JP6025251B2 - Method for producing binder resin for polyester toner - Google Patents

Description

  The present invention relates to a method for producing a polyester resin binder resin used for developing a latent image formed in an electrophotographic method, a binder resin obtained by the method, and an electrostatic image development containing the binder resin. Relates to toner.

In the field of electrophotography, with the development of an electrophotographic system, development of toner for electrophotography corresponding to higher image quality and higher speed is required.
In order to improve image quality and speed, in particular to improve thermal properties, polyester resins that are easy to adjust the composition are widely used as binder resins for toners. Attempts have been made to use it.

  For example, Patent Document 1 contains at least one cyclic compound selected from cyclic oligomers and cyclic polymers having substantially no end groups for the purpose of achieving both chargeability and fixing properties and improving image quality. An electrophotographic toner is disclosed.

  In Patent Document 2, for the purpose of improving the storage stability of the toner and the environmental stability of the charge amount, it is obtained by condensation polymerization of an alcohol component containing 60 mol% or more of an alkylene oxide adduct of bisphenol A and a carboxylic acid component. A polyester resin, a carboxylic acid component containing an aliphatic hydroxycarboxylic acid compound having a total number of hydroxy groups and carboxyl groups of 4 or more, and an alcohol component containing 60 mol% or more of an aliphatic diol having 2 to 5 carbon atoms, And a polyester resin obtained by subjecting a polycondensation reaction to a binder resin for toner.

JP 2003-186236 A JP 2011-257700 A

  In electrophotography, gloss is required for printing photographs and the like. In order to impart gloss, a method of lowering the melting temperature by lowering the glass transition temperature or melting point of the binder resin used for the toner is used. However, the toner that is easily melted at a low temperature is likely to be partly melted by heat generated when it is rubbed with the charging blade. Therefore, there is a demand for a binder resin for toner that has both gloss and durability. In addition, Patent Document 1 discloses a toner containing a cyclic compound in order to obtain a toner excellent in chargeability and fixability, but does not disclose a method for efficiently obtaining the cyclic compound. A method for efficiently obtaining a cyclic compound is also desired.

  The present invention relates to a method for producing a binder resin for a polyester toner that can achieve both the gloss of printed matter and the durability of the obtained toner, the binder resin obtained by the method, and the electrostatic image containing the binder resin. The present invention relates to a developing toner.

  The present inventors have considered that the factors affecting the gloss of printed matter and the durability of the obtained toner are due to the composition of the polyester in the binder resin and the distribution during printing. As a result, the binder resin for toner containing the cyclic polyester exhibits good gloss and durability, and an efficient production method for the cyclic polyester has been found, and the present invention has been completed.

The present invention
[1] A method for producing a binder resin for a polyester toner containing a cyclic polyester (A) and a linear polyester resin (B), wherein the mass ratio of the cyclic polyester (A) and the linear polyester resin (cyclic Polyester (A) / chain polyester-based resin) is 0.01 / 99.99 to 5.0 / 95.0, and an alcohol component and a carboxylic acid component and / or polyester are subjected to condensation polymerization at 200 to 250 ° C. in the presence of a rare earth catalyst. 1, a method for producing a polyester-based toner binder resin,
[2] A polyester resin binder resin obtained by the method described in [1] above, and [3] an electrostatic charge image developing comprising the polyester toner binder resin described in [2] above. It relates to toner.

  By the method of the present invention, it is possible to produce a polyester-based toner binder resin that can achieve both the gloss of printed matter and the durability of the obtained toner.

  The method for producing a binder resin for a polyester toner of the present invention is a method for producing a binder resin for a polyester toner containing a cyclic polyester (A) and a chain polyester resin (B). ) And the chain polyester resin (cyclic polyester (A) / chain polyester resin) is 0.01 / 99.99 to 5.0 / 95.0, and the alcohol component and the carboxylic acid component and / or polyester are mixed with the rare earth catalyst. Step 1 of condensation polymerization at 200 to 250 ° C. in the presence is included.

  Although the toner using the binder resin for polyester toner obtained by the method of the present invention can achieve both the gloss of the printed matter and the durability of the obtained toner, the reason why the cyclic polyester can be obtained efficiently is not clear, It can be considered as follows.

  The rare earth catalyst is very reactive, and if it is normal, a chain polyester can be obtained. However, in the present invention, the cyclic polyester can be efficiently produced by carrying out at a high temperature of 200 to 250 ° C. .

  Furthermore, when the cyclic polyester is used as a binder resin in the toner, it does not have a functional group at the terminal, so hydrogen bonding with other components is impossible, and entanglement like a chain polyester resin is possible. This is considered to be easy to bleed out on the surface of the toner. On the other hand, since the structure of the cyclic polyester is constrained, the resistance to heat is high, and it is considered that the toner is not easily fixed even by frictional heat generated by the blade. As described above, the toner using the binder resin for toner obtained by the method of the present invention has a structure in which the surface is covered with a cyclic polyester. Conceivable. In particular, by using the method of the present invention, it is possible to efficiently obtain a low molecular weight cyclic polyester that easily bleeds out. Therefore, it is considered that the gloss of the obtained printed matter and the durability of the toner are remarkably excellent.

  Hereafter, each component, process, etc. used for this invention are demonstrated.

[Cyclic polyester (A)]
In the present invention, the cyclic polyester (A) does not have a polyester terminal, and therefore has a remarkably low acid value and hydroxyl value. That is, the acid value is preferably 0.1 mgKOH / g or less, and more preferably 0 mgKOH / g. The hydroxyl value is preferably 0.1 mgKOH / g or less, more preferably 0 mgKOH / g. An acid value and a hydroxyl value are measured by the method as described in an Example.

  As described later, the cyclic polyester (A) can be produced by polycondensing an alcohol component, a carboxylic acid component and / or polyester at 200 to 250 ° C. in the presence of a rare earth catalyst.

  As the carboxylic acid component of the cyclic polyester (A), an aromatic dicarboxylic acid compound and an aliphatic dicarboxylic acid compound are preferable from the viewpoint of efficiently obtaining a cyclic structure and improving the glossiness of the obtained toner. From the viewpoint of improving the above, an aromatic dicarboxylic acid compound is more preferable.

  Carboxylic acid compounds include not only free acids but also anhydrides that decompose to produce acids during the reaction and alkyl esters having 1 to 3 carbon atoms.

  The content of the aromatic dicarboxylic acid compound in the carboxylic acid component is preferably 50 mol% or more, more preferably 60 mol% or more, still more preferably 70 mol% or more, from the viewpoint of improving the durability of the toner. 100 mol% is more preferable.

  As the aromatic dicarboxylic acid compound, terephthalic acid, isophthalic acid, anhydrides of these acids and alkyl esters having 1 to 3 carbon atoms are preferable, and terephthalic acid is more preferable from the viewpoint of improving the durability of the toner.

  2-12 are preferable and, as for carbon number (carbon number of an aliphatic group) of an aliphatic dicarboxylic acid compound, 2-6 are more preferable.

  Examples of the aliphatic carboxylic acid compound having 2 to 12 carbon atoms include oxalic acid, malonic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, succinic acid, adipic acid, sebacic acid, 1,12-dodecanediic acid. Examples thereof include acids, anhydrides of these acids and alkyl esters having 1 to 3 carbon atoms, and fumaric acid is preferred from the viewpoint of improving the glossiness of the toner.

  Examples of other carboxylic acid components include trivalent or higher polyvalent carboxylic acid compounds such as trimellitic acid, pyromellitic acid, anhydrides of these acids, and alkyl esters having 1 to 3 carbon atoms.

  The alcohol component of the cyclic polyester (A) is preferably an aromatic diol or an aliphatic diol from the viewpoint of efficiently obtaining a cyclic structure and improving the glossiness of the obtained toner, and from the viewpoint of improving the durability of the toner. Aromatic diols are preferred.

  The content of the aromatic diol in the alcohol component is preferably 50 mol% or more, more preferably 70 mol% or more, and further preferably 90 to 100 mol%.

  As the aromatic diol, an alkylene oxide adduct of bisphenol A is preferable. As the alkylene oxide adduct of bisphenol A, the formula (I):

(In the formula, RO and OR are oxyalkylene groups, R is an ethylene and / or propylene group, x and y indicate the number of added moles of alkylene oxide, each being a positive number, and the sum of x and y. 1 to 16 is preferable, 1 to 8 is more preferable, and 1.5 to 4 is more preferable)
An alkylene oxide adduct of bisphenol A represented by the formula is preferred, and it is more preferred to use a mixture of an ethylene oxide adduct of bisphenol A and a propylene oxide adduct.

  The mixing ratio (molar ratio) of bisphenol A ethylene oxide adduct (BPA-PO) and bisphenol A propylene oxide adduct (BPA-EO) is preferably 10/90 or more, more preferably 90/10 to 30/70. 80/20 to 60/40 is more preferable.

  In the alcohol component, the content of the alkylene oxide adduct of bisphenol A is preferably 60 mol% or more, more preferably 70 mol% or more, and still more preferably 90 to 100 mol%, from the viewpoint of improving the durability of the toner.

  Examples of the aliphatic diol include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 2,3-butanediol, and the like. From the viewpoint of improving gloss, 1,2-propanediol and 2,3-butanediol are preferred.

  Other alcohol components include trihydric or higher polyhydric alcohols such as glycerin.

  The alcohol component may contain a monovalent alcohol, and the carboxylic acid component may contain a monovalent carboxylic acid compound as appropriate.

  From the viewpoint of improving the glossiness of the toner, the number average molecular weight of the cyclic polyester (A) is preferably 100 or more, more preferably 200 or more, and more preferably 300 or more in terms of polystyrene. From the viewpoint of improving the durability of the toner, it is preferably 1000 or less, more preferably 800 or less, and even more preferably 700 or less. Moreover, 100-1000 are preferable, 200-1000 are more preferable, 300-800 are more preferable, 300-700 are still more preferable. The number average molecular weight of the cyclic polyester (A) is determined by the method described in the examples.

[Chain polyester resin (B)]
In the present invention, the chain polyester resin (B) is preferably an amorphous polyester, a crystalline polyester, a polyester composite resin or the like, and among them, an amorphous polyester is preferable.

  The crystallinity of the resin is represented by the ratio between the softening point and the maximum endothermic peak temperature measured by a differential scanning calorimeter, that is, the crystallinity index defined by the value of [softening point / maximum endothermic peak temperature]. The crystalline resin has a crystallinity index of 0.6 to 1.4, preferably 0.7 to 1.2, more preferably 0.9 to 1.2, and the amorphous resin is a resin having a value of 1.4 or less than 0.6. The crystallinity of the resin can be adjusted by the type and ratio of the raw material monomers, production conditions (for example, reaction temperature, reaction time, cooling rate) and the like. The highest endothermic peak temperature refers to the temperature of the peak on the highest temperature side among the observed endothermic peaks. The maximum peak temperature is the melting point if the difference from the softening point is within 20 ° C., and the peak due to the glass transition if the difference from the softening point exceeds 20 ° C.

  When the chain polyester resin (B) is an amorphous polyester, the chain polyester resin (B) can be produced by subjecting a carboxylic acid component and an alcohol component to a polycondensation reaction as described later. .

  The carboxylic acid component of the chain polyester resin (B) is preferably an aromatic dicarboxylic acid compound or an aliphatic dicarboxylic acid compound from the viewpoint of improving the glossiness of the toner. From the viewpoint of improving the durability of the toner, an aromatic A group dicarboxylic acid compound is more preferable.

  Carboxylic acid compounds include not only free acids but also anhydrides that decompose to produce acids during the reaction and alkyl esters having 1 to 3 carbon atoms.

  From the viewpoint of improving the durability of the toner, the content of the aromatic dicarboxylic acid compound in the carboxylic acid component is preferably 50 mol% or more, more preferably 60 mol% or more, and further preferably 90 to 100 mol%.

  As the aromatic dicarboxylic acid compound, terephthalic acid and isophthalic acid are preferable, and terephthalic acid is more preferable.

  2-12 are preferable and, as for carbon number (carbon number of an aliphatic group) of an aliphatic dicarboxylic acid compound, 2-6 are more preferable.

  Examples of the aliphatic carboxylic acid compound having 2 to 12 carbon atoms include oxalic acid, malonic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, succinic acid, adipic acid, sebacic acid, 1,12-dodecanedioic acid. Examples of the acid include fumaric acid from the viewpoint of improving the glossiness of the toner.

  Examples of other carboxylic acid components include trivalent or higher polyvalent carboxylic acid compounds such as trimellitic acid and pyromellitic acid.

  As the alcohol component of the chain polyester resin (B), an aromatic diol and an aliphatic diol are preferable from the viewpoint of improving the glossiness of the obtained toner, and an aromatic diol is preferable from the viewpoint of improving the durability of the toner. preferable.

  The content of the aromatic diol in the alcohol component is preferably 50 mol% or more, more preferably 60 mol% or more, and still more preferably 90 to 100 mol%, from the viewpoint of improving the durability of the toner.

  As the aromatic diol, an alkylene oxide adduct of bisphenol A is preferable, an alkylene oxide adduct of bisphenol A represented by the formula (I) is more preferable, and an ethylene oxide adduct and a propylene oxide adduct of bisphenol A are mixed. More preferably, it is used.

  The mixing ratio (molar ratio) of bisphenol A ethylene oxide adduct (BPA-PO) and bisphenol A propylene oxide adduct (BPA-EO) is preferably 10/90 or more, more preferably 90/10 to 30/70. 80/20 to 60/40 is more preferable.

  In the alcohol component, the content of the alkylene oxide adduct of bisphenol A is preferably 60 mol% or more, more preferably 70 mol% or more, and still more preferably 90 to 100 mol%, from the viewpoint of improving the durability of the toner.

  Examples of the aliphatic diol include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 2,3-butanediol, and the like. From the viewpoint of improving glossiness, 1,2-propanediol and 2,3-butanediol are preferable.

  Other alcohol components include trihydric or higher polyhydric alcohols such as glycerin.

  The alcohol component may contain a monovalent alcohol, and the carboxylic acid component may contain a monovalent carboxylic acid compound as appropriate.

  The alcohol component and the carboxylic acid component constituting the cyclic polyester (A) and the chain polyester resin (B) are preferably the same.

  The softening point of the chain polyester resin (B) is preferably 80 ° C. or higher, more preferably 90 ° C. or higher, further preferably 100 ° C. or higher, and further preferably 110 ° C. or higher, from the viewpoint of improving the durability of the toner. And from a viewpoint of improving the glossiness of the printed matter obtained, 150 degrees C or less is preferable, 140 degrees C or less is more preferable, 130 degrees C or less is more preferable, 120 degrees C or less is further more preferable. Moreover, 80-150 degreeC is preferable, 90-140 degreeC is more preferable, 100-130 degreeC is more preferable, 110-120 degreeC is further more preferable.

  The glass transition temperature of the chain polyester resin (B) is preferably 50 ° C. or higher, more preferably 57 ° C. or higher, and even more preferably 61 ° C. or higher from the viewpoint of improving the durability of the toner. And from a viewpoint of improving the glossiness of the printed matter obtained, 80 degrees C or less is preferable and 70 degrees C or less is more preferable. Moreover, 50-80 degreeC is preferable, 57-70 degreeC is more preferable, 61-70 degreeC is further more preferable.

  The acid value of the chain polyester resin (B) is preferably 5 mgKOH / g or more, more preferably 10 mgKOH / g or more, from the viewpoint of promoting bleeding out of the cyclic polyester (A) and improving the durability of the toner. 11 mgKOH / g or more is more preferable. And it is preferably 30 mgKOH / g or less, more preferably 25 mgKOH / g or less, and further preferably 20 mgKOH / g or less. Moreover, 5-30 mgKOH / g is preferable, 10-25 mgKOH / g is more preferable, and 11-20 mgKOH / g is further more preferable.

  In addition, the softening point, glass transition temperature, and acid value of the chain polyester resin (B) are determined by the method described in the examples.

[Method for producing binder resin for toner]
The method for producing a binder resin for toner of the present invention is a method for producing a binder resin for a polyester toner containing a cyclic polyester (A) and a chain polyester resin (B), wherein the cyclic resin in the binder resin The mass ratio of the polyester (A) and the chain polyester resin is 0.01 / 99.99 to 5.0 / 95.0, and the alcohol component and the carboxylic acid component and / or polyester are subjected to condensation polymerization at 200 to 250 ° C. in the presence of a rare earth catalyst. Step 1 is included. In Step 1, a cyclic polyester is formed. In this invention, it is preferable to carry out by either of the following 2 aspects.

(Aspect 1)
In the aspect 1, as the step 1, the alcohol component and the carboxylic acid component are polycondensed in the presence of a titanium catalyst or a tin catalyst until the reaction rate becomes 70% or more and less than 100%, and then in the presence of the rare earth catalyst. In this method, step 1 ′ is carried out to obtain a mixture of cyclic polyester (A) and chain polyester resin (B) by condensation polymerization at 200 to 250 ° C.

(Aspect 2)
Aspect 2 is a chain obtained by polycondensation of an alcohol component and a carboxylic acid component in the presence of the cyclic polyester (A) obtained in Step 1 and a titanium catalyst or a tin catalyst in addition to Step 1 above. It is a method including the process 2 which mixes polyester (B).

  Among these, from the viewpoint of efficiently obtaining a binder resin excellent in durability and glossiness of the obtained toner, the method of Embodiment 1 is preferable, and the durability and glossiness of the obtained toner are easily within a required range. From the viewpoint of adjustment, the method of aspect 2 is preferred. Among these, the method of aspect 1 is more preferable from the viewpoint of achieving both the durability, glossiness and production efficiency of the obtained toner.

  Hereinafter, each aspect will be described.

[Aspect 1]
In step 1 ′ of embodiment 1, first, an alcohol component and a carboxylic acid component are subjected to polycondensation in the presence of a titanium catalyst or a tin catalyst (step a), whereby a chain polyester resin is obtained.

  The alcohol component and carboxylic acid component used in this embodiment are preferably those described in the alcohol component and carboxylic acid component of the cyclic polyester (A) and the chain polyester resin (B), and suitable alcohol components and carboxylic acid components. Is the same.

  The titanium catalyst or tin catalyst used as the esterification catalyst is preferably a tin catalyst from the viewpoint of promptly reaching the target reaction rate and suppressing coloring.

  As the titanium catalyst, a titanium compound having a Ti-O bond is preferable, a titanium compound having an alkoxy group having 1 to 28 carbon atoms in total, an alkenyloxy group or an acyloxy group is more preferable, and titanium diisopropylate bistriethanolaminate is further included. preferable.

  As the tin catalyst, a tin (II) compound having no Sn—C bond is preferable, and tin (II) 2-ethylhexanoate and dibutyltin oxide are more preferable.

  The amount of the esterification catalyst used is preferably 0.01 to 2.0 parts by mass, more preferably 0.1 to 1.5 parts by mass, and still more preferably 0.2 to 1.0 parts by mass with respect to 100 parts by mass of the total amount of the alcohol component and the carboxylic acid component.

  In this step, it is preferable to use a compound having a benzene ring in which a hydrogen atom bonded to three carbon atoms adjacent to each other is substituted with a hydroxyl group as a co-catalyst together with an esterification catalyst. .

  Examples of the compound having a benzene ring in which hydrogen atoms bonded to three adjacent carbon atoms are substituted with a hydroxyl group include pyrogallol compounds such as pyrogallol, gallic acid, gallic acid ester, and 2,3,4-trihydroxybenzophenone. Benzophenone derivatives such as 2,2 ', 3,4-tetrahydroxybenzophenone and the like, and from the viewpoint of reactivity, pyrogallol, gallic acid, alkyl esters having an alkyl group of 1 to 12 carbon atoms of gallic acid, etc. Among them, gallic acid and alkyl esters having an alkyl group having 1 to 12 carbon atoms of gallic acid are preferable.

  From the viewpoint of reactivity, the mass ratio of the cocatalyst to the catalyst (cocatalyst / catalyst) is preferably 0.01 or more, more preferably 0.02 or more, and further preferably 0.03 or more. And 0.5 or less is preferable, 0.3 or less is more preferable, 0.2 or less is further more preferable. Moreover, 0.01-0.5 are preferable, 0.02-0.3 are more preferable, and 0.03-0.2 are further more preferable.

  In this step, a radical polymerization inhibitor may be used from the viewpoint of preventing side reactions other than condensation polymerization. As the radical polymerization inhibitor, 4-t-butylcatechol is preferred.

  In this step, the condensation polymerization is preferably performed at a temperature of 160 to 250 ° C. in an inert gas atmosphere, and the reaction temperature is preferably 160 to 250 ° C. from the viewpoint of reactivity and thermal decomposability of the monomer. 180 to 240 ° C. is more preferable.

  The polycondensation reaction in this step is preferably carried out until the reaction rate is 70% or more and less than 100%, and is carried out until the reaction rate is 80% or more and less than 100%, and the cyclic polyester (A) and the chain polyester resin ( From the viewpoint of adjusting the abundance ratio and molecular weight of B), it is more preferable. The reaction rate in the present invention refers to a value of product reaction water amount (mol) / theoretical product water amount (mol) × 100.

  Next, polycondensation is performed at 200 to 250 ° C. in the presence of a rare earth catalyst to obtain a mixture of the cyclic polyester (A) and the chain polyester resin (B) (step b). Thereby, a part of chain polyester-type resin cyclizes and cyclic polyester is obtained. In this step, it is preferable to adjust the temperature of the reaction mixture obtained in the presence of the titanium catalyst or tin catalyst to 200 to 250 ° C. and add the rare earth catalyst.

  The rare earth catalyst used in this step is preferably an inorganic acid salt or organic acid salt of a rare earth element from the viewpoint of efficiently obtaining the cyclic polyester (A), and from the viewpoint of reaction efficiency, an organic acid salt is preferable, and a sulfonic acid salt. Is more preferable.

  As the rare earth element, lanthanoids such as scandium, yttrium, lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, etc. are preferable, scandium, lanthanum, samarium, europium. Erbium, lutetium and ytterbium are more preferred, and scandium, lanthanum, samarium and ytterbium are more preferred.

  As the sulfonate, triflate (trifluoromethanesulfonate), dodecylbenzenesulfonate and toluenesulfonate are preferable, and triflate is more preferable.

  In view of the above, the rare earth element sulfonate is preferably scandium, lanthanum, samarium, or ytterbium triflate, and more preferably scandium (III) triflate.

  In this step, from the viewpoint of efficiently obtaining the cyclic polyester (A), the condensation polymerization temperature is 200 ° C. or higher, preferably 210 ° C. or higher. And it is 250 degrees C or less, and 245 degrees C or less is preferable. Moreover, it is 200-250 degreeC, 210-250 degreeC is preferable and 210-245 degreeC is more preferable.

  When the condensation polymerization temperature is 200 ° C. or less, the cyclic polyester is not sufficiently formed, which is not preferable. When it is 250 ° C. or higher, the monomer and polymer are decomposed and coloring occurs, which is not preferable as a resin used for the toner.

  The amount of cyclic polyester produced can be confirmed by liquid chromatography-mass spectrometry (LC-MS) or the like, and can be appropriately adjusted depending on the reaction temperature and reaction time.

  Through the above step 1 ', a mixture of the cyclic polyester (A) and the chain polyester resin is obtained.

[Aspect 2]
In the aspect 2, the cyclic polyester (A) is prepared by the step 1 and a chain polyester resin is prepared by condensation polymerization of an alcohol component and a carboxylic acid component in the presence of a titanium catalyst or a tin catalyst, and both are mixed. Is the method.

(Process 1)
In this step, polyester may be used in addition to the alcohol component and the carboxylic acid component, but from the viewpoint of appropriately adjusting the molecular weight of the resulting cyclic polyester (A), only the alcohol component and the carboxylic acid component should be used. Is preferred.

  The alcohol component and carboxylic acid component used here are preferably the same as the alcohol component and carboxylic acid component constituting the cyclic polyester (A).

  The rare earth catalyst used is the same as in step b in embodiment 1 '.

  The condensation polymerization reaction temperature is also the same as in step b in the embodiment 1 '.

  In this step, the cyclic polyester (A) may be purified in order to control the amount of the cyclic polyester (A) in the binder resin for toner obtained by the subsequent mixing with the chain polyester resin (B). preferable.

  As a purification method, it is preferable to dissolve the reaction mixture in an organic solvent in which the polyester is dissolved, mix the aqueous medium, separate the layers, and remove the aqueous phase.

  The organic solvent used here is preferably a halogen solvent, an ether solvent, an ester solvent, or the like from the viewpoint of the solubility of the polyester, preferably a halogen solvent, and more preferably dichloromethane.

  As the aqueous medium, water is preferable, an aqueous alkaline solution is preferable, and an aqueous ammonia solution is more preferable.

  It is preferable to obtain the cyclic polyester (A) by removing the organic solvent from the organic solvent solution of the polyester obtained by purification.

  The chain polyester resin (B) used in this step is preferably obtained by the same method as in step a of the embodiment 1 ', and is preferably obtained by setting the reaction rate to 90% or more in the step a.

  The alcohol component and carboxylic acid component used are preferably those described as the alcohol component and carboxylic acid component of the chain polyester resin (B).

  The catalyst used is also preferably the one used in step a of the aforementioned embodiment 1 ′, more preferably a tin (II) compound having no Sn—C bond, 2-ethylhexanoic acid tin (II), dibutyl oxide More preferred is tin.

  In this step, the co-catalyst used with the catalyst is also preferably used in the step a, and a compound having a benzene ring in which hydrogen atoms bonded to three adjacent carbon atoms are substituted with a hydroxyl group is used. However, from the viewpoint of improving reactivity, gallic acid and alkyl esters having an alkyl group having 1 to 12 carbon atoms of gallic acid are preferable. From the viewpoint of preventing side reactions other than the condensation polymerization, a radical polymerization inhibitor may be used. As the radical polymerization inhibitor, 4-t-butylcatechol is preferred.

  The condensation polymerization conditions are also preferably the same as in step a above, and the reaction temperature is preferably 160 to 250 ° C., more preferably 180 to 240 ° C. in an inert gas atmosphere.

  The chain polyester resin (B) used in this step is preferably obtained by carrying out the reaction until the reaction rate in the step a is 90% or more, more preferably 93% or more, and 95% or more. Further preferred.

  In this step, the cyclic polyester (A) and the chain polyester resin (B) are mixed to obtain a binder resin for the toner. These are preferably mixed and melted to be uniform, It is more preferable to knead.

  For example, the chain polyester resin (B) and the cyclic polyester (A) are uniformly mixed with a mixer such as a Henschel mixer, and then sealed with a kneader, a single or twin screw extruder, an open roll kneader or the like. It is preferable to melt knead and cool.

  This step may be performed in the step of mixing raw materials other than the resin when the toner is manufactured, and the ratio of the chain polyester resin (B) and the cyclic polyester (A) can be easily set depending on the type of toner. Therefore, it is preferable to carry out the toner production.

[Binder resin for toner]
The binder resin for toner of the present invention is obtained by the above production method, and contains the cyclic polyester (A) and the chain polyester resin (B).

  The mass ratio of the cyclic polyester (A) to the chain polyester resin in the binder resin (cyclic polyester (A) / chain polyester resin) is 0.01 / 99.99 to 5.0 / 95.0. From the viewpoint of improving the ratio, 0.01 / 99.99 to 4.0 / 96.0 is preferable, 0.02 / 99.98 to 3.0 / 97.0 is more preferable, and 0.04 / 99.96 to 1.0 / 99.0 is further preferable. Further, from the viewpoint of improving the durability of the obtained toner, 0.06 / 99.94 to 5.0 / 95.0 is preferable, 0.1 / 99.9 to 5.0 / 95.0 is more preferable, 0.4 / 99.6 to 5.0 / 95.0 is more preferable, and 3.0 / 97.0 to More preferred is 5.0 / 95.0.

  The softening point of the binder resin for toner is preferably 90 ° C. or higher, more preferably 100 ° C. or higher, from the viewpoint of improving the durability of the toner. From the viewpoint of improving the glossiness of the toner, 130 ° C. or lower is preferable, and 110 ° C. or lower is more preferable. Moreover, 90-130 degreeC is preferable and 100-110 degreeC is more preferable.

  The glass transition temperature of the binder resin for toner of the present invention is preferably 50 ° C. or higher, more preferably 55 ° C. or higher, and further preferably 58 ° C. or higher from the viewpoint of improving the durability of the toner. From the viewpoint of improving the glossiness of the toner, it is preferably 100 ° C. or lower, more preferably 80 ° C. or lower, and further preferably 70 ° C. or lower. Moreover, 50-100 degreeC is preferable, 55-80 degreeC is more preferable, and 58-70 degreeC is further more preferable.

  The acid value of the binder resin for toner is preferably 3 mgKOH / g or more, more preferably 10 mgKOH / g or more, from the viewpoint of improving the durability of the toner. And 20 mgKOH / g or less is preferable and 15 mgKOH / g or less is more preferable. 3-20 mgKOH / g is preferable, and 10-15 mgKOH / g is more preferable.

[Toner for electrostatic image development]
The toner for developing an electrostatic image of the present invention contains both the binder resin for toner obtained by the above production method, so that both the gloss of the printed matter and the durability of the obtained toner can be achieved.

  The toner of the present invention may be used in combination with a known resin other than the toner binder resin as long as the effects of the present invention are not impaired. The content of the toner binder resin of the present invention is: The total binder resin in the toner is preferably 70% by mass or more, more preferably 80% by mass or more, still more preferably 90% by mass or more, and still more preferably 100% by mass.

  The toner of the present invention includes a colorant, a release agent, a charge control agent, a charge control resin, magnetic powder, a fluidity improver, a conductivity modifier, a reinforcing filler such as a fibrous substance, an antioxidant, and a cleaning property. Additives such as improvers may be contained, and it is preferred that a colorant, a release agent and a charge control agent are contained.

  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, Disazo Yellow and the like can be used, and the toner of the present invention may be either a black toner or a color toner. The content of the colorant is preferably 1 part by mass or more, more preferably 2 parts by mass or more, preferably 40 parts by mass or less, and more preferably 10 parts by mass or less with respect to 100 parts by mass of the binder resin. Moreover, 1-40 mass parts is preferable, and 2-10 mass parts 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 include ester waxes such as montan wax, sazol wax and their deoxidized wax, fatty acid ester wax, fatty acid amides, fatty acids, higher alcohols, fatty acid metal salts, and the like. It can be used by mixing.

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

  The content of the release agent is preferably 0.5 to 10 parts by mass with respect to 100 parts by mass of the binder resin from the viewpoint of low-temperature fixability and offset resistance of the toner and dispersibility in the binder resin. 1-8 mass parts is more preferable, and 1.5-7 mass parts is further more preferable.

  The charge control agent is not particularly limited, and may contain either a positively chargeable charge control agent or a negatively chargeable charge control agent.

  Examples of positively chargeable charge control agents include nigrosine dyes such as “Nigrosine Base EX”, “Oil Black BS”, “Oil Black SO”, “Bontron N-01”, “Bontron N-04”, “Bontron N-07 ”,“ Bontron N-09 ”,“ Bontron N-11 ”(manufactured by Orient Chemical Co., Ltd.), etc .; triphenylmethane dyes containing tertiary amines as side chains, quaternary ammonium salt compounds such as“ Bontron ” P-51 "(manufactured by Orient Chemical Industries), cetyltrimethylammonium bromide," COPY CHARGE PX VP435 "(manufactured by Clariant), etc .; polyamine resins such as" AFP-B "(manufactured by Orient Chemical Industries); imidazole derivatives Examples thereof include “PLZ-2001”, “PLZ-8001” (manufactured by Shikoku Kasei Co., Ltd.) and the like; styrene-acrylic resins such as “FCA-701PT” (manufactured by Fujikura Kasei Co., Ltd.) and the like.

  In addition, as a negatively chargeable charge control agent, metal-containing azo dyes such as “Varifirst Black 3804”, “Bontron S-31” (above, manufactured by Orient Chemical Industries), “T-77” (Hodogaya Chemical) Manufactured by Kogyo Co., Ltd.), Bontron S-32, Bontron S-34, Bontron S-36 (above, Orient Chemical Co., Ltd.), Eisenspiron Black TRH (Hodogaya Chemical Co., Ltd.) A metal compound of a benzylic acid compound, such as “LR-147”, “LR-297” (manufactured by Nippon Carlit Co., Ltd.); a metal compound of a salicylic acid compound, such as “Bontron E-81”, “Bontron E- 84, “Bontron E-88”, “E-304” (manufactured by Orient Chemical Co., Ltd.), “TN-105” (manufactured by Hodogaya Chemical Co., Ltd.); copper phthalocyanine dye; quaternary ammonium salt such as “ COPY CHARGE NX VP434 "(manufactured by Clariant), nitroimidazole derivative; organometallic Compounds, for example "TN105" (Hodogaya Chemical Co., Ltd.).

  The content of the charge control agent is preferably 0.01 parts by mass or more, more preferably 0.3 parts by mass or more, further preferably 0.5 parts by mass or more, with respect to 100 parts by mass of the binder resin, from the viewpoint of charging stability of the toner. 1 part by mass or more is more preferable, 10 parts by mass or less is preferable, 5 parts by mass or less is more preferable, 3 parts by mass or less is further preferable, and 1 to 2 parts by mass or less is more preferable. Moreover, 0.01-10 mass parts is preferable, 0.01-5 mass parts is more preferable, 0.3-3 mass parts is further more preferable, 0.5-3 mass parts is further more preferable, 1-2 mass parts is still more preferable.

  The toner of the present invention may be a toner obtained by any conventionally known method such as a melt-kneading method, an emulsion phase inversion method, or a polymerization method, but from the viewpoint of productivity and dispersibility of the colorant, A pulverized toner obtained by a melt kneading method is preferred. In the case of pulverized toner by the melt-kneading method, for example, a raw material such as a binder resin, a colorant, and a charge control agent is uniformly mixed with a mixer such as a Henschel mixer, and then a hermetically sealed kneader, a single or twin screw extruder It can be produced by melt-kneading with an open roll kneader or the like, cooling, pulverizing and classifying.

The volume median particle size (D ₅₀ ) of the toner of the present invention is preferably 3 to 15 μm, more preferably 3 to 10 μm. 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.

  In the toner of the present invention, an external additive is preferably used in order to improve transferability, and inorganic fine particles are preferably used as the external additive. Examples of the inorganic fine particles include silica, alumina, titania, zirconia, tin oxide and zinc oxide, and silica is preferable.

  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 10 to 250 nm, preferably 10 to 200 nm, more preferably 15 to 90 nm, from the viewpoint of the 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, and further preferably 0.3 to 3 parts by mass with respect to 100 parts by mass of the toner before being processed with the external additive. 3 parts by mass.

  The toner of the present invention can be used as a one-component developing toner or as a two-component developer mixed with a carrier.

  In relation to the above-described embodiment, the present invention further discloses the following method for producing a polyester-based toner binder resin and toner for developing an electrostatic image.

<1> A method for producing a binder resin for a polyester toner containing a cyclic polyester (A) and a linear polyester resin (B), wherein the mass ratio of the cyclic polyester (A) and the linear polyester resin (cyclic Polyester (A) / chain polyester-based resin) is 0.01 / 99.99 to 5.0 / 95.0, and an alcohol component and a carboxylic acid component and / or polyester are subjected to condensation polymerization at 200 to 250 ° C. in the presence of a rare earth catalyst. A method for producing a polyester resin binder resin, comprising:

<2> The acid value of the cyclic polyester (A) is preferably 0.1 mgKOH / g or less, more preferably 0 mgKOH / g, and the hydroxyl value of the cyclic polyester (A) is 0.1 mgKOH / g or less. The production method according to <1>, preferably having 0 mg KOH / g.

<3> The carboxylic acid component of the cyclic polyester (A) is an aromatic dicarboxylic acid compound, preferably 50 mol% or more, more preferably 60 mol% or more, still more preferably 70 mol% or more, more preferably 90 to 100%. The production method according to <1> or <2>, wherein the production method comprises mol%.

<4> The method according to any one of <1> to <3>, wherein the alcohol component of the cyclic polyester (A) contains an aromatic diol.

<5> The method according to <4>, wherein the aromatic diol is preferably an alkylene oxide adduct of bisphenol A, and more preferably a mixture of an ethylene oxide adduct and a propylene oxide adduct of bisphenol A.

<6> The content of the alkylene oxide adduct of bisphenol A is preferably 60 mol% or more, more preferably 70 mol% or more, and still more preferably 90 to 100 mol% in the alcohol component, Production according to <5> above Method.

<7> The number average molecular weight of the cyclic polyester (A) is preferably 100 or more, more preferably 200 or more, preferably 300 or more, preferably 1000 or less, more preferably 800 or less, and even more preferably 700 or less in terms of polystyrene. The manufacturing method in any one of said <1>-<6>.

<8> The number average molecular weight of the cyclic polyester (A) is preferably 100 to 1000, more preferably 200 to 1000, still more preferably 300 to 800, and still more preferably 300 to 700, <1> to <6>. Any manufacturing method.

<9> The production method according to any one of <1> to <8>, wherein the chain polyester resin (B) is preferably an amorphous polyester.

<10> The carboxylic acid component of the chain polyester resin (B) preferably contains an aromatic dicarboxylic acid compound in an amount of 50 mol% or more, more preferably 60 mol% or more, and even more preferably 90 to 100 mol%. The production method according to any one of <1> to <9>.

<11> The alcohol component of the chain polyester resin (B) preferably contains 50 mol% or more, more preferably 60 mol% or more, and still more preferably 90 to 100 mol% of an alkylene oxide adduct of bisphenol A. The manufacturing method in any one of said <1>-<10>.

<12> The method according to any one of <1> to <11>, wherein the alcohol component and the carboxylic acid component constituting the cyclic polyester (A) and the chain polyester resin (B) are the same.

<13> The softening point of the linear polyester resin (B) is preferably 80 ° C. or higher, more preferably 90 ° C. or higher, further preferably 100 ° C. or higher, more preferably 110 ° C. or higher, and preferably 150 ° C. or lower, 140 The production method according to any one of <1> to <12>, wherein the temperature is more preferably at most ° C, more preferably at most 130 ° C, further preferably at most 120 ° C.

<14> The glass transition temperature of the chain polyester resin (B) is preferably 50 ° C. or higher, more preferably 57 ° C. or higher, further preferably 61 ° C. or higher, preferably 80 ° C. or lower, more preferably 70 ° C. or lower, The production method according to any one of <1> to <13>.

<15> The acid value of the linear polyester resin (B) is preferably 5 mgKOH / g or more, more preferably 10 mgKOH / g or more, further preferably 11 mgKOH / g or more, preferably 30 mgKOH / g or less, and 25 mgKOH / g or less. Is more preferable, The manufacturing method in any one of said <1>-<14> whose 20 mgKOH / g or less is still more preferable.

<16> Step 1 polycondenses an alcohol component and a carboxylic acid component in the presence of a titanium catalyst or a tin catalyst until the reaction rate becomes 70% or more and less than 100%, and then in the presence of a rare earth catalyst, 200 <1>-<15> The manufacturing method in any one of said <1>-<15> which is process 1 'which makes it polycondensate at -250 degreeC and obtain the mixture of a cyclic polyester (A) and a linear polyester-type resin (B).

<17> In addition to step 1, the cyclic polyester (A) obtained in step 1 and a chain polyester obtained by polycondensation of an alcohol component and a carboxylic acid component in the presence of a titanium catalyst or a tin catalyst ( The manufacturing method in any one of said <1>-<16> including the process 2 which mixes B).

<18> The method according to <16> or <17>, wherein the tin catalyst is a tin (II) compound having no Sn—C bond.

<19> The production method according to <16>, wherein the polycondensation reaction in the presence of the titanium catalyst or the tin catalyst in the step 1 'is more preferably performed until the reaction rate becomes 80% or more and less than 100%.

<20> The method according to any one of <1> to <19>, wherein the rare earth catalyst is a sulfonate of a rare earth element.

<21> The method according to <20>, wherein the rare earth element sulfonate is scandium (III) triflate.

<22> The production method according to any one of <16> to <21>, wherein in the step 1 ', the condensation polymerization temperature in the presence of the rare earth catalyst is preferably 210 ° C or higher and preferably 245 ° C or lower.

<23> The mass ratio (cyclic polyester (A) / chain polyester resin) of the cyclic polyester (A) and the chain polyester resin in the binder resin is preferably 0.01 / 99.99 to 4.0 / 96.0, and 0.02 / 99.98 -3.0 / 97.0 is more preferable, 0.04 / 99.96-1.0 / 99.0 is still more preferable, The manufacturing method in any one of said <1>-<22>.

<24> The mass ratio of the cyclic polyester (A) and the chain polyester resin in the binder resin (cyclic polyester (A) / chain polyester resin) is preferably 0.06 / 99.94 to 5.0 / 95.0, 0.1 / 99.9 -5.0 / 95.0 is more preferable, 0.4 / 99.6-5.0 / 95.0 is still more preferable, 3.0 / 97.0-5.0 / 95.0 is still more preferable, The manufacturing method in any one of said <1>-<22>.

<25> The softening point of the binder resin for toner is preferably 90 ° C. or higher, more preferably 100 ° C. or higher, preferably 130 ° C. or lower, more preferably 110 ° C. or lower, and any one of <1> to <24> Manufacturing method.

<26> The glass transition temperature of the binder resin for toner is preferably 50 ° C. or higher, more preferably 55 ° C. or higher, further preferably 58 ° C. or higher, preferably 100 ° C. or lower, more preferably 80 ° C. or lower, and 70 ° C. or lower. Is more preferable, The manufacturing method in any one of said <1>-<25>.

<27> The acid value of the binder resin for toner is preferably 3 mgKOH / g or more, more preferably 10 mgKOH / g or more, preferably 20 mgKOH / g or less, more preferably 15 mgKOH / g or less. 3-20 mgKOH / g is preferable, 10-15 mgKOH / g is more preferable, The manufacturing method in any one of said <1>-<26>.

<28> A polyester resin binder resin obtained by the method according to any one of <1> to <27>.

<29> An electrostatic charge image developing toner comprising the polyester toner binder resin according to <28>.

  The physical properties of the resin and the like were measured by the following method.

(Resin softening point (Tm))
Using a flow tester (Shimadzu Corporation, CFT-500D), a 1 g sample is heated at a heating rate of 6 ° C / min, and a load of 1.96 MPa is applied by a plunger and extruded from a nozzle with a diameter of 1 mm and a length of 1 mm. 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 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. And let it stand for 1 minute. Thereafter, the measurement is performed at a heating rate of 50 ° C./min. Among the observed endothermic peaks, the temperature of the peak on the highest temperature side is defined as the highest endothermic peak temperature.

(Glass transition temperature (Tg) of resin)
Using a differential scanning calorimeter (Seiko Denshi Kogyo Co., Ltd., DSC210), weigh 0.01 to 0.02 g of the sample into an aluminum pan, raise the temperature to 200 ° C, and from that temperature to 0 ° C at a rate of 10 ° C / min. The temperature of the cooled sample is raised at a heating rate of 10 ° C / min, and the temperature at the intersection of the baseline extension below the endothermic peak temperature and the tangent that indicates the maximum slope from the peak rise to the peak apex. The glass transition temperature is assumed.

(Resin acid value (AV))
Measured according to 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 according to the method of JIS K0070.

[Number average molecular weight of 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.
(1) Preparation of sample solution Dissolve the sample in tetrahydrofuran 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 Using the following measuring device and analytical column, tetrahydrofuran is flowed as an eluent at a flow rate of 1 ml / min, and the column is stabilized in a constant temperature bath at 40 ° C. 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)

[Melting point of release agent]
Using a differential scanning calorimeter (Seiko Denshi Kogyo Co., Ltd., DSC210), the temperature was raised to 200 ° C, and the sample was cooled to 0 ° C at a temperature drop rate of 10 ° C / min. The maximum peak temperature of heat of fusion is taken as the melting point.

[Volume-median particle diameter of toner (D ₅₀ )]
Measuring machine: Coulter Multisizer II (Beckman Coulter, Inc.)
Aperture diameter: 50μm
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) 5% electrolyte dispersion condition: 10 mg of measurement sample is added to 5 ml of dispersion, and dispersed for 1 minute with an ultrasonic disperser. Then, 25 ml of the electrolytic solution is added, and further dispersed with an ultrasonic disperser for 1 minute.
Measurement conditions: Add 100 ml of electrolyte and dispersion in a beaker, measure 30,000 particles at a concentration that can measure the particle size of 30,000 particles in 20 seconds, and determine the volume-median particle size ( determine the D _50).

[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.

[Production of cyclic polyester (A)]
Production Examples 1 and 6 (Production of cyclic polyesters A-1 and A-6)
The raw material monomer and esterification catalyst shown in Table 1 were put into a 10-liter four-necked flask equipped with a thermometer, a stainless steel stirring rod, a flow-down condenser and a nitrogen inlet tube, and in a mantle heater in a nitrogen atmosphere, 245 The temperature was raised to ° C and the reaction was carried out at 245 ° C for 5 hours. Thereafter, the reaction mixture was cooled to room temperature to obtain a reaction mixture. Thereafter, 20 g of the reaction mixture was dissolved in 50 g of dichloromethane, and 100 g of a 0.6N aqueous ammonia solution was added and shaken, followed by liquid separation to extract unreacted monomers and the like in the aqueous phase. After repeating this operation three times, ion-exchanged water was added and shaken to obtain a dichloromethane solution. Thereafter, the dichloromethane solution was condensed and dried by a rotary evaporator to obtain a powdered polyester. The acid value and hydroxyl value of this polyester are both 0, indicating that it is a cyclic compound having no end group. The number average molecular weight is shown in Table 1.

Production Examples 2 and 3 (Production of cyclic polyesters A-2 and A-3)
The raw material monomer and the esterification catalyst shown in Table 1 were put into a 10 liter four-necked flask equipped with a thermometer, a stainless steel stirring rod, a flow-down condenser and a nitrogen inlet tube, and in a mantle heater in a nitrogen atmosphere, 180 After raising the temperature to 235C, the temperature was raised to 235 ° C over 3 hours. Thereafter, the reaction was carried out at 235 ° C. for 1 hour and then cooled to obtain a reaction mixture. Thereafter, the reaction mixture was purified in the same manner as in Production Example 1 to obtain a powdered polyester. The acid value and hydroxyl value of this polyester are both 0, indicating that it is a cyclic compound having no end group. The number average molecular weight is shown in Table 1.

Production Examples 4 and 5 (Production of cyclic polyesters A-4 and A-5)
The raw material monomers and esterification catalyst excluding fumaric acid shown in Table 1 were put into a 10 liter four-necked flask equipped with a thermometer, a stainless steel stirring bar, a flow-down condenser and a nitrogen inlet tube, and a mantle heater in a nitrogen atmosphere The temperature was raised to 180 ° C., and then the temperature was raised to 235 ° C. over 3 hours. Then, it cooled to 200 degreeC over 1 hour, and mixed 4-t- butyl catechol (radical polymerization inhibitor) and fumaric acid. Thereafter, the temperature was raised to 210 ° C. over 2 hours. After reacting at 210 ° C. for 1 hour, the reaction mixture was cooled to obtain a reaction mixture. Thereafter, the reaction mixture was purified in the same manner as in Production Example 1 to obtain a powdered polyester. The acid value and hydroxyl value of this polyester are both 0, indicating that it is a cyclic compound having no end group. The number average molecular weight is shown in Table 1.

[Production of chain polyester resin (B)]
Production Examples 7 and 12 (Production of linear polyesters B-1 and B-6)
The raw material monomer, esterification catalyst and cocatalyst shown in Table 2 were put into a 10 liter four-necked flask equipped with a thermometer, a stainless steel stirring rod, a flow-down condenser and a nitrogen inlet tube, and in a mantle heater in a nitrogen atmosphere. The temperature was raised to 235 ° C., and the reaction was carried out at 235 ° C. for 10 hours. Thereafter, the reaction was carried out at 235 ° C. and 8 KPa until the softening point shown in Table 2 was reached to obtain a polyester. The physical properties are shown in Table 2.

Production Examples 8 and 9 (Production of chain polyesters B-2 and B-3)
The raw material monomer, esterification catalyst and cocatalyst shown in Table 2 were put into a 10 liter four-necked flask equipped with a thermometer, a stainless steel stirring rod, a flow-down condenser and a nitrogen inlet tube, and in a mantle heater in a nitrogen atmosphere. Then, the temperature was raised to 180 ° C. and then raised to 210 ° C. over 5 hours. Thereafter, it was confirmed that the reaction rate reached 90% at 210 ° C., and the reaction was carried out at 40 kPa until the softening point shown in Table 2 was reached, thereby obtaining a polyester. The physical properties are shown in Table 2. The reaction rate means a value of the amount of produced reaction water / theoretical product water amount × 100.

Production Examples 10 and 11 (Production of linear polyesters B-4 and B-5)
The raw material monomers and esterification catalyst excluding fumaric acid shown in Table 2 were put into a 10 liter four-necked flask equipped with a thermometer, a stainless steel stirring bar, a flow-down condenser and a nitrogen inlet tube, and a mantle heater in a nitrogen atmosphere The temperature was raised to 180 ° C., and then the temperature was raised to 235 ° C. over 3 hours. Then, it cooled to 200 degreeC over 1 hour, and mixed 4-t- butyl catechol (radical polymerization inhibitor) and fumaric acid. Thereafter, the temperature was raised to 210 ° C. over 2 hours. After reacting at 210 ° C. for 1 hour, the reaction was conducted at 40 kPa until the softening point shown in Table 2 was reached, to obtain a polyester. The physical properties are shown in Table 2.

[Production of Binder Resin for Polyester Toner (Aspect 1)]
Example 1 (Production of binder resin 1)
The raw material monomer, esterification catalyst 1 and cocatalyst shown in Production Example 13 of Table 3 were put into a 10-liter four-necked flask equipped with a thermometer, a stainless steel stirring bar, a flow-down condenser and a nitrogen inlet tube, and a nitrogen atmosphere The temperature was raised to 235 ° C in a mantle heater at 235 ° C, and the reaction was carried out at 235 ° C for 10 hours. Thereafter, the reaction was carried out at 235 ° C. and 8 KPa for 1 hour, and it was confirmed that the reaction rate reached 90%. Then, after returning to normal pressure with nitrogen, esterification catalyst 2 was added at 235 ° C. Thereafter, the reaction was carried out at normal pressure and 235 ° C. for 3 hours. The obtained resin was confirmed to contain 0.3% by mass of cyclic polyester by LC-MS. Table 3 shows the physical properties.

Comparative Example 1 (Production of Binder Resin 2)
The raw material monomer, esterification catalyst 1 and cocatalyst shown in Production Example 14 of Table 3 were put into a 10-liter four-necked flask equipped with a thermometer, a stainless steel stirring bar, a flow-down condenser and a nitrogen inlet tube, and a nitrogen atmosphere The temperature was raised to 235 ° C in a mantle heater at 235 ° C, and the reaction was carried out at 235 ° C for 10 hours. Thereafter, the reaction was performed at 235 ° C. and 8 KPa for 1 hour, and it was confirmed that the reaction rate reached 90%. Then, after returning to normal pressure with nitrogen, esterification catalyst 2 was added. Immediately after that, the temperature was set to 170 ° C., and the reaction was performed at normal pressure and 170 ° C. for 3 hours. The obtained resin was confirmed to contain 0.005% by mass of cyclic polyester by LC-MS. Table 3 shows the physical properties.

[Production of toner for developing electrostatic image (Aspect 2)]
Examples 2 to 14 and Comparative Examples 2 and 3
A total of 20 parts by mass of the chain polyester resin (B) and the cyclic polyester (A) shown in Tables 4 and 5 in the mass ratios shown in Tables 4 and 5, negative charge control agent “Bontron E-81” (Orient Chemical) Kogyo Co., Ltd.) 0.2 parts by weight, Colorant “Regal 330R” (Cabot, carbon black) 1 part by weight, Release agent “Mitsui High Wax NP055” (Mitsui Chemicals, polypropylene wax, melting point: 125 ° C.) 0.4 After adding a part by mass and thoroughly mixing with a Henschel mixer, the mixture was melt-kneaded at a roll rotation speed of 200 r / min and a heating temperature of 80 ° C. using a co-rotating twin screw extruder. The obtained melt-kneaded product was cooled and coarsely pulverized, then pulverized with a jet mill and classified to obtain toner particles having a volume median particle size (D ₅₀ ) of 8 μm.

  To 100 parts by mass of the obtained toner particles, 1.0 part by mass of hydrophobic silica “NAX-50” (manufactured by Nippon Aerosil Co., Ltd., hydrophobizing agent: HMDS, average particle size: 30 nm) is added and mixed with a Henschel mixer. Thus, a toner was obtained.

[Manufacture of toner for developing electrostatic image (Aspect 1)]
Example 15
120 parts by weight of binder resin, 0.2 parts by weight of negatively chargeable charge control agent “Bontron E-81” (manufactured by Orient Chemical Co., Ltd.), 1 part by weight of colorant “Regal 330R” (manufactured by Cabot, carbon black), and release The mold "Mitsui High Wax NP055" (manufactured by Mitsui Chemicals, polypropylene wax, melting point: 125 ° C) was mixed thoroughly with a Henschel mixer, and then the roll rotation speed was 200r / The mixture was melt kneaded at a heating temperature of 80 ° C. in the roll for min. The obtained melt-kneaded product was cooled and coarsely pulverized, then pulverized with a jet mill and classified to obtain toner particles having a volume median particle size (D ₅₀ ) of 8 μm.

  To 100 parts by mass of the obtained toner particles, 1.0 part by mass of hydrophobic silica “NAX-50” (manufactured by Nippon Aerosil Co., Ltd., hydrophobizing agent: HMDS, average particle size: 30 nm) is added and mixed with a Henschel mixer. Thus, a toner was obtained.

Test Example 1 [Durability]
Toner is mounted on a non-magnetic one-component development system "OKI Microline 18" (Oki Data Co., Ltd.) and resists diagonal stripe patterns with a blackening rate of 5.5% under conditions of a temperature of 35 ° C and a humidity of 85%. I made a print. On the way, a black solid image was printed every 500 sheets, and streaks on the image were confirmed. The number of printed sheets up to the time when the streak was visually observed on the image was defined as the number of printed sheets. The larger the value, the better the durability. The results are shown in Tables 4 and 5.

Test Example 2 [Glossiness of printed matter]
Toner was mounted on a copier (Sharp Co., Ltd., trade name: “AR-505”) with an improved fixing machine so that it can be fixed outside the machine, and printed matter was obtained in an unfixed state. (printing area: 2 cm × 12cm, coating weight: 0.5mg / cm ^2). Thereafter, the image was fixed on the paper at 160 ° C. and 400 mm / sec by the fixing machine of the copying machine. Note that J paper (trade name, manufactured by Fuji Xerox Co., Ltd.) was used as a printing medium. A cardboard was laid under the image, and the glossiness of the printed matter was measured using a gloss meter (trade name: “IG-330”, manufactured by HORIBA, Ltd.) under light irradiation conditions at an incident angle of 60 °. The higher the value obtained, the higher the glossiness and the better. The results are shown in Tables 4 and 5.

  From the above results, it can be seen that the toners of the examples are both excellent in durability and gloss of printed matter as compared with the toners of the comparative examples.

  The polyester-based toner binder resin obtained by the method of the present invention is suitably used for toners used for developing latent images formed in electrophotography, electrostatic recording, electrostatic printing, and the like. is there.

Claims (11)

  A method for producing a binder resin for a polyester toner containing a cyclic polyester (A) and a chain polyester resin (B), wherein the mass ratio of the cyclic polyester (A) and the chain polyester resin (cyclic polyester (A) ) / Chain polyester resin) is 0.01 / 99.99 to 5.0 / 95.0, and includes a step 1 in which an alcohol component and a carboxylic acid component and / or polyester are subjected to polycondensation at 200 to 250 ° C. in the presence of a rare earth catalyst. And a method for producing a binder resin for polyester toner.   In Step 1, the alcohol component and the carboxylic acid component are subjected to polycondensation in the presence of a titanium catalyst or a tin catalyst until the reaction rate becomes 70% or more and less than 100%, and then in the presence of a rare earth catalyst, 200 to 250 ° C. The method for producing a binder resin for a polyester toner according to claim 1, which is a step 1 ′ in which a mixture of the cyclic polyester (A) and the chain polyester resin (B) is obtained by condensation polymerization.   Further, Step 2 in which the cyclic polyester (A) obtained in Step 1 is mixed with the chain polyester (B) obtained by polycondensing an alcohol component and a carboxylic acid component in the presence of a titanium catalyst or a tin catalyst. The manufacturing method of the binder resin for polyester-type toners of Claim 1 containing this.   The method for producing a binder resin for a polyester toner according to any one of claims 1 to 3, wherein the cyclic polyester (A) has a number average molecular weight of 100 to 1,000.   The method for producing a binder resin for a polyester-based toner according to any one of claims 1 to 4, wherein the cyclic polyester (A) has an acid value of 0.1 mgKOH / g or less and a hydroxyl value of 0.1 mgKOH / g or less.   The method for producing a binder resin for toner according to claim 2, wherein the tin catalyst is a tin (II) compound having no Sn—C bond.   The method for producing a binder resin for toner according to claim 1, wherein the rare earth catalyst is a sulfonate.   The method for producing a binder resin for a polyester toner according to any one of claims 1 to 7, wherein the alcohol component of the chain polyester resin (B) contains 60 mol% or more of an alkylene oxide adduct of bisphenol A.   The method for producing a binder resin for a polyester toner according to any one of claims 1 to 8, wherein the carboxylic acid component of the chain polyester resin (B) contains 60 mol% or more of an aromatic dicarboxylic acid compound.   The method for producing a binder resin for a polyester-based toner according to any one of claims 1 to 9, wherein the alcohol component of the cyclic polyester (A) contains 60 mol% or more of an alkylene oxide adduct of bisphenol A.   The method for producing a binder resin for a polyester toner according to any one of claims 1 to 10, wherein the carboxylic acid component of the cyclic polyester (A) contains 60 mol% or more of an aromatic dicarboxylic acid compound.