temperature storage, and further from the viewpoint of obtaining a toner excellent in charge stability, In the polyvalent carboxylic acid component, it is preferably at least 3 mol%, more preferably at least 5 mol%, and preferably at most 20 mol%, more preferably at most 15 mol%, still more preferably at most 13 mol%. .
These polyvalent carboxylic acid components can be used alone or in combination of two or more.

  The equivalent ratio of the polycarboxylic acid component to the polyhydric alcohol component (COOH group / OH group) is excellent in low-temperature fixability, good in low-temperature fixability after high-temperature storage, and excellent in charge stability. From the viewpoint of obtaining an amorphous resin having physical properties, it is preferably 0.7 or more, more preferably 0.8 or more, and preferably 1.3 or less, more preferably 1.2 or less.

[Physical properties of amorphous resin (B)]
The softening point of the amorphous resin (B) is preferably 70 ° C. or higher from the viewpoint of obtaining a toner having excellent low-temperature fixability, good low-temperature fixability after high-temperature storage, and excellent charge stability. Preferably it is 90 degreeC or more, More preferably, it is 100 degreeC or more, Preferably it is 140 degrees C or less, More preferably, it is 130 degrees C or less.

  The glass transition temperature of the amorphous resin (B) is preferably 30 ° C. or higher from the viewpoint of obtaining a toner having excellent low-temperature fixability, good low-temperature fixability after high-temperature storage, and excellent charge stability. More preferably, it is 40 degreeC or more, More preferably, it is 50 degreeC or more, Preferably it is 70 degrees C or less, More preferably, it is 65 degrees C or less, More preferably, it is 60 degrees C or less.

  The acid value of the amorphous resin (B) is that the block resin (AB) is produced, the toner has excellent low-temperature fixability, good low-temperature fixability after high-temperature storage, and excellent charge stability. Therefore, it is preferably 5 mgKOH / g or more, more preferably 10 mgKOH / g or more, further preferably 15 mgKOH / g or more, and preferably 40 mgKOH / g or less, more preferably 35 mgKOH / g or less, still more preferably 30 mgKOH / g. It is as follows.

  The hydroxyl value of the amorphous resin (B) produces a block resin (AB), is excellent in low-temperature fixability, has good low-temperature fixability after high-temperature storage, and has a further excellent charge stability. Therefore, it is preferably 4 mgKOH / g or more, more preferably 7 mgKOH / g or more, still more preferably 10 mgKOH / g or more, and preferably 40 mgKOH / g or less, more preferably 25 mgKOH / g or less, still more preferably 20 mgKOH / g. It is as follows.

The softening point, glass transition temperature, acid value, and hydroxyl value of the amorphous resin (B) 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. Moreover, those values are calculated | required by the method as described in an Example.
In addition, when using 2 or more types of amorphous resin (B) in combination, it is preferable that the value of the softening point, glass transition temperature, and acid value which were obtained as those mixtures is in the above-mentioned range, respectively.

[Production of Amorphous Resin (B)]
When the amorphous resin (B) is an amorphous polyester, for example, a polyhydric alcohol component (b-al) and a polyvalent carboxylic acid component (b-ac) are required in an inert gas atmosphere. Depending on the case, it can be produced by polycondensation using an esterification catalyst, an esterification cocatalyst, and a radical polymerization inhibitor if necessary.
It is preferable to use a part of the polycarboxylic acid component together with the polyhydric alcohol component for a polycondensation reaction for a predetermined time and then add the remainder to the reaction system because the polycondensation reaction can be further advanced.

Examples of the esterification catalyst suitably used for the polycondensation reaction include tin compounds such as dibutyltin oxide and di (2-ethylhexanoic acid) tin (II), and titanium compounds such as titanium diisopropylate bistriethanolamate. Can be mentioned. Among these, a tin compound is preferable, and di (2-ethylhexanoic acid) tin (II) is more preferable.
The amount of esterification catalyst used is preferably 0.01 parts by mass or more, more preferably 0.1 parts by mass with respect to 100 parts by mass of the total amount of the polyhydric alcohol component and the polyvalent carboxylic acid component from the viewpoint of reactivity. Part or more, and preferably 5 parts by mass or less, more preferably 2 parts by mass or less.
Examples of the esterification promoter include pyrogallol, gallic acid (same as 3,4,5-trihydroxybenzoic acid), pyrogallol compounds such as gallic acid ester; 2,3,4-trihydroxybenzophenone, 2,2 ′, Examples include benzophenone derivatives such as 3,4-tetrahydroxybenzophenone; catechin derivatives such as epigallocatechin and epigallocatechin gallate, and gallic acid is preferred from the viewpoint of reactivity.
The use amount of the esterification cocatalyst is preferably 0.001 part by mass or more, more preferably 0.01 parts per 100 parts by mass of the total amount of the polyhydric alcohol component and the polyvalent carboxylic acid component from the viewpoint of reactivity. It is at least 0.5 parts by mass, and more preferably at most 0.2 parts by mass.

As a radical polymerization inhibitor in the polycondensation reaction, 4-tert-butylcatechol or the like can be used.
The amount of the radical polymerization inhibitor used is preferably 0.001 part by mass or more, more preferably 0.005 part by mass or more, with respect to 100 parts by mass of the total amount of the polyhydric alcohol component and the polyvalent carboxylic acid component. And Preferably it is 0.5 mass part or less, More preferably, it is 0.2 mass part or less.
The temperature of the polycondensation reaction is preferably 180 ° C. or higher, more preferably 200 ° C. or higher, and preferably 270 ° C. or lower, more preferably 250 ° C. or lower.
Moreover, it is preferable to accelerate the reaction by reducing the pressure of the reaction system in the latter half of the polymerization.

<Resin composition (D)>
The resin composition (D) is a reaction product obtained by a reaction in which a crystalline resin (A) having a vinyl resin segment and a polyester segment and an amorphous resin (B) are chemically bonded at least partially. Including things. Here, “chemically bonded” means that the crystalline resin (A) and the amorphous resin (B) are linked by a covalent bond. Examples of the bond include a bond by an ester group, an ether group, an amide group, a urethane group, or a bond by an organic group containing these groups. The chemical bonding of at least a part means that at least a part of a plurality of crystalline resins (A) and a plurality of amorphous resins (B) are bonded. In other words, the resin composition (D) contains at least a component (block resin (AB)) in which the crystalline resin (A) and the amorphous resin (B) are chemically bonded. May also include unreacted crystalline resin (A) and amorphous resin (B).
As described above, the resin composition (D) containing a reaction product obtained by a reaction in which at least part of the crystalline resin (A) and the amorphous resin (B) is chemically bonded is used as described above. It is thought that block resin (AB), crystalline resin (A), and amorphous resin (B) are included, but the composition actually obtained contains various resin structures, and the structure and characteristics are simply The reality is that it cannot be specified and specified. Furthermore, if the structure is to be specified by a known analysis technique, extremely complicated analysis such as isolation and purification and establishment of a structure defining technique for the polymer is required. That is, the resin composition (D) has a circumstance that is almost impractical to specify directly by its structure or characteristics.

<Step (1)>
A resin composition (D) is obtained by the following process (1), for example.
Step (1): including a reaction product obtained by a reaction in which a crystalline resin (A) having a vinyl resin segment and a polyester segment and an amorphous resin (B) are chemically bonded at least partially. Step of obtaining a resin composition (D)

From the viewpoint of obtaining a toner having excellent low-temperature fixability, good low-temperature fixability after high-temperature storage, and excellent charge stability, step (1) is preferably crystalline having a vinyl resin segment and a polyester segment. Reaction obtained by a reaction in which the resin (A) and the amorphous resin (B) are chemically bonded at least partially with the polyester segment of the crystalline resin (A) and the amorphous resin (B). A step of obtaining a resin composition (D) containing a product, more preferably a crystalline resin (A) having a vinyl resin segment and a polyester segment, and an amorphous resin (B). (A) Resin composition comprising a reaction product obtained by a reaction of chemically bonding at least a part of the polyester segment end and the end of the amorphous resin (B) ( ) To give compound.
The mass ratio of the crystalline resin (A) and the amorphous resin (B) used in the step (1) is excellent in low-temperature fixability, good in low-temperature fixability after high-temperature storage, and more stable in charge. From the viewpoint of obtaining a toner having excellent properties, it is preferably 20/80 or more, more preferably 25/75 or more, still more preferably 35/65 or more, and preferably 80/20 or less, more preferably 70/30. Hereinafter, it is more preferably 60/40 or less.
In the step (1), it is possible to condense and chemically bond the polyester segment terminal and the amorphous resin (B) terminal of the crystalline resin (A), but the polyfunctional compound (S) is used. Is preferable from the viewpoint of easy reaction.

<Polyfunctional compound (S)>
In the reaction for chemically bonding at least a part of the crystalline resin (A) and the amorphous resin (B) of the present invention, it is preferable to use a polyfunctional compound (S).
The polyfunctional compound (S) is a compound having two or more functional groups. The number of functional groups in the polyfunctional compound (S) is preferably 5 or less, more preferably 4 or less, still more preferably 3 or less, still more preferably 2 or less, and preferably 2.
The functional group means a functional group that reacts with at least one selected from the group consisting of a hydroxyl group and a carboxy group to form a covalent bond.
As a functional group, an isocyanate group, an oxazoline group, a glycidyl group, an amino group, an aziridine group etc. are mentioned, for example, An isocyanate group is preferable.
As the polyfunctional compound (S), a polyisocyanate compound is used from the viewpoint of obtaining a toner having excellent ease of reaction, low temperature fixability, good low temperature fixability after high temperature storage, and excellent charge stability. preferable.

As the polyisocyanate compound, a diisocyanate compound is preferable from the viewpoint of reactivity and ease of handling, for example, aliphatic diisocyanate, aromatic diisocyanate, and prepolymer type, isocyanurate type, urea type, carbodiimide type modification of these diisocyanates. The body is mentioned.
Examples of the aliphatic diisocyanate include alicyclic diisocyanate and chain aliphatic diisocyanate.
Examples of the alicyclic diisocyanate include isophorone diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, 4-methyl-1,3-cyclohexylene diisocyanate, 1,2-bis (isocyanatomethyl) cyclohexane, and the like.
Examples of the chain aliphatic diisocyanate include hexamethylene diisocyanate.
Examples of the aromatic diisocyanate include 4,4′-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, 1,3-xylylene diisocyanate, Examples include 1,4-xylylene diisocyanate, 1,5-naphthalene diisocyanate, and 3,3′-dimethyl-4,4′-biphenylene diisocyanate.
Among these diisocyanate compounds, aliphatic diisocyanates are preferable, alicyclic diisocyanates are more preferable, at least one selected from isophorone diisocyanate and 4,4′-dicyclohexylmethane diisocyanate is further preferable, and isophorone diisocyanate is still more preferable.

Step (1) is preferably performed in an organic solvent. The organic solvent is preferably 15 when expressed by a solubility parameter (SP value: POLYMER HANDBOOK THIRD EDITION 1989 by John Wiley & Sons, Inc) from the viewpoint of dissolving the resin and facilitating phase inversion into an aqueous medium. 1.0 MPa ^1/2 or more, more preferably 16.0 MPa ^1/2 or more, still more preferably 17.0 MPa ^1/2 or more, and preferably 26.0 MPa ^1/2 or less, more preferably 24.0 MPa ^{1 / 2} or less, more preferably 22.0 MPa ^1/2 or less.
Specific examples include ketone solvents such as acetone (20.3), methyl ethyl ketone (19.0), methyl isobutyl ketone (17.2), diethyl ketone (18.0); dibutyl ether (16.5), tetrahydrofuran Ether solvents such as (18.6) and dioxane (20.5); and acetate solvents such as ethyl acetate (18.6) and isopropyl acetate (17.4). In addition, the numerical value in the parenthesis after each solvent is each SP value (unit: MPa < ^1/2 >). Among these, from the viewpoint of easy removal from the mixed solution after addition of the aqueous medium, preferably one or more selected from ketone solvents and acetate solvents, more preferably from methyl ethyl ketone, ethyl acetate and isopropyl acetate. One or more selected, more preferably methyl ethyl ketone is used.

The resin composition (D) is preferably obtained by the following steps (1-1) and (1-2).
Step (1-1): By introducing a functional group with a polyfunctional compound (S) into one resin (i) selected from the group X consisting of a crystalline resin (A) and an amorphous resin (B). Step of obtaining a reaction intermediate Step (1-2): Step of reacting the reactive intermediate with a resin (ii) selected from the group X and different from the resin (i)

The resin (i) is one selected from the group X consisting of a crystalline resin (A) and an amorphous resin (B). That is, either a crystalline resin (A) or an amorphous resin (B) is used, and a functional group is introduced into the resin.
From the viewpoint of easy reaction and from the viewpoint of obtaining a toner having excellent low-temperature fixability, good low-temperature fixability after high-temperature storage, and excellent charge stability, a crystalline resin (A) is used as the resin (i). ), It is preferable to select the amorphous resin (B) as the resin (ii).

<< Step (1-1) >>
Step (1-1) introduces a functional group with a polyfunctional compound (S) into one resin (i) selected from the group X consisting of a crystalline resin (A) and an amorphous resin (B). To obtain a reaction intermediate.
From the viewpoint of ease of reaction, and from the viewpoint of obtaining a toner having excellent low-temperature fixability, good low-temperature fixability after high-temperature storage, and excellent charge stability, the polyester segment terminal of the crystalline resin (A) It is preferable to select the crystalline resin (A) as the resin (i) and the amorphous resin (B) as the resin (ii).
As the polyfunctional compound (S), a diisocyanate compound is preferable from the viewpoint of obtaining a toner which is excellent in the ease of reaction and low-temperature fixability, has good low-temperature fixability after high-temperature storage, and has excellent charge stability. .
The method for producing the reaction intermediate is not particularly limited, and examples thereof include a method of reacting the resin (i) with a diisocyanate compound in the presence of a urethanization catalyst in an organic solvent. Next, a method for reacting the resin (i) and the diisocyanate compound will be described.

  The molar ratio (OH / NCO) of the hydroxyl group of the resin (i) and the isocyanate group of the diisocyanate compound is preferably 1.0 or less, more preferably less than 1.0, from the viewpoint of leaving the isocyanate group in the resin (i). And preferably 0.1 or more, more preferably 0.25 or more, and still more preferably 0.3 or more.

The use equivalent ratio of the diisocyanate compound in the reaction with the hydroxyl group of the resin (i) is preferably 0.70 or more, more preferably 0.80 or more, still more preferably 0.90 or more, and further preferably 1.00. It is above, and is preferably 1.20 or less, more preferably 1.10 or less, and still more preferably 1.05 or less.
Equivalent ratio of diisocyanate compound = {Used mass of diisocyanate compound (g) / Molecular weight of diisocyanate compound} / [{Hydroxyl value of resin (i) (mgKOH / g) × Blend amount of resin (i) (g)} / (56x1000)]

As the urethanization catalyst, a catalyst such as a tin compound such as dibutyltin oxide or di (2-ethylhexanoic acid) tin (II), or a titanium compound such as titanium diisopropylate bistriethanolamate can be used.
Although there is no restriction | limiting in the usage-amount of a urethanization catalyst, Preferably it is 0.01 mass part or more with respect to 100 mass parts of total amounts of resin (i) and a diisocyanate compound, More preferably, it is 0.1 mass part or more, And preferably it is 1.5 mass parts or less, More preferably, it is 1.0 mass part or less.

  The reaction between the resin (i) and the diisocyanate compound is preferably performed in the organic solvent described above. As the organic solvent, various known organic solvents having no functional group capable of reacting with an isocyanate group, such as acetone, methyl ethyl ketone, and tetrahydrofuran, can be used.

  The amount of the organic solvent used in the case of using the organic solvent is preferably 30 parts by mass or more, more preferably 50 parts by mass with respect to 100 parts by mass of the total amount of the resin (i) and the diisocyanate compound from the viewpoint of reactivity. More preferably, it is 70 parts by mass or more, and preferably 500 parts by mass or less, more preferably 300 parts by mass or less, and still more preferably 200 parts by mass or less.

The reaction temperature is preferably 20 ° C. or higher and 100 ° C. or lower.
The reaction time is preferably 0.2 hours or more, more preferably 0.5 hours or more, still more preferably 1 hour or more, and preferably 6 hours or less, more preferably 5 hours or less, still more preferably 4 hours. It is as follows.

≪Process (1-2) ≫
Step (1-2) is a step of reacting the reaction intermediate obtained in the step (1-1) with a resin (ii) selected from the group X and different from the resin (i). .
The reaction can be carried out, for example, by adding the resin (ii) to the reaction system following the step (1-1) and heating and mixing the reaction intermediate and the resin (ii) in an organic solvent. When the reaction intermediate is obtained by reacting the resin (i) with the diisocyanate compound in the step (1-1), it can be produced by reacting with a urethanization catalyst as necessary. . As the urethanization catalyst, the same catalyst as in step (1-1) can be used.
About the organic solvent to be used, the same kind as a process (1-1) can be used. The reaction temperature is preferably 20 ° C. or higher and 100 ° C. or lower.
The reaction time in the step (1-2) is preferably 0.2 hours or more, more preferably 0.5 hours or more, further preferably 1 hour or more, and preferably 6 hours or less, more preferably 5 hours. Hereinafter, it is more preferably 4 hours or less.
Through the steps (1-1) and (1-2), preferably, the polyester segment terminal of the crystalline resin (A) and the terminal of the amorphous resin (B) are at least partially chemically. Combined. When a diisocyanate compound is selected as the polyfunctional compound (S), they are linked by a group containing a urethane bond.

The equivalent ratio of the hydroxyl groups of the crystalline resin (A) and the amorphous resin (B) used in the step (1) is excellent in low-temperature fixability and good in low-temperature fixability after high-temperature storage. From the viewpoint of obtaining a toner having excellent charge stability, it is preferably 0.20 or more, more preferably 0.30 or more, and preferably 1.80 or less, more preferably 1.50 or less, and still more preferably 1. .30 or less, more preferably 1.00 or less.
The equivalent ratio of hydroxyl groups is determined by the following formula.
Equivalent ratio of hydroxyl group = [hydroxyl value of crystalline resin (A) (mgKOH / g) × amount of crystalline resin (A) (g)] / [hydroxyl value of amorphous resin (B) (mgKOH / g ) × Amorphous resin (B) blending amount (g)]
From the viewpoint of obtaining a toner having excellent low-temperature fixability, good low-temperature fixability after high-temperature storage, and excellent charge stability, amorphous polyester (polyfunctional compound (S)) as amorphous resin (B) It is preferable to use a diisocyanate compound. That is, it is preferable to have the following steps (1-1 ′) and (1-2 ′).
Step (1-1 ′): A step of obtaining a reaction intermediate by introducing an isocyanate group with a diisocyanate compound at the end of the polyester segment of the crystalline resin (A) Step (1-2 ′): The reaction intermediate and non- The step of reacting the terminal of the crystalline polyester

  The resin composition (D) obtained by the above-mentioned step (1) includes a block resin (AB), a crystalline resin in which the polyester segment of the crystalline resin (A) and the amorphous resin (B) are chemically bonded. (A) and an amorphous resin (B) may be included.

[Method for producing toner for developing electrostatic image]
As a method for producing the electrostatic image developing toner of the present invention,
(1) A method for producing a toner by obtaining toner base particles by aggregating and fusing resin particles in a mixture containing a dispersion liquid in which a resin composition (D) is dispersed in an aqueous medium (hereinafter referred to as “the toner composition”) Also called "emulsion aggregation method"),
(2) A method of producing a toner by melt-kneading a mixture containing the resin composition (D) and pulverizing the obtained melt-kneaded product (hereinafter also referred to as “melt-kneading method”),
Etc.
From the viewpoint of obtaining a toner having excellent low-temperature fixability, good low-temperature fixability after high-temperature storage, and excellent charge stability, the emulsion aggregation method (1) is preferred. The toner may be obtained by the melt kneading method (2).

(1) Emulsion Aggregation Method The method for producing an electrostatic charge image developing toner of the present invention preferably includes the following steps (1) to (4).
Step (1): including a reaction product obtained by a reaction in which a crystalline resin (A) having a vinyl resin segment and a polyester segment and an amorphous resin (B) are chemically bonded at least partially. Step of obtaining resin composition (D) Step (2): Step of obtaining a dispersion of resin particles (E) by dispersing the resin composition (D) obtained in step (1) in an aqueous medium. 3): Step of aggregating the resin particles (E) obtained in step (2) in an aqueous medium to obtain aggregated particles Step (4): Step of fusing the aggregated particles obtained in step (3)

  Step (1) is as described in the above-described step (1-1) and step (1-2), or step (1-1 ') and step (1-2').

<Step (2)>
Step (2) is a step of obtaining a dispersion of resin particles (E) by dispersing the resin composition (D) obtained in step (1) in an aqueous medium. As a method for obtaining the resin particle (E) dispersion, the resin composition (D) is added to an aqueous medium, and the dispersion treatment is performed by a disperser or the like. The aqueous medium is gradually added to the resin composition (D). From the viewpoint of obtaining a toner having excellent low-temperature fixability, low-temperature fixability after high-temperature storage, and excellent charge stability, a method using phase-inversion emulsification is preferred. . When obtaining a dispersion of the resin particles (E), other resin components such as a crystalline resin (A) and an amorphous resin (B) may be added in addition to the resin composition (D).

≪Aqueous medium≫
As the aqueous medium, those containing water as a main component are preferable. From the viewpoint of improving the dispersion stability of the dispersion of resin particles and from the viewpoint of environmental properties, the content of water in the aqueous medium is preferably 80% by mass. % Or more, more preferably 90% by mass or more, still more preferably 95% by mass or more, still more preferably 98% by mass or more, and 100% by mass or less, and still more preferably 100% by mass. As water, deionized water or distilled water is preferred.
Components other than water that can form an aqueous medium together with water include alkyl alcohols having 1 to 5 carbon atoms; dialkyl ketones having 3 to 5 carbon atoms such as acetone and methyl ethyl ketone; dissolved in water such as cyclic ethers such as tetrahydrofuran An organic solvent is used. Among these, from the viewpoint of preventing the organic solvent from being mixed into the toner, an alkyl alcohol having 1 to 5 carbon atoms that does not dissolve the polyester is preferable, and methanol, ethanol, isopropanol, and butanol are more preferable.

[Phase inversion emulsification]
As the phase inversion emulsification method, after preparing an organic solvent solution of the resin composition (D), an aqueous medium is added to the obtained solution to perform phase inversion emulsification, and the molten resin composition (D) The method of adding an aqueous medium and carrying out phase inversion emulsification is mentioned. From the viewpoint of obtaining a dispersion of homogeneous resin particles (E), the former method is preferred.
At the time of phase inversion emulsification, other resin components such as a crystalline resin (A) and an amorphous resin (B) may be further added to the organic solvent solution of the resin composition (D).
The preferable aspect of the organic solvent which can be used is the same as the organic solvent which can be used for manufacture of the resin composition (D) of a process (1). In the step (1), the resin composition (D) may be produced in an organic solvent and may be subjected to the step (2) as an organic solvent solution.
The mass ratio between the organic solvent and the resin constituting the resin particles (E) (organic solvent / resin constituting the resin particles (E)) is a viewpoint that dissolves the resin and facilitates phase inversion to an aqueous medium, and the resin. From the viewpoint of improving the dispersion stability of the particles (E), it is preferably 0.1 or more, more preferably 0.2 or more, still more preferably 0.4 or more, and preferably 4 or less, more preferably 2 It is as follows.
It is preferable to add a neutralizing agent to the solution of the resin composition (D).
Examples of the neutralizing agent include basic substances. Examples of the basic substance include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide; nitrogen-containing substances such as ammonia, trimethylamine, ethylamine, diethylamine, triethylamine, diethanolamine, triethanolamine, and tributylamine. Examples include basic substances. Among these, from the viewpoint of improving the dispersion stability and cohesiveness of the resin particles (E), an alkali metal hydroxide is preferable, and sodium hydroxide is more preferable.

The use equivalent amount (mol%) of the neutralizing agent with respect to the acid groups of the resin is preferably 10 mol% or more, more preferably 30 mol% or more, and preferably 150 mol% or less, more preferably 120 mol% or less. More preferably, it is 100 mol% or less.
In addition, the use equivalent (mol%) of a neutralizing agent can be calculated | required by a following formula. When the equivalent of the neutralizer is 100 mol% or less, it is synonymous with the degree of neutralization. When the equivalent of the neutralizer exceeds 100 mol% in the following formula, the neutralizer is an acid group of the resin. In this case, the degree of neutralization of the resin is regarded as 100 mol%.
Equivalent (mole%) of neutralizing agent = [{added mass of neutralizing agent (g) / equivalent of neutralizing agent} / [{weighted average acid value of resin constituting resin particle (E) (mgKOH / g ) × mass of resin constituting resin particles (E) (g)} / (56 × 1000)]] × 100

  The amount of the aqueous medium to be added is 100 mass of resin constituting the resin particles (E) from the viewpoint of improving the dispersion stability of the resin particles (E) and obtaining uniform aggregated particles in the subsequent step (3). The amount is preferably 100 parts by mass or more, more preferably 150 parts by mass or more, still more preferably 200 parts by mass or more, and preferably 900 parts by mass or less, more preferably 600 parts by mass or less.

  Further, from the viewpoint of improving the dispersion stability of the resin particles (E), the mass ratio of the aqueous medium to the organic solvent (aqueous medium / organic solvent) is preferably 20/80 or more, more preferably 50/50 or more. More preferably, it is 60/40 or more, and preferably 97/3 or less, more preferably 93/7 or less, and still more preferably 90/10 or less.

  The temperature at which the aqueous medium is added is preferably equal to or higher than the glass transition temperature of the amorphous resin (B) constituting the resin particles (E) from the viewpoint of improving the dispersion stability of the resin particles (E). Specifically, the temperature is preferably 50 ° C. or higher, more preferably 60 ° C. or higher, still more preferably 70 ° C. or higher, and preferably 85 ° C. or lower, more preferably 80 ° C. or lower, still more preferably 75. It is below ℃.

  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 resin constituting the resin particles until phase inversion is completed. More preferably 0.5 parts by weight or more, further preferably 1 part by weight or more, still more preferably 3 parts by weight or more, and preferably 50 parts by weight or less, more preferably 30 parts by weight. It is 20 parts by mass or less, more preferably 20 parts by mass or less. There is no restriction | limiting in the addition rate of the aqueous medium after phase inversion.

You may have the process of removing an organic solvent from the obtained dispersion liquid as needed after phase inversion emulsification. The method for removing the organic solvent is preferably distilled because it dissolves in water. In this case, it is preferable to raise the temperature to a temperature equal to or higher than the boiling point of the organic solvent to be distilled off while stirring. Further, from the viewpoint of maintaining the dispersion stability of the resin particles (E), it is more preferable to perform distillation under reduced pressure, and it is preferable to perform distillation at a constant temperature and pressure. Note that the temperature may be increased after the pressure is reduced, or the pressure may be decreased after the temperature is increased.
Further, the organic solvent may not be completely removed and may remain in the aqueous dispersion. In this case, the remaining amount of the organic solvent is preferably 1% by mass or less, more preferably 0.5% by mass or less, and still more preferably substantially 0% in the aqueous dispersion.

  The solid content concentration of the obtained dispersion of resin particles (E) is preferably 5% by mass from the viewpoint of improving the productivity of the toner and the dispersion stability of the dispersion of the resin particles (E). Or more, more preferably 10% by mass or more, further preferably 15% by mass or more, and 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%. It is below mass%. In addition, solid content is the total amount of non-volatile components, such as resin, a coloring agent, and surfactant.

The volume median particle size (D ₅₀ ) of the resin particles (E) in the dispersion is preferably 0.05 μm or more, more preferably 0.08 μm or more from the viewpoint of obtaining a toner capable of obtaining a high-quality image. And, it is preferably 0.80 μm or less, more preferably 0.40 μm or less, further preferably 0.20 μm or less, and still more preferably 0.15 μm or less.
Here, the volume-median particle size (D ₅₀ ) is a particle size at which the cumulative volume frequency calculated by the volume fraction is 50% when calculated from the smaller particle size, and is described in Examples described later. Required by the method.
Further, the coefficient of variation (CV value) (%) of the particle size distribution of the resin particles (E) is preferably 5% or more, more preferably 10 from the viewpoint of improving the productivity of the dispersion of the resin particles (E). % Or more, more preferably 15% or more, and from the viewpoint of obtaining a toner capable of obtaining a high-quality image, it is preferably 50% or less, more preferably 40% or less, and still more preferably 30% or less.
The CV value is a value represented by the following formula. The volume average particle size in the following formula is a particle size obtained by multiplying the particle size measured on a volume basis by the ratio of particles having the particle size value and dividing the value obtained by the number of particles. is there. The CV value is determined by the method described in the examples.
CV value (%) = [standard deviation of particle size distribution (nm) / volume average particle size (nm)] × 100
In addition to the crystalline resin (A), the amorphous resin (B), and the resin composition (D), the resin particles (E) may further include a resin used for toner, such as a crystalline resin (A), A polyester other than the amorphous resin (B), a styrene-acrylic copolymer, an epoxy, a polycarbonate, a polyurethane, or the like may be contained.
Moreover, you may make a resin particle (E) contain a coloring agent and a charge control agent as needed. Moreover, additives such as reinforcing fillers such as fibrous substances, antioxidants, and anti-aging agents may be included as long as the effects of the present invention are not impaired.

The mass ratio [(A) / (B)] of the crystalline resin (A) and the amorphous resin (B) is excellent in low-temperature fixability and good in low-temperature fixability after high-temperature storage, and more stable in charge. From the viewpoint of obtaining a toner having excellent properties, it is preferably 2/98 or more, more preferably 5/95 or more, still more preferably 10/90 or more, and preferably 45/55 or less, more preferably 40/60. Hereinafter, it is more preferably 35/65 or less, and still more preferably 30/70 or less.
The total amount of the crystalline resin (A) and the amorphous resin (B) used is from the viewpoint of obtaining a toner having excellent low-temperature fixability, good low-temperature fixability after high-temperature storage, and excellent charge stability. In the resin component constituting the resin particles (E), preferably 70% by mass or more, more preferably 90% by mass or more, still more preferably 95% by mass or more, still more preferably 98% by mass or more, and preferably Is 100% by mass or less, more preferably 100% by mass.
The total use amount of the crystalline resin (A) with respect to the total use amount of the crystalline resin (A) and the amorphous resin (B) is excellent in low temperature fixability and good in low temperature fixability after high temperature storage, Further, from the viewpoint of obtaining a toner having excellent charge stability, it is preferably 5% by mass or more, more preferably 10% by mass or more, still more preferably 20% by mass or more, and preferably 45% by mass or less, more preferably It is 40 mass% or less, More preferably, it is 35 mass% or less.
The “total amount used of the crystalline resin (A)” means the crystalline resin (A) added as a raw material for the resin composition (D) and the raw material for the dispersion of the resin particles (E). It means the total amount of the crystalline resin (A).

<Step (3)>
In step (3), the resin particles (E) obtained in step (2) are aggregated in an aqueous medium to obtain aggregated particles. Specifically, the dispersion of resin particles (E) and, if necessary, optional components such as a wax (W2) particle dispersion containing wax (W2), an aggregating agent, a surfactant, and a colorant A method of mixing in an aqueous medium and aggregating the resin particles (E) and other components to obtain aggregated particles is preferred.
The step (3) includes the next step (3A), and the step (3B) may be performed subsequently.
Step (3A): Step of obtaining the aggregated particles (1) by aggregating the resin particles (E) obtained in the step (2) in an aqueous medium, preferably in the presence of the wax (W2). Step (3B) : Aggregated particles (2) obtained by adding resin particles (G) containing an amorphous resin to the aggregated particles (1) obtained in the step (3A) and adhering the resin particles (G). Step <Step (3A)>
Step (3A) is a step of aggregating the resin particles (E) obtained in step (2) in an aqueous medium to obtain aggregated particles (1), preferably obtained in step (2). The obtained resin particles (E) are aggregated in the presence of wax (W2) in an aqueous medium to obtain aggregated particles (1).

[Agglomerated particles (1)]
Aggregated particles (1) are a dispersion of resin particles (E) obtained in step (2), a wax particle dispersion containing wax (W2) as necessary, an aggregating agent, a surfactant, and a colorant. It is obtained by mixing and coagulating arbitrary components such as. From the viewpoint of improving the charging characteristics of the toner, it is preferable to use a wax particle dispersion containing wax (W2).
Specifically, first, a dispersion of resin particles (E), a dispersion of wax (W2) particles, and, if necessary, optional components such as an aggregating agent, a surfactant, and a colorant are mixed in an aqueous medium. Thus, it is preferable to obtain a mixed dispersion (hereinafter, a mixed dispersion containing a dispersion of resin particles (E) and a wax (W2) particle dispersion is also simply referred to as a mixed dispersion). And when the component in this mixed dispersion liquid is aggregated and the dispersion liquid of aggregated particle (1) is obtained, it is preferable to add a flocculant from a viewpoint of performing aggregation efficiently.
In addition, when not mixing a coloring agent with the resin particle (E), it is preferable to mix a coloring agent in this mixed dispersion liquid.
There is no restriction | limiting in particular in the mixing order of each component, Each component may be added in what kind of order, and all each component may be added simultaneously.

≪Wax particle dispersion≫
The wax particle dispersion can be obtained by using a surfactant, but it is possible to improve the dispersion stability of the wax particles by mixing the wax (W2) and the resin particles (F) described later. It is preferable from the viewpoints and from the viewpoint of improving the low-temperature fixability and charging characteristics of the toner.

(Wax (W2))
Examples of the wax (W2) include mineral or petroleum waxes; synthetic waxes; low molecular weight polyolefins; silicone waxes; fatty acid amides; plant waxes;
Examples of the mineral or petroleum-based wax include montan wax, paraffin wax, and Fischer-Tropsch wax. Paraffin wax is preferable from the viewpoint of improving toner releasability and low-temperature fixability.
As the synthetic wax, ester wax is preferable.
As the low molecular weight polyolefin, polyethylene, polypropylene, polybutene and the like are preferable.
As the fatty acid amide, oleic acid amide, stearic acid amide and the like are preferable.
As the plant wax, carnauba wax, rice wax, candelilla wax and the like are preferable.
The animal wax is preferably beeswax or the like.

Among these, from the viewpoint of improving the releasability and low-temperature fixability of the toner, mineral or petroleum wax and synthetic wax are preferable, one or more selected from ester wax and paraffin wax are more preferable, and paraffin wax is more preferable. .
In the wax (W2), the content of the paraffin wax is preferably 95% by mass or more, more preferably 97% by mass or more, and further preferably 99% by mass or more from the viewpoint of improving the releasability and low-temperature fixability of the toner. And 100% by mass or less, preferably 100% by mass.
The melting point of the wax (W2) is preferably 60 ° C. or higher, more preferably 65 ° C. or higher, still more preferably 70 ° C. or higher, from the viewpoint of improving the releasability of the toner, and has excellent low-temperature fixability and From the viewpoint of obtaining a toner having good low-temperature fixability after high-temperature storage and further excellent charge stability, it is preferably 100 ° C. or lower, more preferably 95 ° C. or lower, still more preferably 90 ° C. or lower, and still more preferably 85 ° C. It is as follows. When two or more kinds of waxes are used in combination, any melting point is preferably 60 ° C. or more and 100 ° C. or less, and any melting point is more preferably 60 ° C. or more and 90 ° C. or less.

The melting point of the wax (W2) is determined by the method described in the examples. When two or more kinds of waxes (W2) are used in combination, the melting point of the wax (W2) having the largest mass ratio among the waxes (W2) contained in the obtained toner is the same as that of the wax (W2) in the present invention. The melting point. In addition, when all are the same ratio, let the lowest melting | fusing point be melting | fusing point of the wax (W2) in this invention.
The amount of the wax (W2) used is from the viewpoint of obtaining a toner having good releasability, excellent low-temperature fixability, good low-temperature fixability after high-temperature storage, and excellent charge stability. The total amount of the resin is preferably 1 part by mass or more, more preferably 2 parts by mass or more, still more preferably 3 parts by mass or more, and preferably 30 parts by mass or less, more preferably 20 parts by mass. Hereinafter, it is more preferably 15 parts by mass or less.

(Resin particles (F))
The resin constituting the resin particles (F) used for the dispersion of the wax (W2) is not particularly limited, but is preferably a resin containing a polyester segment, and the viewpoint of improving the dispersion stability of the wax particles, as well as the toner From the viewpoint of improving low-temperature fixability and charging characteristics, it is more preferable to use an amorphous composite resin (C) having a polyester segment and a vinyl resin segment. It is preferable that the amorphous composite resin (C) further has a component derived from both reactive monomers.

(Amorphous composite resin (C))
The amorphous composite resin (C) is a resin having a vinyl resin segment and a polyester segment, and is preferably a graft polymer type resin having a vinyl resin segment in the main chain and a polyester segment side chain.
Here, “main chain” means the main chain of the graft polymer. The “side chain” means a polymer chain branched from the main chain of the graft polymer.
The amorphous composite resin (C) preferably has a constituent part derived from a bireactive monomer capable of reacting with both the vinyl resin segment and the polyester segment.
The amorphous composite resin of the present invention has a crystallinity index greater than 1.4 or less than 0.6.

The polyester segment has a polyhydric alcohol component (c-al) and a polyhydric carboxylic acid component (c-ac) from the viewpoint of improving the dispersion stability of the wax particles and improving the low-temperature fixability and charging characteristics of the toner. ) And polycondensation.
As the polyhydric alcohol component (c-al), those described above for the polyhydric alcohol component (b-al) in the amorphous resin (B) can be used, and the polyhydric alcohol component that is preferably used The same is true for the types. As the polyvalent carboxylic acid component (c-ac), those described above for the polyvalent carboxylic acid component (b-ac) can be used. As the polyvalent carboxylic acid component (c-ac), terephthalic acid and succinic acid, which are dicarboxylic acids, are preferable, and the viewpoint of improving the dispersion stability of the wax particles, and the viewpoint of improving the low-temperature fixability and charging characteristics of the toner Therefore, it is preferable to use these in combination.
The content of the dicarboxylic acid in the polycarboxylic acid component (c-ac) is preferably 90 mol% or more, more preferably 95 mol% or more, still more preferably 98 mol% or more, and 100 mol% or less. More preferably, it is 100 mol%.
The equivalent ratio (COOH group / OH group) of the polyvalent carboxylic acid component (c-ac) to the polyhydric alcohol component (c-al) is also the same as the polyvalent carboxylic acid relative to the polyhydric alcohol component (b-al). This is the same as the equivalent ratio of component (b-ac) (COOH group / OH group).

As the vinyl resin segment of the amorphous composite resin (C), those described as the vinyl segment of the crystalline resin (A) can be used.
The amorphous composite resin (C) preferably has a component derived from both reactive monomers. When an amphoteric monomer is used as a raw material monomer for the amorphous composite resin (C), the amphoteric monomer reacts with both the polyester segment and the vinyl resin segment, thereby producing an amorphous composite resin (C). It becomes easy to manufacture. Therefore, it is preferable to use a bireactive monomer as a raw material monomer for the amorphous composite resin (C). The structural unit derived from the both reactive monomers is preferably a bonding point between the vinyl resin segment and the polyester segment.
As the bireactive monomer used in the amorphous composite resin (C), the bireactive monomer described in the above-described crystalline resin (A) can be used.

The content of the constituent components of the both reactive monomers is 100% of the total amount of polyhydric alcohol components that are the raw materials of the polyester segment from the viewpoint of improving the dispersibility of the wax (W2), and the reaction control of the addition polymerization reaction and the polycondensation reaction. Preferably, it is 1 mol part or more, more preferably 5 mol part or more, still more preferably 10 mol part or more, and preferably 30 mol part or less, more preferably 25 mol part or less, still more preferably with respect to mol part. Is 20 mol parts or less. In addition, when using both reactive monomers and calculating the content of each segment in the amorphous composite resin, the structural unit derived from the both reactive monomers is included in the structural unit of the polyester segment. Calculate as a thing.
The content of the polyester segment in the amorphous composite resin (C) is preferably 40% by mass or more from the viewpoint of improving the dispersion stability of the wax particles and improving the low-temperature fixability and charging characteristics of the toner. More preferably, it is 50% by mass or more, more preferably 55% 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. From the same viewpoint, the content of the polyester segment in the amorphous composite resin (C) is preferably 40% by mass or more, more preferably 50% by mass, based on the total content of the polyester segment and the vinyl resin segment. More preferably, it is 55% by mass or more, and preferably 90% by mass or less, more preferably 80% by mass or less, and still more preferably 70% by mass or less.

Further, the content of the vinyl resin segment in the amorphous composite resin (C) is preferably from the viewpoint of improving the dispersion stability of the wax particles, and from the viewpoint of improving the low-temperature fixability and charging characteristics of the toner. It is 10 mass% or more, More preferably, it is 20 mass% or more, More preferably, it is 30 mass% or more, Preferably it is 60 mass% or less, More preferably, it is 50 mass% or less, More preferably, it is 45 mass% or less. From the same viewpoint, the content of the vinyl resin segment in the amorphous composite resin (C) is preferably 10% by mass or more, more preferably 20%, based on the total content of the polyester segment and the vinyl resin segment. It is at least mass%, more preferably at least 30 mass%, and preferably at most 60 mass%, more preferably at most 50 mass%, still more preferably at most 45 mass%.
Further, the total content of the polyester segment and the vinyl resin segment in the amorphous composite resin (C) improves the dispersion stability of the wax particles, and improves the low-temperature fixability and charging characteristics of the toner. From the viewpoint, it is preferably 80% by mass or more, more preferably 90% by mass or more, further preferably 93% by mass or more, still more preferably 95% by mass or more, and preferably 100% by mass or less, and still more preferably. 100% by mass.

The method for producing the amorphous composite resin (C) is not particularly limited, but from the viewpoint of a high degree of freedom in the reaction temperature of the polycondensation reaction, after the polycondensation reaction with the polyhydric alcohol component and the polycarboxylic acid component, vinyl A method of performing an addition polymerization reaction using a raw material monomer and an amphoteric monomer of the resin segment is preferable.
From the viewpoint of reactivity, it is preferable that both reactive monomers are supplied to the reaction system together with the raw material monomers of the vinyl resin segment. Further, from the viewpoint of reactivity, a catalyst such as an esterification catalyst or an esterification cocatalyst may be used, and a radical polymerization initiator and a radical polymerization inhibitor may be further used. As the esterification catalyst, esterification co-catalyst, and radical polymerization inhibitor, those described in the production of the amorphous resin (B) can be used. As the radical polymerization initiator, the crystallinity described above can be used. What was demonstrated by manufacture of resin (A) can be used.
From the viewpoint of further proceeding with the polycondensation reaction and, if necessary, the reaction with both reactive monomers, the polyvalent carboxylic acid component is partially subjected to the polycondensation reaction and then subjected to the addition polymerization reaction and then the reaction temperature is increased again. It is preferable to add the remainder to the reaction system.

  The temperature of the polycondensation reaction is preferably 180 ° C. or higher, more preferably 200 ° C. or higher, and preferably 260 ° C. or lower, more preferably 250 ° C., from the viewpoint of the productivity of the amorphous composite resin (C). It is as follows.

Although the temperature of the addition polymerization reaction varies depending on the type of radical polymerization initiator used, etc., from the viewpoint of productivity of the amorphous composite resin (C), it is preferably 110 ° C. or higher, more preferably 130 ° C. or higher, And preferably it is 220 degrees C or less, More preferably, it is 200 degrees C or less.
Moreover, it is preferable to accelerate the reaction by reducing the pressure of the reaction system in the latter half of the polymerization.

[Physical properties of amorphous composite resin (C)]
The softening point of the amorphous composite resin (C) is preferably 70 ° C. or higher from the viewpoint of improving the dispersion stability of the resin particles (E) described later, and improving the low-temperature fixability and charging characteristics of the toner. Preferably it is 80 degreeC or more, Preferably it is 140 degrees C or less, More preferably, it is 120 degrees C or less, More preferably, it is 100 degrees C or less.

  The glass transition temperature of the amorphous composite resin (C) is preferably 30 ° C. or higher from the viewpoint of improving the dispersion stability of the resin particles (E) described below, and improving the low-temperature fixability and charging characteristics of the toner. More preferably, it is 35 degreeC or more, More preferably, it is 40 degreeC or more, Preferably it is 70 degrees C or less, More preferably, it is 60 degrees C or less, More preferably, it is 55 degrees C or less.

  The acid value of the amorphous composite resin (C) is preferably 5 mgKOH / g or more from the viewpoint of improving the dispersion stability of the resin particles (E) described below, and improving the low-temperature fixability and charging characteristics of the toner. More preferably, it is 10 mgKOH / g or more, More preferably, it is 15 mgKOH / g or more, Preferably it is 40 mgKOH / g or less, More preferably, it is 35 mgKOH / g or less, More preferably, it is 30 mgKOH / g or less.

  The hydroxyl value of the amorphous composite resin (C) is preferably 15 mgKOH / g or more from the viewpoint of improving the dispersion stability of the resin particles (E) described below, and improving the low-temperature fixability and charging characteristics of the toner. More preferably, it is 20 mgKOH / g or more, More preferably, it is 25 mgKOH / g or more, Preferably it is 50 mgKOH / g or less, More preferably, it is 40 mgKOH / g or less, More preferably, it is 30 mgKOH / g or less.

The softening point, glass transition temperature, acid value and hydroxyl value of the amorphous composite resin (C) 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. These values can be obtained by the method described in the examples.
In addition, when using 2 or more types of amorphous composite resins (C), the softening point, glass transition temperature, and acid value obtained as a mixture thereof are within the above-mentioned ranges. preferable.

  The dispersion of resin particles (F) can be obtained, for example, by the above-described phase inversion emulsification method. The specific conditions and procedures for phase inversion emulsification, that is, the aqueous medium to be used, the components other than water that can constitute the aqueous medium, the amount of the aqueous medium, the addition temperature, and the addition rate should also apply the explanations in step (2). Can do.

The solid content concentration of the obtained dispersion of resin particles (F) is preferably 5% by mass from the viewpoint of improving the productivity of the toner and the dispersion stability of the aqueous dispersion of the resin particles (F). More preferably, it is 10% by mass or more, more preferably 15% by mass or more, and preferably 50% by mass or less, more preferably 40% by mass or less, still more preferably 30% by mass or less, still more preferably 25%. It is below mass%. In addition, solid content is the total amount of non-volatile components, such as resin, a coloring agent, and surfactant.
From the viewpoint of improving the dispersion stability of the wax particles, the volume median particle size (D ₅₀ ) of the resin particles (F) in the dispersion is preferably 0.01 μm or more, more preferably 0.03 μm or more, And preferably it is 0.30 micrometer or less, More preferably, it is 0.15 micrometer or less, More preferably, it is 0.10 micrometer or less.
The coefficient of variation (CV value) (%) of the particle size distribution of the resin particles (F) is preferably 5% or more, more preferably 10 from the viewpoint of improving the productivity of the dispersion of the resin particles (F). % Or more, more preferably 15% or more. From the viewpoint of obtaining a toner capable of obtaining a high-quality image, it is preferably 50% or less, more preferably 40% or less, and still more preferably 30% or less.
The CV value is a value represented by the following formula.
CV value (%) = [standard deviation of particle size distribution (nm) / volume average particle size (nm)] × 100

(Manufacture of wax particle dispersion)
The wax particle dispersion is obtained by mixing the wax (W2) and the dispersion of the resin particles (F).
By preparing wax particles using wax (W2) and resin particles (F), the polyester segment has a moderate polarity, so that the wax can be dispersed in an aqueous medium without using a surfactant. It becomes possible to make it.
That is, the wax particles contain wax and resin particles (F). It is considered that the wax particle dispersion has a structure in which wax is dispersed through resin particles (F) having an appropriate polarity, and a large number of resin particles (F) are adsorbed around the wax particles. Thereby, it is considered that the wax particles are easily taken into the aggregate of the (binding) resin particles (E) in the subsequent aggregation step.

  For the wax particle dispersion, for example, a dispersion machine having a strong shearing force at a temperature equal to or higher than the melting point of the wax (W2) is used with the wax (W2), the resin particle (F) dispersion, and an aqueous medium as necessary. And dispersed. The disperser is preferably a homogenizer, a high-pressure disperser, an ultrasonic disperser, or the like from the viewpoint of the stability of the wax particles, and more preferably an ultrasonic disperser. What is necessary is just to set dispersion | distribution time suitably with the disperser to be used.

Examples of the ultrasonic disperser include an ultrasonic homogenizer. The commercially available products include “US-150T”, “US-300T”, “US-600T” (manufactured by Nippon Seiki Seisakusho Co., Ltd.), “SONIFIER (registered trademark) 4020-400”, “SONIFIER (registered trademark) 4020. -800 "(manufactured by Branson).
Further, before using the disperser, the wax (W2), the resin particle (F) dispersion, and an aqueous medium as necessary may be preliminarily dispersed in a mixer such as a homomixer or a ball mill in advance. Good.
A preferred embodiment of the aqueous medium used in the production is the same as that used when obtaining the resin particles (E).

From the viewpoint of improving the dispersion stability of the wax particles, from the viewpoint of obtaining uniform aggregated particles in the subsequent aggregation process, and from the viewpoint of containing the wax (W2) in the toner even after heating in the fusing process, the wax (W2) 100 The amount of the resin particles (F) relative to parts by mass is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, still more preferably 20 parts by mass or more, still more preferably 30 parts by mass or more, and preferably 100 It is at most 70 parts by mass, more preferably at most 60 parts by mass, even more preferably at most 50 parts by mass.
The wax particle dispersion may contain a surfactant, but from the viewpoint of obtaining a toner having excellent low-temperature fixability and excellent low-temperature fixability after high-temperature storage, it is preferable not to contain a surfactant. When the surfactant is contained, the amount of the surfactant with respect to 100 parts by mass of the wax in the wax particles is preferably 1 part by mass or less, more preferably 0.5 parts by mass or less, and further preferably 0.1 parts by mass or less. And when used for improving the dispersion stability of the wax particles, preferably 0.01 parts by mass or more, more preferably 0.02 parts by mass or more, and further preferably 0.05 parts by mass or more. It is.

It is preferable to add the dispersion of the wax (W2) and the resin particles (F) to the aqueous medium and disperse while heating at a temperature equal to or higher than the melting point of the wax (W2).
Specifically, the heating temperature at the time of dispersion is preferably at least the melting point of the wax (W2) and at least 80 ° C., more preferably at least 85 ° C., and even more preferably from the viewpoint of improving the productivity of the wax particle dispersion. 90 ° C or higher, and preferably 100 ° C or lower, more preferably 98 ° C or lower, and further preferably 95 ° C or lower.
The heating time during dispersion is preferably 5 minutes or more, more preferably 10 minutes or more, still more preferably 15 minutes or more, and preferably 3 hours or less from the viewpoint of improving the productivity of the wax particle dispersion. More preferably, it is 2 hours or less, More preferably, it is 1 hour or less.

  The solid concentration of the wax (W2) particle dispersion is preferably 5% by mass or more from the viewpoint of improving the dispersion stability of the wax particles, facilitating handling, and improving the productivity of the toner. Preferably it is 10 mass% or more, More preferably, it is 15 mass% or more, Preferably it is 40 mass% or less, More preferably, it is 30 mass% or less, More preferably, it is 25 mass% or less.

The volume median particle size (D ₅₀ ) of the wax (W2) particles is preferably 0.05 μm or more from the viewpoint of obtaining uniform aggregated particles in the subsequent aggregation step and obtaining a toner excellent in charging stability. Preferably it is 0.20 μm or more, more preferably 0.30 μm or more, still more preferably 0.40 μm or more, and preferably 1.00 μm or less, more preferably 0.80 μm or less, still more preferably 0.70 μm or less. More preferably, it is 0.65 μm or less, and still more preferably 0.60 μm or less.
Here, the volume-median particle size (D ₅₀ ) is a particle size at which the cumulative volume frequency calculated by the volume fraction is 50% when calculated from the smaller particle size, and is described in Examples described later. Required by the method.
Further, the coefficient of variation (CV value) (%) of the particle size distribution of the wax (W2) particles is preferably 5% or more, more preferably 10% or more, from the viewpoint of improving the productivity of the dispersion of wax particles. More preferably, it is 15% or more, and from the viewpoint of obtaining a toner capable of obtaining a high-quality image, it is preferably 50% or less, more preferably 40% or less, and still more preferably 30% or less.
The CV value is a value represented by the following formula.
CV value (%) = [standard deviation of particle size distribution (nm) / volume average particle size (nm)] × 100
Ratio of volume median particle size (D ₅₀ ) of wax (W2) particles to volume median particle size (D ₅₀ ) of resin particles (F) (volume median particle size of wax (W2) particles (D ₅₀ ) / The volume median particle size (D ₅₀ ) of the resin particles (F) is preferably 1.0 or more, more preferably from the viewpoint of improving the dispersion stability of the wax particles and obtaining a toner having excellent charge stability. Is 1.5 or more, more preferably 2.0 or more, and preferably 50 or less, more preferably 30 or less, still more preferably 15 or less, and still more preferably 10 or less.

≪Colorant≫
When mixing a colorant in the mixed dispersion containing the resin particles (E), it is preferable to use a dispersion of colorant particles in which a colorant is dispersed in an aqueous medium.
As the colorant, pigments and dyes are used, and pigments are preferable from the viewpoint of improving the image density of the toner.
Specific examples of the pigment include carbon black, inorganic composite oxide, benzidine yellow, brilliantamine 3B, brilliantamine 6B, bengal, aniline blue, ultramarine blue, copper phthalocyanine, and phthalocyanine green. Among these, copper Phthalocyanine is preferred.

Specific examples of the dye include acridine series, azo series, benzoquinone series, azine series, anthraquinone series, indigo series, phthalocyanine series, and aniline black series.
A coloring agent can be used individually or in combination of 2 or more types.
The amount of the colorant used is preferably 2 parts by mass or more, more preferably 5 parts by mass with respect to 100 parts by mass of the total amount of resin in the toner from the viewpoint of improving the image density of the printed matter and obtaining a high-quality image. It is not less than 7 parts by mass, more preferably not less than 7 parts by mass, and preferably not more than 30 parts by mass, more preferably not more than 20 parts by mass, still more preferably not more than 15 parts by mass.

The colorant dispersion is preferably obtained by dispersing a colorant and an aqueous medium using a disperser. As the disperser, a homogenizer, an ultrasonic disperser or the like is preferable.
As an aqueous medium, what was mentioned by manufacture of the above-mentioned resin particle (E) dispersion liquid is preferable.
The dispersion of the colorant in the aqueous medium is preferably performed in the presence of a surfactant from the viewpoint of improving the dispersion stability of the colorant.
Examples of the surfactant used in the production of the colorant dispersion include nonionic surfactants, anionic surfactants, and cationic surfactants. From the viewpoint of improving the dispersion stability of the colorant particles, agglomeration From the viewpoint of improving the property, an anionic surfactant is preferable. Examples of the anionic surfactant include sodium dodecylbenzenesulfonate, sodium dodecylsulfate, sodium lauryl ether sulfate, dipotassium alkenyl succinate, and preferably sodium dodecylbenzenesulfonate.

  From the viewpoint of improving the dispersion stability of the colorant, the content of the surfactant in the colorant dispersion is preferably 1 part by mass or more, more preferably 5 parts by mass or more, with respect to 100 parts by mass of the colorant. More preferably, it is 10 parts by mass or more, and preferably 40 parts by mass or less, more preferably 30 parts by mass or less, and still more preferably 25 parts by mass or less.

  The solid content concentration of the colorant dispersion is preferably 5% by mass or more, more preferably 10% by mass or more, and still more preferably, from the viewpoint of improving the productivity of the toner and improving the dispersion stability of the colorant. It is 15% by mass or more, and preferably 50% by mass or less, more preferably 40% by mass or less, and further preferably 30% by mass or less.

The volume median particle size (D ₅₀ ) of the colorant particles in the colorant dispersion is preferably 0.050 μm or more, more preferably 0.08 μm or more, still more preferably 0.10 μm or more, and preferably It is 0.30 μm or less, more preferably 0.20 μm or less, and still more preferably 0.15 μm or less.
The content of the resin particles (E) in the mixed dispersion is preferably 5 from the viewpoint of obtaining a toner having excellent low-temperature fixability, good low-temperature fixability after high-temperature storage, and excellent charge stability. % By mass or more, more preferably 10% by mass or more, and further preferably 12% by mass or more, and from the viewpoint of controlling aggregation and obtaining aggregated particles having a desired particle size, preferably 40% by mass or less, more preferably Is 30% by mass or less, more preferably 20% by mass or less.
The mass ratio of the resin particles (E) and the wax (W2) particles in the mixed dispersion (wax (W2) particles / resin particles (E)) is excellent in low temperature fixability and low temperature fixability after high temperature storage. Is preferably 0.05 or more, more preferably 0.10 or more, and preferably 1.0 or less, more preferably 0.5 or less, from the viewpoint of obtaining a toner that is also excellent in charge stability. More preferably, it is 0.3 or less, and still more preferably 0.2 or less.
The mixing temperature is preferably 0 ° C. or higher, more preferably 10 ° C. or higher, further preferably 20 ° C. or higher, and preferably 40 ° C. or lower, from the viewpoint of controlling aggregation and obtaining aggregated particles having a target particle size. More preferably, it is 30 ° C. or lower.

When preparing the mixed dispersion, it is carried out in the presence of a surfactant from the viewpoint of improving the dispersion stability of the resin particles (E) and optional components such as wax (W2) particles added as necessary. Also good.
Examples of the surfactant include anionic surfactants such as sulfate, sulfonate, phosphate, and soap (eg, alkyl ether carboxylate); amine salt type and quaternary ammonium Cationic surfactants such as salt forms; polyoxyethylene alkyl aryl ethers such as polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ethers such as polyoxyethylene oleyl ether and polyoxyethylene lauryl ether, and polyoxyethylene alkenyl ethers Polyoxyethylene sorbitan esters such as polyoxyethylene sorbitan monolaurate and polyoxyethylene sorbitan monostearate, polyethylene glycol monolaurate, polyethylene glycol monostearate Rate and polyoxyethylene fatty acid esters such as polyethylene glycol monooleate, non-ionic surfactants such as polyoxyethylene / polyoxypropylene block copolymers, and the like. Among these, nonionic surfactants are preferable, polyoxyethylene alkyl ethers and polyoxyethylene alkenyl ethers are preferable, and polyoxyethylene lauryl ether is more preferable.
When using the surfactant, the amount used is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, and preferably 100 parts by mass or more, and preferably 0.5 parts by mass or more. It is 10 mass parts or less, More preferably, it is 5 mass parts or less, More preferably, it is 3 mass parts or less.

≪Flocculant≫
Next, the particles in the mixed dispersion can be aggregated to suitably obtain a dispersion of aggregated particles (1). It is preferable to add a flocculant for efficient aggregation.
The flocculant is preferably an electrolyte, and more preferably a salt, from the viewpoint of obtaining a toner having a desired particle size while preventing excessive aggregation. Specific examples of the flocculant include quaternary salt cationic surfactants, organic flocculants such as polyethyleneimine; inorganic flocculants such as inorganic metal salts, inorganic ammonium salts, and bivalent metal complexes. It is done. From the viewpoint of improving cohesion and obtaining uniform aggregated particles, inorganic coagulants are preferred, inorganic metal salts and inorganic ammonium salts are more preferred, and inorganic ammonium salts are even more preferred.

  The valence of the cation of the inorganic flocculant is preferably 5 or less, more preferably 2 or less, and even more preferably 1 from the viewpoint of obtaining a toner having a desired particle size while preventing excessive aggregation. Examples of the monovalent cation of the inorganic flocculant include sodium ion, potassium ion, ammonium ion, and the like. From the viewpoint of improving low-temperature fixability and low-temperature fixability of the resulting toner over time, ammonium ions are preferable. .

Examples of the inorganic metal salt include metal salts such as sodium sulfate, sodium nitrate, sodium chloride, calcium chloride, and calcium nitrate, and inorganic metal salt polymers such as polyaluminum chloride and polyaluminum hydroxide.
Examples of inorganic ammonium salts include ammonium sulfate, ammonium chloride, and ammonium nitrate.
As the flocculant, ammonium sulfate is more preferable.
The amount of the flocculant used is preferably 5 parts by mass or more with respect to 100 parts by mass of the total amount of the resin constituting the agglomerated particles (1) from the viewpoint of controlling the aggregation of the resin particles to obtain the desired particle size. It is preferably 10 parts by mass or more, more preferably 20 parts by mass or more, preferably from the viewpoint of obtaining a toner having excellent low-temperature fixability, good low-temperature fixability after high-temperature storage, and excellent charge stability. 50 parts by mass or less, more preferably 45 parts by mass or less, and still more preferably 40 parts by mass or less.

The flocculant may be added at once, or may be added intermittently or continuously. It is preferable to perform sufficient stirring during and after the addition.
The flocculant is preferably added dropwise as an aqueous solution from the viewpoint of controlling aggregation and obtaining aggregated particles having a desired particle diameter. The concentration of the aqueous flocculant solution is preferably 2% by mass or more, more preferably 4% by mass. More preferably, it is 6% by mass or more, and preferably 40% by mass or less, more preferably 30% by mass or less, and still more preferably 20% by mass or less.
From the viewpoint of controlling aggregation and obtaining aggregated particles having a desired particle diameter and particle size distribution, the aqueous solution of the aggregating agent is preferably used by adjusting the pH to 7.0 or more and 9.0 or less.
The dropping time of the aggregating agent is preferably 1 minute or more, more preferably 3 minutes or more from the viewpoint of controlling aggregation and obtaining aggregated particles having a desired particle diameter, and from the viewpoint of improving toner productivity. , Preferably 120 minutes or less, more preferably 30 minutes or less, still more preferably 10 minutes or less.
Further, the temperature at which the flocculant is dropped is preferably 0 ° C. or higher, more preferably 10 ° C. or higher, further preferably 20 ° C. or higher, and preferably 40 ° C. or lower, from the viewpoint of improving toner productivity. More preferably, it is 35 degrees C or less, More preferably, it is 30 degrees C or less.

  Further, from the viewpoint of promoting aggregation and obtaining aggregated particles having a desired particle size and particle size distribution, it is preferable to increase the temperature of the dispersion after adding the flocculant. The holding temperature is preferably 45 ° C. or higher, more preferably 50 ° C. or higher, further preferably 55 ° C. or higher, from the viewpoint of improving the low-temperature fixability and low-temperature fixability of the resulting toner over time. The temperature is preferably 75 ° C. or lower, more preferably 70 ° C. or lower, and still more preferably 65 ° C. or lower.

It is preferable to confirm the progress of aggregation by monitoring the volume-median particle size of the aggregated particles in the temperature range.
The volume-median particle size (D ₅₀ ) of the obtained aggregated particles (1) is preferably 2 μm or more, more preferably 3 μm or more from the viewpoint of improving the low-temperature fixability and low-temperature fixability of the obtained toner over time. More preferably, it is 4 μm or more, and preferably 10 μm or less, more preferably 8 μm or less, and still more preferably 6 μm or less. The volume-median particle size of the aggregated particles is determined by the method described in the examples described later.

<Process (3B)>
In the step (3B), resin particles (G) containing an amorphous resin are added to the aggregated particles (1) obtained in the step (3A), and the resin particles (G) are added to the aggregated particles (1). Is a step of obtaining agglomerated particles (2) formed by attaching
In the step (3), the charging stability of the toner, which is the effect of the present invention, can be improved only by the step (3A). However, by further performing the step (3B), the components of the aggregated particles (1) are converted into the core. On the side, the aggregated particles (2) having the resin particles (G) on the shell side can be obtained, and the crystalline resin (A) or wax (W2) finely dispersed in the aggregated particles (1) is the next step. It is considered that, when the particles in the agglomerated particles in (4) are fused, it is more difficult to detach and the exposure of the wax (W2) to the surface of the obtained toner base particles can be further suppressed.
The resin particles (G) are preferably obtained as a dispersion of resin particles (G) by dispersing a resin component containing an amorphous resin in an aqueous medium. The method for obtaining the dispersion is preferably a method in which an aqueous medium is gradually added to a resin organic solvent solution or the like to carry out phase inversion emulsification as in the case of the resin particles (E).

In step (3), the aggregation may be stopped when the aggregated particles have grown to an appropriate particle size as a toner.
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.

≪Aggregation stopping agent≫
As the aggregation terminator, a surfactant is preferable, and an anionic surfactant is more preferable. Examples of the anionic surfactant include alkylbenzene sulfonate, alkyl sulfate, alkyl ether sulfate, polyoxyalkylene alkyl ether sulfate and the like. Among these, polyoxyalkylene alkyl ether sulfate is preferable, polyoxyethylene lauryl ether sulfate is more preferable, and sodium polyoxyethylene lauryl ether sulfate is still more preferable.

An aggregation terminator can be used individually or in combination of 2 or more types.
The addition amount of the aggregation terminator is preferably 0.1 parts by mass or more, more preferably 1 part by mass or more, with respect to 100 parts by mass of the total amount of the resin in the toner, from the viewpoint of surely preventing unnecessary aggregation. More preferably, it is 2 parts by mass or more, and from the viewpoint of reducing residual toner, it is preferably 15 parts by mass or less, more preferably 10 parts by mass or less, and even more preferably 7 parts by mass or less. The aggregation terminator is preferably added as an aqueous solution from the viewpoint of improving toner productivity.

The temperature at which the aggregation terminator is added is preferably the same as the temperature at which the dispersion liquid of the aggregated particles is retained from the viewpoint of improving the productivity of the toner. The said temperature becomes like this. Preferably it is 40 degreeC or more, More preferably, it is 45 degreeC or more, 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.
Further, from the viewpoint of stabilizing the aggregated particles and preventing the aggregated particles from being dispersed before fusion, it is preferable to add an acid together with the stop of aggregation to make the dispersion of the aggregated particles neutral to acidic. .
The acid to be added is not limited, and examples thereof include sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, and acetic acid. From the viewpoint of rapid pH change with respect to addition, hydrochloric acid, sulfuric acid, nitric acid, and acetic acid are preferred. And at least one selected from hydrochloric acid, sulfuric acid, and nitric acid, and more preferably sulfuric acid.
The acid is preferably added in the form of an aqueous solution. Moreover, you may add with the said aggregation stopper.

<Process (4)>
Step (4) is a step of fusing the aggregated particles obtained in step (3).
Here, the “aggregated particles obtained in the step (3)” means the aggregated particles (1) obtained in the step (3A) when the step (3B) is not performed, and the step (3B). In the case of carrying out the step, it means the aggregated particles (2) obtained in the step (3B).
In this step, the particles in the aggregated particles obtained in step (3), which were mainly physically attached to each other, are fused and integrated to form fused particles.
When the agglomerated particles (2) are fused, toner base particles having a core-shell structure can be obtained.

In this step, from the viewpoint of improving the fusing property of the aggregated particles, and from the viewpoint of obtaining a toner having excellent low-temperature fixability, good low-temperature fixability after high-temperature storage, and excellent charge stability. It is preferable to hold at a temperature of 10 ° C. or more lower than the melting point of the resin (A).
The holding temperature is more preferably at least 5 ° C. lower than the melting point of the crystalline resin (A), more preferably the crystalline resin, from the viewpoint of improving the fusibility of the aggregated particles and improving the productivity of the toner. It is above the melting point of (A).

  At that time, the toner is maintained at a temperature lower by 10 ° C. than the melting point of the crystalline resin (A) for a toner having excellent low-temperature fixability, good low-temperature fixability after high-temperature storage, and excellent charging stability. From the viewpoint, it is preferably 1 minute or more, more preferably 10 minutes or more, still more preferably 30 minutes or more, and preferably 240 minutes or less, more preferably 180 minutes or less, still more preferably 120 minutes or less, even more preferably. Is 90 minutes or less.

The volume median particle size (D ₅₀ ) of the fused particles in the dispersion obtained in the step (4) is preferably 2 μm or more, more preferably 3 μm or more, and further preferably 4 μm, from the viewpoint of obtaining a high-quality image. The thickness is preferably 10 μm or less, more preferably 8 μm or less, and still more preferably 6 μm or less. The circularity of the fused particles in the dispersion is preferably 0.955 or more, more preferably 0.960 or more, and still more preferably 0.965, from the viewpoint of reducing toner scattering and obtaining a high-quality image. And preferably 0.990 or less, more preferably 0.985 or less, and still more preferably 0.980 or less.

<Post-processing process>
A post-treatment step may be performed after the step (4), and it is preferable to obtain the toner base particles by isolating the fused particles from the dispersion obtained in the step (4).
Since the fused particles in the dispersion obtained in the step (4) are present in the aqueous medium, it is preferable to first perform solid-liquid separation. For solid-liquid separation, a suction filtration method or the like is preferably used.
It is preferable to perform washing after the solid-liquid separation. At this time, since it is preferable to remove the added surfactant, it is preferable to wash with an aqueous medium below the cloud point of the surfactant. The washing is preferably performed a plurality of times.

Next, it is preferable to perform drying. The drying temperature is preferably such that the temperature of the fused particles themselves is lower than the minimum glass transition temperature of the resin constituting the resin particles. As a drying method, it is preferable to use a vacuum low temperature drying method, a vibration type fluidized drying method, a spray drying method, a freeze drying method, a flash jet method, or the like. The water content after drying is preferably adjusted to 1.5% by mass or less, more preferably 1.0% by mass or less, from the viewpoint of improving the charging characteristics of the toner.
The toner base particles can be obtained by drying the fused particles.

(2) Melt-kneading method The method of (2) is preferably a step of melt-kneading a mixture containing the resin composition (D) and the wax (W2), and pulverizing the melt-kneaded product obtained in the above step. And classifying.
Examples of the wax (W2) used in the method (2) include the same preferred examples as the wax (W2) described above.
In the melt-kneading step, it is preferable to further melt-knead the colorant, and it is preferable to melt-knead other additives such as other release agents and charge control agents.
The melt-kneading can be performed using a known kneader such as a closed kneader, a single-screw extruder, a twin-screw extruder, or an open roll kneader.

The toner raw materials such as the resin, the colorant, and the release agent are preferably mixed in advance with a mixer such as a Henschel mixer or a ball mill and then supplied to the kneader.
The set temperature (barrel set temperature) of the twin-screw extruder is appropriately set so that the temperature _Kt falls within a predetermined range, for example, preferably 50 ° C. or higher, more preferably 60 ° C. or higher, and Preferably it is 160 degrees C or less, More preferably, it is 140 degrees C or less.
Rotational speed is the same direction rotation from the viewpoint of improving the dispersibility of additives such as colorants, charge control agents, and release agents in the toner, reducing the mechanical force during melt kneading, and suppressing heat generation. In the case of a twin screw extruder, it is preferably 100 r / min or more, more preferably 130 r / min or more, more preferably 150 r / min or more, and preferably 300 r / min or less, more preferably 280 r / min or less, more Preferably it is 250 r / min or less.
The melt-kneaded product obtained in the above step is cooled to such an extent that it can be crushed and then subjected to the subsequent step.

  The pulverization process may be performed in multiple stages. For example, the resin kneaded material obtained by curing the melt-kneaded material may be coarsely pulverized to about 1 mm to 5 mm and then further pulverized to a desired particle size. The pulverizer used in the pulverization step is not particularly limited, and examples of the pulverizer suitably used for coarse pulverization include a hammer mill, an atomizer, and a rotplex. Further, examples of the pulverizer suitably used for fine pulverization include a fluidized bed jet mill, a collision plate jet mill, and a rotary mechanical mill. From the viewpoint of pulverization efficiency, it is preferable to use a fluidized bed jet mill and a collision plate jet mill, and more preferably a fluidized bed jet mill.

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

[Toner for electrostatic image development]
<Toner base particles>
The toner base particles obtained by the above-described method can be used as the toner for developing an electrostatic image as it is. However, as described later, a toner whose surface is treated can be used as a toner for developing an electrostatic image. preferable.

In the toner base particles, the total content of the crystalline resin (A) relative to the total content of the crystalline resin (A) and the amorphous resin (B) is excellent in low-temperature fixability and low-temperature fixability over time. From the viewpoint of obtaining a toner that can suppress a decrease in image quality and is excellent in image density and long-term storage stability of a printed material, it is preferably 5% by mass or more, more preferably 10% by mass or more, and still more preferably 15% by mass or more, and , Preferably 45% by mass or less, more preferably 40% by mass or less, still more preferably 35% by mass or less.
In addition, the total content of the crystalline resin (A) is excellent in low-temperature fixability, can suppress a decrease in low-temperature fixability over time, and further from the viewpoint of obtaining a toner excellent in image density and long-term storage properties of printed matter. The total amount of the resin components in the toner is preferably 5% by mass or more, more preferably 10% by mass or more, still more preferably 15% by mass or more, and preferably 45% by mass or less, more preferably 40% by mass. It is not more than mass%, more preferably not more than 35 mass%.
The “total content of the crystalline resin (A)” means the crystalline resin (A) added as a raw material of the resin composition (D) and the crystalline resin (A) added in another step. Means the total amount.

The volume median particle size (D ₅₀ ) of the toner base particles is preferably 2 μm or more, more preferably 3 μm or more, still more preferably 4 μm or more, and preferably 10 μm or less, from the viewpoint of obtaining a high-quality image. More preferably, it is 8 micrometers or less, More preferably, it is 6 micrometers or less.
The CV value of the toner base particles is preferably 12% or more, more preferably 14% or more, and still more preferably 16% or more from the viewpoint of improving toner productivity, and from the viewpoint of obtaining a high-quality image. , Preferably 30% or less, more preferably 26% or less.

  The circularity of the toner base particles is preferably 0.955 or more, more preferably 0.960 or more, and still more preferably 0.965 or more, from the viewpoint of reducing toner scattering and obtaining a high-quality image. Preferably it is 0.990 or less, More preferably, it is 0.985 or less, More preferably, it is 0.980 or less.

The toner for developing an electrostatic charge image is preferably obtained by adding a surface of a toner base particle with a fluidizing agent or the like as an external additive.
Examples of the external additive include hydrophobic silica, titanium oxide fine particles, alumina fine particles, cerium oxide fine particles, inorganic fine particles such as carbon black, and polymer fine particles such as polycarbonate, polymethyl methacrylate, and silicone resin. Among these, Hydrophobic silica is preferred.
When the external additive is used, the amount of the external additive added is preferably 1 part by mass or more, more preferably 2 parts by mass or more, and further preferably 3 parts by mass or more with respect to 100 parts by mass of the toner base particles. And preferably it is 5 mass parts or less, More preferably, it is 4.5 mass parts or less, More preferably, it is 4 mass parts or less.

  The toner for developing an electrostatic image can be used as a one-component developer or as a two-component developer by mixing with a carrier.

Each property value was measured and evaluated by the following method.
[Hydroxyl value and acid value of resin]
The hydroxyl value and acid value of the resin were measured according to the neutralization titration method described in JIS K 0070-1992. However, the measurement solvent was chloroform.

[Softening point, crystallinity index, melting point and glass transition temperature of resin]
(1) Softening point Using a flow tester “CFT-500D” (manufactured by Shimadzu Corporation), a 1 g sample was heated at a heating rate of 6 ° C./min, and a load of 1.96 MPa was applied by a plunger. Extruded from a nozzle of 1 mm length 1 mm. The amount of plunger drop of the flow tester was plotted against the temperature, and the temperature at which half of the sample flowed out was taken as the softening point.
(2) Crystallinity Index Using a differential scanning calorimeter “Q100” (manufactured by TA Instruments Japan Co., Ltd.), 0.02 g of a sample is weighed into an aluminum pan, and the rate of temperature decrease from room temperature (25 ° C.) to 10 ° C. / Cooled to 0 ° C. in min. Next, the sample was allowed to stand still for 1 minute, and then heated to 180 ° C. at a heating rate of 10 ° C./min, and the amount of heat was measured. Of the observed endothermic peaks, the temperature of the peak with the largest peak area is defined as the maximum endothermic peak temperature (1), and (softening point (° C)) / (maximum endothermic peak temperature (1) (° C)), The crystallinity index was determined.
(3) Melting point and glass transition temperature Using a differential scanning calorimeter “Q100” (manufactured by TA Instruments Japan Co., Ltd.), 0.02 g of a sample was weighed into an aluminum pan, heated to 200 ° C., and the temperature Then, it was cooled to 0 ° C. at a temperature lowering rate of 10 ° C./min. Next, the sample was heated at a temperature rising rate of 10 ° C./min, and the amount of heat was measured. Among the observed endothermic peaks, the temperature of the peak having the maximum peak area was defined as the maximum endothermic temperature (2). In the case of a crystalline resin, the peak temperature was taken as the melting point.
In the case of an amorphous resin, when the peak is observed, the temperature of the peak is measured, and when the step is observed without the peak being observed, the tangent indicating the maximum slope of the curve of the step and the step The temperature at the intersection with the extension of the base line on the low temperature side was defined as the glass transition temperature.

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

[Volume Median Particle Size (D ₅₀ ) and CV Value of Resin Particles, Colorant Particles, and Wax 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 ) and the volume average particle size were measured at a concentration at which the absorbance was in an appropriate range. The CV value was calculated according to the following formula.
CV value (%) = (standard deviation of particle size distribution / volume average particle size) × 100

[Solid content concentration of resin particle dispersion, colorant dispersion, and wax particle dispersion]
Using an infrared moisture meter “FD-230” (manufactured by Kett Scientific Laboratory Co., Ltd.), a measurement sample 5 g was dried at a temperature of 150 ° C., a measurement mode 96 (monitoring time 2.5 minutes, fluctuation range of moisture content 0.05% ), Moisture (mass%) was measured. The solid content concentration was calculated according to the following formula.
Solid content concentration (% by mass) = 100-water content (% by mass)

[Volume Median Particle Size of Aggregated Particles (D ₅₀ )]
The volume-median particle size (D ₅₀ ) of the aggregated particles was measured as follows.
Measuring instrument: “Coulter Multisizer (registered trademark) III” (manufactured by Beckman Coulter, Inc.)
・ Aperture diameter: 50μm
Analysis software: “Multisizer (registered trademark) III version 3.51” (manufactured by Beckman Coulter, Inc.)
Electrolyte: “Isoton (registered trademark) II” (manufactured by Beckman Coulter, Inc.)
Measurement conditions: After adjusting the particle size of 30,000 particles to a concentration that can be measured in 20 seconds by adding the sample dispersion to 100 mL of the electrolyte, 30,000 particles are measured again, and the particle size The volume-median particle size (D ₅₀ ) was determined from the distribution.

[Circularity of fused particles]
The circularity of the fused particles was measured under the following conditions.
Measurement device: Flow type particle image analyzer “FPIA-3000” (manufactured by Sysmex Corporation)
-Preparation of dispersion: A dispersion of fused particles (Ma) was prepared by diluting with deionized water so that the solid content concentration was 0.001 to 0.05 mass%.
・ Measurement mode: HPF measurement mode

[Volume Median Particle Size (D ₅₀ ) and CV Value of Toner Base Particles]
The volume median particle size (D ₅₀ ) of the toner base particles was measured as follows.
The measuring device, aperture diameter, analysis software, and electrolyte used were the same as those used in the measurement of the volume-median particle size (D ₅₀ ) of the above-mentioned aggregated particles.
Dispersion: Polyoxyethylene lauryl ether “Emulgen (registered trademark) 109P” (manufactured by Kao Corporation, HLB (Hydrophile-Lipophile Balance) = 13.6) was dissolved in the electrolyte solution, and a dispersion solution having a concentration of 5% by mass was dissolved. Obtained.
Dispersion condition: 10 mg of a measurement sample of toner mother particles after drying is added to 5 mL of the dispersion, and dispersed for 1 minute with an ultrasonic disperser, and then 25 mL of an electrolyte is added, and further to the ultrasonic disperser. For 1 minute to prepare a sample dispersion.
Measurement conditions: After adding the sample dispersion to 100 mL of the electrolyte solution, the particle size of 30,000 particles is adjusted to a concentration that can be measured in 20 seconds, and then 30,000 particles are measured. The volume-median particle size (D ₅₀ ) and the volume average particle size were determined from the distribution.
The CV value (%) was calculated according to the following formula.
CV value (%) = (standard deviation of particle size distribution / volume average particle size) × 100

[Low temperature fixability of toner and low temperature fixability after high temperature storage]
<Low temperature fixability>
Using a commercially available printer “Microline (registered trademark) 5400” (manufactured by Oki Data Co., Ltd.) on high-quality paper “J paper A4 size” (manufactured by Fuji Xerox Co., Ltd.), the toner adhesion amount on the paper is 1.45 to 1. A solid image of .55 mg / cm ² was output without being fixed at a length of 50 mm, leaving a margin of 5 mm from the top edge of A4 paper.
Next, the same printer with a variable temperature fixing device was prepared, the fixing device temperature was set to 90 ° C., and toner was fixed at a speed of 1.2 seconds per sheet in the A4 longitudinal direction to obtain a printed matter.
In the same manner, the temperature of the fixing device was increased by 5 ° C. to fix the toner, and a printed matter was obtained.
From the margin at the top edge of the printed image to the solid image, lightly paste a 50 mm long mending tape “Scotch (registered trademark) mending tape 810” (manufactured by Sumitomo 3M Limited, width 18 mm). After that, a 500 g weight was placed and pressed once back and forth at a speed of 10 mm / s. Thereafter, the affixed tape was peeled off from the lower end side at a peeling angle of 180 ° and a speed of 10 mm / s to obtain a printed matter after peeling off the tape. 30 sheets of high quality paper “Excellent White Paper A4 Size” (made by Oki Data Co., Ltd.) is laid under the printed material before and after the tape is applied, and the reflected image density of the fixed image portion before and after the tape is applied to each printed material. , Using a colorimeter “SpectroEye” (manufactured by GretagMacbeth, light conditions; standard light source D50, observation field of view 2 °, density standard DINNB, absolute white standard), and fixing rate from each reflected image density according to the following formula Was calculated.
Fixing rate (%) = (Reflected image density after peeling tape / Reflected image density before applying tape) × 100
The lowest temperature at which the fixing rate was 90% or higher was defined as the lowest fixing temperature (T ₁ ). The lower the minimum fixing temperature, the better the low temperature fixing property.

<Low temperature fixability after high temperature storage>
After the toner was held in a constant temperature bath at 40 ° C. for 200 hours, the minimum fixing temperature (T ₂ ) was measured by the same method as in the evaluation of the low temperature fixing property. The lower the minimum fixing temperature, the better the low temperature fixing property.

[Toner charging stability]
0.6 g of toner and 19.4 g of a ferrite carrier (ferrite core, silicone coat, saturation magnetization: 71 Am ^{2 /} kg) are placed in a 50 mL polypropylene bottle “PP sampler bottle Hiroguchi” (manufactured by Sampratec Co., Ltd.) and ball milled. After stirring for 20 minutes, 5 g was collected and measured with a charge measuring device “q-test” (manufactured by Epping) under the following measurement conditions.
Toner Flow (ml / min): 160
・ Electrode Voltage (V): 4000
Deposition Time (s): 2
The median q / d was defined as the toner charge amount Q / d (fC / 10 μm). At that time, the Specific Density was 1.2 g / cm ^3, and the median diameter was a value of the volume median particle size (D ₅₀ ) of the toner. The obtained Q / d was connected by a straight line in the range of −0.4 to 0.4 (fC / 10 μm), and a charge amount distribution graph was created.
Evaluation was made by the size of the half-value width of the maximum peak of this charge amount distribution (the width of the cut when the distribution was cut at half the maximum peak height in the distribution). The smaller the value, the narrower the charge amount distribution and the better the charging stability.

[Production of resin]
Production Example A1
(Production of crystalline resin A-1)
The inside of a 10 L four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple was purged with nitrogen, 3133 g of 1,10-decanediol, half amount of 3565 g of sebacic acid (1782.5 g), And 15 g of di (2-ethylhexanoic acid) tin (II). While stirring, the temperature was raised to 135 ° C., and the temperature was raised from 135 ° C. to 160 ° C. over 6 hours. The reaction was performed at 160 ° C., and after confirming that the reaction rate reached 95% or more, a mixed solution of 532 g of styrene, 117 g of stearyl methacrylate, 52 g of acrylic acid and 26 g of dibutyl peroxide was added dropwise over 1 hour. Then, after maintaining at 160 ° C. for 30 minutes, the mixture was cooled to 135 ° C., the remaining amount of sebacic acid (1782.5 g) was added, the temperature was raised to 200 ° C. over 8 hours, the pressure in the flask was lowered, and − Holding at 8 kPa (G) for 2 hours, a crystalline resin A-1 was obtained. The physical properties are shown in Table 1. 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.

Production Examples A2 to A6
(Production of crystalline resins A-2 to A-6)
Crystalline resins A-2 to A-6 were obtained in the same manner as in Production Example A1, except that the raw material composition was changed as shown in Table 1. The physical properties are shown in Table 1.

Production Example A7
(Production of crystalline resin A-7)
The inside of a 10 L four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple was purged with nitrogen, and 3471 g of 1,10-decandiol and 4029 g of sebacic acid were added. While stirring, the temperature was raised to 135 ° C., held at 135 ° C. for 3 hours, and then heated from 135 ° C. to 200 ° C. over 10 hours. Thereafter, 15 g of di (2-ethylhexanoic acid) tin (II) was added, and the mixture was further maintained at 200 ° C. for 1 hour. Resin A-7 was obtained. The physical properties are shown in Table 1.

Production Example B1
(Production of amorphous resin B-1)
The inside of a 10 L four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple was purged with nitrogen, 4940 g of a polyoxypropylene (2.2) adduct of bisphenol A, 1523 g of terephthalic acid, Di (2-ethylhexanoic acid) tin (II) (35 g) and 3,4,5-trihydroxybenzoic acid (3.5 g) were added, and the temperature was raised to 235 ° C. while stirring in a nitrogen atmosphere. After holding for a period of time, the pressure in the flask was lowered and held at -8 kPa (G) for 1 hour. Then, after returning to atmospheric pressure, it cooled to 190 degreeC, fumaric acid 164g, adipic acid 103g, trimellitic anhydride 271g, and 4-tert- butyl catechol 3.5g were added, and 10 degreeC / hr to 210 degreeC. Then, the reaction was carried out at −10 kPa (G) to the desired softening point to obtain amorphous resin B-1. The physical properties are shown in Table 2.

Production Example B2
(Production of amorphous resin B-2)
The inside of a 10 L four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple was purged with nitrogen, and 3458 g of a polyoxypropylene (2.2) adduct of bisphenol A, poly of bisphenol A Add 1376 g of oxyethylene (2.2) adduct, 1640 g of terephthalic acid, 35 g of di (2-ethylhexanoic acid) tin (II), and 3.5 g of 3,4,5-trihydroxybenzoic acid. While stirring, the temperature was raised to 235 ° C. and held at 235 ° C. for 8 hours, and then the pressure in the flask was lowered and held at −8 kPa (G) for 1 hour. Then, after returning to atmospheric pressure, it cooled to 190 degreeC, fumaric acid 164g, trimellitic anhydride 271g, and 4-tert- butyl catechol 3.5g were added, and it heated up at 210 degreeC at 10 degreeC / hr. Thereafter, the reaction was carried out at −10 kPa (G) to the desired softening point to obtain amorphous resin B-2. The physical properties are shown in Table 2.

Production Example C1
(Production of amorphous resin C-1)
The inside of a 10 L four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple was purged with nitrogen, and 4313 g of a polyoxypropylene (2.2) adduct of bisphenol A, 818 g of terephthalic acid, 727 g of succinic acid, 30 g of di (2-ethylhexanoic acid) tin (II), and 3.0 g of 3,4,5-trihydroxybenzoic acid were added, and the temperature was raised to 235 ° C. with stirring in a nitrogen atmosphere. After holding at 235 ° C. for 5 hours, the pressure in the flask was lowered and held at −8 kPa (G) for 1 hour. Then, after returning to atmospheric pressure, the mixture of styrene 2756g, stearyl methacrylate 689g, acrylic acid 142g, and dibutyl peroxide 413g was dripped over 1 hour in the state which cooled to 160 degreeC and was hold | maintained at 160 degreeC. Then, after maintaining at 160 ° C. for 30 minutes, the temperature was raised to 200 ° C., the pressure in the flask was further lowered, and the reaction was carried out to −8 kPa (G) to a desired softening point to produce an amorphous resin C-1. Got. The physical properties are shown in Table 2.

[Production of resin composition]
Production Example D1
(Production of resin composition D-1)
In a 3 L container equipped with a stirrer, reflux condenser, thermometer, and nitrogen inlet tube, 60 g of crystalline resin A-1 in a nitrogen atmosphere, 60 g of methyl ethyl ketone dehydrated with molecular sieves, and di 0.3 g of (2-ethylhexanoic acid) tin (II) was added, the temperature was raised to 80 ° C. while stirring, and the resin was dissolved at 80 ° C. over 30 minutes. To the obtained solution, 2.4 g of isophorone diisocyanate was added as the polyfunctional compound (S) and held at 73 ° C. for 1 hour.
Next, a solution in which 60 g of amorphous resin B-1 was dissolved in 60 g of methyl ethyl ketone was added to the solution, and kept at 73 ° C. for 2 hours to obtain a methyl ethyl ketone solution of resin composition D-1.

Production Example D2
(Production of resin composition D-2)
In Production Example D1, the same procedure as in Production Example D1 was conducted except that a solution obtained by dissolving 60 g of amorphous resin B-1 in 60 g of methyl ethyl ketone was changed to a solution obtained by dissolving 140 g of amorphous resin B-1 in 140 g of methyl ethyl ketone. Thus, a methyl ethyl ketone solution of the resin composition D-2 was obtained.

Production Examples D3 to D9
(Production of resin compositions D-3 to D-9)
Resin compositions D-3 to D-9 in the same manner as in Production Example D1, except that the types of crystalline resin and amorphous resin to be used and the amount of isophorone diisocyanate to be added were changed as shown in Table 3. A methyl ethyl ketone solution was obtained.

[Production of resin particle dispersion]
Production Example E1
(Production of resin particle dispersion E-1)
A solution prepared by dissolving 80 g of amorphous resin B-1 in 80 g of methyl ethyl ketone was added to the total amount of the methyl ethyl ketone solution of the resin composition D-1 obtained in Production Example D1, and the mixture was stirred at 73 ° C. for 1 hour, and further 5 23 g of a mass% aqueous sodium hydroxide solution was added and stirred for 30 minutes.
Next, while maintaining the temperature at 73 ° C., 700 g of deionized water was added over 60 minutes while stirring at 200 r / min (circumferential speed 63 m / min), and phase inversion emulsification was performed. While maintaining the temperature at 73 ° C., methyl ethyl ketone was distilled off under reduced pressure to obtain an aqueous dispersion. Thereafter, the aqueous dispersion is cooled to 30 ° C. while stirring at 280 r / min (circumferential speed 88 m / min), and then deionized water is added so that the solid content concentration becomes 20% by mass, thereby dispersing the resin particles. A liquid E-1 was obtained. Table 4 shows the physical properties.

Production Example E2
(Production of resin particle dispersion E-2)
A solution prepared by dissolving 280 g of amorphous resin B-1 in 280 g of methyl ethyl ketone was added to the total amount of the methyl ethyl ketone solution of the resin composition D-1 obtained in Production Example D1, and the mixture was stirred at 73 ° C. for 1 hour, and further 5 48 g of a mass% aqueous sodium hydroxide solution was added and stirred for 30 minutes.
Next, while maintaining the temperature at 73 ° C., 700 g of deionized water was added over 60 minutes while stirring at 200 r / min (circumferential speed 63 m / min), and phase inversion emulsification was performed. While maintaining the temperature at 73 ° C., methyl ethyl ketone was distilled off under reduced pressure to obtain an aqueous dispersion. Thereafter, the aqueous dispersion is cooled to 30 ° C. while stirring at 280 r / min (circumferential speed 88 m / min), and then deionized water is added so that the solid content concentration becomes 20% by mass, thereby dispersing the resin particles. Liquid E-2 was obtained. Table 4 shows the physical properties.

Production Example E3
(Production of resin particle dispersion E-3)
23 g of 5% by mass aqueous sodium hydroxide solution was added to the total amount of the methyl ethyl ketone solution of the resin composition D-2 obtained in Production Example D2, and the mixture was stirred at 73 ° C. for 30 minutes.
Next, while maintaining the temperature at 73 ° C., 700 g of deionized water was added over 60 minutes while stirring at 200 r / min (circumferential speed 63 m / min), and phase inversion emulsification was performed. While maintaining the temperature at 73 ° C., methyl ethyl ketone was distilled off under reduced pressure to obtain an aqueous dispersion. Thereafter, the aqueous dispersion is cooled to 30 ° C. while stirring at 280 r / min (circumferential speed 88 m / min), and then deionized water is added so that the solid content concentration becomes 20% by mass, thereby dispersing the resin particles. Liquid E-3 was obtained. Table 4 shows the physical properties.

Production Examples E4 to E9, E11
(Production of resin particle dispersions E-4 to E-9, E-11)
Resin particle dispersions E-4 to E-9 and E-11 were obtained in the same manner as in Production Example E1, except that the types of the resin composition and the amorphous resin were changed as shown in Table 4. Table 4 shows the physical properties.

Production Example E10
(Production of resin particle dispersion E-10)
In a 3 L vessel equipped with a stirrer, reflux condenser, thermometer and nitrogen inlet tube, under a nitrogen atmosphere, 60 g of crystalline resin A-1, 140 g of amorphous resin B-1 and 200 g of methyl ethyl ketone The resin was dissolved for 2 hours at 73 ° C. with stirring. 27 g of 5% by mass aqueous sodium hydroxide was added to the resulting solution and stirred for 30 minutes.
Next, while maintaining at 73 ° C., 600 g of deionized water was added over 60 minutes while stirring at 200 r / min (circumferential speed 63 m / min), and phase inversion emulsification was performed. While maintaining the temperature at 73 ° C., methyl ethyl ketone was distilled off under reduced pressure to obtain an aqueous dispersion. Thereafter, the aqueous dispersion is cooled to 30 ° C. while stirring at 280 r / min (circumferential speed 88 m / min), and then deionized water is added so that the solid content concentration becomes 20% by mass, thereby dispersing the resin particles. A liquid E-10 was obtained. Table 4 shows the physical properties.

Production Example F1
(Production of resin particle dispersion F-1)
200 g of amorphous resin C-1 and 200 g of methyl ethyl ketone were placed in a 3 L container equipped with a stirrer, reflux condenser, dropping funnel, thermometer and nitrogen inlet tube, and the resin was added at 73 ° C. for 2 hours. Was dissolved. 41 g of 5 mass% sodium hydroxide aqueous solution was added to the obtained solution, and it stirred for 30 minutes.
Next, while maintaining at 73 ° C., 700 g of deionized water was added over 50 minutes while stirring at 200 r / min (peripheral speed 63 m / min), and phase inversion emulsification was performed. While maintaining the temperature at 73 ° C., methyl ethyl ketone was distilled off under reduced pressure to obtain an aqueous dispersion. Thereafter, the aqueous dispersion is cooled to 30 ° C. while stirring at 280 r / min (circumferential speed 88 m / min), and then deionized water is added so that the solid content concentration becomes 20% by mass, thereby dispersing the resin particles. A liquid F-1 was obtained. The volume median particle size (D ₅₀ ) of the resin particles in the dispersion was 0.09 μm, and the CV value was 23%.

[Production of wax particle dispersion]
Production Example G1
(Production of Wax Particle Dispersion G-1)
120 g of deionized water, 86 g of resin particle dispersion F-1 and 40 g of paraffin wax “HNP-9” (manufactured by Nippon Seiki Co., Ltd., melting point 75 ° C.) are added to a beaker having an internal volume of 1 L, and 90 to 95 ° C. The mixture was melted while maintaining the temperature and stirred to obtain a molten mixture.
The obtained molten mixture was further dispersed for 20 minutes using an ultrasonic homogenizer “US-600T” (manufactured by Nippon Seiki Seisakusyo Co., Ltd.) while maintaining the temperature at 90 to 95 ° C. to room temperature (25 ° C.). Cooled down. Deionized water was added to adjust the solid content concentration to 20% by mass to obtain a wax particle dispersion G-1. The volume median particle size (D ₅₀ ) of the wax particles in the dispersion was 0.47 μm, and the CV value was 27%.

[Production of Colorant Particle Dispersion]
Production Example H1
(Production of colorant particle dispersion H-1)
In a beaker with an internal volume of 1 L, 150 g of copper phthalocyanine pigment “ECB-301” (manufactured by Dainichi Seika Kogyo Co., Ltd.), anionic surfactant “Neopelex (registered trademark) G-15” (manufactured by Kao Corporation, 15 mass) % Sodium dodecylbenzenesulfonate aqueous solution) and 257 g of deionized water were mixed and dispersed for 10 hours at room temperature using an ultrasonic homogenizer “US-600T” (manufactured by Nippon Seiki Seisakusho Co., Ltd.). Colorant dispersion H-1 was obtained by adding deionized water to a concentration of 24% by mass. The volume median particle size (D ₅₀ ) of the colorant particles in the dispersion was 0.10 μm.

[Production of toner]
Example 1
(Preparation of Toner 1)
Into a 3 L four-necked flask equipped with a dehydrating tube, a stirrer and a thermocouple, 300 g of resin particle dispersion E-1, 30 g of wax particle dispersion G-1, and colorant particle dispersion H-1 30 g and 9 g of a 10% by mass aqueous solution of a nonionic surfactant “Emulgen (registered trademark) 150” (manufactured by Kao Corporation, polyoxyethylene (average added mole number: 50) lauryl ether) were mixed at a temperature of 25 ° C. Next, while stirring the mixture, a solution adjusted to pH 8.5 by adding 20 g of a 4.8 mass% potassium hydroxide aqueous solution to an aqueous solution in which 19 g of ammonium sulfate was dissolved in 187 g of deionized water was added at 25 ° C. for 5 minutes. After dropping, the temperature is raised to 63 ° C. over 2 hours, and the aggregated particles (1) are dispersed by holding at 63 ° C. until the volume median particle size (D ₅₀ ) of the aggregated particles becomes 5.6 μm. A liquid was obtained.
10 g of anionic surfactant “Emar (registered trademark) E-27C” (manufactured by Kao Corporation, sodium polyoxyethylene lauryl ether sulfate, effective concentration: 27 mass%), deionized in the dispersion of the aggregated particles (1) An aqueous solution in which 900 g of water and 30 g of 0.1 mol / L sulfuric acid were mixed was added. Then, after heating up to 83 degreeC over 1 hour, it hold | maintained at 83 degreeC until circularity became 0.975, and the dispersion liquid of the fused particle which the aggregated particle fused was obtained. The obtained fused particle dispersion was cooled to 30 ° C., and the dispersion was subjected to suction filtration to separate the solid content, then washed with deionized water at 25 ° C., and suction filtered at 25 ° C. for 2 hours. Thereafter, using a vacuum constant temperature dryer “DRV622DA” (manufactured by ADVANTEC), vacuum drying was performed at 33 ° C. for 48 hours to obtain toner mother particles. Table 5 shows the physical properties of the obtained toner mother particles.
100 parts by mass of the toner base particles, 2.5 parts by mass of hydrophobic silica “RY50” (manufactured by Nippon Aerosil Co., Ltd., number average particle size: 0.04 μm), and hydrophobic silica “Cabosil® TS720” (Cabot) Toner 1 was obtained by putting 1.0 part by mass of Japan Co., Ltd. (number average particle size; 0.012 μm) into a Henschel mixer and stirring, and passing through a 150-mesh sieve. Table 5 shows the evaluation results of the obtained toner 1.

Examples 2 to 9, Comparative Examples 1 and 2
(Production of toners 2-9, 11, 12)
A toner was prepared in the same manner as in Example 1 except that the type of resin particle dispersion used was changed as shown in Table 5. Table 5 shows the physical properties of the obtained toner base particles and the evaluation results of the toner.

Example 10
(Production of Toner 10)
The methyl ethyl ketone solution of the resin composition D-1 was kept at 80 ° C., and the methyl ethyl ketone was distilled off under reduced pressure to obtain a resin composition D-1.
In a Henschel mixer, 60 parts by mass of resin composition D-1, 40 parts by mass of amorphous resin B-1, copper phthalocyanine pigment “ECB-301” (manufactured by Dainichi Seika Kogyo Co., Ltd.), 10 parts by mass, paraffin wax After adding 6 parts by mass of “HNP-9” (manufactured by Nippon Seiwa Co., Ltd., melting point 75 ° C.) and mixing for 5 minutes, the same direction twin screw extruder PCM-30 (Ikegai Co., Ltd., shaft diameter 2) 9.9 cm, shaft cross-sectional area of 7.06 cm ² ), melt kneading at a roll rotation speed of 200 r / min, a heating temperature in the roll of 70 ° C., and a mixture supply temperature of 10 kg / h. The obtained melt-kneaded product was cooled and coarsely pulverized, then pulverized with a jet mill and classified to obtain toner mother particles. Table 5 shows the physical properties of the obtained toner mother particles.
100 parts by mass of the toner base particles, 2.5 parts by mass of hydrophobic silica “RY50” (manufactured by Nippon Aerosil Co., Ltd., number average particle size: 0.04 μm), and hydrophobic silica “Cabosil® TS720” (Cabot) Toner 10 was obtained by putting 1.0 part by mass of Japan Corporation, number average particle size; 0.012 μm) into a Henschel mixer, stirring, and passing through a 150 mesh sieve. Table 5 shows the evaluation results of the toner.

From Table 5, it can be seen that the toners of Examples 1 to 10 have excellent low-temperature fixability, good low-temperature fixability after high-temperature storage, and excellent charging stability as compared with the toners of Comparative Examples 1 and 2. Recognize.
Moreover, it turns out that Example 1-9 which is the toner manufactured using the emulsion aggregation method among Examples 1-10 is excellent in charging stability.

Claims (16)

  A resin composition (D) containing a reaction product obtained by a reaction in which at least a part of a crystalline resin (A) having a vinyl resin segment and a polyester segment and an amorphous resin (B) are chemically bonded. A toner for developing electrostatic images.   The electrostatic image developing toner according to claim 1, wherein a polyfunctional compound (S) is used in the reaction. The electrostatic image developing toner according to claim 2, wherein the resin composition (D) is obtained by the following steps (1-1) and (1-2).
Step (1-1): introducing a functional group with a polyfunctional compound (S) into one resin (i) selected from the group X consisting of the crystalline resin (A) and the amorphous resin (B). The process of obtaining a reaction intermediate by this process (1-2): The process of reacting the said reaction intermediate and resin (ii) different from the said resin (i) chosen from the said group X   The electrostatic image developing toner according to claim 2, wherein the polyfunctional compound (S) is a polyisocyanate compound.   The crystalline resin (A) has a hydroxyl value of 3 mgKOH / g or more and 35 mgKOH / g or less, and the amorphous resin (B) has a hydroxyl value of 4 mgKOH / g or more and 40 mgKOH / g or less. The toner for developing an electrostatic image according to any one of 1 to 4.   The toner for developing an electrostatic charge image according to claim 1, wherein the crystalline resin (A) has a component derived from a bireactive monomer.   The toner for developing an electrostatic charge image according to claim 1, wherein the vinyl resin segment has a component derived from a vinyl monomer having a hydrocarbon group.   The total amount of the crystalline resin (A) used is 5% by mass or more and 45% by mass or less based on the total of the crystalline resin (A) and the amorphous resin (B) in the toner. The toner for developing an electrostatic charge image according to any one of?   The electrostatic image developing toner according to claim 1, wherein the polyester segment is a crystalline polyester.   The electrostatic image developing toner according to claim 1, wherein the amorphous resin (B) is an amorphous polyester.   A resin composition comprising a reaction product obtained by a reaction in which at least a part of a crystalline resin (A) having a vinyl resin segment and a polyester segment and an amorphous resin (B) are chemically bonded.   A resin composition (D) containing a reaction product obtained by a reaction in which at least a part of a crystalline resin (A) having a vinyl resin segment and a polyester segment and an amorphous resin (B) are chemically bonded. And a method for producing a toner for developing an electrostatic image. A method for producing a toner for developing an electrostatic charge image, comprising the following steps (1) to (4).
Step (1): including a reaction product obtained by a reaction in which a crystalline resin (A) having a vinyl resin segment and a polyester segment and an amorphous resin (B) are chemically bonded at least partially. Step of obtaining resin composition (D) Step (2): Step of obtaining a dispersion of resin particles (E) by dispersing the resin composition (D) obtained in step (1) in an aqueous medium. 3): Step of aggregating the resin particles (E) obtained in step (2) in an aqueous medium to obtain aggregated particles Step (4): Step of fusing the aggregated particles obtained in step (3)   The method for producing a toner for developing an electrostatic charge image according to claim 13, wherein the polyfunctional compound (S) is used in the reaction of the step (1). The method for producing a toner for developing an electrostatic charge image according to claim 13 or 14, wherein the step (1) is the following steps (1-1) and (1-2).
Step (1-1): introducing a functional group with a polyfunctional compound (S) into one resin (i) selected from the group X consisting of the crystalline resin (A) and the amorphous resin (B). The process of obtaining a reactive intermediate by this process (1-2): The process with which the said reactive intermediate and resin (ii) different from the said resin (i) chosen from the said group X are made to react.   The step (2) is a step in which, after the step (1) is performed in an organic solvent, an aqueous medium is added to perform phase inversion emulsification to obtain a resin particle dispersion. A method for producing a toner for developing electrostatic images.