JP2022092199A - Binding resin for toner, electrostatic charge image development toner and electrostatic charge image developer - Google Patents

Abstract

To provide a toner binding resin capable of heightening low temperature fixability and chargeability of a toner.SOLUTION: A toner binder resin which is a block copolymer having a crystalline polyester block and an amorphous polyester block, in which an acid value of the crystalline polyester block is in the range of 4.0 to 16.0, and the acid value of the amorphous polyester block is in the range of 4.0 to 16.0, and has a structure represented by the following formula (1).SELECTED DRAWING: None

Description

The present invention relates to a binder resin for toner, a toner for developing an electrostatic charge image, and a developer for an electrostatic charge image.

In an image forming method via an electrostatic latent image (electrostatic charge image), two-component development usually includes toner particles containing a binder resin and a colorant and carrier particles for stirring and transporting the toner particles. An agent (toner) is used.
In the above image forming method, reduction of thermal energy at the time of fixing toner particles (low temperature fixing) is required for the purpose of speeding up image formation and reducing the load on the environment.

As a means for fixing the toner particles at a low temperature, it has been proposed to use a binder resin having both a crystalline resin moiety and an amorphous resin moiety at the same time. In the binder resin having both a crystalline resin moiety and an amorphous resin moiety, when the melting point of the crystalline resin moiety is exceeded by heating at the time of fixing, the crystalline resin moiety in the binder resin melts. As a result, the crystalline resin moiety and the amorphous resin moiety are compatible with each other, and low-temperature fixing of the toner particles can be realized.

As a binder resin for toner particles having further improved low-temperature fixability, a block copolymer in which a crystalline polyester block and an amorphous polyester block are chemically bonded has been proposed (Patent Document 1). By forming a block copolymer in which a crystalline polyester block and an amorphous polyester block are bonded, the compatibility between the crystalline polyester and the amorphous polyester is improved, and the toner particles can be finely dispersed.

Japanese Unexamined Patent Publication No. 2014-92642

Since the binding resin disclosed in Patent Document 1 has a low acid value in both the crystalline polyester block and the amorphous polyester block, there is a problem that the emulsifying property of the binding resin is lowered, and in particular, the charge stability is lowered. rice field. A binder resin having reduced charge stability has a problem of causing image defects.

An object to be solved by the present invention is to provide a binder resin for toner, which is excellent in both low temperature fixability and charging performance.

As a result of diligent studies to solve the above problems, the present inventors have found that the crystalline polyester block and the amorphous polyester block each have an acid value within a specific range, and these polyester blocks have an aromatic ring. The present invention has been completed by finding that the above-mentioned problems can be solved if the block copolymer is linked by a specific structure including.

That is, the present invention is a binder resin for toner which is a block copolymer having a crystalline polyester block and an amorphous polyester block, and the acid value of the crystalline polyester block is 4.0 to 16.0. It is a range, and the acid value of the amorphous polyester block is in the range of 4.0 to 16.0, and it relates to a binder resin for toner having a structure represented by the following formula (1). ..

（前記式（１）中、
Ａｒは芳香族環であり、
Ｕ^１及びＵ^２の一方は前記結晶性ポリエステルブロックであり、他方は前記非晶性ポリエステルブロックである。）

(In the above formula (1),
Ar is an aromatic ring,
One of U ¹ and U ² is the crystalline polyester block, and the other is the amorphous polyester block. )

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a binder resin for toner which is excellent in both low temperature fixability and charging performance.

Hereinafter, an embodiment of the present invention will be described. The present invention is not limited to the following embodiments, and can be carried out with appropriate modifications as long as the effects of the present invention are not impaired.
When expressed as "range of XX to □□" in the present application, it means XX or more and □□ or less.

[Toner binding resin]
The binder resin for toner of the present invention (hereinafter, may be simply referred to as “the binding resin of the present invention”) is a block copolymer having a crystalline polyester block and an amorphous polyester block, and is said to be crystalline. The acid value of the polyester block is in the range of 4.0 to 16.0, the acid value of the amorphous polyester block is in the range of 4.0 to 16.0, and the structure is represented by the following formula (1). Has.

（前記式（１）中、
Ａｒは芳香族環であり、
Ｕ^１及びＵ^２の一方は前記結晶性ポリエステルブロックであり、他方は前記非晶性ポリエステルブロックである。）

(In the above formula (1),
Ar is an aromatic ring,
One of U ¹ and U ² is the crystalline polyester block, and the other is the amorphous polyester block. )

The binder resin of the present invention has a structure in which an aromatic tetracarboxylic acid derivative forms an ester bond with a crystalline polyester and an amorphous polyester, respectively, and the crystalline polyester block and the amorphous polyester block are specified respectively. It has an acid value within the range.
In the present invention, the crystalline polyester block and the amorphous polyester block each have an acid value within a specific range, so that the end of the polyester block (which does not form an ester bond with the aromatic tetracarboxylic acid derivative) is a carboxyl group. It is presumed that the reaction between the binder resins is suppressed and the emulsifying property is maintained.
Not only the charge amount but also the charge stability that the charge amount does not change with the passage of time is important for the charge performance of the toner particles, and the binder resin of the present invention that maintains the emulsifying property gives the toner particles high charge stability. be able to.

In the binder resin of the present invention, it is preferable that the structure of the portion excluding the crystalline polyester block and the amorphous polyester block has high symmetry, and the structure of the portion excluding U ¹ and U ² of the above formula (1) is line symmetric. Alternatively, point symmetry is more preferable.

The weight average molecular weight (Mw) of the binder resin of the present invention is, for example, in the range of 5,000 to 100,000, preferably in the range of 10,000 to 50,000, and more preferably in the range of 15,000 to 50. It is in the range of 000, more preferably in the range of 15,000 to 45,000.
The number average molecular weight (Mn) of the binder resin of the present invention is, for example, in the range of 1,000 to 50,000, preferably in the range of 2,000 to 30,000, and more preferably in the range of 3,000 to 20. It is in the range of 000, more preferably in the range of 3,000 to 15,000.
The weight average molecular weight and the number average molecular weight of the binder resin of the present invention are measured by the methods described in Examples.

The binder resin of the present invention includes a crystalline polyester resin having an acid value in the range of 4.0 to 16.0, an amorphous polyester resin having an acid value in the range of 4.0 to 16.0, and an aromatic fragrance. It is a copolymer using a group tetracarboxylic acid derivative as a reaction raw material, and the aromatic tetracarboxylic acid derivative functions as a blocking agent for linking a crystalline polyester resin and an amorphous polyester resin.
The reaction raw material means a raw material constituting the binder resin of the present invention, and does not contain a solvent or a catalyst that does not constitute the binder resin of the present invention.

In the above formula (1), the portion other than U ¹ and U ² has a structure corresponding to an aromatic tetracarboxylic acid derivative, and U ¹ and U ² correspond to a crystalline polyester resin and an amorphous polyester resin, respectively. It is a structure to be used.
Hereinafter, each component constituting the binder resin of the present invention will be described.

(Crystalline polyester resin)
The crystalline polyester resin is a crystalline polyester resin. Here, "crystalline" means that in differential scanning calorimetry (DSC), the polyester resin does not show a stepwise endothermic change, but shows a clear endothermic peak. Specifically, the polyester resin showing a clear endothermic peak when the differential scanning calorimetry described in the examples is performed is a crystalline polyester resin.

The acid value of the crystalline polyester resin is in the range of 4.0 to 16.0, preferably in the range of 5.0 to 15.0, and more preferably in the range of 8.1 to 15.0. In order to maintain the emulsifying property of the block copolymer, the acid value of the crystalline polyester resin is more preferably more than 10.0 at the lower limit.
The acid value of the crystalline polyester resin is measured by the method described in Examples.

The melting point of the crystalline polyester resin is preferably 55 to 90 ° C, more preferably 61 to 88 ° C, and even more preferably 64 to 85 ° C.
The melting point of the crystalline polyester resin is measured by the method described in Examples.

The weight average molecular weight (Mw) of the crystalline polyester resin is, for example, in the range of 5,000 to 100,000, preferably in the range of 10,000 to 60,000, and more preferably in the range of 15,000 to 40,000. The range is, more preferably 19,000 to 39,000.
The number average molecular weight (Mn) of the crystalline polyester resin is, for example, in the range of 1,000 to 50,000, preferably in the range of 2,000 to 10,000, and more preferably in the range of 3,000 to 10,000. It is in the range of 4,000 to 9,900, more preferably 4,000 to 9,900.
The weight average molecular weight and the number average molecular weight of the crystalline polyester are measured by the method described in Examples.

Examples of the crystalline polyester resin include a crystalline polyester resin obtained by using an aliphatic dibasic acid (c1) and an aliphatic diol (c2) as essential reaction raw materials.
The polyester resin is usually obtained as an amorphous polyester resin, but a crystalline polyester resin can be obtained by using a combination of an aliphatic dibasic acid (c1) and an aliphatic diol (c2) as a reaction raw material. It is more preferable that the aliphatic dibasic acid (c1) and the aliphatic diol (c2) both have high symmetry and / or have a long hydrocarbon chain.

Examples of the aliphatic dibasic acid (c1) include malonic acid, succinic acid, glutaric acid, adipic acid, pimelliic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid, and tetradecane. Examples thereof include aliphatic dibasic acids such as diacid, pentadecanedioic acid, hexadecanedioic acid, heptadecanedioic acid, octadecanedioic acid and nonyldecanedioic acid. Of these, aliphatic dibasic acids having 6 to 18 carbon atoms are preferable, and adipic acid, pimelli acid, suberic acid, azelaic acid, sebacic acid, undecaneic acid, dodecanedioic acid, tridecanoic acid, tetradecanedioic acid, Pentadecane diic acid, hexadecane diic acid, heptadecane diic acid, and octadecane diic acid are more preferable.
These aliphatic dibasic acids may be used alone or in combination of two or more.

Examples of the aliphatic diol (c2) include ethylene glycol, diethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, and 1,7-heptane. Diol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,12-dodecanediol, 1,14-tetradecanediol, 1,16-hexadecanediol, 1,18-octadecanediol , 1,20-Linear alkylene diol such as icosandiol; Ether glycol such as polyoxyethylene glycol and polyoxypropylene glycol; The linear alkylene diol and ethylene oxide, propylene oxide, tetrahydrofuran, ethylglycidyl ether and propyl Modified polyether polyols obtained by ring-open polymerization with various cyclic ether bond-containing compounds such as glycidyl ether, butyl glycidyl ether, phenyl glycidyl ether, and allyl glycidyl ether; the linear alkylene diol and various types such as ε-caprolactone. Examples thereof include a lactone-based polyester polyol obtained by a polycondensation reaction with the lactone of the above.
These aliphatic diols (c2) may be used alone or in combination of two or more.

The aliphatic diol (c2) is preferably a linear alkylene diol having 4 to 18 carbon atoms, and is preferably 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, or 1,7-heptan. Diol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,12-dodecanediol, 1,14-tetradecanediol, 1,16-hexadecanediol, 1,18-octadecanediol Is more preferable. All of these are aliphatic diols with high symmetry.

As the crystalline polyester resin, a polyfunctional epoxy compound (c3) may be used as a reaction raw material.
Examples of the polyfunctional epoxy compound (c3) include ethylene glycol diglycidyl ether, 2,2'-(2,6-dioxaheptane-1,7-diyl) bisoxylane, and 1,4-bis (glycidyloxy). Butane, 2,3-butylene glycol diglycidyl ether, 1,5-pentylene glycol diglycidyl ether, 1,6-bis (glycidyloxy) hexane, 1,7-heptylene glycol diglycidyl ether, 1,8 -Adiglycicidyl ethers such as octylene glycol diglycidyl ether; aliphatic polyglycidyl ethers having three or more epoxy groups in the molecular structure such as trimethylolpropane triglycidyl ether and pentaerythritol tetraglycidyl ether; (meth). Glycidyl group-containing compounds such as glycidyl acrylate and α-ethyl (meth) glycidyl acrylate, and aliphatic compounds containing vinyl groups such as butadiene, methyl (meth) acrylate, ethyl (meth) acrylate, and dimethyl fumarate. Epoxy group-containing vinyl polymer obtained by polymerizing with; bisphenol A diglycidyl ether, bisphenol B diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, 1,4-naphthalenediol diglycidyl ether, 1, Aromatic diglycidyl ethers such as 5-naphthalenediol diglycidyl ether, 2,6-naphthalenediol diglycidyl ether, naphthalene-2,6-dimethanol diglycidyl ether; 4,4', 4''-methyridin trisphenol Aromatic polyglycidyl ether having 3 or more epoxy groups in the molecular structure such as triglycidyl ether; novolak type epoxy resin such as phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol novolak type epoxy resin; ( A glycidyl group-containing compound such as glycidyl acrylate or α-ethyl (meth) glycidyl acrylate, an aromatic compound containing a vinyl group such as styrene, and butadiene, methyl (meth) acrylate, if necessary, (meth). Examples thereof include an epoxy group obtained by polymerizing an aliphatic compound containing a vinyl group such as ethyl acrylate and dimethyl fumarate, and a vinyl polymer containing an aromatic ring. Of these, the novolak type epoxy resin is preferable.
These polyfunctional epoxy compounds (c3) may be used alone or in combination of two or more.

The crystalline polyester resin can be used as a reaction raw material as a reaction raw material, such as methanic acid, ethane acid, propanoic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanic acid, octanoic acid, nonanoic acid, decanoic acid, dodecanoic acid and tetradecanoic acid. An aliphatic monocarboxylic acid such as hexadecanoic acid, heptadecanoic acid and octadecanoic acid; aromatic dicarboxylic acids such as phthalic acid, phthalic anhydride, terephthalic acid, isophthalic acid and orthophthalic acid may be used.
The acid components other than these aliphatic dibasic acids (c1) may be used alone or in combination of two or more.
The melting point of the crystalline polyester resin can be adjusted by using an acid component other than the aliphatic dibasic acid (c1).

The crystalline polyester resin can be used as a reaction raw material as a reaction raw material, such as hexanol, octanol, n-decanol, n-undecanol, n-dodecanol, n-tridecanol, n-tetradecanol, n-pentadecanol and n-heptadeca. Monoalcohols such as anol, n-octadecanol, n-nonadecanol, eikosanol; trimethylolethane, trimethylolpropane, 2,2,4-trimethyl-1,3-pentanediol, glycerin, hexanetriol, pentaerythritol and the like. Trifunctional or higher aliphatic polyols; bisphenols such as bisphenol A, bisphenol B, bisphenol F, bisphenol S; even if an alkylene oxide adduct of bisphenol obtained by adding ethylene oxide, proprene oxide, etc. to the bisphenol is used. good.
Alcohol components other than these aliphatic diols (c2) may be used alone or in combination of two or more.
The melting point of the crystalline polyester resin can be adjusted by using an alcohol component other than the aliphatic diol (c2).

As the crystalline polyester resin, a monoepoxy compound may be used as a reaction raw material, if necessary.
Examples of the monoepoxy compound include butyl glycidyl ether, 2-ethoxyethyl glycidyl ether, pentyl glycidyl ether, hexyl glycidyl ether, heptyl glycidyl ether, octyl glycidyl ether, 2-ethylhexyl glycidyl ether, nonyl glycidyl ether, decyl glycidyl ether and the like. Monoglycidyl ether; monoglycidyl ether having an aromatic ring in the molecular structure such as phenylglycidyl ether, cresyl glycidyl ether, 4-butylphenylglycidyl ether, glycidyl-2-naphthyl ether; 2,2-dimethylpropionic acid Alibo monoglycidyl esters such as cyclopropylmethyl, neodecanoic acid glycidyl ester, stearate glycidyl ester; aromatic α-olefin oxides such as styrene oxide and the like can be mentioned.
These monoepoxy compounds may be used alone or in combination of two or more.

Crystalline polyesters having an acid value in the range of 4.0 to 16.0 can be produced by adjusting the ratio of dibasic acid to diol.

When the crystalline polyester resin is a crystalline polyester resin obtained by using an aliphatic dibasic acid (c1) and an aliphatic diol (c2) as essential reaction raw materials, the crystalline polyester resin is an aliphatic dibasic acid. The ratio [(N _COOH ) / (N _OH )] of the number of moles of the carboxyl group (N _COOH ) contained in (c1) to the number of moles (NO _H ) of the hydroxyl group contained in the aliphatic diol (c1) is 1.00. Using an aliphatic dibasic acid (c1) and an aliphatic diol (c2) so as to be in the range of /0.95 to 1.00 / 1.00, dibutyltin oxide or the like is used at a temperature of 180 to 260 ° C. A crystalline polyester resin reacted in the presence of an esterification catalyst is preferred.

(Amorphous polyester resin)
The amorphous polyester resin is an amorphous polyester resin. Here, "amorphous" means that it does not show a clear endothermic peak in differential scanning calorimetry (DSC). Specifically, the polyester resin that does not show a clear endothermic peak when the differential scanning calorimetry described in the examples is performed is an amorphous polyester resin.

The acid value of the amorphous polyester resin is in the range of 4.0 to 16.0, preferably in the range of 5.0 to 15.0, and more preferably in the range of 8.1 to 15.0. .. In order to maintain the emulsifying property of the block copolymer, the acid value of the amorphous polyester is more preferably more than 10.0 at the lower limit.
The acid value of the amorphous polyester is measured by the method described in Examples.

Amorphous polyester resin is in a glass state with low molecular motion and no fluidity in a low temperature environment, but as the temperature rises, the molecular motion increases, and the rigidity and viscosity decrease, resulting in increased fluidity. It has the property of becoming a state. At this time, the temperature at which the glass state changes to the rubber state is called the glass transition temperature (Tg).
The glass transition temperature of the amorphous polyester resin is, for example, 45 to 100 ° C, preferably 50 to 90 ° C, more preferably 50 to 80 ° C, still more preferably 50 to 70 ° C.
The glass transition temperature of the amorphous polyester resin is measured by the method described in Examples.

The weight average molecular weight (Mw) of the amorphous polyester resin is, for example, 3,000 to 150,000, preferably 4,000 to 80,000, and more preferably 10,000 to 60,000. More preferably, it is 10,500 to 44,000.
The number average molecular weight (Mn) of the amorphous polyester resin is, for example, 1,000 to 50,000, preferably 2,000 to 10,000, and more preferably 2,500 to 8,000. More preferably, it is 2,500 to 6,000.
The weight average molecular weight and the number average molecular weight of the amorphous polyester are measured by the method described in Examples.

Examples of the amorphous polyester resin include an amorphous polyester resin obtained by using a dibasic acid (a1) and a diol (a2) as essential reaction raw materials.
The reaction raw material of the amorphous polyester resin is preferably a combination of a dibasic acid and a diol other than the combination of the aliphatic dibasic acid (c1) and the aliphatic diol (c2), which are the reaction raw materials of the crystalline polyester. ..

Examples of the dibasic acid (a1) include malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, hexahydrophthalic acid, 1,4-cyclohexanedicarboxylic acid, and dodecyl succinic acid. Acids, aliphatic dicarboxylic acids such as dodecyl anhydride succinic acid, dodecenyl succinic acid, dodecenyl succinic acid, octenyl succinic acid, octenyl anhydride succinic acid; maleic acid, maleic anhydride, citraconic acid, dimethylmaleic acid, cyclopentene-1,2-dicarboxylic acid Acids, 1-cyclohexene-1,2-dicarboxylic acid, 4-cyclohexene-1,2-dicarboxylic acid, fumaric acid, mesaconic acid, itaconic acid, glutaconic acid and other aliphatic unsaturated dicarboxylic acids; phthalic acid , Aromatic dicarboxylic acids such as phthalic acid anhydride, terephthalic acid, isophthalic acid, orthophthalic acid and the like can be mentioned. Of these, the aromatic dicarboxylic acid is preferable, and terephthalic acid and isophthalic acid are more preferable.
These dibasic acids may be used alone or in combination of two or more.

Examples of the diol (a2) include ethylene glycol, diethylene glycol, propylene glycol, 1,3-propanediol, 1,2,2-trimethyl-1,3-propanediol, and 2,2-dimethyl-3-isopropyl-1. , 3-Propanediol, 1,4-butanediol, 1,3-butanediol, 3-methyl-1,3-butanediol, 1,5-pentanediol, 3-methyl1,5-pentanediol, neopentyl An aliphatic diol such as glycol, 1,6-hexanediol or 1,4-bis (hydroxymethyl) cyclohesane; an ether glycol such as polyoxyethylene glycol or polyoxypropylene glycol; the aliphatic diol and ethylene oxide or propylene oxide, Modified polyether polyol obtained by ring-opening polymerization with various cyclic ether bond-containing compounds such as tetrahydrofuran, ethyl glycidyl ether, propyl glycidyl ether, butyl glycidyl ether, phenyl glycidyl ether, allyl glycidyl ether; the aliphatic diol and ε. -Lactone-based polyester polyol obtained by polycondensation reaction with various lactones such as caprolactone; bisphenol such as bisphenol A, bisphenol B, bisphenol F, bisphenol S; obtained by adding ethylene oxide, proprene oxide, etc. to the bisphenol. Examples thereof include an alkylene oxide adduct of bisphenol. Of these, the alkylene oxide adduct of the bisphenol is preferable.
These diols may be used alone or in combination of two or more.

The amorphous polyester resin can be used as a reaction raw material as a reaction raw material, such as methanic acid, ethanoic acid, propanoic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanic acid, octanoic acid, nonanoic acid, decanoic acid, dodecanoic acid and tetradecanoic acid. , Hexadecanoic acid, heptadecanoic acid, octadecanoic acid, benzoic acid, parat-butylbenzoic acid and other monocarboxylic acids; 1,2,5-hexanetricarboxylic acid, 1,2,4-cyclohexanetricarboxylic acid, trimellitic acid, Trifunctional or higher polycarboxylic acids such as trimellitic anhydride, 1,2,5-benzenetricarboxylic acid, 2,5,7-naphthalenetricarboxylic acid, pyromellitic acid, and pyromellitic anhydride may be used.
The acid components other than the dibasic acid (a1) may be used alone or in combination of two or more.
The glass transition point of the amorphous polyester resin can be adjusted by using an acid component other than the dibasic acid (a1).

As a reaction raw material, the amorphous polyester resin may be hexanol, 2-ethylhexanol, octanol, n-decanol, n-undecanol, n-dodecanol, n-tridecanol, n-tetradecanol, n-pentadecanol, if necessary. Knoll, n-heptadecanol, n-octadecanol, n-nonadecanol, eikosanol, 5-ethyl-2-nonanol, trimethylnonyl alcohol, 2-hexyldecanol, 3,9-diethyl-6-tridecanol, 2-isoheptyl Monoalcohols such as isoundecanol, 2-octyldodecanol, 2-decyltetradecanol; trimethylolethane, trimethylolpropane, 2,2,4-trimethyl-1,3-pentanediol, glycerin, hexanetriol, Trifunctional or higher functional polyols such as pentaerythritol may be used.
The alcohol component of these diols (a2) may be used alone or in combination of two or more.
The glass transition point of the amorphous polyester resin can be adjusted by using an alcohol component other than the diol (a2).

As the amorphous polyester resin, a polyfunctional epoxy compound may be used as a reaction raw material, if necessary. As the polyfunctional epoxy compound that can be used for the amorphous polyester resin, the same polyfunctional epoxy compound (c3) that can be used for the crystalline polyester resin can be used.

As the amorphous polyester resin, a monoepoxy compound may be used as a reaction raw material, if necessary.
Examples of the monoepoxy compound include butyl glycidyl ether, 2-ethoxyethyl glycidyl ether, pentyl glycidyl ether, hexyl glycidyl ether, heptyl glycidyl ether, octyl glycidyl ether, 2-ethylhexyl glycidyl ether, nonyl glycidyl ether, decyl glycidyl ether and the like. Monoglycidyl ether; monoglycidyl ether having an aromatic ring in the molecular structure such as phenylglycidyl ether, cresyl glycidyl ether, 4-butylphenylglycidyl ether, glycidyl-2-naphthyl ether; 2,2-dimethylpropionic acid Alibo monoglycidyl esters such as cyclopropylmethyl, neodecanoic acid glycidyl ester, stearate glycidyl ester; aromatic α-olefin oxides such as styrene oxide and the like can be mentioned.
These monoepoxy compounds may be used alone or in combination of two or more.

The amorphous polyester having an acid value in the range of 4.0 to 16.0 can be produced by adjusting the ratio of the dibasic acid and the diol.

When the amorphous polyester resin is an amorphous polyester resin obtained by using a dibasic acid (a1) and a diol (a2) as essential reaction raw materials, the amorphous polyester resin is a dibasic acid (a1). The ratio [(N _COOH ) / (N _OH )] of the number of moles of the carboxyl group (N _COOH ) of the carboxyl group contained in the diol (a2) to the number of moles (NO _H ) of the hydroxyl group contained in the diol (a2) is 1.00 / 0. Using a dibasic acid (a1) and a diol (a2) so as to be in the range of .96 to 1.00 / 1.04, at a temperature of 180 to 260 ° C., in the presence of an esterification catalyst such as dibutyltin oxide. It is preferable that it is an amorphous polyester resin reacted with.

(Aromatic tetracarboxylic acid derivative)
The aromatic ring of the aromatic tetracarboxylic acid derivative corresponds to Ar of the above formula (1), and the aromatic ring of the aromatic tetracarboxylic acid derivative is selected from, for example, a benzene ring, a naphthalene ring, and 2 thereof. Examples thereof include a structure in which two rings are linked by any one of a single bond, an ether bond, an amide bond, and a carbonyl bond, and a benzene ring is preferable.
The aromatic ring is further composed of an alkyl group having 1 to 6 carbon atoms such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group and an n-pentyl group. It may be replaced.

The aromatic tetracarboxylic acid derivative is preferably a compound in which all four carboxyl groups (-COOH) are directly substituted with an aromatic ring because of its high reactivity with crystalline polyester and amorphous polyester. Aromatic tetracarboxylic acid dianhydride is preferred.
Examples of the aromatic tetracarboxylic acid dianhydride include pyromellitic acid dianhydride, 3,3', 4,4'-biphenyltetracarboxylic acid dianhydride, 2,2', 3,3'-biphenyltetracarboxylic acid. Acid dianhydride, 2,3', 3,4'-biphenyltetracarboxylic acid dianhydride, oxydiphthalic acid dianhydride, 3,3', 4,4'-benzophenone tetracarboxylic acid dianhydride, 3,3 ', 4,4'-Diphenylsulfone tetracarboxylic acid dianhydride, m-terphenyl-3,3', 4,4'-tetracarboxylic acid dianhydride, 4,4'-(2,2-hexafluoro) Isopropylene) diphthalic acid dianhydride, 2,2'-bis (3,4-dicarboxyphenyl) propane, 1,4,5,8-naphthalenetetracarboxylic acid dianhydride, 2,3,6,7 -Naphthalene tetracarboxylic acid dianhydride, (1,1': 3', 1 "-terphenyl) -3,3", 4,4 "-tetracarboxylic acid dianhydride, 4,4'-(dimethylshira) Examples thereof include diyl) diphthalic acid dianhydride and 4,4'-(1,4-phenylenebis (oxy)) diphthalic acid dianhydride.

Regarding the structure represented by the above formula (1), if the structure of the portion other than U ¹ and U ² is line-symmetrical or point-symmetrical, higher electrical dielectric constant and higher crystallinity can be exhibited. , The aromatic tetracarboxylic acid derivative is preferably an aromatic tetracarboxylic acid derivative having a line-symmetrical structure or a point-symmetrical structure.

[Manufacturing method of binder resin for toner]
In the method for producing a binder resin of the present invention, a crystalline polyester resin having an acid value in the range of 4.0 to 16.0 and an amorphous polyester resin having an acid value in the range of 4.0 to 16.0 And the reaction raw material which contains the aromatic tetracarboxylic acid derivative indispensably are reacted.

The crystalline polyester resin as a reaction raw material may be used alone or in combination of two or more having different structures.
The amorphous polyester resin as a reaction raw material may be used alone or in combination of two or more having different structures.
The aromatic tetracarboxylic acid derivative as a reaction raw material may be used alone or in combination of two or more having different structures.

The reaction temperature is, for example, 130 ° C. or higher and lower than 200 ° C., preferably 140 ° C. or higher and lower than 170 ° C., and more preferably 140 ° C. or higher and 160 ° C. or lower.
When the aromatic tetracarboxylic acid derivative has a carboxylic acid anhydride structure, the reactivity with the polyester resin can be enhanced, and even if the temperature is lower than 200 ° C., it can be reacted with the crystalline polyester resin and the amorphous polyester resin. can. By producing the binder resin of the present invention at a temperature lower than 200 ° C., the crystallinity of the crystalline polyester resin is not impaired, and the low temperature fixability of the obtained binder resin can be enhanced.

Even if the reaction raw material containing the crystalline polyester resin, the amorphous polyester resin, and the aromatic tetracarboxylic acid derivative is only the crystalline polyester resin, the amorphous polyester resin, and the aromatic tetracarboxylic acid derivative. Any reaction raw material other than these may be used.

The mass ratio of the crystalline polyester resin to the amorphous polyester resin used in the production of the binder resin of the present invention is preferably crystalline polyester resin: amorphous polyester resin = 20: 80 to 80:20. Crystalline polyester resin: amorphous polyester resin = 25: 75 to 75:25 is more preferable, and crystalline polyester resin: amorphous polyester resin = 25: 75 to 50:50 is even more preferable.

The amount of the aromatic tetracarboxylic acid derivative used in the production of the binder resin of the present invention is based on 100 parts by mass when the total amount of the crystalline polyester resin and the amorphous polyester resin is 100 parts by mass. For example, it is 0.1 to 10 parts by mass, preferably 0.5 to 7 parts by mass, and more preferably 1 to 6 parts by mass.

The reaction of the reaction raw material containing the crystalline polyester resin, the amorphous polyester resin, and the aromatic tetracarboxylic acid derivative is solvent-free because the reaction between the binder resins and the like can be suppressed and the increase in viscosity can be suppressed. Can be carried out at. Since no solvent is required, the manufacturing cost can be suppressed.
The reaction is preferably carried out in an atmosphere of an inert gas such as argon or nitrogen while removing water generated by the reaction.

In the method for producing a binder resin of the present invention, not only a resin in which a crystalline polyester resin and an amorphous polyester resin are linked by an aromatic tetracarboxylic acid derivative, but also two crystalline polyester resins are aromatic tetracarboxylic acid derivatives. A resin in which two amorphous polyester resins are linked with an aromatic tetracarboxylic acid derivative can also be obtained, but the effect of the present invention is not impaired.

The structure of the resin obtained by the production method of the present invention can be confirmed or estimated, for example, by a known instrumental analysis method such as NMR or electrospray ionization mass spectrometry (ESI-MS) for the binder resin or its hydrolyzate. ..

[Toner for developing static charge image]
The toner for developing an electrostatic charge image of the present invention includes the binder resin for toner of the present invention.
The toner for developing an electrostatic charge image of the present invention (hereinafter, may be simply referred to as "toner of the present invention") is excellent in both low-temperature fixability and charging performance by containing the binder resin of the present invention.

The content of the binder resin of the present invention in the toner of the present invention is not particularly limited, but is preferably 10 to 95% by mass, preferably 25 to 90% by mass, based on the total mass of the toner. More preferably, it is more preferably 45 to 85% by mass.
When the content of the binder resin of the present invention is within the above range, excellent low-temperature fixability and charging performance can be obtained.

(Other binding resin)
The toner of the present invention may contain the binder resin of the present invention, and may contain other binder resins other than the binder resin of the present invention.
The other binder resin is not particularly limited, and examples thereof include polystyrene, styrene-butadiene polymer, styrene acrylic polymer, and polyester resin. These other binder resins may be further modified with urethane, urea, epoxy or the like.

The content of the binder resin of the present invention in the toner of the present invention is preferably 20 to 100% by mass, more preferably 50 to 100% by mass, based on the total mass of the binder resin in the toner. preferable.

(Colorant)
The toner of the present invention preferably contains a colorant for the purpose of coloring the obtained image.
As the colorant, a known colorant may be appropriately selected and used according to the purpose, and pigments and dyes of each color can be used.

The pigments include black pigments such as carbon black, copper oxide, manganese dioxide, aniline black, activated carbon, non-magnetic ferrite, and magnetite; yellow lead, zinc yellow, yellow iron oxide, cadmium yellow, chrome yellow, Hansa yellow, and Hansa yellow. Yellow pigments such as 10G, Benzidine Yellow G, Benzidine Yellow GR, Slen Yellow, Kinolin Yellow, Permanent Yellow NCG; , Induslen Brilliant Orange GK and other orange pigments; Bengala, Cadmium Red, Lead Tan, Mercury Sulfide, Watching Red, Permanent Red 4R, Lisole Red, Brilliant Carmine 3B, Brilliant Carmine 6B, Pyrazolon Red, Rhodamin Lake B, Lake Red C , Rose Bengal, Eosin Red, Arizarin Lake, etc.; Blue pigments such as Navy Blue, Cobalt Blue, Alkaline Blue Lake, Victoria Blue Lake, Fast Sky Blue, Induslen Blue BC, Ultra Marine Blue, Phtalocyanin Blue, Phtalussinin Green, etc.; Purple pigments such as manganese purple, fast violet B, methyl violet lake; green pigments such as chromium oxide, chromium green, pigment green B, malakite green lake, fanal yellow green G; zinc flower, titanium oxide, antimony white, zinc sulfide White pigments such as: Barite powder, barium carbonate, clay, silica, white carbon, talc, alumina white and the like.
These pigments may be used alone or in combination of two or more.

Examples of the dye include various dyes such as basic dyes, acid dyes, disperse dyes, and direct dyes.
Specific examples of the dye include niglocin, methylene blue, rose bengal, quinoline yellow and the like.
These dyes may be used alone or in combination of two or more.

The colorant may be used, for example, as a dispersion of colorant particles.
As a method for preparing the dispersion liquid of the colorant particles, a media type disperser such as a rotary shear homogenizer, a ball mill, a sand mill, and an attritor; a high pressure counter-collision type disperser or the like is used to prepare a dispersion liquid of the colorant particles. Alternatively, a surface active agent having polarity may be added to prepare a dispersion of colorant particles with a homogenizer.

The content of the colorant of the toner of the present invention is preferably 0.1 to 40% by mass, and 0.5 to 20% by mass, based on the total solid content of the toner, in order to secure the color development property at the time of fixing. Is more preferable. However, when a magnetic material is used as the black colorant, the content of the black colorant is preferably 12 to 48% by mass, more preferably 15 to 40% by mass, based on the total solid content of the toner.

By appropriately selecting the type of the colorant, each color toner such as yellow toner, magenta toner, cyan toner, and black toner can be obtained.

(Release agent)
The toner of the present invention preferably contains a mold release agent for the purpose of improving the mold release property.
Examples of the mold release agent include low molecular weight polyolefins such as polyethylene, polypropylene and polybutene; silicones having a softening point by heating; fatty acid amides such as oleic acid amide, erucic acid amide, ricinoleic acid amide and stearic acid amide; Vegetable waxes such as Uva wax, rice wax, candelilla wax, wood wax, jojoba oil; animal waxes such as beeswax; Based waxes; Examples include ester waxes such as fatty acid esters, montanic acid esters, and carboxylic acid esters.
These release agents may be used alone or in combination of two or more.

The amount of the release agent added is preferably 0.5 to 50% by mass, more preferably 1 to 30% by mass, and 5 to 15% by mass with respect to the total amount of the toner particles. Is even more preferable.

The toner of the present invention may contain other components other than the binder resin, the colorant, and the release agent as long as the effects of the present invention are not impaired, and the other components include inorganic particles, organic particles, and internal additives. Known additives such as agents and charge control agents can be mentioned.

The inorganic particles are generally used for the purpose of improving the fluidity of the toner.
Examples of the inorganic particles include silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, zinc oxide, silica sand, clay, mica, silica ash stone, silica soil, and cerium chloride. , Bengala, chromium oxide, cerium oxide, antimony trioxide, magnesium oxide, zirconium oxide, silicon carbide, silicon nitride and the like. Among these, silica particles are preferable, and hydrophobized silica particles are particularly preferable.

The organic particles are used for the purpose of improving cleaning property, transferability, chargeability and the like.
Examples of the organic particles include particles such as polystyrene, polymethylmethacrylate, polyvinylidene fluoride, and polystyrene-acrylic copolymer.

Examples of the internal additive include metals such as ferrite, magnetite, reduced iron, cobalt, nickel and manganese, alloys, and magnetic materials such as compounds containing these metals.
Examples of the charge control agent include salicylic acid metal salt, metal-containing azo compound, niglocin, quaternary ammonium salt and the like.

The toner of the present invention can be produced by a known method, and examples thereof include a kneading and pulverizing method, an emulsion aggregation method, a suspension polymerization method, and a dissolution suspension method, and the emulsion aggregation method is preferable.
The kneading and pulverizing method is a method in which a binder resin is kneaded with a colorant, a mold release agent, a charge control agent and the like, and the obtained kneaded product is pulverized and classified to produce toner matrix particles. .. The obtained toner mother particles may be further changed in shape by applying mechanical impact force or thermal energy.
In the emulsification / aggregation method, a dispersion liquid obtained by emulsifying and dispersing a binder resin and a dispersion liquid such as a colorant, a mold release agent, and a charge control agent are mixed, aggregated, and heat-fused to obtain toner matrix particles. It is a manufacturing method.
In the suspension polymerization method, a polymerizable monomer for obtaining a binder resin and a solution of a colorant, a mold release agent, a charge control agent, etc. are suspended in an aqueous solvent to produce toner matrix particles. The method.
The dissolution-suspension method is a method of granulating toner mother particles by suspending a binder resin and a solution of a colorant, a mold release agent, a charge control agent, or the like in an aqueous solvent.
The toner mother particles obtained by the above method may be used as a core, aggregated particles may be attached to the core surface, and the toner may be heat-fused to obtain a toner having a core-shell structure.

[Static charge image developer]
The toner of the present invention is suitably used as a static charge image developer.
The electrostatic charge image developer of the present invention may contain the toner of the present invention. For example, when the toner of the present invention is used alone as the electrostatic charge image developer, the electrostatic charge image developer of the present invention becomes a one-component static charge image developer, and the toner of the present invention is used as the electrostatic charge image developer. When used in combination with a known carrier, it becomes a two-component static charge image developer.

Examples of the core material of the carrier include magnetic metals such as iron, steel, nickel and cobalt; alloys of the magnetic metal with manganese, chromium, rare earths and the like; magnetic oxides such as ferrite and magnetite.

The surface of the core material of the carrier may be coated with a resin. Resins that coat the surface of the core material include polyolefin resins such as polyethylene and polypropylene; polystyrene, acrylic resin, polyacrylonitrile, polyvinyl acetate, polyvinyl alcohol, polyvinyl butyral, polyvinyl chloride, polyvinylcarbazole, polyvinyl ether, polyvinyl ketone and the like. Polyvinyl resin and polyvinylidene resin; Vinyl chloride-vinyl acetate copolymer; Styrene-acrylic acid copolymer; Straight silicone resin composed of organosiloxane bonds or modified products thereof; Polytetrafluoroethylene, polyvinyl fluoride, polyfluoride Fluorine resins such as vinylidene and polychlorotrifluoroethylene; silicone resins; polyesters; polyurethanes; polycarbonates; phenolic resins; urea-formaldehyde resins, melamine resins, benzoguanamine resins, urea resins, polyamide resins and other amino resins; epoxy resins, etc. Can be mentioned.
These resins may be used alone or in combination of two or more.

When the carrier is a carrier made of a core material coated with a resin, it is preferable that the resin particles and / or the conductive particles are dispersed in the resin coating layer.
Examples of the resin particles include thermoplastic resin particles and thermosetting resin particles. The resin particles may be used alone or in combination of two or more.
The conductive particles include metal particles such as gold, silver, and copper; carbon black particles; particles having a surface covered with carbon black or metal such as titanium oxide, zinc oxide, barium sulfate, aluminum borate, and potassium titanate. Can be mentioned. These conductive particles may be used alone or in combination of two or more.

The toner of the present invention or the electrostatic charge image developer of the present invention is used, for example, in a state of being housed in a cartridge. By accommodating the toner of the present invention or the electrostatic charge image developer of the present invention in the cartridge, the toner or the electrostatic charge image developer of the present invention can be attached to and detached from the image forming apparatus, and the toner or the electrostatic charge image developing agent can be easily supplied to the image forming apparatus. Can be done.

Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples.
The present invention is not limited to the following examples.

Various evaluations in the examples were performed by the following methods.

(Acid value and hydroxyl value)
The acid value and hydroxyl value of the resin were measured according to JISK0070-1992 (neutralization titration method).

(Number average molecular weight and weight average molecular weight)
The number average molecular weight (Mn) and the weight average molecular weight (Mw) of the resin were evaluated by using a gel permeation chromatography (GPC) method under the following conditions.
Measuring device: HLC-8120GPC manufactured by Tosoh Corporation
Column: TSK-GUARDCOLUMN HXL-H manufactured by Tosoh Corporation
+ TSK-GEL G5000HXL manufactured by Tosoh Corporation
+ TSK-GEL G4000HXL manufactured by Tosoh Corporation
+ TSK-GEL G3000HXL manufactured by Tosoh Corporation
+ TSK-GEL G2000HXL manufactured by Tosoh Corporation
Detector: RI (Differential Refractometer)
Data processing: Multi-station GPC-8020modelII manufactured by Tosoh Corporation
Column temperature: 40 ° C
Solvent: Tetrahydrofuran Flow velocity: 1.0 ml / min Standard: Monodisperse polystyrene Sample: Tetrahydrofuran solution of 0.5% by mass in terms of resin solid content filtered through a microfilter (100 μl)

(Melting point)
The melting point of the resin was determined by the differential scanning calorimetry (DSC) method under the following conditions.
Measuring device: DSC-220C manufactured by Seiko Instruments Inc.
Data processing: EXSTAR6000 PC station Measurement conditions: (1) Temperature rise from 20 ° C to 150 ° C (10 ° C / min)
(2) Hold at 150 ° C for 10 minutes
(3) Temperature down from 150 ° C to 0 ° C (10 ° C / min)
(4) Hold at 0 ° C for 10 minutes
(5) Temperature rise from 0 ° C to 150 ° C (10 ° C / min)
Analysis: In (5), the maximum endothermic peak temperature of the heat of fusion was taken as the melting point.

(Glass-transition temperature)
The glass transition temperature of the resin was determined by the differential scanning calorimetry (DSC) method under the following conditions.
Measuring device: DSC-220C manufactured by Seiko Instruments Inc.
Data processing: EXSTAR6000 PC station Measurement conditions: (1) Temperature rise from 20 ° C to 150 ° C (10 ° C / min)
(2) Hold at 150 ° C for 10 minutes
(3) Temperature down from 150 ° C to 0 ° C (10 ° C / min)
(4) Hold at 0 ° C for 10 minutes
(5) Temperature rise from 0 ° C to 150 ° C (10 ° C / min)
Analysis: In (5), the intersection of the extension of the baseline on the low temperature side and the tangent drawn at the point where the slope of the curve of the stepwise change portion of the glass transition is maximized was defined as the glass transition point.

(Synthesis Example 1-8: Synthesis of crystalline polyester resin)
The raw materials shown in Table 1 were placed in a four-port 3L stainless steel flask equipped with a stirrer, a nitrogen gas inlet, and a thermometer. After charging the raw materials, the temperature is raised to 220 ° C. over 6 hours under a nitrogen stream while removing the water to be generated, and the reaction is carried out at 220 ° C. until the desired acid value and molecular weight are reached, and the crystalline polyester resin C-1 to Obtained C-8.
The acid value, hydroxyl value, number average molecular weight, weight average molecular weight and melting point of the obtained crystalline polyester resins C-1 to C-8 were evaluated. The results are shown in Table 1.

In Table 1, each abbreviation of composition represents the following.
EG: Ethylene glycol BG: 1,4-Butanediol HD: 1,6-Hexanediol DDD: 1,12-Dodecanediol SeA: Sebacic acid DDDA: Dodecanedioic acid

(Synthesis Examples 9 to 14: Synthesis of Amorphous Polyester Resin)
The raw materials shown in Table 3 were placed in a four-port 3L stainless steel flask equipped with a stirrer, a nitrogen gas inlet, and a thermometer, and 0.8 part of titanium tetraisopropoxide was added as a catalyst. After charging the raw materials, the reaction was carried out at 240 ° C. for 3 hours under a nitrogen stream while removing the water to be produced, and then further reacted at 220 ° C. under a reduced pressure of 5 kPa until the desired acid value and molecular weight were reached to achieve amorphous properties. Polyester resins A-1 to A-6 were obtained, respectively.
The acid value, hydroxyl value, number average molecular weight, weight average molecular weight, and glass transition point of the obtained amorphous polyester resins A-1 to A-6 were evaluated. The results are shown in Table 2.
The obtained amorphous polyester resins A-1 to A-6 did not have a clear endothermic peak in the differential scanning calorimetry.

In Table 2, each abbreviation represents the following.
BPAEO: Bisphenol A ethylene oxide adduct BPAPO: Bisphenol A propylene oxide adduct TPA: Terephthalic acid TMAN: Trimellitic anhydride DSA: Dodecenyl succinic anhydride

(Examples 1 to 12: Synthesis of block copolymers B-1 to B-12)
Crystalline polyester resin and amorphous polyester resin shown in Tables 3 and 4 were placed in a four-port 1L stainless steel flask equipped with a stirrer, a nitrogen gas inlet, and a thermometer, and melted by heating at 150 ° C. The blocking agents shown in Tables 3 and 4 are added to this melt and reacted at 150 ° C. for 4 hours to obtain block copolymers B-1 to B-12 having a crystalline polyester block and an amorphous polyester block, respectively. rice field.
The acid value, number average molecular weight, weight average molecular weight and melting point of the obtained block copolymer were evaluated. The results are shown in Tables 3 and 4.

In Tables 3 and 4, each abbreviation represents the following.
PMAn: Piromellitic anhydride

(Comparative Examples 1 to 6: Synthesis of Block Copolymers B'-1 to B'-6)
The crystalline polyester resin and the amorphous polyester resin shown in Table 5 were placed in a four-port 1L stainless steel flask equipped with a stirrer, a nitrogen gas inlet, and a thermometer, and melted by heating at 150 ° C. The blocking agents shown in Table 5 are added to this melt and reacted at 150 ° C. for 4 hours to obtain block copolymers B'-1 to B'-6 having a crystalline polyester block and an amorphous polyester block, respectively. rice field.
The acid value, number average molecular weight, weight average molecular weight and melting point of the obtained block copolymer were evaluated. The results are shown in Table 5.

In Table 5, each abbreviation represents the following.
An1: 1,2,3,4-butanetetracarboxylic acid dianhydride An2: 1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic acid anhydride

(Examples 13 to 24 and Comparative Examples 7 to 12: Manufacture of toner)
(Synthesis of resin for dispersion)
In a four-port 3L stainless steel flask equipped with a stirrer, a nitrogen gas inlet, and a thermometer, 281.7 parts by mass of bisphenol A ethylene oxide adduct, 828.6 parts by mass of bisphenol A propylene oxide adduct, and 400 parts of terephthalic acid. 6 parts by mass, 72.4 parts by mass of adipic acid and 23.8 parts by mass of trimellitic anhydride were charged, and 0.8 parts by mass of titanium tetraisopropoxide was added as a catalyst. After charging the raw materials, the reaction was carried out at 240 ° C. for 7 hours under a nitrogen stream while removing the generated water to obtain a resin for dispersion.

(Preparation of pigment dispersion)
200 parts by mass of Fastgen Blue TGR (β-type copper phthalocyanine pigment, CI Pigment Blue 15: 3, manufactured by DIC Corporation) and 200 parts by mass of the dispersion resin were kneaded with two rolls. The obtained kneaded product and 740 parts by mass of methyl ethyl ketone were charged in a ball mill and stirred for 6 hours, and the solid content was adjusted to 20% by mass with methyl ethyl ketone to obtain a pigment dispersion.

(Preparation of mold release agent dispersion)
200 parts by mass of carnauba wax No. 1 (melting point 83.1 ° C., manufactured by Hiroyuki Kato Co., Ltd., plant wax) and 200 parts by mass of the dispersion resin were kneaded with a pressure kneader. The obtained kneaded product and 740 parts by mass of methyl ethyl ketone were charged in a ball mill and stirred for 6 hours, and the solid content was adjusted to 20% by mass with methyl ethyl ketone to obtain a release agent dispersion.

(Preparation of wet kneading mill base)
Block copolymers B-1 to B-12, block copolymers B'-1 to B'-6, the pigment dispersion, and the release agent dispersion are prepared in the amounts shown in Tables 6 to 8, respectively. The mixture was mixed, and methyl ethyl ketone was added to adjust the solid content to 55% by mass to obtain mil-based MB-1 to MB-12 and mil-based MB'-1 to MB'-6.

(Manufacturing of toner)
To a 2L separable flask having Maxblend blades, add 545.5 parts by mass of Millbase MB-1 to MB-12 and Millbase MB'-1 to MB'-6, respectively, and 23.8 parts by mass of 1-defined ammonia water. After sufficiently stirring at 350 rpm with a three-one motor, the temperature was adjusted to 30 ° C., and 266 parts by mass of deionized water was dropped to emulsify the phase. After phase inversion emulsification, 333 parts by mass of deionized water was added to prepare a fine particle dispersion.
Next, 4.1 parts by mass of polyoxyethylene polyoxypropylene glycol (Epan 450, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.), which is a nonionic emulsifier, was added, and the rotation speed was adjusted to 250 rpm while maintaining the temperature at 30 ° C., 3 410 parts by mass of a% ammonium sulfate aqueous solution was added dropwise, and the mixture was stirred for 5 minutes for coalescence to obtain a slurry.
The obtained slurry was separated into solid and liquid by a centrifuge, washed, and dried in a vacuum dryer to obtain toner particles. Using a Henshell mixer, 0.5 parts by mass of hydrophobic silica (H-2018, manufactured by Clariant Co., Ltd.) and 0.5 parts by mass of titanium oxide (JMT-150AO, manufactured by Teika Co., Ltd.) are added to 100 parts by mass of toner particles. Toners T-1 to T-12 and toners T'-1 to T'-6 were obtained as external additions, respectively.
The obtained toner was evaluated as follows. The results are shown in Tables 6-8.

(Low temperature fixability)
The copying machine was filled with toner, and the set temperature of the heat roll was changed in 5 ° C increments from 80 ° C to 140 ° C to perform solid printing. When the fastness test is performed on the solid printed part, the image density before and after the test is measured with a Macbeth densitometer (RD-918), and the ratio of the density value after peeling to the value before the test is displayed in%. The temperature at which the value was 80% or more was defined as the fixing start temperature. The lower the temperature, the better the low temperature fixability.
The evaluation criteria for low temperature fixability of toner are as follows. The fastness test was performed using a Gakushin type friction fastness tester (load: 200 g, rubbing operation: 5 strokes).
⊚: When the fixing start temperature is less than 110 ° C ○: When the fixing start temperature is 110 ° C or more and less than 115 ° C Δ: When the fixing start temperature is 115 ° C or more and less than 120 ° C ×: The fixing start temperature is 120 ° C or more in the case of

(Heat-resistant storage)
Toner left under a load of 66 g / cm ² in an environment of 40 ° C. and 50% RH for 48 hours was used as a sample. 400 g of this sample was vibrated at an amplitude of 1 mm for 30 seconds with a vibrating sieve set with a sieve having an opening of 45 μm. The proportion of agglomerates remaining on the sieve was evaluated according to the following criteria. The smaller the proportion of agglomerates, the better the heat-resistant storage stability.
⊚: When less than 10% by mass
◯: In the case of less than 10 to 20% by mass Δ: In the case of less than 20 to 30% by mass ×: In the case of 30% by mass or more

(Charging amount and charging stability)
Using a suction blow-off type charge measuring device (210HS-2A, manufactured by Trek Japan Co., Ltd.), a mixture of 1.5 g of toner and 48.5 g of a ferrite carrier (MF-1008, manufactured by Nippon Iron Powder Co., Ltd.) is mixed in 50 ml of poly. The mixture was mixed in a container for 1 minute, 10 minutes, 30 minutes and 60 minutes with a turbo shaker mixer, respectively, and the charge amount of each of the obtained mixtures was measured by the charge amount measuring device. The average value of the charged amount obtained by the measurement was taken as the charged amount of the toner. The evaluation criteria for the amount of charge are as follows.
⊚: −45 μC / g or more ○: −40 μC / g or more and less than −45 μC / g Δ: −35 μC / g or more and less than -40 μC / g ×: -30 μC / g or more and less than −35 μC / g ××: -30 μC / g Less than The difference between the maximum charge amount and the minimum charge amount was obtained for the charge amount of the mixture mixed for 10 minutes, 30 minutes and 60 minutes, and this value was used as the evaluation of charge stability. The smaller this value is, the better the charge stability is. The evaluation criteria for the evaluation criteria for charge stability are as follows.
⊚: Difference between maximum charge amount and minimum charge amount is less than -3 μC / g ○: Difference between maximum charge amount and minimum charge amount is -3 μC / g or more and less than -6 μC / g Δ: Difference between maximum charge amount and minimum charge amount Is -6 μC / g or more and less than -9 μC / g ×: The difference between the maximum charge amount and the minimum charge amount is -9 μC / g or more and less than -12 μC / g.

As can be seen from the results in Tables 6 to 8, the toner containing the block copolymer of the present invention is excellent in both low temperature fixability and chargeability. On the other hand, in Comparative Example 7-10, the emulsifying property was lowered due to the low acid value of the polyester block, and the low-temperature fixability and the amount of charge were impaired. In Comparative Example 11, the block copolymer formed an aromatic ring. Since it is not contained, the amount of charge and charge stability are not sufficient, and in Comparative Example 12, the blocking agent of the block copolymer is not one in which the carboxyl group is replaced with an aromatic ring, and the structural symmetry is insufficient. Therefore, it can be seen that the amount of charge is impaired.

Claims (9)

A binder resin for toner, which is a block copolymer having a crystalline polyester block and an amorphous polyester block.
The acid value of the crystalline polyester block is in the range of 4.0 to 16.0, and the acid value is in the range of 4.0 to 16.0.
The acid value of the amorphous polyester block is in the range of 4.0 to 16.0, and the acid value is in the range of 4.0 to 16.0.
A binder resin for toner having a structure represented by the following formula (1).

(In the above formula (1),
Ar is an aromatic ring,
One of U ¹ and U ² is the crystalline polyester block, and the other is the amorphous polyester block. ) The binder resin for toner according to claim 1, wherein the structure of the portion of the formula (1) other than U ¹ and U ² is line-symmetrical or point-symmetrical. The binder resin for toner according to claim 1 or 2, wherein Ar in the formula (1) is a benzene ring. The binder resin for toner according to any one of claims 1 to 3, wherein the acid value of at least one of the crystalline polyester block and the amorphous polyester block is in the range of more than 10.0 and 16.0 or less. A toner for static charge image development containing the binder resin for toner according to any one of claims 1 to 4. A static charge image developer containing the toner for static charge image development according to claim 5 and a carrier. It contains a crystalline polyester resin having an acid value in the range of 4.0 to 16.0, an amorphous polyester resin having an acid value in the range of 4.0 to 16.0, and an aromatic tetracarboxylic acid derivative. A method for producing a binder resin for toner that reacts a reaction raw material. The method for producing a binder resin for toner according to claim 7, wherein the aromatic tetracarboxylic acid derivative is an aromatic tetracarboxylic acid derivative in which all four carboxyl groups are directly substituted with an aromatic ring. The method for producing a binder resin for toner according to claim 7 or 8, wherein the reaction is performed without a solvent.