JP2016021060A - Toner binder and toner - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a toner comprising a polyester based toner binder containing a plant material-derived component, the toner being capable of realizing both low-temperature fusibility and heat-resistant storage stability and excellent in moist heat-resistant storage stability, charge stability and durability.SOLUTION: A toner binder contains a polyester resin (P) obtained by reacting a diol composition (A) containing a compound (a), which is represented by the general formula (1) in the figure, with a dicarboxylic acid or a modification thereof (B).SELECTED DRAWING: None

Description

  The present invention relates to a toner binder and a toner.

Electrophotographic toner binders for heat fixing systems, which are commonly used as image fixing systems in copying machines, printers, etc., are low because the toner does not fuse to the heat roll (hot offset resistance) even at high fixing temperatures. It is required that the toner can be fixed even at the fixing temperature (low temperature fixability), and further, heat resistant storage stability as a toner particle, moist heat storage stability, charging stability, even during continuous printing, it can be used to prevent stains on the printing surface. There is a demand for durability, such as no fogging.
In recent years, there has been a strong need for reducing the environmental burden (energy saving) for copiers and printers, and as a toner that satisfies such needs, development of a toner that can achieve both low-temperature fixability and heat-resistant storage stability is required. It has been. Furthermore, carbon neutral has been attracting attention from the viewpoint of global warming suppression and the like, and the conversion from conventional plastics derived from petroleum raw materials to plastics derived from plant raw materials with less environmental impact is being actively promoted.
Also in the toner, it is desired to use a component derived from the plant material in the toner, and the binder resin constituting the toner is also desired to contain a component derived from the plant material.
As a polyester resin containing a plant material-derived component, a toner composed of a polyester-based toner binder using a plant material-derived isosorbide has been proposed (see Patent Document 1 and Patent Document 2), but low-temperature fixability and heat-resistant storage stability. The level of compatibility was not satisfactory.

Special table 2008-5377786 gazette JP 2010-285555 A

The present invention is a toner comprising a polyester-based toner binder containing a component derived from a plant raw material, and can achieve both low-temperature fixability and heat-resistant storage stability of the toner. An object is to provide a toner having excellent properties.

The inventors of the present invention have arrived at the present invention as a result of intensive studies to solve the above problems.
That is, the present invention is the following two inventions.
[1] Contains a polyester resin (P) obtained by reacting a diol composition (A) containing a compound (a) represented by the following general formula (1) with a dicarboxylic acid or a modified product (B) thereof And a toner binder.

[Wherein, R ¹ and R ² each independently represents a linear or branched alkylene group having 2 to 8 carbon atoms. m and n are each independently a positive integer of 0 or 1 to 5, and m + n is a number satisfying 1 to 10. ]

[2] A toner containing the toner binder, a colorant and a release agent.

The toner binder containing a polyester resin having the diol component of an isosorbide alkylene oxide adduct according to the present invention contains a plant-derived component, has a low environmental impact, and has both low-temperature fixability and heat-resistant storage stability of the toner. It is possible and is excellent in wet heat storage stability, charging stability and durability. Further, the toner binder containing a polyester resin used in combination with a specific diol has a feature that the charge amount does not decrease even in a high humidity environment.

It is a flowchart of the experimental apparatus used for manufacture of the toner containing the toner binder of this invention.

The toner binder of the present invention comprises a polyester resin (A) obtained by reacting a diol composition (A) containing a compound (a) represented by the following general formula (1) with a dicarboxylic acid or a modified product (B) thereof. P).

[Wherein, R ¹ and R ² each independently represents a linear or branched alkylene group having 2 to 8 carbon atoms. m and n are each independently a positive integer of 0 or 1 to 5, and m + n is a number satisfying 1 to 10. ]

That is, the polyester resin (P) in the present invention is obtained by reacting the diol composition (A) containing the compound (a) with a dicarboxylic acid or a modified product (B) thereof.

R ¹ and R ² of the compound (a) in the general formula (1) are a linear alkylene group or branched alkylene group having 2 to 8 carbon atoms. These R ¹ and R ² may be the same or different.

Examples of the linear alkylene group having 2 to 8 carbon atoms include an ethylene group, an n-propylene group, an n-butylene group, an n-pentylene group, and an n-hexylene group.

The branch position of the branched alkylene group having 2 to 8 carbon atoms may be any position, and the number of branches is not particularly limited.
Examples of the branched alkylene group having 2 to 8 carbon atoms include 1,2-propylene group, 1,2- or 1,3-butylene group, 1,2-, 1,3- or 1,4-pentylene group, 2-, 1,3-, 1,4- or 1,5-hexylene group, 1,2-, 1,3-, 1,4-, 1,5- or 1,6-heptylene group, 1,2 -, 1,3-, 1,4-, 1,5-, 1,6- or 1,7-octylene group and the like can be mentioned.

From the viewpoint of heat-resistant storage stability, R ¹ and R ² are preferably a linear alkylene group having 2 to 6 carbon atoms or a branched alkylene group having 2 to 6 carbon atoms, and more preferably 2 to 4 carbon atoms. A linear alkylene group or a branched alkylene group having 2 to 4 carbon atoms, particularly preferably an ethylene group or a propylene group, and most preferably a propylene group.

Compound (a) is produced by addition polymerization of alkylene oxide to isosorbide, as will be described later.
M and n of the compound (a) in the general formula (1) are each independently 0 or a positive integer of 1 to 5, and m + n is a number satisfying 1 to 10.

  As described later, compound (a) is produced by addition polymerization of alkylene oxide to isosorbide, and m and n represent the number of added moles of alkylene oxide at that time, and the reaction product is a compound having a different number of added moles. It becomes a mixture of (a) and has a distribution.

From the viewpoint of heat-resistant storage stability, m and n are preferably each independently 0 or a positive integer of 1 to 5, and m + n is a number of 1 to 6, and more preferably m + n is 1. -4 and particularly preferred is m + n of 1-2.
Most preferred is when m and n are both 1, that is, the compound (a1).

  Since the production of the compound (a) is obtained by addition polymerization of alkylene oxide to isosorbide, the reaction product is a mixture of the compound (a) having a different number of added moles and unreacted isosorbide.

The diol composition (A) used for obtaining the polyester resin (P) is a diol composition containing the compound (a). As the compound (a), m = 1 in the general formula (1), and It is preferable to use the compound (a1) where n = 1.
However, when alkylene oxide is addition-polymerized to isosorbide, it always has a distribution of added moles, and unreacted isosorbide tends to remain.

The content of the compound (a1) in which m and n in the general formula (1) are both 1 is preferably 50 based on the total weight of the compound (a) and isosorbide from the viewpoint of heat-resistant storage stability. -100% by weight, more preferably 70-100% by weight, and particularly preferably 85-100% by weight.

The content rate of the compound (a1) in a diol composition (A) can be measured with the following method.
<Method for Measuring Content of Compound (a1)>
The content rate of a compound (a1) can be measured by gas chromatography (GC). An example of GC measurement conditions is shown below.
[GC measurement conditions]
Device: GC-2014 (manufactured by Shimadzu Corporation)
Column: Restec Rtx-1
(4.6mmO x 250mm)
Sample solution: 10% by weight methanol solution Injection volume: 2 μl

In the general formula (1), m + n is 3 to 10, and both m and n are 1 or more compounds (a2), that is, methylene oxide addition mole number (m + n) of isosorbide is 3 to 10. Is preferably 50% by weight or less based on the total weight of the compound (a) and isosorbide from the viewpoint of heat-resistant storage stability. More preferred is 30% by weight or less, and particularly preferred is 10% by weight or less.
In addition, the content rate of a compound (a2) can be measured by the method similar to the measurement of the content rate of said (a1).

Compound (a3) in which either m or n in the general formula (1) is 0 and the other is an integer of 1 to 5, that is, alkylene oxide is 1 to 5 only on one of two hydroxyl groups of isosorbide. From the viewpoint of heat-resistant storage stability, the content of the total amount of the added compounds in the diol composition (A) is preferably 50% by weight or less based on the total weight of the compound (a) and isosorbide. More preferred is 30% by weight or less, and particularly preferred is 10% by weight or less.
In addition, the content rate of a compound (a3) can also be measured by the method similar to the measurement of the content rate of said (a1).

The content of isosorbide in the diol composition (A) is preferably 2% by weight or less, more preferably 1% by weight, based on the total weight of the compound (a) and isosorbide, from the viewpoint of low-temperature fixability. It is as follows.
In addition, the content rate of isosorbide can also be measured by the method similar to the measurement of the content rate of said (a1).

Although a compound (a) can be manufactured by a well-known method, the following method is mentioned, for example.
Isosorbide is charged into a pressurized reaction vessel, and an alkylene oxide having 2 to 8 carbon atoms is added dropwise in the presence of no catalyst or in the presence of a catalyst, and the reaction is carried out in one step or multiple steps. Examples of the alkylene oxide having 2 to 8 carbon atoms include ethylene oxide, propylene oxide, butylene oxide, pentylene oxide, hexylene oxide, and styrene oxide. Two or more kinds can be used in combination.

The reaction temperature is preferably 60 to 200 ° C, more preferably 70 to 140 ° C. The reaction pressure is preferably 0.001 to 0.5 MPa. The reaction time is preferably 2 to 24 hours, more preferably 3 to 10 hours.

As a catalyst, lithium hydroxide, triethylamine, tributylamine, N, N, N ′, N′-tetramethylethylenediamine, N, N, N ′, N′-tetramethylhexanediamine, tetramethylammonium hydroxide (hereinafter referred to as TMAH) And 1,8-diazabicyclo [5.4.0] undec-7-ene, etc., one of which may be used alone or two or more of them may be used in combination. .

From the viewpoint of increasing the content of (a1) based on the total weight of the compound (a) and isosorbide and improving the heat resistant storage stability, it is preferable to use lithium hydroxide, triethylamine, tributylamine, or TMAH as a catalyst. It is particularly preferable to use lithium hydroxide or TMAH.

The amount of the catalyst used is preferably 0.01 to 5% by weight, more preferably 0.1 to 0.5% by weight, based on the weight of the compound (a).
After completion of the reaction, the catalyst may be left in the compound (a) as it is, or may be treated by adsorption, filtration and removal using an adsorbent, or neutralization with an acid to deactivate the catalyst. Can do.

You may use a solvent at the time of manufacture of a compound (a). Solvents used include water, methyl ethyl ketone (hereinafter abbreviated as MEK), methyl butyl ketone, acetone, cyclohexanone, tetrahydrofuran, methyl acetate, ethyl acetate, methanol, ethanol, butanol, isopropyl alcohol, hexanol, cyclohexanol, ethylene glycol, diethylene glycol, Examples include butanediol, acetonitrile, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, and diethylene glycol monomethyl ether. One of these is used alone. Or two or more of them may be used in combination.
Solvents are not limited to those described.

The diol composition (A) used in the production of the polyester resin (P) of the present invention is a diol containing the compound (a) as an essential component, and the compound (a) may be used alone. Other diols may be used in combination.
Furthermore, in addition to the diol composition (A), a tri- or higher valent polyol may be partially used together.

Other diols include alkylene glycols having 2 to 30 carbon atoms (for example, ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, octanediol, Decanediol, dodecanediol, tetradecanediol, neopentyl glycol and 2,2-diethyl-1,3-propanediol);
Alkylene ether glycol having a number average molecular weight (hereinafter abbreviated as Mn) of 100 to 5,000 (for example, diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol and polytetramethylene ether glycol);
An alicyclic diol having 6 to 24 carbon atoms (for example, 1,4-cyclohexanedimethanol and hydrogenated bisphenol A);
Alkylene oxide (hereinafter referred to as “alkylene oxide” is abbreviated as AO) adduct (addition mole number 2-100) of the above alicyclic diol having Mn of 100 to 5,000 [for example, ethylene of 1,4-cyclohexanedimethanol Oxide (hereinafter, “ethylene oxide” is abbreviated as EO) 10 mol adduct, etc.];
AO [EO, propylene oxide (hereinafter referred to as “propylene oxide”) of bisphenols having 13 to 30 carbon atoms (such as bisphenol A, bisphenol F, and bisphenol S) or polyphenols having 12 to 24 carbon atoms (such as catechol, hydroquinone, and resorcinol). Abbreviated as PO) and butylene oxide etc.] adducts (addition mole number 2-100) (for example, bisphenol A · EO 2-4 mol adduct and bisphenol A · PO 2-4 mol adduct, etc.);
Weight average molecular weight (hereinafter abbreviated as Mw) = 100 to 10,000 polylactone diol (for example, poly-ε-caprolactone diol);
Examples thereof include polybutadiene diol having an Mw of 100 to 10,000.

Among these other exemplified diols, the alkylene oxide adduct (b1) of bisphenol A and the alkanediol (b2) having 3 to 6 carbon atoms are used as the diol composition (A) and the compound (a) of the present invention. Use in combination is preferable because a higher performance toner binder can be obtained.

Examples of the adduct (b1) of bisphenol A alkylene oxide include EO and / or PO adducts of bisphenol A, and the average number of moles added is preferably 2.0 to 6.0.
Of the alkylene oxide adducts (b1) of bisphenol A, from the viewpoint of heat-resistant storage stability, preferred are an EO adduct of bisphenol A, a PO adduct of bisphenol A, and a combination thereof. The average number of moles of alkylene oxide added is preferably 2.0 to 6.0 moles, more preferably 2.0 to 3.0 moles per mole of bisphenol A.
Examples of the alkanediol (b2) having 3 to 6 carbon atoms include 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, and 2,2-dimethyl. -1,3-propanediol, 1,4-cyclohexanediol and the like. Among these, from the viewpoint of heat-resistant storage stability, a diol having 3 to 4 carbon atoms is preferable, and 1,2-propylene glycol, 1,3-propylene glycol, 2,2-dimethyl-1 are more preferable. 1,3-propanediol, particularly preferably 1,2-propylene glycol and 2,2-dimethyl-1,3-propanediol.

From the viewpoint of improving the charge amount, low-temperature fixability, heat-resistant storage stability, etc. in a high humidity environment as a whole, the content of compound (a) with respect to the total weight of compounds (a), (b1) and (b2) is 10 to 80% by weight, preferably 20 to 75% by weight.

In the present invention, a trivalent or higher polyol may be used in combination with the diol composition (A).
Examples of the trivalent or higher polyol include trivalent or higher aliphatic polyhydric alcohols having 3 to 10 carbon atoms (for example, glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitan, sorbitol, etc.);
AO (carbon number 2 to 4) adduct (addition mole number 2 to 100) of trisphenol having 25 to 50 carbon atoms (for example, trisphenol · EO 2 to 4 mol adduct and trisphenol · PO 2 to 4 mol adduct) An AO (carbon number 2 to 4) adduct (2 to 100 addition moles) of a novolak resin having a polymerization degree of 3 to 50 (for example, phenol novolak and cresol novolak) (for example, phenol novolak PO 2 mol adduct and phenol novolak EO 4 mol) Adduct);
AO (carbon number 2 to 4) adduct (addition mol number 2 to 100) (pyrogallol EO 4 mol adduct) of polyphenols having 6 to 30 carbon atoms (for example, pyrogallol, fluoroglucinol and 1,2,4-benzenetriol) );
Acrylic polyol having a polymerization degree of 20 to 2,000 (with hydroxyethyl (meth) acrylate and other monomer having a polymerizable double bond [for example, styrene, (meth) acrylic acid, (meth) acrylic acid ester, etc.)] Copolymer, etc.}.

The polyester resin (P) of the present invention is obtained by reacting the diol composition (A) with a dicarboxylic acid or a modified product thereof (B).
Examples of the dicarboxylic acid in the present invention include alkane dicarboxylic acids having 4 to 32 carbon atoms (for example, succinic acid, adipic acid, sebacic acid, azelaic acid, dodecanedicarboxylic acid and octadecanedicarboxylic acid); alkenedicarboxylic acids having 4 to 32 carbon atoms. (Eg, maleic acid, fumaric acid, citraconic acid, mesaconic acid, etc.); branched alkene dicarboxylic acids having 8 to 40 carbon atoms [eg, dimer acid, alkenyl succinic acid (dodecenyl succinic acid, pentadecenyl succinic acid, and octadecenyl succinic acid) Branched alkane dicarboxylic acids having 12 to 40 carbon atoms [eg alkyl succinic acid (decyl succinic acid, dodecyl succinic acid and octadecyl succinic acid etc.); aromatic dicarboxylic acids having 8 to 20 carbon atoms (eg phthalic acid, isophthalic acid, etc.) , Terephthalic acid and naphthalene dicarboxylic Etc.) and the like.
Of these, preferred are alkane dicarboxylic acids, alkene dicarboxylic acids and aromatic dicarboxylic acids, more preferred are adipic acid, fumaric acid and aromatic dicarboxylic acids, and particularly preferred are adipic acid, fumaric acid, terephthalic acid. Acids and isophthalic acid.

Examples of the modified form of dicarboxylic acid include acid anhydrides of dicarboxylic acids and lower alkyl esters.
Examples of the acid anhydride of dicarboxylic acid include phthalic anhydride and maleic anhydride.
Examples of the lower alkyl ester of dicarboxylic acid include methyl ester, ethyl ester and isopropyl ester.

In the present invention, a tricarboxylic or higher polycarboxylic acid or a modified product thereof may be used in combination with a dicarboxylic acid or a modified product (B) thereof.
Examples of the trivalent or higher polycarboxylic acid include aromatic polycarboxylic acids having 9 to 20 carbon atoms (such as trimellitic acid and pyromellitic acid), and aliphatic polycyclic acids (including alicyclic) having 6 to 36 carbon atoms. Carboxylic acid (hexane tricarboxylic acid, decane tricarboxylic acid, etc.) etc. are mentioned. These acid anhydrides or lower alkyl esters can also be used.

In the production of the polyester resin (P), a monocarboxylic acid (C) and / or a monoalcohol (D) may be used in combination with the diol composition (A) and the dicarboxylic acid or the modified product (B) thereof.

Examples of the monocarboxylic acid (C) include an aromatic monocarboxylic acid (C1), a chain saturated monocarboxylic acid (C2), a chain unsaturated monocarboxylic acid (C3), and an alicyclic monocarboxylic acid (C4). Can be mentioned. In addition, (C) may be used independently and may use 2 or more types together.
Examples of the aromatic monocarboxylic acid (C1) include aromatic monocarboxylic acids having 7 to 36 carbon atoms. Specific examples include benzoic acid, vinyl benzoic acid, toluic acid, dimethyl benzoic acid, and t-butyl benzoic acid. , Cumic acid, naphthoic acid, biphenyl monocarboxylic acid and furic acid.
As the chain saturated monocarboxylic acid (C2), a linear or branched chain saturated monocarboxylic acid having 2 to 30 carbon atoms (acetic acid, propionic acid, butyric acid, valeric acid, 2-ethylhexanoic acid, caproic acid, enanthate) Acid, caprylic acid, pelargonic acid, capric acid, lauric acid, myristic acid, pentadecylic acid, palmitic acid, margaric acid, stearic acid, tuberculostearic acid, arachidic acid, behenic acid, and lignoceric acid).
As the chain unsaturated monocarboxylic acid (C3), a linear or branched chain unsaturated monocarboxylic acid having 3 to 30 carbon atoms (acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, palmitoleic acid, oleic acid Vacenoic acid, linoleic acid, α-linolenic acid, γ-linolenic acid, eleostearic acid, 8,11-eicosadienoic acid, 5,8,11-eicosatrienoic acid, arachidonic acid, stearidonic acid, eicosapentaenoic acid, Docosapentaenoic acid, docosahexaenoic acid, dihomo-γ-linolenic acid, elaidic acid, erucic acid, nervonic acid and the like.
Examples of the alicyclic monocarboxylic acid (C4) include alicyclic monocarboxylic acids having 4 to 14 carbon atoms (such as cyclopropanecarboxylic acid, cyclobutanecarboxylic acid, cyclopentanecarboxylic acid, cyclohexanecarboxylic acid, and cycloheptanecarboxylic acid). Is mentioned.

Examples of the monoalcohol (D) include an aliphatic monoalcohol (D1) and an aromatic monoalcohol (D2).
In addition, (D) may be used independently and may use 2 or more types together.
Examples of the aliphatic monoalcohol (D1) include a chain saturated monoalcohol and a chain unsaturated monoalcohol.

Examples of the chain saturated monoalcohol include linear or branched chain saturated monoalcohol having 1 to 30 carbon atoms (methanol, ethanol, 1-propyl alcohol, isopropyl alcohol, butanol, pentanol, 2-methyl-1-butanol, 2,2-dimethyl-1-propanol, hexanol, 4-methyl-1-pentanol, 2,3-dimethyl-2-butanol, heptanol, 3-ethyl-3-pentanol, octanol, 2-ethyl-1- Hexanol, nonanol, 2,6-dimethyl-4-heptanol, decanol, undecanol, lauryl alcohol, myristyl alcohol, cetyl alcohol and stearyl alcohol), and linear or branched chain saturated monoalcohol having 1 to 30 carbon atoms. Attached with C2-4 AO (Addition molar number of 1 to 20 mol), and the like.

Examples of the chain unsaturated monoalcohol include linear or branched chain unsaturated monoalcohol having 2 to 30 carbon atoms (allyl alcohol, 2-buten-1-ol, 2-penten-1-ol, 2-hexene- 1-ol, 2-hepten-1-ol, 2-octen-1-ol, 2-nonen-1-ol, 2-decen-1-ol, 2-dodecenol, palmitolyl alcohol, oleyl alcohol and linoleyl alcohol Etc.), and those obtained by adding AO having 2 to 4 carbon atoms to a linear or branched chain unsaturated monoalcohol having 1 to 30 carbon atoms (added mole number 1 to 20 mol).

As the aromatic monoalcohol (D2), an aromatic monoalcohol having 6 to 30 carbon atoms (phenol, ethylphenol, isobutylphenol, pentylphenol, octylphenol, dodecylphenol, tetradecylphenol, benzyl alcohol, etc.) and 6 carbon atoms. The thing which added C2-C4 AO to -30 aromatic monoalcohol (addition mole number 1-20 mol) etc. are mentioned.

The polyester resin (P) may have a structure in which a vinyl monomer (E) is grafted as necessary.

Examples of the vinyl monomer (E) include vinyl esters such as vinyl chloride, vinyl bromide, vinyl iodide, vinyl acetate, vinyl propionate, vinyl formate, and vinyl caproate; for example, acrylic acid, methyl acrylate, ethyl acrylate , N-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, amyl acrylate, cyclohexyl acrylate, n-octyl acrylate, isooctyl acrylate, decyl acrylate, acrylic Lauryl acid, 2-ethylhexyl acrylate, stearyl acrylate, methoxyethyl acrylate, 2-hydroxyethyl acrylate, glycidyl acrylate, 2-chloroethyl acrylate, phenyl acrylate, methyl α-chloroacrylate, meta Rylic acid, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, amyl methacrylate, cyclohexyl methacrylate, n-octyl methacrylate , Isooctyl methacrylate, decyl methacrylate, lauryl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, methoxyethyl methacrylate, 2-hydroxyethyl methacrylate, glycidyl methacrylate, phenyl methacrylate, dimethylaminoethyl methacrylate, methacryl Ethylenic monocarboxylic acids such as diethylaminoethyl acid and esters thereof; for example, ethylenic monomers such as acrylonitrile, methacrylonitrile, acrylamide Nocarboxylic acid substituted products; ethylenic dicarboxylic acids such as dimethyl maleate and substituted products thereof; vinyl ketones such as vinyl methyl ketone; vinyl ethers such as vinyl ethyl ether; vinylidene halides such as vinylidene chloride.

The polyester resin (P) can be produced by a known method. Specifically, the diol composition (A) containing the compound (a), the dicarboxylic acid or the modified product (B) thereof, and, if necessary, the polycarboxylic acid (C) and / or the monoalcohol (D) are polycondensed. Thus, (P) can be produced.

The reaction temperature during polycondensation is preferably 100 to 250 ° C., the reaction pressure is preferably 0.001 to 0.2 MPa, and the reaction time is preferably 1 to 50 hours.
The polycondensation is preferably performed while removing generated water from the reaction system in order to improve the reaction rate.
In order to accelerate the reaction, it is preferable to use a catalyst. Examples of the catalyst include inorganic acids (for example, sulfuric acid and hydrochloric acid), organic sulfonic acids (for example, methanesulfonic acid, paratoluenesulfonic acid, xylenesulfonic acid, naphthalenesulfonic acid, and the like) and organic metal compounds (for example, dibutyltin oxide, tetraisopropoxy). Titanate, bistriethanolamine titanate, terephthalic acid titanate, potassium oxalate titanate, etc.). When a catalyst is used, it may be left in the resin after completion of the esterification reaction, or the catalyst may be neutralized if necessary and treated with an adsorbent to remove and purify the catalyst.

The content of the unreacted diol composition (A) remaining in the polyester resin (P) of the present invention is 0.001 to 5% by weight based on the weight of (P), and is heat resistant storage stability. And from a viewpoint of wet heat storage stability, Preferably it is 0.001-2 weight%, More preferably, it is 0.001-1 weight%, Most preferably, it is 0.001-0.5 weight%.

In addition, the content rate of a diol composition (A) can be measured by a liquid chromatography / mass spectrum (LC / MS). Examples of LC / MS measurement conditions include the following conditions.

<Measurement conditions for LC / MS>
LC / MS measuring device: “LCMS-8030” [manufactured by Shimadzu Corporation]
Column: “Inert Sustain C18” (particle diameter 2.0 μm, inner diameter 2.1 mm,
Length 100mm) [manufactured by GL Sciences Inc.]
Detector: “PDA detector” [manufactured by Shimadzu Corporation]
Detection wavelength: 230 nm
Eluent: Ammonium acetate aqueous solution / methanol = 24/76 (volume%)
Injection volume: 2 μl
Flow rate: 1.0 ml / min

The glass transition temperature (hereinafter abbreviated as Tg) of the polyester resin (P) is 40 to 80 ° C., and preferably 40 to 75 ° C. from the viewpoint of low-temperature fixability, heat and storage stability. More preferably, it is 40-72 degreeC, Most preferably, it is 40-70 degreeC.
In addition, Tg of (P) can be measured by the method (DSC) prescribed | regulated to ASTM D3418-82 using "DSC20, SSC / 580" [made by Seiko Instruments Inc.].

Mn of the polyester resin (P) is preferably 1,000 to 500,000, more preferably 1,200 to 300,000, and particularly preferably 1,500 to 200,000 from the viewpoint of resin strength. It is.

  Mw of the polyester resin (P) is 1,000 to 1,000,000, and from the viewpoint of resin strength, it is preferably 2,000 to 800,000, and more preferably 3,000 to 600,000. And particularly preferably 3,500 to 500,000.

Mw / Mn of the polyester resin (P) is 1.0 to 50.0, and from the viewpoint of resin strength, it is preferably 1.0 to 45.0, and more preferably 1.0 to 40.0. Yes, particularly preferably 1.0 to 35.0.

Mn and Mw of (P) in the present invention can be measured under the following conditions using gel permeation chromatography (GPC).
Apparatus (example): “HLC-8120” [manufactured by Tosoh Corporation]
Column (example): “TSK GEL GMH6” [manufactured by Tosoh Corporation] Measurement temperature: 40 ° C.
Sample solution: 0.25% by weight tetrahydrofuran solution (insoluble matter filtered off with glass filter)
Solution injection volume: 100 μl
Detection apparatus: Refractive index detector Reference material: Standard polystyrene (TSK standard POLYSTYRENE) 12 points (Molecular weight: 500, 1,050, 2,800, 5,970, 9,100,
18,100,37,900,96,400,190,000,355,000,
1,090,000, 2,890,000) [manufactured by Tosoh Corporation]

The acid value (mgKOH / g) of the polyester resin (P) is 0 to 40, preferably 0 to 35, more preferably 1 to 33, from the viewpoint of wet heat storage stability and charging stability. Especially preferably, it is 1-30.
In addition, the acid value of (P) can be measured by the method of JIS K0070-1992.

The hydroxyl value (mgKOH / g) of the polyester resin (P) is 5 to 80, preferably 6 to 75, more preferably 7 to 70, from the viewpoints of heat and storage stability. Particularly preferred is 8 to 65.
In addition, the hydroxyl value of (P) can be measured by the method of JIS K0070-1992.

  The storage elastic modulus (Pa) at 70 ° C. and 150 ° C. of the polyester resin (P) preferably satisfies the following relational expressions (1) and (2) from the viewpoint of low-temperature fixability and heat-resistant storage stability. It is more preferable to satisfy the expressions (1 ′) and (2 ′).

10 ³ ≦ [G′70] ≦ 10 ¹⁰ (1)
1 ≦ [G′150] ≦ 10 ⁶ (2)
Here, in the relational expression, [G′70] means the storage elastic modulus (Pa) of the polyester resin (P) at 70 ° C., and [G′150] means the storage elastic modulus (Pa) at 150 ° C.

10 ³ ≦ [G′70] ≦ 10 ⁹ (1 ′)
1 ≦ [G′150] ≦ 10 ⁵ (2 ′)

The storage elastic modulus (G ′) of (P) in the present invention can be measured using the following viscoelasticity measuring device under the following conditions.
Apparatus: ARES-24A (Rheometric)
Jig: 8mmφ parallel plate Frequency: 1Hz
Distortion rate: 5%
Temperature increase rate: 5 ° C / min

  The softening point (Tm) of the polyester resin (P) is 70 to 170 ° C., and preferably 70 to 165 ° C., more preferably 75 to 160 ° C. from the viewpoints of low-temperature fixability and heat-resistant storage stability. Especially preferably, it is 80-155 degreeC.

The softening point (Tm) of (P) in the present invention is a value measured as follows.
Using an elevated flow tester {for example, CFT-500D, manufactured by Shimadzu Corporation), a load of 1.96 MPa was applied by a plunger while heating a 1 g measurement sample at a heating rate of 6 ° C./min. Extrude from a nozzle with a diameter of 1 mm and a length of 1 mm, draw a graph of “plunger descent amount (flow value)” and “temperature”, and graph the temperature corresponding to 1/2 of the maximum plunger descent amount This value (temperature when half of the measurement sample flows out) is taken as the softening point (Tm).

  The polyester resin (P) has a moisture content in (P) after storage (humidity and heat resistance test) for 20 hours under the conditions of 40 ° C. and 90% relative humidity from the viewpoint of moisture and heat storage stability. However, it is preferable that it is 15,000 ppm or less based on the weight of (P), More preferably, it is 13,000 ppm or less, Most preferably, it is 12,000 ppm or less.

The water content (P) in the present invention is a value measured using a Karl Fischer moisture measuring device [for example, trade name: AQV-200 (manufactured by Hiranuma Sangyo)].

The volume resistivity value R (Ω · cm) of the polyester resin (P) is preferably 10 ¹⁰ to 10 ¹⁴ , more preferably 10 ^10.5 to 10 ¹⁴ , particularly from the viewpoint of charging stability. preferably from ^{1011 to 14.}
The volume specific resistance value R (Ω · cm) of (P) in the present invention can be measured using a TR-1100 type dielectric loss automatic measuring device, SE-70 type solid electrode [manufactured by Ando Electric Co., Ltd.]. it can.

In the toner binder of the present invention, the polyester resin (P) of the present invention may be used alone, or two or more (P) having different chemical structures may be used in combination.

Further, in the toner binder of the present invention, a resin (H) other than the polyester resin (P) of the present invention may be used in combination with the polyester resin (P) of the present invention.

As the resin (H) that is preferably used in combination with the polyester resin (P) of the present invention in the toner binder of the present invention, polyester resin (H1), polyurethane resin (H2), polyurea resin (H3), vinyl resin (H4) ) And epoxy resin (H5).

The polyester resin (H1) preferably used in combination with the polyester resin (P) of the present invention includes a polyester resin obtained by polycondensation of an alcohol component and a carboxylic acid component.
Examples of the alcohol component include the diol not containing the compound (a), the trivalent or higher polyol, and the monoalcohol (D).
Examples of the carboxylic acid component include the dicarboxylic acid or a modified product thereof (B), the trivalent or higher polycarboxylic acid or a modified product thereof, and a monocarboxylic acid (C).
Further, (H1) may be a linear polyester resin or a non-linear polyester resin. The linear polyester resin is a chain polyester resin having no three-dimensional crosslinked structure, which is obtained by polycondensation of the alcohol component and the carboxylic acid component.
The non-linear polyester resin is a network-like polyester resin having a three-dimensional cross-linked structure obtained by polycondensation of the alcohol component and the carboxylic acid component.

The polyurethane resin (H2) preferably used in combination with the polyester resin (P) of the present invention includes those obtained by polycondensation of the diol and / or diamine and diisocyanate, the polyester resin (P) and the diol and / or diamine and diisocyanate. And the like obtained by polycondensation.

Examples of the diamine include aliphatic diamines having 2 to 18 carbon atoms and aromatic diamines having 6 to 20 carbon atoms.
Examples of the aliphatic diamine having 2 to 18 carbon atoms include a chain aliphatic diamine and a cyclic aliphatic diamine.

  Examples of chain aliphatic diamines include alkylene diamines having 2 to 12 carbon atoms (such as ethylene diamine, trimethylene diamine, tetramethylene diamine, and hexamethylene diamine).

  Cycloaliphatic diamines include alicyclic diamines having 4 to 15 carbon atoms {1,3-diaminocyclohexane, isophorone diamine, mensen diamine, 4,4′-methylene dicyclohexane diamine (hydrogenated methylene dianiline) and 3 , 9-bis (3-aminopropyl) -2,4,8,10-tetraoxaspiro [5,5] undecane etc.}.

  Examples of the aromatic diamine having 6 to 20 carbon atoms include 1,2-, 1,3- or 1,4-phenylenediamine, 2,4′- or 4,4′-diphenylmethanediamine, diaminodiphenylsulfone, benzidine, and thiodianiline. Bis (3,4-diaminophenyl) sulfone, 2,6-diaminopyridine, m-aminobenzylamine, naphthylenediamine, 2,4- or 2,6-tolylenediamine, crude tolylenediamine, diethyltolylenediamine Amine, 4,4′-diamino-3,3′-dimethyldiphenylmethane, 4,4′-bis (o-toluidine), dianisidine, diaminoditolylsulfone, 1,3-dimethyl-2,4-diaminobenzene, 1 , 3-diethyl-2,4-diaminobenzene, 1,3-dimethyl-2,6-diaminobenzene, 1, -Diethyl-2,5-diaminobenzene, 1,4-diisopropyl-2,5-diaminobenzene, 1,4-dibutyl-2,5-diaminobenzene, 2,4-diaminomesitylene, 1,3,5-triethyl -2,4-diaminobenzene, 1,3,5-triisopropyl-2,4-diaminobenzene, 1-methyl-3,5-diethyl-2,4-diaminobenzene, 1-methyl-3,5-diethyl -2,6-diaminobenzene, 2,3-dimethyl-1,4-diaminonaphthalene, 2,6-dimethyl-1,5-diaminonaphthalene, 2,6-diisopropyl-1,5-diaminonaphthalene, 2,6 -Dibutyl-1,5-diaminonaphthalene, 3,3 ', 5,5'-tetramethylbenzidine, 3,3', 5,5'-tetraisopropylbenzidine, 3 3 ′, 5,5′-tetramethyl-4,4′-diaminodiphenylmethane, 3,3 ′, 5,5′-tetraethyl-4,4′-diaminodiphenylmethane, 3,3 ′, 5,5′-tetra Isopropyl-4,4′-diaminodiphenylmethane, 3,3 ′, 5,5′-tetrabutyl-4,4′-diaminodiphenylmethane, 3,5-diethyl-3′-methyl-2 ′, 4-diaminodiphenylmethane, 3 , 5-diisopropyl-3′-methyl-2 ′, 4-diaminodiphenylmethane, 3,3′-diethyl-2,2′-diaminodiphenylmethane, 4,4′-diamino-3,3′-dimethyldiphenylmethane, 3, 3 ′, 5,5′-tetraethyl-4,4′-diaminobenzophenone, 3,3 ′, 5,5′-tetraisopropyl-4,4′-diaminoben Examples include zophenone, 3,3 ′, 5,5′-tetraethyl-4,4′-diaminodiphenyl ether, 3,3 ′, 5,5′-tetraisopropyl-4,4′-diaminodiphenyl sulfone, and mixtures thereof. It is done.

  As the diisocyanate, an aromatic diisocyanate having 6 to 20 carbon atoms (excluding carbon in the NCO group; the same shall apply hereinafter), an aliphatic diisocyanate having 2 to 18 carbon atoms, a modified product of these diisocyanates (urethane group, carbodiimide group, And allophanate group, urea group, burette group, uretdione group, uretoimine group, isocyanurate group and oxazolidone group-containing modified product) and mixtures of two or more thereof.

  Examples of the aromatic diisocyanate having 6 to 20 carbon atoms include 1,3- or 1,4-phenylene diisocyanate, 2,4- or 2,6-tolylene diisocyanate (TDI), crude TDI, m- or p-xylylene diene. Isocyanate (XDI), α, α, α ′, α′-tetramethylxylylene diisocyanate (TMXDI), 2,4′- or 4,4′-diphenylmethane diisocyanate (MDI), crude MDI {crude diaminophenylmethane [formaldehyde And condensation products of these with aromatic amines (aniline) or mixtures thereof, and mixtures thereof.

Examples of the aliphatic diisocyanate having 2 to 18 carbon atoms include chain aliphatic diisocyanates and cyclic aliphatic diisocyanates.
Examples of chain aliphatic diisocyanates include ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), dodecamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, and 2,6-diisocyanatomethylcaproate. Bis (2-isocyanatoethyl) fumarate, bis (2-isocyanatoethyl) carbonate and mixtures thereof.

  Cycloaliphatic diisocyanates include isophorone diisocyanate (IPDI), dicyclohexylmethane-4,4′-diisocyanate (hydrogenated MDI), cyclohexylene diisocyanate, methylcyclohexylene diisocyanate (hydrogenated TDI), and bis (2-isocyanatoethyl). -4-cyclohexene-1,2-dicarboxylate, 2,5- or 2,6-norbornane diisocyanate, and mixtures thereof.

  As the modified product of diisocyanate, a modified product containing a urethane group, a carbodiimide group, an allophanate group, a urea group, a burette group, a uretdione group, a uretoimine group, an isocyanurate group and / or an oxazolidone group is used. Urethane-modified MDI, carbodiimide-modified MDI, trihydrocarbyl phosphate-modified MDI, etc.), urethane-modified TDI, and mixtures thereof (for example, a mixture of modified MDI and urethane-modified TDI (isocyanate-containing prepolymer)).

  Among the diisocyanates, preferred are aromatic diisocyanates having 6 to 15 carbon atoms and aliphatic diisocyanates having 4 to 15 carbon atoms, and more preferred are TDI, MDI, HDI, hydrogenated MDI and IPDI.

The polyurea resin (H3) preferably used in combination with the polyester resin (P) of the present invention includes those having the diamine and diisocyanate as structural units.

The vinyl resin (H4) preferably used in combination with the polyester resin (P) of the present invention is a polymer obtained by homopolymerizing or copolymerizing a monomer having a polymerizable double bond. Examples of the monomer having a polymerizable double bond include the following (d) to (l).

(D) Hydrocarbon compound having a polymerizable double bond:
For example, the following (d1) to (d3) can be mentioned.
A chain hydrocarbon compound having a polymerizable double bond (d1):
Alkenes having 2 to 30 carbon atoms (for example, ethylene, propylene, butene, isobutylene, pentene, heptene, diisobutylene, octene, dodecene and octadecene); alkadienes having 4 to 30 carbon atoms (for example, butadiene, isoprene, 1,4-pentadiene) 1,5-hexadiene and 1,7-octadiene).

Cyclic hydrocarbon compound having a polymerizable double bond (d2):
Mono- or dicycloalkene having 6 to 30 carbon atoms (for example, cyclohexene, vinylcyclohexene, and ethylidenebicycloheptene) and mono- or dicycloalkadiene having 5 to 30 carbon atoms [for example, (di) cyclopentadiene and the like].

Aromatic hydrocarbon compound having a polymerizable double bond (d3):
Styrene; hydrocarbyl (alkyl, cycloalkyl, aralkyl and / or alkenyl having 1 to 30 carbon atoms) substitution of styrene (for example, α-methylstyrene, vinyltoluene, 2,4-dimethylstyrene, ethylstyrene, isopropylstyrene, Butyl styrene, phenyl styrene, cyclohexyl styrene, benzyl styrene, crotyl benzene, divinyl benzene, divinyl toluene, divinyl xylene, and trivinyl benzene); and vinyl naphthalene.

(E) Monomers having a carboxyl group and a polymerizable double bond and their salts:
As a monomer which has a carboxyl group and a polymerizable double bond, C3-C15 unsaturated monocarboxylic acid {For example, (meth) acrylic acid ["(meth) acryl" means acryl or methacryl. ], Crotonic acid, isocrotonic acid, cinnamic acid and the like}; C3-C30 unsaturated dicarboxylic acid (anhydride) [for example, (anhydrous) maleic acid, fumaric acid, itaconic acid, (anhydrous) citraconic acid, mesaconic acid, etc. And monoalkyl (C1-10) esters of unsaturated dicarboxylic acids having 3 to 10 carbon atoms (eg maleic acid monomethyl ester, maleic acid monodecyl ester, fumaric acid monoethyl ester, itaconic acid monobutyl ester and citracone) Acid monodecyl ester, etc.).

Examples of the salt of the monomer having a carboxyl group and a polymerizable double bond include alkali metal salts (such as sodium salt and potassium salt), alkaline earth metal salts (such as calcium salt and magnesium salt), ammonium salt, amine salt, and the like. A quaternary ammonium salt etc. are mentioned.
Examples of alkali metal salts, alkaline earth metal salts, and ammonium salts include sodium acrylate, sodium methacrylate, monosodium maleate, disodium maleate, potassium acrylate, potassium methacrylate, monopotassium maleate, lithium acrylate, Examples include cesium acrylate, ammonium acrylate, calcium acrylate, and aluminum acrylate.
The amine salt is not particularly limited as long as it is an amine compound. For example, primary amine salts (such as ethylamine salts, butylamine salts and octylamine salts), secondary amines (such as diethylamine salts and dibutylamine salts), tertiary amines ( Triethylamine salt and tributylamine salt). Examples of the quaternary ammonium salt include tetraethylammonium salt, triethyllaurylammonium salt, tetrabutylammonium salt, and tributyllaurylammonium salt.

(F) Monomers having a sulfo group and a polymerizable double bond and their salts:
Alkene sulfonic acids having 2 to 14 carbon atoms (for example, vinyl sulfonic acid, (meth) allyl sulfonic acid and methyl vinyl sulfonic acid); styrene sulfonic acid and alkyl (2 to 24 carbon) derivatives thereof (for example, α-methyl styrene sulfone) Acid etc .; C5-C18 sulfo (hydroxy) alkyl (meth) acrylate (for example, sulfopropyl (meth) acrylate, 2-hydroxy-3- (meth) acryloxypropanesulfonic acid, 2- (meth) acryloyloxyethane) Sulfonic acid and 3- (meth) acryloyloxy-2-hydroxypropanesulfonic acid); sulfo (hydroxy) alkyl (meth) acrylamide having 5 to 18 carbon atoms [for example, 2- (meth) acryloylamino-2,2-dimethyl Ethanesulfonic acid, 2- (meth) acrylamid 2-methylpropanesulfonic acid and 3- (meth) acrylamide-2-hydroxypropanesulfonic acid, etc.]; alkyl (C3-C18) allylsulfosuccinic acid (for example, propylallylsulfosuccinic acid, butylallylsulfosuccinic acid, 2-ethylhexyl) -Allylsulfosuccinic acid, etc.]; poly [n (degree of polymerization; the same applies hereinafter) = 2-30] oxyalkylene (oxyethylene, oxypropylene, oxybutylene, etc.) Oxyalkylene may be used alone or in combination. The form may be random addition or block addition.) Mono (meth) acrylate sulfate [for example, poly (n = 5-15) oxyethylene monomethacrylate sulfate and poly (n = 5-15) oxypropylene monomethacrylate sulfate Etc.]; And compounds represented by the general chemical formulas (2) to (4); and salts thereof.

In chemical formulas (2) to (4), R ³ represents an alkylene group having 2 to 4 carbon atoms, and R ³ O may be used singly or in combination of two or more, and when two or more are used in combination, The format may be random or block. R ⁴ and R ⁵ each independently represents an alkyl group having 1 to 15 carbon atoms, Ar represents a benzene ring, and R ⁶ represents an alkyl group having 1 to 15 carbon atoms which may be substituted with a fluorine atom. Represent. x and y each independently represents a number from 1 to 50.

  In addition, as a salt, what was illustrated as a salt which comprises the salt of the monomer which has (e) a carboxyl group and a polymerizable double bond is mentioned.

(G) Monomers having a phosphono group and a polymerizable double bond and salts thereof:
(Meth) acryloyloxyalkyl phosphate monoester (alkyl group having 1 to 24 carbon atoms) (for example, 2-hydroxyethyl (meth) acryloyl phosphate and phenyl-2-acryloyloxyethyl phosphate), (meth) acryloyloxyalkyl Phosphonic acid (alkyl group having 1 to 24 carbon atoms) (for example, 2-acryloyloxyethylphosphonic acid).
Examples of the salt include (e) those exemplified as the salt of a monomer having a carboxyl group and a polymerizable double bond.

(H) Monomer having a hydroxyl group and a polymerizable double bond:
Hydroxystyrene, N-methylol (meth) acrylamide, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, (meth) allyl alcohol, crotyl alcohol, isocrotyl alcohol, 1- Buten-3-ol, 2-buten-1-ol, 2-butene-1,4-diol, propargyl alcohol, 2-hydroxyethylpropenyl ether, sucrose allyl ether, and the like.

(I) Nitrogen-containing monomer having a polymerizable double bond:
For example, the following (i1) to (i4) can be mentioned.
Monomer having amino group and polymerizable double bond (i1):
Aminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, t-butylaminoethyl methacrylate, N-aminoethyl (meth) acrylamide, (meth) allylamine, morpholinoethyl (meth) acrylate, 4-vinylpyridine, 2-vinylpyridine, crotylamine, N, N-dimethylaminostyrene, methyl-α-acetaminoacrylate, vinylimidazole, N-vinylpyrrole, N-vinylthiopyrrolidone, N-arylphenylenediamine, aminocarbazole , Aminothiazole, aminoindole, aminopyrrole, aminoimidazole, aminomercaptothiazole and salts thereof.

Monomer having amide group and polymerizable double bond (i2):
(Meth) acrylamide, N-methyl (meth) acrylamide, N-butyl acrylamide, diacetone acrylamide, N-methylol (meth) acrylamide, N, N′-methylene-bis (meth) acrylamide, cinnamic amide, N, N -Dimethylacrylamide, N, N-dibenzylacrylamide, N-methyl-N-vinylacetamide, N-vinylpyrrolidone and the like.

Monomer having 3 to 10 carbon atoms having a nitrile group and a polymerizable double bond (i3):
(Meth) acrylonitrile, cyanostyrene, cyanoacrylate and the like.

Monomer having 8 to 12 carbon atoms having a nitro group and a polymerizable double bond (i4):
Nitrostyrene etc.

(J) A monomer having 6 to 18 carbon atoms having an epoxy group and a polymerizable double bond:
Glycidyl (meth) acrylate and p-vinylphenylphenyl oxide.

(K) C2-C16 monomer having a halogen element and a polymerizable double bond:
Vinyl chloride, vinyl bromide, vinylidene chloride, allyl chloride, chlorostyrene, bromostyrene, dichlorostyrene, chloromethylstyrene, tetrafluorostyrene, chloroprene and the like.

(L) Other compounds having a polymerizable double bond (l)
For example, an ester (11) having a polymerizable double bond, an ether (12) having a polymerizable double bond, a ketone (13) having a polymerizable double bond, and a sulfur-containing compound having a polymerizable double bond (14) ) And the like.
C4-16 ester having a polymerizable double bond (l1):
Vinyl acetate, vinyl propionate, vinyl butyrate, diallyl phthalate, diallyl adipate, isopropenyl acetate, vinyl methacrylate, methyl-4-vinyl benzoate, cyclohexyl methacrylate, benzyl methacrylate, phenyl (meth) acrylate, vinyl methoxyacetate, vinyl benzoate, ethyl -Α-ethoxyacrylate, alkyl (meth) acrylate having an alkyl group having 1 to 50 carbon atoms [methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl ( (Meth) acrylate, dodecyl (meth) acrylate, hexadecyl (meth) acrylate, heptadecyl (meth) acrylate and eicosyl (meth) a Relate, etc.], dialkyl fumarate (two alkyl groups are linear, branched or alicyclic groups having 2 to 8 carbon atoms), dialkyl maleate (two alkyl groups are carbon atoms 2-8 linear, branched or alicyclic groups), poly (meth) allyloxyalkanes (diallyloxyethane, triaryloxyethane, tetraallyloxyethane, tetraallyloxypropane, tetra Monomers having a polyalkylene glycol chain and a polymerizable double bond [polyethylene glycol [Mn = 300] mono (meth) acrylate, polypropylene glycol (Mn = 500) mono), such as allyloxybutane and tetrametaallyloxyethane) Acrylate, methyl alcohol EO 10 mol adduct (meth) acrylate and lauryl alcohol EO 30 mol adduct (meth) Acrylates, etc.], poly (meth) acrylates [poly (meth) acrylates of polyhydric alcohols: ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropane Tri (meth) acrylate and polyethylene glycol di (meth) acrylate, etc.].

C3-C16 ether having a polymerizable double bond (l2):
Vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether, vinyl butyl ether, vinyl-2-ethylhexyl ether, vinyl phenyl ether, vinyl-2-methoxyethyl ether, methoxybutadiene, vinyl-2-butoxyethyl ether, 3,4-dihydro -1,2-pyran, 2-butoxy-2′-vinyloxydiethyl ether, acetoxystyrene, phenoxystyrene, and the like.

C4-C12 ketone having a polymerizable double bond (l3):
Examples include vinyl methyl ketone, vinyl ethyl ketone, and vinyl phenyl ketone.
C2-C16 sulfur-containing compound having a polymerizable double bond (l4):
Examples thereof include divinyl sulfide, p-vinyl diphenyl sulfide, vinyl ethyl sulfide, vinyl ethyl sulfone, divinyl sulfone, and divinyl sulfoxide.

  The epoxy resin (H5) preferably used in combination with the polyester resin (P) of the present invention includes a ring-opening polymer of polyepoxide (o), polyepoxide (o) and an active hydrogen-containing compound [water, the diol, the dicarboxylic acid. (B) and diamine (b) etc.] and the like.

  The polyepoxide (o) used as a raw material for the epoxy resin (H5) includes an aromatic polyepoxy compound (o1), a heterocyclic polyepoxy compound (o2), an alicyclic polyepoxy compound (o3), and an aliphatic group. Based polyepoxy compounds (o4) and the like.

Examples of the aromatic polyepoxy compound (o1) include glycidyl ethers and glycidyl ethers of polyhydric phenols, glycidyl aromatic polyamines, and glycidylates of aminophenols.

Examples of glycidyl ethers of polyhydric phenols include bisphenol F diglycidyl ether, bisphenol A diglycidyl ether, bisphenol B diglycidyl ether, bisphenol AD diglycidyl ether, bisphenol S diglycidyl ether, halogenated bisphenol A diglycidyl, and tetrachlorobisphenol. A diglycidyl ether, catechin diglycidyl ether, resorcinol diglycidyl ether, hydroquinone diglycidyl ether, pyrogallol triglycidyl ether, 1,5-dihydroxynaphthalene diglycidyl ether, dihydroxybiphenyl diglycidyl ether, octachloro-4,4'-dihydroxybiphenyl Diglycidyl ether, tetramethylbiphenyl diglycidyl Ether, dihydroxynaphthylcresol triglycidyl ether, tris (hydroxyphenyl) methane triglycidyl ether, dinaphthyltriol triglycidyl ether, tetrakis (4-hydroxyphenyl) ethanetetraglycidyl ether, p-glycidylphenyldimethyltolylbisphenol A glycidyl ether, trismethyl -T-butyl-butylhydroxymethane triglycidyl ether, 9,9'-bis (4-hydroxyphenyl) furorange glycidyl ether, 4,4'-oxybis (1,4-phenylethyl) tetracresol glycidyl ether, 4 , 4′-oxybis (1,4-phenylethyl) phenylglycidyl ether, bis (dihydroxynaphthalene) tetraglycidyl ether, Or cresol novolak resin, glycidyl ether of limonene phenol novolak resin, diglycidyl ether obtained from the reaction of 2 mol of bisphenol A and 3 mol of epichlorohydrin, phenol and glyoxal, glutaraldehyde or formaldehyde Examples thereof include polyglycidyl ethers of polyphenols obtained by a condensation reaction and polyglycidyl ethers of polyphenols obtained by a condensation reaction of resorcin and acetone.

Examples of the glycidyl ester of polyhydric phenols include phthalic acid diglycidyl ester, isophthalic acid diglycidyl ester, and terephthalic acid diglycidyl ester.

Examples of the glycidyl aromatic polyamine include N, N-diglycidylaniline, N, N, N ′, N′-tetraglycidylxylylenediamine and N, N, N ′, N′-tetraglycidyldiphenylmethanediamine. Furthermore, as the aromatic system, tolylene diisocyanate or a diglycidyl urethane compound obtained by addition reaction of diphenylmethane diisocyanate and glycidol, a glycidyl group-containing polyurethane (pre) polymer obtained by reacting the two reactants with a polyol, and bisphenol A The diglycidyl ether form of the AO adduct is also included.

Examples of the heterocyclic polyepoxy compound (o2) include triglycidyl melamine.

Examples of the alicyclic polyepoxy compound (o3) include vinylcyclohexene dioxide, limonene dioxide, dicyclopentadiene dioxide, bis (2,3-epoxycyclopentyl) ether, ethylene glycol bisepoxy dicyclopentyl ether, 3,4 -Epoxy-6-methylcyclohexylmethyl-3 ', 4'-epoxy-6'-methylcyclohexanecarboxylate, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, bis (3,4-epoxy-6 -Methylcyclohexylmethyl) butylamine and dimer acid diglycidyl ester. The alicyclic group also includes hydrogenated products of the aromatic polyepoxide compound (o1).

Examples of the aliphatic polyepoxy compound (o4) include polyglycidyl ethers of polyhydric aliphatic alcohols, polyglycidyl esters of polyhydric fatty acids, and glycidyl aliphatic amines.
Polyglycidyl ethers of polyhydric aliphatic alcohols include ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tetramethylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol Examples include diglycidyl ether, polytetramethylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, trimethylolpropane polyglycidyl ether, glycerol polyglycidyl ether, pentaerythritol polyglycidyl ether, sorbitol polyglycidyl ether and polyglycerol polyglycidyl ether. It is done.
Examples of polyglycidyl ester of polyvalent fatty acid include diglycidyl oxalate, diglycidyl malate, diglycidyl succinate, diglycidyl glutarate, diglycidyl adipate and diglycidyl pimelate.
Examples of the glycidyl aliphatic amine include N, N, N ′, N′-tetraglycidylhexamethylenediamine. As the aliphatic group, a (co) polymer of diglycidyl ether and glycidyl (meth) acrylate is also included.
Of the polyepoxides (o), an aliphatic polyepoxy compound (o4) and an aromatic polyepoxy compound (o1) are preferable. Two or more polyepoxides (o) may be used in combination.

These resins (H) may be obtained from the precursor (H0).
The precursor (H0) is not particularly limited as long as it can be converted into a resin (H) by a chemical reaction, but the resin (H) is a polyester resin (H1), a polyurethane resin (H2), a polyurea resin (H3) or In the case of the epoxy resin (H5), (H0) includes a combination of a prepolymer (α) having a reactive group and a curing agent (β).
When the resin (H) is a vinyl resin (H4), examples of the precursor (H0) include the monomers (d) to (l).
Among the precursors (H0), from the viewpoint of productivity, a combination of a prepolymer (α) having a reactive group and a curing agent (β) is preferable.

  When a combination of a prepolymer (α) having a reactive group and a curing agent (β) is used as the precursor (H0), the “reactive group” possessed by (α) is a reaction with the curing agent (β). A possible group. In this case, examples of the method of forming the resin (H) by reacting the precursor (H0) include a method of forming the resin (H) by reacting (α) and (β) by heating.

The following [1] or [2] etc. are mentioned as a combination of the reactive group which a reactive group containing prepolymer ((alpha)) and a hardening | curing agent ((beta)).
[1] A combination in which the reactive group of (α) is a functional group (α1) capable of reacting with an active hydrogen compound, and (β) is an active hydrogen group-containing compound (β1).
[2] A combination in which the reactive group of (α) is an active hydrogen-containing group (α2), and (β) is a compound (β2) that can react with the active hydrogen-containing group.

In the combination [1], the functional group (α1) capable of reacting with the active hydrogen compound includes an isocyanate group (α1a), a blocked isocyanate group (α1b), an epoxy group (α1c), an acid anhydride group (α1d) and An acid halide group (α1e) and the like can be mentioned. Of these, (α1a), (α1b) and (α1c) are preferable, and (α1a) and (α1b) are more preferable.
The blocked isocyanate group (α1b) refers to an isocyanate group blocked with a blocking agent.

Examples of the blocking agent include oximes (acetoxime, methyl isobutyl ketoxime, diethyl ketoxime, cyclopentanone oxime, cyclohexanone oxime, methyl ethyl ketoxime, etc.); lactams (γ-butyrolactam, ε-caprolactam and γ-valerolactam) C1-20 aliphatic alcohols (ethanol, methanol, octanol, etc.); phenols (phenol, m-cresol, xylenol, nonylphenol, etc.); active methylene compounds (acetylacetone, ethyl malonate, and ethyl acetoacetate) Etc.); basic nitrogen-containing compounds (N, N-diethylhydroxylamine, 2-hydroxypyridine, pyridine N-oxide, 2-mercaptopyridine, etc.); and mixtures of two or more thereof Etc. The.
Of these, oximes are preferred, and methyl ethyl ketoxime is more preferred.

Examples of the structural unit of the reactive group-containing prepolymer (α) include polyether (αv), polyester (αw), epoxy resin (αx), polyurethane (αy), and polyurea (αz).
Examples of the polyether (αv) include polyethylene oxide, polypropylene oxide, and polybutylene oxide.
Examples of polyester (αw) include polyester resin (H).
Examples of the epoxy resin (αx) include addition condensates of bisphenols (such as bisphenol A, bisphenol F and bisphenol S) and epichlorohydrin.
Examples of the polyurethane (αy) include a polyaddition product of the diol and diisocyanate (c) and a polyaddition product of polyester (αw) and diisocyanate (c).
Examples of polyurea (αz) include polyaddition products of diamine (b) and diisocyanate (c).

As a method of adding a reactive group to polyether (αv), polyester (αw), epoxy resin (αx), polyurethane (αy), polyurea (αz), etc.,
[I] A method of leaving a functional group of a constituent at the terminal by using one of two or more constituents in excess.
[II] The functional group of the constituent component is left at the terminal by excessively using one of the two or more constituent components, and further contains a functional group and a reactive group capable of reacting with the remaining functional group. A method of reacting a compound.
Etc.

  In the method [I], a hydroxyl group-containing polyester prepolymer, a carboxyl group-containing polyester prepolymer, an acid halide group-containing polyester prepolymer, a hydroxyl group-containing epoxy resin prepolymer, an epoxy group-containing epoxy resin prepolymer, a hydroxyl group-containing polyurethane prepolymer, and an isocyanate A group-containing polyurethane prepolymer or the like is obtained.

  For example, in the case of a hydroxyl group-containing polyester prepolymer, the ratio of the constituent components is preferably such that the ratio of the polyol component and the polycarboxylic acid component is the equivalent ratio [OH] / [COOH] of the hydroxyl group [OH] and the carboxyl group [COOH]. 2/1 to 1/1, more preferably 1.5 / 1 to 1/1, and particularly preferably 1.3 / 1 to 1.02 / 1. In the case of other skeleton and end group prepolymers, the ratios are the same except that the constituent components are changed.

In the method [II], the prepolymer obtained by the method [I] is reacted with a polyisocyanate to obtain an isocyanate group-containing prepolymer, and the blocked polyisocyanate is reacted to contain a blocked isocyanate group. A prepolymer is obtained, an epoxy group-containing prepolymer is obtained by reacting a polyepoxide, and an acid anhydride group-containing prepolymer is obtained by reacting a polyacid anhydride.
The amount of the compound containing the functional group and the reactive group is, for example, when the isocyanate group-containing polyester prepolymer is obtained by reacting the hydroxyl group-containing polyester with a polyisocyanate, and the ratio of the polyisocyanate is the isocyanate group [NCO] and the hydroxyl group. The equivalent ratio [NCO] / [OH] of the hydroxyl group [OH] of the containing polyester is preferably 5/1 to 1/1, more preferably 4/1 to 1.2 / 1, and particularly preferably 2.5. / 1 to 1.5 / 1. In the case of prepolymers having other skeletons and terminal groups, the ratio is the same except that the constituent components are changed.

The number of reactive groups contained per molecule in the reactive group-containing prepolymer (α) is preferably 1 or more, more preferably 1.5 to 3 on average, and particularly preferably 1.8 to 2 on average. .5. By setting it in the above range, the molecular weight of the cured product obtained by reacting with the curing agent (β) is increased.
The Mn of the reactive group-containing prepolymer (α) is preferably 500 to 30,000, more preferably 1,000 to 20,000, and particularly preferably 2,000 to 10,000.
The Mw of the reactive group-containing prepolymer (α) is preferably 1,000 to 50,000, more preferably 2,000 to 40,000, and particularly preferably 4,000 to 20,000.

Examples of the active hydrogen group-containing compound (β1) include diamine (β1a), diol (β1b), dimercaptan (β1c) and water which may be blocked with a detachable compound. Among these, (β1a), (β1b) and water are preferable, (β1a) and water are more preferable, and blocked polyamines and water are particularly preferable.
Examples of (β1a) include the same as the diamine (b). Preferred as (β1a) is 4,4′-diaminodiphenylmethane, xylylenediamine, isophoronediamine, ethylenediamine, diethylenetriamine, triethylenetetramine, and mixtures thereof.

Examples of the diol (β1b) include the same diols as described above, and preferred ranges thereof are also the same.
Examples of dimercaptan (β1c) include ethanedithiol, 1,4-butanedithiol, 1,6-hexanedithiol, and the like.

If necessary, a reaction terminator (βs) can be used together with the active hydrogen group-containing compound (β1). By using a reaction terminator in combination with (β1) at a certain ratio, it is possible to adjust the resin (H) to a predetermined molecular weight.
As the reaction terminator (βs), monoamine (diethylamine, dibutylamine, butylamine, laurylamine, monoethanolamine, diethanolamine, etc.); monoamine blocked (ketimine compound, etc.); monool (methanol, ethanol, isopropanol, butanol) And monophenols (such as butyl mercaptan and lauryl mercaptan); monoisocyanates (such as lauryl isocyanate and phenyl isocyanate); and monoepoxides (such as butyl glycidyl ether).

As the active hydrogen-containing group (α2) of the reactive group-containing prepolymer (α) in the combination [2], an amino group (α2a), a hydroxyl group (alcoholic hydroxyl group and phenolic hydroxyl group) (α2b), a mercapto group (Α2c), a carboxyl group (α2d), and an organic group (α2e) blocked with a compound from which they can be removed. Of these, (α2a), (α2b) and (α2e) are preferable, and (α2b) is more preferable.
Examples of the organic group blocked with the compound from which the amino group can be removed include the same groups as in the case of (β1a).

  Examples of the compound (β2) capable of reacting with the active hydrogen-containing group include diisocyanate (β2a), polyepoxide (β2b), polycarboxylic acid (β2c), polyacid anhydride (β2d), and polyacid halide (β2e). . Of these, (β2a) and (β2b) are preferred, and (β2a) is more preferred.

  Examples of the diisocyanate (β2a) include those similar to the diisocyanate (c), and preferred ones are also the same.

Examples of the polyepoxide (β2b) include the aromatic polyepoxy compound (o1), heterocyclic polyepoxy compound (o2), alicyclic polyepoxy compound (o3), and aliphatic polyepoxy compound (o4). Is mentioned.

  Examples of the dicarboxylic acid (β2c) include those similar to the dicarboxylic acid (B), and preferred ones are also the same.

  The ratio of the curing agent (β) is equivalent ratio [α] / [β of the reactive group [α] in the reactive group-containing prepolymer (α) and the active hydrogen-containing group [β] in the curing agent (β). ] Is preferably 1/2 to 2/1, more preferably 1.5 / 1 to 1 / 1.5, and particularly preferably 1.2 / 1 to 1 / 1.2. In addition, when a hardening | curing agent ((beta)) is water, water is handled as a bivalent active hydrogen compound.

The method of mixing the polyester resin (P) and the resin (H) is not particularly limited, and can be performed by an existing method such as melt mixing or powder mixing with each solid.
As a method of melt mixing, generally, a method of heating and mixing the polyester resin (P) and the resin (H) in a pellet or powder form with an appropriate mixer (Henschel mixer or the like) can be mentioned.

The content of the polyester resin (P) in the toner binder of the present invention is 1 to 100% by weight based on the weight of the toner binder, and from the viewpoint of reducing environmental burden, it is preferable to contain a large amount of plant-derived components. Based on the weight of the toner binder, 20 to 100% by weight is preferable, more preferably 50 to 100% by weight, and particularly preferably 70 to 100% by weight.

The production of the toner binder of the present invention may include a step of removing alcohol having a boiling point of 250 ° C. or less contained in (P) after obtaining the polyester resin (P).
By removing the alcohol having a boiling point of 250 ° C. or less contained in the polyester resin (P), the low-temperature fixability, heat-resistant storage stability, and moisture-heat storage stability of the obtained toner binder are improved.

Examples of the step of removing the alcohol having a boiling point of 250 ° C. or less contained in the polyester resin (P) include a method of removing it by decompression.
The pressure when the alcohol having a boiling point of 250 ° C. or less contained in the polyester resin (P) is removed under reduced pressure is preferably 0.001 to 0.050 MPa, more preferably 0.002 to 0.040 MPa. Particularly preferred is 0.003 to 0.020 MPa.
When the alcohol is removed under reduced pressure, it may be removed under heating, preferably 100 to 270 ° C, more preferably 150 to 260 ° C, and particularly preferably 170 to 250 ° C.

When the toner binder of the present invention is used as a toner, the toner of the present invention contains a colorant and a release agent in addition to the toner binder.
The content of the toner binder of the present invention is preferably 30 to 98% by weight, more preferably 40 to 95% by weight, and particularly preferably 45 to 92% by weight based on the weight of the toner.

As the colorant, all of dyes and pigments used as toner colorants can be used. Specifically, carbon black, iron black, Sudan black SM, first yellow G, benzidine yellow, solvent yellow (21, 77, 114, etc.), pigment yellow (12, 14, 17, 83, etc.), Indian first orange, Irgasin Red, Paranitonianiline Red, Toluidine Red, Solvent Red (17, 49, 128, 5, 13, 22 and 48.2, etc.), Disperse Red, Carmine FB, Pigment Orange R, Lake Red 2G, Rhodamine FB, Rhodamine B lake, methyl violet B lake, phthalocyanine blue, solvent blue (25, 94, 60, 15.3, etc.), pigment blue, brilliant green, phthalocyanine green, oil yellow GG, Kayaset YG, o Mentioned tetrazole brown B and oil pink OP etc. These may be used alone or may be used in combination of two or more. Further, magnetic powder (a powder of ferromagnetic metal such as iron, cobalt and nickel, a compound such as magnetite, hematite and ferrite) may also be included to serve as a colorant.
The content of the colorant is preferably 0.1 to 60% by weight, more preferably 0.3 to 55% by weight, and particularly preferably 0.5 to 50% by weight based on the weight of the toner. .

As the mold release agent, those having a softening point of 50 to 170 ° C. are preferable, polyolefin wax, natural wax (for example, carnauba wax, montan wax, paraffin wax and rice wax), aliphatic alcohol having 30 to 50 carbon atoms ( For example, triacontanol and the like), fatty acids having 30 to 50 carbon atoms (e.g., triacontanecarboxylic acid and the like), and mixtures thereof.
Polyolefin waxes include (co) polymers [obtained by (co) polymerization] of olefins (for example, ethylene, propylene, 1-butene, isobutylene, 1-hexene, 1-dodecene, 1-octadecene, and mixtures thereof). And olefin (co) polymer oxides by oxygen and / or ozone, maleic acid modifications of olefin (co) polymers [eg maleic acid and its derivatives (maleic anhydride, Modified products such as monomethyl maleate, monobutyl maleate and dimethyl maleate), olefins and unsaturated carboxylic acids [(meth) acrylic acid, itaconic acid and maleic anhydride, etc.] and / or unsaturated carboxylic acid alkyl esters [(meta ) Alkyl acrylate (alkyl of 1 to 18 carbon atoms) ester and Copolymers of maleic acid alkyl (having 1 to 18 carbon atoms in the alkyl) esters, etc.] and the like.
In addition, waxes such as polymethylene wax (for example, Fischer-Tropsch wax such as Sasol wax), fatty acid metal salt (such as calcium stearate) and fatty acid ester (such as behenyl behenate) can be mentioned.

The content of the release agent is preferably 0.1 to 30% by weight, more preferably 0.5 to 20% by weight, and particularly preferably 1 to 10% by weight based on the weight of the toner.

The toner of the present invention can contain a charge control agent, a fluidizing agent and the like in addition to the colorant and the release agent.

As charge control agents, nigrosine dyes, triphenylmethane dyes containing tertiary amines as side chains, quaternary ammonium salts, polyamine resins, imidazole derivatives, quaternary ammonium base-containing polymers, metal-containing azo dyes, copper phthalocyanine dyes , Salicylic acid metal salts, boron complexes of benzylic acid, sulfonic acid group-containing polymers, fluorine-containing polymers, halogen-substituted aromatic ring-containing polymers, metal complexes of salicylic acid alkyl derivatives, cetyltrimethylammonium bromide, and the like.
The content of the charge control agent is preferably 0 to 20% by weight, more preferably 0.1 to 10% by weight, and particularly preferably 0.5 to 7.5% by weight based on the weight of the toner. is there.

As a fluidizing agent, colloidal silica, alumina powder, titanium oxide powder, calcium carbonate powder, barium titanate, magnesium titanate, calcium titanate, strontium titanate, zinc oxide, silica sand, clay, mica, wollastonite, Examples include diatomaceous earth, chromium oxide, cerium oxide, bengara, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, and barium carbonate.
The content of the fluidizing agent is preferably 0 to 10% by weight, more preferably 0 to 5% by weight, and particularly preferably 0.1 to 4% by weight based on the weight of the toner.

  The toner is mixed with carrier particles [iron powder, glass beads, nickel powder, ferrite, magnetite, and ferrite (surface coated with acrylic resin, silicone resin, etc.), etc.] as necessary, and an electric latent image is mixed. It can be used as a developer. Further, instead of carrier particles, an electric latent image can be formed by rubbing with a charging blade or the like, and the electric latent image can be formed on a support (paper, polyester film, etc.) by a known heat roll fixing method. ).

The volume average particle diameter of the toner is preferably 1 to 15 μm, more preferably 2 to 10 μm, and particularly preferably 3 to 8 μm.
The particle size distribution of the toner is preferably 1.30 or less, particularly preferably 1.25 or less.
The volume average particle diameter and particle size distribution of the toner can be measured using a Coulter counter “Multisizer III” (manufactured by Beckman Coulter, Inc.).

The method for producing the toner is not particularly limited, and may be obtained by a known kneading and pulverizing method, emulsion phase inversion method, polymerization method or the like.
For example, when a toner is obtained by a kneading and pulverizing method, the components constituting the toner excluding the fluidizing agent are dry blended, then melt-kneaded, then coarsely pulverized, and finally finely divided using a jet mill pulverizer or the like. Further, by further classifying, fine particles having a volume average particle diameter of preferably 1 to 15 μm can be obtained and then mixed with a fluidizing agent.
When the toner is obtained by the emulsion phase inversion method, the components constituting the toner excluding the fluidizing agent can be dissolved or dispersed in an organic solvent, and then emulsified by adding water, etc., and then separated and classified. .
Further, it may be produced by a method using organic fine particles described in JP-A No. 2002-284881 or a method of dispersing in carbon dioxide in a supercritical state described in JP-A No. 2007-277511.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further, this invention is not limited to these.

<Production of alkylene oxide addition reaction product of isosorbide>
<Production Example 1>
[Production of Isosorbide / Propylene Oxide Addition Reaction Product (a-1)]
The autoclave was charged with 557 parts by weight of isosorbide (3.8 parts by mole), 100 parts by weight of water, and 4 parts by weight of TMAH, and was purged with nitrogen. . Thereafter, 443 parts by weight (7.6 mole parts) of propylene oxide was dropped over 5 hours in a range of 90 to 100 ° C. and a pressure of 0.4 MPa or less. During the reaction, the reaction was carried out while measuring the propylene oxide addition molar distribution of isosorbide by GC using the above method.
Subsequently, the temperature is raised to 150 to 160 ° C., the pressure is reduced at 0.002 MPa or less at the same temperature, and water and TMAH in the system are removed, whereby an isosorbide / propylene oxide addition reaction product (a-1) 970 parts by weight were obtained.

The composition distribution of this addition reaction product (a-1) is a compound in which R ¹ and R ^{2 in} the general formula (1) of the present invention are both propylene groups, and m and n are both ¹ , as determined by GC analysis. Compound in which (a1-1) is 92% by weight, m + n is 3 to 10 in total (a2-1) is 2% by weight, either m or n is 0 and the other is an integer of 1 to 5 ( The sum of a3-1) was 5% by weight, and unreacted isosorbide was 1% by weight.

<Production Example 2>
[Production of Isosorbide / Propylene Oxide Addition Reaction Product (a-2)]
In Production Example 1, all operations were the same except that 4 parts by weight of tributylamine was used instead of TMAH, and 970 parts by weight of an isosorbide / propylene oxide addition reaction product (a-2) was obtained.
The composition distribution of this addition reaction product (a-2) is determined by GC analysis, wherein R ¹ and R ^{2 in} the general formula (1) of the present invention are both propylene groups, and m and n are both 1 compounds ( Compound (a3) in which a1-2) is 66% by weight and m + n is 3 to 10 in total (a2-2) is 8% by weight, either m or n is 0 and the other is an integer of 1 to 5 -2) was 25% by weight, and unreacted isosorbide was 1% by weight.

<Production Example 3>
[Production of Isosorbide / Ethylene Oxide Addition Reaction Product (a-3)]
In Production Example 1, all operations were the same except that 624 parts by weight (4.3 parts by mole) of isosorbide and 376 parts by weight (8.5 parts by weight) of ethylene oxide were used instead of propylene oxide, and isosorbide / ethylene oxide. 970 parts by weight of addition reaction product (a-3) was obtained.
The composition distribution of the addition reaction product (a-3) is determined by GC analysis, wherein R ¹ and R ^{2 in} the general formula (1) of the present invention are both ethylene groups, and m and n are both 1 compounds ( Compound (a3) in which a1-3) is 92% by weight, m + n is 3 to 10% (a2-3) is a total of 3% by weight, and either m or n is 0 and the other is an integer of 1 to 5 -3) was 4% by weight, and unreacted isosorbide was 1% by weight.

<Production Example 4>
[Production of Isosorbide / Ethylene Oxide Addition Reaction Product (a-4)]
In Production Example 3, all operations were the same except that 4 parts by weight of tributylamine was used instead of TMAH, to obtain 970 parts by weight of an isosorbide-ethylene oxide addition reaction product (a-4).
The composition distribution of this addition reaction product (a-4) is determined by GC analysis, and R ¹ and R ^{2 in} the general formula (1) of the present invention are both ethylene groups, and m and n are both 1 compounds ( Compound (a3) wherein a1-4) is 66% by weight, m + n is 3 to 10% of the total compound (a2-4) (7% by weight), either m or n is 0 and the other is an integer of 1 to 5 -4) was 26% by weight, and unreacted isosorbide was 1% by weight.

<Manufacture of polyester resin>
<Example 1>
[Synthesis of Polyester Resin (P-1)]
In a reaction vessel equipped with a stirrer, a heating / cooling device, a thermometer, a cooling pipe and a nitrogen introduction pipe, 468 parts by weight (1.8 mol) of the isosorbide-propylene oxide addition reaction product (a-1) obtained in Production Example 1 was obtained. Part), 263 parts by weight (1.9 mole parts) of terephthalic acid (B-1), and 1.8 parts by weight of bistriethanolamine titanate as a polymerization catalyst were distilled off at 215 ° C. under a nitrogen stream. The reaction was allowed to proceed for 3 hours under reduced pressure of 0.007 to 0.026 MPa until the acid value reached 2 mgKOH / g or less.
Subsequently, 24 weight part (0.1 mol part) of trimellitic anhydride (B-2) was added at 180 degreeC, and it was made to react for 1 hour, and polyester resin (P-1) was obtained.

<Example 2>
[Synthesis of polyester resin (P-2)]
In a reaction vessel equipped with a stirrer, a heating / cooling device, a thermometer, a cooling pipe and a nitrogen introduction pipe, 461 parts by weight (1.8 mol) of the isosorbide-propylene oxide addition reaction product (a-1) obtained in Production Example 1 was obtained. Part), 252 parts by weight (1.5 mol parts) of terephthalic acid (B-1), 25 parts by weight (0.2 mol parts) of adipic acid (B-3), and bistriethanolamine titanate 1.8 as a polymerization catalyst. After adding part by weight and reacting for 3 hours while distilling off the water generated under a nitrogen stream at 215 ° C., the reaction was performed under a reduced pressure of 0.007 to 0.026 MPa until the acid value reached 2 mgKOH / g or less. I let you.
Subsequently, 22 weight part (0.1 mol part) of trimellitic anhydride (B-2) was added at 180 degreeC, and it was made to react for 1 hour, and polyester resin (P-2) was obtained.

<Example 3>
[Synthesis of polyester resin (P-3)]
In a reaction vessel equipped with a stirrer, a heating / cooling device, a thermometer, a cooling tube and a nitrogen introduction tube, 458 parts by weight (1.9 mol) of the isosorbide / propylene oxide addition reaction product (a-2) obtained in Production Example 2 was obtained. Part), 278 parts by weight (1.6 mole parts) of terephthalic acid (B-1), and 1.8 parts by weight of bistriethanolamine titanate as a polymerization catalyst are distilled off at 215 ° C. under a nitrogen stream. The reaction was allowed to proceed for 3 hours under reduced pressure of 0.007 to 0.026 MPa until the acid value reached 2 mgKOH / g or less.
Subsequently, 24 weight part (0.1 mol part) of trimellitic anhydride (B-2) was added at 180 degreeC, and it was made to react for 1 hour, and the polyester resin (P-3) was obtained.

<Example 4>
[Synthesis of polyester resin (P-4)]
In a reaction vessel equipped with a stirrer, a heating / cooling device, a thermometer, a cooling pipe and a nitrogen introduction pipe, 451 parts by weight (1.9 mol) of the isosorbide-propylene oxide addition reaction product (a-2) obtained in Production Example 2 was obtained. Part), 265 parts by weight (1.6 mol parts) of terephthalic acid (B-1), 26 parts by weight (0.1 mol parts) of adipic acid (B-3), and bistriethanolamine titanate 1.8 as a polymerization catalyst. After adding part by weight and reacting for 3 hours while distilling off the water generated under a nitrogen stream at 215 ° C., the reaction was performed under a reduced pressure of 0.007 to 0.026 MPa until the acid value reached 2 mgKOH / g or less. I let you.
Subsequently, 22 weight part (0.1 mol part) of trimellitic anhydride (B-2) was added at 180 degreeC, and it was made to react for 1 hour, and the polyester resin (P-4) was obtained.

<Example 5>
[Synthesis of polyester resin (P-5)]
In a reaction vessel equipped with a stirrer, a heating / cooling device, a thermometer, a cooling tube and a nitrogen introduction tube, 458 parts by weight (1.7 mol) of the isosorbide-propylene oxide addition reaction product (a-1) obtained in Production Example 1 was obtained. Part), 277 parts by weight (1.6 mole parts) of terephthalic acid (B-1), and 1.8 parts by weight of bistriethanolamine titanate as a polymerization catalyst are distilled off at 215 ° C. under a nitrogen stream. The reaction was allowed to proceed for 3 hours under reduced pressure of 0.007 to 0.026 MPa until the acid value reached 2 mgKOH / g or less.
Subsequently, 24 weight (0.1 mol part) part of trimellitic anhydride (B-2) was added at 180 degreeC, and it was made to react for 1 hour, and polyester resin (P-5) was obtained.

<Example 6>
[Synthesis of polyester resin (P-6)]
In a reaction vessel equipped with a stirrer, a heating / cooling device, a thermometer, a cooling pipe and a nitrogen introduction pipe, 209 parts by weight (0.8 mol) of the isosorbide-propylene oxide addition reaction product (a-1) obtained in Production Example 1 Part), bisphenol A / propylene oxide 2 mol adduct [Sanyo Chemical Industries, Ltd .: Newpol BP-2P] (b1-1) 293 parts by weight (0.8 mol part), terephthalic acid (B-1) 202 1 part by weight (1.2 parts by mole), 20 parts by weight (0.1 part by mole) of adipic acid (B-3), and 1.8 parts by weight of bistriethanolamine titanate as a polymerization catalyst were put under a nitrogen stream at 215 ° C. The reaction was carried out for 3 hours while distilling off the water produced, and then the reaction was carried out under a reduced pressure of 0.007 to 0.026 MPa until the acid value became 2 mgKOH / g or less.
Subsequently, 24 weight part (0.1 mol part) of trimellitic anhydride (B-2) was added at 180 degreeC, and it was made to react for 1 hour, and the polyester resin (P-6) was obtained.

<Example 7>
[Synthesis of polyester resin (P-7)]
In a reaction vessel equipped with a stirrer, a heating / cooling device, a thermometer, a cooling pipe and a nitrogen introduction pipe, 305 parts by weight (1.2 mol) of the isosorbide-propylene oxide addition reaction product (a-1) obtained in Production Example 1 Parts), 1,2-propylene glycol (b2-1) 161 parts by weight (2.1 mole parts), terephthalic acid (B-1) 352 parts by weight (2.1 mole parts), and bistriethanolamine as a polymerization catalyst After adding 1.8 parts by weight of titanate and reacting for 3 hours while distilling off the water and 1,2-propylene glycol (b2-1) produced at 215 ° C. under a nitrogen stream, 0.007 to 0.026 MPa The reaction was continued until the acid value was 2 mgKOH / g or less.
Subsequently, 24 weight part (0.1 mol part) of trimellitic anhydride (B-2) was added at 180 degreeC, and it was made to react for 1 hour, and the polyester resin (P-7) was obtained.

<Example 8>
[Synthesis of polyester resin (P-8)]
In a reaction vessel equipped with a stirrer, a heating / cooling device, a thermometer, a cooling pipe and a nitrogen introduction pipe, 449 parts by weight (1.9 mol) of the isosorbide-ethylene oxide addition reaction product (a-3) obtained in Production Example 3 was obtained. Part), 288 parts by weight (1.7 mol parts) of terephthalic acid (B-1), and 1.8 parts by weight of bistriethanolamine titanate as a polymerization catalyst are distilled off at 215 ° C. under a nitrogen stream. The reaction was allowed to proceed for 3 hours under reduced pressure of 0.007 to 0.026 MPa until the acid value reached 2 mgKOH / g or less.
Subsequently, 24 weight part (0.1 mol part) of trimellitic anhydride (B-2) was added at 180 degreeC, and it was made to react for 1 hour, and the polyester resin (P-8) was obtained.

<Example 9>
[Synthesis of polyester resin (P-9)]
In a reaction vessel equipped with a stirrer, a heating / cooling device, a thermometer, a cooling pipe and a nitrogen introduction pipe, 198 parts by weight (0.8 mol) of the isosorbide-ethylene oxide addition reaction product (a-3) obtained in Production Example 3 Part), bisphenol A / propylene oxide 2 mol adduct ((b1-1) 295 parts by weight (0.8 mol parts), terephthalic acid (B-1) 231 parts by weight (1.3 mol parts), and polymerization catalyst After adding 1.8 parts by weight of bistriethanolamine titanate and reacting for 3 hours while distilling off the water generated in a nitrogen stream at 215 ° C., the acid value is 0.007 to 0.026 MPa under reduced pressure. It was made to react until it became 2 mgKOH / g or less.
Subsequently, 24 weight part (0.1 mol part) of trimellitic anhydride (B-2) was added at 180 degreeC, and it was made to react for 1 hour, and the polyester resin (P-9) was obtained.

<Example 10>
[Synthesis of polyester resin (P-10)]
In a reaction vessel equipped with a stirrer, a heating / cooling device, a thermometer, a cooling pipe and a nitrogen introduction pipe, 74 parts by weight (0.3 mol) of the isosorbide-ethylene oxide addition reaction product (a-3) obtained in Production Example 3 Part), bisphenol A / propylene oxide 2-mole adduct (b1-1) 439 parts by weight (1.3 parts by mole), terephthalic acid (B-1) 207 parts by weight (1.2 parts by mole), and a polymerization catalyst After adding 1.8 parts by weight of bistriethanolamine titanate and reacting for 3 hours while distilling off the water produced at 215 ° C. under a nitrogen stream, the acid value was 2 mg KOH under a reduced pressure of 0.007 to 0.026 MPa. It was made to react until it became below / g.
Subsequently, 24 weight part (0.1 mol part) of trimellitic anhydride (B-2) was added at 180 degreeC, and it was made to react for 1 hour, and the polyester resin (P-10) was obtained.

<Example 11>
[Synthesis of Polyester Resin (P-11)]
In a reaction vessel equipped with a stirrer, a heating / cooling device, a thermometer, a cooling tube and a nitrogen introduction tube, 200 parts by weight (0.8 mol) of the isosorbide-ethylene oxide addition reaction product (a-4) obtained in Production Example 4 Part), bisphenol A / propylene oxide 2-mole adduct (b1-1) 294 parts by weight (0.8 parts by mole), terephthalic acid (B-1) 230 parts by weight (1.3 parts by mole), and polymerization catalyst After adding 1.8 parts by weight of bistriethanolamine titanate and reacting for 3 hours while distilling off the water produced at 215 ° C. under a nitrogen stream, the acid value was 2 mg KOH under a reduced pressure of 0.007 to 0.026 MPa. It was made to react until it became below / g.
Subsequently, 24 weight part (0.1 mol part) of trimellitic anhydride (B-2) was added at 180 degreeC, and it was made to react for 1 hour, and the polyester resin (P-11) was obtained.

<Example 12>
[Synthesis of polyester resin (P-12)]
In a reaction vessel equipped with a stirrer, a heating / cooling device, a thermometer, a cooling pipe and a nitrogen introduction pipe, 319 parts by weight (1.4 mol) of the isosorbide-ethylene oxide addition reaction product (a-3) obtained in Production Example 3 was obtained. Part), bisphenol A / propylene oxide 2 mole adduct (b1-1) 158 parts by weight (0.4 mole part), terephthalic acid (B-1) 251 parts by weight (1.5 mole part), and polymerization catalyst After adding 1.8 parts by weight of bistriethanolamine titanate and reacting for 3 hours while distilling off the water produced at 215 ° C. under a nitrogen stream, the acid value was 2 mg KOH under a reduced pressure of 0.007 to 0.026 MPa. It was made to react until it became below / g.
Subsequently, 24 weight part (0.1 mol part) of trimellitic anhydride (B-2) was added at 180 degreeC, and it was made to react for 1 hour, and the polyester resin (P-12) was obtained.

<Example 13>
[Synthesis of polyester resin (P-13)]
In a reaction vessel equipped with a stirrer, a heating / cooling device, a thermometer, a cooling pipe, and a nitrogen introduction pipe, 291 parts by weight (1.2 mol) of the isosorbide-ethylene oxide addition reaction product (a-3) obtained in Production Example 3 Part), 1,2-propylene glycol (b2-1) 170 parts by weight (2.2 moles), terephthalic acid (B-1) 354 parts by weight (2.1 moles), adipic acid (B-3) 16 parts by weight (0.1 mol part) and 1.8 parts by weight of bistriethanolamine titanate as a polymerization catalyst were added, and water and 1,2-propylene glycol (b2-1) produced under a nitrogen stream at 215 ° C. After reacting for 3 hours while distilling off, the reaction was continued under reduced pressure of 0.007 to 0.026 MPa until the acid value became 2 mgKOH / g or less.
Subsequently, 24 weight part (0.1 mol part) of trimellitic anhydride (B-2) was added at 180 degreeC, and it was made to react for 1 hour, and the polyester resin (P-13) was obtained.

<Comparative Example 1>
[Synthesis of Comparative Polyester Resin (P′-1)]
In a reaction vessel equipped with a stirrer, a heating / cooling device, a thermometer, a cooling tube, and a nitrogen introduction tube, 676 parts by weight of isosorbide (4.6 mole parts), 307 parts by weight of terephthalic acid (B-1) (1.8 moles) Part), 68 parts by weight (0.5 mol part) of adipic acid (B-3), and 1.8 parts by weight of bistriethanolamine titanate as a polymerization catalyst, and water and isosorbide generated under a nitrogen stream at 215 ° C. After reacting for 5 hours while distilling off, the reaction was continued under reduced pressure of 0.007 to 0.026 MPa until the acid value became 2 mgKOH / g or less.
Subsequently, 24 weight part (0.1 mol part) of trimellitic anhydride (B-2) was added at 180 degreeC, and it was made to react for 1 hour, and the polyester resin for comparison (P'-1) was obtained.

<Comparative Example 2>
[Synthesis of Comparative Polyester Resin (P′-2)]
In a reaction vessel equipped with a stirrer, a heating / cooling device, a thermometer, a cold tube, and a nitrogen introduction tube, 420 parts by weight (1.0 mole part) of isosorbide and 2 moles of adduct of bisphenol A / propylene oxide (b1-1) 50 Parts by weight (0.05 mol), 1,2-propylene glycol (b2-1) 800 parts by weight (3.6 mols), terephthalic acid (B-1) 550 parts by weight (1.15 mols), 145 parts by weight (0.3 parts by mole) of trimellitic anhydride (B-2), 300 parts by weight (0.6 parts by weight) of isophthalic acid (B-4) and 1.8 parts by weight of bistriethanolamine titanate as a polymerization catalyst The reaction is carried out for 5 hours while distilling off the water generated at 215 ° C. under a nitrogen stream and 1,2-propylene glycol, and further reacted under a reduced pressure of 0.007 to 0.026 MPa. It was obtained ester resin (P'-2).

Table 1 shows the blending weight% of the above polyester resins (P-1) to (P-13) and (P′-1) to (P′-2) and the content of the unreacted diol composition (A). It was summarized in.

Table 2 shows the physical property measurement results of the polyester resins of (P-1) to (P-13) of Examples 1 to 13 and (P'-1) to (P'-2) of Comparative Examples 1 and 2.

[Manufacture of non-linear polyester resin blended in toner]
<Production Example 5>
[Synthesis of Non-Linear Polyester Resin (H1-1)]
In a reaction vessel equipped with a stirrer, a heating / cooling device, a thermometer, a cooling pipe and a nitrogen introducing pipe, 565 parts by weight of 1,2-propylene glycol (b2-1), 3 mol of bisphenol A / propylene oxide adduct [Sanyo Kasei Industrial Co., Ltd .: Newpol BP-3P] (b1-2) 449 parts by weight, bisphenol A / propylene oxide 2-mol adduct (b1-1) 388 parts by weight, terephthalic acid (B-1) 494 parts by weight, 143 parts by weight of trimellitic anhydride (B-2), 3.7 parts by weight of tetrabutoxytitanate as a condensation catalyst, water generated at 230 ° C. under a nitrogen stream, 1,2-propylene glycol (b2-1) The reaction was allowed to proceed for 5 hours while distilling off. Subsequently, it was made to react under the reduced pressure of 0.007-0.026 MPa, and it pick_out | removed when the softening point (Tm) became 145 degreeC, and obtained the nonlinear polyester resin (H1-1).
Tg of (H1-1) was 65 ° C., Mw was 13,000, the acid value was 1 mgKOH / g, and the hydroxyl value was 15 mgKOH / g.

[Production of toner]
<Examples 14 to 26, Comparative Examples 3 to 4>
Polyester resins (P-1) to (P-13) obtained in Examples 1 to 13, comparative polyester resins (P′-1) to (P′-2) obtained in Comparative Examples 1 and 2, and The non-linear polyester resin (H1-1) obtained in Production Example 5 is mixed according to the blending ratio (parts by weight) shown in Table 3, and the toner binders (R-1) to (R-13) of the present invention and a comparative toner Binders (R′-1) to (R′-2) were produced.

Next, 8 parts by weight of carbon black MA-100 [Mitsubishi Chemical Co., Ltd.], 5 parts by weight of carnauba wax, 1 part by weight of charge control agent T-77 [Hodogaya Chemical Co., Ltd.] were added, and Henschel mixer [Japan The mixture was premixed using FM10B manufactured by Coke Kogyo Co., Ltd., and then kneaded using a biaxial kneader [PCM-30 manufactured by Ikegai Co., Ltd.] Next, the mixture was finely pulverized using a supersonic jet crusher lab jet [manufactured by Nippon Pneumatic Industry Co., Ltd.] and then classified by an airflow classifier [MDS-I made by Nippon Pneumatic Industry Co., Ltd.] To 8 μm toner particles were obtained.
Next, 100 parts by weight of the toner particles are mixed with 0.5 parts by weight of colloidal silica [manufactured by Nippon Aerosil Co., Ltd .: Aerosil R972] using a sample mill, and the toners of the present invention, (T-1) to (T-13). ) And comparative toners (T′-1) to (T′-2).

[Preparation for toner production]
<Production Example 6>
[Preparation of precursor solution (H0-1)]
In a reaction vessel equipped with a stirrer, a heating / cooling device, a thermometer, a cooling pipe and a nitrogen introduction pipe, a bisphenol A / ethylene oxide 2-mol adduct [manufactured by Sanyo Chemical Industries, Ltd .: New Pole BPE-20] (b1- 3) 681 parts by weight, bisphenol A / propylene oxide 2-mole adduct (b1-1) 81 parts by weight, terephthalic acid (B-1) 275 parts by weight, adipic acid (B-3) 7 parts by weight, trimellitic anhydride (B-2) 22 parts by weight and 2 parts by weight of dibutyltin oxide as a condensation catalyst were added, and after 5 hours of dehydration reaction at 230 ° C. at normal pressure, 5 hours under a reduced pressure of 0.007 to 0.026 MPaMPa. A dehydration reaction was performed to obtain a polyester resin (H0).
A pressure-resistant reaction vessel equipped with a stirrer, a heating / cooling device and a thermometer was charged with 350 parts by weight of a polyester resin (H0), 50 parts by weight of isophorone diisocyanate, 600 parts by weight of ethyl acetate, and 0.5 parts by weight of ion-exchanged water. Reaction was carried out at 90 ° C. for 5 hours in a sealed state to obtain a precursor solution (H0-1) having an isocyanate group at the molecular end.
The urethane group concentration of the precursor solution (H0-1) was 5.2% by weight, and the urea group concentration was 0.3% by weight. The solid content was 45% by weight.

<Production Example 7>
[Production of Fine Particle Dispersion (1)]
In a reaction vessel equipped with a stirrer, a heating / cooling device, a thermometer, a cooling pipe and a nitrogen introduction pipe, 690 parts by weight of water, sodium salt of polyoxyethylene monomethacrylate sulfate [Sanyo Chemical Industries, Ltd .: Eleminol RS-30 9 parts by weight, 90 parts by weight of styrene, 90 parts by weight of methacrylic acid, 110 parts by weight of butyl acrylate and 1 part by weight of ammonium persulfate were added and stirred for 15 minutes at 350 rpm, and a white emulsion was obtained. It was. Next, the temperature was raised to 75 ° C., and the reaction was carried out at the same temperature for 5 hours.
Next, 30 parts by weight of a 1% by weight ammonium persulfate aqueous solution was added, and the mixture was aged at 75 ° C. for 5 hours to vinyl resin (a copolymer of styrene-methacrylic acid-butyl acrylate-methacrylic acid ethylene oxide adduct sulfate sodium salt). A fine particle dispersion (1) was obtained.
The volume average particle size of the particles dispersed in the fine particle dispersion (1) was measured using a laser diffraction / scattering particle size distribution measuring device “LA-920” (manufactured by Horiba, Ltd.). .1 μm.
A part of the fine particle dispersion (1) was taken out and Tg and Mw thereof were measured. As a result, Tg was 65 ° C. and Mw was 150,000.

<Production Example 8>
[Production of Colorant Dispersion (1)]
In a reaction vessel equipped with a stirrer, a heating / cooling device, a thermometer, a cooling tube, and a nitrogen introduction tube, 557 parts by weight (17.5 moles) of 1,2-propylene glycol (b2-1), dimethyl terephthalate 569 Part by weight (7.0 moles), 184 parts by weight (3.0 moles) of adipic acid (B-3) and 3 parts by weight of tetrabutoxytitanate as a condensation catalyst are added and produced at 180 ° C. under a nitrogen stream. The reaction was allowed to proceed for 8 hours while distilling off the methanol.
Next, while gradually raising the temperature to 230 ° C., the reaction was conducted for 4 hours while distilling off 1,2-propylene glycol (b2-1) and water generated under a nitrogen stream, and further 0.007 to 0.026 MPa. The reaction was carried out for 1 hour under reduced pressure. The recovered 1,2-propylene glycol (b2-1) was 175 parts by weight (5.5 mol parts).
Next, the mixture was cooled to 180 ° C., 121 parts by weight (1.5 mol parts) of trimellitic anhydride (B-2) was added, reacted for 2 hours under normal pressure sealing, and then the softening point (Tm at 220 ° C. and normal pressure). ) Until it reached 180 ° C. to obtain a polyester resin (Mn = 8,500).
In a beaker, 20 parts by weight of copper phthalocyanine, 4 parts by weight of a colorant dispersant “Solspers 28000” (manufactured by Avicia), 20 parts by weight of the polyester resin obtained above and 56 parts by weight of ethyl acetate are added and stirred. Then, copper phthalocyanine was finely dispersed by a bead mill to obtain a colorant dispersion (1).
The colorant dispersion (1) was measured by “LA-920”, and the volume average particle diameter was 0.2 μm.

<Production Example 9>
[Production of modified wax (1)]
In a pressure-resistant reaction vessel equipped with a stirrer, a heating / cooling device, a thermometer and a dropping cylinder, 454 parts by weight of xylene, low molecular weight polyethylene “Sun Wax LEL-400” [softening point: 128 ° C., manufactured by Sanyo Chemical Industries, Ltd.] 150 parts by weight were added, and after nitrogen substitution, the temperature was raised to 170 ° C. with stirring. At the same temperature, 595 parts by weight of styrene, 255 parts by weight of methyl methacrylate, 34 parts by weight of di-t-butylperoxyhexahydroterephthalate and xylene 119 parts by weight of the mixed solution was added dropwise over 3 hours, and further maintained at the same temperature for 30 minutes.
Subsequently, xylene was distilled off under reduced pressure of 0.039 MPa to obtain a modified wax (1).
The SP value of the graft chain of the modified wax (1) was 10.35 (cal / cm ³ ) ^1/2 , Mn was 1,900, Mw was 5,200, and Tg was 56.9 ° C.

<Production Example 10>
[Production of release agent dispersion (1)]
In a reaction vessel equipped with a stirrer, a heating / cooling device, a cooling tube and a thermometer, paraffin wax “HNP-9” [Maximum heat of fusion peak temperature: 73 ° C., manufactured by Nippon Seiki Co., Ltd.] 10 parts by weight, production example 1 part by weight of the modified wax (1) obtained in 9 and 33 parts by weight of ethyl acetate were added, the temperature was raised to 78 ° C. with stirring, the mixture was stirred at the same temperature for 30 minutes, and then cooled to 30 ° C. over 1 hour. Paraffin wax was crystallized into fine particles, and further wet pulverized with Ultraviscomyl (manufactured by Imex) to obtain a release agent dispersion (1). The volume average particle diameter was 0.25 μm.

<Production Examples 11-14>
[Production of Resin Solutions (q-1) to (q-3) and (q′-1)]
Using the polyester resins (P-1) to (P-3) obtained in Examples 1 to 3 and the comparative polyester resin (P′-1) obtained in Comparative Example 1, a resin solution was prepared by the following method. It was created.
In a reaction vessel equipped with a stirrer and a thermometer, 100 parts by weight of each of the polyester resins (P-1) to (P-3) and (P′-1), the colorant dispersion obtained in Production Example 8 ( 1) 30 parts by weight, 140 parts by weight of the release agent dispersion (1) obtained in Production Example 10 and 153 parts by weight of ethyl acetate were added, and the mixture was stirred and dissolved uniformly. 1) to (q-3) and (q′-1) were obtained.

<Production Example 15>
[Synthesis of Curing Agent (1)]
Into a reaction vessel equipped with a stirrer, heating / cooling device, cooling tube and thermometer, 50 parts by weight of isophorone diamine and 300 parts by weight of methyl ethyl ketone were added, reacted at 50 ° C. for 5 hours, then desolvated to ketiminate. A cured curing agent (1) was obtained.
The total amine value of the curing agent (1) was 415.

[Production of toner]
<Examples 27 to 29 and Comparative Example 5)
Using the resin solutions (q-1) to (q-3) and (q′-1) obtained in Production Examples 11 to 14, toners were produced by the following method.
In a beaker, 170.2 parts by weight of ion-exchanged water, 0.3 part by weight of the fine particle dispersion (1) obtained in Production Example 7, 1 part by weight of sodium carboxymethyl cellulose, 48.5% by weight aqueous solution of sodium dodecyl diphenyl ether disulfonate [Sanyo Chemical Industry Co., Ltd .: Eleminol MON-7] 36 parts by weight and 15.3 parts by weight of ethyl acetate were added and stirred to dissolve uniformly.
Next, the temperature was raised to 50 ° C., and 11.2 parts by weight of the precursor solution (H0-1) obtained in Production Example 6 was stirred while the TK auto homomixer was stirred at 10,000 rpm at the same temperature. 5.5 parts by weight of the obtained curing agent (1) and 63.8 parts by weight of resin solutions (q-1) to (q-3) and (q′-1) were respectively added and stirred for 2 minutes. .
Next, this mixed solution was transferred to a reaction vessel equipped with a stirrer and a thermometer, and ethyl acetate was distilled off at 30 ° C. until the concentration became 0.5% by weight or less to obtain an aqueous resin dispersion of toner particles. . Next, it was washed, filtered, dried at 40 ° C. for 18 hours, the volatile content was adjusted to 0.5% by weight or less, and the toners (T-14) to (T-16) of the present invention and the comparative toner (T ′ -3) was obtained.

<Examples 30 to 31 and Comparative Example 6>
Using the resin solutions (q-1) to (q-2) and (q′-1) obtained in Production Examples 11 to 14, toners were produced by the following method.
In a beaker, 108 parts by weight of decane and 2.1 parts by weight of the fine particle dispersion (1) obtained in Production Example 7 were added and stirred to dissolve uniformly.
Next, the temperature was raised to 50 ° C., and 11.2 parts by weight of the precursor solution (H0-1) obtained in Production Example 6 was obtained in Production Example 15 while stirring the TK auto homomixer at 10,000 rpm at the same temperature. The obtained curing agent (1) 5.5 parts by weight and the resin solutions (q-1) to (q-2) and (q′-1) were each independently charged with 63.8 parts by weight and stirred for 2 minutes.
Then, this mixed solution was transferred to a reaction vessel equipped with a stirrer and a thermometer, and ethyl acetate was distilled off at 50 ° C. until the concentration became 0.5% by weight or less, then washed, filtered, and filtered at 40 ° C. The toner (T-17) to (T-18) and the comparative toner (T′-4) of the present invention were obtained by drying for 18 hours and setting the volatile content to 0.5 wt% or less.

<Example 32>
In the experimental apparatus of FIG. 1, first, the valves V1 and V2 were closed, and carbon dioxide (purity 99.99%) was introduced into the particle recovery tank T4 from the cylinder B2 using the pump P4, and the pressure was adjusted to 14 MPa and 40 ° C. In addition, the resin solution tank T1 is mixed with the resin solution (q-1), the colorant dispersion (1) and the release agent dispersion (1), and the fine particle dispersion tank T2 is mixed with the fine particle dispersion (1). I put it in.
Next, liquid carbon dioxide is introduced into the dispersion tank T3 from the liquid carbon dioxide cylinder B1 using the pump P3, adjusted to a supercritical state (9 MPa, 40 ° C.), and further the pump P2 is connected from the tank T2. The fine particle dispersion (1) was introduced.

Next, while stirring the inside of the dispersion tank T3 at 2,000 rpm, the resin solution (q-1), the colorant dispersion (1), and the release agent dispersion (1) are discharged from the tank T1 using the pump P1. ) Was introduced into the dispersion tank T3. After the introduction, the pressure inside T3 was 14 MPa.
In addition, the weight ratio of the preparation composition to the dispersion tank T3 is as follows.
Resin solution (q-1) 270 parts by weight Colorant dispersion (1) 60 parts by weight Release agent dispersion (1) 160 parts by weight Fine particle dispersion (1) 45 parts by weight Carbon dioxide 550 parts by weight

  The weight of the introduced carbon dioxide is obtained by calculating the density of carbon dioxide from the temperature of carbon dioxide (40 ° C.) and the pressure (15 MPa) from the state equation described in the following document, and multiplying this by the volume of the dispersion tank T3. (The same applies hereinafter).

  Literature: Journal of Physical and Chemical Reference data, vol. 25, p. 1509-1596.

After introducing the mixed solution of the resin solution (q-1), the colorant dispersion (1), and the release agent dispersion (1), the mixture is stirred for 1 minute, and the resin particles (K-1 Dispersion (L-1) in which) was dispersed was obtained.
Next, the valve V1 was opened, and the dispersion (L-1) was transferred from T3 to T4 by introducing supercritical carbon dioxide into T3 and T4 using B1 to P3. While the dispersion (L-1) was transferred from T3 to T4, the opening degree of V2 was adjusted so that the pressure was kept constant. This operation was performed for 30 seconds, and V1 was closed. By this operation, the solvent was extracted from the resin dispersion (L-1) transferred into T4. Further, T4 was heated to 60 ° C. and held for 15 minutes.
By this operation, the fine particles in the fine particle dispersion (1) were fixed to the surface of the resin particles (K-1) formed from the resin solution (q-1), and resin particles (K-1-2) were generated. .

Next, the pressure was maintained at 14 MPa by adjusting the opening of the pressure adjusting valve V2 while introducing carbon dioxide from the pressure cylinder B2 into the particle recovery tank T4 using the pump P4.
By this operation, carbon dioxide containing the solvent was discharged into the solvent trap tank T5, and the resin particles (K-1-2) were captured by the filter F1.
The operation of introducing carbon dioxide from the pressure cylinder B2 into the particle recovery tank T4 using the pump P4 was stopped when 5 times the amount of carbon dioxide introduced into the dispersion tank T3 was introduced into the particle recovery tank T4. . At the time of this stop, the operation of replacing carbon dioxide containing the solvent with carbon dioxide not containing the solvent and capturing the resin particles (K-1-2) in the filter F1 was completed.
Further, the fine particle dispersion (1) is formed on the surface of the resin particles (K-1-2) captured by the filter F1 by opening the pressure adjusting valve V2 little by little and reducing the pressure inside the particle recovery tank to atmospheric pressure. A toner (T-19) of the present invention in which a film derived from the fine particles therein was formed and the colorant and the release agent were finely and uniformly dispersed in (K-1-2) was obtained.

<Example 33>
A toner (T-20) of the present invention was obtained in the same manner as in Example 32 except that the resin solution (q-1) was changed to the resin solution (q-2) obtained in Production Example 12.

<Comparative Example 7>
A comparative toner (T′-5) was obtained in the same manner as in Example 32 except that the resin solution (q-1) was changed to the resin solution (q′-1) obtained in Production Example 14. .

For toners (T-1) to (T-20) and comparative toners (T′-1) to (T′-5) of the present invention, the volume average particle diameter and particle size distribution were measured by the following methods. Low temperature fixability, durability, heat-resistant storage stability, wet heat storage stability, and saturation charge were evaluated.
The results are shown in Tables 3 and 4.

[1] Volume average particle size and particle size distribution The toner is dispersed in water to a concentration of about 0.1%, and the volume average particle size and particle size distribution are obtained using a Coulter counter “Multisizer III” (manufactured by Beckman Coulter). Was measured. For the particle size distribution, the ratio (Dv / Dn) of the volume average particle size (Dv) to the number average particle size (Dn) was used as an index.

[2] Low temperature fixability (° C)
To the toner, 1.0% by weight of colloidal silica [manufactured by Nippon Aerosil Co., Ltd .: Aerosil R972] is added and mixed well to make uniform, then the powder is uniformly applied to the paper surface at 0.6 mg / cm ^2. (At this time, the method of placing the powder on the paper is to use a printer from which the heat fixing machine is removed. However, other methods can be used as long as the powder can be uniformly placed at the above-mentioned weight density. Good).
Cold offset generation temperature when the paper on which the toner is placed is passed through a pressure roller [conditions: fixing speed (heating roller peripheral speed) 213 mm / sec, fixing pressure (pressure roller pressure) 10 kg / cm ² ] ( ° C).
The lower the temperature at which cold offset occurs, the better the low-temperature fixability.

[3] Durability In a 50 cc glass bottle with a stopper, 1.0 part by weight of toner, 0.1 part by weight of colloidal silica [manufactured by Nippon Aerosil Co., Ltd .: Aerosil R972], iron powder “F-150” [Japan [Iron Powder Co., Ltd.] Weighed exactly 10 parts by weight, plugged and shaken for 5 hours at 15 Hz in an atmosphere of 23 ° C. and 50% relative humidity, and then sieved with a sieve having an aperture of 106 μm. The toner remaining on the sieve was visually judged, and the durability was evaluated according to the following criteria.

[Evaluation criteria]
A: No toner remains on the sieve.
○: Blocked toner remains on the sieve, but disperses easily when force is applied.
X: Blocked toner remains on the sieve and does not disperse even when force is applied.

[4] Heat-resistant storage stability The toner was allowed to stand in an atmosphere of 40 ° C. for 1 day, the degree of blocking was judged visually, and the heat-resistant storage stability was evaluated according to the following criteria.

[Evaluation criteria]
○: Blocking has not occurred.
X: Blocking has occurred.

[5] Humidity and heat storage stability The toner was allowed to stand for 20 hours in an atmosphere of 40 ° C. and a relative humidity of 90%, the degree of blocking was judged visually, and the moisture and heat resistance storage stability was evaluated according to the following criteria.

[Evaluation criteria]
A: Blocking does not occur.
○: Blocking occurs, but disperses easily when force is applied.
X: Blocking occurs and does not disperse even when force is applied.

[6] Saturation charge (μC / g)
1 part by weight of toner and 24 parts by weight of electrophotographic carrier iron powder [manufactured by Powdertech Co., Ltd., ASR-10] were conditioned for 8 hours or more at 23 ° C. and 50% relative humidity, and then 50 rpm × using a tumbler shaker mixer. Friction stirring was performed for 1, 3, 7, 20, 60 and 120 minutes, and the charge amount (μC / g) was measured for each time.
A blow-off charge amount measuring device [manufactured by Kyocera Chemical Co., Ltd.] was used for the measurement. The amount of charge during the friction time when the amount of charge disappeared was taken as the saturation charge amount.

[7] High humidity environment saturation charge (μC / g)
The charge amount is measured after the humidity is adjusted under the conditions of higher temperature and higher humidity than the above [6].
1 part by weight of toner and 24 parts by weight of electrophotographic carrier iron powder [ASR-10, manufactured by Powder Tech Co., Ltd.] were conditioned for 8 hours or more at 30 ° C. and a relative humidity of 80%, and then 50 rpm × using a tumbler shaker mixer. Friction stirring was performed for 1, 3, 7, 20, 60 and 120 minutes, and the charge amount (μC / g) was measured for each time.
A blow-off charge amount measuring device [manufactured by Kyocera Chemical Co., Ltd.] was used for the measurement. The amount of charge during the friction time when the amount of charge disappeared was taken as the saturation charge amount.

From the results of Tables 3 and 4, the toners of Examples 14 to 33 using the toner binder of the present invention can achieve both low-temperature fixability and heat-resistant storage stability. Performance with excellent durability was obtained. In particular, the toners of Examples 19, 20, and 22 to 26 are excellent in charging stability in a high humidity environment.
On the other hand, the toners of Comparative Examples 3 to 7 using polyester obtained by reacting isosorbide itself without addition of alkylene oxide and dicarboxylic acid as a toner binder have poor or insufficient low-temperature fixability, and have a low charge amount and charge stability. Inferior to

T1: Resin solution tank T2: Fine particle dispersion tank T3: Dispersion tank (maximum operating pressure: 20 MPa, maximum operating temperature: 100 ° C., with stirrer)
T4: Particle recovery tank (maximum operating pressure: 20 MPa, maximum operating temperature: 100 ° C.)
F1: Ceramic filter (mesh: 0.5 μm)
T5: Solvent trap B1, B2: Carbon dioxide cylinder P1, P2: Solution pump P3, P4: Carbon dioxide pump V1, V3, V4, V5, V6, V7, V8: Valve V2: Pressure adjustment valve

  The toner using the toner binder of the present invention has a low environmental load, can be compatible with both low-temperature fixability and heat-resistant storage stability, and is excellent in moisture-heat storage stability, charging stability, and durability. It is useful as an electrophotographic toner, electrostatic recording toner, electrostatic printing toner, and the like.

Claims (19)

Containing a polyester resin (P) obtained by reacting a diol composition (A) containing the compound (a) represented by the following general formula (1) with a dicarboxylic acid or a modified product (B) thereof. Toner binder featuring.
[Wherein, R ¹ and R ² each independently represent a linear or branched alkylene group having 2 to 8 carbon atoms, and when there are a plurality of R ^{1 s} , they may be the same or different, and R ² may be the same or different. m and n are each independently a positive integer of 0 or 1 to 5, and m + n is a number satisfying 1 to 10. ] The toner binder according to claim ¹ , wherein R ¹ and R ^{2 in} the general formula (1) of the compound (a) are each independently an ethylene group or a propylene group. The toner binder according to claim ¹ , wherein R ¹ and R ^{2 in} the general formula (1) of the compound (a) are both propylene groups. The toner binder according to claim 1, wherein the compound (a) comprises a compound (a1) in which m and n in the general formula (1) are both 1. The toner according to claim 1, wherein the diol composition (A) further contains an alkylene oxide adduct (b1) of bisphenol A and / or an alkanediol (b2) having 3 to 6 carbon atoms. binder. The content of the compound (a) in the diol (A) is based on the total weight of the compound (a), the alkylene oxide adduct (b1) of bisphenol A, and the alkanediol (b2) having 3 to 6 carbon atoms. The toner binder according to claim 5, wherein the toner binder is 10 to 80%. The toner binder according to claim 5 or 6, wherein the average addition mole number of the adduct (b1) of alkylene oxide of bisphenol A is 2.0 to 6.0. The content in the diol composition (A) of the compound (a2) in which m + n in the general formula (1) is an integer of 3 to 10 and both m and n are 1 or more is the compound (a). The toner binder according to claim 1, wherein the toner binder is 50% by weight or less based on the total weight of styrene and isosorbide. The content in the diol composition (A) of the compound (a3) in which either m or n is 0 and the other is an integer of 1 to 5 in the general formula (1) is the compound (a) and isosorbide The toner binder according to claim 1, which is 50% by weight or less based on the total weight of the toner binder. The toner binder according to claim 1, wherein the content of isosorbide in the diol composition (A) is 2% by weight or less based on the total weight of the compound (a) and isosorbide. The content of the unreacted diol composition (A) remaining in the polyester resin (P) is 0.001 to 5% by weight based on the weight of (P). The toner binder described in 1. The toner binder according to claim 1, wherein the polyester resin (P) has a glass transition temperature of 40 to 80 ° C. The weight average molecular weight (Mw) of the polyester resin (P) is 1,000 to 1,000,000, and the weight average molecular weight (Mw) / number average molecular weight (Mn) is 1.0 to 50.0. The toner binder according to any one of 1 to 12. The toner binder according to any one of claims 1 to 13, wherein the polyester resin (P) has an acid value of 0 to 40 mgKOH / g and a hydroxyl value of 5 to 80 mgKOH / g. The toner binder according to claim 1, wherein the polyester resin (P) satisfies the following relational expressions (1) and (2).
10 ³ ≦ [G′70] ≦ 10 ¹⁰ (1)
1 ≦ [G′150] ≦ 10 ⁶ (2)
[In the above relational expression, [G′70] means the storage elastic modulus (Pa) of the polyester resin (P) at 70 ° C., and [G′150] means the storage elastic modulus (Pa) at 150 ° C.). ] The toner binder according to any one of claims 1 to 15, wherein the softening point (Tm) of the polyester resin (P) is 70 to 170 ° C. The water content in (P) after storing the polyester resin (P) at 40 ° C. and 90% relative humidity for 20 hours is 15,000 ppm or less based on the weight of (P). The toner binder according to any one of -16. The toner binder according to claim 1, wherein the polyester resin (P) has a volume resistivity R (Ω · cm) of 10 ¹⁰ to 10 ¹⁴ . A toner containing the toner binder according to claim 1, a colorant, and a release agent.