WO2013146347A1

WO2013146347A1 - Resin mixture, aqueous resin dispersion containing same, toner, and developer

Info

Publication number: WO2013146347A1
Application number: PCT/JP2013/057400
Authority: WO
Inventors: 清隆深川; 細川　隆史; 俊英芳谷; 俊光佐久間
Original assignee: 富士フイルム株式会社
Priority date: 2012-03-30
Filing date: 2013-03-15
Publication date: 2013-10-03
Also published as: JP2013209564A

Abstract

This resin mixture contains: a high-molecular-weight resin (A) having a weight average molecular weight of 35,000-120,000 inclusive; and a low-molecular-weight resin (B) having a weight average molecular weight of at least 5,000 and less than 30,000. Resin (A) has in the primary chain a repeating unit derived from dehydroabietic acid and a constituent unit derived from a tri- or higher-valent polyvalent carboxylic acid (a) or a tri- or higher-valent polyvalent alcohol (b). Resin (B) has a repeating unit derived from dehydroabietic acid.

Description

Resin mixture, aqueous resin dispersion containing the same, toner and developer

The present invention relates to a resin mixture, an aqueous resin dispersion containing the same, a toner and a developer.

The electrophotographic method applied to various printing devices such as copiers is now widespread and can be used to instantly copy many good color images as well as black and white images. This electrophotography is typically performed by the following apparatus and process (see FIG. 1). First, the surface of the photosensitive member (latent image holding member) 1 using a photoconductive substance is charged by the charging unit 8 and exposed to light L to form a latent image electrically. A toner image is formed by applying toner from the drum 3 stored in the toner supply chamber 2 to the latent image formed here. At this time, the toner 5 is charged to a charge opposite to that of the photoreceptor. Thereafter, the toner image is transferred onto the surface of a transfer medium such as paper 4 via an intermediate transfer body (not shown) as necessary. A desired image can be obtained by fixing the transfer image 51 by heating, pressurization, solvent vapor or the like. The toner remaining on the surface of the photoreceptor is cleaned by the cleaner 7 as necessary, and is used again for developing the toner image. Further, the photoconductor is neutralized by a static eliminator 9 to prepare for the next copy.

In recent years, due to technological evolution in the field of electrophotography, the electrophotographic process has been used not only for copying machines and printers but also for printing applications. In addition to speeding up and high reliability of the apparatus, it has been increasingly demanded that the copy has the same high image quality and hue as the printed material.

International Publication No. 2011-125795A1 Pamphlet

On the other hand, the toner contains a resin mainly composed of a high molecular compound, and the influence on the environment related to its production cannot be ignored. Since there is no external shape like a molded body, it tends to be overlooked, but there is a great potential for improving environmental compatibility as a resin product that is consumed in large quantities. In the currently distributed toners, polymers derived from fossil fuels are usually used, and from the viewpoint of recent environmental problems, it is desired to replace them with those derived from natural resources with low equivalent carbon dioxide emission.

The present applicant has previously focused on a resin derived from a natural resource, dehydroabietic acid, and succeeded in synthesizing a polymer incorporating this in the main chain. And it has proposed using the polymer as resin for toners (refer the said patent document 1). This makes it possible to provide a high-performance toner using a natural material.
The present inventor was not satisfied with the above development results, and continued research and development seeking further improvements in performance in toner applications. In particular, the development goal was to achieve both the reduction of the fixing temperature on the printing medium in electrophotography and the prevention of hot offset. Specifically, the fixing temperature is usually about 150 ° C., and it is preferable to lower this. As a result, the printing temperature can be reduced, and energy consumption can be reduced. On the other hand, hot offset is a problem in the vicinity of 190 ° C., and the higher the generated temperature, the less likely to cause printing smearing. In other words, although the target temperature ranges are different, the two are in conflict with each other, and this problem cannot be solved by simply oscillating the temperature characteristics of the resin used in the toner in one direction.

The present invention contributes to the preservation of the global environment by utilizing a plant-derived compound, and the resin having a structure derived from dehydroabietic acid that has already achieved high performance in toner applications has been improved in toner. An object of the present invention is to provide a resin mixture that realizes low-temperature fixability and hot-offset prevention properties, and exhibits good stability over time, an aqueous resin dispersion containing the same, a toner, and a developer.

The object of the present invention has been achieved by the following resin mixture, aqueous resin dispersion, toner, toner production method, developer, resin, and resin production method.

[1] A resin mixture comprising a high molecular weight resin (A) having a weight average molecular weight of 35,000 or more and 120,000 or less and a low molecular weight resin (B) having a weight average molecular weight of 5,000 or more and less than 30,000. And
The resin (A) has a repeating unit derived from dehydroabietic acid and a structural unit derived from a trivalent or higher polyvalent carboxylic acid (a) or a trivalent or higher polyhydric alcohol (b) in the main chain. The resin (B) is a resin mixture having a repeating unit derived from dehydroabietic acid.
[2] The resin mixture according to [1], wherein the repeating unit derived from dehydroabietic acid is represented by the following formula (IA) or (IB).

[Wherein, ring A represents a non-aromatic 6-membered ring. Ring Cy represents a saturated or unsaturated 6- or 7-membered ring which may contain a hetero atom. X ¹ represents a single bond or a divalent linking group. X ² , Y ¹ , Y ² , Y ³ represent a divalent linking group. R represents a substituent that may be substituted on the ring A, the ring Cy, and the benzene ring. n1 represents an integer of 0 to 18. ]
[3] The resin mixture according to [1] or [2], wherein the repeating unit derived from dehydroabietic acid is a repeating unit represented by the following formula (IA-1) or (IB-1).

[Wherein, ring A, X ¹ , X ² , Y ¹ to Y ³ and R are as defined in formula (IA) or (IB). Ring B represents a non-aromatic 6-membered ring, and n2 represents an integer of 0 to 17. ]
[4] The resin according to any one of [1] to [3], wherein the repeating unit derived from dehydroabietic acid is a repeating unit represented by the following formula (IA-2) or (IB-2): blend.

[Wherein, X ¹ , X ² and Y ¹ to Y ³ have the same meanings as in formula (IA) or (IB). ]
[5] The resin mixture according to any one of [1] to [4], wherein both the resins (A) and (B) have a repeating unit represented by the following formula (II).

[Wherein L ² and L ³ represent —O—, —S—, —N (Ra) —, —C (═O) — or —NHC (═O) —, and L ¹ represents a divalent linkage. Represents a group. Ra represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group. ]
[6] The resin mixture according to any one of [1] to [5], wherein the resins (A) and (B) are both polyester resins.
[7] The ratio of the resin (A) to the resin (B) in the solid content mass is 30:70 to 70:30 (based on mass), and any one of [1] to [6] Resin mixture.
[8] The molecular weight distribution (weight average molecular weight / number average molecular weight) of the resin (A) is 7 to 25, and the molecular weight distribution of the resin (B) is 2 to 6. Any one of [1] to [7] The resin mixture described in 1.
[9] The proportion of the structural unit derived from the trivalent or higher polyvalent carboxylic acid (a) or the trivalent or higher polyhydric alcohol (b) is 1 to 20 mol% with respect to the total mol of the resin (A). The resin mixture according to any one of [1] to [8].
[10] A structural unit derived from a trivalent or higher polyvalent carboxylic acid (a) or a trivalent or higher polyhydric alcohol (b) is represented by the following formula (III-a) or (III-b): [1] ] The resin mixture as described in any one of [9].

[In the formula, Ar represents an aromatic ring residue. Z represents a cyclic or chain aliphatic hydrocarbon residue which may contain an ether bond. m1 and m2 represent an integer of 3 or more. * Is a bond. ]
[11] The resin (A) comprises a tripolymer or higher polyvalent carboxylic acid (a) or a trivalent or higher carboxylic acid having a repeating unit derived from dehydroabietic acid and having a weight average molecular weight of 3,000 to 25,000. The resin mixture according to any one of [1] to [10], wherein the resin mixture has a branched structure linked via a structural unit derived from the polyhydric alcohol (b).
[12] X ¹ is an alkylene group, X ² is ** — C (═O) —L ^a —C (═O) — (** represents a bond bonded to a benzene ring, and ^La is alkylene Y ¹ to Y ³ are all —C (═O) —, —O—, or an alkyleneoxy group bonded to a ring A or a benzene ring by a carbon atom. [1] to [3] represents a group or an alkenylene group) 11]. The resin mixture as described in any one of [11].
[13] An aqueous resin dispersion comprising the resin mixture according to any one of [1] to [12] in an aqueous medium.
[14] The aqueous resin dispersion according to [13], further comprising a pigment and a release agent.
[15] A toner comprising the resin mixture according to any one of [1] to [12].
[16] An aqueous dispersion of a high molecular weight resin (A) having a weight average molecular weight of 35,000 or more and 120,000 or less and an aqueous dispersion of a low molecular weight resin (B) having a weight average molecular weight of 5,000 or more and less than 30,000 Manufacturing a product, a crystalline polyester resin dispersion, and a colorant dispersion;
Mixing each dispersion, and aggregating the resin,
The resin (A) has a repeating unit derived from dehydroabietic acid and a structural unit derived from a trivalent or higher polyvalent carboxylic acid (a) or a trivalent or higher polyhydric alcohol (b) in the main chain. And the resin (B) has a repeating unit derived from dehydroabietic acid.
[17] A toner produced by the production method according to [16].
[18] A developer comprising the toner according to [15] or [17] and a carrier.
[19] A resin having a repeating unit derived from dehydroabietic acid and a structural unit derived from a trivalent or higher polyvalent carboxylic acid (a) or a trivalent or higher polyhydric alcohol (b) in the main chain. A resin having a weight average molecular weight of 35,000 or more and 120,000 or less and branched via a structural unit derived from a trivalent or higher polyvalent carboxylic acid (a) or a trivalent or higher polyhydric alcohol (b). .
[20] A process for producing a resin as described in [19], wherein a prepolymer having a repeating unit derived from dehydroabietic acid, a trivalent or higher polyvalent carboxylic acid (a) or a trivalent or higher polyhydric alcohol The manufacturing method of resin including the process made to react with (b).

In the present specification, when there are a plurality of substituents or linking groups (hereinafter referred to as substituents) indicated by specific symbols, or when a plurality of substituents are specified simultaneously or alternatively, The groups and the like may be the same as or different from each other. The same applies to the definition of the number of substituents and the like. Further, even if not specifically stated, when a plurality of substituents and the like are close (especially when adjacent), they may be connected to each other or condensed to form a ring.

The resin mixture of the present invention, the aqueous resin dispersion containing the resin mixture, the toner and the developer contribute to the preservation of the global environment by utilizing a plant-derived compound, and improve the toner at a high level of low-temperature fixability, hot Demonstrates the prevention of offset and the stability over time (storability).

1 is a side view of an apparatus schematically shown for explaining a copying machine based on electrophotography and a copying process thereof.

The resin mixture of the present invention contains a resin having a repeating unit derived from dehydroabietic acid (hereinafter, this may be referred to as a dehydroabietic acid skeleton [DA skeleton]). This has good properties as a toner application while being derived from a plant (see Patent Document 1). The reason is considered that the tricyclic portion including the benzene ring of the DA skeleton is structurally stable and contributes to the stabilization of the toner characteristics. After developing this toner, the present inventor made progress in improving and developing the resin having the DA skeleton by various molecular modifications and blending changes. In such a case, the polymer constituting the resin is made to have a specific molecular weight, a branched structure is imparted, and the polymer is similarly used in combination with a low molecular weight resin having a DA skeleton. It has been found that it is excellent in the prevention of offset. The present invention has been made based on such findings. Hereinafter, the present invention will be described in detail focusing on preferred embodiments thereof.

<Resin A>
Resin A used in the present invention is derived from a repeating unit derived from dehydroabietic acid (DA skeleton) and a trivalent or higher polyvalent carboxylic acid (a) or a trivalent or higher polyhydric alcohol (b) in the main chain. And a structural unit. The weight average molecular weight of this resin is 35,000 or more and 120,000 or less. The DA skeleton is preferably a repeating unit represented by the following formula (I) (hereinafter, the tricyclic portion may be referred to as “DA main skeleton”).

[Repeating unit containing structure represented by formula (I)]

・ Ring A
Ring A is a non-aromatic 6-membered ring, and examples thereof include a cyclohexane ring and a dehydrocyclohexene ring. In the case of a dehydrocyclohexane ring, 1 to 2 double bonds are preferable, and a cyclohexene ring and a cyclohexadiene ring are exemplified. . In ring A, R may be substituted.

・ Ring Cy
Ring Cy represents a saturated or unsaturated 6- or 7-membered ring which may contain a hetero atom, but a non-aromatic ring is preferred, and a non-aromatic 6-membered ring is preferred. Ring Cy is preferably an aliphatic ring, and may have a carbon-carbon double bond in a ring-constituting part other than a shared part with a benzene ring, but preferably has no double bond.
The heterocyclic ring may have a double bond in a ring constituent part other than a shared part with the benzene ring, but preferably does not have a double bond. Examples of the hetero atom constituting the hetero ring include a nitrogen atom, an oxygen atom, and a sulfur atom, but a nitrogen atom is preferred, and the number of hetero atoms constituting the hetero ring is preferably one. In the case of a heterocycle, a 7-membered ring is preferred, and a constituent part constituting the heterocycle is more preferably contained in —C (═O) NH—, and one of the parts connecting the benzene ring and ring A (dehydroabietine) More preferably, the bond at the 9th and 10th positions is a single bond and the other is —CH ₂ C (═O) NH—.

・ X ⁰
X ⁰ represents a single bond or a divalent linking group. Examples of the divalent linking group include an alkylene group, a cycloalkylene group, an alkenylene group, an alkynylene group, an arylene group, a divalent heterocyclic group, —O—, —S—, —SO—, —SO ₂ —, —N (Ra) —, —C (═O) — or a combination of these groups (eg, -alkylene-O—, —C (═O) —O -, -N (Ra) -C (= O)-, -N (Ra) -SO _2- , -O-C (= O) -N (Ra)-). Here, Ra represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group. Preferable examples of the alkyl group, aryl group or heterocyclic group include examples of the substituent T described later.

X ⁰ may form a bis group having a structure represented by the formula (I) through a single bond or the divalent linking group, and is derived from a copolymer component constituting the main chain. a bond or Y ¹ and may be combined.
In the case of forming a bis group, X ⁰ is preferably a single bond or an alkylene group, and the alkylene group is preferably a methylene group. The methylene group may be substituted with an alkyl group (preferably having 1 to 8 carbon atoms). Examples of the substituted methylene group include dimethylalkylene such as methylmethylene, dimethylmethylene, isopropylmethylene, and t-octylmethylene. It is done. X ⁰ is particularly preferably an unsubstituted methylene group.

On the other hand, in the case of bonding with a bond derived from a copolymerization component constituting the main chain, X ⁰ is —C (═O) —, —O—, ** — C (═O) —L ^a —C (= O)-, **-L ^b -C (= O)-, **-L ^c -Ar ¹ -O-, **-L ^e -O- are preferred. Here, ** represents a bond bonded to the benzene ring. L ^a represents an alkylene group or alkenylene group. If L ^a is an alkylene group, it preferably has 1 to 10 carbon atoms, more preferably 2 to 10, more preferably 2. If L ^a is an alkenylene group, it preferably has 2 to 10 carbon atoms, more preferably 2. L ^b represents an alkylene group or an alkenylene group, preferably having 1 to 4 carbon atoms, more preferably 2, and further preferably —CH (CH ₃ ) —. L ^c represents an alkylene group or an alkenylene group, preferably having 1 to 4 carbon atoms, more preferably 3, and further preferably —C (CH ₃ ) ₂ —. L ^e represents a hydrocarbon group, it preferably has 1 to 10 carbon atoms, more preferably 1-4. Ar ¹ represents an arylene group and is preferably phenylene.

・ Y ¹
Y ¹ represents a divalent linking group, preferably the divalent linking group exemplified for X ⁰ (the bond ** binds to ring A), and the preferred range is also the same.

・ R
R represents a substituent, and examples of such a group include a substituent T described later. When R is substituted with ring Cy or ring A, R may be = 0. R is preferably an alkyl group, an alkenyl group, an alkoxy group or a halogen atom, more preferably an alkyl group, an alkenyl group or an alkoxy group, and particularly preferably an alkyl group. The alkyl group or alkoxy group preferably has 1 to 8 carbon atoms, more preferably 1 to 3 carbon atoms. Of the alkyl groups, a methyl group and an isopropyl group are preferable.

・ N1
n1 represents an integer of 0 to 18, preferably 1 to 5, and more preferably 3 to 5.

Specific examples of the repeating unit (DA main skeleton) represented by the formula (I) include the structures represented by the following.

The structure represented by the formula (I) is preferably a structure represented by the following formula (IA) or (IB).

In the formula, ring A, ring Cy, Y ¹ , R and n1 have the same meanings as in formula (I), and preferred ranges are also the same.

・ X ¹
X ¹ represents a single bond or a divalent linking group. Examples of the divalent linking group for X ¹ include the divalent linking groups listed for X ⁰ . Among these, X ¹ is preferably a single bond or an alkylene group, and the alkylene group is preferably a methylene group. The methylene group may be substituted with an alkyl group (preferably having 1 to 8 carbon atoms). Examples of the substituted methylene group include dimethylalkylene such as methylmethylene, dimethylmethylene, isopropylmethylene, and t-octylmethylene. It is done. X ⁰ is particularly preferably an unsubstituted methylene group.

・ X ² , Y ² , Y ³
X ² , Y ² and Y ³ represent a divalent linking group. X ² , Y ² and Y ³ have the same meaning as Y ¹ , and the preferred range is also the same.

The structure represented by the above formula (IA) or (IB) is preferably a structure represented by the following formula (IA-1) or (IB-1), and is represented by the following formula (IA-2) or (IB-2) The structure represented by is more preferable.

In the formula (IA-1) or (IB-1), the rings A, X ¹ , X ² , Y ¹ to Y ³ and R are the same as those in the above formula (IA) or (IB), and the preferred ranges are also the same. is there.

・ Ring B
Ring B represents a non-aromatic 6-membered ring. Ring B may have a double bond in addition to the bond shared with the benzene ring. In this case, one double bond is preferred. That is, even if the bond shared with ring A is a double bond, the bond not shared with either the benzene ring or ring A may be a double bond. In ring B, R may be substituted, and as a substituent, in addition to substituent T described later, ═O is preferable.

N2 represents an integer from 0 to 17.

In the formula (IA-2) or (IB-2), X ¹ , X ² and Y ¹ to Y ³ have the same meanings as the formula (IA-1) or (IB-1), and preferred ranges are also the same. .

In the formulas (IA), (IB), (IA-1), (IB-1), (IA-2) and (IB-2), X ¹ is an alkylene group, and X ² is the above-mentioned **- C (═O) —L ^a —C (═O) — (** represents a bond bonded to the benzene ring, L ^a represents an alkylene group or an alkenylene group), or —C (═O) — Y ¹ to Y ³ are all preferably —C (═O) —, —O—, or an alkyleneoxy group bonded to the ring A or the benzene ring by a carbon atom, and X ¹ is a methylene group. X ² is ** — C (═O) —L ^a ′ —C (═O) — (L ^a ′ represents an alkylene group), and Y ¹ to Y ³ are all —C (═O )-Is more preferable.

[Method for producing resin A]
The structure represented by the formula (I) can be incorporated into the polymer chain length using a compound represented by the following formula (I ′) as a raw material monomer.

In formula (I ′), ring A, ring Cy, X ⁰ , Y ¹ , R and n1 have the same meanings as in formula (I), and preferred ranges are also the same. G ¹ represents a hydrogen atom or a hydroxyl group, and G ² represents a hydrogen atom, a hydroxyl group, or a hydroxy group, a carboxyl group, a mercapto group, an amino group, or an organic group having —N═C═O.

Of these, compounds represented by the following formula (IA ′) or (IB ′) are preferable.

In formula (IA ′) or (IB ′), ring A, ring Cy, X ¹ , R and n1 have the same meanings as formula (IA) or (IB), and preferred ranges are also the same. G represents a carboxyl group, a hydroxyl group, a mercapto group, an amino group, —N═C═O, or an organic group substituted by these.
These preferred groups are, in short, the preferred groups mentioned for X ⁰ , X ² , Y ¹ , Y ² , Y ³ in the formulas (I), (IA), (IB), and the benzene ring or ring A A bond in which a hydrogen atom or a hydroxyl group is bonded to the bond on the side opposite to the bond bonded to is preferable.

The structure represented by the formula (I) does not limit stereoisomerism, and may be any stereoisomer or a mixture thereof.
Here, the repeating unit including the structure represented by the formula (I) of the resin A is within the range represented by the formula (I), and even if it is one type of repeating unit, two or more different structures are used. May be a repeating unit.
In addition, the compound represented by the formula (I) preferably has a structure derived from dehydroabietic acid, an analog thereof or a compound derived therefrom.

Note that dehydroabietic acid is one of the components constituting rosin contained in pine resin of plant origin. That is, since a material of natural origin can be used as its substrate, it is offset in the amount of carbon dioxide emission, and the equivalent emission amount can be greatly reduced as compared with a plastic material of fossil fuel origin. It is an environmentally-friendly material derived from biomass resources that is desired as a next-generation material.

Examples of dehydroabietic acid analogs or compounds derived therefrom include the following compounds.

These are all commercially available from Sigma-Aldrich, Tokyo Chemical Industry Co., Ltd., or can be synthesized from dehydroabietic acid.
In particular, dehydroabietic acid can be obtained, for example, from rosin. Constituents contained in rosin vary depending on the method of collection and the production area of pine, but in general, abietic acid (1), neoabietic acid (2), parastrinic acid (3), levopimaric acid (4), It is a mixture of diterpene resin acids such as dehydroabietic acid (5), pimaric acid (6) and isopimaric acid (7). Among these diterpene resin acids, the compounds represented by the above (1) to (4) are disproportionated by heat treatment in the presence of a certain metal catalyst, and dehydroabietic acid (5 ) And dihydroabietic acid (8). Thus, dehydroabietic acid (5) can be obtained relatively easily by subjecting rosin, which is a mixture of various resin acids, to an appropriate chemical treatment, and can be produced industrially and inexpensively. Dihydroabietic acid (8) and dehydroabietic acid (5) can be easily separated by a known method.

Here, the dimerization can be synthesized by the method described in JP 2011-26569 A. Specifically, when linking with a single bond, the reaction can proceed by adding a catalytic amount of N, N-dimethylformamide using oxalyl chloride. When connecting with alkylene, the method of replacing the said oxalyl chloride with a dichloromethane etc. is mentioned. Alternatively, the reaction may proceed by mixing the monomer with an aldehyde compound (for example, formalin, acetaldehyde) or a ketone compound (for example, acetone) and adding a catalytic amount of trifluoroacetic acid. In the present invention, even when alkyleneation occurs at different positions on the benzene ring, these may be used in combination.
Further, acylation to the benzene ring is easily synthesized by usual acylation, for example, Friedel-Crafts reaction with Lewis acid such as succinic anhydride and aluminum chloride or iron chloride.

Among the above compounds, dicarboxylic acid compounds or diol compounds can synthesize polyester resins by the condensation reaction of the former with a diol compound and the latter with a dicarboxylic acid compound, and those having one carboxyl group and one hydroxyl group A polyester resin can be synthesized by condensation or condensation with another compound having one carboxyl group and one hydroxyl group.
Moreover, resins other than polyester resins can be produced using these as raw materials.

(Copolymerization unit)
In the present invention, the resin A has a structure derived from a trivalent or higher polyvalent carboxylic acid (a) or a trivalent or higher polyhydric alcohol (b). Resin A may include only one type of structure derived from a trivalent or higher polyvalent carboxylic acid (a) or a trivalent or higher polyhydric alcohol (b), or a trivalent or higher polyvalent carboxylic acid ( You may be comprised including 2 or more types of structures derived from a) or a trihydric or more polyhydric alcohol (b). The trivalent or higher polyvalent carboxylic acid (a) may be any trivalent or higher polyvalent aliphatic or polyvalent aromatic carboxylic acid. preferable. Examples of the trivalent or higher polyvalent aliphatic carboxylic acid include citric acid, aconitic acid, butane-1,2,3,4-tetracarboxylic acid, 3-butene-1,2,3-tricarboxylic acid, and the like. It is done.

In the present invention, the structure derived from a trivalent or higher polyvalent carboxylic acid (a) or a trivalent or higher polyhydric alcohol (b) is a structure represented by the following formula (III-a) or (III-b): These compounds can incorporate a compound represented by the following formula (III-a ′) or (III-b ′) as a raw material monomer into a polymer.

* Represents a bond.

・ M1, m2
m1 and m2 represent an integer of 3 or more. m1 and m2 are preferably 3 to 6.

・ Ar
Ar represents an aromatic ring residue, and Ar may be either a benzene ring residue, a naphthalene ring residue, or an aromatic ring residue in which two or more aromatic rings are linked, but a benzene ring residue or a naphthalene ring Residues are preferred, and benzene ring residues are particularly preferred.

When the compound represented by the formula (III-a ′) is used as the raw material monomer, it is preferable to use the —CO ₂ H moiety as an acid anhydride, an acid halide such as —COCl, or an ester.

Examples of the raw material monomer for obtaining such a residue include the following compounds.

These are preferably used as acid anhydrides, halides, and ester compounds when used as raw material monomers.

・ Z
Z represents a cyclic or chain aliphatic hydrocarbon residue (preferably having 3 to 6 carbon atoms) which may contain an ether bond. Of these, saturated aliphatic residues are preferable, and chain aliphatic groups are more preferable. Examples of the raw material monomer for obtaining such a residue include the following compounds.

In the present invention, the proportion of the structure derived from the trivalent or higher polyvalent carboxylic acid (a) or the trivalent or higher polyhydric alcohol (b) depends on these valences. The content is preferably 1 to 20 mol%, more preferably 2 to 15 mol%, based on the total mol of each repeating unit.

For this reason, the mol% contained in the resin A of the skeleton derived from dehydroabietic acid (DA skeleton) is 1 to 49.5 mol% with respect to the total components of the constituent raw materials or each repeating unit in the resin A. It is preferably 5 to 49.5 mol%. When the raw material monomer containing the DA skeleton is self-condensed containing both a hydroxyl group and a carboxyl group, it is preferably 2 to 99 mol%, more preferably 10 to 99 mol%.
On the other hand, when it is not self-condensation, raw material monomers such as diol compounds and dicarboxylic acid compounds other than the repeating unit containing the structure represented by formula (I) are based on the constituent raw materials in resin A or the total moles of each repeating unit. The DA skeleton is preferably 1 to 49.5 mol%, more preferably 5 to 49.5 mol%.

Resin A is branched by the above trivalent or higher polyvalent carboxylic acid (a) or trivalent or higher polyhydric alcohol (b). This branch is a straight chain having a weight average molecular weight of 1,000 or more. It is preferably branched from a main chain, more preferably branched from a linear main chain having a weight average molecular weight of 1,000 or more and 20,000 or less, and a straight chain having a weight average molecular weight of 1,500 or more and 15,000 or less. More preferably, it is branched from a chain-like main chain. Such branching can be adjusted by a method of adding a trivalent or higher polyvalent carboxylic acid (a) or a trivalent or higher polyhydric alcohol (b) as a raw material monomer.

For example, (a) the above-mentioned trivalent or higher polyvalent carboxylic acid (a) or a derivative thereof or a trivalent or higher polyhydric alcohol (b) is added to a prepolymer having no branched structure, or (b) these It is possible to adjust by adding the polyvalent compound separately. In the case of adding the trivalent or higher polyvalent carboxylic acid (a) of the present invention, the method (b) is preferable from the viewpoint of adjusting the acid value, and the number of times of addition in divided addition is preferably 2 times or more, preferably 2 to 5 times, more preferably 2 to 3 times.

The weight average molecular weight (M _high ) of the resin A is from 35,000 to 120,000, preferably from 40,000 to 120,000, more preferably from 50,000 to 120,000. By setting the molecular weight to be equal to or higher than the lower limit, occurrence of hot offset can be suppressed. By setting the upper limit value or less, the fixing lower limit temperature can be set within a suitable range.

The molecular weight distribution (weight average molecular weight / number average molecular weight) of the resin (A) is preferably 7 to 25, and more preferably 7 to 20.

The weight average molecular weight, number average molecular weight, and molecular weight distribution in the present invention are values obtained by molecular weight measurement (polystyrene conversion) by gel permeation chromatography (GPC). Further, the weight average molecular weight of the polymer defined in the present invention is within a range in which no gel or THF-insoluble matter is usually observed even if the branch-crosslinking reaction proceeds.
Unless otherwise specified, in this specification, tetrahydrofuran is used as a carrier, and molecular weight is indicated by a value using TSK-gel Super AWM-H (trade name) manufactured by Tosoh Corporation as a column.

<Resin B>
The resin B used in the present invention is a resin containing a structure represented by the formula (I) in the main chain, and has a weight average molecular weight of 5,000 or more and less than 30,000.
Also in the resin B, the structure represented by the formula (I) is the same as that of the resin A, and the preferred range is also the same.
Also, the resin B preferably includes a structure derived from a trivalent or higher polyvalent carboxylic acid (a) or a trivalent or higher polyhydric alcohol (b), and is the same as the resin A except for the weight average molecular weight. .

The weight average molecular weight (M _low ) of the resin (B) is 5,000 or more and less than 30,000, preferably 10,000 or more and less than 30,000, and preferably 15,000 or more and 25,000 or less. More preferred. By setting the weight average molecular weight to the lower limit value or more, the particle shape of the aqueous dispersion can be controlled. By setting the upper limit value or less, the fixing lower limit temperature can be set within a suitable range.

The molecular weight distribution (weight average molecular weight / number average molecular weight) of the resin (B) is preferably 2 to 6, and more preferably 3 to 6.
In addition, the measuring method of a weight average molecular weight, a number average molecular weight, and molecular weight distribution is the same as that of the said resin (A).
The resin (B) may or may not have a branch. Among them, the resin (B) is a structural unit derived from a repeating unit derived from dehydroabietic acid and a trivalent or higher polyvalent carboxylic acid (a) or a trivalent or higher polyhydric alcohol (b) in the main chain. It is preferable that it has. In this specification, the presence or absence of branching may be interpreted and judged in the usual sense. However, when a strict comparison is required, etc., when there is a side chain having a weight average molecular weight of 1,000 or more, this is determined. Consider it a branch.

(Other structural units)
Resins A and B preferably have a repeating unit represented by the following formula (II) in addition to the repeating unit containing the structure represented by the above formula (I). This repeating unit may incorporate two or more repeating units having different structures. However, as described above, when the raw material monomer having the structure represented by the formula (I) has a hydroxyl group and a carboxyl group, a polyester resin can be produced by self-condensation.

・ L ²
In the formula (II), L ² and L ³ represent —O—, —S—, —N (Ra) —, —C (═O) — or —NHC (═O) —. Ra has the same definition as Ra in X ⁰ in formula (I).

The raw material monomer giving the repeating unit of the formula (II) may be replaced with the following groups in L ² and L ³ of L ¹ . The following including L ² or L ³ is preferable.
In the case of -O-: -OH
For -S-: -SH
In the case of —N (Ra) —: —NH (Ra)
In the case of —C (═O) —: —CO ₂ H or a derivative thereof (an carboxylic acid anhydride, halide, ester)
In the case of —NHC (═O) —: —N═C═O
Here, Ra has the same definition as Ra in X ⁰ in formula (I).

・ L ¹
L ¹ represents a divalent linking group, an alkylene group (preferably having 1 to 18 carbon atoms), an alkenylene group (preferably having 2 to 18 carbon atoms), an alkynylene group (preferably having 2 to 18 carbon atoms), an arylene group ( Preferably 6 to 18 carbon atoms), a divalent heterocyclic group (preferably a 5- or 6-membered ring having 0 to 18 carbon atoms and containing any of an oxygen atom, a nitrogen atom and a sulfur atom as a ring-constituting atom) And combinations of these groups are preferred, and —O—, —S—, —SO—, —SO ₂ —, —N (Ra) —, —C (═O) are present in the linking chain formed by the combination of these groups. -Or a combination of these groups (eg, -alkylene-O-, -C (= O) -O-, -N (Ra) -C (= O)-, -N (Ra) -SO ₂ -,- O—C (═O) —N (Ra) —) may be linked via Here, Ra has the same definition as Ra in X ⁰ in formula (I).
The total carbon number of the divalent linking group is preferably 1-18.

Examples of the raw material monomer for obtaining the repeating unit of the formula (II) include a dicarboxylic acid compound or a derivative thereof, a diol compound, a diamine compound, a diisocyanate compound, and a compound having a hydroxyl group and a carboxyl group.
In the present invention, the resin A is preferably a polyester resin. Therefore, in the present invention, a dicarboxylic acid compound or a derivative thereof, or a diol compound is preferable. Here, in the present invention, a divalent carboxylic acid compound or a divalent alcohol compound is used to adjust the branching of the polymer chain. The branched component will be described later.

Examples of the diol compound include ethylene glycol, 1,2-propanediol, 1.3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol, Alicyclic diols such as 1,12-dodecanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, cyclohexanediol, cyclohexanedimethanol, hydrogenated bisphenol A; bisphenol A ethylene oxide adducts, bisphenol A, etc. And aromatic diols such as propylene oxide adducts of bisphenols.
Here, examples of bisphenol include bisphenol F, bisphenol S, bisphenol SF and the like in addition to bisphenol A.
Examples of the dicarboxylic acid compound include aliphatic, aromatic or heterocyclic dicarboxylic acids. Specifically, for example, aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, cyclohexanedicarboxylic acid, dicarboxylic acid, and the like. Examples thereof include saturated or unsaturated aliphatic dicarboxylic acids such as cyclohexanedicarboxylic acid, malonic acid, succinic acid, glutaric acid, pimelic acid, adipic acid, maleic acid and fumaric acid.

<Blend resin>
The resin of the present invention is a resin obtained by blending resin A and resin B. That is, the resin A and the resin B are those synthesized separately, and the resin of the present invention is a resin obtained by blending them. The resin of the present invention preferably contains resin A: resin B at 30:70 to 70:30, preferably 40 to 60, when the total of resin A and resin B is 100 (mass basis). Is more preferable.

<Substituent T>
In the present specification, a substituent or a linking group for which substitution / non-substitution is not specified means that the group may have an arbitrary substituent. This is also synonymous for compounds that do not specify substitution / non-substitution. Preferred substituents include the following substituent T.

Examples of the substituent T include the following.
An alkyl group (preferably an alkyl group having 1 to 20 carbon atoms, such as methyl, ethyl, isopropyl, t-butyl, pentyl, heptyl, 1-ethylpentyl, benzyl, 2-ethoxyethyl, 1-carboxymethyl, etc.), alkenyl A group (preferably an alkenyl group having 2 to 20 carbon atoms such as vinyl, allyl, oleyl and the like), an alkynyl group (preferably an alkynyl group having 2 to 20 carbon atoms such as ethynyl, butadiynyl, phenylethynyl and the like), A cycloalkyl group (preferably a cycloalkyl group having 3 to 20 carbon atoms, such as cyclopropyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, etc.), an aryl group (preferably an aryl group having 6 to 26 carbon atoms, for example, Phenyl, 1-naphthyl, 4-methoxyphenyl, -Chlorophenyl, 3-methylphenyl, etc.), heterocyclic groups (preferably heterocyclic groups of 2 to 20 carbon atoms, preferably 5- or 6-membered heterocycles having at least one oxygen atom, sulfur atom, nitrogen atom) A cyclic group is preferred, for example, 2-pyridyl, 4-pyridyl, 2-imidazolyl, 2-benzimidazolyl, 2-thiazolyl, 2-oxazolyl, etc.), an alkoxy group (preferably an alkoxy group having 1 to 20 carbon atoms, for example, Methoxy, ethoxy, isopropyloxy, benzyloxy, etc.), aryloxy groups (preferably aryloxy groups having 6 to 26 carbon atoms, such as phenoxy, 1-naphthyloxy, 3-methylphenoxy, 4-methoxyphenoxy, etc.), An alkoxycarbonyl group (preferably an alkoxycarbonyl group having 2 to 20 carbon atoms) Nyl groups such as ethoxycarbonyl, 2-ethylhexyloxycarbonyl and the like, amino groups (preferably containing an amino group having 0 to 20 carbon atoms, alkylamino group, arylamino group, such as amino, N, N-dimethyl) Amino, N, N-diethylamino, N-ethylamino, anilino, etc.), sulfamoyl groups (preferably sulfonamido groups having 0 to 20 carbon atoms, such as N, N-dimethylsulfamoyl, N-phenylsulfamoyl) Etc.), an acyl group (preferably an acyl group having 1 to 20 carbon atoms such as acetyl, propionyl, butyryl, benzoyl etc.), an acyloxy group (preferably an acyloxy group having 1 to 20 carbon atoms such as acetyloxy, Benzoyloxy, etc.), carbamoyl groups (preferably those having 1 to 20 carbon atoms) Rubamoyl groups such as N, N-dimethylcarbamoyl and N-phenylcarbamoyl), acylamino groups (preferably acylamino groups having 1 to 20 carbon atoms such as acetylamino and benzoylamino), sulfonamide groups (preferably Is a sulfamoyl group having 0 to 20 carbon atoms, such as methanesulfonamide, benzenesulfonamide, N-methylmethanesulfonamide, N-ethylbenzenesulfonamide, etc., an alkylthio group (preferably an alkylthio having 1 to 20 carbon atoms) Groups such as methylthio, ethylthio, isopropylthio, benzylthio, etc., arylthio groups (preferably arylthio groups having 6 to 26 carbon atoms, such as phenylthio, 1-naphthylthio, 3-methylphenylthio, 4-methoxyphenylthio ), An alkyl or arylsulfonyl group (preferably an alkyl or arylsulfonyl group having 1 to 20 carbon atoms, such as methylsulfonyl, ethylsulfonyl, benzenesulfonyl, etc.), a hydroxyl group, a cyano group, a halogen atom (such as a fluorine atom, chlorine) Atoms, bromine atoms, iodine atoms, etc.), more preferably alkyl groups, alkenyl groups, aryl groups, heterocyclic groups, alkoxy groups, aryloxy groups, alkoxycarbonyl groups, amino groups, acylamino groups, hydroxyl groups or halogen atoms. And particularly preferably an alkyl group, an alkenyl group, a heterocyclic group, an alkoxy group, an alkoxycarbonyl group, an amino group, an acylamino group or a hydroxyl group.
In addition, each of the groups listed as the substituent T may be further substituted with the substituent T described above.

<Method for producing resins A and B>
The resin of the present invention can be produced by an ordinary polymer synthesis reaction.
The resin of the present invention is preferably a polyester resin. For example, a method described in New Polymer Experimental Science 3, Polymer Synthesis / Reaction (2), pages 78 to 95, Kyoritsu Publishing (1996) (for example, ester Exchange polymerization, direct esterification, melt polymerization such as acid halide, low-temperature solution polymerization, high-temperature solution polycondensation, interfacial polycondensation, etc.). A transesterification method and a direct ester method are preferably used.

In particular, the resin A of the present invention has a specific branched structure, and the resin B preferably has such a branched structure.
Although the manufacturing method of resin A of this invention is demonstrated below, the preferable aspect of resin B can also be manufactured by the same method except a weight average molecular weight.

The resin can be obtained by reacting a prepolymer having a repeating unit derived from dehydroabietic acid with a trivalent or higher polyvalent carboxylic acid (a) or a trivalent or higher polyhydric alcohol (b). it can. The molecular weight of the prepolymer is preferably 1000 to 20000 in terms of weight average molecular weight, and more preferably 1500 to 15000 in terms of weight average molecular weight. The mixing ratio of the prepolymer to the trivalent or higher polyvalent carboxylic acid (a) or the trivalent or higher polyhydric alcohol (b) is preferably in the same range as described above as the copolymerization ratio.

The toner of the present invention includes an aqueous dispersion of a high molecular weight resin (A) having a weight average molecular weight of 35,000 or more and 120,000 or less, and a low molecular weight resin (B) having a weight average molecular weight of 5,000 or more and less than 30,000. The aqueous dispersion, the crystalline polyester resin dispersion, and the colorant dispersion are prepared, and the dispersions are aggregated. Here, the resin (A) is derived from a repeating unit derived from dehydroabietic acid and a trivalent or higher polyvalent carboxylic acid (a) or a trivalent or higher polyhydric alcohol (b) in the main chain. With units. Resin (B) has a repeating unit derived from dehydroabietic acid. The weight average molecular weight, number average molecular weight, and molecular weight distribution of the resin (A) and resin (B) used herein are as defined above, including their preferred ranges. Hereinafter, the preparation of the toner will be described in detail focusing on preferred embodiments thereof.

Examples of the method of mixing the resin (A) and the resin (B) include melt mixing using a biaxial kneader, and a method of mixing after forming an aqueous resin dispersion. Although the preparation of the aqueous resin dispersion will be described in detail in the next section, it is particularly preferable to mix the aqueous resin dispersions from the viewpoint of controlling the dispersion state of the mixture.

(Aqueous resin dispersion)
For the preparation of the toner of this embodiment, it is preferable to use a dispersion of resin fine particles. From this viewpoint, the aqueous resin dispersion of the present embodiment (hereinafter also simply referred to as “resin dispersion”) is configured by dispersing the resin mixture (hereinafter also simply referred to as resin) in an aqueous medium. The In particular, the acid value of the resin is preferably 10 mgKOH / g or more and 18 mgKOH / g or less. Since the hydrophilicity of the resin itself of the present invention is good when the acid value is not less than the above lower limit value, the dispersion stability of the resulting aqueous resin dispersion is good, aggregation can be suppressed, and the resin having a desired particle size It is preferable because particles can be obtained. Further, when the acid value is not more than the above upper limit, hydrophilicity is appropriate, generation of coarse particles can be suppressed, and a good particle size distribution can be obtained. Further, the acid value is more preferably 10 mgKOH / g or more and 15 mgKOH / g or less from the viewpoint of the dispersion stability.

Here, the self-dispersibility is, for example, in the absence of a surfactant, when it is in a dispersed state (particularly a dispersed state by a phase inversion emulsification method), depending on a functional group (particularly an acidic group or a salt thereof) of the resin itself It means that it can be dispersed in an aqueous medium, and it means that a resin dispersion containing no free emulsifier can be constituted.

The dispersed state includes both an emulsified state (emulsion) in which a resin is dispersed in an aqueous medium and a dispersed state (suspension) in which a resin is dispersed in a solid state in an aqueous medium. .
This resin is preferably a water-insoluble polymer. The water-insoluble polymer is a polymer having a dissolution amount of 10 g or less when the polymer is dried at 105 ° C. for 2 hours and then dissolved in 100 g of water at 25 ° C., and the dissolution amount is preferably 5 g. Hereinafter, it is more preferably 1 g or less. The dissolution amount is the dissolution amount when neutralized with sodium hydroxide or acetic acid according to the kind of the salt-forming group of the water-insoluble polymer.

As a method for preparing an emulsified or dispersed state of the resin, that is, an aqueous dispersion of the resin, a phase inversion emulsification method may be mentioned. As the phase inversion emulsification method, for example, a resin is dissolved or dispersed in a solvent (for example, a hydrophilic organic solvent) and then poured into water as it is without adding a surfactant. A method of obtaining an aqueous dispersion in an emulsified or dispersed state after stirring and mixing with the neutralized (for example, acidic group) and removing the solvent.

The dispersion state of the resin is a solution in which 30 g of resin is dissolved in 70 g of an organic solvent (for example, methyl ethyl ketone), a neutralizing agent that can neutralize 100% of the salt-forming group of the resin (if the salt-forming group is anionic) Sodium hydroxide, acetic acid if cationic) and 200 g of water are mixed and stirred (apparatus: stirring apparatus with stirring blades, rotation speed 200 rpm, 30 minutes, 25 ° C.), and then the organic solvent is obtained from the resulting mixture. The state where it can be visually confirmed that the dispersed state is stably present at 25 ° C. for at least one week even after removing.

[Binder for toner]
The binder for toner according to the exemplary embodiment includes at least one of the above resins and includes other components (for example, a resin) as necessary. The toner binder can be applied to either a dry kneading and pulverizing method or a wet method of granulating toner particles in a liquid. In particular, since this resin is excellent in self-dispersibility and dispersion stability, it can be suitably used in a wet method for granulating toner with the resin dispersed.

The toner binder of the present embodiment can contain at least one other resin as its component. Examples of other resins include crystalline resins, and examples include polyester resins other than resins (hereinafter, also referred to as “other polyester resins”). In the present invention, it is preferable to use a resin composition containing a resin (resin mixture) and a crystalline resin, particularly considering toner applications.

In the present invention, the “composition” means that two or more components exist in a specific composition substantially homogeneously. Here, “substantially uniform” means that each component may be unevenly distributed within the range where the effects of the invention are exerted. The composition is not particularly limited as long as the above definition is satisfied, is not limited to a fluid liquid or a paste, and includes a solid or powder composed of a plurality of components. Furthermore, even when there is a sediment, it means that the composition maintains a dispersion state for a predetermined time by stirring. In contrast, a “mixture” includes a mixture in which two or more components are not uniformly distributed.

Other polyester resins are obtained, for example, mainly by polycondensation of polyvalent carboxylic acids and polyhydric alcohols.

Examples of the polyvalent carboxylic acids include the dicarboxylic acids described above and trivalent or higher polyvalent carboxylic acids. Examples of the polyhydric alcohols include the diol compounds described above and trihydric or higher polyhydric alcohols.

The glass transition temperature (hereinafter sometimes abbreviated as “Tg”) of other polyester resins is preferably 40 ° C. or higher and 80 ° C. or lower, and more preferably 50 ° C. or higher and 70 ° C. or lower. When the Tg of the polyester resin is 80 ° C. or lower, low-temperature fixability is obtained, and when the Tg is 40 ° C. or higher, sufficient heat storage properties and storability of fixed images are obtained.
The molecular weight (weight average molecular weight) of other polyester resins is preferably 5,000 or more and 40,000 or less from the viewpoints of resin manufacturability, fine dispersion during toner production, and compatible toner during melting.

-Crystalline polyester resin It is preferable that other polyester resins contain at least 1 type of crystalline polyester resin. When the other polyester resin contains the crystalline polyester resin, the low-temperature fixability of the toner becomes better. Further, since the heating temperature in the fixing process is low, deterioration of the fixing device is suppressed. When the other polyester resin contains a crystalline polyester resin and an amorphous polyester resin, the crystalline polyester resin is compatible with the amorphous polyester resin when melted, and the toner viscosity is remarkably reduced. A toner having excellent image gloss can be obtained.
Among the crystalline polyester resins, aliphatic crystalline polyester resins are particularly preferable because many of them have a preferable melting point as compared with aromatic crystalline resins.

The content of the crystalline polyester resin in the other polyester resins is preferably 2% by mass or more and 20% by mass or less, and more preferably 2% by mass or more and 14% by mass or less. When the content of the crystalline polyester resin is 2% by mass or more, the non-crystalline polyester resin can be sufficiently reduced in viscosity at the time of melting, and an improvement in low-temperature fixability is easily obtained. Further, if the content of the crystalline polyester resin is 20% by mass or less, the deterioration of the charging property of the toner due to the presence of the crystalline polyester resin can be suppressed, so the image strength after fixing on the recording medium Is easy to obtain.

The melting point of the crystalline polyester resin is preferably in the range of 50 ° C. or higher and 100 ° C. or lower, preferably in the range of 55 ° C. or higher and 95 ° C. or lower, and more preferably in the range of 60 ° C. or higher and 90 ° C. or lower. . If the melting point of the crystalline polyester resin is 50 ° C. or higher, the storage stability of the toner and the storage stability of the toner image after fixing are good, and if it is 100 ° C. or lower, the low-temperature fixability is easily improved.
Such a crystalline polyester resin is preferably a resin described in paragraph Nos. 0124 to 0135 of International Publication No. 2011-125795A1, and can also be suitably applied to this embodiment.

The crystalline polyester resin is synthesized from an acid (dicarboxylic acid) component and an alcohol (diol) component. In the following, the “acid-derived component” is a polyester resin, and before the polyester resin is synthesized. The component part which was an acid component is pointed out, and the "alcohol-derived component" refers to the component part which was an alcohol component before the synthesis of the polyester resin.

Acid-derived constituent component Examples of the acid for forming the acid-derived constituent component include various dicarboxylic acids, but the acid-derived constituent component in the crystalline polyester resin according to the embodiment is a linear aliphatic dicarboxylic acid. Is desirable. For example, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelic acid, sebacic acid, 1,9-nonanedicarboxylic acid, 1,10-decanedicarboxylic acid, 1,11-undecane Dicarboxylic acid, 1,12-dodecanedicarboxylic acid, 1,13-tridecanedicarboxylic acid, 1,14-tetradecanedicarboxylic acid, 1,16-hexadecanedicarboxylic acid, 1,18-octadecanedicarboxylic acid, etc., or lower alkyl esters thereof And acid anhydrides, but are not limited thereto. Of these, adipic acid, sebacic acid, and 1,10-decanedicarboxylic acid are preferable in view of availability.

As the acid-derived component, other components such as a dicarboxylic acid-derived component having a double bond and a dicarboxylic acid-derived component having a sulfonic acid group may be contained.

The “constituent mol%” here means 1 unit of each of the acid-derived constituent component in the entire acid-derived constituent component in the crystalline polyester resin or the alcohol constituent component in the entire alcohol-derived constituent component ( Mol).

Alcohol-derived constituent component The alcohol to be an alcohol-derived constituent component is preferably an aliphatic diol, such as ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1, 6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-dodecanediol, 1,12-undecanediol, 1,13 -Tridecanediol, 1,14-tetradecanediol, 1,18-octadecanediol, 1,20-eicosanediol, and the like, but are not limited thereto. Of these, 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, and 1,10-decanediol are preferable in view of availability and cost.

The weight average molecular weight of the crystalline polyester resin is preferably 8,000 or more and 40,000 or less, and preferably 10,000 or more and 30 or less from the viewpoint of resin manufacturability, fine dispersion at the time of toner production, and a compatible toner at the time of melting. Is more preferable. If it is 8,000 or more, the resistance reduction of the crystalline polyester resin can be suppressed, so that the charging property can be prevented from decreasing. If it is 40,000 or less, the cost of resin synthesis is suppressed, and the low-temperature fixability is not adversely affected in order to prevent a decrease in sharp melt properties.

The toner binder of the present embodiment may contain other resins than the polyester resin. For example, ethylene resins such as polyethylene and polypropylene; styrene resins such as polystyrene and α-polymethylstyrene; (meth) acrylic resins such as polymethyl methacrylate and polyacrylonitrile; polyamide resins, polycarbonate resins, polyether resins and These copolymer resins are exemplified.

The content of the resin (resin mixture) in the toner binder of the present embodiment is preferably 10 to 95% by mass, and more preferably 20 to 80% by mass in the total solid content.

<Toner>
The resin (resin mixture) can be suitably used particularly as a binder for toner. The toner of the exemplary embodiment only needs to contain a pigment, a release agent, and the resin of the present invention. If necessary, a charge control agent, a carrier, an external additive and the like can be contained.

Inorganic fine powders and organic fine particles may be externally added for the purpose of imparting fluidity improvement and charge control to the toner. For example, silica fine particles and titania fine particles whose surface is treated with an alkyl group-containing coupling agent or the like are preferably used. These particles preferably have a number average primary particle size of 10 to 500 nm, and more preferably 0.1 to 20% by mass in the toner.

The pigment is not limited, and either an organic pigment or an inorganic pigment can be used. Examples of organic pigments include azo pigments, polycyclic pigments, dye chelates, nitro pigments, nitroso pigments, and aniline black. Among these, azo pigments and polycyclic pigments are more preferable. Examples of the inorganic pigment include titanium oxide, iron oxide, calcium carbonate, barium sulfate, aluminum hydroxide, barium yellow, cadmium red, chrome yellow, and carbon black. Among these, carbon black is particularly preferable as the black pigment. These are preferably added to the toner in an amount of, for example, 1 to 30% by mass, preferably 5 to 20% by mass, and 30 to 85% by mass when a magnetic material is used as the black pigment.

-Binder The binder may contain the above-mentioned resin, and it is more preferable to add, for example, 10 to 95% by mass, and further 20 to 80% by mass in the toner. Also, other commonly used binders can be used in combination. For example, ethylene resins such as polyethylene and polypropylene; styrene resins such as polystyrene and α-polymethylstyrene; (meth) acrylic resins such as polymethyl methacrylate and polyacrylonitrile; polyamide resins, polycarbonate resins, polyether resins and These copolymer resins are exemplified.
Further, the toner binder may be used.

-Release agent As a release agent, all the release agents conventionally used for toner can be used. Specific examples include olefins such as low molecular weight polypropylene, low molecular weight polyethylene, and ethylene-propylene copolymer, microcrystalline wax, carnauba wax, sazol wax, and paraffin wax. The amount of these added is preferably 3 to 20% by mass, more preferably 5 to 18% by mass, in the toner.

-Charge control agent As a charge control agent, you may add as needed, but a colorless thing is preferable from the point of color development. Examples include quaternary ammonium salt structures, calixarene structures, azo complex dyes, and the like. The addition amount of the charge control agent is preferably 0.5 to 10% by mass, and more preferably 1 to 5% by mass, in the toner.

-Carrier As the carrier, either an uncoated carrier composed only of magnetic material particles such as iron or ferrite, or a resin-coated carrier in which the surface of the magnetic material particles is coated with a resin or the like may be used. The average particle size of the carrier is preferably 30 to 150 μm in terms of volume average particle size.

・ External additives External additives include silica fine particles, titanium oxide fine particles, alumina fine particles, cerium oxide fine particles, inorganic particles such as carbon black, polymer particles such as polycarbonate, polymethyl methacrylate, and silicone resin. Known particles can be used. Among these, two or more types of external additives are used, and at least one of the external additives has an average primary particle size (number average primary particles) in the range of 30 nm to 200 nm, and further in the range of 30 nm to 180 nm. Size).

-Toner Characteristics Further, the toner according to the exemplary embodiment preferably has an average circularity in the range of 0.960 to 0.980, and more preferably in the range of 0.960 to 0.970. As for the shape of the toner, spherical toner is advantageous in terms of developability and transferability, but in terms of cleaning properties, it may be inferior to indeterminate toner. When the average circularity of the toner is in the above range, transfer efficiency and image density can be improved, high-quality image formation can be performed, and the cleaning property of the photoreceptor surface can be improved. .

Further, the volume average particle diameter D50 of the toner of the present embodiment is desirably 3 μm or more and 9 μm or less, more desirably 3.5 μm or more and 8.5 μm or less, and further desirably 4 μm or more and 8 μm or less. If the volume average particle diameter is equal to or greater than the lower limit value, it is possible to suppress a decrease in toner fluidity, and it is easy to maintain the chargeability of each particle. In addition, the charge distribution does not spread, preventing fogging on the background and preventing toner from spilling from the developer. Furthermore, the cleaning property is improved. If the volume average particle size is not more than the above upper limit value, a decrease in resolution can be suppressed, so that a sufficient image quality can be obtained and a recent demand for high image quality can be satisfied.

As the particle size distribution index of the toner, the volume average particle size distribution index GSDv is preferably 1.30 or less, more preferably 1.15 or more and 1.28 or less, and 1.17 or more and 1.26 or less. More preferably it is. If GSDv is larger than the upper limit, the image sharpness and resolution may be lowered. Further, since the ratio of the small particle size toner becomes high, electrostatic control may be difficult.

The volume average particle diameter D50 can be calculated based on the particle size distribution measured with a measuring instrument such as Coulter Counter TAII, Multisizer II (manufactured by Beckman Coulter, Inc.). Specifically, the cumulative distribution is drawn from the smaller diameter side with respect to the divided particle size range (channel), and the particle diameter at which the accumulation is 16% is defined as volume D16v and number D16P. In addition, the particle diameter which becomes 50% cumulative is defined as a volume D50v and a number D50P. Furthermore, the particle diameter that is 84% cumulative is defined as volume D84v and number D84P. Using these, the volume average particle size distribution index (GSDv) is calculated as (D84v / D16V) ^1/2 .

[Toner Production Method]
The toner manufacturing method according to the present embodiment includes an aqueous dispersion of a high molecular weight resin (A) having a weight average molecular weight of 35,000 or more and 120,000 or less and a low dispersion having a weight average molecular weight of 5,000 or more and less than 30,000. It includes a step of preparing an aqueous dispersion of the molecular weight resin (B), a crystalline polyester resin dispersion, and a colorant dispersion, and a step of mixing each dispersion and aggregating the resin. In addition, a process for forming toner particles by a wet manufacturing method (for example, aggregation coalescence method, suspension polymerization method, dissolution suspension granulation method, dissolution suspension method, dissolution emulsion aggregation aggregation method, etc.) and washing the toner particles It is preferable to include the process to do.
As a method for forming toner particles, as described above, a wet production method for producing toner particles in an aqueous medium is preferable, but an emulsion aggregation method is particularly desirable, and an emulsion aggregation method using a phase inversion emulsification method is more desirable. .

The emulsion aggregation method is a method of preparing dispersions (emulsion liquid, pigment dispersion liquid, etc.) each containing components (binder resin, colorant, etc.) contained in the toner, and mixing these dispersion liquids to combine the toner components. In this method, aggregated particles are produced by agglomeration, and then the aggregated particles are heated to the melting point or glass transition temperature of the binder resin or higher to thermally fuse the aggregated particles.

The emulsion aggregation method makes it easier to produce toner with a smaller particle size and has a narrower particle size distribution compared to the dry kneading and pulverization method and other wet methods such as the melt suspension method and the dissolution suspension method. Easy to obtain. Further, the shape of the toner particles can be easily controlled as compared with the melt suspension method, the dissolution suspension method, and the like, and a uniform amorphous toner can be produced. Further, the structure of the toner, such as film formation, is controlled, and when a release agent or a crystalline polyester resin is contained, exposure of these surfaces is suppressed, so that deterioration of chargeability and storage stability is prevented.
Further, when a toner is prepared by an emulsion aggregation method using the binder for toner containing the resin, a toner having good resin particle stability in an aqueous resin dispersion, a small particle size and an excellent particle size distribution is prepared.
The details of the wet manufacturing method of the toner are disclosed in, for example, JP2009-229919A, JP2009-46559A, JP2009-151241, JP3344169A, and JP31411783A. The methods described in Japanese Patent Application Laid-Open No. 2008-165017, Japanese Patent Application Laid-Open No. 2010-20170, Japanese Patent Application Laid-Open No. 2010-210959, and the like can also be suitably applied to this embodiment.

<Image forming method>
The image forming method to which the toner of the exemplary embodiment is applied is not particularly limited. For example, a method of forming an image after forming an image on a photoconductor to form an image, or an image forming method formed on the photoconductor. For example, a method may be used in which an image is sequentially transferred to an intermediate transfer member or the like, and the image is formed on the intermediate transfer member or the like and then transferred to a recording medium such as paper to form an image.

Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not construed as being limited thereto.

Example 1
[Synthesis example]
Synthesis Examples of Monomers Derived from Dehydroabietic Acid (DHA-1 to 3) In the following synthesis examples of monomers derived from dehydroabietic acid, the structure of the synthesized monomer is ¹ H-NMR, liquid chromatography Confirmed using graphy.

(Synthesis Example 1)

Oxalyl chloride (13 g) was added dropwise at room temperature to a mixture of dehydroabietic acid (30.0 g) and methylene chloride (60 ml). After stirring for 3 hours, the solvent was distilled off under reduced pressure, and 16 g of methanol was added dropwise thereto. After stirring at room temperature for 3 hours, excess methanol was distilled off under reduced pressure to obtain Intermediate Compound A (31 g).
Intermediate compound A (31 g) and paraformaldehyde (2.1 g) were added to methylene chloride (150 ml), and sulfuric acid (50 ml) was added dropwise at 10 to 15 ° C. After dripping, after stirring at room temperature for 5 hours, 500 ml of ice water was added, and the organic layer was separated. The organic layer was washed with water until the washing solution became neutral, dried over anhydrous magnesium sulfate, and then methylene chloride was distilled off. 50 ml of methanol was added to the residue, and the mixture was stirred at room temperature for 3 hours, and then white crystals were collected by filtration and dried to obtain DHA-1 (20.2 g).

(Synthesis Example 2)

Sulfuric acid (30 ml) was added dropwise to acetic acid (100 ml) under ice cooling. Next, dehydroabietic acid (Arakawa Chemical Industries, 30.0 g) and paraformaldehyde (2.1 g) were added at room temperature, the temperature was raised to 40 ° C., and the mixture was stirred for 3 hours. The resulting reaction solution was poured into 1 L of cold water and extracted with ethyl acetate. The extract was washed with water until the washing became almost neutral, dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. 80 ml of methanol was added to the residue, and white crystals were collected by filtration and dried to obtain DHA-2 (19.8 g).

(Synthesis Example 3)

Dehydroabietic acid (75 g) and succinic anhydride (38 g) were dissolved in methylene chloride (1 L), and anhydrous aluminum chloride was added in small portions (total 130 g) in several portions under ice cooling. After stirring at 10-15 ° C. for 2 hours, the reaction solution was poured into ice water. The produced white crystals were collected by filtration, washed with water, and further washed with methanol to obtain DHA-3 (72 g).

[Polymerization example]
(Polymerization example 1)
DHA-1 (200 g), sebacic acid (manufactured by Wako Pure Chemical Industries, 10.5 g), dimethyl terephthalate (manufactured by Wako Pure Chemical Industries, 80.8 g), dodecenyl succinic anhydride (manufactured by Sanyo Chemical Industries, 69.3 g), 1, A mixture of 3-propanediol (Dupont, 55.4 g), cyclohexanedimethanol (Eastman Chemical, 45.0 g) and tetraethyl orthotitanate (Wako Pure Chemicals, 250 μL) was mixed at 240 ° C. under a nitrogen stream. And stirred for 30 minutes, and the water and methanol produced were distilled off. Next, the temperature was raised to 270 ° C., and water and methanol produced as the polymerization proceeded, while stirring for 4 hours (# 1: reaction time 1). Next, after adding trimellitic anhydride (Wako Pure Chemicals, 9.99 g), the reaction was continued for another 35 minutes (# 2: reaction time 2), and trimellitic anhydride (Wako Pure Chemicals, 20 0.0 g) was added, and the reaction was allowed to proceed for 55 minutes (# 3: reaction time 3). Thereafter, the obtained reaction product was taken out into a Teflon (registered trademark) heat-resistant container, and polymer H-1 (weight average molecular weight 87,000, molecular weight distribution 19.0, glass transition point 58 ° C., acid value 11 mgKOH / g). )

In Polymerization Example 1, polymers H-2 to H-11 (high molecular weight) were obtained in the same manner as in Polymerization Example 1, except that the type and amount of each monomer were changed according to Table A below, and the reaction time was changed. Polymers L-1 to L-2 (low molecular weight) and comparative polymers cP-1 to cP-2 were obtained, respectively. Table 1 shows the weight average molecular weight, molecular weight distribution, glass transition point, and acid value of each polymer obtained.

[Table A]

* The mol% of the branched component is described as a ratio in the total monomer components.

<Notes on the table>
SA: sebacic acid TPA-Me: dimethyl terephthalate DSA: dodecenyl succinic anhydride PDO: 1,3-propanediol CHDM: cyclohexanedimethanol TMAN: trimellitic anhydride (trifunctional)
PMDA: pyromellitic anhydride (tetrafunctional)
MA: Mellitic acid (hexafunctional)
GLY: Glycerin (trifunctional)
The acid value and Tg are measured as follows.

In Table 1 above, a plurality of prepolymer weight average molecular weights (Mw) being described indicate that a branching component was added when the prepolymer weight average molecular weight reached the described value.

-Acid value-
The acid value was measured by the method described in JIS standard (JIS K 0070: 1992). Table 1 shows the physical property values of the obtained polymer.

-Tg-
It measured on condition of the following using the differential scanning calorimeter (the product made by SII technology, DSC6200). The measurement was performed twice on the same sample, and the second measurement result was adopted.
・ Atmosphere in measurement chamber: Nitrogen (50 mL / min)
・ Raising rate: 10 ° C / min
・ Measurement start temperature: 0 ℃
-Measurement end temperature: 200 ° C
-Sample pan: Aluminum pan-Mass of measurement sample: 5 mg
-Calculation of Tg: Tg is the intermediate temperature between the descent start point and descent end point of the DSC chart

(Preparation of aqueous dispersion (aqueous resin dispersion))
A mixture of 10 g of the resin A described in Table 2 below and 7.5 g of methyl ethyl ketone was stirred at 60 ° C. and dissolved by heating. Next, 2.5 g of isopropanol was added and the mixture was allowed to cool to room temperature. Then, 0.55 ml of 10% by mass aqueous ammonia was added at room temperature, and 40 g of ion-exchanged water was gradually added to the solution at a flow rate of 1.57 g / ml. Phase inversion emulsification was performed. Thereafter, the solvent was distilled off with an evaporator under reduced pressure to prepare an aqueous dispersion A (aqueous resin dispersion A).
Further, in the production of the aqueous dispersion A, an aqueous dispersion B (aqueous resin dispersion B) was produced in the same manner as in the production of the aqueous dispersion A except that the resin A was replaced with the resin B.

(Crystalline polyester resin dispersion)
Into a heat-dried three-necked flask, 100 mol% of 1,10-decanedicarboxylic acid and 100 mol% of 1,9-nonanediol are added in a monomer composition ratio, and dibutyltin oxide becomes 0.3 mass% as a catalyst. Then, the air in the container was brought into an inert atmosphere with nitrogen gas by a depressurization operation, and stirred and refluxed at 180 ° C. for 5 hours with mechanical stirring.
Then, it heated up gradually to 230 degreeC under pressure reduction, and stirred at this temperature for 2 hours. When the reaction product in the system became viscous, it was air-cooled to stop the reaction, and a crystalline polyester resin (I) was synthesized.
The obtained crystalline polyester resin had a weight average molecular weight of 25,000 and a number average molecular weight of 5,800. Further, when the melting point (Tm) of the crystalline polyester resin (I) was measured using a differential scanning calorimeter (DSC) by the above-described measurement method, it showed a clear endothermic peak, and the endothermic peak temperature was 75 ° C. there were.

-Crystalline polyester resin (I): 90 parts by mass-Ionic surfactant (Neogen RK, Daiichi Kogyo Seiyaku): 2.0 parts by mass-Ion exchange water: 210 parts by mass The above is mixed and heated to 100 ° C Then, after dispersion with IKA Ultra Turrax T50, the dispersion was heated to 110 ° C. with a pressure discharge type gorin homogenizer for 1 hour, the volume average particle size was 0.15 μm, and the solid content was 30% by mass. A crystalline polyester resin dispersion was obtained.

(Preparation of colorant dispersion)
100 parts by mass of a cyan pigment (manufactured by Dainichi Seika Co., Ltd., Pigment Blue 15: 3, copper phthalocyanine), 10 parts by mass of an anionic surfactant (Neogen R, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) and 350 parts by mass of ion-exchanged water were mixed. The mixture was dispersed with a high-pressure impact disperser (HJP30006, manufactured by Sugino Machine Co.) for 1 hour to obtain a cyan colorant dispersion.

(Preparation of release agent dispersion)
60 parts by mass of paraffin wax (HNP-9: Nippon Seiwa Co., Ltd.), 6 parts by mass of an anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd., Neogen R) and 200 parts by mass of ion-exchanged water are mixed and heated to 100 ° C Then, the mixture was melted and dispersed with a high-pressure homogenizer (manufactured by Gorin) to obtain a release agent dispersion.

(Production of toner)
280 parts by mass of ion-exchanged water, 2.8 parts by mass of anionic surfactant (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., Neogen RK (20%)), dispersion of resin A prepared above (aqueous resin dispersion A) ) And a dispersion of resin B (aqueous resin dispersion B) according to the blend ratio of Table 2, 334 parts by mass of the resin dispersion mixed, and 33 parts by mass of the crystalline polyester resin dispersion prepared above were thermometers, The mixture was placed in a 3 L three-necked flask equipped with a pH meter and a stirrer, and stirred at a temperature of 30 ° C. and a rotation speed of 150 rpm for 30 minutes.
Next, 60 parts by weight of the colorant dispersion and 80 parts by weight of the release agent dispersion were added to the dispersion obtained by stirring, and stirred for 5 minutes. Further, 1% nitric acid was added little by little to adjust the pH to 3.0. Thereafter, 0.4 parts by mass of polyaluminum chloride was added, the temperature was raised to 50 ° C., and 180 parts of a crystalline polyester resin dispersion was added. This was stirred for 30 minutes while maintaining 50 ° C., and then 5% by mass aqueous sodium hydroxide solution was added to adjust the pH to 9.0. Subsequently, the temperature was raised to 90 ° C., stirred at this temperature for 3 hours, and then cooled to obtain each toner particle dispersion.

(Preparation of toner particles)
Each toner particle dispersion obtained above was filtered and washed with ion-exchanged water. Each toner particle was again dispersed in ion exchange water, filtered and washed. This operation was further repeated twice, and 1% nitric acid was added to each toner particle dispersion to adjust the pH to 4.0. Each toner particle dispersion was filtered, washed with ion-exchanged water until the electric conductivity of the filtrate was 15 μS / cm or less, and then dried under reduced pressure in an oven at 40 ° C. for 5 hours to obtain each toner particle. . Furthermore, with respect to 100 parts by mass of each obtained toner particle, 1.5 parts by mass of hydrophobic silica (manufactured by Nippon Aerosil Co., Ltd., RY50) and 1.0 part by mass of hydrophobic titanium oxide (manufactured by Nippon Aerosil Co., Ltd., T805) Was mixed and blended at 10,000 rpm for 30 seconds using a sample mill. Thereafter, each toner was obtained by sieving with a vibration sieving machine equipped with a screen having an opening of 45 μm.

(Preparation of carrier)
300 parts by mass of silicon resin (SR2411 manufactured by Toray Dow Corning Co., Ltd.), 1200 parts by mass of toluene and 5 kg of ferrite core material having an average particle size of 50 μm are placed in a rotating disk type fluidized bed coating apparatus, and the surface of the ferrite core material is coated with silicon resin did. Subsequently, the coating was taken out and heated at 250 ° C. for 2 hours, and the coating film was aged to prepare a carrier.

(Preparation of developer)
Each developer obtained by the above preparation method was mixed with the above carrier so that the toner concentration was 5% by mass and the total amount was 1 kg to obtain each developer.
Each of these developers was used, and the following evaluation was performed.

(Evaluation)
-Minimum fixing temperature (min. Temp.)-
An unfixed image was formed by an image forming apparatus from which a fixing device of a copying machine (manufactured by Sharp Corporation, AR-505) was removed. Specifically, using the copying machine, the toner application amount is adjusted so that 1.0 ± 0.05 mg / cm ² of toner is developed as a solid image on transfer paper (P paper manufactured by Fuji Xerox). An unfixed image was formed. Next, with respect to the fixing device including the heating roll (fixing belt) and the pressure belt in the copying machine, an unfixed image is heated while changing the fixing temperature by using a copying machine modified so that the fixing temperature is variable. Thus, a fixed image was formed. The image fixability was evaluated by measuring the minimum fixing temperature of the image. The fixing lower limit temperature was defined as the fixing belt temperature at which the remaining ratio of the image density after rubbing the obtained fixed image with the pad provided in the copying machine was 70% or more.
-Evaluation criteria-
A: Less than 150 ° C. B: 150 ° C. or more and less than 160 ° C. C: 160 ° C. or more

-Hot offset generation temperature (HOS temp.)-
The developer obtained is mounted on a device (number of prints: 50 sheets / min) modified from a copier (Sharp, AR-505), and the temperature of the fixing belt is gradually increased from 90 ° C to 250 ° C. The image was output. After the image was printed at each temperature, the white transfer paper was continuously sent to the fixing belt under the same conditions, and the temperature of the fixing roller where the toner smears on the white paper first was defined as the hot offset occurrence temperature.
-Evaluation criteria-
A: 220 ° C. or higher B: less than 220 ° C. 190 ° C. or higher C: less than 190 ° C.

The results obtained are summarized in Table 2 below.

* 1: Mass ratio of aqueous dispersion * 2: No branching * 3: c11 to c17 are comparative examples

From Table 1 above, it can be seen that all of the toners of the present invention are excellent in image fixability and have reduced occurrence of hot offset.

(Example 2)
Toner No. prepared in Example 1 The following evaluation was performed using 101 and 106.
-Resistance to hydrolysis-
0.5 g of each toner is put in a molding jig (25 mmΦ), and pressed using a simple molding machine (trade name: Table Press TB-50H, manufactured by NPa System) at room temperature of 25 ° C. and pressure of 30 MPa for 1 minute. A plate-like sample was prepared. The weight average molecular weight (Mw) of the sample after storing for 72 hours in the high temperature and high humidity of 80 degreeC / 85% RH was measured. For the evaluation of hydrolysis resistance, the molecular weight retention rate (%) obtained by the following formula was obtained and evaluated according to the following rank.

Molecular weight retention (%) = (weight average molecular weight after 72 hours / initial weight average molecular weight) × 100

-Evaluation criteria-
A: Molecular weight retention 90% or more B: Molecular weight retention 80% or more and less than 90% C: Molecular weight retention 80% or less

-Preservability in high temperature and high humidity environment-
Toner No. after storage in high temperature and high humidity of 80 ° C./85% RH for 72 hours. 101 and 106 were used, and a developer was prepared in the same manner as in Example 1. Using this developer, a copier “AR-505” (manufactured by Sharp) was remodeled (number of printed sheets: 50 / Minutes), the hot offset occurrence temperature was evaluated.
-Evaluation criteria-
A: 220 ° C. or higher B: less than 220 ° C. 190 ° C. or higher C: less than 190 ° C.

* 1: Petroleum toner prepared according to the method described in paragraph Nos. 0190 to 0192 of JP2008-165017A

As described above, since the molecular weight of the resin contained in the toner can be maintained even in a high temperature and high humidity environment by using the toner of the present invention, it is possible to suppress a change in toner performance with time. As a result, the fixing property of the toner can be kept good, and a good image can be stably formed over a long period of time.

1 Photoconductor (latent image carrier)
2 Toner supply chamber 3 Drum 4 Paper 5 Toner 51 Transfer image 7 Cleaner 8 Charging means 9 Static eliminator L Exposure

Claims

A resin mixture comprising a high molecular weight resin (A) having a weight average molecular weight of 35,000 or more and 120,000 or less and a low molecular weight resin (B) having a weight average molecular weight of 5,000 or more and less than 30,000,
The resin (A) includes a repeating unit derived from dehydroabietic acid and a structural unit derived from a trivalent or higher polyvalent carboxylic acid (a) or a trivalent or higher polyhydric alcohol (b) in the main chain. A resin mixture in which the resin (B) has a repeating unit derived from dehydroabietic acid.
The resin mixture according to claim 1, wherein the repeating unit derived from dehydroabietic acid is represented by the following formula (IA) or (IB).

[Wherein, ring A represents a non-aromatic 6-membered ring. Ring Cy represents a saturated or unsaturated 6- or 7-membered ring which may contain a hetero atom. X 1 represents a single bond or a divalent linking group. X 2 , Y 1 , Y 2 , Y 3 represent a divalent linking group. R represents a substituent that may be substituted on the ring A, the ring Cy, and the benzene ring. n1 represents an integer of 0 to 18. ]
The resin mixture according to claim 1 or 2, wherein the repeating unit derived from dehydroabietic acid is a repeating unit represented by the following formula (IA-1) or (IB-1).

[Wherein, ring A, X 1 , X 2 , Y 1 to Y 3 and R are as defined in the above formula (IA) or (IB). Ring B represents a non-aromatic 6-membered ring, and n2 represents an integer of 0 to 17. ]
The resin mixture according to any one of claims 1 to 3, wherein the repeating unit derived from dehydroabietic acid is a repeating unit represented by the following formula (IA-2) or (IB-2).

[Wherein, X 1 , X 2 and Y 1 to Y 3 have the same meanings as those in the formula (IA) or (IB). ]
The resin mixture according to any one of claims 1 to 4, wherein both the resins (A) and (B) have a repeating unit represented by the following formula (II).

[Wherein L 2 and L 3 represent —O—, —S—, —N (Ra) —, —C (═O) — or —NHC (═O) —, and L 1 represents a divalent linkage. Represents a group. Ra represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group. ]
The resin mixture according to any one of claims 1 to 5, wherein the resins (A) and (B) are both polyester resins.
The resin mixture according to any one of claims 1 to 6, which contains a ratio of the resin (A) to the resin (B) in a solid mass of 30:70 to 70:30 (mass basis). .
The molecular weight distribution (weight average molecular weight / number average molecular weight) of the resin (A) is 7 to 25, and the molecular weight distribution of the resin (B) is 2 to 6. Resin mixture.
The ratio of the structural unit derived from the trivalent or higher polyvalent carboxylic acid (a) or the trivalent or higher polyhydric alcohol (b) is 1 to 20 mol% with respect to the total mole of the resin (A). Item 9. The resin mixture according to any one of Items 1 to 8.
The structural unit derived from the trivalent or higher polyvalent carboxylic acid (a) or the trivalent or higher polyhydric alcohol (b) is represented by the following formula (III-a) or (III-b): 10. The resin mixture according to any one of 9 above.

[In the formula, Ar represents an aromatic ring residue. Z represents a cyclic or chain aliphatic hydrocarbon residue which may contain an ether bond. m1 and m2 represent an integer of 3 or more. * Is a bond. ]
In the resin (A), a prepolymer having a repeating unit derived from dehydroabietic acid and having a weight average molecular weight of 3,000 to 25,000 is a trivalent or higher polyvalent carboxylic acid (a) or a trivalent or higher polyvalent carboxylic acid. The resin mixture according to any one of claims 1 to 10, which has a branched structure linked via a structural unit derived from a monohydric alcohol (b).
X 1 is an alkylene group, X 2 is ** - C (= O) -L a -C (= O) - (** represents a bond that binds to the benzene ring, L a is alkylene or alkenylene And Y 1 to Y 3 are each —C (═O) —, —O—, or an alkyleneoxy group bonded to the ring A or the benzene ring by a carbon atom. The resin mixture according to claim 1.
An aqueous resin dispersion comprising the resin mixture according to any one of claims 1 to 12 in an aqueous medium.
The aqueous resin dispersion according to claim 13, further comprising a pigment and a release agent.
A toner comprising the resin mixture according to any one of claims 1 to 12.
An aqueous dispersion of a high molecular weight resin (A) having a weight average molecular weight of 35,000 or more and 120,000 or less, and an aqueous dispersion of a low molecular weight resin (B) having a weight average molecular weight of 5,000 or more and less than 30,000, Producing a crystalline polyester resin dispersion and a colorant dispersion;
Mixing each of the dispersions and aggregating the resin,
The resin (A) includes a repeating unit derived from dehydroabietic acid and a structural unit derived from a trivalent or higher polyvalent carboxylic acid (a) or a trivalent or higher polyhydric alcohol (b) in the main chain. And a resin (B) having a repeating unit derived from dehydroabietic acid.
A toner produced by the production method according to claim 16.
A developer comprising the toner according to claim 15 or 17 and a carrier.
A resin having a repeating unit derived from dehydroabietic acid and a structural unit derived from a trivalent or higher polyvalent carboxylic acid (a) or a trivalent or higher polyhydric alcohol (b) in the main chain, the weight average A resin having a molecular weight of 35,000 or more and 120,000 or less and branched via a structural unit derived from the trivalent or higher polyvalent carboxylic acid (a) or the trivalent or higher polyhydric alcohol (b).
A method for producing a resin according to claim 19,
A method for producing the resin, comprising a step of reacting a prepolymer having a repeating unit derived from dehydroabietic acid with a trivalent or higher polyvalent carboxylic acid (a) or a trivalent or higher polyhydric alcohol (b).