JP6095288B2 - Binder resin for toner - Google Patents

Description

  The present invention relates to a binder resin for toner used for developing a latent image formed in an electrophotographic method, an electrostatic recording method, an electrostatic printing method, etc., an electrophotographic toner containing the binder resin, and a method for producing the same About.

  Patent Document 1 discloses a toner that is granulated in an aqueous medium with the object of providing a toner that has excellent smearing properties, good low-temperature fixability, and a high-quality image. A first resin that is a polyester-based resin, and a second resin that is present outside the first resin and has a glass transition temperature (° C.) higher than the glass transition temperature (° C.) of the first resin. And a crystalline polyester resin, wherein the first resin contains a urea-modified polyester resin.

JP 2010-170151 A

  Unlike the pulverization method, the toner production by the suspension method does not require a great deal of energy to reduce the toner particle size. Unlike the emulsion aggregation method, toner particles having a target particle size can be formed in one step. As a result, the production process is simple and the process time can be shortened. On the other hand, when polyester is used as the binder resin, the particle size distribution is easy to spread during suspension, especially with a large amount of fine particles. It has a problem that the durability tends to decrease.

  Further, as one of the characteristics required for the printed matter, there is a case where the toner layer does not peel off when being folded. When printing with ink, it penetrates into the paper, so there is no problem of peeling even if it is folded. However, in the case of toner, a toner layer is formed on the paper, so the toner layer is broken and folded. Comes out white.

  The present invention uses a binder resin for toner that can be used for producing toner by a suspension method to obtain a toner having excellent durability, an electrophotographic toner containing the binder resin, and the binder resin. The present invention relates to a method for producing a toner having excellent bending resistance.

The present invention
[1] An alcohol component and a carboxylic acid component containing 5 to 25 mol of adipic acid with respect to 100 mol of the alcohol component in the presence of a tin catalyst and / or a titanium catalyst having no Sn-C bond Amorphous polyester (A) having a number average molecular weight of 1000 to 2400, a weight average molecular weight of 3000 to 6000, and a glass transition temperature of 38 to 48 ° C., and an aliphatic group having 6 to 12 carbon atoms, obtained by condensation polymerization with A crystalline polyester (B) obtained by condensation polymerization of an alcohol component containing 70 to 100 mol% of a diol and a carboxylic acid component containing 70 to 100 mol% of an aliphatic dicarboxylic acid compound having 8 to 14 carbon atoms; A toner binder resin, the amorphous polyester (A) having a turbidity of 22 to 30 measured when 30 parts by mass of the amorphous polyester is dissolved in 70 parts by mass of ethyl acetate. 150, a binder resin for toner,
[2] An electrophotographic toner comprising the toner binder resin according to [1], and [3] at least a toner binder resin according to [1], an isocyanate group in an organic solvent. A step of dissolving / dispersing the amorphous polyester (C) having colorant, a colorant, and a release agent, a compound that crosslinks or extends the binder resin in the obtained oil phase, and then the oil phase Are dispersed in an aqueous medium in which a fine particle dispersant is present to obtain an emulsified dispersion, the binder resin is crosslinked and / or elongated in the emulsified dispersion, and the resulting suspension is filtered. The manufacturing method of the toner for electrophotography including the process to carry out.

  The binder resin for toner of the present invention has an excellent effect that the durability of the toner is excellent. Furthermore, by the method of the present invention, a toner having excellent bending resistance can be obtained using the binder resin of the present invention.

  The binder resin for toner of the present invention contains an amorphous polyester (A) and a crystalline polyester (B) having a low molecular weight, a low glass transition temperature, and a specific turbidity.

  In the present invention, the crystallinity of a resin such as polyester is the ratio between the softening point and the highest endothermic peak temperature measured by a differential scanning calorimeter (DSC), that is, the crystal defined by “softening point / the highest endothermic peak temperature”. Expressed by sex index. Generally, when the crystallinity index exceeds 1.4, the resin is amorphous, and when it is less than 0.6, the crystallinity is low and there are many amorphous portions. In the present invention, “crystalline polyester” means a polyester having a crystallinity index of 0.6 to 1.4, preferably 0.9 to 1.2, more preferably 1.0 to 1.2, and “amorphous polyester” means a crystallinity index. Refers to polyesters with a value greater than 1.4 or less than 0.6.

  The “maximum endothermic peak temperature” refers to the temperature of the peak on the highest temperature side among the endothermic peaks observed under the conditions of the measurement methods described in the examples. If the maximum peak temperature is within 20 ° C of the softening point, the maximum peak temperature is the melting point of the crystalline resin (crystalline polyester), and the peak with a difference of more than 20 ° C from the softening point is amorphous polyester glass. The peak is attributed to the transition.

  The crystallinity of the resin can be adjusted by the types and ratios of the raw material monomers, production conditions (for example, reaction temperature, reaction time, cooling rate) and the like.

  The amorphous polyester (A) has a number average molecular weight of 1000 to 2400, a weight average molecular weight of 3000 to 6000, a glass transition temperature of 38 to 48 ° C., and 30 parts by mass of the amorphous polyester with 70 parts by mass of ethyl acetate. 30 to 150 measured when dissolved in a part.

  The amorphous polyester (A) having a moderately low molecular weight and a low glass transition temperature is effective in improving durability from the viewpoint of flexibility.

  Furthermore, the turbidity of the amorphous polyester (A) is adjusted within a predetermined range. When using polyester as a binder resin in the production of toner by the suspension method, the particle size distribution tends to be widened during suspension, and in particular, a large amount of fine particles with a particle size of 1 μm or less are generated, resulting in reduced durability. It's easy to do. In general, it is common knowledge of those skilled in the art that it is preferable that the turbidity of polyester is low, but in the present invention, surprisingly, by using a polyester having a certain degree of turbidity, a toner is obtained by a suspension method. Can produce a toner having a small content of fine particles and good durability. This mechanism is presumed as follows.

  The minute toner particles are considered to be suspended in the solvent in a very unstable state, and the turbidity component acts as an aggregating agent on the unstable minute particles, and the fine particles are aggregated to form. The coarse particles can be easily removed by filtration. When a general flocculant is used, the influence on the emulsified particles is large, but the turbidity component has a weak aggregation effect and can preferentially act on the unstable microparticles.

  The turbidity of the amorphous polyester (A) is measured when 30 parts by mass of amorphous polyester is dissolved in 70 parts by mass of ethyl acetate. If the turbidity is less than 22, Is insufficient. On the other hand, when the turbidity exceeds 150, particles composed of a high molecular weight component having a small number of terminal acid groups per molecule start to aggregate, leading to deterioration in yield and reduction in high temperature offset resistance.

  From the above viewpoint, the turbidity of the amorphous polyester (A) is 22 or more, preferably 40 or more, more preferably 45 or more. And it is 150 or less, Preferably it is 120 or less, More preferably, it is 70 or less. The turbidity of the amorphous polyester (A) is 22 to 150, preferably 40 to 120, more preferably 45 to 70.

  In the present invention, the complex of adipic acid and tin (adipic acid Sn) and the complex of adipic acid and titanium (adipic acid Ti) are effective as turbidity components that can act as the aggregating agent as described above.

  Therefore, the amorphous polyester (A) is a tin catalyst having no Sn—C bond comprising an alcohol component and a carboxylic acid component containing 5 to 25 mol of adipic acid per 100 mol of the alcohol component. And / or obtained by condensation polymerization in the presence of a titanium catalyst.

  As the alcohol component, from the viewpoint of the bending resistance of the printed matter and the durability of the toner, the formula (I):

(In the formula, R ¹ O and OR ¹ are oxyalkylene groups, R ¹ is an ethylene and / or propylene group, x and y indicate the number of added moles of alkylene oxide, and each is a positive number; The average value of the sum of y and y is preferably 1 to 16, more preferably 1 to 8, and even more preferably 1.5 to 4)
It is preferable to contain the alkylene oxide adduct of bisphenol A represented by these.

  The content of the alkylene oxide adduct of bisphenol A is 70 to 100 mol%, preferably 80 to 100 mol%, preferably 90 to 90 mol% in the alcohol component from the viewpoint of heat-resistant storage stability of the toner and bending resistance of the printed matter. 100 mol% is more preferable.

In formula (I), R ¹ of R ¹ O and OR ¹ may be mixed and the ethylene group and propylene group but alkylene oxide adduct of bisphenol A, propylene oxide adducts and ethylene oxide bisphenol A Adducts are preferred.

  Examples of propylene oxide adducts of bisphenol A represented by the formula (I) include polyoxypropylene adducts of 2,2-bis (4-hydroxyphenyl) propane and the like of the bisphenol A represented by the formula (I). Examples of the ethylene oxide adduct include a polyoxyethylene adduct of 2,2-bis (4-hydroxyphenyl) propane and the like.

  From the viewpoint of the bending resistance of the printed matter, at least a part of the alkylene oxide adduct of bisphenol A has a primary hydroxyl group. Among the hydroxyl groups of the alkylene oxide adduct of bisphenol A, the proportion of primary hydroxyl groups (also referred to as primary hydroxylation rate) is 60 to 100% from the viewpoint of heat-resistant storage stability of the toner and bending resistance of printed matter. Preferably, 80 to 100% is more preferable, 90 to 100% is more preferable, and 95 to 100% is still more preferable.

  Usually, even if an amorphous polyester having a low molecular weight and a low glass transition temperature is used, the resin itself is fragile, so that it does not lead to improvement in bending resistance. However, in the present invention, an amorphous material having a high primary hydroxylation rate is used. The combination of the polyester (A) and the amorphous polyester (C) having an isocyanate group described later can improve the bending resistance of the printed matter. The amorphous polyester (A) has a hydroxyl group (hereinafter also referred to as a primary hydroxyl group) bonded to a primary carbon atom (a carbon atom at the end of the carbon chain and bonded to only one other carbon atom). As a structural unit, it has a high reactivity with the polyester (B) having an isocyanate group, and the obtained reaction product contributes to the reaction in the high molecular weight reaction product. The amorphous polyester (A) that was not present is finely dispersed, and since the amorphous polyester (A) has a low glass transition temperature and a low molecular weight, it is considered that the printed material is also excellent in bending resistance. .

In the present invention, the primary hydroxylation rate is determined from ¹ H-NMR measurement described in Examples described later. The ratio is calculated according to the following formula using the ratio of the proton derived from the methylene group to which the primary hydroxyl group is bonded to the proton derived from the methine group to which the secondary hydroxyl group is bonded.
Primary hydroxylation rate (%) = [a / (a + 2 × b)] × 100 (1)
(Wherein, a is an integral value of a proton signal obtained from ¹ H-NMR measurement and a hydroxyl group is bonded to a methylene group, b is obtained from ¹ H-NMR measurement, and a hydroxyl group is bonded to a methine group. Is the integral value of the proton signal

When several kinds of alkylene oxide adducts of bisphenol A having different primary hydroxylation rates are used, a mixture in which all alkylene oxide adducts of bisphenol A are mixed can be obtained from ¹ H-NMR measurement as described above. The value obtained by multiplying the primary hydroxylation rate of each bisphenol compound obtained from ¹ H-NMR measurement by the mole fraction of each bisphenol A alkylene oxide adduct in the bisphenol A alkylene oxide adduct was added. The total value is the same.

  In the present invention, from the viewpoint of heat-resistant storage stability of the toner and bending resistance of the printed matter, an ethylene oxide adduct of bisphenol A (for example, a polyoxyethylene adduct of 2,2-bis (4-hydroxyphenyl) propane) is used. Is preferably a propylene oxide adduct of bisphenol A (for example, a polyoxypropylene adduct of 2,2-bis (4-hydroxyphenyl) propane).

  A propylene oxide adduct of bisphenol A having a primary hydroxyl group, such as a polyoxypropylene adduct of 2,2-bis (4-hydroxyphenyl) propane, is triphenylborane described in JP-A No. 2006-17954, Triphenylaluminum, tris (pentafluorophenyl) borane, and tris (pentafluorophenyl) aluminum, and more preferable by using a specific catalyst such as tris (pentafluorophenyl) borane and tris (pentafluorophenyl) aluminum Can be manufactured.

  The primary hydroxylation rate of the propylene oxide adduct of bisphenol A is preferably high, and is preferably 60% or more, more preferably 80% or more, from the viewpoint of improving the heat resistance storage stability of the toner and the bending resistance of the printed matter. Preferably it is 90% or more, More preferably, it is 95% or more, More preferably, it is 98% or more. The primary hydroxylation rate is adjusted by the ratio of the amount of the propylene oxide adduct of the compound having a bisphenol skeleton produced by the specific catalyst and the amount of the propylene oxide adduct of bisphenol A produced by a normal alkali catalyst. can do.

  In addition, all the hydroxyl groups which the ethylene oxide adduct of bisphenol A has are primary hydroxyl groups.

  Examples of other alcohol components include aliphatic diols having 2 to 12 carbon atoms; trivalent or higher alcohols such as glycerin, pentaerythritol, and trimethylolpropane.

  Examples of the aliphatic diol having 2 to 12 carbon atoms include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,2-pentanediol, 1,3-pentanediol, 1,4-pentanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1 , 8-octanediol, neopentyl glycol, 2,3-pentanediol, 2,4-pentanediol and the like.

  The carboxylic acid component of the amorphous polyester (A) contains adipic acid.

  The content of adipic acid is 5 mol or more, preferably 8 mol or more, more preferably 10 mol or more, from the viewpoint of the bending resistance of printed matter and the durability of the toner with respect to 100 mol of the alcohol component. . And from a heat resistant viewpoint, it is 25 mol or less, Preferably it is 20 mol or less, More preferably, it is 15 mol or less. Moreover, content of adipic acid is 5-25 mol with respect to 100 mol of alcohol components, Preferably it is 8-20 mol, More preferably, it is 10-15 mol.

  As the carboxylic acid component other than adipic acid, an aromatic dicarboxylic acid compound is preferable from the viewpoint of bending resistance of printed matter and durability of the toner.

  Examples of aromatic dicarboxylic acid compounds include aromatic dicarboxylic acids such as phthalic acid, isophthalic acid, and terephthalic acid, anhydrides of these acids, and alkyl (C1-3) esters. From the viewpoint of the bending resistance of the product and the durability of the toner, an isophthalic acid compound is preferable.

  In the present invention, carboxylic acids, acid anhydrides thereof, derivatives thereof such as alkyl (C1-3) esters, and the like are collectively referred to as carboxylic acid compounds. When the carboxylic acid compound is an alkyl ester, the carbon number described as the carbon number of the carboxylic acid compound does not include the carbon number of the alkyl group of the alkyl ester.

  The content of the isophthalic acid compound is preferably 30 to 70 mol%, more preferably 35 to 60 mol%, still more preferably 40 to 55 mol% in the carboxylic acid component.

  In addition to adipic acid and an aromatic dicarboxylic acid compound, the carboxylic acid component may contain an aliphatic dicarboxylic acid compound other than adipic acid or a trivalent or higher polyvalent carboxylic acid compound.

  Aliphatic dicarboxylic acid compounds other than adipic acid include oxalic acid, fumaric acid, malonic acid, maleic acid, citraconic acid, itaconic acid, glutaconic acid, succinic acid, sebacic acid, azelaic acid, their acid anhydrides, alkyl ( Examples thereof include esters having 1 to 6 carbon atoms.

  Examples of the trivalent or higher polyvalent carboxylic acid compounds include trimellitic acid, pyromellitic acid, acid anhydrides thereof, and alkyl (C1-6) esters.

  The carboxylic acid component preferably contains a trivalent or higher polyvalent carboxylic acid compound from the viewpoint of bending resistance of the printed matter, and the content of the trivalent or higher polyvalent carboxylic acid compound is the carboxylic acid component. Among them, 5 to 30 mol% is preferable, 10 to 25 mol% is more preferable, and 13 to 20 mol% is more preferable.

  A monovalent alcohol may be appropriately contained in the alcohol component, and a monovalent carboxylic acid compound may be appropriately contained in the carboxylic acid component from the viewpoint of adjusting the molecular weight of the resin.

  The molar ratio of the alcohol component and the carboxylic acid component (carboxylic acid component / alcohol component), which is the raw material monomer of the amorphous polyester (A), is preferably 0.5 to 1 from the viewpoint of bending resistance of the printed matter. Preferably it is 0.6-0.95, More preferably, it is 0.65-0.95.

  In the present invention, the polyester includes not only polyester but also modified resins thereof.

  Examples of the modified resin include urethane-modified polyester in which polyester is modified with a urethane bond, epoxy-modified polyester in which polyester is modified with an epoxy bond, and a hybrid resin having two or more kinds of resin components including a polyester component. .

  A hybrid resin having a polyester component and a vinyl resin component is prepared by a method of melt-kneading each resin in the presence of an initiator or the like, a method of dissolving and mixing each resin in a solvent, It may be produced by any method such as a method of polymerizing the raw material monomer mixture. Preferably, it is a resin obtained by the method of performing a polycondensation reaction and an addition polymerization reaction using the raw material monomer of the said polyester component, and the raw material monomer of a vinyl-type resin component (Unexamined-Japanese-Patent No. 7-98518).

Raw material monomers for vinyl resin components include styrene compounds such as styrene and α-methylstyrene; ethylenically unsaturated monoolefins such as ethylene and propylene; diolefins such as butadiene; halovinyls such as vinyl chloride; vinyl acetate Vinyl esters such as vinyl propionate; alkyl (carbon number 1 to 18) esters of (meth) acrylic acid; esters of ethylenic monocarboxylic acids such as dimethylaminoethyl (meth) acrylate; vinyl ethers such as vinyl methyl ether And vinylidene halides such as vinylidene chloride; N-vinyl compounds such as N-vinylpyrrolidone and the like. Styrene, butyl acrylate, 2-ethylhexyl acrylate, and methyl methacrylate are preferable, and the alkyl ester of styrene and / or (meth) acrylic acid is preferably contained in an amount of 50% by mass or more in the vinyl resin component. More preferably, it is 80-100 mass%.
In addition, when polymerizing the raw material monomer of a vinyl-type resin component, you may use a polymerization initiator, a crosslinking agent, etc. as needed.

  The mass ratio of the raw material monomer of the polyester component to the raw material monomer of the vinyl resin component (the raw material monomer of the polyester component / the raw material monomer of the vinyl resin component) is preferably 55/45 to from the viewpoint of forming a continuous phase with the polyester component. 95/5, more preferably 60/40 to 95/5, and 70/30 to 90/10 are even more preferable.

  The softening point of the amorphous polyester (A) is preferably 60 to 120 ° C, more preferably 65 to 100 ° C, from the viewpoints of low-temperature fixability of the toner, bending resistance of the printed matter, and heat-resistant storage stability of the toner. Preferably it is 68-88 degreeC. In the present invention, it is considered that a part of the amorphous polyester (A) is increased in molecular weight by the reaction with the polyester (B) having an isocyanate group.

  The glass transition temperature of the amorphous polyester (A) is 38 ° C. or higher, preferably 39 ° C. or higher, more preferably 40 ° C. or higher, from the viewpoint of bending resistance of printed matter and toner durability. From the viewpoint of bendability, it is 48 ° C. or lower, preferably 46 ° C. or lower, more preferably 44 ° C. or lower. Moreover, the glass transition temperature of amorphous polyester (A) is 38-48 degreeC, Preferably it is 39-46 degreeC, More preferably, it is 39-45 degreeC.

  The acid value of the amorphous polyester (A) is preferably 5 to 50 mgKOH / g, more preferably 10 to 40 mgKOH / g, and further preferably 15 to 35 mgKOH / g, from the viewpoint of low-temperature fixability of the toner.

  The hydroxyl value is 40 to 100 mgKOH / g and 45 to 90 mgKOH / g from the viewpoint of improving the reactivity with the polyester (B) having an isocyanate group and improving the bending resistance of the printed matter and the heat resistant storage stability of the toner. g is preferable, and 50 to 85 mgKOH / g is more preferable.

  The value of the hydroxyl value / acid value of the amorphous polyester (A) is increased from the viewpoint of improving the reactivity with the polyester (B) having an isocyanate group and improving the folding resistance of the printed matter and the heat resistant storage stability of the toner. 2-5 are preferred, 2.5-5 are more preferred, and 2.8-4.5 are even more preferred.

  The number average molecular weight of the amorphous polyester (A) is 1000 or more, preferably 1150 or more, more preferably 1300 or more, from the viewpoint of the bending resistance of the printed matter and the durability of the toner. Therefore, it is 2400 or less, preferably 2200 or less, more preferably 2000 or less. The number average molecular weight of the amorphous polyester (A) is 1000 to 2400, preferably 1150 to 2200, and more preferably 1300 to 2000.

  The weight average molecular weight of the amorphous polyester (A) is 3000 or more, preferably 3500 or more, more preferably 4000 or more, from the viewpoint of the bending resistance of the printed matter and the durability of the toner. To 6000 or less, preferably 5500 or less, more preferably 5000 or less. The weight average molecular weight of the amorphous polyester (A) is 3000 to 6000, preferably 3500 to 5500, and more preferably 4000 to 5000. The number average molecular weight and the weight average molecular weight of the amorphous polyester (A) are both values obtained by measuring the tetrahydrofuran soluble content.

  The softening point, glass transition temperature, acid value, hydroxyl value, number average molecular weight, and weight average molecular weight can be adjusted by adjusting the raw material monomer composition, polymerization initiator, molecular weight, catalyst amount, etc., or by selecting reaction conditions. .

  The crystalline polyester (B) is used from the viewpoint of improving printed matter bendability.

  From the viewpoint of low-temperature fixability of the toner, the crystalline polyester (B) contains an alcohol component containing 70 to 100 mol% of an aliphatic diol having 6 to 12 carbon atoms and an aliphatic dicarboxylic acid compound having 8 to 14 carbon atoms. It is obtained by polycondensation with a carboxylic acid component containing ˜100 mol%.

  The alcohol component which is a raw material monomer of the crystalline polyester (B) contains an aliphatic diol having 6 to 12 carbon atoms from the viewpoint of enhancing the crystallinity of the polyester.

  Examples of the aliphatic diol having 6 to 12 carbon atoms in the present invention include 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, Examples include 1,11-undecanediol, 1,12-dodecanediol, neopentyl glycol, and 1,4-butenediol. Among these, from the viewpoint of low-temperature fixability of the toner, the alcohol component preferably contains an aliphatic diol having 6 to 12 carbon atoms, and more preferably contains an aliphatic diol having 6 to 8 carbon atoms. From the viewpoint of crystallinity, it is preferable to contain an α, ω-linear alkanediol having 6 to 12 carbon atoms, and an α, ω-linear alkanediol having 6 to 8 carbon atoms. More preferably, it contains 1,6-hexanediol.

  The content of the aliphatic diol having 6 to 12 carbon atoms is 70 to 100 mol%, more preferably 80 to 100 mol% in the alcohol component, from the viewpoint of further improving the crystallinity of the crystalline polyester. 100 mol% is more preferable. The content of one kind of C6-12 α, ω-linear alkanediol in the alcohol component is preferably 70 mol% or more, more preferably 80 to 100 mol%, still more preferably 90 to 100 mol%. The content of 1,6-hexanediol in the alcohol component is preferably 70 mol% or more, more preferably 80 to 100 mol%, still more preferably 90 to 100 mol%.

  Examples of alcohol components other than aliphatic diols having 6 to 12 carbon atoms include carbon numbers such as ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, and 1,5-pentanediol. Includes aliphatic diols other than 6-12, polyoxypropylene adducts of 2,2-bis (4-hydroxyphenyl) propane, polyoxyethylene adducts of 2,2-bis (4-hydroxyphenyl) propane, etc. Aromatic diols such as alkylene oxide adducts of bisphenol A represented by the following formula (II); trivalent or higher alcohols such as glycerin, pentaerythritol, trimethylolpropane and the like. From the viewpoint of improving crystallinity, 1 1,5-pentanediol is preferred.

(Wherein R ² O and OR ² are oxyalkylene groups, R ² is an ethylene and / or propylene group, x and y indicate the number of moles of alkylene oxide added, each being a positive number, The average value of the sum of y and y is preferably 1 to 16, more preferably 1 to 8, and even more preferably 1.5 to 4)

  The carboxylic acid component of the crystalline polyester (B) contains at least an aliphatic dicarboxylic acid compound having 8 to 14 carbon atoms from the viewpoint of improving the low-temperature fixability of the toner and improving the bending resistance of the printed matter.

  Examples of the aliphatic dicarboxylic acid compound having 8 to 14 carbon atoms include suberic acid, azelaic acid, sebacic acid, 1,10-decanedicarboxylic acid and the like. Among these, an aliphatic dicarboxylic acid compound having 10 to 12 carbon atoms is preferable, and sebacic acid is more preferable from the viewpoint of improving the low-temperature fixability of the toner and improving the bending resistance of the printed matter.

  The content of the aliphatic dicarboxylic acid compound having 8 to 14 carbon atoms is from 70 to 100 mol%, preferably from 90 to 100 mol%, more preferably substantially from the viewpoint of low-temperature fixability of the toner. 100 mol%.

  Examples of the carboxylic acid component other than the aliphatic dicarboxylic acid compound having 8 to 14 carbon atoms include an aromatic dicarboxylic acid compound, an aliphatic dicarboxylic acid compound having 2 to 7 carbon atoms, and an aromatic polycarboxylic acid compound having 3 or more valences. Although it is mentioned, it is not particularly limited to these.

  Preferred examples of the aromatic dicarboxylic acid compound include aromatic dicarboxylic acids such as phthalic acid, isophthalic acid and terephthalic acid, anhydrides of these acids, and alkyl (C1 to C3) esters thereof.

  Examples of the aliphatic dicarboxylic acid compound having 2 to 7 carbon atoms include oxalic acid, malonic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, succinic acid, adipic acid and the like; anhydrides of these acids and the like And alkyl (carbon number 1 to 3) esters of these acids.

  Examples of the trivalent or higher polyvalent carboxylic acid compounds include 1,2,4-benzenetricarboxylic acid (trimellitic acid), 2,5,7-naphthalenetricarboxylic acid, pyromellitic acid and other aromatic carboxylic acids, and these Derivatives such as acid anhydrides and alkyl (C1-3) esters are exemplified.

  A monovalent alcohol may be appropriately contained in the alcohol component, and a monovalent carboxylic acid compound may be appropriately contained in the carboxylic acid component from the viewpoint of adjusting the molecular weight of the resin.

  The softening point of the crystalline polyester (B) is preferably 40 to 120 ° C., more preferably 50 to 100 ° C., from the viewpoint of improving the low temperature fixability and durability of the toner and improving the bending resistance of the printed matter. 60-80 degreeC is further more preferable.

  The melting point of the crystalline polyester (B) is preferably from 40 to 120 ° C., more preferably from 50 to 100 ° C., from the viewpoint of improving the low-temperature fixability and durability of the toner and improving the bending resistance of the printed matter. Preferably it is 60-80 degreeC.

  The number average molecular weight of the crystalline polyester (B) is preferably 1000 or more, more preferably 1500 or more, from the viewpoint of improving the low-temperature fixability and durability of the toner and improving the bending resistance of the printed matter. However, considering the productivity of the crystalline polyester, the number average molecular weight is preferably 6000 or less, more preferably 5000 or less, and further preferably 4500 or less. From the above viewpoint, the number average molecular weight of the crystalline polyester (B) is preferably 1000 to 6000, more preferably 1000 to 5000, and further preferably 1500 to 4500.

  The weight average molecular weight is also preferably 3,000 to 100,000, more preferably 5,000 to 50,000, still more preferably 5,000 to 30,000, and even more preferably 8,000 to 20,000, from the same viewpoint as the number average molecular weight.

  In the present invention, the number average molecular weight and the weight average molecular weight of the crystalline polyester are both values obtained by measuring the chloroform-soluble content. The number average molecular weight and the weight average molecular weight can be increased by increasing the reaction temperature of polycondensation, increasing the amount of catalyst, using a cocatalyst together, or lengthening the reaction time.

  The molar ratio of the alcohol component to the carboxylic acid component (carboxylic acid component / alcohol component), which is the raw material monomer of the crystalline polyester (B), is mainly composed of a carboxy group at the end of the polyester, and the viewpoint of improving the low-temperature fixability of the toner Therefore, it is preferably 1.03 to 1.20, more preferably 1.03 to 1.15, still more preferably 1.04 to 1.12, and still more preferably 1.05 to 1.1.

  In the production of the amorphous polyester (A) and the crystalline polyester (B), the polycondensation reaction between the alcohol component and the carboxylic acid component is carried out in an inert gas atmosphere as necessary. It can be produced by condensation polymerization at a temperature of about 180 to 250 ° C. in the presence of a cocatalyst, a polymerization inhibitor and the like. Conventionally, dibutyltin oxide or the like has been widely used as an esterification catalyst, but the condensation polymerization of the alcohol component and the carboxylic acid component of the amorphous polyester (A) forms a complex of adipic acid and tin or titanium. As a catalyst which is easy to do, it carries out in presence of the tin catalyst and / or titanium catalyst which do not have a Sn-C bond. Further, from the viewpoint of reactivity, the polycondensation of the alcohol component and the carboxylic acid component of the crystalline polyester (B) may also be performed in the presence of a tin catalyst and / or a titanium catalyst having no Sn-C bond. preferable.

  As a tin catalyst having no Sn-C bond, a tin (II) compound having no Sn-C bond and having a Sn-O bond, Sn-X (X represents a halogen atom) bond is used. Preferred are tin (II) compounds having Sn—O bonds, and more preferred are tin (II) compounds having Sn—O bonds.

Examples of tin (II) compounds having Sn-O bonds include tin (II) oxalate, tin (II) acetate, tin (II) octoate, tin (II) 2-ethylhexanoate, and tin (II) laurate. , Tin (II) carboxylate having a carboxylic acid group having 2 to 28 carbon atoms such as tin (II) stearate, tin (II) oleate; octyloxy tin (II), lauroxy tin (II), stearoxy tin (II) ), Alkoxytin (II) having an alkoxy group having 2 to 28 carbon atoms such as oleyloxytin (II); tin (II) oxide; tin (II) sulfate, Sn—X (X represents a halogen atom) Examples of the tin (II) compound having a bond include tin (II) halides such as tin (II) chloride and tin (II) bromide, and among these, from the standpoint of charge rising effect and catalytic ability , (R ³ COO) ₂ Sn (where R ³ represents an alkyl group or alkenyl group having 5 to 19 carbon atoms), (R ⁴ O) ₂ Sn (where R ⁴ Is C 6-20 alk Alkoxy tin (II) and tin oxide represented by SnO (II) is preferably represented by a group or an alkenyl group), (R ³ COO) fatty tin represented by ₂ Sn (II) and tin oxide ( II) is more preferable, tin (II) octoate, tin (II) 2-ethylhexanoate, tin (II) stearate and tin (II) oxide are more preferable, tin (II) 2-ethylhexanoate is more Further preferred.

Examples of the titanium catalyst having no Sn—C bond include titanium diisopropylate bistriethanolamate [Ti (C ₆ H ₁₄ O ₃ N) ₂ (C ₃ H ₇ O) ₂ ], titanium diisopropylate bisdiethanolamidate. [Ti (C ₄ H ₁₀ O ₂ N) ₂ (C ₃ H ₇ O) ₂ ], titanium dipentylate bistriethanolaminate [Ti (C ₆ H ₁₄ O ₃ N) ₂ (C ₅ H ₁₁ O) _2], titanium di ethylate bis triethanolaminate _{[Ti (C 6 H 14 O 3} N) 2 (C 2 H 5 O) 2 ], titanium dihydroxy octylate bis triethanolaminate [Ti (C ₆ H ₁₄ O ₃ N) ₂ (OHC ₈ H ₁₆ O) ₂ ], titanium distearate bistriethanolamate [Ti (C ₆ H ₁₄ O ₃ N) ₂ (C ₁₈ H ₃₇ O) ₂ ], titanium triisopropylate triethanolamine Nate [Ti (C ₆ H _{1 4} O ₃ N) (C ₃ H ₇ O) ₃ ], titanium monopropylate tris (triethanolaminate) [Ti (C ₆ H ₁₄ O ₃ N) ₃ (C ₃ H ₇ O)] and the like. Of these, titanium diisopropylate bistriethanolamate, titanium diisopropylate bisdiethanolamate and titanium dipentylate bistriethanolamate are preferred, and these are also available as commercial products of Matsumoto Trading Co., Ltd. .

Specific examples of other preferable titanium catalysts include tetra-n-butyl titanate [Ti (C ₄ H ₉ O) ₄ ], tetrapropyl titanate [Ti (C ₃ H ₇ O) ₄ ], tetrastearyl titanate [Ti ( C ₁₈ H ₃₇ O) ₄ ], tetramyristyl titanate [Ti (C ₁₄ H ₂₉ O) ₄ ], tetraoctyl titanate [Ti (C ₈ H ₁₇ O) ₄ ], dioctyl dihydroxyoctyl titanate [Ti (C ₈ H ₁₇ O) ₂ (OHC ₈ H ₁₆ O) ₂ ], dimyristyl dioctyl titanate [Ti (C ₁₄ H ₂₉ O) ₂ (C ₈ H ₁₇ O) ₂ ] and the like. Among these, tetrastearyl titanate, tetra Myristyl titanate, tetraoctyl titanate and dioctyl dihydroxy octyl titanate are preferred. These can be obtained, for example, by reacting a titanium halide with a corresponding alcohol, or can be obtained as a commercial product such as Nisso.

  The amount of the tin catalyst or titanium catalyst having no Sn-C bond used in the amorphous polyester (A) is usually 0.01 to 2.0 parts by mass with respect to 100 parts by mass of the total amount of the alcohol component and the carboxylic acid component. Is preferable, 0.1-1.5 mass parts is more preferable, 0.2-1.0 mass part is further more preferable.

  The amount of the tin catalyst or titanium catalyst that does not have Sn-C bond used for the crystalline polyester (B) is preferably 0.01 to 2.0 parts by mass with respect to 100 parts by mass of the total amount of the alcohol component and the carboxylic acid component, 0.1-1.5 mass parts is more preferable, and 0.2-1.0 mass part is further more preferable. Here, the amount of the catalyst present means the total amount of the catalyst subjected to the condensation polymerization reaction.

  In the present invention, a pyrogallol compound having a benzene ring in which hydrogen atoms bonded to three adjacent carbon atoms are substituted with a hydroxyl group may be used together with an esterification catalyst.

  Examples of pyrogallol compounds include pyrogallol, gallic acid, gallic acid esters, 2,3,4-trihydroxybenzophenone, benzophenone derivatives such as 2,2 ', 3,4-tetrahydroxybenzophenone, epigallocatechin, epigallocatechin gallate, etc. Among these, from the viewpoint of storage stability of the obtained toner, the formula (III):

Wherein R ^{5 to} R ⁷ are each independently a hydrogen atom or —COOR ⁸ (R ⁸ is a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, preferably an alkyl group or carbon having 1 to 12 carbon atoms. Represents an alkenyl group of 2 to 12)
The compound represented by these is preferable. In the formula, the hydrocarbon group of R ⁸ preferably has 1 to 8 carbon atoms, and more preferably 1 to 4 carbon atoms from the viewpoint of reaction activity. Among the compounds represented by the formula (III), a compound in which R ⁵ and R ⁷ are hydrogen atoms and R ⁶ is a hydrogen atom or —COOR ⁸ is more preferable. Specific examples include pyrogallol (R ^{5 to} R ⁷ : hydrogen atom), gallic acid (R ⁵ and R ⁷ : hydrogen atom, R ⁶ : —COOH), ethyl gallate (R ⁵ and R ⁷ : hydrogen atom, R ^6: -COOC ₂ H _5), propyl gallate (R ⁵ and R ^7: a hydrogen _{^{atom, R 6: -COOC 3 H 7}} ), butyl gallate (R ⁵ and R ^7: a hydrogen atom, R ^6: -COOC ₄ H _9), octyl gallate (R ⁵ and R ^7: a hydrogen _{^{atom, R 6: -COOC 8 H 17}} ), lauryl gallate (R ⁵ and R ^7: a hydrogen _{^{atom, R 6: -COOC 12 H 25}} ) And gallic acid esters. From the viewpoint of toner storage stability, gallic acid and gallic acid esters are preferred.

  The amount of the pyrogallol compound used in the polycondensation reaction is usually preferably 0.001 to 1.0 part by mass, and 0.005 to 0.4 part by mass, from the viewpoint of the storage stability of the toner, with respect to 100 parts by mass of the total amount of the alcohol component and the carboxylic acid component. More preferred is 0.01 to 0.2 part by mass.

  The pyrogallol compound is considered to function as a promoter for the esterification catalyst. As an esterification catalyst used with a pyrogallol compound, the tin catalyst and titanium catalyst which do not have a Sn-C bond are preferable.

  The mass ratio of the pyrogallol compound to the esterification catalyst (pyrogallol compound / esterification catalyst) is preferably from 0.01 to 0.5, more preferably from 0.03 to 0.3, and even more preferably from 0.05 to 0.2, from the viewpoint of storage stability of the toner.

  In the present invention, the polycondensation reaction of the alcohol component and the carboxylic acid component may be performed in one step, but the production of the amorphous polyester (A) may be performed in two steps from the viewpoint of adjusting turbidity. preferable.

  A complex of an aromatic dicarboxylic acid compound and tin or titanium is also a component of turbidity like the adipic acid Sn and the adipic acid Ti, but it has been confirmed that there is almost no action as a flocculant. Therefore, from the viewpoint of suppressing the formation of a complex of an aromatic dicarboxylic acid compound and tin or titanium, it is preferable to react adipic acid after reacting the aromatic dicarboxylic acid compound. That is, when an aromatic dicarboxylic acid compound is used, the amorphous polyester (A) is obtained by subjecting the alcohol component and adipine to the step (a) of condensing the alcohol component and the aromatic dicarboxylic acid compound and the step (a). Amorphous polyesters obtained by a method comprising the step (b) of condensation polymerization with an acid are preferred.

  In the step (a), when the turbidity of the polyester produced by the reaction between the alcohol and the aromatic dicarboxylic acid compound in the presence of a tin catalyst or a titanium catalyst having no Sn—C bond is high, for example, When isophthalic acid is used as the aromatic dicarboxylic acid compound, isophthalic acid forms a complex with tin or titanium (isophthalic acid Sn or isophthalic acid Ti). Since the isophthalic acid complex is more stable than the adipic acid complex, it is not decomposed in the subsequent reaction and maintains the state of the complex. As described above, the complex of isophthalic acid does not exhibit the aggregation effect like the complex of adipic acid and inhibits the effect of the complex of adipic acid when it is present in a large amount. Therefore, it is formed before step (b). The lower turbidity of the polyester is preferable.

  Therefore, the turbidity of the polyester produced before the step (b) is preferably 0 to 25, more preferably 0 to 20, more preferably 0 to 15 from the viewpoint of the bending resistance of the printed matter and the durability of the toner. preferable.

As a method of suppressing the formation of a complex of an aromatic dicarboxylic acid compound and tin or titanium and reducing turbidity,
(1) Avoid mixing oxygen into the reaction system (normally prevented by introducing nitrogen, but the oxygen mixed when the aromatic dicarboxylic acid compound is charged will affect the reaction system. It is effective to charge the catalyst after substituting with nitrogen and introducing nitrogen)
(2) Use a co-catalyst such as gallic acid (by using the co-catalyst, the complex of the aromatic dicarboxylic acid compound and tin can be made more stable than the complex of the aromatic dicarboxylic acid compound and tin. In this case, the formation of adipic acid complex is also suppressed, and therefore, when this method is used, the Sn-C bond is not again present after the addition of adipic acid. Addition of tin catalyst or titanium catalyst)
(3) The reaction between the alcohol component and the aromatic dicarboxylic acid compound is carried out in the presence of a tin catalyst having a Sn—C bond such as dibutyltin oxide (also in this case, it has a Sn—C bond after addition of adipic acid). No tin catalyst or titanium catalyst required)
Etc. Therefore, the condensation polymerization of the alcohol component and adipic acid in the step (b) is preferably performed in the presence of a tin catalyst and / or a titanium catalyst having no Sn—C bond. In the step (b), the amount of the tin catalyst or titanium catalyst having no Sn—C bond, and the total amount of both used in combination are determined from the viewpoint of the bending resistance of the printed matter and the durability of the toner. Therefore, 3 to 25 parts by mass is preferable and 5 to 20 parts by mass is more preferable with respect to 100 parts by mass of adipic acid.

  Usually, when the reaction is carried out in two or more stages, after the reaction in the first stage, in the present invention, after the reaction of the aromatic dicarboxylic acid compound and the alcohol, until the end by the reduced pressure reaction or the like (until the acid value becomes 3 mgKOH / g or less). ) It is preferable to carry out the following reaction after the reaction. However, when the reaction under reduced pressure is performed, the turbidity after the addition of adipic acid tends to be too high, and extra steps such as filtration and holding at 220 ° C. or higher are required. Furthermore, even if the turbidity is within an appropriate range, if the acid value is too high, the effect is weakened.

  Accordingly, the acid value of the polyester produced immediately before step (b) is preferably 5 to 18 mgKOH / g, more preferably 7 to 16 mgKOH / g, from the viewpoint of the bending resistance of the printed matter and the durability of the toner. More preferred is ˜15 mg KOH / g.

  If the resulting amorphous polyester (A) has too high turbidity, a part of the amorphous polyester (A) is dissolved in a solvent and filtered to prepare a turbidity of 0. It can be adjusted to the target turbidity by mixing with the one before filtration. Moreover, when the turbidity by adipic acid Sn and adipic acid Ti is too high, a complex can be decomposed | disassembled and reduced by hold | maintaining polyester at the temperature of 220 degreeC or more.

  The mass ratio of the amorphous polyester (A) to the crystalline polyester (B) is preferably 95/5 to 60/40, more preferably 90/10 to 70/30, from the viewpoint of bendability.

  The toner containing the binder resin of the present invention is excellent in toner durability.

  The binder resin may contain a resin other than the binder resin of the present invention as long as the effect of the present invention is not impaired, but the content of the binder resin of the present invention is the chroma of the printed matter. 80% by mass or more, preferably 90% by mass in the binder resin, from the viewpoint of improving the low-temperature fixing property, heat-resistant storage stability and durability of the toner, and from the viewpoint of improving the bending resistance of the printed matter. The above is more preferable, 95% by mass or more is further preferable, and substantially 100% by mass is even more preferable. Examples of the other binder resins include polyesters other than the polyester used in the binder resin of the present invention, vinyl resins, epoxy resins, polycarbonates, polyurethanes, and the like.

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

  As the colorant, all of dyes and pigments used as toner colorants can be used, such as carbon black, phthalocyanine blue, permanent brown FG, brilliant first scarlet, pigment green B, rhodamine-B base, Solvent Red 49, Solvent Red 146, Solvent Blue 35, Quinacridone, Carmine 6B, Isoindoline, Disazo Yellow and the like can be used, and the toner of the present invention may be either black toner or color toner. The content of the colorant in the toner is preferably 1 to 20 parts by weight, more preferably 2 to 10 parts by weight with respect to 100 parts by weight of the binder resin, from the viewpoint of improving the print density and fixability of the toner. 3 to 8 parts by mass is more preferable.

  As the release agent, low molecular weight polypropylene, low molecular weight polyethylene, low molecular weight polypropylene polyethylene copolymer, aliphatic hydrocarbon wax such as microcrystalline wax, paraffin wax, Fischer-Tropsch wax and oxides thereof, carnauba wax, Examples thereof include montan wax, sazol wax and their deoxidized wax, ester waxes such as fatty acid ester wax, fatty acid amides, fatty acids, higher alcohols, fatty acid metal salts and the like. These may be used alone or in admixture of two or more.

  The melting point of the release agent is preferably 60 to 160 ° C., more preferably 60 to 150 ° C., from the viewpoint of improving the low-temperature fixability and high-temperature offset resistance of the toner.

  The content of the release agent is preferably 10 parts by mass or less and more preferably 7 parts by mass or less with respect to 100 parts by mass of the binder resin from the viewpoint of improving the heat resistant storage stability of the toner. Further, from the viewpoint of improving the low-temperature fixability and high-temperature offset resistance of the toner, it is preferably 2 parts by mass or more, more preferably 3 parts by mass or more. Moreover, 2-10 mass parts is preferable and, as for content of a mold release agent, 3-7 mass parts is more preferable.

  As the charge control agent, either a negative charge control agent or a positive charge control agent can be used.

  Examples of the negatively chargeable charge control agent include metal-containing azo dyes such as `` Bontron S-28 '' (manufactured by Orient Chemical Co., Ltd.), `` T-77 '' (manufactured by Hodogaya Chemical Co., Ltd.), `` Bontron S-34 '' ( (Orient Chemical Co., Ltd.), “Eisenspiron Black TRH” (Hodogaya Chemical Co., Ltd.), etc .; copper phthalocyanine dyes; metal complexes of alkyl derivatives of salicylic acid, such as “Bontron E-81”, “Bontron E-84” , “Bontron E-304” (manufactured by Orient Chemical Co., Ltd.), etc .; nitroimidazole derivatives; boron benzylate complexes, such as “LR-147” (manufactured by Nippon Carlit), etc .; Bontron F-21, Bontron E-89 (above, Orient Chemical Co., Ltd.), T-8 (Hodogaya Chemical Co., Ltd.), FCA-2521NJ, FCA-2508N (above, Fujikura Kasei Co., Ltd.).

  Examples of positively chargeable charge control agents include nigrosine dyes such as `` Bontron N-01 '', `` Bontron N-04 '', `` Bontron N-07 '' (above, manufactured by Orient Chemical Industries), `` CHUO CCA-3 '' ( Chuo Gosei Co., Ltd.), etc .; Triphenylmethane dyes containing tertiary amines as side chains; Quaternary ammonium salt compounds such as “Bontron P-51” (Orient Chemical Industries), “TP-415” And Tetsuya Chemical Industry Co., Ltd.), cetyltrimethylammonium bromide, “COPY CHARGE PXVP435” (manufactured by Clariant), and the like.

  The content of the charge control agent in the toner is preferably 0.5 to 5 parts by mass and more preferably 1 to 3 parts by mass with respect to 100 parts by mass of the binder resin from the viewpoint of improving the charging stability of the toner.

  The toner may further contain additives such as a magnetic powder, a fluidity improver, a conductivity modifier, a reinforcing filler such as a fibrous substance, an antioxidant, and a cleaning property improver as appropriate. Good.

  The electrophotographic toner containing the binder resin of the present invention dissolves / disperses at least the binder resin, the amorphous polyester (C) having an isocyanate group, the colorant, and the release agent in an organic solvent. A step of dissolving a compound that crosslinks or extends the binder resin in the obtained oil phase, and then dispersing the oil phase in an aqueous medium containing a fine particle dispersant to obtain an emulsified dispersion, It is preferable that the binder resin is produced by a method including a step of subjecting the binder resin to a crosslinking reaction and / or an extension reaction in an emulsified dispersion, and a step of filtering the obtained suspension.

  In the above method, from the viewpoint of increasing the molecular weight of the amorphous polyester (A) and improving the bending resistance of the printed matter and the durability of the toner, the amorphous polyester (A) is used as a crosslinking agent as a binder resin. An amorphous polyester (C) having an isocyanate group that acts is used.

  The amorphous polyester (C) having an isocyanate group can be obtained by reacting an amorphous polyester having a hydroxyl group (also referred to as a hydroxyl group-containing polyester) with one isocyanate group of isophorone diisocyanate to form a urethane bond. it can. The hydroxyl group-containing polyester used for the reaction with isophorone diisocyanate is an alkylene oxide adduct of bisphenol A represented by the above formula (II) from the viewpoint of improving heat storage stability and durability of the toner and bending resistance of printed matter. Preferred is an amorphous polyester obtained by condensation polymerization of an alcohol component and a carboxylic acid component. The content of the alkylene oxide adduct of bisphenol A represented by the formula (II) is preferably 60 to 100 mol%, more preferably 70 to 100 mol% in the alcohol component, from the viewpoint of reactivity with isophorone diisocyanate. Examples of the carboxylic acid component include the aforementioned aliphatic dicarboxylic acid compounds and aromatic dicarboxylic acid compounds.

  From the viewpoint of reactivity with isophorone diisocyanate, the hydroxyl value of the hydroxyl group-containing polyester subjected to the reaction with isophorone diisocyanate is preferably 10 to 100 mgKOH / g, more preferably 20 to 80 mgKOH / g, and even more preferably 20 to 50 mgKOH / g. .

  The number average molecular weight of the hydroxyl group-containing polyester used for the reaction with isophorone diisocyanate is preferably 1500 to 5000, more preferably 2000 to 4000, and even more preferably 2500 to 3500, from the viewpoint of heat-resistant storage stability of the toner. The weight average molecular weight is preferably 5000 to 15000, more preferably 5000 to 10000, and further preferably 6000 to 9000, from the viewpoint of heat-resistant storage stability of the toner. The number average molecular weight and the weight average molecular weight of the hydroxyl group-containing polyester used as the raw material for the amorphous polyester (C) having an isocyanate group are values obtained by measuring the tetrahydrofuran-soluble content.

  When producing the amorphous polyester (C) having an isocyanate group, the amount of isophorone diisocyanate to be reacted with the hydroxyl group-containing polyester is preferably 1 to 100 parts by mass with respect to 100 parts by mass of the hydroxyl group-containing polyester. -50 mass parts is more preferable.

  In producing the amorphous polyester (C) having an isocyanate group, the reaction temperature between the hydroxyl group-containing polyester and isophorone diisocyanate is preferably about 40 to 160 ° C., and the reaction time is preferably about 2 to 10 hours.

  The introduction of the isocyanate group can be confirmed by NMR or IR.

  The mass ratio of the amorphous polyester (A) and the amorphous polyester (C) contained in the binder resin is preferably 95/5 to 60/40 from the viewpoint of the bending resistance of the printed matter and the durability of the toner. 90/10 to 70/30 are more preferable.

  The binder resin, amorphous polyester (C), colorant, release agent and additives used as necessary may be mixed when forming the dispersion in the aqueous medium, It is preferable to mix uniformly by kneading and then mix with an organic solvent. In the present invention, raw materials other than the binder resin such as the colorant, the release agent, and the additive and the amorphous polyester (C) are always mixed when the particles are formed in the aqueous medium. It is not necessary and may be added after the particles are formed. For example, after forming particles not containing a colorant, the colorant can be added by a known dyeing method.

  Examples of the kneader used for melt kneading include a hermetic kneader, a uniaxial or biaxial extruder, and an open roll type kneader. The temperature (heating set temperature) of the kneader at the time of melt kneading is preferably 80 to 180 ° C, more preferably 80 to 160 ° C.

  As an organic solvent, the crystalline polyester (B) is completely dissolved at a high temperature to form a uniform solution. On the other hand, when cooled to a low temperature, the crystalline polyester (B) is phase-separated to form an opaque heterogeneous solution. Those that do are preferred. Specifically, based on the melting point (Tm) of the crystalline polyester resin, if it exhibits non-solvent characteristics at temperatures below (Tm-40) ° C., and exhibits good solvent characteristics at temperatures higher than that, Well, specific examples include toluene, ethyl acetate, butyl acetate, methyl ethyl ketone, methyl isobutyl ketone and the like, and these can be used alone or in combination of two or more.

  The amount of the organic solvent used is preferably 100 parts by mass or more, and more preferably 100 to 1000 parts by mass with respect to 100 parts by mass of the binder resin.

  A raw material such as a binder resin is mixed with an organic solvent, stirred under heating to dissolve the raw material, and then cooled and dispersed to a temperature at which the crystalline polyester (B) is phase-separated. .

  The heating temperature is not particularly limited as long as it is a temperature at which the crystalline polyester (B) is dissolved, and is preferably 40 to 90 ° C, more preferably 50 to 80 ° C, although it varies depending on the type of organic solvent.

  From the viewpoint of solubility, it is preferable to hold for about 0.5 to 10 hours under heating.

  A compound that crosslinks or extends the binder resin is dissolved in the oil phase in which the raw materials are dispersed.

  Examples of the compound that crosslinks or extends the binder resin include compounds having an active hydrogen group, and representative examples thereof include amines.

  Examples of amines include diamine compounds, triamine or higher polyamine compounds, amino alcohol compounds, amino mercaptan compounds, amino acid compounds, and compounds in which these amino groups are blocked.

  Examples of diamine compounds include aromatic diamines (phenylenediamine, diethyltoluenediamine, 4,4′-diaminodiphenylmethane, etc.); alicyclic diamines (4,4′-diamino-3,3′-dimethyldicyclohexylmethane, diaminecyclohexane, Isophoronediamine, etc.); aliphatic diamines (ethylenediamine, tetramethylenediamine, hexamethylenediamine, etc.) and the like.

  Examples of the trivalent or higher polyamine compound include diethylenetriamine and triethylenetetramine.

  Examples of amino alcohol compounds include ethanolamine and hydroxyethylaniline.

  Examples of amino mercaptan compounds include aminoethyl mercaptan and aminopropyl mercaptan.

  Examples of amino acid compounds include aminopropionic acid and aminocaproic acid.

  Examples of the compounds in which these amino groups are blocked include ketimine compounds and oxazoline compounds obtained from the amines and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.). Among these amines, a ketimine compound is preferable.

  The amount of the compound that crosslinks or extends the binder resin is preferably 30 to 80 parts by mass and more preferably 30 to 70 parts by mass with respect to 100 parts by mass of the crystalline polyester (B).

  The oil phase and a compound that crosslinks or extends the binder resin are mixed and stirred to dissolve the compound, and then dispersed in an aqueous medium in which a fine particle dispersant is present to obtain an emulsified dispersion.

  The aqueous medium preferably contains 50% by mass or more, preferably 70% by mass or more, more preferably 90% by mass or more, and still more preferably 99% by mass or more. Water alone may be used, but a solvent miscible with water may be used in combination. Solvents miscible with water include alcohols (methanol, isopropanol, ethylene glycol, etc.), dimethylformamide, tetrahydrofuran, cellosolve (registered trademark) (methylcellosolve, etc.), lower ketones (acetone, methyl ethyl ketone, etc.), etc. It is done.

  Fine particle dispersants include anionic surfactants such as alkane sulfonates, alkylbenzene sulfonates, α-olefin sulfonates, phosphate esters; alkylamine salts, aminoalcohol fatty acid derivatives, polyamine fatty acid derivatives, imidazoline, etc. Cationic surfactants such as amine salt types and quaternary ammonium salt types such as alkyltrimethylammonium salts, dialkyldimethylammonium salts, alkyldimethylbenzylammonium salts, pyridinium salts, alkylisoquinolinium salts, benzethonium chloride; fatty acids Nonionic surfactants such as amide derivatives and polyhydric alcohol derivatives; amphoteric interfaces such as alanine, dodecyldi (aminoethyl) glycine, di (octylaminoethyl) glycine and N-alkyl-N, N-dimethylammonium betaine Gender, and the like.

  The fine particle dispersant can be left on the surface of the toner particles, but it is preferable to wash and remove from the charged surface of the toner after the reaction.

  The amount of the dispersant is preferably 0.5 to 10 parts by mass and more preferably 1 to 5 parts by mass with respect to 100 parts by mass of the binder resin.

  The dispersion method is not particularly limited, and known equipment such as a low-speed shear method, a high-speed shear method, a friction method, a high-pressure jet method, and an ultrasonic wave can be applied. Considering the particle size of the dispersion, the high-speed shearing method is preferable.

  When a high-speed shearing disperser is used, the rotational speed is not particularly limited, but is usually 1000 to 30000 r / min, preferably 5000 to 20000 r / min. The dispersion time is not particularly limited, but in the case of a batch method, it is usually 0.1 to 60 minutes. The temperature during dispersion is usually 0 to 80 ° C. (under pressure), preferably 10 to 40 ° C.

  The obtained emulsified dispersion is subjected to elongation and / or crosslinking reaction.

  The elongation and / or cross-linking reaction time is selected depending on the reactivity depending on the combination of the amorphous polyester (A) and the compound that extends and / or accelerates the binder resin, and is usually 10 minutes to 40 hours, preferably 30 minutes. ~ 24 hours. The reaction temperature is preferably 40 to 90 ° C, more preferably 43 to 70 ° C.

  The removal of the organic solvent may be performed either before or after the crosslinking and / or elongation reaction, but is preferably performed before the crosslinking and / or elongation reaction from the viewpoint of improving printed matter bendability. In order to remove the organic solvent, it is possible to employ a method in which the temperature of the entire system is gradually raised and the organic solvent in the droplets is completely removed by evaporation.

  In the present invention, the turbidity component of the amorphous polyester (A) acts as a flocculant, and coarse particles produced by agglomeration of fine particles are contained in the obtained suspension. The coarse particles usually have a particle size of about 500 to 2000 μm and can be easily removed by filtration.

  A wire mesh or the like can be used for filtration of the suspension. The opening of the filter is preferably 50 to 400 μm, more preferably 70 to 200 μm, from the viewpoint of removing coarse particles and manufacturability.

  The toner can be obtained by subjecting the filtrate to a washing step, a drying step and the like as appropriate.

  In the washing step, it is preferable to use an acid in order to remove metal ions on the toner surface in order to ensure sufficient charging characteristics and reliability as the toner. Moreover, it is preferable to perform washing several times.

  In the drying step, any method such as a vibration type fluidized drying method, a spray drying method, a freeze drying method, a flash jet method, or the like can be employed.

  The toner production method of the present invention preferably further includes a step of mixing the obtained toner particles (toner base particles) with an external additive.

  Examples of the external additive include inorganic fine particles such as silica, alumina, titania, zirconia, tin oxide, and zinc oxide, and organic fine particles such as melamine resin fine particles and polytetrafluoroethylene resin fine particles. Among these, silica is preferable, and silica having a low specific gravity is more preferable from the viewpoint of preventing embedding.

  Silica is preferably hydrophobic silica that has been subjected to a hydrophobic treatment, from the viewpoint of toner transferability.

  Examples of the hydrophobizing agent for hydrophobizing the surface of silica particles include organochlorosilane, organoalkoxysilane, organodisilazane, cyclic organopolysilazane, linear organopolysiloxane, and the like. Examples thereof include silazane (HMDS), dimethyldichlorosilane (DMDS), silicone oil, octyltriethoxysilane (OTES), methyltriethoxysilane, and the like. Among these, hexamethyldisilazane is preferable.

  The average particle diameter of the external additive is preferably from 10 to 250 nm, more preferably from 10 to 200 nm, and even more preferably from 15 to 150 nm, from the viewpoint of chargeability, fluidity, and transferability of the toner.

  The content of the external additive is preferably 0.05 to 5 parts by mass, more preferably 0.1 to 3 parts by mass with respect to 100 parts by mass of the toner base particles, from the viewpoints of toner chargeability, fluidity, and transferability. And more preferably 0.3 to 3 parts by mass.

  For mixing the toner base particles and the external additive, it is preferable to use a mixer equipped with a stirring tool such as a rotary blade, a high speed mixer such as a Henschel mixer or a super mixer is preferable, and a Henschel mixer is more preferable.

The volume median particle size (D ₅₀ ) of the toner is preferably 3 to 15 μm, more preferably 4 to 12 μm, and even more preferably 4.5 to 7.0 μm from the viewpoint of improving the image quality of the toner. In the present specification, the volume-median particle size (D ₅₀ ) means a particle size at which the cumulative volume frequency calculated by the volume fraction is 50% when calculated from the smaller particle size. When the toner is treated with an external additive, the volume median particle size of the toner base particles is set.

  The toner of the present invention can be used in an image forming apparatus of a one-component development system or a two-component development system as a one-component development toner as it is or as a two-component development toner mixed with a carrier. The present invention further discloses the following toner binder resin, an electrophotographic toner containing the binder resin, and a method for producing the same, with respect to the above-described embodiment.

<1> An alcohol component and a carboxylic acid component containing 5 to 25 mol of adipic acid with respect to 100 mol of the alcohol component in the presence of a tin catalyst and / or a titanium catalyst having no Sn-C bond Amorphous polyester (A) having a number average molecular weight of 1000 to 2400, a weight average molecular weight of 3000 to 6000, and a glass transition temperature of 38 to 48 ° C., and an aliphatic group having 6 to 12 carbon atoms, obtained by condensation polymerization with A crystalline polyester (B) obtained by condensation polymerization of an alcohol component containing 70 to 100 mol% of a diol and a carboxylic acid component containing 70 to 100 mol% of an aliphatic dicarboxylic acid compound having 8 to 14 carbon atoms; A toner binder resin, the amorphous polyester (A) having a turbidity of 22 to 30 measured when 30 parts by mass of the amorphous polyester is dissolved in 70 parts by mass of ethyl acetate. A binder resin for toner, which indicates 150.

<2> The alcohol component of the amorphous polyester (A) contains an alkylene oxide adduct of bisphenol A represented by the formula (I), and at least a part of the alkylene oxide adduct of bisphenol A is the first. It has a primary hydroxyl group bonded to a primary carbon atom, and among the hydroxyl groups of the bisphenol A alkylene oxide adduct, the ratio of the primary hydroxyl group determined from ¹ H-NMR measurement is 60-100. % Of the binder resin for toner according to <1>.

<3> The aliphatic diol having 6 to 12 carbon atoms in the alcohol component of the crystalline polyester (B) is 1,6-hexanediol, and the aliphatic dicarboxylic acid compound having 8 to 14 carbon atoms in the carboxylic acid component is sebacic acid. The binder resin for toner according to <1> or <2>.

<4> The toner bond according to any one of <1> to <3>, wherein the molar ratio of the alcohol component to the carboxylic acid component (carboxylic acid component / alcohol component) of the crystalline polyester (B) is 1.03 to 1.20. Landing resin.

<5> The above <1> to <4, wherein the polycondensation of the alcohol component and the carboxylic acid component of the crystalline polyester (B) is performed in the presence of a tin catalyst and / or a titanium catalyst having no Sn—C bond. > Binder resin for toner according to any one of the above.

<6> The turbidity of the amorphous polyester (A) is 22 or more, preferably 40 or more, more preferably 45 or more, and 150 or less, preferably 120 or less, more preferably 70 or less. The toner binder resin according to any one of <1> to <5>.

<7> The content of the alkylene oxide adduct of bisphenol A used in the amorphous polyester (A) is 70 to 100 mol%, preferably 80 to 100 mol%, preferably 90 to 100 mol% in the alcohol component. More preferably, the binder resin for toner according to any one of <2> to <6>.

<8> Of the hydroxyl groups of the alkylene oxide adduct of bisphenol A used in the amorphous polyester (A), the proportion of primary hydroxyl groups is preferably 60 to 100%, more preferably 80 to 100%, and more preferably 90 to 100%. %, More preferably 95 to 100%, and the binder resin for toner according to any one of <2> to <7>.

<9> The content of adipic acid is 5 mol or more, preferably 8 mol or more, more preferably 10 mol or more, and 25 mol with respect to 100 mol of the alcohol component of the amorphous polyester (A). The binder resin for toner according to any one of <1> to <8>, which is preferably 20 mol or less, more preferably 15 mol or less.

<10> In the carboxylic acid component of the amorphous polyester (A), the content of the trivalent or higher polyvalent carboxylic acid compound is preferably 5 to 30 mol%, more preferably 10 to 25 mol%, and 13 to 20 The binder resin for toner according to any one of <1> to <9>, wherein the mol% is more preferable.

<11> The molar ratio of the alcohol component to the carboxylic acid component (carboxylic acid component / alcohol component) of the amorphous polyester (A) is preferably 0.5 to 1, preferably 0.6 to 0.95, more preferably. The binder resin for toner according to any one of <1> to <10>, which is 0.65 to 0.95.

<12> The acid value of the amorphous polyester (A) is preferably 5 to 50 mgKOH / g, more preferably 10 to 40 mgKOH / g, and further preferably 15 to 35 mgKOH / g, any of the above <1> to <11> A binder resin for toner according to any of the above.

<13> The hydroxyl value of the amorphous polyester (A) is 40 to 100 mgKOH / g, preferably 45 to 90 mgKOH / g, more preferably 50 to 85 mgKOH / g, any of the above <1> to <12> The binder resin for toner described.

<14> The number average molecular weight of the amorphous polyester (A) is 1000 or more, preferably 1150 or more, more preferably 1300 or more, and 2400 or less, preferably 2200 or less, more preferably 2000 or less. The binder resin for toner according to any one of <1> to <13>, wherein

<15> The weight average molecular weight of the amorphous polyester (A) is 3000 or more, preferably 3500 or more, more preferably 4000 or more, and 6000 or less, preferably 5500 or less, more preferably 5000 or less. The binder resin for toner according to any one of <1> to <14>.

<16> Melting | fusing point of crystalline polyester (B) becomes like this. Preferably it is 40-120 degreeC, More preferably, it is 50-100 degreeC, More preferably, it is 60-80 degreeC, Any one of said <1>-<15>. Binder resin for toner.

<17> The number average molecular weight of the crystalline polyester (B) is preferably 1000 or more, more preferably 1500 or more, preferably 6000 or less, more preferably 5000 or less, and further preferably 4500 or less, <1> ~ <16> The binder resin for toner according to any one of the above.

<18> The weight average molecular weight of the crystalline polyester (B) is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, further preferably 5,000 to 30,000, and further preferably 8,000 to 20,000, <1> to <17 > Binder resin for toner according to any one of the above.

<19> The molar ratio of the alcohol component to the carboxylic acid component (carboxylic acid component / alcohol component) of the crystalline polyester (B) is preferably 1.03 to 1.20, more preferably 1.03 to 1.15, and even more preferably. The binder resin for toner according to any one of <4> to <18>, which is 1.04 to 1.12, more preferably 1.05 to 1.1.

<20> The amount of tin catalyst or titanium catalyst having no Sn-C bond used for the crystalline polyester (B) is 0.01 to 2.0 parts by mass with respect to 100 parts by mass of the total amount of the alcohol component and the carboxylic acid component. The binder resin for toner according to any one of <5> to <19>, wherein 0.1 to 1.5 parts by mass is more preferable, and 0.2 to 1.0 part by mass is further preferable.

<21> Amorphous polyester (A) is a step of polycondensing an alcohol component and an aromatic dicarboxylic acid compound (a) and a step of polycondensing an alcohol component and adipic acid after the step (a) ( The binder resin for toner according to any one of <1> to <20>, wherein an amorphous polyester obtained by a method comprising b) is preferred. .

<22> The binder resin for toner according to <21>, wherein the turbidity of the polyester produced before step (b) is preferably 0 to 25, more preferably 0 to 20, and further preferably 0 to 15.

<23> An electrophotographic toner comprising the toner binder resin according to any one of <1> to <22>.

<24> Dissolve at least the binder resin for toner according to any one of <1> to <22>, an amorphous polyester (C) having an isocyanate group, a colorant, and a release agent in an organic solvent. A step of dispersing, a step of dissolving a compound that crosslinks or extends the binder resin in the obtained oil phase, and then dispersing the oil phase in an aqueous medium containing a fine particle dispersant to obtain an emulsified dispersion. A method for producing an electrophotographic toner, comprising: a step of crosslinking and / or extending the binder resin in the emulsified dispersion, and a step of filtering the obtained suspension.

<25> The method according to <24>, wherein the binder resin in the emulsion dispersion is subjected to crosslinking and / or elongation reaction at 40 to 90 ° C.

[Softening point of resin]
Using a flow tester (manufactured by Shimadzu Corporation, CFT-500D), a 1 g sample was heated at a heating rate of 6 ° C / min, and a load of 1.96 MPa was applied by a plunger, from a nozzle with a diameter of 1 mm and a length of 1 mm. Extrude. The amount of plunger drop of the flow tester is plotted against the temperature, and the temperature at which half of the sample flows out is taken as the softening point.

[Maximum peak temperature and melting point of resin endotherm]
Using a differential scanning calorimeter (Q-100 Japan, Q-100), weigh 0.01 to 0.02 g of the sample into an aluminum pan and cool it from room temperature to 0 ° C at a rate of 10 ° C / min. Then, it was left still for 1 minute. Thereafter, the measurement is performed at a heating rate of 50 ° C./min. Of the endothermic peaks observed, the peak temperature on the highest temperature side was defined as the highest endothermic peak temperature. If the maximum peak temperature is within 20 ° C of the softening point, the peak temperature is taken as the melting point.

[Glass transition temperature of resin]
Using a differential scanning calorimeter (Q-100 Japan, Q-100), 0.01 to 0.02 g of sample was weighed into an aluminum pan, heated to 200 ° C, and the temperature drop rate was 10 Cool to 0 ° C at ° C / min. Next, the sample is heated at a heating rate of 10 ° C./min and measured. The glass transition temperature is defined as the temperature at the intersection of the base line extension below the maximum peak temperature of endotherm and the tangent line indicating the maximum slope from the peak rising portion to the peak apex.

[Acid value of the resin]
Measured by the method of JIS K0070. However, only the measurement solvent is changed from the mixed solvent of ethanol and ether specified in JIS K0070 to the mixed solvent of acetone and toluene (acetone: toluene = 1: 1 (volume ratio)).

[Hydroxyl value of the resin]
Measured by the method of JIS K0070.

[Number average molecular weight and weight average molecular weight of the resin]
The molecular weight distribution is measured by the gel permeation chromatography (GPC) method according to the following method to determine the number average molecular weight and the weight average molecular weight.
(1) Preparation of sample solution The sample is dissolved in chloroform (crystalline polyester) or tetrahydrofuran (amorphous polyester) at 25 ° C. so that the concentration is 0.5 g / 100 ml. Next, this solution is filtered using a fluororesin filter (manufactured by ADVANTEC, DISMIC-25JP) having a pore size of 0.2 μm to remove insoluble components, thereby obtaining a sample solution.
(2) Molecular weight measurement Chloroform (crystalline polyester) or tetrahydrofuran (amorphous polyester) as an eluent was flowed at a flow rate of 1 ml per minute using the following measuring apparatus and analytical column, and the column was placed in a constant temperature bath at 40 ° C. To stabilize. Measurement is performed by injecting 100 μl of the sample solution. The molecular weight of the sample is calculated based on a calibration curve prepared in advance. At this time, several types of monodisperse polystyrene (A-500 (5.0 × 10 ² ), A-1000 (1.01 × 10 ³ ), A-2500 (2.63 × 10 ³ ), A- 5000 (5.97 × 10 ³ ), F-1 (1.02 × 10 ⁴ ), F-2 (1.81 × 10 ⁴ ), F-4 (3.97 × 10 ⁴ ), F-10 (9.64 × 10 ⁴ ), F- 20 (1.90 × 10 ⁵ ), F-40 (4.27 × 10 ⁵ ), F-80 (7.06 × 10 ⁵ ), F-128 (1.09 × 10 ⁶ )) prepared as standard samples are used.
Measuring device: HLC-8220GPC (manufactured by Tosoh Corporation)
Analytical column: GMHXL + G3000HXL (manufactured by Tosoh Corporation)

[Resistance of resin]
30 parts by mass of the resin is dissolved in 70 parts by mass of ethyl acetate.
Using a turbidimeter "Turbidimeter TN-100" (manufactured by EUTECH INSTRUMENTS), first correct with 4 standard samples (CAL1: 800NTU, CAL2: 100NTU, CAL3: 20NTU, CAL4: 0.02NTU) Put the above solution in a glass sample bottle to the specified line, press the measurement button, and obtain the turbidity value (unit: NTU).

[Melting point of release agent]
Using a differential scanning calorimeter (DS Instruments Q20, manufactured by T.A. Instruments Japan Co., Ltd.), the temperature was increased to 200 ° C. at a temperature increase rate of 10 ° C./min, and from that temperature, the temperature decrease rate was 5 ° C./min. The sample cooled to 0 ° C. is heated to 180 ° C. at a temperature rising rate of 10 ° C./min, and the highest endothermic peak temperature observed from the melting endothermic curve obtained here is taken as the melting point of the release agent.

[Average particle diameter of external additive]
The average particle diameter refers to the number average particle diameter and refers to the average value of the particle diameters of 500 particles measured from a scanning electron microscope (SEM) photograph of the external additive. When there is a major axis and a minor axis, the major axis is indicated.

[Volume-median particle diameter of toner (D ₅₀ )]
Measuring machine: Coulter Multisizer II (Beckman Coulter, Inc.)
Aperture diameter: 100μm
Analysis software: Coulter Multisizer AccuComp version 1.19 (Beckman Coulter)
Electrolyte: Isoton II (Beckman Coulter, Inc.)
Dispersion: Emulgen 109P (manufactured by Kao Corporation, polyoxyethylene lauryl ether, HLB: 13.6) is dissolved in the electrolyte so as to have a concentration of 5% by mass.
Dispersion conditions: 10 mg of a measurement sample was added to 5 ml of the dispersion, and dispersed for 1 minute with an ultrasonic disperser, then 25 ml of the electrolyte was added, and further dispersed for 1 minute with an ultrasonic disperser. Prepare sample dispersion.
Measurement conditions: The sample dispersion is added to 100 ml of the electrolytic solution so that the particle size of 30,000 particles can be measured in 20 seconds, and 30,000 particles are measured. Determine the median particle size (D ₅₀ ).

Production Example 1 of bisphenol A propylene oxide adduct [BPA-PO (a)]
In an autoclave equipped with stirring and temperature control, 228 g (1 mol) of bisphenol A and 5 g of tris (pentafluorophenyl) borane were introduced, and 130 g of propylene oxide was introduced at 135 ° C. under a pressure in the range of 0.1 to 0.4 MPa. Thereafter, an addition reaction was carried out for 3 hours. 16 g of an adsorbent “KYOWARD 600” (manufactured by Kyowa Chemical Industry Co., Ltd .: 2MgO · 6SiO ₂ · XH ₂ O) was added to the reaction product, and the mixture was aged by stirring at 90 ° C. for 30 minutes. Thereafter, filtration was performed to obtain a propylene oxide adduct (BPA-PO (a)) of bisphenol A. ^{The primary} hydroxylation rate was determined from the measurement result of ¹ H-NMR chemical shift δ value (solvent: CDCl ₃ ) and found to be 98%.

Production Example 2 of bisphenol A propylene oxide adduct [BPA-PO (b)]
In an autoclave equipped with stirring and temperature control, 228 g (1 mol) of bisphenol A and 2 g of potassium hydroxide are introduced, 130 g of propylene oxide is introduced at 135 ° C. under a pressure in the range of 0.1 to 0.4 MPa, and then added for 3 hours. Reacted. 16 g of an adsorbent “KYOWARD 600” (manufactured by Kyowa Chemical Industry Co., Ltd .: 2MgO · 6SiO ₂ · XH ₂ O) was added to the reaction product, and the mixture was aged by stirring at 90 ° C. for 30 minutes. Thereafter, filtration was performed to obtain a propylene oxide adduct (BPA-PO (b)) of bisphenol A.
^{The primary} hydroxylation rate of the terminal hydroxyl group was determined from the measurement result of ¹ H-NMR chemical shift δ value (solvent: CDCl ₃ ) and found to be 0%.

The specific measurement method of the primary hydroxyl group ratio is described below.

1. ¹ H-NMR method <sample preparation method>
About 30 mg of a measurement sample is weighed into an NMR sample tube having a diameter of 5 mm, and about 0.5 ml of deuterated solvent is added and dissolved. Thereafter, about 0.1 ml of trifluoroacetic anhydride is added to obtain a sample for analysis. Deuterated chloroform is used as the deuterated solvent.
<NMR measurement>
Equipment: Mercury-400 (manufactured by VARIAN)
Observation nucleus: 1H
Observation range: 6410.3Hz
Number of data points: 65536
Pulse width: 45 ° (4.5μs)
Wait time: 10s
Integration count: 128 times Measurement temperature: room temperature Measurement solvent: deuterated chloroform (CDCl ₃ )
Sample concentration: 1%

2.1 Method for calculating the degree of hydroxylation of the hydroxyl group By the above pretreatment method, the hydroxyl group at the end of the propylene oxide adduct of bisphenol A reacts with the added trifluoroacetic anhydride to become a trifluoroacetic acid ester. As a result, a signal derived from a methylene group to which a primary hydroxyl group is bonded is observed at around 4.3 ppm, and a signal derived from a methine group to which a secondary hydroxyl group is bonded is observed at around 5.2 ppm.
The primary hydroxylation rate is calculated by the following formula.
Primary hydroxylation rate (%) = [a / (a + 2 × b)] × 100
(In the formula, a is an integral value of a proton signal derived from a methylene group bonded with a primary hydroxyl group around 4.3 ppm, and b is an integral value of a proton signal derived from a methine group bonded to a secondary hydroxyl group around 5.2 ppm)

Resin production example A1 [resins AA to AH]
The alcohol components shown in Table 1 were placed in a 10 L four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple, and the temperature was raised to 100 ° C. while stirring to charge isophthalic acid. After the preparation, the pressure was reduced to 8.3 kPa, the pressure was returned to normal pressure with nitrogen, and the system was completely replaced with nitrogen. Thereafter, 20 g of tin (II) 2-ethylhexanoate and 1 g of gallic acid were charged and reacted at 230 ° C. for 8 hours. After the reaction, the temperature was lowered to 180 ° C., charged with 10 g of tin (II) 2-ethylhexanoate and adipic acid, heated to 210 ° C. over 3 hours, reacted at 210 ° C. for 2 hours, then 220 ° C. For 2 hours. Further, the temperature was lowered to 210 ° C., trimellitic anhydride was added and reacted at normal pressure for 1 hour, then the pressure was reduced to 8.3 kPa and the reaction was continued until a predetermined softening point was obtained, thereby obtaining an amorphous polyester.

Resin Production Example A2 [Resin AI]
The alcohol components shown in Table 2 were put into a 10 L four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple, heated to 100 ° C. while stirring, and isophthalic acid was charged. After the preparation, the pressure was reduced to 8.3 kPa, the pressure was returned to normal pressure with nitrogen, and the system was completely replaced with nitrogen. Thereafter, 20 g of titanium dihydroxybis (triethanolaminate) and 1 g of gallic acid were charged and reacted at 230 ° C. for 8 hours. After the reaction, the temperature was lowered to 180 ° C., charged with 10 g of titanium dihydroxybis (triethanolamate) and adipic acid, heated to 210 ° C. over 3 hours, reacted at 210 ° C. for 2 hours, then 220 ° C. For 2 hours. Further, the temperature was lowered to 210 ° C., trimellitic anhydride was added and reacted at normal pressure for 1 hour, then the pressure was reduced to 8.3 kPa and the reaction was continued until a predetermined softening point was obtained, thereby obtaining an amorphous polyester.

Resin Production Example A3 [Resin AJ]
The alcohol components shown in Table 2 were put into a 10 L four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple, heated to 100 ° C. while stirring, and isophthalic acid was charged. After the preparation, the pressure was reduced to 8.3 kPa, the pressure was returned to normal pressure with nitrogen, and the system was completely replaced with nitrogen. Thereafter, 20 g of dibutyltin oxide was charged, and the reaction was performed at 230 ° C. for 8 hours. After the reaction, the temperature was lowered to 180 ° C., charged with 10 g of tin (II) 2-ethylhexanoate and adipic acid, heated to 210 ° C. over 3 hours, reacted at 210 ° C. for 2 hours, then 220 ° C. For 2 hours. Further, the temperature was lowered to 210 ° C., trimellitic anhydride was added and reacted at normal pressure for 1 hour, then the pressure was reduced to 8.3 kPa and the reaction was continued until a predetermined softening point was obtained, thereby obtaining an amorphous polyester.

Resin Production Example A4 [Resin AK]
The alcohol components shown in Table 2 were put into a 10 L four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple, heated to 100 ° C. while stirring, and isophthalic acid was charged. After the preparation, the pressure was reduced to 8.3 kPa, the pressure was returned to normal pressure with nitrogen, and the system was completely replaced with nitrogen. Thereafter, 20 g of tin (II) 2-ethylhexanoate was charged, and the reaction was performed at 230 ° C. for 8 hours. After the reaction, the temperature was lowered to 180 ° C., adipic acid was added, the temperature was raised to 210 ° C. over 3 hours, the reaction was carried out at 210 ° C. for 2 hours, and then held at 220 ° C. for 1 hour. Further, trimellitic anhydride was added and reacted at 210 ° C. for 1 hour at normal pressure, then the pressure was reduced to 8.3 kPa and the reaction was continued until a predetermined softening point was obtained, thereby obtaining an amorphous polyester.

Resin production example A5 [Resin AL]
The alcohol components shown in Table 2 were put into a 10 L four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple, heated to 100 ° C. while stirring, and isophthalic acid was charged. After the preparation, the pressure was reduced to 8.3 kPa, the pressure was returned to normal pressure with nitrogen, and the system was completely replaced with nitrogen. Thereafter, 20 g of tin (II) 2-ethylhexanoate and 1 g of gallic acid were added and reacted at 230 ° C. for 8 hours. After the reaction, the temperature was lowered to 180 ° C., 10 g of 2-ethylhexanoic acid tin (II) and adipic acid were added, the temperature was raised to 210 ° C. over 3 hours, and the reaction was carried out at 210 ° C. for 2 hours. Held for 0.5 hour. Further, the temperature was lowered to 210 ° C., trimellitic anhydride was added, and the mixture was reacted at normal pressure for 1 hour, and then the pressure was reduced to 8.3 kPa and the reaction was performed until a predetermined softening point was reached, thereby obtaining an amorphous polyester.

Resin Production Example A6 [Resin AM]
The alcohol components shown in Table 2 were put into a 10 L four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple, heated to 100 ° C. while stirring, and isophthalic acid was charged. After the preparation, the pressure was reduced to 8.3 kPa, the pressure was returned to normal pressure with nitrogen, and the system was completely replaced with nitrogen. Thereafter, 20 g of tin (II) 2-ethylhexanoate and 1 g of gallic acid were added and reacted at 230 ° C. for 8 hours. After the reaction, the temperature was lowered to 180 ° C., charged with 10 g of tin (II) 2-ethylhexanoate and adipic acid, heated to 210 ° C. over 3 hours, reacted at 210 ° C. for 2 hours, then 220 ° C. Held for 1 hour. Further, the temperature was lowered to 210 ° C., trimellitic anhydride was added, and the mixture was reacted at normal pressure for 1 hour, and then the pressure was reduced to 8.3 kPa and the reaction was performed until a predetermined softening point was reached, thereby obtaining an amorphous polyester.

Resin Production Example A7 [Resin AN]
The alcohol components shown in Table 2 were put into a 10 L four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple, heated to 100 ° C. while stirring, and isophthalic acid was charged. After the preparation, the pressure was reduced to 8.3 kPa, the pressure was returned to normal pressure with nitrogen, and the system was completely replaced with nitrogen. Thereafter, 20 g of tin (II) 2-ethylhexanoate and 1 g of gallic acid were added and reacted at 230 ° C. for 8 hours. After the reaction, the temperature was lowered to 180 ° C., charged with 10 g of tin (II) 2-ethylhexanoate and adipic acid, heated to 210 ° C. over 3 hours, reacted at 210 ° C. for 2 hours, then 220 ° C. Held for 4 hours. Further, the temperature was lowered to 210 ° C., trimellitic anhydride was added, and the mixture was reacted at normal pressure for 1 hour, and then the pressure was reduced to 8.3 kPa and the reaction was performed until a predetermined softening point was reached, thereby obtaining an amorphous polyester.

Resin Production Example A8 [Resin AO]
The alcohol components shown in Table 2 were put into a 10 L four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple, heated to 100 ° C. with stirring, and isophthalic acid and 2-ethylhexanoic acid. 20 g of tin (II) was charged and reacted at 230 ° C. for 8 hours. After the reaction, the temperature was lowered to 180 ° C., adipic acid was added, the temperature was raised to 210 ° C. over 3 hours, and the reaction was carried out at 210 ° C. for 2 hours. Further, the temperature was lowered to 210 ° C., trimellitic anhydride was added, and the mixture was reacted at normal pressure for 1 hour, and then the pressure was reduced to 8.3 kPa and the reaction was performed until a predetermined softening point was reached, thereby obtaining an amorphous polyester.

Resin Production Example A9 [Resin AP]
Put the alcohol components shown in Table 2 into a 10L four-necked flask equipped with a nitrogen inlet tube, dehydration tube, stirrer and thermocouple, heat up to 100 ° C with stirring, and add 20g of isophthalic acid and dibutyltin oxide. The reaction was performed at 230 ° C. for 8 hours. After the reaction, the temperature was lowered to 180 ° C., adipic acid was added, the temperature was raised to 210 ° C. over 3 hours, and the reaction was carried out at 210 ° C. for 2 hours. Further, the temperature was lowered to 210 ° C., trimellitic anhydride was added, and the mixture was reacted at normal pressure for 1 hour, and then the pressure was reduced to 8.3 kPa and the reaction was performed until a predetermined softening point was reached, thereby obtaining an amorphous polyester.

Resin production example B1 [Resin B]
A 10-L four-necked flask equipped with a nitrogen inlet tube, dehydration tube, stirrer, and thermocouple was charged with the raw material monomer in the blending amount shown in Table 3, heated to 140 ° C. and reacted for 6 hours (reaction The reaction was carried out while raising the temperature up to 200 ° C. at 10 ° C./hr. After reacting to a reaction rate of 80% at 200 ° C., 20 g of tin (II) 2-ethylhexanoate was added, and the reaction was further carried out at 200 ° C. for 2 hours. The reaction was further performed at 8 kPa for 2 hours to obtain a crystalline polyester.

Resin Production Example C1 [Resin C]
Into a 10L four-necked flask equipped with a nitrogen inlet tube, dehydration tube, stirrer and thermocouple, the raw material monomer of the blending amount shown in Table 4 was placed, 20 g of tin (II) 2-ethylhexanoate, 2 g of gallic acid And reacted at 200 ° C. for 4 hours. Furthermore, it was made to react to 230 degreeC, heating up at 10 degreeC / hr. After making it react at 230 degreeC for 6 hours, it was made to react to the target softening point at 8.3 Kpa, and resin C 'was obtained.

  Put 2 kg of resin C 'in a 10 L four-necked flask equipped with a nitrogen inlet tube, dehydration tube, stirrer and thermocouple, add 400 g of isophorone diisocyanate and 2500 g of ethyl acetate, and react at 100 ° C for 5 hours. Ethyl was removed to obtain an amorphous polyester having an isocyanate group.

Ketimine Production Example 100 parts by mass of isophoronediamine and 40 parts by mass of methyl ethyl ketone were charged into a reaction vessel equipped with a stir bar and a thermometer, and reacted at 50 ° C. for 5 hours to obtain ketimine A. The amine value was 435.

Examples 1-11 and Comparative Examples 1-5 (Examples 5 and 6 are reference examples)
70 parts by weight of amorphous polyester shown in Table 5, 15 parts by weight of resin B, 15 parts by weight of resin C, 5 parts by weight of colorant “ECB-301” (manufactured by Dainichi Seika Co., Ltd., CI Pigment Blue 15: 3), negative 1 part by mass of chargeable charge control agent “LR-147” (manufactured by Nippon Carlit) and 5 parts by mass of mold release agent “Carnauba wax C1” (manufactured by Kato Yoko Co., Ltd., melting point: 83 ° C.) are sufficiently obtained Then, the mixture was melt-kneaded using a continuous two-roll kneader having a roll outer diameter of 0.12 m and an effective roll length of 0.8 m. The operating conditions of the continuous two-roll kneader are as follows: high rotation side roll (front roll) peripheral speed 9m / min, low rotation side roll (back roll) peripheral speed 6m / min, roll at the end of the kneaded product supply port The gap was 0.1 mm. The heating medium temperature and cooling medium temperature in the roll were 90 ° C on the raw material input side of the high-rotation roll and 90 ° C on the kneaded product discharge side, 30 ° C on the raw material input side of the low-rotation roll, and 30 ° C on the kneaded material discharge side. . The feed rate of the raw material mixture was 4 kg / hour, and the average residence time was about 10 minutes. The obtained melt-kneaded product was rolled and cooled with a cooling roller.

  100 parts by mass of the melt-kneaded product was added to 500 parts by mass of ethyl acetate, the temperature was raised to 80 ° C. with stirring, and the mixture was held at 80 ° C. with stirring for 5 hours. Then, it cooled to 30 degreeC in 1 hour.

  After mixing 500 parts by mass of the raw material mixture (oil phase) and 4 parts by mass of ketimine A, the mixture was mixed for 1 minute at 5000 r / min with a TK homomixer (manufactured by Koki Co., Ltd.), then 760 parts by mass of water and sodium alkanesulfonate 4 parts by mass of a 40% by mass solution (Latemul PS, manufactured by Kao Corporation) was added, and the mixture was stirred for 20 minutes at a rotation speed of 12000 r / min with a TK homomixer (manufactured by Koki Co., Ltd.). Transfer to a container with a stirrer and thermometer, remove the solvent at 30 ° C. for 8 hours to obtain an emulsified dispersion, and further perform extension and / or crosslinking reaction at 45 ° C. for 4 hours to obtain a suspension. Got.

The obtained suspension was filtered through a 200 mesh (mesh opening 105 μm) wire mesh, washed thoroughly with ion-exchanged water, and dried to obtain toner particles. The resulting toner particles had a volume-median particle size (D ₅₀ ) of about 5.5 μm.

  External additive “Aerosil R-972” (hydrophobic silica, manufactured by Nippon Aerosil Co., Ltd., trade name, average particle diameter 16 nm) 2.0 mass parts “Aerosil NAX-50” hydrophobic silica, Nippon Aerosil for 100 parts by mass of toner particles Toner was obtained by adding 2.0 parts by mass (trade name, average particle diameter 30 nm) and mixing with a Henschel mixer at 3600 r / min for 5 minutes to perform external additive treatment.

Comparative Example 6
A toner was obtained in the same manner as in Example 1 except that the resin C was not used, the amount of the resin AA used was changed to 70 parts by mass, and the amount of the resin B used was changed to 15 parts by mass.

Test Example 1 [Durability]
The toner is mounted on the non-magnetic one-component developing device "MicroLine 9300PS" (Oki Data Co., Ltd.). After printing 50 images with a printing rate of 5% in an environment of 30 ° C and 90%, the optical reflection density is reflected density. Measurement was performed using a total of “RD-915” (manufactured by Macbeth). Furthermore, after printing 200 sheets, the optical reflection density was measured again using a reflection densitometer “RD-915” (manufactured by Macbeth). The difference in image density between the two was calculated to evaluate the durability. The results are shown in Table 5.

Test Example 2 [Bending resistance of printed matter]
The toner was mounted on a copier “AR-505” (manufactured by Sharp) and the image was printed without fixing (printing area: 2 cm × 12 cm, adhesion amount: 0.6 mg / cm ² ). The unfixed image was fixed in an oven at 100 ° C. for 1 minute, and then the paper was folded in half so that the printed image appeared on the surface at the center (6 cm) of the printed image. The state of the folded part was observed, and the bending resistance of the printed matter was evaluated according to the following evaluation criteria. The results are shown in Table 5. As the fixing paper, “CopyBond SF-70NA” (manufactured by Sharp Corporation, 75 g / m ² ) was used.

〔Evaluation criteria〕
A: Print peeling at the bent portion is not observed at all.
B: A slight white spot is observed in the bent portion.
C: A defect of less than 10% (less than 0.2 cm within a width of 2 cm) is observed at the bent portion.
D: Defects are confirmed in the bent part at 10% or more and less than 90% (0.2cm or more and less than 1.8cm within 2cm width).
E: The bent part is missing 90% or more (1.8 cm or more in a width of 2 cm).

From the above results, it can be seen that the toners obtained in Examples 1 to 11 have good durability and bending resistance.
On the other hand, in Comparative Example 1 using a polyester having a low average molecular weight and a low glass transition temperature, since it is thermally weak, it becomes soft during durability, lacks durability, has a large average molecular weight, and has a glass transition. In Comparative Example 2 using polyester having a high temperature, the glass transition temperature is high, so that the flexibility is lacking and the bending resistance is lacking.
Further, in Comparative Examples 3 and 4, since the polyester having too much turbidity component acting as a flocculant is used, as a result of the small particle size component (thermally weak component) adhering to the large particle size component surface, The durability has deteriorated. In Comparative Example 5, since polyester having too little turbidity component is used, fine particles cannot be sufficiently removed, and durability is poor.
Further, Comparative Example 6 in which an amorphous polyester having an isocyanate group is not used in the production of toner lacks bending resistance.

  The binder resin for toner of the present invention is used for a toner suitably used for developing a latent image formed in an electrophotographic method, an electrostatic recording method, an electrostatic printing method or the like.

Claims (5)

In an organic solvent, at least a binder resin, an amorphous polyester (C) having an isocyanate group (C), a colorant, and a release agent are dissolved and dispersed, and the obtained resin phase is crosslinked with the binder resin. Alternatively, after dissolving the extending compound, the step of dispersing the oil phase in an aqueous medium containing a fine particle dispersant to obtain an emulsified dispersion, and crosslinking and / or extending the binder resin in the emulsified dispersion. A process for producing an electrophotographic toner comprising a step of reacting and a step of filtering the obtained suspension,
A tin catalyst and / or a titanium catalyst in which the binder resin is an alcohol component and a carboxylic acid component containing 5 to 25 mol of adipic acid with respect to 100 mol of the alcohol component does not have a Sn-C bond. An amorphous polyester (A) having a number average molecular weight of 1000 to 2400, a weight average molecular weight of 3000 to 6000, and a glass transition temperature of 38 to 48 ° C., obtained by condensation polymerization in the presence of A crystalline polyester obtained by polycondensation of an alcohol component containing 70 to 100 mol% of an aliphatic diol and a carboxylic acid component containing 70 to 100 mol% of an aliphatic dicarboxylic acid compound having 8 to 14 carbon atoms (B The amorphous polyester (A) has a turbidity measured when 30 parts by mass of the amorphous polyester is dissolved in 70 parts by mass of ethyl acetate. ~ 92, and
The alcohol component of the amorphous polyester (A) has the formula (I):

(Wherein, R ¹ O and OR ¹ is an oxyalkylene group, R ¹ is flop propylene group, x and y represents the molar number of addition of alkylene oxide, the number of positive respectively, the x and y (The average value of the sum is 1-16)
In a propylene oxide adduct of bisphenol A and also contains 80 to 100 mol% represented, here, 1) primary hydroxyl group of a propylene oxide adduct of the bisphenol A is attached to a primary carbon atom It includes those having, and 2) of the hydroxyl groups of propylene oxide adduct of the bisphenol a has the proportion of primary hydroxyl groups obtained from the ¹ H-NMR measurement is 80 100%, a binder resin, an electron A method for producing a photographic toner.   The aliphatic diol having 6 to 12 carbon atoms in the alcohol component of the crystalline polyester (B) is 1,6-hexanediol, and the aliphatic dicarboxylic acid compound having 8 to 14 carbon atoms in the carboxylic acid component is sebacic acid. The manufacturing method according to claim 1.   The manufacturing method of Claim 1 or 2 whose molar ratio (carboxylic acid component / alcohol component) of the alcohol component of a crystalline polyester (B) and a carboxylic acid component is 1.03-1.20.   The production according to any one of claims 1 to 3, wherein the polycondensation of the alcohol component and the carboxylic acid component of the crystalline polyester (B) is carried out in the presence of a tin catalyst and / or a titanium catalyst having no Sn-C bond. Method.   The manufacturing method according to any one of claims 1 to 4, wherein the binder resin in the emulsified dispersion is subjected to crosslinking and / or elongation reaction at 40 to 90 ° C.