JP6777282B2 - Toner for static charge image development - Google Patents

Description

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

In the field of electrophotographic, with the development of electrophotographic systems, there is a demand for the development of toner for static charge image development corresponding to high image quality and high speed. 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 the amorphous resin conventionally used as a binder resin. Further, in order to improve the basic characteristics of the toner such as storage stability, it is being studied to give the resin a specific structure.

For example, Patent Document 1 describes a toner binder containing a non-crystalline polyester resin, a crystalline polyester resin composed of only a crystalline portion, and a block resin composed of a crystalline portion and a non-crystalline portion. The toner composition is disclosed, and it is described that both low temperature fixability and hot offset resistance can be achieved, and that the toner composition is excellent in storage stability and charge stability.
Further, Patent Document 2 describes 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 block copolymer resin contains 50 mol% or more of an aliphatic diol and further contains a trivalent or higher valent aliphatic alcohol or acid as a cross-linking component, and the block copolymer resin is composed of a crystalline segment and an amorphous segment, and the difference between the toners. An image-forming toner characterized in that the glass transition temperature (Tg1st) of the first temperature rise by scanning calorimetry (DSC) is 20 ° C. or higher and 50 ° C. or lower is disclosed, and has excellent low-temperature fixability and fixing width. It is described that the toner has a wide range, has both heat and storage stability, and has excellent abrasion resistance.
Further, Patent Document 3 includes resin particles containing crystalline polyester having a polyester portion obtained by using a monomer having a molar average carbon number of 8 to 12, a polyester segment, and an addition polymerization resin segment. In the addition polymerization resin segment, an agglomerate X containing 3% by mass or more and 15% by mass or less of resin particles containing an amorphous composite resin containing a component derived from both reactive monomers is obtained in an aqueous medium. It has a step I and a step II of fusing the aggregate X, and the mass ratio of the crystalline polyester to the amorphous composite resin (crystalline polyester / amorphous composite resin) is 1/99 to 40 /. A method for producing a static charge image developing toner, which is 60, is disclosed, and it is described that a static charge image developing toner that achieves both low-temperature fixability and heat-resistant storage stability and is excellent in bending resistance of the obtained printed matter can be produced. ing.

JP-A-2015-42737 JP-A-2015-79240 Japanese Unexamined Patent Publication No. 2014-235409

However, it has been found that even if a crystalline resin is mixed with a binder resin to improve the low-temperature fixability of the toner, there is a problem that the low-temperature fixability is lowered during high-temperature storage. Further, the conventional techniques such as giving a specific structure to a resin, which has been studied to improve the basic characteristics of toner such as storage stability, are insufficient to suppress a decrease in low temperature fixability during high temperature storage. I've come to understand.
Therefore, the present invention provides a toner for electrostatic charge image development, which is excellent in low-temperature fixability, good low-temperature fixability after high-temperature storage, and also excellent in charge stability, a resin composition from which the toner can be obtained, and its production. The challenge is to provide a method.

The present inventors have considered that the factor affecting the characteristics of the toner using the crystalline resin is the dispersed state of the crystalline resin in the toner particles. As a result, the toner contains a resin composition containing a reaction product obtained by chemically bonding at least a part of the amorphous resin and the crystalline resin having a vinyl resin segment and a polyester segment. It has been found that a toner for electrostatic charge image development, which is excellent in low-temperature fixability, good low-temperature fixability after high-temperature storage, and also excellent in charge stability, can be obtained.

That is, the present invention relates to the following [1] to [3].
[1] A resin composition containing a reaction product obtained by chemically bonding at least a part of a crystalline resin (A) having a vinyl-based resin segment and a polyester segment and an amorphous resin (B). A toner for developing an electrostatic charge image, which contains a substance (D).
[2] A resin composition containing a reaction product obtained by chemically bonding at least a part of a crystalline resin (A) having a vinyl-based resin segment and a polyester segment and an amorphous resin (B). Stuff.
[3] A resin composition containing a reaction product obtained by chemically bonding at least a part of a crystalline resin (A) having a vinyl-based resin segment and a polyester segment and an amorphous resin (B). A method for producing a toner for developing an electrostatic charge image, which comprises a step of obtaining a product (D).

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

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

The reason why the toner for static charge image development of the present invention is excellent in low-temperature fixability, good low-temperature fixability after high-temperature storage, and further excellent in charge stability is not clear, but it is considered as follows.
Since the crystalline resin in the toner does not necessarily have good compatibility with the resin components constituting other binder resins, even if the crystalline resin is sufficiently finely dispersed in the toner mother particles during the manufacture of the toner, the toner The size of the crystal domain cannot be fixed during storage after production, and the size of the crystal domain tends to gradually increase as the crystallization progresses. As a result, the interface between the crystalline resin and the other binder resin is relatively reduced, and it becomes difficult for the surrounding amorphous resin to melt as the crystalline resin melts when the toner is fixed. It is thought that it will decrease.

In the resin composition (D), a crystalline resin (A), an amorphous resin (B), a polyester segment end of the crystalline resin (A), and an amorphous resin (B) end are chemically formed. It is considered that the block resin (AB) bound to is contained. The block resin (AB) forms a block structure in which the polyester segment of the crystalline resin (A) and the amorphous resin segment are connected.
When the crystalline resin (A) having the vinyl resin segment and the polyester segment is mixed with the amorphous resin (B) to form a microhydrophobic field, in the present invention, the non-crystalline resin (AB) is interposed. It is mixed with the crystalline resin (B). Since the block resin (AB) enters both the domain of the crystalline resin and the matrix of the amorphous resin component, the crystalline resin domain is finely dispersed and then substantially bonded to the amorphous resin component. Can be maintained 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 also good.
In addition, since the finely dispersed crystalline resin domain has a structure in which the amorphous resin is encapsulated, the highly hydrophobic crystalline resin domain is exposed on the surface of the toner mother particle and is removed from the toner mother particle. Since the separation is also suppressed, it is considered that the charge amount distribution of the toner is narrowed and the charge stability is improved.
Hereinafter, the constituent components of the toner for developing an electrostatic charge image of the present invention will be described.

<Crystalline resin (A)>
The crystalline resin (A) has a vinyl-based 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 of the softening point of the resin to the maximum endothermic peak temperature (softening point (° C.) / maximum endothermic peak temperature (° C.)) in the measurement method described in Examples described later. The crystalline resin has a crystallinity index of 0.6 or more and 1.4 or less.
The crystallinity index of the crystalline resin (A) is 0.6 or more and 1.4 or less, and a toner having excellent low-temperature fixability, good low-temperature fixability after high-temperature storage, and excellent charge stability can be obtained. 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 depending on the type and ratio of the raw material monomers, and the production conditions such as reaction temperature, reaction time, and cooling rate.
The crystalline resin (A) preferably has a constituent portion derived from both reactive monomers capable of reacting with both the vinyl resin segment and the polyester segment.

[Vinyl resin segment]
The vinyl-based 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 a unit. The vinyl-based resin segment more preferably further contains a structural unit derived from a styrene-based 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. Above, more preferably 6 or more, still more preferably 8 or more, even more preferably 10 or more, even more preferably 12 or more, even more preferably 14 or more, and preferably 22 or less, more preferably 20 or less. More preferably, it is 18 or less.
When the vinyl-based resin segment has a hydrophobic hydrocarbon group, it is considered that the highly hydrophobic crystalline resin is easily dispersed 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.
As the vinyl monomer having a hydrocarbon group, an alkyl ester of (meth) acrylic acid is preferable, and an alkyl (meth) acrylic acid is more preferable, from the viewpoint of availability and reactivity. In the case of alkyl esters 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 -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 , (Meta) acrylic acid (iso) stearyl, (meth) acrylic acid (iso) behenyl and the like, 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) acrylic acid (iso) decyl, (meth) acrylic acid (iso) lauryl, ( Meta) acrylic acid (iso) stearyl, more preferably (meth) acrylic acid (iso) lauryl, (meth) acrylic acid (iso) stearyl, and even more preferably (meth) acrylic acid (iso) stearyl.
Here, "alkyl (meth) acrylate" means alkyl acrylate or alkyl methacrylate. Further, with respect to the alkyl moiety, "(iso)" 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 low temperature fixability after high temperature storage, and further excellent 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, still more preferably 40% by mass. It is mass% or less.

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 and the like. Specific examples thereof include styrenes such as styrene, methylstyrene, α-methylstyrene, β-methylstyrene, t-butylstyrene, chlorostyrene, chloromethylstyrene, methoxystyrene, styrenesulfonic acid or salts thereof, which are preferable. Contains styrene, more preferably styrene.
The content of the structural unit derived from the styrene-based compound in the vinyl-based resin segment is 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. Is 50% by mass or more, more preferably 55% by mass or more, still more 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, raw material vinyl monomers that can be used for vinyl-based resin segments include ethylenically unsaturated monoolefins such as ethylene and propylene; conjugated dienes such as butadiene; halovinyls such as vinyl chloride; vinyl acetate and vinyl propionate. Vinyl esters such as; (meth) acrylic acid aminoalkyl esters such as (meth) dimethylaminoethyl acrylate; vinyl ethers such as methyl vinyl ether; vinylidene halides such as vinylidene chloride; N-vinyl such as N-vinylpyrrolidone. Examples include compounds.

The raw material vinyl monomer, which is a component derived from the vinyl-based resin segment, has excellent low-temperature fixability, good low-temperature fixability after high-temperature storage, and also has excellent charge stability. From the viewpoint of obtaining a toner, the carbon number is 4 or more and 22. The combined use of the following vinyl monomer having a hydrocarbon group and a styrene compound is preferable, and the combined use of an alkyl ester of (meth) acrylic acid having an alkyl group having 4 or more and 22 or less 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 in the vinyl resin segment and the structural unit derived from the styrene compound [carbonation] [Constituent unit derived from vinyl monomer having a hydrogen group / Structural unit derived from styrene compound] is excellent in low-temperature fixability, good low-temperature fixability after high-temperature storage, and further excellent in 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 constituent units derived from the vinyl monomer having a hydrocarbon group and the constituent units derived from the styrene compound in the vinyl-based resin segment is excellent in low-temperature fixability and also good in 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, further preferably 95% by mass or more, and 100% by mass or less, even more preferably. Is 100% by mass.

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

(Multivalent 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. 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, still more preferably 95 mol% or more in the polyhydric alcohol component. Yes, and less than 100 mol%, even more preferably 100 mol%.

The carbon number of 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 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, and 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. Can be mentioned. Among these, ethylene glycol, 1,6-hexanediol, and 1,9-nonane are excellent in low-temperature fixability, good low-temperature fixability after high-temperature storage, and excellent charge stability. Diol, 1,10-decanediol and 1,12-dodecanediol are preferable, 1,6-hexanediol, 1,10-decanediol and 1,12-dodecanediol are more preferable, and 1,10-decanediol is further preferable. preferable.

The polyhydric alcohol component (a-al) may contain a polyhydric alcohol component other than 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 and the like. Examples thereof include alcohols having a trivalent value or higher.
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) contains 80 mol of an aliphatic dicarboxylic acid 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 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, still more preferably 95 mol% or more in the polyvalent carboxylic acid component (a-ac). % Or more and 100 mol% or less, even more preferably 100 mol%.

The carbon number 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. , More preferably 8 or more, even 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 free acids, but also anhydrides that decompose to produce acids during the reaction, and alkyl esters 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 (COOH group / OH group) of the polyvalent carboxylic acid component to the polyhydric alcohol component is preferably 0.7 or more, more preferably 0.8 or more, and further, from the viewpoint of obtaining a crystalline resin having desired physical properties. It is preferably 0.9 or more, preferably 1.3 or less, more preferably 1.2 or less, and even more preferably 1.1 or less.

(Bi-reactive monomer)
The crystalline resin (A) preferably has components derived from both reactive monomers. When a bireactive monomer is used as the raw material monomer of the crystalline resin (A), the bireactive 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). It is preferable that the structural unit derived from the bireactive monomer serves as a bonding point between the vinyl resin segment and the polyester segment.
Examples of the bireactive monomer include a vinyl monomer 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 reactivity of both the polycondensation reaction and the addition polymerization reaction.

The constituent components derived from both reactive monomers are polyester segments from the viewpoint of improving the dispersibility of the crystalline resin (A) in the amorphous resin (B) and from the viewpoint of controlling the reaction of the addition polymerization reaction and the polycondensation reaction. With respect to 100 mol parts of the total amount of the polyhydric alcohol component which is the raw material of, preferably 0.5 mol part or more, more preferably 1 mol part or more, further preferably 3 mol part or more, and preferably 30 mol part or more. Below, it is more preferably 20 mol parts or less, still more preferably 15 mol parts or less. When both reactive monomers are used and the content of each segment in the crystalline resin (A) is calculated, the structural units derived from the bireactive monomers are included in the constituent units of the polyester segment. It is calculated as being.

The content of the polyester segment in the crystalline resin (A) is preferably 60 mass 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, still more 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. It is more preferably 70% by mass or more, and preferably 97% by mass or less, more preferably 95% by mass or less, still more preferably 92% by mass or less.
Further, the content of the vinyl-based resin segment in the crystalline resin (A) is excellent in low-temperature fixability, good low-temperature fixability after high-temperature storage, and further excellent in charge stability from the viewpoint of obtaining a toner. It is preferably 3% by mass or more, more preferably 5% by mass or more, further preferably 8% by mass or more, and preferably 40% by mass or less, more preferably 35% by mass or less, still more preferably 30% by 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. As mentioned above, it is more preferably 8% by mass or more, and preferably 40% by mass or less, more preferably 35% by mass or less, still more preferably 30% by mass or less.
Further, the total content of the polyester segment and the vinyl resin segment in the crystalline resin (A) is excellent in low-temperature fixability, good low-temperature fixability after high-temperature storage, and further excellent in charge stability. From the viewpoint of obtaining, 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 100% by mass or less, preferably 100% by mass or less. It is 99% by mass or less, more preferably 97% by mass or less, still more preferably 96% by mass or less.

[Physical properties of crystalline resin (A)]
The softening point of the crystalline resin (A) is preferably 60 ° C. or higher, 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 higher, more preferably 50 ° 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. 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), excellent in low-temperature fixability, good low-temperature fixability after high-temperature storage, and further excellent in charge stability. It is 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.

The hydroxyl value of the crystalline resin (A) is from the viewpoint of producing a block resin (AB), excellent in low-temperature fixability, good low-temperature fixability after high-temperature storage, and further excellent in charge stability. It is 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), which is excellent in low-temperature fixability and also good low-temperature fixability after high-temperature storage. From the viewpoint of obtaining a toner further excellent in 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 type and ratio of the raw material monomers, and the production conditions such as reaction temperature, reaction time, and cooling rate. Those values are obtained by the method described in Examples described later. When two or more kinds of crystalline resins are used in combination, it is preferable that the softening point, melting point, acid value, and hydroxyl value obtained as a mixture thereof are within the above ranges.

[Manufacturing of crystalline resin (A)]
The method for producing the crystalline resin (A) is not particularly limited, and examples thereof include the following methods (i) to (iii).
(I) Method of performing an addition polymerization reaction with a raw material monomer of a vinyl resin segment and a bireactive monomer 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, catalysts such as an esterification catalyst and an esterification co-catalyst may be used, and a radical polymerization initiator and a radical polymerization inhibitor may be used.
From the viewpoint of further advancing the polycondensation reaction and, if necessary, the reaction with the bireactive monomer, the polyvalent carboxylic acid component is partially subjected to the polycondensation reaction, and then the reaction temperature is raised again after the addition polymerization reaction. It is preferable to add the balance to the reaction system.

It can also be produced by the following method (ii) or (iii).
(Ii) Method of performing polycondensation reaction with raw material monomer of polyester segment after addition polymerization reaction with raw material monomer of vinyl resin segment and bireactive monomer (iii) Polycondensation with polyvalent alcohol component and polyvalent carboxylic acid component Method of performing the reaction and the addition polymerization reaction using the raw material monomer of the vinyl resin segment and the bireactive monomer in parallel The polycondensation reaction and the addition polymerization reaction of the methods (i) to (iii) above are all in the same container. It is preferable to carry out in-house.
The crystalline resin (A) is preferably produced by the method of (i) above because it has a high degree of freedom in the reaction temperature of the polycondensation reaction.

From the viewpoint of productivity of the crystalline resin (A), the temperature of the polycondensation reaction is preferably 120 ° C. or higher, more preferably 140 ° C. or higher, further preferably 150 ° C. or higher, and preferably 230 ° C. or lower. It is more preferably 220 ° C. or lower, still more preferably 200 ° C. or lower.
Examples of the esterification catalyst preferably used for the polycondensation reaction include tin compounds such as dibutyltin oxide and tin (II) di (2-ethylhexanoic acid), and titanium compounds such as titanium diisopropyrate bistriethanolamine. Can be mentioned. Among these, a tin compound is preferable, and di (2-ethylhexanoic acid) tin (II) is more preferable.
From the viewpoint of reactivity, the amount of the esterification catalyst used is preferably 0.01 part by mass or more, more preferably 0.1 part by mass, based on 100 parts by mass of the total amount of the polyhydric alcohol component and the polyvalent carboxylic acid component. It is 5 parts by mass or less, and more preferably 2 parts by mass or less.
Pyrogallol compounds such as pyrogallol, gallic acid (same as 3,4,5-trihydroxybenzoic acid), and gallic acid esters; 2,3,4-trihydroxybenzophenone, 2,2', as the esterification co-catalyst Benzophenone derivatives such as 3,4-tetrahydroxybenzophenone; catechin derivatives such as epigallocatechin and epigallocatechin gallate are mentioned, and gallic acid is preferable from the viewpoint of reactivity.
As the radical polymerization inhibitor in the polycondensation reaction, 4-tert-butylcatechol or the like can be used.

The temperature of the addition polymerization reaction varies depending on the type of radical polymerization initiator used and the like, but from the viewpoint of the productivity of the crystalline resin (A), it is preferably 110 ° C. or higher, more preferably 130 ° C. or higher, and It is preferably 220 ° C. or lower, more preferably 200 ° C. or lower.
Further, 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 the addition polymerization reaction include peroxides such as dibutyl peroxide, persulfates such as sodium persulfate, and azo compounds such as 2,2'-azobis (2,4-dimethylvaleronitrile). The radical polymerization initiator of the above 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. It is preferably 15 parts by mass or less.

<Amorphous resin (B)>
The amorphous resin (B) is preferably a resin having a functional group at the end, and obtains a toner having 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 the above-mentioned crystallinity index of more than 1.4 or less than 0.6.
Amorphous polyester is obtained by polycondensing a polyhydric alcohol component (bal) and a polyvalent carboxylic acid component (b-ac).

(Multivalent alcohol component (bal))
The polyhydric alcohol component (bal) is an alkylene oxide adduct of bisphenol A from the viewpoint of obtaining a toner having excellent low-temperature fixability, good low-temperature fixability after high-temperature storage, and excellent charge stability. Those containing 80 mol% or more are 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, still more preferably 95 mol% or more. , More preferably 98 mol% or more, and even more preferably 100 mol% or less, even more preferably 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-). It is at least one selected from 2,2-bis (4-hydroxyphenyl) propane), and more preferably a propylene oxide adduct of bisphenol A.

The average number of moles of alkylene oxide adduct 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 even more preferably 4 or less.

The polyhydric alcohol component (b-al) may contain a polyhydric alcohol other than the alkylene oxide adduct of bisphenol A. Other polyhydric alcohol components that can be contained in the polyhydric alcohol component (bal) include aliphatic diols, aromatic diols, alicyclic diols, trihydric or higher polyhydric alcohols, or their carbon atoms of 2 or more and 4 or more. Examples thereof include the following alkylene oxide (average addition molar number 1 or more and 16 or less) adducts. 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 An aliphatic diol such as dodecanediol; an aromatic diol such as bisphenol A (2,2-bis (4-hydroxyphenyl) propane); hydrogenated bisphenol A (2,2-bis (4-hydroxycyclohexyl) propane) and the like. Alicyclic diols, or alkylene oxides having 2 or more and 4 or less carbon atoms (average addition molars of 2 or more and 12 or less); trivalent or higher polyvalent alcohols such as glycerin, pentaerythritol, trimethylolpropane, and sorbitol. , Or an alkylene oxide (average addition molar number 1 or more and 16 or less) adduct having 2 or more and 4 or less carbon atoms thereof.
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 or more and 3 or less carbon atoms thereof. Among these, a dicarboxylic acid is preferable, and it is more preferable to use a dicarboxylic acid and a polyvalent carboxylic acid having a trivalent or higher valence 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 free acids, but also anhydrides that decompose to produce acids during the reaction, and alkyl esters 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.
From the viewpoint of availability and reactivity, the aliphatic dicarboxylic acid preferably has 2 or more carbon atoms, more preferably 3 or more carbon atoms, and preferably 30 or less, more preferably 20 or less carbon atoms.

Examples of aliphatic dicarboxylic acids having 2 or more and 30 or less carbon atoms include oxalic acid, malonic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, succinic acid, adipic acid, sebacic acid, and dodecanedioic acid. Examples thereof 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, good 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, and octenyl succinic acid.
Among these, terephthalic acid, adipic acid, and fumaric acid are preferable, and they are combined 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 more preferable to use it.
The content of the dicarboxylic acid is preferably 80 mol% or more, more preferably 85 mol% or more, still more preferably 87 mol% or more, and preferably 97 mol% or more in the polyvalent carboxylic acid component (b-ac). % Or less, more preferably 95 mol% or less.

As the trivalent or higher valent carboxylic acid, a trivalent carboxylic acid is preferable, a trimellitic acid or an anhydride thereof is more preferable, and a trimellitic anhydride is further preferable, from the viewpoint of reaction control.
Further, when a polyvalent carboxylic acid having a valence of 3 or more is contained, the content thereof is excellent in low-temperature fixability, good low-temperature fixability after high-temperature storage, and further excellent in charge stability from the viewpoint of obtaining a toner. Among the polyvalent carboxylic acid components, it is preferably 3 mol% or more, more preferably 5 mol% or more, and preferably 20 mol% or less, more preferably 15 mol% or less, still more preferably 13 mol% or less. ..
These polyvalent carboxylic acid components can be used alone or in combination of two or more.

The equivalent ratio of the polyvalent carboxylic acid component to the polyhydric alcohol component (COOH group / OH group) is excellent in low-temperature fixability, good low-temperature fixability after high-temperature storage, and further excellent 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. It is preferably 90 ° C. or higher, more preferably 100 ° C. or higher, and preferably 140 ° C. or lower, more preferably 130 ° C. or lower.

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. It is more preferably 40 ° C. or higher, further preferably 50 ° C. or higher, and preferably 70 ° C. or lower, more preferably 65 ° C. or lower, still more preferably 60 ° C. or lower.

The acid value of the amorphous resin (B) is from the viewpoint of obtaining a toner that produces a block resin (AB), has excellent low-temperature fixability, has good low-temperature fixability after high-temperature storage, and has excellent charge stability. Therefore, it is preferably 5 mgKOH / g or more, more preferably 10 mgKOH / g or more, still more 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), which is excellent in low-temperature fixability, good low-temperature fixability after high-temperature storage, and further excellent in 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 depending on the type and ratio of the raw material monomers and the production conditions such as reaction temperature, reaction time and cooling rate. , And those values are determined by the method described in the examples.
When two or more amorphous resins (B) are used in combination, it is preferable that the softening point, the glass transition temperature and the acid value obtained as a mixture thereof are within the above ranges.

[Manufacturing 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. It can be produced by polycondensation using an esterification catalyst, an esterification auxiliary catalyst, and if necessary, a radical polymerization inhibitor or the like.
It is preferable to use a part of the polyvalent carboxylic acid component together with the polyhydric alcohol component to carry out a polycondensation reaction for a certain period of time, and then add the rest to the reaction system because the polycondensation reaction can be further advanced.

Examples of the esterification catalyst preferably used for the polycondensation reaction include tin compounds such as dibutyltin oxide and tin (II) di (2-ethylhexanoic acid), and titanium compounds such as titanium diisopropyrate bistriethanolamine. Can be mentioned. Among these, a tin compound is preferable, and di (2-ethylhexanoic acid) tin (II) is more preferable.
From the viewpoint of reactivity, the amount of the esterification catalyst used is preferably 0.01 part by mass or more, more preferably 0.1 part by mass, based on 100 parts by mass of the total amount of the polyhydric alcohol component and the polyvalent carboxylic acid component. It is 5 parts by mass or less, and more preferably 2 parts by mass or less.
Pyrogallol compounds such as pyrogallol, gallic acid (same as 3,4,5-trihydroxybenzoic acid), and gallic acid esters; 2,3,4-trihydroxybenzophenone, 2,2', as the esterification co-catalyst Benzophenone derivatives such as 3,4-tetrahydroxybenzophenone; catechin derivatives such as epigallocatechin and epigallocatechin gallate, and the like, and gallic acid is preferable from the viewpoint of reactivity.
From the viewpoint of reactivity, the amount of the esterification co-catalyst used is preferably 0.001 part by mass or more, more preferably 0.01 with respect to 100 parts by mass of the total amount of the polyhydric alcohol component and the polyvalent carboxylic acid component. It is 5 parts by mass or more, preferably 0.5 parts by mass or less, and more preferably 0.2 parts by mass or less.

As the 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, based on 100 parts by mass of the total amount of the polyhydric alcohol component and the polyvalent carboxylic acid component. Then, it is preferably 0.5 parts by mass or less, and more preferably 0.2 parts by mass 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.
Further, 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 chemically bonding at least a part of a crystalline resin (A) having a vinyl resin segment and a polyester segment and an amorphous resin (B). 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 with an ester group, an ether group, an amide group, a urethane group, or a bond with an organic group containing these groups. To chemically bond at least a part thereof means to bond at least a part of a plurality of crystalline resin (A) and a plurality of amorphous resins (B). That is, 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, and other components. Can also include unreacted crystalline resin (A) and amorphous resin (B).
As described above, the resin composition (D) containing the reaction product obtained by chemically bonding at least a part of the crystalline resin (A) and the amorphous resin (B) to the resin composition (D). It is considered that a block resin (AB), a crystalline resin (A), and an amorphous resin (B) are contained, but the composition actually obtained contains various resin structures, and simply has a structure and characteristics. The reality is that it is not possible to specify and specify. Further, if the structure is to be specified by a known analysis method, extremely complicated analysis such as isolation and purification, establishment of a polymer structure definition method, etc. is required. That is, there are circumstances in which the resin composition (D) is approximately impractical to directly specify by its structure or properties.

<Process (1)>
The resin composition (D) is obtained, for example, by the following step (1).
Step (1): Contains a reaction product obtained by chemically bonding at least a part of a crystalline resin (A) having a vinyl resin segment and a polyester segment and an amorphous resin (B). Step of obtaining the resin composition (D)

The step (1) preferably has a vinyl resin segment and a polyester segment, 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 reaction obtained by chemically binding at least a part of the resin (A) and the amorphous resin (B) 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-based resin segment and a polyester segment, and an amorphous resin (B) are obtained from the crystalline resin. This is a step of obtaining a resin composition (D) containing a reaction product obtained by a reaction in which at least a part of the polyester segment end of (A) and the end of the amorphous resin (B) are chemically bonded.
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 low-temperature fixability after high-temperature storage, and stable charging. From the viewpoint of obtaining a toner having excellent properties, it is preferably 20/80 or more, more preferably 25/75 or more, further preferably 35/65 or more, and preferably 80/20 or less, more preferably 70/30. Below, it is more preferably 60/40 or less.
In the step (1), the polyester segment end and the amorphous resin (B) end of the crystalline resin (A) can be condensed and chemically bonded, but the polyfunctional compound (S) is used. Is preferable because of the ease of reaction.

<Polyfunctional compound (S)>
In the reaction of the present invention in which at least a part of the crystalline resin (A) and the amorphous resin (B) is chemically bonded, it is preferable to use the 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.
Examples of the functional group include an isocyanate group, an oxazoline group, a glycidyl group, an amino group, an aziridine group and the like, and an isocyanate group is preferable.
As the polyfunctional compound (S), a polyisocyanate compound is used from the viewpoint of obtaining a toner which is excellent in reaction ease, low temperature fixability, low temperature fixability after high temperature storage, and also excellent charge stability. preferable.

As the polyisocyanate compound, a diisocyanate compound is preferable from the viewpoint of reactivity and ease of handling, and for example, an aliphatic diisocyanate, an aromatic diisocyanate, and prepolymer type, isocyanurate type, urea type, and carbodiimide type modification of these diisocyanates are used. The body is mentioned.
Examples of the aliphatic diisocyanate include an alicyclic diisocyanate and a 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-phenylenedi isocyanate, p-phenylenediocyanate, 1,3-xylylene diisocyanate, and the like. Examples thereof include 1,4-xylylene diisocyanate, 1,5-naphthalenediocyanate, and 3,3'-dimethyl-4,4'-biphenylenediocyanate.
Among these diisocyanate compounds, an aliphatic diisocyanate is preferable, an alicyclic diisocyanate is more preferable, at least one selected from isophorone diisocyanate and 4,4'-dicyclohexylmethane diisocyanate is more preferable, and isophorone diisocyanate is even more preferable.

The step (1) is preferably carried out in an organic solvent. The organic solvent is preferably 15 when represented 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 the phase inversion to the aqueous medium. It is 9.0 MPa ^1/2 or more, more preferably 16.0 MPa ^1/2 or more, further preferably 17.0 MPa ^1/2 or more, and preferably 26.0 MPa ^1/2 or less, more preferably 24.0 MPa ^{1 It is / 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-based solvents such as (18.6) and dioxane (20.5); acetate-based solvents such as ethyl acetate (18.6) and isopropyl acetate (17.4) can be mentioned. The numerical value in parentheses after each solvent is each SP value (unit: MPa ^1/2 ). Among these, one or more selected from a ketone solvent and an acetate ester solvent are preferable, and more preferably methyl ethyl ketone, ethyl acetate and isopropyl acetate from the viewpoint of easy removal from the mixed solution after addition of the aqueous medium. 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 type of 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): A 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 composed of the crystalline resin (A) and the amorphous resin (B). That is, either the crystalline resin (A) or the amorphous resin (B) is used, and a functional group is introduced into the resin.
The crystalline resin (A) is used as the resin (i) from the viewpoint of easiness of reaction and excellent low-temperature fixability, good low-temperature fixability after high-temperature storage, and excellent charge stability. ), It is preferable to select the amorphous resin (B) as the resin (ii).

≪Process (1-1) ≫
In the step (1-1), a functional group is introduced into one resin (i) selected from the group X consisting of the crystalline resin (A) and the amorphous resin (B) with the polyfunctional compound (S). This is a step of obtaining a reaction intermediate.
From the viewpoint of easiness of reaction and from the viewpoint of obtaining a toner which is excellent in low-temperature fixability, good low-temperature fixability after high-temperature storage, and also excellent in charge stability, the polyester segment terminal of the crystalline resin (A) It is preferable to select a method for introducing an isocyanate group into the hydroxyl group of the above, that is, a crystalline resin (A) as the resin (i) and an 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 reaction ease and low temperature fixability, good low temperature fixability after high temperature storage, and also 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 the diisocyanate compound in the presence of a urethanization catalyst in an organic solvent. Next, a method of reacting the resin (i) with the diisocyanate compound will be described.

The molar ratio (OH / NCO) of the hydroxyl group of the resin (i) to 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, still more preferably 0.3 or more.

The equivalent ratio of the diisocyanate compound used 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, still more preferably 1.00. The above, and preferably 1.20 or less, more preferably 1.10 or less, still more preferably 1.05 or less.
Equivalent ratio of diisocyanate compound = {mass used of diisocyanate compound (g) / molecular weight of diisocyanate compound} / [{hydroxyl value of resin (i) (mgKOH / g) x compounding amount of resin (i) (g)} / (56 x 1000)]

As the urethanization catalyst, a catalyst such as a tin compound such as dibutyltin oxide and tin (II) di (2-ethylhexanoic acid), and a titanium compound such as titanium diisopropyrate bistriethanolaminate can be used.
The amount of the urethanization catalyst used is not limited, but is preferably 0.01 parts by mass or more, more preferably 0.1 parts by mass or more, based on 100 parts by mass of the total amount of the resin (i) and the diisocyanate compound. Then, it is preferably 1.5 parts by mass or less, more preferably 1.0 part by mass or less.

The reaction between the resin (i) and the diisocyanate compound is preferably carried out in the above-mentioned organic solvent. 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.

When an organic solvent is used, the amount of the organic solvent used is preferably 30 parts by mass or more, more preferably 50 parts by mass, based on 100 parts by mass of the total amount of the resin (i) and the diisocyanate compound from the viewpoint of reactivity. As mentioned above, it is more preferably 70 parts by mass or more, and preferably 500 parts by mass or less, more preferably 300 parts by mass or less, 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) ≫
The 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, which is different from the resin (i). ..
The reaction can be carried out, for example, by adding the resin (ii) to the reaction system and heating and mixing the reaction intermediate and the resin (ii) in an organic solvent, following the step (1-1). When the resin (i) and the diisocyanate compound are reacted in the step (1-1) to obtain a reaction intermediate, the reaction intermediate can be subsequently produced by reacting with a urethanization catalyst as needed. .. As the urethanization catalyst, the same catalyst as in step (1-1) can be used.
As the organic solvent to be used, the same type as in step (1-1) can be used. The reaction temperature is preferably 20 ° C. or higher and 100 ° C. or lower.
The reaction time of step (1-2) 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. Hereinafter, it is more preferably 4 hours or less.
By going through the steps (1-1) and (1-2), preferably, at least a part of the end of the polyester segment of the crystalline resin (A) and the end of the amorphous resin (B) are chemically chemically. To be combined. When a diisocyanate compound is selected as the polyfunctional compound (S), it is 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, good low-temperature fixability after high-temperature storage, and further. 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, still more preferably 1. It is .30 or less, more preferably 1.00 or less.
The equivalent ratio of hydroxyl groups is calculated by the following formula.
Equivalent ratio of hydroxyl groups = [hydroxyl value of crystalline resin (A) (mgKOH / g) × compounding amount of crystalline resin (A) (g)] / [hydroxyl value of amorphous resin (B) (mgKOH / g) ) × Amorphous resin (B) compounding amount (g)]
Amorphous polyester and polyfunctional compound (S) are used as the amorphous resin (B) 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 use a diisocyanate compound. That is, it is preferable to have the following steps (1-1') and (1-2').
Step (1-1'): 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'): Non-reaction intermediate Step of reacting with the end of crystalline polyester

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

[Manufacturing method of toner for static charge image development]
The method for producing the toner for static charge image development of the present invention includes
(1) A method for producing toner by aggregating and fusing resin particles in a mixture containing a dispersion liquid in which the resin composition (D) is dispersed in a water-soluble medium to obtain toner mother particles (hereinafter, Also called "emulsification aggregation method"),
(2) A method of melt-kneading a mixture containing the resin composition (D) and pulverizing the obtained melt-kneaded product to produce a toner (hereinafter, also referred to as "melt-kneading method").
And so on.
The emulsion aggregation method (1) is 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. Further, the toner may be obtained by the melt-kneading method of (2).

(1) Emulsification and Aggregation Method The method for producing a toner for static charge image development of the present invention preferably has the following steps (1) to (4).
Step (1): Contains a reaction product obtained by chemically bonding at least a part of a crystalline resin (A) having a vinyl resin segment and a polyester segment and an amorphous resin (B). Step of obtaining the resin composition (D) Step (2): Step of dispersing the resin composition (D) obtained in the step (1) in an aqueous medium to obtain a dispersion liquid of the resin particles (E). 3): A step of aggregating the resin particles (E) obtained in the step (2) in an aqueous medium to obtain agglomerated particles Step (4): A step of fusing the agglomerated particles obtained in the step (3)

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

<Process (2)>
The step (2) is a step of dispersing the resin composition (D) obtained in the step (1) in an aqueous medium to obtain a dispersion liquid of the resin particles (E). As a method for obtaining the resin particle (E) dispersion liquid, a method of adding the resin composition (D) to an aqueous medium and performing a dispersion treatment with a disperser or the like, or a method of gradually adding the aqueous medium to the resin composition (D). However, the method of phase inversion emulsification is 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. .. When obtaining the dispersion liquid of the resin particles (E), other resin components such as the crystalline resin (A) and the amorphous resin (B) may be added in addition to the resin composition (D).

≪Aqueous medium≫
The aqueous medium preferably contains water as a main component, and the content of water in the aqueous medium is preferably 80% by mass from the viewpoint of improving the dispersion stability of the dispersion liquid of the resin particles and from the viewpoint of environmental friendliness. % 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, still more preferably 100% by mass. As the water, deionized water or distilled water is preferable.
As a component other than water that can form an aqueous medium together with water, an alkyl alcohol having 1 to 5 carbon atoms; a dialkyl ketone having 3 to 5 carbon atoms such as acetone and methyl ethyl ketone; and a cyclic ether such as tetrahydrofuran dissolved in water. 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 or more and 5 or less carbon atoms that does not dissolve polyester is preferable, and methanol, ethanol, isopropanol, and butanol are more preferable.

[Phase inversion emulsification]
As the phase inversion emulsification method, a method of preparing an organic solvent solution of the resin composition (D) and then adding an aqueous medium to the obtained solution for phase inversion emulsification, and a melted resin composition (D). A method of inversion emulsification by adding an aqueous medium can be mentioned. The former method is preferable from the viewpoint of obtaining a dispersion liquid of homogeneous resin particles (E).
At the time of phase inversion emulsification, other resin components such as the crystalline resin (A) and the amorphous resin (B) may be further added to the organic solvent solution of the resin composition (D).
A preferred embodiment of the organic solvent that can be used is the same as that of the organic solvent that can be used for producing the resin composition (D) of the step (1). The resin composition (D) may be produced in the organic solvent in the step (1) and subjected to the step (2) as it is in the organic solvent solution.
The mass ratio of the organic solvent to the resin constituting the resin particles (E) (the organic solvent / the resin constituting the resin particles (E)) is a viewpoint of dissolving the resin and facilitating the phase inversion to the 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 hydroxides of alkali metals such as lithium hydroxide, sodium hydroxide and potassium hydroxide; and 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), alkali metal hydroxide is preferable, and sodium hydroxide is more preferable.

The equivalent amount (mol%) of the neutralizing agent to the acid group 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 100 mol% or less.
The equivalent amount (mol%) of the neutralizing agent used can be calculated by the following formula. When the equivalent amount of the neutralizing agent is 100 mol% or less, it is synonymous with the degree of neutralization, and when the equivalent amount of the neutralizing agent used exceeds 100 mol% by the following formula, the neutralizing agent is the acid group of the resin. The degree of neutralization of the resin at this time is considered to be 100 mol%.
Equivalent to use of neutralizer (mol%) = [{Equivalent mass of neutralizer (g) / Equivalent of neutralizer} / [{Weighted average acid value (mgKOH / g) of resin constituting resin particles (E) ) × Mass of resin constituting resin particles (E) (g)} / (56 × 1000)]] × 100

The amount of the aqueous medium to be added is 100 mass of the 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). With respect to parts, it is preferably 100 parts by mass or more, more preferably 150 parts by mass or more, further 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 (aqueous medium / organic solvent) of the aqueous medium to the organic solvent is preferably 20/80 or more, more preferably 50/50 or more. , More preferably 60/40 or more, and preferably 97/3 or less, more preferably 93/7 or less, 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, further preferably 70 ° C. or higher, and preferably 85 ° C. or lower, more preferably 80 ° C. or lower, still more preferably 75 ° C. or higher. It is below ° C.

From the viewpoint of obtaining resin particles having a small particle size, the addition rate of the aqueous medium is preferably 0.1 part by mass or more with respect to 100 parts by mass of the resin constituting the resin particles until the phase inversion is completed. It is more preferably 0.5 parts by mass or more, still more preferably 1 part by mass or more, still more preferably 3 parts by mass or more, and preferably 50 parts by mass or less, more preferably 30 parts by mass or more. It is less than or equal to parts by mass, more preferably 20 parts by mass or less. There is no limit to the rate of addition of the aqueous medium after phase inversion.

After the phase inversion emulsification, if necessary, a step of removing the organic solvent from the obtained dispersion may be provided. The method for removing the organic solvent is preferably distillation because it is dissolved 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 used and distill off while stirring. Further, from the viewpoint of maintaining the dispersion stability of the resin particles (E), it is more preferable to distill under reduced pressure, and it is preferable to distill at a constant temperature and pressure. The temperature may be increased after the pressure is reduced, or the temperature may be reduced 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 residual amount of the organic solvent is preferably 1% by mass or less, more preferably 0.5% by mass or less, still more preferably substantially 0% in the aqueous dispersion.

The solid content concentration of the dispersion liquid of the obtained 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 liquid of the resin particles (E). The above is 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, still more preferably 25. It is mass% or less. The solid content is the total amount of non-volatile components such as resin, colorant, and surfactant.

The volume median particle diameter (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, preferably 0.80 μm or less, more preferably 0.40 μm or less, still more preferably 0.20 μm or less, still more preferably 0.15 μm or less.
Here, the volume median particle size (D ₅₀ ) is a particle size in which the cumulative volume frequency calculated by the volume fraction is 50% calculated from the smaller particle size, and is described in Examples described later. Required by the method.
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 liquid of the resin particles (E). % Or more, more preferably 15% or more, and from the viewpoint of obtaining a toner that can obtain a high-quality image, it is preferably 50% or less, more preferably 40% or less, 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 the particle size obtained by multiplying the particle size measured on a volume basis by the ratio of particles having that particle size value and dividing the value obtained thereby by the number of particles. is there. The CV value is determined by the method described in Examples.
CV value (%) = [standard deviation of particle size distribution (nm) / volume average particle size (nm)] x 100
In addition to the crystalline resin (A), the amorphous resin (B), and the resin composition (D), the resin particles (E) further include a resin used for the toner, for example, a crystalline resin (A). Polyester, styrene-acrylic copolymer, epoxy, polycarbonate, polyurethane and the like other than the amorphous resin (B) may be contained.
Further, the resin particles (E) may contain a colorant and a charge control agent, if necessary. Further, an additive such as a reinforcing filler such as a fibrous substance, an antioxidant, and an antiaging agent may be contained as long as the effect of the present invention is not impaired.

The mass ratio [(A) / (B)] of the crystalline resin (A) to the amorphous resin (B) is excellent in low-temperature fixability, good low-temperature fixability after high-temperature storage, and stable charging. From the viewpoint of obtaining a toner having excellent properties, it is preferably 2/98 or more, more preferably 5/95 or more, further 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 even 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. Of the resin components 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 amount of the crystalline resin (A) used is excellent in low-temperature fixability with respect to the total amount of the crystalline resin (A) and the amorphous resin (B), and the low-temperature fixability after high-temperature storage is also good. 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, further preferably 20% by mass or more, and preferably 45% by mass or less, more preferably 45% by mass or less. It is 40% by mass or less, more preferably 35% by mass or less.
The "total amount of the crystalline resin (A) used" is added as a raw material for the dispersion liquid of the crystalline resin (A) added as the raw material of the resin composition (D) and the resin particles (E). It means the total amount of the crystalline resin (A).

<Process (3)>
The step (3) is a step of aggregating the resin particles (E) obtained in the step (2) in an aqueous medium to obtain agglomerated particles. Specifically, the dispersion liquid of the resin particles (E) and, if necessary, an optional component such as a wax (W2) particle dispersion liquid containing a wax (W2), a flocculant, a surfactant, and a colorant are added. A method of mixing in an aqueous medium and aggregating the resin particles (E) and other components to obtain agglomerated particles is preferable.
The step (3) may include the next step (3A), followed by the step (3B).
Step (3A): The resin particles (E) obtained in the step (2) are agglomerated in an aqueous medium preferably in the presence of wax (W2) to obtain the agglomerated particles (1). Step (3B) : The agglomerated particles (2) formed by adding the resin particles (G) containing an amorphous resin to the agglomerated particles (1) obtained in the step (3A) and adhering the resin particles (G). Obtaining process <Process (3A)>
The step (3A) is a step of agglomerating the resin particles (E) obtained in the step (2) in an aqueous medium to obtain agglomerated particles (1), preferably obtained in the step (2). This is a step of aggregating the resin particles (E) in the presence of wax (W2) in an aqueous medium to obtain agglomerated particles (1).

[Aggregated particles (1)]
The agglomerated particles (1) are a wax particle dispersion containing a wax (W2), if necessary, in the dispersion of the resin particles (E) obtained in the step (2), an aggregating agent, a surfactant, and a coloring agent. It is obtained by mixing and aggregating arbitrary components such as. From the viewpoint of improving the charging characteristics of the toner, it is preferable to use a wax particle dispersion liquid containing wax (W2).
Specifically, first, a dispersion of resin particles (E), a dispersion of wax (W2) particles, and, if necessary, an optional component such as a flocculant, a surfactant, and a colorant are mixed in an aqueous medium. It is preferable to obtain a mixed dispersion liquid (hereinafter, a mixed dispersion liquid containing a dispersion liquid of resin particles (E) and a wax (W2) particle dispersion liquid is also simply referred to as a mixed dispersion liquid). Then, when the components in the mixed dispersion liquid are aggregated to obtain the dispersion liquid of the aggregated particles (1), it is preferable to add a flocculant from the viewpoint of efficiently performing the aggregation.
When the colorant is not mixed with the resin particles (E), it is preferable to mix the colorant in the mixed dispersion.
The mixing order of each component is not particularly limited, and each component may be added in any order, or each component may be added at the same time.

≪Wax particle dispersion liquid≫
The wax particle dispersion can be obtained by using a surfactant, but obtaining by mixing the wax (W2) and the resin particles (F) described later improves the dispersion stability of the wax particles. It is preferable 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 wax; synthetic wax; low molecular weight polyolefin; silicone wax; fatty acid amide; plant wax; animal wax and the like.
Examples of the mineral or petroleum wax include montan wax, paraffin wax, Fischer-Tropsch wax and the like, and paraffin wax is preferable from the viewpoint of improving the mold releasability and low temperature fixability of the toner.
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.
As the animal wax, beeswax or the like is preferable.

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

The melting point of the wax (W2) is determined by the method described in 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 melting point of the wax (W2) in the present invention. Let it be the melting point. When all have the same ratio, the lowest melting point is the melting point of the wax (W2) in the present invention.
The amount of wax (W2) used is in the toner 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. With respect to 100 parts by mass of the total amount of the resin, it is preferably 1 part by mass or more, more preferably 2 parts by mass or more, further 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 dispersing the wax (W2) is not particularly limited, but is preferably a resin containing a polyester segment, from the viewpoint of improving the dispersion stability of the wax particles, and 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. The amorphous composite resin (C) preferably further has a constituent component derived from a bireactive monomer.

(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, the "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 component derived from a bireactive monomer capable of reacting with both a vinyl resin segment and a polyester segment.
The amorphous composite resin of the present invention has the above-mentioned crystallinity index of more than 1.4 or less than 0.6.

The polyester segment has a polyhydric alcohol component (cal) and a polyvalent 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), the one described in the polyhydric alcohol component (bal) in the amorphous resin (B) described above can be used, and the polyhydric alcohol component preferably used. The same applies to the types of. As the polyvalent carboxylic acid component (c-ac), the one described in the above-mentioned 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, from the viewpoint of improving the dispersion stability of wax particles, and from 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 is preferably 90 mol% or more, more preferably 95 mol% or more, still more preferably 98 mol% or more, and 100 mol% or less in the polyvalent carboxylic acid component (c-ac). It is even more preferably 100 mol%.
Further, 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 polyvalent carboxylic acid to the polyhydric alcohol component (bal) described above. It is the same as the equivalent ratio (COOH group / OH group) of the component (b-ac).

As the vinyl-based resin segment of the amorphous composite resin (C), those described as the vinyl-based segment of the crystalline resin (A) described above can be used.
The amorphous composite resin (C) preferably has components derived from both reactive monomers. When a bireactive monomer is used as the raw material monomer of the amorphous composite resin (C), the bireactive monomer reacts with both the polyester segment and the vinyl resin segment, so that the amorphous composite resin (C) Will be easier to manufacture. Therefore, it is preferable to use a bireactive monomer as a raw material monomer for the amorphous composite resin (C). It is preferable that the structural unit derived from the bireactive monomer serves as 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 crystalline resin (A) described above can be used.

The content of the constituent components of the bireactive monomer is 100, which is the raw material of the polyester segment, from the viewpoint of improving the dispersibility of the wax (W2) and controlling the reaction of the addition polymerization reaction and the polycondensation reaction. With respect to the molar portion, it is preferably 1 mol part or more, more preferably 5 mol parts or more, further preferably 10 mol parts or more, and preferably 30 mol parts or less, more preferably 25 mol parts or less, still more preferably. Is 20 mol parts or less. When both reactive monomers are used and the content of each segment in the amorphous composite resin is calculated, the structural units derived from the bireactive monomers are included in the structural units 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 50% by mass or more, further 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. As mentioned above, it is 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.

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% by mass or more, more preferably 20% by mass or more, further preferably 30% by mass or more, and preferably 60% by mass or less, more preferably 50% by mass or less, still more preferably 45% by mass or less. From the same viewpoint, the content of the vinyl-based resin segment in the amorphous composite resin (C) is preferably 10% by mass or more, more preferably 20% by mass or more, based on the total content of the polyester segment and the vinyl-based resin segment. It is 0% by mass or more, more preferably 30% by mass or more, and preferably 60% by mass or less, more preferably 50% by mass or less, still more preferably 45% by mass or less.
Further, the total content of the polyester segment and the vinyl-based resin segment in the amorphous composite resin (C) improves the dispersion stability of the wax particles, as well as 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, still more preferably 93% by mass or more, still more preferably 95% by mass or more, and preferably 100% by mass or less, still more preferably. It is 100% by mass.

The method for producing the amorphous composite resin (C) is not particularly limited, but vinyl is added after the polycondensation reaction with the polyhydric alcohol component and the polyvalent carboxylic acid component because the reaction temperature of the polycondensation reaction is highly flexible. A method of carrying out an addition polymerization reaction using a raw material monomer of the based resin segment and a bireactive monomer 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 monomer of the vinyl resin segment. Further, from the viewpoint of reactivity, catalysts such as an esterification catalyst and an esterification co-catalyst may be used, and a radical polymerization initiator and a radical polymerization inhibitor may be used. As the esterification catalyst, the esterification co-catalyst, and the radical polymerization inhibitor, those described in the above-mentioned production of the amorphous resin (B) can be used, and as the radical polymerization initiator, the above-mentioned crystallinity The one described in the production of the resin (A) can be used.
From the viewpoint of further advancing the polycondensation reaction and, if necessary, the reaction with the bireactive monomer, the polyvalent carboxylic acid component is partially subjected to the polycondensation reaction, and then the reaction temperature is raised again after the addition polymerization reaction. It is preferable to add the balance to the reaction system.

From the viewpoint of the productivity of the amorphous composite resin (C), 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. or higher. It is as follows.

The temperature of the addition polymerization reaction varies depending on the type of radical polymerization initiator used and the like, but is preferably 110 ° C. or higher, more preferably 130 ° C. or higher, from the viewpoint of productivity of the amorphous composite resin (C). The temperature is preferably 220 ° C. or lower, more preferably 200 ° C. or lower.
Further, 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. It is preferably 80 ° C. or higher, and preferably 140 ° C. or lower, more preferably 120 ° C. or lower, and further preferably 100 ° C. or lower.

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 later, and improving the low temperature fixability and charging characteristics of the toner. It is more preferably 35 ° C. or higher, further preferably 40 ° C. or higher, and preferably 70 ° C. or lower, more preferably 60 ° C. or lower, still more preferably 55 ° C. or lower.

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 later, and improving the low temperature fixability and charging characteristics of the toner. It is more preferably 10 mgKOH / g or more, still more 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 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 later, and improving the low temperature fixability and charging characteristics of the toner. It is more preferably 20 mgKOH / g or more, still more preferably 25 mgKOH / g or more, and preferably 50 mgKOH / g or less, more preferably 40 mgKOH / g or less, still more preferably 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 type and ratio of the raw material monomers and the production conditions such as reaction temperature, reaction time and cooling rate. Yes, and their values are determined by the method described in the examples.
When two or more amorphous composite resins (C) are mixed and used, the softening point, the glass transition temperature, and the acid value obtained as the mixture thereof must be within the above ranges. preferable.

The dispersion liquid of the resin particles (F) can be obtained, for example, by the above-mentioned 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 are also applied to the items described in step (2). Can be done.

The solid content concentration of the obtained dispersion liquid of the resin particles (F) is preferably 5% by mass from the viewpoint of improving the productivity of the toner and improving the dispersion stability of the aqueous dispersion liquid of the resin particles (F). The above is 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, still more preferably 25. It is mass% or less. The solid content is the total amount of non-volatile components such as resin, colorant, and surfactant.
The volume median particle diameter (D ₅₀ ) of the resin particles (F) in the dispersion is preferably 0.01 μm or more, more preferably 0.03 μm or more, from the viewpoint of improving the dispersion stability of the wax particles. Then, it is preferably 0.30 μm or less, more preferably 0.15 μm or less, and further preferably 0.10 μm 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 liquid of the resin particles (F). % Or more, more preferably 15% or more, and preferably 50% or less, more preferably 40% or less, still more preferably 30% or less, from the viewpoint of obtaining a toner that can obtain a high-quality image.
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)] x 100

(Manufacturing of wax particle dispersion)
The wax particle dispersion liquid is obtained by mixing the wax (W2) and the dispersion liquid of the resin particles (F).
By preparing the wax particles using the wax (W2) and the resin particles (F), the polyester segment has an appropriate polarity, so that the wax is dispersed in the 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 is dispersed in the dispersion liquid of the wax particles via the resin particles (F) having an appropriate polarity, and has a structure in which a large number of the resin particles (F) are adsorbed around the wax particles. It is considered that this makes it easier for the wax particles to be incorporated into the aggregate of the (binding) resin particles (E) in the subsequent agglutination step.

As the wax particle dispersion liquid, for example, a disperser having a strong shearing force at a temperature equal to or higher than the melting point of the wax (W2) is used by using a wax (W2), a resin particle (F) dispersion liquid, and an aqueous medium as needed. Obtained by dispersing. The disperser is preferably a homogenizer, a high-pressure disperser, an ultrasonic disperser, or the like, and more preferably an ultrasonic disperser, from the viewpoint of the stability of the wax particles. The dispersion time may be appropriately set depending on the disperser used.

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

Wax (W2) 100 from the viewpoint of improving the dispersion stability of the wax particles, obtaining uniform agglomerated particles in the subsequent agglomeration step, and including the wax (W2) in the toner even after heating in the fusion step. The amount of the resin particles (F) with respect to parts by mass is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, further preferably 20 parts by mass or more, still more preferably 30 parts by mass or more, and preferably 100 parts by mass. It is less than or equal to parts by mass, more preferably 70 parts by mass or less, still more preferably 60 parts by mass or less, and even more preferably 50 parts by mass or less.
The wax particle dispersion may contain a surfactant, but it is preferable not to contain a surfactant from the viewpoint of obtaining a toner having excellent low-temperature fixability and excellent low-temperature fixability after high-temperature storage. When a surfactant is contained, the amount of the surfactant in the wax particles with respect to 100 parts by mass of the wax is preferably 1 part by mass or less, more preferably 0.5 part by mass or less, still more preferably 0.1 part by mass or less. And when used to improve the dispersion stability of wax particles, it is preferably 0.01 part by mass or more, more preferably 0.02 part by mass or more, still more preferably 0.05 part by mass or more. Is.

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

The solid content 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. It is preferably 10% by mass or more, more preferably 15% by mass or more, and preferably 40% by mass or less, more preferably 30% by mass or less, still more preferably 25% by mass or less.

The volume median particle diameter (D ₅₀ ) of the wax (W2) particles is preferably 0.05 μm or more from the viewpoint of obtaining uniform agglomerated particles in the subsequent agglomeration step and obtaining a toner having excellent charge stability. It is preferably 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 0.65 μm or less, and even more preferably 0.60 μm or less.
Here, the volume median particle size (D ₅₀ ) is a particle size in which the cumulative volume frequency calculated by the volume fraction is 50% calculated from the smaller particle size, and is described in Examples described later. Required by the method.
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 liquid of the wax particles. It is 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, 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)] x 100
Wax (W2) ratio of the volume median particle size of a volume-median particle size of the particles _{(D 50)} and the resin particles _{(F) (D 50)} (Wax (W2) a volume-median particle size of the particles _(D 50) / The volume median particle diameter (D ₅₀ ) of the resin particles (F) is preferably 1.0 or more, more preferably 1.0 or more, 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, still more preferably 10 or less.

≪Colorant≫
When the colorant is mixed in the mixed dispersion containing the resin particles (E), it is preferable to use a dispersion of the colorant particles in which the colorant is dispersed in an aqueous medium.
Pigments and dyes are used as the colorant, 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, brilliarchamine 3B, brilliarchamine 6B, Bengal, aniline blue, ultramarine blue, copper phthalocyanine, phthalocyanine green, and the like. Phthalocyanine is preferred.

Specific examples of the dye include acridine-based, azo-based, benzoquinone-based, azine-based, anthraquinone-based, indigo-based, phthalocyanine-based, and aniline black-based dyes.
The colorants can be used alone or in combination of two or more.
The amount of the colorant used is preferably 2 parts by mass or more, more preferably 5 parts by mass, based on 100 parts by mass of the total amount of the resin in the toner from the viewpoint of improving the image density of the printed matter and obtaining a high-quality image. It is more than parts by mass, more preferably 7 parts by mass or more, and preferably 30 parts by mass or less, more preferably 20 parts by mass or less, still more preferably 15 parts by mass or less.

The colorant dispersion is preferably obtained by dispersing the colorant and an aqueous medium using a disperser. As the disperser, a homogenizer, an ultrasonic disperser, or the like is preferable.
As the aqueous medium, those mentioned in the above-mentioned production of the resin particle (E) dispersion liquid are preferable.
The dispersion of the colorant in an aqueous medium is preferably carried out 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 liquid include nonionic surfactants, anionic surfactants, cationic surfactants, etc., and aggregates from the viewpoint of improving the dispersion stability of the colorant particles. From the viewpoint of improving the properties, an anionic surfactant is preferable. Examples of the anionic surfactant include sodium dodecylbenzenesulfonate, sodium dodecylsulfate, sodium lauryl ether sulfate, dipotassium alkenylsuccinate and the like, and sodium dodecylbenzenesulfonate is preferable.

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, based on 100 parts by mass of the colorant, from the viewpoint of improving the dispersion stability of the colorant. It is more preferably 10 parts by mass or more, and preferably 40 parts by mass or less, more preferably 30 parts by mass or less, 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, still more preferably 10% by mass or more, from the viewpoint of improving the productivity of the toner and 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 diameter (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 0.10 μm or more. It is 0.30 μm or less, more preferably 0.20 μm or less, 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. It is preferably 10% by mass or more, more preferably 10% by mass or more, still more preferably 12% by mass or more, and preferably 40% by mass or less, more preferably from the viewpoint of controlling aggregation to obtain agglomerated particles having a desired particle size. Is 30% by mass or less, more preferably 20% by mass or less.
The mass ratio of the resin particles (E) to 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. From the viewpoint of obtaining a toner which is also good and has excellent charge stability, it is preferably 0.05 or more, more preferably 0.10 or more, and preferably 1.0 or less, more preferably 0.5 or less. , More preferably 0.3 or less, and even more preferably 0.2 or less.
The mixing temperature is preferably 0 ° C. or higher, more preferably 10 ° C. or higher, still more preferably 20 ° C. or higher, and preferably 40 ° C. or lower, from the viewpoint of controlling aggregation to obtain agglomerated particles having a desired particle size. , More preferably 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 arbitrary components such as resin particles (E) and wax (W2) particles added as needed. May be good.
Examples of the surfactant include anionic surfactants such as sulfate ester type, sulfonate type, phosphoric acid ester type and soap type (for example, alkyl ether carboxylate); amine salt type and quaternary ammonium. Cationic surfactants such as salt type; polyoxyethylene alkylaryl 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, polyoxyethylene fatty acid esters such as polyethylene glycol monolaurate, polyethylene glycol monostearate and polyethylene glycol monooleate. Examples include nonionic surfactants such as oxyethylene / oxypropylene block copolymers. Among these, nonionic surfactants are preferable, polyoxyethylene alkyl ethers and polyoxyethylene alkenyl ethers are preferable, and polyoxyethylene lauryl ethers are more preferable.
When a surfactant is used, the amount used is preferably 0.1 part by mass or more, more preferably 0.5 part by mass or more, and preferably 0.5 part by mass or more, based on 100 parts by mass of the resin particles (E). It is 10 parts by mass or less, more preferably 5 parts by mass or less, still more preferably 3 parts by mass or less.

≪Coagulant≫
Next, the particles in the mixed dispersion can be aggregated to preferably obtain the dispersion of the aggregated particles (1). It is preferable to add a flocculant for efficient coagulation.
As the coagulant, it is preferable to use an electrolyte, and more preferably a salt, from the viewpoint of obtaining a toner having a target particle size while preventing excessive coagulation. Specific examples of the flocculant include a cationic surfactant for a quaternary salt, an organic flocculant such as polyethyleneimine; and an inorganic flocculant such as an inorganic metal salt, an inorganic ammonium salt, and a divalent or higher metal complex. Be done. From the viewpoint of improving the cohesiveness and obtaining uniform agglomerated particles, an inorganic flocculant is preferable, an inorganic metal salt and an inorganic ammonium salt are more preferable, and an inorganic ammonium salt is further preferable.

The cation valence of the inorganic flocculant is preferably pentavalent or less, more preferably divalent or less, and even more preferably monovalent, 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, and ammonium ion is preferable from the viewpoint of improving the low temperature fixability and low temperature fixability of the obtained toner over time. ..

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 the inorganic ammonium salt include ammonium sulfate, ammonium chloride, ammonium nitrate and the like.
Ammonium sulfate is more preferable as the flocculant.
The amount of the aggregating agent used is preferably 5 parts by mass or more, based on 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, and is preferable from the viewpoint of obtaining a toner having excellent low-temperature fixability, good low-temperature fixability after high-temperature storage, and further excellent charge stability. It is 50 parts by mass or less, more preferably 45 parts by mass or less, still more preferably 40 parts by mass or less.

The flocculant may be added at one time, intermittently or continuously. Sufficient stirring is preferable at the time of addition and after the addition is completed.
The flocculant is preferably added dropwise as an aqueous solution from the viewpoint of controlling aggregation to obtain aggregated particles having a desired particle size, and the concentration of the aqueous solution of the flocculant is preferably 2% by mass or more, more preferably 4% by mass. As mentioned above, it is more preferably 6% by mass or more, and preferably 40% by mass or less, more preferably 30% by mass or less, still more preferably 20% by mass or less.
Further, from the viewpoint of controlling aggregation to obtain aggregated particles having a desired particle size and particle size distribution, it is preferable to use the aqueous solution of the flocculant by adjusting the pH to 7.0 or more and 9.0 or less.
The dropping time of the coagulant is preferably 1 minute or more, more preferably 3 minutes or more from the viewpoint of controlling the coagulation to obtain agglomerated particles having a desired particle size, and from the viewpoint of improving the productivity of the toner. It is preferably 120 minutes or less, more preferably 30 minutes or less, and further 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 the productivity of the toner. It is more preferably 35 ° C. or lower, still more preferably 30 ° C. or lower.

Further, from the viewpoint of promoting aggregation and obtaining aggregated particles having a desired particle size and particle size distribution, it is preferable to raise the temperature of the dispersion after adding the aggregating agent. The temperature to be held is preferably 45 ° C. or higher, more preferably 50 ° C. or higher, still more preferably 55 ° C. or higher, and from the viewpoint of improving the low-temperature fixability and low-temperature fixability of the obtained toner over time. It is preferably 75 ° C. or lower, more preferably 70 ° C. or lower, and even more preferably 65 ° C. or lower.

It is preferable to confirm the progress of aggregation by monitoring the volume median particle diameter of the aggregated particles in the above temperature range.
The volume median particle diameter (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. It is more preferably 4 μm or more, and preferably 10 μm or less, more preferably 8 μm or less, still more preferably 6 μm or less. The volume median particle diameter of the agglomerated particles is determined by the method described in Examples described later.

<Process (3B)>
In the step (3B), the resin particles (G) containing an amorphous resin are added to the agglomerated particles (1) obtained in the step (3A), and the resin particles (G) are added to the agglomerated particles (1). This is a step of obtaining agglomerated particles (2) formed by adhering.
In the step (3), the charge stability of the toner, which is the effect of the present invention, can be improved only by the step (3A), but by further performing the step (3B), the component of the agglomerated particles (1) is cored. Aggregated particles (2) having resin particles (G) on the shell side can be formed on the side, and the crystalline resin (A) and wax (W2) finely dispersed in the aggregated particles (1) are the next step. It is considered that when each particle in the agglomerated particles in (4) is fused, it becomes more difficult to detach and the wax (W2) can be further suppressed from being exposed on the surface of the obtained toner matrix particles.
The resin particles (G) are preferably obtained as a dispersion liquid of the resin particles (G) by dispersing a resin component containing an amorphous resin in an aqueous medium. As for the method of obtaining the dispersion liquid, as in the case of the resin particles (E), a method of gradually adding an aqueous medium to an organic solvent solution of the resin or the like and emulsifying the phase inversion is preferable.

In the step (3), the agglomeration may be stopped when the agglomerated 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 inhibitor, a method of diluting the dispersion, and the like. From the viewpoint of surely preventing unnecessary aggregation, a method of adding an aggregation terminator to stop aggregation is preferable.

≪Coagulation terminator≫
As the aggregation terminator, a surfactant is preferable, and an anionic surfactant is more preferable. Examples of the anionic surfactant include alkylbenzene sulfonates, alkyl sulfates, alkyl ether sulfates, polyoxyalkylene alkyl ether sulfates and the like. Among these, polyoxyalkylene alkyl ether sulfate is preferable, polyoxyethylene lauryl ether sulfate is more preferable, and polyoxyethylene lauryl ether sulfate sodium is further preferable.

The aggregation terminator can be used alone or in combination of two or more.
The amount of the aggregation terminator added is preferably 0.1 part by mass or more, more preferably 1 part by mass or more, based on 100 parts by mass of the total amount of the resin in the toner, from the viewpoint of surely preventing unnecessary aggregation. It is more preferably 2 parts by mass or more, and from the viewpoint of reducing the residue on the toner, it is preferably 15 parts by mass or less, more preferably 10 parts by mass or less, and further preferably 7 parts by mass or less. The aggregation terminator is preferably added in an aqueous solution from the viewpoint of improving the productivity of the toner.

The temperature at which the aggregation terminator is added is preferably the same as the temperature at which the dispersion liquid of aggregated particles is held from the viewpoint of improving the productivity of the toner. The temperature is preferably 40 ° C. or higher, more preferably 45 ° C. or higher, further preferably 50 ° C. or higher, and preferably 80 ° C. or lower, more preferably 70 ° C. or lower, still more preferably 65 ° C. or lower.
Further, from the viewpoint of stabilizing the agglomerated particles and preventing the once agglomerated particles from being dispersed before fusion, it is preferable to stop the agglomeration and add an acid to make the dispersion liquid of the agglomerated 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. However, from the viewpoint of rapid pH change with respect to addition, hydrochloric acid, hydrochloric acid, nitric acid, and acetic acid are preferable. At least one selected from, more preferably at least one selected from hydrochloric acid, sulfuric acid, and nitric acid, still more preferably sulfuric acid.
The acid is preferably added in the form of an aqueous solution. Further, it may be added together with the aggregation terminator.

<Process (4)>
The step (4) is a step of fusing the agglomerated particles obtained in the step (3).
Here, the "aggregated particles obtained in the step (3)" refer to the agglomerated particles (1) obtained in the step (3A) when the step (3B) is not performed, and the agglomerated particles (1) obtained in the step (3B). When the above is carried out, it refers to the agglomerated particles (2) obtained in the step (3B).
In this step, among the agglomerated particles obtained in step (3), the particles that were mainly physically attached to each other are fused and integrated to form fused particles.
When the agglomerated particles (2) are fused, toner mother particles having a core-shell structure can be obtained.

In this step, crystallinity is obtained from the viewpoint of improving the fusion property of the agglomerated 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 keep the temperature at a temperature equal to or higher than 10 ° C. lower than the melting point of the resin (A).
The holding temperature is more preferably 5 ° C. lower than the melting point of the crystalline resin (A), more preferably a crystalline resin, from the viewpoint of improving the fusion property of the aggregated particles and improving the productivity of the toner. It is equal to or higher than the melting point of (A).

At that time, a toner having excellent low-temperature fixability, good low-temperature fixability after high-temperature storage, and excellent charge stability can be obtained for a period of time held at a temperature 10 ° C. lower than the melting point of the crystalline resin (A). 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 diameter (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, still more preferably 4 μm from the viewpoint of obtaining a high-quality image. The above, and preferably 10 μm or less, more preferably 8 μm or less, 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, still more preferably 0.965, from the viewpoint of reducing toner scattering and obtaining a high-quality image. The above, and preferably 0.990 or less, more preferably 0.985 or less, still more preferably 0.980 or less.

<Post-treatment process>
A post-treatment step may be performed after the step (4), and it is preferable to obtain the toner mother particles by isolating the fused particles from the dispersion liquid obtained in the step (4).
Since the fused particles in the dispersion liquid obtained in the step (4) are present in the aqueous medium, it is preferable to first perform solid-liquid separation. A suction filtration method or the like is preferably used for solid-liquid separation.
It is preferable to perform cleaning after solid-liquid separation. At this time, since it is preferable to remove the added surfactant as well, 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 temperature at the time of drying is preferably such that the temperature of the fused particles themselves is lower than the minimum value of the glass transition temperature of the resin constituting the resin particles. As the drying method, it is preferable to use a vacuum low temperature drying method, a vibration type fluid 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.
Toner mother 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 a wax (W2), and pulverizing the melt-kneaded product obtained in the above step. Including the process of classifying.
Examples of the wax (W2) used in the method (2) include the same preferred examples as the wax (W2) described above.
In the step of melt-kneading, it is preferable that the colorant is also melt-kneaded, and it is preferable that the colorant is also melt-kneaded together with other additives such as a release agent and a charge control agent.
The melt kneading can be performed by using a known kneader such as a closed kneader, a uniaxial extruder, a twin extruder, or an open roll type kneader.

It is preferable that the toner raw materials such as the resin, the above-mentioned colorant, and the release agent are mixed in advance with a mixer such as a Henschel mixer or a ball mill, and then supplied to the kneader.
The set temperature (barrel set temperature) of the twin-screw extruder is appropriately set so that the temperature _Kt is in a predetermined range, and is, for example, preferably 50 ° C. or higher, more preferably 60 ° C. or higher, and It is preferably 160 ° C. or lower, more preferably 140 ° C. or lower.
The rotation speed is the same direction from the viewpoint of improving the dispersibility of additives such as colorants, charge control agents, and mold 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. It is preferably 250 r / min or less.
The melt-kneaded product obtained in the above step is cooled to a degree that allows pulverization, and then subjected to the subsequent step.

The crushing step may be divided into a plurality of steps. For example, the resin kneaded product obtained by curing the melt-kneaded product may be roughly pulverized to about 1 mm or more and 5 mm or less, and then finely pulverized to a desired particle size. The crusher used in the crushing step is not particularly limited, and examples of the crusher preferably used for coarse crushing include a hammer mill, an atomizer, and a rotoplex. Further, examples of the pulverizer preferably used for fine pulverization include a fluidized bed type jet mill, a collision plate type jet mill, and a rotary mechanical type mill. From the viewpoint of pulverization efficiency, it is preferable to use a fluidized bed type jet mill and a collision plate type jet mill, and it is more preferable to use a fluidized bed type jet mill.

Examples of the classifier used in the classification process include a rotor type classifier, an air flow type classifier, an inertial type classifier, and a sieve type classifier. In the classification step, the pulverized product removed due to insufficient pulverization may be subjected to the pulverization step again, or the pulverization step and the classification step may be repeated as necessary.
Toner mother particles can be obtained by this step.

[Toner for static charge image development]
<Toner mother particles>
The toner matrix obtained by the above method can be used as it is as a toner for static charge image development, but a toner having a surface treated with the toner matrix particles as described later can be used as a toner for static charge image development. preferable.

The total content of the crystalline resin (A) with respect to the total content of the crystalline resin (A) and the amorphous resin (B) in the toner mother particles is excellent in low-temperature fixability and low-temperature fixability over time. It is preferably 5% by mass or more, more preferably 10% by mass or more, still more preferably 15% by mass or more, and from the viewpoint of obtaining a toner which is excellent in image density and long-term storage property of the printed matter. It is preferably 45% by mass or less, more preferably 40% by mass or less, and further preferably 35% by mass or less.
Further, 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 is also excellent in image density and long-term storage of printed matter from the viewpoint of obtaining toner. , 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 or more, based on the total amount of the resin component in the toner. It is mass% or less, more preferably 35 mass% or less.
The "total content of the crystalline resin (A)" refers to the crystalline resin (A) added as a raw material for the resin composition (D) and the crystalline resin (A) added in another step. Means the total amount of.

The volume median particle diameter (D ₅₀ ) of the toner mother 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. It is more preferably 8 μm or less, still more preferably 6 μm or less.
The CV value of the toner matrix particles is preferably 12% or more, more preferably 14% or more, still more preferably 16% or more from the viewpoint of improving the productivity of the toner, and from the viewpoint of obtaining a high-quality image. It is preferably 30% or less, more preferably 26% or less.

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

The toner for developing an electrostatic charge image is preferably a toner obtained by adding a fluidizing agent or the like as an external additive to the surface of the toner matrix particles.
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 an 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 mother particles. Then, it is preferably 5 parts by mass or less, more preferably 4.5 parts by mass or less, and further preferably 4 parts by mass or less.

The static charge image developing toner can be used as a one-component developer or mixed with a carrier as a two-component developer.

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

[Resin softening point, crystallinity index, melting point and glass transition temperature]
(1) Softening point Using a flow tester "CFT-500D" (manufactured by Shimadzu Corporation), a 1 g sample is heated at a heating rate of 6 ° C./min while a load of 1.96 MPa is applied by a plunger to give a diameter of 1.96 MPa. Extruded from a 1 mm, 1 mm long nozzle. The amount of plunger drop of the flow tester was plotted against the temperature, and the temperature at which half of the sample flowed out was used as the softening point.
(2) Crystallinity index 0.02 g of a sample is weighed on an aluminum pan using a differential scanning calorimeter "Q100" (manufactured by TA Instruments Japan Co., Ltd.), and the temperature drops from room temperature (25 ° C) to 10 ° C / It was cooled to 0 ° C. in min. Then, the sample was allowed to stand still for 1 minute, and then the temperature was raised to 180 ° C. at a heating rate of 10 ° C./min to measure the amount of heat. Of the observed endothermic peaks, the temperature of the peak with the largest endothermic area is set as the maximum endothermic peak temperature (1), and (softening point (° C)) / (maximum endothermic peak temperature (1) (° C)). The crystallinity index was calculated.
(3) Melting point and glass transition temperature Using a differential scanning calorimeter "Q100" (manufactured by TA Instruments Japan Co., Ltd.), 0.02 g of the sample is weighed in an aluminum pan, heated to 200 ° C, and the temperature thereof. The temperature was lowered to 0 ° C. at a temperature lowering rate of 10 ° C./min. Next, the temperature of the sample was raised at a heating rate of 10 ° C./min, and the amount of heat was measured. Among the observed endothermic peaks, the temperature of the peak having the largest peak area was defined as the maximum endothermic peak temperature (2). In the case of crystalline resin, the peak temperature was taken as the melting point.
In the case of amorphous resin, when a peak is observed, the temperature of the peak is observed, and when a step is observed without a peak, a tangent line indicating the maximum inclination of the curve of the step portion and the step The temperature at the intersection with the extension of the baseline 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.), weigh 0.02 g of a sample into an aluminum pan, raise the temperature to 200 ° C, and then lower the temperature from 200 ° C to 10 ° C / min. Was cooled to 0 ° C. Next, the sample was heated at a heating rate of 10 ° C./min, the amount of heat was measured, and the maximum peak temperature of endothermic reaction was taken as the melting point.

[Volume medium particle size (D ₅₀ ) and CV value of resin particles, colorant particles, and wax particles]
(1) Measuring device: Laser diffraction type particle size measuring machine "LA-920" (manufactured by HORIBA, Ltd.)
(2) Measurement conditions: Distilled water was added to the measurement cell, and the volume median particle diameter (D ₅₀ ) and the volume average particle diameter were measured at a concentration at which the absorbance was within 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) x 100

[Solid concentration of resin particle dispersion, colorant dispersion, and wax particle dispersion]
Using an infrared moisture meter "FD-230" (manufactured by Ketsuto Kagaku Kenkyusho Co., Ltd.), 5 g of the measurement sample was dried at a drying temperature of 150 ° C. ), The water content (% by mass) was measured. The solid content concentration was calculated according to the following formula.
Solid content concentration (mass%) = 100-moisture (mass%)

[Volume medium particle size of aggregated particles (D ₅₀ )]
The volume median particle diameter (D ₅₀ ) of the agglomerated particles was measured as follows.
-Measuring machine: "Coulter Multi-Sizar (registered trademark) III" (manufactured by Beckman Coulter Co., Ltd.)
・ Aperture diameter: 50 μm
-Analysis software: "Multisizer (registered trademark) III version 3.51" (manufactured by Beckman Coulter Co., Ltd.)
-Electrolytic solution: "Isoton (registered trademark) II" (manufactured by Beckman Coulter Co., Ltd.)
-Measurement conditions: By adding the sample dispersion to 100 mL of the electrolytic 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 again and the particle size is measured. 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.
-Measuring device: Flow type particle image analyzer "FPIA-3000" (manufactured by Sysmex Corporation)
-Preparation of dispersion: The dispersion of fused particles (Ma) was diluted with deionized water so that the solid content concentration was 0.001 to 0.05% by mass.
-Measurement mode: HPF measurement mode

[Volume medium particle size (D ₅₀ ) and CV value of toner matrix particles]
The volume median particle diameter (D ₅₀ ) of the toner mother particles was measured as follows.
Measuring device, aperture diameter, analysis software, the electrolytic solution used was the same as that used in the measurement of the volume-median particle size of the aggregated particles described above (D _50).
Dispersion: Polyoxyethylene lauryl ether "Emargen (registered trademark) 109P" [manufactured by Kao Corporation, HLB (Hydrophile-Lipopfile Balance) = 13.6] is dissolved in the electrolytic solution to prepare a dispersion having a concentration of 5% by mass. Obtained.
-Dispersion condition: 10 mg of a measurement sample of the toner matrix particles after drying is added to 5 mL of the dispersion liquid, dispersed for 1 minute with an ultrasonic disperser, then 25 mL of an electrolytic solution is added, and further to an ultrasonic disperser. The mixture was dispersed for 1 minute to prepare a sample dispersion.
-Measurement conditions: By adding the sample dispersion to 100 mL of the electrolytic 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 and the particle size is measured. The volume median particle size (D ₅₀ ) and 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) x 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 Corporation) on high-quality paper "J paper A4 size" (manufactured by Fuji Xerox Co., Ltd.), the amount of toner adhered to the paper is 1.45 to 1. A solid image of .55 mg / cm ² was output with a length of 50 mm without fixing, leaving a margin of 5 mm from the upper end of the A4 paper.
Next, the same printer in which the fuser was modified to have a variable temperature was prepared, the temperature of the fuser was set to 90 ° C., and toner was fixed at a speed of 1.2 seconds per sheet in the A4 vertical direction to obtain a printed matter.
In the same manner, the temperature of the fuser was raised by 5 ° C. to fix the toner, and a printed matter was obtained.
From the top margin of the printed matter to the solid image, lightly paste the mending tape "Scotch (registered trademark) Mending Tape 810" (manufactured by Sumitomo 3M Ltd., width 18 mm) cut to a length of 50 mm. After that, a weight of 500 g was placed and pressed back and forth at a speed of 10 mm / s. Then, the attached 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 the tape was peeled off. 30 sheets of high-quality paper "Excellent White Paper A4 size" (manufactured by Oki Data Co., Ltd.) are laid under the printed matter before and after the tape is applied, and the reflected image density of the fixed image part before and after the tape is applied to each printed matter is measured. , Colorimeter "SpectroEye" (manufactured by GretagMacbeth, light emission conditions; standard light source D50, observation field of view 2 °, density standard DINNB, absolute white standard), and the fixation rate from each reflected image density according to the following formula. Was calculated.
Fixing rate (%) = (reflection image density after tape peeling / reflection image density before tape application) x 100
The lowest temperature at which the fixing rate was 90% or more 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 holding the toner 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 low temperature fixability. The lower the minimum fixing temperature, the better the low temperature fixing property.

[Toner charge stability]
Put 0.6 g of toner and 19.4 g of ferrite carrier (ferrite core, silicone coat, saturation magnetization: 71 Am ^{2 /} kg) into a 50 mL polypropylene bottle "PP Sampler Bottle Wide Mouth" (manufactured by Sampler Tech Co., Ltd.) and use a ball mill. After stirring for 20 minutes, 5 g was collected and measured with the charge amount measuring device "q-test" (manufactured by Epping Co., Ltd.) 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 charge amount Q / d (fC / 10 μm) of the toner. At that time, the Relative Density (specific gravity) was set to 1.2 g / cm ³ , and the Median Diameter adopted the value of the volume median particle diameter (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 graph of the charge amount distribution was created.
It was evaluated by the size of the half width of the maximum peak of this charge amount distribution (the width at half maximum when the distribution was cut at half the value of the maximum peak height in the distribution). The smaller the value, the narrower the charge amount distribution and the better the charge stability.

[Manufacturing of resin]
Manufacturing example A1
(Manufacturing of crystalline resin A-1)
Nitrogen was substituted inside a four-necked flask with an internal volume of 10 L equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple. And 15 g of di (2-ethylhexanoic acid) tin (II) was added. The temperature was raised to 135 ° C. with stirring, and the temperature was raised from 135 ° C. to 160 ° C. over 6 hours. The reaction was carried out 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 holding at 160 ° C. for 30 minutes, cooling to 135 ° C., the remaining amount of sebacic acid (1782.5 g) was added, the temperature was raised to 200 ° C. over 8 hours, and then the pressure in the flask was lowered to- It was held at 8 kPa (G) for 2 hours to obtain a crystalline resin A-1. The physical properties are shown in Table 1. The reaction rate in the present invention means a value of the amount of produced reaction water (mol) / the theoretical amount of produced water (mol) × 100.

Production Examples A2 to A6
(Manufacture 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.

Manufacturing example A7
(Manufacturing of crystalline resin A-7)
The inside of a four-necked flask with an internal volume of 10 L equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple was replaced with nitrogen, and 3,471 g of 1,10-decanediol and 4029 g of sebacic acid were added. The temperature was raised to 135 ° C. with stirring, held at 135 ° C. for 3 hours, and then raised from 135 ° C. to 200 ° C. over 10 hours. Then, 15 g of di (2-ethylhexanoic acid) tin (II) was added and held at 200 ° C. for 1 hour, then the pressure in the flask was lowered and held at -8 kPa (G) for 1 hour to obtain crystallinity. Resin A-7 was obtained. The physical properties are shown in Table 1.

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

Production example B2
(Manufacturing of amorphous resin B-2)
The inside of a four-necked flask with an internal volume of 10 L equipped with a nitrogen introduction pipe, a dehydration pipe, a stirrer, and a thermocouple was replaced with nitrogen, and 3458 g of polyoxypropylene (2.2) adduct of bisphenol A and poly of bisphenol A were prepared. 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 were added in a nitrogen atmosphere. While stirring, the temperature was raised to 235 ° C. and held at 235 ° C. for 8 hours, then the pressure in the flask was lowered and held at −8 kPa (G) for 1 hour. Then, after returning to atmospheric pressure, the mixture was cooled to 190 ° C., 164 g of fumaric acid, 271 g of trimellitic anhydride, and 3.5 g of 4-tert-butylcatechol were added, and the temperature was raised to 210 ° C. at 10 ° C./hr. After that, the reaction was carried out at −10 kPa (G) to a desired softening point to obtain an amorphous resin B-2. The physical properties are shown in Table 2.

Production example C1
(Manufacturing of amorphous resin C-1)
The inside of a four-necked flask with an internal volume of 10 L equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple was replaced 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 under a nitrogen atmosphere. After holding at 235 ° C. for 5 hours, the pressure in the flask was reduced and the flask was held at -8 kPa (G) for 1 hour. Then, after returning to atmospheric pressure, the mixture was cooled to 160 ° C. and kept at 160 ° C., and a mixture of 2756 g of styrene, 689 g of stearyl methacrylate, 142 g of acrylic acid, and 413 g of dibutyl peroxide was added dropwise over 1 hour. Then, after holding the temperature at 160 ° C. for 30 minutes, the temperature is raised to 200 ° C., the pressure in the flask is further lowered, and the reaction is carried out at -8 kPa (G) to a desired softening point to carry out the reaction to the desired softening point, and the amorphous resin C-1 Got The physical properties are shown in Table 2.

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

Production example D2
(Production of Resin Composition D-2)
Same as Production Example D1 except that the solution in which 60 g of the amorphous resin B-1 was dissolved in 60 g of methyl ethyl ketone was changed to the solution in which 140 g of the amorphous resin B-1 was dissolved in 140 g of methyl ethyl ketone in Production Example D1. To obtain a methyl ethyl ketone solution of the resin composition D-2.

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

[Manufacturing of resin particle dispersion]
Production example E1
(Manufacture of Resin Particle Dispersion Liquid E-1)
A solution prepared by dissolving 80 g of amorphous resin B-1 in 80 g of methyl ethyl ketone is 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 is stirred at 73 ° C. for 1 hour, and further 5 23 g of a mass% aqueous sodium hydroxide solution was added, and the mixture was stirred for 30 minutes.
Then, while maintaining the temperature at 73 ° C., 700 g of deionized water was added over 60 minutes while stirring at 200 r / min (peripheral speed 63 m / min) for phase inversion emulsification. While continuously maintaining the temperature at 73 ° C., methyl ethyl ketone was distilled off under reduced pressure to obtain an aqueous dispersion. Then, the aqueous dispersion is cooled to 30 ° C. while stirring at 280 r / min (peripheral speed 88 m / min), and then deionized water is added so that the solid content concentration becomes 20% by mass to disperse the resin particles. Liquid E-1 was obtained. The physical properties are shown in Table 4.

Production example E2
(Manufacture of Resin Particle Dispersion Liquid 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 the mixture was stirred for 30 minutes.
Then, while maintaining the temperature at 73 ° C., 700 g of deionized water was added over 60 minutes while stirring at 200 r / min (peripheral speed 63 m / min) for phase inversion emulsification. While continuously maintaining the temperature at 73 ° C., methyl ethyl ketone was distilled off under reduced pressure to obtain an aqueous dispersion. Then, the aqueous dispersion is cooled to 30 ° C. while stirring at 280 r / min (peripheral speed 88 m / min), and then deionized water is added so that the solid content concentration becomes 20% by mass to disperse the resin particles. Liquid E-2 was obtained. The physical properties are shown in Table 4.

Production example E3
(Manufacture of Resin Particle Dispersion Liquid E-3)
To the total amount of the methyl ethyl ketone solution of the resin composition D-2 obtained in Production Example D2, 23 g of a 5 mass% sodium hydroxide aqueous solution was added, and the mixture was stirred at 73 ° C. for 30 minutes.
Then, while maintaining the temperature at 73 ° C., 700 g of deionized water was added over 60 minutes while stirring at 200 r / min (peripheral speed 63 m / min) for phase inversion emulsification. While continuously maintaining the temperature at 73 ° C., methyl ethyl ketone was distilled off under reduced pressure to obtain an aqueous dispersion. After that, the aqueous dispersion was cooled to 30 ° C. while stirring at 280 r / min (peripheral speed 88 m / min), and then deionized water was added so that the solid content concentration became 20% by mass to disperse the resin particles. Liquid E-3 was obtained. The physical properties are shown in Table 4.

Manufacturing Examples E4 to E9, E11
(Manufacturing of resin particle dispersions E-4 to E-9 and 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, respectively. The physical properties are shown in Table 4.

Production example E10
(Manufacture of Resin Particle Dispersion Liquid E-10)
In a container with an internal volume of 3 L equipped with a stirrer, a reflux condenser, a thermometer and a nitrogen introduction tube, 60 g of crystalline resin A-1, 140 g of amorphous resin B-1 and 200 g of methyl ethyl ketone were placed in a nitrogen atmosphere. The resin was dissolved at 73 ° C. for 2 hours with stirring. To the obtained solution, 27 g of a 5 mass% sodium hydroxide aqueous solution was added, and the mixture was stirred for 30 minutes.
Then, while maintaining the temperature at 73 ° C., 600 g of deionized water was added over 60 minutes while stirring at 200 r / min (peripheral speed 63 m / min) for phase inversion emulsification. While continuously maintaining the temperature at 73 ° C., methyl ethyl ketone was distilled off under reduced pressure to obtain an aqueous dispersion. After that, the aqueous dispersion was cooled to 30 ° C. while stirring at 280 r / min (peripheral speed 88 m / min), and then deionized water was added so that the solid content concentration became 20% by mass to disperse the resin particles. Liquid E-10 was obtained. The physical properties are shown in Table 4.

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

[Manufacturing of wax particle dispersion]
Production example G1
(Manufacturing 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 Seiro Co., Ltd., melting point 75 ° C.) were 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 at 90 to 95 ° C. using an ultrasonic homogenizer "US-600T" (manufactured by Nissei Tokyo Office Co., Ltd.) for 20 minutes and then up to room temperature (25 ° C.). Cooled. 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 diameter (D ₅₀ ) of the wax particles in the dispersion was 0.47 μm, and the CV value was 27%.

[Manufacturing of colorant particle dispersion]
Production example H1
(Manufacture of Colorant Particle Dispersion Solution 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.) and anionic surfactant "Neoperex (registered trademark) G-15" (manufactured by Kao Co., Ltd., 15 mass) 200 g of% dodecylbenzene benzene sulfonate aqueous solution) and 257 g of deionized water were mixed and dispersed at room temperature for 10 hours using an ultrasonic homogenizer "US-600T" (manufactured by Nippon Seiki Seisakusho Co., Ltd.), and then the solid content. Deionized water was added so as to have a concentration of 24% by mass to obtain a colorant dispersion H-1. The volume median particle diameter (D ₅₀ ) of the colorant particles in the dispersion was 0.10 μm.

[Manufacturing of toner]
Example 1
(Preparation of toner 1)
300 g of resin particle dispersion E-1, 30 g of wax particle dispersion G-1, and colorant particle dispersion H-1 are placed in a 4-necked flask having an internal volume of 3 L equipped with a dehydration tube, a stirrer, and a thermocouple. 30 g and 9 g of a 10 mass% aqueous solution of the nonionic surfactant "Emargen (registered trademark) 150" (manufactured by Kao Co., Ltd., polyoxyethylene (average number of added moles 50) lauryl ether) were mixed at a temperature of 25 ° C. Next, while stirring the mixture, a solution prepared by adding 20 g of a 4.8 mass% potassium hydroxide aqueous solution to an aqueous solution prepared by dissolving 19 g of ammonium sulfate in 187 g of deionized water to adjust the pH to 8.5 was prepared at 25 ° C. for 5 minutes. The temperature was raised to 63 ° C. over 2 hours, and the temperature was maintained at 63 ° C. until the volume median particle diameter (D ₅₀ ) of the aggregated particles reached 5.6 μm, and the aggregated particles (1) were dispersed. I got the liquid.
10 g of anionic surfactant "Emar (registered trademark) E-27C" (manufactured by Kao Corporation, sodium polyoxyethylene lauryl ether sulfate, effective concentration 27% by mass), deionized in the dispersion of the aggregated particles (1). An aqueous solution containing 900 g of water and 30 g of 0.1 mol / L sulfuric acid was added. Then, the temperature was raised to 83 ° C. over 1 hour, and then the temperature was maintained at 83 ° C. until the circularity became 0.975 to obtain a dispersion of fused particles in which aggregated particles were fused. The obtained fused particle dispersion was cooled to 30 ° C., the dispersion was suction-filtered to separate solids, washed with deionized water at 25 ° C., and suction-filtered at 25 ° C. for 2 hours. Then, using a vacuum constant temperature dryer "DRV622DA" (manufactured by ADVANTEC), vacuum drying was performed at 33 ° C. for 48 hours to obtain toner matrix particles. Table 5 shows the physical properties of the obtained toner matrix particles.
100 parts by mass of the toner mother particles, 2.5 parts by mass of hydrophobic silica "RY50" (manufactured by Nippon Aerosil Co., Ltd., number average particle size; 0.04 μm), and hydrophobic silica "Cabosil (registered trademark) TS720" (Cabot) Made by Japan Co., Ltd., number average particle size; 0.012 μm) 1.0 part by mass was placed in a Henshell mixer and stirred, and passed through a 150 mesh sieve to obtain toner 1. The evaluation results of the obtained toner 1 are shown in Table 5.

Examples 2-9, Comparative Examples 1 and 2
(Preparation of toners 2-9, 11 and 12)
Toners were 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 matrix particles and the evaluation results of the toner.

Example 10
(Preparation of toner 10)
The methyl ethyl ketone solution of the resin composition D-1 was maintained at 80 ° C., and the methyl ethyl ketone was distilled off under reduced pressure to obtain the resin composition D-1.
60 parts by mass of resin composition D-1, 40 parts by mass of amorphous resin B-1, 10 parts by mass of copper phthalocyanine pigment "ECB-301" (manufactured by Dainichiseika Kogyo Co., Ltd.), paraffin wax in a henschel mixer. Add 6 parts by mass of "HNP-9" (manufactured by Nippon Seiro Co., Ltd., melting point 75 ° C.), mix for 5 minutes, and then PCM-30 (manufactured by Ikekai Co., Ltd., shaft diameter 2) rotating in the same direction. Using 9.9 cm and a shaft cross-sectional area of 7.06 cm ² ), melt-kneading was performed 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 roughly pulverized, then pulverized by a jet mill and classified to obtain toner matrix particles. Table 5 shows the physical properties of the obtained toner matrix particles.
100 parts by mass of the toner mother particles, 2.5 parts by mass of hydrophobic silica "RY50" (manufactured by Nippon Aerosil Co., Ltd., number average particle size; 0.04 μm), and hydrophobic silica "Cabosil (registered trademark) TS720" (Cabot) Made by Japan Co., Ltd., number average particle size; 0.012 μm) 1.0 part by mass was placed in a Henshell mixer, stirred, and passed through a 150 mesh fluy to obtain toner 10. The evaluation results of the toner are shown in Table 5.

From Table 5, the toners of Examples 1 to 10 have excellent low-temperature fixability, good low-temperature fixability after high-temperature storage, and further excellent charge stability as compared with the toners of Comparative Examples 1 and 2. Understand.
Further, it can be seen that among Examples 1 to 10, Examples 1 to 9, which are toners produced by using the emulsion aggregation method, are excellent in charge stability.

Claims (11)

A polyester segment ends of the crystalline resin (A) having a vinyl-based resin segments and polyester segments and ends of the amorphous resin (B), at least a portion of the chemically reaction product obtained by reacting to bond A toner for developing an electrostatic charge image, which contains the resin composition (D) containing the mixture .
The resin composition (D) contains the crystalline resin (A) and the non-crystalline resin (B).
The polyfunctional compound (S) was used in the reaction, and
The vinyl-based resin segment has a component derived from a vinyl monomer having a hydrocarbon group having 10 or more and 22 or less carbon atoms.
The acid value of the amorphous resin (B) is 5 mgKOH / g or more and 35 mgKOH / g or less.
The content of the polyester segment in the crystalline resin (A) is 60% by mass or more and 97% by mass or less.
A toner for developing an electrostatic charge image in which the polyester segment is a crystalline polyester . The toner for developing an electrostatic charge image according to claim 1 , wherein the polyfunctional compound (S) is a polyisocyanate compound. The claim that 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 charge image according to 1 or 2 . The toner for developing an electrostatic charge image according to any one of claims 1 to 3 , wherein the crystalline resin (A) has a constituent component derived from both reactive monomers. Claim 1 in which the total amount of the crystalline resin (A) used is 5% by mass or more and 45% by mass or less with respect to the total amount 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 4 to 4 . The polyester segment is a polycondensation of a polyhydric alcohol component (a-al) and a polyvalent carboxylic acid component (a-ac), and the polyhydric alcohol component (a-al) contains α, ω-aliphatic diol. The static charge image developing toner according to any one of claims 1 to 5, which contains 80 mol% or more and has 10 or more and 16 or less carbon atoms of the α, ω-aliphatic diol. A polyester segment ends of the crystalline resin (A) having a vinyl-based resin segments and polyester segments and ends of the amorphous resin (B), at least a portion of the chemically reaction product obtained by reacting to bond A resin composition for a toner for developing an electrostatically charged image , which comprises
The resin composition (D) contains the crystalline resin (A) and the non-crystalline resin (B).
The polyfunctional compound (S) was used in the reaction, and
The vinyl-based resin segment has a component derived from a vinyl monomer having a hydrocarbon group having 10 or more and 22 or less carbon atoms.
The acid value of the amorphous resin (B) is 5 mgKOH / g or more and 35 mgKOH / g or less.
The content of the polyester segment in the crystalline resin (A) is 60% by mass or more and 97% by mass or less.
A resin composition for a toner for developing an electrostatic charge image, wherein the polyester segment is a crystalline polyester. A polyester segment ends of the crystalline resin (A) having a vinyl-based resin segments and polyester segments and ends of the amorphous resin (B), at least a portion of the chemically reaction product obtained by reacting to bond A method for producing a toner for developing an electrostatic charge image, which comprises a step of obtaining a resin composition (D) containing the mixture .
The resin composition (D) contains the crystalline resin (A) and the non-crystalline resin (B).
The polyfunctional compound (S) was used in the reaction, and
The vinyl-based resin segment has a component derived from a vinyl monomer having a hydrocarbon group having 10 or more and 22 or less carbon atoms.
The acid value of the amorphous resin (B) is 5 mgKOH / g or more and 35 mgKOH / g or less.
The content of the polyester segment in the crystalline resin (A) is 60% by mass or more and 97% by mass or less.
A method for producing a toner for developing an electrostatic charge image, wherein the polyester segment is a crystalline polyester . A method for producing a toner for static charge image development, which comprises the following steps (1) to (4) .
Step (1): Obtained by a reaction in which at least a part of the end of the polyester segment of the crystalline resin (A) having the vinyl resin segment and the polyester segment is chemically bonded to the end of the amorphous resin (B). Step of obtaining the resin composition (D) containing the reaction product to be obtained Step (2): Disperse the resin composition (D) obtained in the step (1) in an aqueous medium to disperse the resin particles (E). Step of obtaining a liquid Step (3): A step of aggregating the resin particles (E) obtained in the step (2) in an aqueous medium to obtain agglomerated particles Step (4): Agglomerated particles obtained in the step (3) Process of fusing
The resin composition (D) contains the crystalline resin (A) and the non-crystalline resin (B).
The polyfunctional compound (S) is used in the reaction of the step (1).
The vinyl-based resin segment has a component derived from a vinyl monomer having a hydrocarbon group having 10 or more and 22 or less carbon atoms.
The acid value of the amorphous resin (B) is 5 mgKOH / g or more and 35 mgKOH / g or less.
The content of the polyester segment in the crystalline resin (A) is 60% by mass or more and 97% by mass or less.
A method for producing a toner for developing an electrostatic charge image, wherein the polyester segment is a crystalline polyester. The method for producing a toner for static charge image development according to claim 9 , wherein the step (1) is the following steps (1-1) and (1-2).
Step (1-1): Introduce 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). Step (1-2): A step of reacting the reactive intermediate with a resin (ii) selected from the group X, which is different from the resin (i). The static charge according to claim 9 or 10 , wherein the step (2) is a step of performing the step (1) in an organic solvent and then adding an aqueous medium and emulsifying the phase inversion to obtain a resin particle dispersion. A method for manufacturing a toner for image development.