JP6367535B2 - Binder resin composition for toner - Google Patents

Description

  The present invention relates to a toner binder resin composition used for developing a latent image formed in an electrophotographic method, and an electrostatic charge image developing toner containing the binder resin composition.

  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 response to higher image quality and higher speed, polyester resins that are easy to adjust in composition are widely used as binder resins for toners, particularly to improve thermal properties, and attempts to use more than one resin Has been made.

  For example, Patent Document 1 discloses a process for obtaining a melt-kneaded product by melt-kneading a component containing a binder resin and a colorant for the purpose of improving low-temperature fixability, heat-resistant storage stability, grindability, and grinding classification yield. And a step of pulverizing and classifying the obtained melt-kneaded product, wherein the binder resin contains an alcohol component and a rosin compound containing an aliphatic diol having 2 to 6 carbon atoms and an aliphatic dicarboxylic acid having 6 to 10 carbon atoms. A polyester A obtained by polycondensation with a carboxylic acid component containing an acid compound, and a polyester B obtained by polycondensation of an alcohol component containing an ethylene oxide adduct of bisphenol A and a carboxylic acid component, The content of polyester B is 4 to 20% by mass in the binder resin, and the content of ethylene oxide adduct of bisphenol A is 45% in the alcohol component of polyester B. A method for producing a toner for developing an electrostatic image containing a binder resin and a colorant that is at least 1% by weight is disclosed.

  In addition, Patent Document 2 discloses that 5 to 25 moles of alcohol component and 100 moles of alcohol component are used for the purpose of improving low-temperature fixability, storage stability of printed matter, and curling of printed matter. Contains 70 to 100 mol% of an amorphous polyester having a number average molecular weight of 1000 to 2400 obtained by polycondensation with a carboxylic acid component containing an adipic acid compound and an aliphatic diol having 6 to 12 carbon atoms A toner binder resin comprising a crystalline polyester obtained by polycondensation of an alcohol component and a carboxylic acid component containing 70 to 100 mol% of an aliphatic dicarboxylic acid compound having 8 to 12 carbon atoms is disclosed. Has been.

  Patent Document 3 contains a crystalline polyester resin, an amorphous polyester resin, a release agent, and a colorant for the purpose of suppressing the occurrence of soft aggregates in the developing device. The electrostatic charge image developing toner has a glass transition temperature measured by a differential scanning calorimeter (DSC) of 40 ° C. or higher and 60 ° C. or lower, and the toner particle spacing after storage of the electrostatic charge image developing toner at 50 ° C. An electrostatic charge image developing toner characterized in that the adhesion is 1.4 mN or more and 2.2 mN or less is disclosed.

JP 2013-125177 A JP 2012-118395 A JP 2012-118504 A

  In electrophotography, development of a toner having a wide non-offset range and even better low-temperature fixability is required. Particularly, in a high-speed machine, energy transferred to the toner with respect to the temperature of the fixing machine. Since the amount is reduced, further improvement in low-temperature fixability is required. In order to improve the low-temperature fixability, a method of adjusting the melting behavior by adding wax, crystalline polyester or the like to the toner is used. However, wax, crystalline polyester, or the like is likely to become a charging leak site. On the other hand, there is also a problem that the printed matter adheres to the fixing roller and does not separate. Accordingly, there is a need for a toner that is excellent in low-temperature fixability, charge stability under high temperature and high humidity, and releasability of the fixing roller.

  The present invention relates to a binder resin composition for toner excellent in low-temperature fixability, charge stability under high temperature and high humidity, and fixing roller peelability of the obtained toner, and an electrostatic charge image containing the binder resin composition The present invention relates to a developing toner.

  The inventors have found that the factors affecting the low-temperature fixability, the charging stability under high temperature and high humidity, and the peelability of the fixing roller of the obtained toner are the state of the resin in the binder resin composition contained in the toner. Considered that it was due to. As a result, the binder resin composition is obtained by reacting a carboxylic acid component containing a specific softening point and an aliphatic dicarboxylic acid compound having 8 to 14 carbon atoms with an alcohol component containing an aromatic diol. In order to complete the present invention, it has been found that by incorporating a high quality polyester and a crystalline polyester, the resulting toner exhibits excellent low temperature fixability, charging stability under high temperature and high humidity, and fixing roller peelability. It came.

The present invention
[1] A binder resin composition for toner containing amorphous polyester L and crystalline polyester C, wherein the amorphous polyester L has an alcohol component containing an aromatic diol and a carbon number of 8 to 14. A binder resin composition for toner, which is an amorphous polyester having a softening point of 80 to 110 ° C., obtained by polycondensation with a carboxylic acid component containing an aliphatic dicarboxylic acid compound;
[2] An electrostatic charge image developing toner containing the toner binder resin composition according to [1], and [3] An electrostatic charge image developing toner containing amorphous polyester L and crystalline polyester C Wherein the amorphous polyester L is obtained by polycondensation of an alcohol component containing an aromatic diol and a carboxylic acid component containing an aliphatic dicarboxylic acid compound having 8 to 14 carbon atoms. The present invention relates to an electrostatic charge image developing toner which is an amorphous polyester at 80 to 110 ° C.

  The binder resin composition for toner of the present invention exhibits excellent effects that the obtained toner is excellent in low-temperature fixability, charging stability under high temperature and high humidity, and fixing roller peelability.

  The toner binder resin composition of the present invention is a toner binder resin composition containing amorphous polyester L and crystalline polyester C, wherein the amorphous polyester L is a fatty acid having 8 to 14 carbon atoms. It is an amorphous polyester having a softening point of 80 to 110 ° C. obtained by polycondensation of a carboxylic acid component containing an aromatic dicarboxylic acid compound and an alcohol component containing an aromatic diol.

  The reason why the toner containing the binder resin composition of the present invention is excellent in low-temperature fixability, charging stability under high temperature and high humidity, and fixing roller peelability is not clear, but can be considered as follows.

  The binder resin composition of the present invention contains an amorphous polyester and a crystalline polyester. However, when these compatibility is poor, the low-temperature fixability is also lowered, and the crystalline polyester tends to be a charge leakage site. On the other hand, if the compatibility is too good, the crystalline polyester plasticizes the amorphous polyester and the low-temperature fixability is improved, but the peelability of the printed matter from the fixing roller is deteriorated.

In the present invention, an amorphous polyester (amorphous polyester L) having a relatively low softening point contains an aliphatic dicarboxylic acid compound having a relatively long main chain and an aromatic diol as raw material monomers. Aliphatic dicarboxylic acid compounds with a long main chain have high affinity with crystalline polyester, and also become an entangled part in amorphous polyester, so that the viscosity during melting can be improved and the crystalline polyester can be finely dispersed it is conceivable that. Furthermore, since the aromatic diol part which has a rigid structure is included, it is thought that compatibility with crystalline polyester can be reduced. As described above, in the toner containing the binder resin composition of the present invention, the crystalline polyester can be finely dispersed while preventing the amorphous polyester from being plasticized. It is considered that it is excellent in charging stability below and fixing roller peelability.
Furthermore, since the amorphous polyester to be used has a relatively low softening point, it is considered that the amorphous polyester is melted together with the crystalline polyester by heating at the time of printing to further improve the low-temperature fixability.

  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.

  The amorphous polyester L is obtained by using at least an alcohol component and a carboxylic acid component as raw material monomers and polycondensing them.

  The alcohol component of the amorphous polyester L contains an aromatic diol from the viewpoint of low-temperature fixability of the obtained toner, charging stability under high temperature and high humidity, and fixing roller peelability.

  As the aromatic diol, the formula (I):

(Wherein R ¹ O is an alkylene oxide, R ¹ is an alkylene group having 2 or 3 carbon atoms, x and y are positive numbers indicating the average number of moles of alkylene oxide added, and the sum of x and y is 1 to 16, preferably 1.5 to 5.0)
An alkylene oxide adduct of bisphenol A represented by Examples of alkylene oxide adducts of bisphenol A represented by the formula (I) include polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, polyoxyethylene (2.2) -2,2-bis (4-hydroxyphenyl) propane and the like.

The alkylene oxide adduct of bisphenol A represented by the formula (I) is a compound in which R ¹ O is propylene oxide from the viewpoint of low-temperature fixability of the toner obtained, charging stability under high temperature and high humidity, and fixing roller peelability. The propylene oxide adduct of bisphenol A and R ¹ O are preferably one or more selected from the ethylene oxide adduct of bisphenol A in which ethylene oxide is used, and at least contains a propylene oxide adduct of bisphenol A. More preferably, it consists of a propylene oxide adduct of bisphenol A and an ethylene oxide adduct of bisphenol A.

  The molar ratio of the ethylene oxide adduct of bisphenol A and the propylene oxide adduct of bisphenol A contained in the alcohol component (the ethylene oxide adduct / propylene oxide adduct) is the low-temperature fixability of the toner and the storage stability under high humidity. In view of the above, 0/100 to 70/30 is preferable, 3/97 to 65/35 is more preferable, 5/95 to 60/40 is more preferable, 10/90 to 50/50 is further preferable, and 20/80 More preferred is ˜40 / 60.

  The content of the aromatic diol is preferably 40 to 100 mol%, more preferably 70 to 100 mol%, and still more preferably 90 to 100 mol% in the alcohol component.

  Examples of alcohols other than aromatic diols include diols such as ethylene glycol, 1,2-propylene glycol, 1,4-butanediol, neopentyl glycol, polyethylene glycol, polypropylene glycol, hydrogenated bisphenol A; sorbitol, pentaerythritol, glycerin And trihydric or higher polyhydric alcohols such as trimethylolpropane.

  From the viewpoint of improving the dispersibility of the crystalline polyester and improving the low temperature fixability of the resulting toner, the charging stability under high temperature and high humidity, and the fixing roller peelability, the carboxylic acid component of the amorphous polyester L Contains an aliphatic dicarboxylic acid compound having 8 to 14 carbon atoms. In the present invention, the carbon number is the carbon number including the carbon of the carboxy group. The aliphatic dicarboxylic acid compound having 8 to 14 carbon atoms preferably has a main chain having 6 to 12 carbon atoms.

  Examples of aliphatic dicarboxylic acid compounds having 8 to 14 carbon atoms include suberic acid (main chain carbon number: 6), azelaic acid (main chain carbon number: 7), sebacic acid (main chain carbon number: 8), 1,10 -Decanedicarboxylic acid (main chain carbon number: 10), 1,12-dodecanedicarboxylic acid (main chain carbon number: 12), succinic acid having an alkyl group or alkenyl group in the side chain, anhydrides of these acids, they And an alkyl ester having 1 to 3 carbon atoms. In the present invention, the carboxylic acid compound includes not only a free acid but also an anhydride that decomposes during the reaction to produce an acid and an alkyl ester having 1 to 3 carbon atoms. However, the carbon number of the alkyl group in the alkyl ester portion is not included in the carbon number of the aliphatic dicarboxylic acid compound.

  The chain hydrocarbon group in the aliphatic dicarboxylic acid compound may be linear or branched, and the number of carbon atoms of the aliphatic dicarboxylic acid compound is preferably 8 or more, from the viewpoint of charging stability, 10 or more Is more preferable, and 12 or more is more preferable. From the viewpoint of low-temperature fixability, it is preferably 14 or less, and preferably 13 or less.

  The carboxylic acid component may contain a carboxylic acid compound other than the aliphatic dicarboxylic acid compound having 8 to 14 carbon atoms, but the content of the aliphatic dicarboxylic acid compound having 8 to 14 carbon atoms is Among these, from the viewpoint of low-temperature fixability of the obtained toner, it is preferably 10 mol% or more, more preferably 15 mol% or more, and further preferably 17 mol% or more. Further, from the viewpoint of toner storage stability and charging stability, it is preferably 35 mol% or less, more preferably 30 mol% or less, and even more preferably 25 mol% or less.

  Further, the content of the aliphatic dicarboxylic acid compound having 8 to 14 carbon atoms is preferably 2 moles or more, more preferably 5 moles or more, from the viewpoint of low-temperature fixability of the resulting toner with respect to 100 moles of the alcohol component. 10 mol or more is more preferable. Further, from the viewpoint of storage stability and charge stability of the toner, it is preferably 40 mol or less, more preferably 30 mol or less, and further preferably 20 mol or less.

  As the other carboxylic acid compound, an aromatic dicarboxylic acid compound is preferable from the viewpoint of chargeability of the toner. Examples of the aromatic dicarboxylic acid compound include terephthalic acid, isophthalic acid, anhydrides of these acids, alkyl esters having 1 to 3 carbon atoms, and the like.

  The content of the aromatic dicarboxylic acid compound is preferably 30 mol% or more, more preferably 50 mol% or more in the carboxylic acid component. Further, from the viewpoint of low-temperature fixability and charging stability of the toner, 85 mol% or less is preferable, 80 mol% or less is more preferable, and 70 mol% or less is more preferable.

  Other carboxylic acid components include aliphatic dicarboxylic acid compounds having 2 to 7 carbon atoms, trivalent or higher polyvalent carboxylic acid compounds such as trimellitic acid and pyromellitic acid, anhydrides of these acids, and their carbon numbers. Examples thereof include 1 to 3 alkyl esters.

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

  The temperature during the polycondensation reaction between the alcohol component and the carboxylic acid component is preferably 180 ° C. or higher, more preferably 200 ° C. or higher, from the viewpoint of reactivity. Further, from the viewpoint of thermal decomposability, 250 ° C. or lower is preferable. Moreover, 180-250 degreeC is preferable and the temperature at the time of polycondensation reaction has more preferable 200-250 degreeC.

  The polycondensation reaction may be performed in the presence of an esterification catalyst, an esterification cocatalyst, a polymerization inhibitor, or the like, if necessary.

  Examples of esterification catalysts include tin catalysts and titanium catalysts. Examples of the tin catalyst include dibutyltin oxide and tin (II) 2-ethylhexanoate. From the viewpoints of reactivity, molecular weight adjustment, and resin physical property adjustment, tin (II) having no Sn—C bond is used. It is preferably obtained by polycondensation using a compound as a catalyst.

  As the tin (II) compound 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) ) A tin (II) compound having a bond is preferable, and a tin (II) compound having a Sn-O bond is more preferable.

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 ² COO) ₂ Sn (wherein R ² represents an alkyl group or alkenyl group having 5 to 19 carbon atoms), (R ³ O) ₂ Sn (where R ³ 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 ² COO) fatty tin represented by ₂ Sn (II) and tin oxide ( II) is more preferred, tin (II) octoate, tin (II) 2-ethylhexanoate, tin (II) stearate and tin (II) oxide are more preferred, tin (II) 2-ethylhexanoate and oxidation Even more preferred is tin (II).

  Examples of the titanium catalyst include titanium diisopropylate bistriethanolamate.

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

  Examples of the esterification promoter include gallic acid. The amount of the esterification cocatalyst used is preferably 0.001 to 0.5 parts by mass, more preferably 0.01 to 0.1 parts by mass with respect to 100 parts by mass of the total amount of the alcohol component and the carboxylic acid component. Examples of the polymerization inhibitor include tert-butylcatechol. The amount of the polymerization inhibitor used is preferably 0.001 to 0.5 parts by mass and more preferably 0.01 to 0.1 parts by mass with respect to 100 parts by mass of the total amount of the alcohol component and the carboxylic acid component.

  In the present invention, the term “polyester” includes polyester that has been modified to such an extent that its properties are not substantially impaired. Examples of the modified polyester include a urethane-modified polyester in which the polyester is modified with a urethane bond, an epoxy-modified polyester in which the polyester is modified with an epoxy bond, and two or more resin components including a polyester component and an addition polymerization resin component. The amorphous polyester in the present invention preferably has a polyester portion of 98% by mass or more, more preferably consists essentially of the polyester portion, and more preferably only from the polyester portion. Become.

  The softening point of the amorphous polyester L is 80 ° C. or higher, preferably 90 ° C. or higher, more preferably 92 ° C. or higher, and still more preferably 94 ° C. or higher, from the viewpoint of toner storage stability. Further, from the viewpoint of low-temperature fixability of the toner, it is 110 ° C. or lower, preferably 100 ° C. or lower, more preferably 98 ° C. or lower, and even more preferably 97 ° C. or lower. Further, from the viewpoint of charging stability of the toner, 90 to 100 ° C is preferable, 92 to 98 ° C is more preferable, and 94 to 97 ° C is further preferable.

  The glass transition temperature of the amorphous polyester L is preferably 40 ° C. or higher, more preferably 45 ° C. or higher, further preferably 49 ° C. or higher, and further preferably 50 ° C. or higher, from the viewpoint of toner charging stability and storage stability. Further, from the viewpoint of low-temperature fixability of the toner, 60 ° C. or lower is preferable, 57 ° C. or lower is more preferable, 55 ° C. or lower is further preferable, and 50 ° C. or lower is further preferable.

  The acid value of the amorphous polyester L is preferably 3 mgKOH / g or more, more preferably 5 mgKOH / g or more, from the viewpoint of chargeability of the toner. Further, from the viewpoint of charging stability of the toner at high temperature and high humidity, it is preferably 30 mgKOH / g or less, more preferably 20 mgKOH / g or less.

  The alcohol component of the crystalline polyester C preferably contains an aliphatic diol having 6 to 12 carbon atoms, preferably 9 to 12 carbon atoms, from the viewpoint of storage stability.

  Examples of the aliphatic diol having 6 to 12 carbon atoms include 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11 -Undecanediol, 1,12-dodecanediol and the like.

  The number of carbon atoms of the aliphatic diol is preferably 6 or more, more preferably 9 or more, and further preferably 10 or more, from the viewpoint of storage stability. From the viewpoint of low-temperature fixability, 12 or less is preferable.

  The aliphatic diol having 6 to 12 carbon atoms preferably has a hydroxyl group at the end of the carbon chain from the viewpoint of improving the low-temperature fixability of the toner, and is an α, ω-linear alkanediol. Is preferred.

  The alcohol component may contain an alcohol other than the aliphatic diol having 6 to 12 carbon atoms, but the content of the aliphatic diol having 6 to 12 carbon atoms is 70 to 100 mol% in the alcohol component. Preferably, 80 to 100 mol% is more preferable, 90 to 100 mol% is further preferable, and substantially 100 mol% is further more preferable.

  As alcohol components other than aliphatic diols having 6 to 12 carbon atoms, aliphatic diols having 2 to 5 carbon atoms such as ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, Examples thereof include aromatic diols such as alkylene oxide adducts of bisphenol A and trihydric or higher polyhydric alcohols such as glycerin.

  The carboxylic acid component of the crystalline polyester C preferably contains an aliphatic dicarboxylic acid compound having 8 to 14 carbon atoms.

  Examples of aliphatic dicarboxylic acid compounds having 8 to 14 carbon atoms include suberic acid (main chain carbon number: 6), azelaic acid (main chain carbon number: 7), sebacic acid (main chain carbon number: 8), 1,10 -Decanedicarboxylic acid (main chain carbon number: 10), 1,12-dodecanedicarboxylic acid (main chain carbon number: 12), succinic acid having an alkyl group or alkenyl group in the side chain, anhydrides of these acids, they And an alkyl ester having 1 to 3 carbon atoms.

  The chain hydrocarbon group in the aliphatic dicarboxylic acid compound may be linear or branched, and the aliphatic dicarboxylic acid compound preferably has 10 or more carbon atoms. From the viewpoint of low-temperature fixability, 13 or less is preferable.

  The carboxylic acid component may contain a carboxylic acid compound other than the aliphatic dicarboxylic acid compound having 8 to 14 carbon atoms, but the content of the aliphatic dicarboxylic acid compound having 8 to 14 carbon atoms is Among these, 70 mol% or more is preferable, 80 mol% or more is more preferable, and 90 mol% or more is more preferable. Further, from the viewpoint of charging stability of the toner under high temperature and high humidity, it is preferably 100 mol% or less, more preferably 97 mol% or less, and further preferably 95 mol% or less.

  The carboxylic acid component preferably contains an aliphatic monocarboxylic acid compound having 8 to 24 carbon atoms from the viewpoint of toner grindability.

  Examples of the aliphatic monocarboxylic acid compound having 8 to 24 carbon atoms include stearic acid, capric acid, lauric acid, myristic acid, palmitic acid, arachidic acid, behenic acid and lignoceric acid. Among these, stearic acid Is preferred.

  The content of the aliphatic monocarboxylic acid compound having 8 to 24 carbon atoms is preferably 5 to 30 mol% in the carboxylic acid component from the viewpoint of low-temperature fixability of the toner and charging stability under high temperature and high humidity. -20 mol% is more preferable.

  Other carboxylic acid compounds include aromatic dicarboxylic acid compounds such as terephthalic acid and isophthalic acid, aliphatic dicarboxylic acid compounds having 2 to 7 carbon atoms, trivalent or higher polyvalent carboxylic acids such as trimellitic acid and pyromellitic acid. Compounds and the like.

  The polycondensation reaction between the alcohol component and the carboxylic acid component is performed in an inert gas atmosphere at a temperature of about 200 to 250 ° C. in the presence of an esterification catalyst, an esterification cocatalyst, a polymerization inhibitor, etc., if necessary. And can be produced by polycondensation. Examples of the esterification catalyst include tin compounds such as dibutyltin oxide and tin (II) 2-ethylhexanoate, and titanium compounds such as titanium diisopropylate bistriethanolamate. The amount of the esterification catalyst used is preferably 0.01 to 1.5 parts by mass, more preferably 0.1 to 1.0 part by mass with respect to 100 parts by mass of the total amount of the alcohol component and the carboxylic acid component. Examples of the esterification promoter include gallic acid. The amount of the esterification cocatalyst used is preferably 0.001 to 0.5 parts by mass, more preferably 0.01 to 0.1 parts by mass with respect to 100 parts by mass of the total amount of the alcohol component and the carboxylic acid component. Examples of the polymerization inhibitor include tert-butylcatechol. The amount of the polymerization inhibitor used is preferably 0.001 to 0.5 parts by mass and more preferably 0.01 to 0.1 parts by mass with respect to 100 parts by mass of the total amount of the alcohol component and the carboxylic acid component.

  The softening point of the crystalline polyester C is preferably 65 ° C. or higher, more preferably 70 ° C. or higher, and further preferably 80 ° C. or higher, from the viewpoints of storage stability and fixing roller peelability. Further, from the viewpoint of low temperature fixability and charging stability under high temperature and high humidity, it is preferably 100 ° C. or lower, more preferably 95 ° C. or lower, and further preferably 90 ° C. or lower.

  The melting point of the crystalline polyester C is preferably 60 ° C. or higher, more preferably 80 ° C. or higher, from the viewpoints of storage stability and fixing roller peelability. Further, from the viewpoint of low temperature fixability and charging stability under high temperature and high humidity, 100 ° C. or lower is preferable, and 90 ° C. or lower is more preferable.

  The binder resin composition of the present invention preferably contains an amorphous polyester H having a softening point higher than that of the amorphous polyester L from the viewpoints of storage stability and hot offset resistance.

  The softening point of the amorphous polyester H is preferably 111 ° C. or higher, more preferably 120 ° C. or higher, and further preferably 125 ° C. or higher, from the viewpoints of storage stability and hot offset resistance. From the viewpoint of low-temperature fixability, 170 ° C. or lower is preferable, 160 ° C. or lower is more preferable, 140 ° C. or lower is further preferable, and 135 ° C. or lower is further preferable.

  The alcohol component of the amorphous polyester H preferably contains an aromatic diol from the viewpoint of chargeability of the toner.

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

The alkylene oxide adduct of bisphenol A represented by the formula (I) is a propylene oxide adduct of bisphenol A in which R ¹ O is propylene oxide and R ¹ O is ethylene oxide from the viewpoint of storage stability and low-temperature fixability. It is preferably composed of at least one selected from ethylene oxide adducts of bisphenol A, more preferably contains at least propylene oxide adducts of bisphenol A, and propylene oxide adducts of bisphenol A and ethylene oxide additions of bisphenol A. More preferably, it consists of a product.

  The molar ratio of the ethylene oxide adduct of bisphenol A and the propylene oxide adduct of bisphenol A contained in the alcohol component (the ethylene oxide adduct / propylene oxide adduct) is the low-temperature fixability of the toner and the storage stability under high humidity. In view of the above, 0/100 to 70/30 is preferable, 3/97 to 65/35 is more preferable, 5/95 to 60/40 is more preferable, 10/90 to 50/50 is further preferable, and 20/80 More preferred is ˜40 / 60.

  The content of the aromatic diol is preferably 40 to 100 mol%, more preferably 70 to 100 mol%, and still more preferably 90 to 100 mol% in the alcohol component.

  Examples of alcohols other than aromatic diols include diols such as ethylene glycol, 1,2-propylene glycol, 1,4-butanediol, neopentyl glycol, polyethylene glycol, polypropylene glycol, hydrogenated bisphenol A; sorbitol, pentaerythritol, glycerin And trihydric or higher polyhydric alcohols such as trimethylolpropane.

  The carboxylic acid component of the amorphous polyester H preferably contains an aromatic dicarboxylic acid compound from the viewpoint of toner charging stability.

  Examples of the aromatic dicarboxylic acid compound include phthalic acid, isophthalic acid, terephthalic acid, anhydrides of these acids, and alkyl (carbon number 1 to 3) esters of these acids.

  The content of the aromatic dicarboxylic acid compound is preferably 30 mol% or more, and more preferably 40 mol% or more in the carboxylic acid component of the amorphous polyester H, from the viewpoint of charging stability and storage stability of the toner. Further, from the viewpoint of low-temperature fixability of the toner, it is preferably 80 mol% or less, and more preferably 60 mol% or less.

  Examples of the carboxylic acid component other than the aromatic dicarboxylic acid compound include an aromatic dicarboxylic acid compound, an aliphatic dicarboxylic acid compound, an alicyclic dicarboxylic acid compound, a trivalent or higher polyvalent carboxylic acid compound, and the like.

  Examples of the aliphatic dicarboxylic acid compound include alkyl having 1 to 20 carbon atoms such as oxalic acid, malonic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, succinic acid, adipic acid, dodecenyl succinic acid, octyl succinic acid, etc. And aliphatic dicarboxylic acids such as succinic acid substituted with a group or an alkenyl group having 2 to 20 carbon atoms, anhydrides of these acids, and alkyl (C1 to C3) esters of these acids.

  The carboxylic acid component of the amorphous polyester H preferably contains a trivalent or higher polyvalent carboxylic acid compound. 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, anhydrides of these acids, and the like. Examples include alkyl (1 to 3 carbon atoms) esters of the above acid, and among these, trimellitic anhydride is preferable from the viewpoint of hot offset resistance and durability.

  The content of the trivalent or higher polyvalent carboxylic acid compound in the carboxylic acid component of the amorphous polyester H is preferably 3 mol or more with respect to 100 mol of the alcohol component from the viewpoint of hot offset resistance and durability. Mole or more is more preferable, and 20 mol or more is more preferable. Further, from the viewpoint of charging stability under high temperature and high humidity, it is preferably 40 mol or less, more preferably 30 mol or less.

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

  The conditions for the polycondensation reaction between the alcohol component and the carboxylic acid component (reaction temperature, use of esterification catalyst, esterification cocatalyst, polymerization inhibitor, etc.) are the same as for amorphous polyester L.

  The glass transition temperature of the amorphous polyester H is preferably 45 ° C. or higher, more preferably 50 ° C. or higher, from the viewpoint of storage stability. Further, from the viewpoints of low-temperature fixability of the toner, charging stability under high temperature and high humidity, and fixing roller peelability, it is preferably 70 ° C. or lower, more preferably 65 ° C. or lower, and further preferably 60 ° C. or lower.

  The acid value of the amorphous polyester H is preferably 5 mgKOH / g or more, more preferably 15 mgKOH / g or more, and further preferably 20 mgKOH / g or more, from the viewpoints of toner chargeability, low-temperature fixability, and fixing roller peelability. . Further, from the viewpoint of charging stability under high temperature and high humidity, 40 mgKOH / g or less is preferable, and 30 mgKOH / g or less is more preferable.

  The mass ratio of the amorphous polyester H to the amorphous polyester L (amorphous polyester H / amorphous polyester L) is 90% from the viewpoint of charging stability of the toner under high temperature and high humidity and releasability of the fixing roller. / 10/40/60 is preferable, 85 / 15-45 / 55 is more preferable, 85 / 15-60 / 40 is further more preferable, and 80 / 20-70 / 30 is further more preferable.

  The mass ratio of amorphous polyester to crystalline polyester (amorphous polyester / crystalline polyester) is 65/65 from the viewpoint of low temperature fixability of toner, charging stability under high temperature and high humidity, and fixing roller peelability. 35-97 / 3 is preferable, 70 / 30-97 / 3 is more preferable, and 80 / 20-95 / 5 is further more preferable. Here, the amorphous polyester includes the amorphous polyester L as an amorphous polyester, and when the amorphous polyester H is not included, the amorphous polyester L is converted to an amorphous polyester. When the polyester L and the amorphous polyester H are contained, the whole amorphous polyester which combined both is meant.

  The toner for developing an electrostatic charge image containing the binder resin composition of the present invention is excellent in low temperature fixability, charging stability under high temperature and high humidity, and fixing roller peelability. Note that the binder resin composition of the present invention is obtained by a process of mixing other binder resin such as amorphous polyester H and crystalline polyester C, and if necessary amorphous polyester L. Each resin may be directly used for mixing raw materials when the toner is manufactured.

  In the toner of the present invention, known resins other than the binder resin composition of the present invention may be used in combination as long as the effects of the present invention are not impaired. When the total content or further amorphous polyester H is contained, the total content of the three polyesters is preferably 90 to 100% by mass, more preferably 93 to 100% by mass in the binder resin, 95 More preferred is ˜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 and more preferably 2 parts by mass or more with respect to 100 parts by mass of the binder resin from the viewpoint of improving the toner image density and low-temperature fixability. Moreover, 40 mass parts or less are preferable, and 10 mass parts or less are 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 parts by mass or more 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. More preferably, it is more preferably 1.5 parts by mass or more. Moreover, 10 mass parts or less are preferable, 8 mass parts or less are more preferable, and 7 mass parts or less are 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.

  Further, as a negatively chargeable charge control agent, metal-containing azo dyes such as “Varifast Black 3804”, “Bontron S-31”, “Bontron S-32”, “Bontron S-34”, “Bontron S-” “36” (manufactured by Orient Chemical Co., Ltd.), “Eisenspiron Black TRH”, “T-77” (manufactured by Hodogaya Chemical Co., Ltd.), etc .; metal compounds of benzylic acid compounds such as “LR-147”, “LR-297” (manufactured by Nippon Carlit Co., Ltd.), etc .; metal compounds of salicylic acid compounds such as “Bontron E-81”, “Bontron E-84”, “Bontron E-88”, “E-304” ( Above, manufactured by Orient Chemical Co., Ltd.), “TN-105” (manufactured by Hodogaya Chemical Co., Ltd.), etc .; copper phthalocyanine dyes; quaternary ammonium salts such as “COPY CHARGE NX VP434” (manufactured by Clariant), nitroimidazole derivatives, etc. Organic metal compounds such as “TN105” (Hodogaya Chemical Co., Ltd.) And the like.

  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 2 parts by mass or less is further 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 containing amorphous polyester L, amorphous polyester H and crystalline polyester C, a colorant, a charge control agent, and the like is mixed with a mixer such as a Henschel mixer. After uniformly mixing, it can be manufactured by melt-kneading with a closed kneader, a single-screw or twin-screw extruder, an open roll kneader, etc., cooling, pulverizing and classifying.

  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 hexamethyldisilazane (HMDS), dimethyldichlorosilane (DMDS), silicone oil, octyltriethoxysilane (OTES), and methyltriethoxysilane. Of these, hexamethyldisilazane is preferred.

  The average particle diameter of the external additive is preferably 10 nm or more, and more preferably 15 nm or more, from the viewpoint of the chargeability, fluidity, and transferability of the toner. Further, it is preferably 250 nm or less, more preferably 200 nm or less, and further preferably 90 nm or less.

  The content of the external additive is preferably 0.05 parts by mass or more, more preferably 0.1 parts by mass or more, and further preferably 0.3 parts by mass or more with respect to 100 parts by mass of the toner before being processed with the external additive. Moreover, 5 mass parts or less are preferable, and 3 mass parts or less are more preferable.

The volume median particle size (D ₅₀ ) of the toner of the present invention is preferably from 3 to 15 μm, more preferably from 4 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. When the toner is treated with an external additive, the volume median particle size of the toner particles before being treated with the external additive is defined as the volume median particle size of the toner.

  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.

  The present invention further discloses the following binder resin composition for toner, toner for developing an electrostatic charge image containing the binder resin, and a method for producing the same with respect to the above-described embodiments.

<1> A binder resin composition for a toner containing amorphous polyester L and crystalline polyester C, wherein the amorphous polyester L has an alcohol component containing an aromatic diol and a carbon number of 8 to 14 A binder resin composition for toner, which is an amorphous polyester having a softening point of 80 to 110 ° C., obtained by polycondensation with a carboxylic acid component containing an aliphatic dicarboxylic acid compound.

<2> The binder resin for toner according to <1>, further comprising amorphous polyester H having a softening point of 111 to 170 ° C.
<3> The above <1>, wherein the amount of the aliphatic dicarboxylic acid compound having 8 to 14 carbon atoms contained in the carboxylic acid component of the amorphous polyester L is 2 to 40 mol with respect to 100 mol of the alcohol component. The binder resin for toner according to <2>.
<4> Any of <1> to <3>, wherein the crystalline polyester C is a crystalline polyester obtained by polycondensation of an alcohol component containing an aliphatic diol having 6 to 12 carbon atoms and a carboxylic acid component. A binder resin for toner according to any of the above.
<5> The above <1> to <4, wherein the crystalline polyester C is a crystalline polyester obtained by polycondensation of an alcohol component and a carboxylic acid component containing an aliphatic dicarboxylic acid compound having 8 to 14 carbon atoms. > Binder resin for toner according to any one of the above.
<6> The toner bond according to any one of <1> to <6>, wherein a mass ratio of the amorphous polyester to the crystalline polyester (amorphous polyester / crystalline polyester) is 65/35 to 97/3. Landing resin.
<7> The binder resin for toner according to any one of <1> to <7>, wherein the alcohol component which is a raw material monomer of the amorphous polyester L contains 40 to 100 mol% of an aromatic diol.
<8> The above <1> to <8>, wherein the aromatic diol contained in the alcohol component of the amorphous polyester L is an alkylene oxide adduct of bisphenol A represented by the formula (I). Binder resin for toner.
<9> Any of the above <2> to <9>, wherein the mass ratio of the amorphous polyester H to the amorphous polyester L (amorphous polyester H / amorphous polyester L) is 90/10 to 40/60 A binder resin for toner according to any of the above.
<10> The binder resin for toner according to any one of <1> to <10>, wherein the carboxylic acid component, which is a raw material monomer of the amorphous polyester L, contains 30 to 80 mol% of an aromatic dicarboxylic acid compound.
<11> The binder resin for toner according to any one of <1> to <11>, wherein the crystalline polyester C has a melting point of 60 to 100 ° C.
<12> The alkylene oxide adduct of bisphenol A represented by the formula (I) contained in the alcohol component of the amorphous polyester L is selected from a propylene oxide adduct of bisphenol A and an ethylene oxide adduct of bisphenol A. The binder resin for toner according to any one of <9 to 12>, comprising at least one kind.
<13> The binder resin for toner according to any one of <2> to <13>, wherein the carboxylic acid component that is a raw material monomer of the amorphous polyester H contains a trivalent or higher polyvalent carboxylic acid compound.
<14> The content of the trivalent or higher polyvalent carboxylic acid compound contained in the carboxylic acid component which is a raw material monomer of the amorphous polyester H is 3 to 40 mol with respect to 100 mol of the alcohol component. 14> The binder resin for toner according to item 14.
<15> For toner according to <14> or <15>, wherein the trivalent or higher polyvalent carboxylic acid compound contained in the carboxylic acid component which is a raw material monomer of amorphous polyester H is trimellitic anhydride. Binder resin.
<16> The binder resin for toner according to any one of <1> to <16>, wherein the crystalline polyester C has a softening point of 65 to 100 ° C.
<17> An electrostatic charge image developing toner containing the binder resin composition for toner according to any one of <1> to <16>.
<18> An electrostatic charge image developing toner containing amorphous polyester L and crystalline polyester C, wherein the amorphous polyester L comprises an alcohol component containing an aromatic diol and a C8-14 fat. A toner for developing an electrostatic charge image, which is an amorphous polyester having a softening point of 80 to 110 ° C. obtained by polycondensation with a carboxylic acid component containing an aromatic dicarboxylic acid compound.
<19> The electrostatic image developing toner according to <18>, further comprising amorphous polyester H having a softening point of 111 to 170 ° C.

[Softening point of resin]
Using a flow tester “CFT-500D” (manufactured by Shimadzu Corporation), 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 of resin endotherm]
Using a differential scanning calorimeter “Q-100” (manufactured by TA Instruments Japan Co., Ltd.), 0.01 to 0.02 g of sample is weighed in an aluminum pan, and the temperature drops from room temperature to 0 ° C. at a rate of 10 ° C./min. Cool and let stand for 1 minute. Thereafter, the measurement is performed at a heating rate of 50 ° C./min. Among the observed endothermic peaks, the peak temperature at the highest temperature side is defined as the highest endothermic peak temperature.

[Glass transition temperature of resin]
Using a differential scanning calorimeter “DSC210” (manufactured by Seiko Denshi Kogyo Co., Ltd.), 0.01 to 0.02 g of sample is weighed into an aluminum pan, heated up to 200 ° C., and from that temperature to 0 ° C. at a cooling rate of 10 ° C./min. Cooling. Next, the sample is heated at a heating rate of 10 ° C / min, and the temperature at the intersection of the baseline extension line below the maximum peak temperature of endotherm and the tangent line indicating the maximum slope from the peak rise to the peak apex. The glass transition temperature is assumed.

[Acid value of the resin]
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)).

[Melting point of release agent]
Using a differential scanning calorimeter “DSC210” (manufactured by Seiko Denshi Kogyo Co., Ltd.), 0.01 to 0.02 g of sample is weighed into an aluminum pan, heated up to 200 ° C., and from that temperature to 0 ° C. at a cooling rate of 10 ° C./min. Cooling. Next, the sample is heated at a heating rate of 10 ° C./min, and the maximum peak temperature of the heat of fusion is taken as the melting point.

[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: 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).

[Production of resin]
Resin Production Example 1 [Resin a-1 to Resin a-5, Resin a-8, Resin a-11]
Raw material monomers other than adipic acid, sebacic acid, 1,10-decanedicarboxylic acid and trimellitic anhydride shown in Tables 1 and 2, 40 g of tin (II) 2-ethylhexanoate and 2 g of gallic acid, and a nitrogen introduction tube The mixture was placed in a 10-liter four-necked flask equipped with an equipped dehydration tube, stirrer, and thermocouple, and subjected to a polycondensation reaction at 230 ° C. for 6 hours in a nitrogen atmosphere. After reacting at 230 ° C 8.0 kPa for 1 hour, adipic acid, sebacic acid, 1,10-decanedicarboxylic acid and trimellitic anhydride were further added and reacted at 210 ° C. The reaction was carried out until the softening point shown was reached to obtain an amorphous polyester.

Resin Production Example 2 [Resin a-6, Resin a-7]
Raw material monomers other than fumaric acid and trimellitic anhydride shown in Tables 1 and 2, 40 g of tin (II) 2-ethylhexanoate and 2 g of gallic acid, a dehydration tube equipped with a nitrogen introduction tube, a stirrer and a thermocouple The mixture was placed in a 10-liter four-necked flask equipped and subjected to a polycondensation reaction at 230 ° C. for 6 hours in a nitrogen atmosphere. After cooling to 180 ° C., fumaric acid and 5 g of tert-butylcatechol as a polymerization inhibitor were added, the temperature was raised from 180 ° C. to 210 ° C. at 10 ° C./hour, reacted at 210 ° C. for 1 hour, 210 ° C. The reaction was carried out at 10 kPa until the softening points shown in Tables 1 and 2 were reached to obtain amorphous polyester.

Resin Production Example 3 [Resin a-9, Resin a-10]
Equipped with a raw material monomer other than sebacic acid and trimellitic anhydride shown in Table 2, 40 g of tin (II) 2-ethylhexanoate and 2 g of gallic acid, a nitrogen introduction tube, and a fractionation tube through which 100 ° C hot water was passed. Was placed in a 10-liter four-necked flask equipped with a dehydrating tube, a stirrer and a thermocouple, kept at 180 ° C for 1 hour in a nitrogen atmosphere, and then heated from 180 ° C to 230 ° C at 10 ° C / hour, Thereafter, a polycondensation reaction was carried out at 230 ° C. for 8 hours. Further, sebacic acid and trimellitic anhydride were added and reacted at 210 ° C., and the reaction was carried out at 10 kPa until the softening point shown in Table 2 was reached, thereby obtaining an amorphous polyester.

Resin Production Example 4 [Production of Resin C-1 to Resin C-5]
The raw material monomers shown in Table 3 were placed in a 10 L four-necked flask equipped with a nitrogen inlet tube, dehydration tube, stirrer and thermocouple, held at 140 ° C for 6 hours, and further heated to 200 ° C over 6 hours. Then, 20 g of tin (II) 2-ethylhexanoate and 2 g of gallic acid were added, reacted at 200 ° C. for 1 hour, and then reacted at 8.3 kPa for 1 hour to obtain a crystalline polyester.

Resin Production Example 5 [Resin C6]
The raw material monomer and 2 g of tert-butylcatechol shown in Table 3 were put into a 10 L four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer and a thermocouple, held at 140 ° C. for 6 hours, and further up to 200 ° C. After heating up over time, 20 g of tin (II) 2-ethylhexanoate and 2 g of gallic acid were added, reacted at 200 ° C. for 1 hour, and then reacted at 8.3 kPa for 1 hour to obtain a crystalline polyester. It was.

[Manufacture of toner for developing electrostatic image]
Examples 1-11 and Comparative Examples 1-7
100 parts by mass of a binder resin mixed with the resins shown in Table 4, 5 parts by mass of a colorant “ECB-301” (manufactured by Dainichi Seika Co., Ltd., CI Pigment Blue 15: 3), a negatively chargeable charge control agent “LR-147” ”(Nippon Carlit Co., Ltd.) 1 part by weight and mold release agent“ NP-105 ”(Mitsui Chemicals, polypropylene wax, melting point: 140 ° C.) were thoroughly stirred in a Henschel mixer, and the total length of the kneaded part The mixture was melt kneaded using a co-rotating twin screw extruder having a 1560 mm, screw diameter of 42 mm, and a barrel inner diameter of 43 mm. The rotation speed of the roll was 200 r / min, the heating temperature in the roll was 120 ° C., the feed rate of the mixture was 10 kg / hr, and the average residence time was about 18 seconds. The obtained kneaded product was rolled and cooled with a cooling roller, and then a powder with a volume-median particle size (D ₅₀ ) of 6.5 μm was obtained with a jet mill.

To 100 parts by mass of the obtained powder, 1.0 part by mass of external additive “Aerosil R-972” (hydrophobic silica, manufactured by Nippon Aerosil Co., Ltd., average particle size: 16 nm) and “SI-Y” (hydrophobic silica, Japan Aerosil, average particle size: 40 nm) 1.0 part by mass was added and mixed with a Henschel mixer at 3600 r / min for 5 minutes to treat the external additive, and the volume median particle size (D ₅₀ ) was 6.5 μm. A toner was obtained.

Test Example 1 [low temperature fixability]
The obtained toner was mounted on a copying machine “AR-505” (manufactured by Sharp Corporation), and an unfixed image (2 cm × 12 cm) having a toner adhesion amount of 0.7 mg / cm ² was obtained. Using a fixing machine (fixing speed 200mm / sec) that is improved so that the fixing machine of the copier “AR-505” (manufactured by Sharp Corporation) can be fixed off-line, the fixing temperature is increased from 90 ° C to 240 ° C. The fixing test was conducted at each fixing temperature while increasing the temperature in steps of ° C. As the fixing paper, “CopyBond SF-70NA” (manufactured by Sharp Corporation, 75 g / m ² ) was used.
The minimum fixing temperature is a sand eraser with a bottom of 15mm x 7.5mm with a load of 500g. The image fixed through the fixing machine is rubbed 5 times, and the reflection density meter "RD-915" (Macbeth) The temperature of the fixing roller in which the ratio between the two (after rubbing / before rubbing) first exceeds 70% is defined as the minimum fixing temperature. The lower the minimum fixing temperature, the better the low-temperature fixing property. The results are shown in Table 4.

Test Example 2 [Charging stability under high temperature and high humidity]
Place the toner 0.6g and silicone ferrite carrier (Kanto Denka Kogyo Co., Ltd., average particle size 90μm) 19.4g in a 50ml polyethylene container under high temperature and high humidity conditions of 32 ℃ and relative humidity 85%. The toner was mixed at 250 r / min using a ball mill, and the charge amount of the toner was measured using a Q / M meter (manufactured by EPPING) by the following method.
After a predetermined mixing time, a specified amount of toner and carrier mixture is put into the cell attached to the Q / M meter, and only the toner is sucked for 90 seconds through a 32 μm sieve (stainless steel, twill, wire diameter: 0.0035 mm). did. The voltage change on the carrier generated at that time was monitored, and the value of [total amount of electricity after 90 seconds (μC) / amount of attracted toner (g)] was defined as the charge amount (μC / g). The ratio of the charge amount after 60 seconds of mixing time and the charge amount after 600 seconds of mixing time (charge amount after mixing time of 60 seconds / charge amount after mixing time of 600 seconds) was calculated to evaluate the charging stability. The larger the value, the better the charging stability under high temperature and high humidity. The results are shown in Table 4.

Test Example 3 [Fixing roller peelability]
Toner was mounted on a copier “AR-505” (manufactured by Sharp Corporation), and an unfixed image having a solid image portion of 2 cm × 12 cm (toner adhesion amount: 0.5 mg / cm ² ) was obtained. Using a fixing machine (fixing speed: 100 mm / sec) that has been improved so that the fixing machine of the copier “AR-505” (manufactured by Sharp Corporation) can be fixed outside the machine, the fixing temperature is set to 170 ° C. The paper was passed through the fixing roller and visually observed whether it peeled off from the fixing roller or adhered to the fixing roller, and the fixing roller peelability was evaluated according to the following evaluation criteria. The results are shown in Table 4.

〔Evaluation criteria〕
A: The paper peels off from the fixing roller, and the paper does not bend after passing.
B: Paper peels off from the fixing roller, but the paper after passing is bent.
C: Paper adheres to the fixing roller.

  From the above results, it can be seen that the toners of the examples are all excellent in low-temperature fixability, charging stability under high temperature and high humidity, and fixing roller peelability as compared with the toner of the comparative example.

  The toner binder resin composition of the present invention is suitably used as a toner binder resin composition used for developing a latent image formed in electrophotography, electrostatic recording method, electrostatic printing method and the like. Is.

Claims (6)

Binder resin composition for toner containing amorphous polyester L and crystalline polyester C, wherein the amorphous polyester L comprises an alcohol component containing an aromatic diol and suberic acid, azelaic acid, sebacic acid, The softening point obtained by polycondensation with a carboxylic acid component containing at least one aliphatic dicarboxylic acid compound selected from the group consisting of 1,10-decanedicarboxylic acid and 1,12-dodecanedicarboxylic acid 80 to 110 Ri amorphous polyester der of ° C., the crystalline polyester C is a C 6-12 alpha, an alcohol component and a carboxylic acid component containing a ω- linear alkanediol by polycondensation to give The amorphous polyester H having a softening point of 111 to 170 ° C., and a carboxylic acid component that is a raw material monomer of the amorphous polyester H. But containing a trivalent or higher polycarboxylic acid compound, a binder resin for toner compositions. At least one fat selected from the group consisting of suberic acid, azelaic acid, sebacic acid, 1,10-decanedicarboxylic acid, and 1,12-dodecanedicarboxylic acid, contained in the carboxylic acid component of amorphous polyester L The binder resin composition for toner according to claim 1, wherein the amount of the aliphatic dicarboxylic acid compound is 2 to 40 mol with respect to 100 mol of the alcohol component. Alcohol component as a raw material monomer of the amorphous polyester L is an aromatic diol containing 40 to 100 mol%, according to claim 1 or 2 for toner binder resin composition. The toner bond according to any one of claims 1 to 3 , wherein a mass ratio of the amorphous polyester H to the amorphous polyester L (amorphous polyester H / amorphous polyester L) is 90/10 to 40/60. Resin composition . Claim 1-4 contained toner binder resin composition according to any one of a toner for developing electrostatic images. An electrostatic charge image developing toner containing an amorphous polyester L and a crystalline polyester C, wherein the amorphous polyester L comprises an alcohol component containing an aromatic diol, suberic acid, azelaic acid, sebacic acid, 1 , 10-decanedicarboxylic acid and 1,12-dodecanedicarboxylic acid are obtained by polycondensation with a carboxylic acid component containing at least one aliphatic dicarboxylic acid compound selected from the group consisting of 1,12-dodecanedicarboxylic acid, and a softening point of 80 A crystal obtained by polycondensation of an alcohol component containing an α, ω-linear alkanediol having 6 to 12 carbon atoms and a carboxylic acid component, which is an amorphous polyester at ˜110 ° C. A carboxylic acid component which is an amorphous polyester, further contains amorphous polyester H having a softening point of 111 to 170 ° C., and is a raw material monomer of the amorphous polyester H , Containing a trivalent or higher polycarboxylic acid compound, a toner for developing electrostatic images.