JP2020024358A - Binder resin composition for toner - Google Patents

Abstract

To provide a binder resin composition for toner that has a wide non-offset range and with which an image with high glossiness can be obtained, and an electrophotographic toner that contains the binder resin composition.SOLUTION: There are provided a binder resin composition for toner that contains a composite resin A having a polyester resin portion that is a reactant of a raw material monomer containing an alcohol component and a carboxylic acid component, and a vinyl resin portion that is a reactant of a raw material monomer containing a (meth)acrylic compound in an amount of 20 mass% or more, wherein the composite resin A has a softening point of 110°C or more and 150°C or less and a glass-transition temperature of 50°C or more and 65°C or less, and contains a methyl ethyl ketone insoluble material in an amount of 5 mass% or more and 32 mass% or less, and the glass-transition temperature of the methyl ethyl ketone insoluble material is lower than the glass-transition temperature of the composite resin A by 5°C or more and 40°C or less; a method for manufacturing the same; and an electrophotographic toner that contains the binder resin composition for toner.SELECTED DRAWING: None

Description

  The present invention relates to, for example, a binder resin composition for toner used for developing a latent image formed in an electrophotographic method, an electrostatic recording method, an electrostatic printing method, and the like, and an electrophotography containing the binder resin composition. For toner.

  The use of office copiers is not limited to conventional office documents, but is also expanding to commercial uses such as flyers and pamphlets. In commercial applications, high gloss images and a wider range of paper compatibility (from thin paper to thick paper) are required. To print on a wide range of paper without changing the settings of the copier, a wide fusing area (non-offset) is required. Area) is required.

  Patent Document 1 discloses a polyester resin which is a polycondensate of an alcohol component and a carboxylic acid component as a binder resin composition for an electrophotographic toner having excellent low-temperature fixing properties, hot offset resistance, and long-term storage properties. An amorphous composite resin composed of a resin P and a vinyl resin, which contains an amorphous composite resin AC having a softening point of 107 ° C. or more and 140 ° C. or less, and an aliphatic diol having 2 to 16 carbon atoms of 95 mol% or more. Resin composition containing a crystalline polyester resin CP, which is a polycondensate of an alcohol component and a carboxylic acid component containing 95 mol% or more of an aliphatic dicarboxylic acid compound having 4 to 14 carbon atoms Wherein the carboxylic acid component of the polyester resin P contains 3 to 18 moles of a trivalent or more aromatic carboxylic acid compound based on 100 moles of the alcohol component, and the vinyl resin contains A binder resin composition for a toner, which is an addition polymer of a raw material monomer containing an alkyl (meth) acrylate having a kill group having 2 to 6 carbon atoms and having a carbon number of 2 or more and 6 or less, is disclosed. .

  Patent Document 2 discloses, as a binder resin composition for an electrophotographic toner having excellent low-temperature fixability, gloss, and roller releasability, an alcohol component containing an ethylene oxide adduct of bisphenol A in an amount of 10 mol% or more and 100 mol% or less. A raw material containing a polycondensation resin component obtained by polycondensation of a carboxylic acid component and a (meth) acrylic acid alkyl ester having an alkyl group having 2 to 8 carbon atoms in an amount of 10 mass% to 60 mass%. Containing an amorphous composite resin having a softening point of 100 ° C. or more and 130 ° C. or less, and a methyl ethyl ketone insoluble content of 5% by mass or more and 50% by mass or less, comprising an addition polymerization resin component obtained by addition polymerization of a monomer, A binder resin composition for a toner is disclosed.

JP 2017-203831 A JP-A-2006-130797

  The present invention relates to a binder resin composition for a toner capable of obtaining an image having a wide non-offset region and a high gloss, and an electrophotographic toner containing the binder resin composition.

In order to widen the non-offset range, a resin containing a high molecular weight component (solvent-insoluble component) is required as a binder resin composition for a toner. However, since the high molecular weight component hardly melts during fixing, the printed image surface Has the problem that the surface is rough and the gloss is reduced. This is thought to be due to the fact that the higher the molecular weight of the polyester, the higher the glass transition temperature. In other words, even if the resin as a whole is a polyester having a glass transition temperature of 60 ° C., the glass transition temperature of the solvent-insoluble component is often as high as 70 ° C., and contains a high molecular weight component that is very difficult to soften. This is presumed to be the cause.
Therefore, as a result of investigations by the present inventors, since the solvent-insoluble component is a high molecular weight component, taking into account that the mobility is low, by making the glass transition temperature of the solvent-insoluble component somewhat lower than the glass transition temperature of the resin. And high gloss images can be obtained.

The present invention
[1] A composite resin A having a polyester resin portion, which is a reaction product of a raw material monomer containing an alcohol component and a carboxylic acid component, and a vinyl resin portion, which is a reaction product of a raw material monomer containing a (meth) acrylic compound, is prepared as follows. A binder resin composition for toner containing at least 10% by mass of the composite resin A, wherein the composite resin A has a softening point of 110 ° C. or more and 150 ° C. or less, a glass transition temperature of 50 ° C. or more and 65 ° C. or less, A binder resin composition for toner, wherein the glass transition temperature of the methyl ethyl ketone-insoluble component is 5 ° C. to 40 ° C. lower than the glass transition temperature of the composite resin A.
[2] An electrophotographic toner containing the binder resin composition for toner according to [1], and [3] a method for producing the binder resin composition for toner according to [1], wherein the composite Resin A,
Step A: a step of performing an addition polymerization reaction of a raw material monomer of a vinyl resin portion in the presence of a carboxylic acid component of 5 mol% or more and 50 mol% or less of all carboxylic acid components,
Step B: A step of placing the reaction solution obtained in Step A under a temperature condition of 180 ° C. or more and 250 ° C. or less for 2.5 hours or more and 10 hours or less, and allowing the reaction to occur. Step C performed in the presence of at least mol% of an alcohol component: a toner produced by a method including a step of adding a raw material monomer of the remaining polyester resin portion to the reaction solution obtained in Step B and performing a polycondensation reaction The present invention relates to a method for producing a binder resin composition for use.

  The electrophotographic toner containing the binder resin composition of the present invention has an excellent effect of obtaining an image having a wide non-offset region and a high glossiness.

  The binder resin composition for a toner of the present invention contains a composite resin A having a polyester resin portion and a vinyl resin portion, and the composite resin A is insoluble in methyl ethyl ketone whose glass transition temperature is lower than the glass transition temperature of the resin. It has one feature in that it includes minutes. The non-offset region can be widened by the solvent insoluble component (methyl ethyl ketone insoluble component), which is a high molecular weight component. When the entire resin is softened, the solvent insoluble component having a low glass transition temperature is also softened at the same time, and a high gloss image is obtained. It is assumed that

  The content of the methyl ethyl ketone insoluble component in the composite resin A is 5% by mass or more, preferably 15% by mass or more, more preferably 20% by mass or more, from the viewpoint of expanding the non-offset region. From the viewpoints of gloss and gloss, the content is 32% by mass or less, preferably 30% by mass or less, more preferably 28% by mass or less, and further preferably 26% by mass or less.

  The glass transition temperature of the methyl ethyl ketone insoluble component is lower than the glass transition temperature of the composite resin A, and the difference is 5 ° C. or higher, preferably 15 ° C. or higher, more preferably 20 ° C. from the viewpoint of the glossiness of the image. As described above, the temperature is more preferably 25 ° C. or higher, and from the viewpoint of securing a non-offset region, the temperature is 40 ° C. or lower, preferably 35 ° C. or lower, more preferably 30 ° C. or lower.

  The polyester resin portion is a reaction product of a raw material monomer containing an alcohol component and a carboxylic acid component.

  From the viewpoint of adjusting the glass transition temperature of the toner in order to ensure the storage stability, the alcohol component of the polyester resin portion has the formula (I):

(Where OR and RO are oxyalkylene groups, R is an ethylene group and / or a propylene group, x and y indicate the average number of moles of alkylene oxide added, and are each a positive number, x and y Is 1 or more, preferably 1.5 or more, and 16 or less, preferably 8 or less, more preferably 6 or less, and still more preferably 4 or less.
It is preferable to include an alkylene oxide adduct of bisphenol A represented by the following formula: As the alkylene oxide adduct of bisphenol A represented by the formula (I), a polyoxypropylene adduct of 2,2-bis (4-hydroxyphenyl) propane, and a 2,2-bis (4-hydroxyphenyl) propane And polyoxyethylene adducts. It is preferable to use one or more of these.

  The content of the alkylene oxide adduct of bisphenol A represented by the formula (I) in the alcohol component is preferably 70 mol% or more, more preferably 80 mol% or more, further more preferably 90 mol% or more, and still more preferably It is at least 95 mol%, more preferably 100 mol%.

  Other alcohol components include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,4-butene Examples thereof include diols, aliphatic diols such as 1,3-butanediol and neopentyl glycol, and tri- or higher-valent alcohols such as glycerin.

  The carboxylic acid component of the polyester resin portion preferably contains an aromatic dicarboxylic acid-based compound from the viewpoint of adjusting the glass transition temperature of the toner in order to ensure storage stability. Examples of the aromatic dicarboxylic acid-based compound include phthalic acid, isophthalic acid, terephthalic acid, anhydrides of these acids, and alkyl esters having 1 to 3 carbon atoms of these acids. Terephthalic acid is preferred. In the present invention, the carboxylic acid compound includes not only a free acid but also an anhydride which is decomposed during the reaction to generate an acid, and an alkyl ester having 1 to 3 carbon atoms.

  The content of the aromatic dicarboxylic acid compound in the carboxylic acid component is preferably 70 mol% or more, more preferably 80 mol% or more, further preferably 90 mol% or more, further preferably 95 mol% or more, and further preferably 100 mol%.

  Other carboxylic acid components include aliphatic dicarboxylic acids, trivalent or higher carboxylic acids, anhydrides of these acids, and alkyl esters of these acids having 1 to 3 carbon atoms.

  In the present invention, from the viewpoint of glossiness, it is preferable that the carboxylic acid component does not contain a trivalent or higher valent carboxylic acid compound, or that the carboxylic acid component contains a small amount even if it is contained. Therefore, the proportion of the trivalent or higher carboxylic acid compound in the carboxylic acid component is preferably 5 mol or less, more preferably 3 mol or less, still more preferably 1 mol or less, and still more preferably 100 mol of the alcohol component. It is 0.5 mol or less, more preferably 0 mol.

  The alcohol component may appropriately contain a monohydric alcohol, and the carboxylic acid component may appropriately contain a monovalent carboxylic acid-based compound from the viewpoint of adjusting the molecular weight and softening point of the polyester resin.

  From the viewpoint of adjusting the softening point of the polyester resin, the equivalent ratio of the carboxylic acid component to the alcohol component (COOH group / OH group) is preferably 0.6 or more, more preferably 0.7 or more, and still more preferably 0.8 or more, and , Preferably 1.1 or less, more preferably 1 or less, and even more preferably 0.9 or less.

  The polyester resin portion is, for example, an alcohol component and a carboxylic acid component in an inert gas atmosphere, preferably in the presence of an esterification catalyst, and further, if necessary, in the presence of an esterification co-catalyst, a polymerization inhibitor, and the like. It can be produced by polycondensation. Temperature conditions suitable for the polycondensation reaction are preferably 180 ° C. or higher, more preferably 210 ° C. or higher, and preferably 250 ° C. or lower, more preferably 240 ° C. or lower.

  Examples of the esterification catalyst include tin compounds such as dibutyltin oxide and tin (II) 2-ethylhexanoate, and titanium compounds such as titanium diisopropylate bistriethanolaminate. Titanium compounds are preferred. The amount of the esterification catalyst used is preferably at least 0.01 part by mass, more preferably at least 0.1 part by mass, and preferably at most 1.5 parts by mass, based on 100 parts by mass of the total amount of the alcohol component and the carboxylic acid component. It is preferably at most 1 part by mass. Examples of the esterification promoter include gallic acid. The amount of the esterification promoter used is preferably at least 0.001 part by mass, more preferably at least 0.01 part by mass, and preferably at most 0.5 part by mass, based on 100 parts by mass of the total amount of the alcohol component and the carboxylic acid component. It is more preferably 0.1 part by mass or less. Examples of the polymerization inhibitor include t-butyl catechol and the like. The amount of the polymerization inhibitor used is preferably at least 0.001 part by mass, more preferably at least 0.01 part by mass, and preferably at most 0.5 part by mass, based on 100 parts by mass of the total amount of the alcohol component and the carboxylic acid component. Preferably it is 0.1 part by mass or less.

  In the present invention, the polyester resin may be a modified polyester resin to such an extent that its properties are not substantially impaired. Examples of the modified polyester resin include, for example, phenol, urethane, epoxy grafting or block by a method described in JP-A-11-133668, JP-A-10-239903, JP-A-8-206636, and the like. Among the modified polyester resins, a urethane-modified polyester resin obtained by elongating the polyester resin with a polyisocyanate compound is preferred.

  The vinyl resin portion is a reaction product of a raw material monomer containing a (meth) acrylic compound. It is considered that by causing the (meth) acrylic compound to act as a crosslinking agent for the polyester resin portion in the production of the composite resin A, a methyl ethyl ketone insoluble component having a low glass transition temperature can be generated. Therefore, the composite resin A in the present invention is more preferably a resin in which a polyester resin portion and a vinyl resin portion are chemically bonded via a (meth) acrylic compound.

  As the (meth) acrylic compound, an alkyl (meth) acrylate is preferable. Examples of the alkyl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, (iso) propyl (meth) acrylate, (iso) butyl (meth) acrylate, and the like. It is preferable to use one or more of these. In addition, in this specification, "(iso)" means including both the case where this group exists and the case where it is not, and when these groups do not exist, it is normal. Indicates that Further, “(meth) acrylic acid” refers to acrylic acid, methacrylic acid, or both.

  The carbon number of the alkyl group in the acrylic acid alkyl ester is preferably 1 or more, more preferably 2 or more, and still more preferably 3 or more, from the viewpoint of glossiness, and, from the viewpoint of expanding the non-offset region, preferably It is 6 or less, more preferably 5 or less, further preferably 4 or less, and particularly preferably 4.

  The content of the (meth) acrylic compound is preferably at least 40% by mass, more preferably at least 50% by mass in the raw material monomer of the vinyl resin portion, and the glass of the toner for ensuring the storage stability. From the viewpoint of adjusting the transition temperature, the content is preferably 90% by mass or less, more preferably 80% by mass or less, and further preferably 70% by mass or less.

  It is preferable that the raw material monomer of the vinyl resin portion further contains a styrene compound from the viewpoint of adjusting the glass transition temperature of the toner in order to secure storage stability.

  Examples of the styrene compound include styrene, α-methylstyrene, and styrene derivatives such as vinyltoluene.

  The content of the styrene compound is preferably 0% by mass or more, more preferably 15% by mass or more, still more preferably 30% by mass or more, in the raw material monomer of the vinyl resin portion, and from the viewpoint of glossiness, Is 50% by mass or less, more preferably 45% by mass or less, still more preferably 40% by mass or less.

  The total content of the (meth) acrylic compound and the styrene compound is preferably 70% by mass or more, more preferably 80% by mass or more, still more preferably 90% by mass or more, more preferably It is at least 95% by mass, more preferably 100% by mass.

  As the raw material monomers for the vinyl resin portion other than the (meth) acrylic compound and the styrene compound, ethylenically unsaturated monoolefins such as ethylene and propylene; diolefins such as butadiene; halovinyls such as vinyl chloride; vinyl acetate , Vinyl esters such as vinyl propionate; ethylenic monocarboxylic esters such as dimethylaminoethyl (meth) acrylate; vinyl ethers such as methyl vinyl ether; vinylidene halides such as vinylidene chloride; And vinyl compounds.

  The addition polymerization reaction of the raw material monomer of the vinyl resin portion can be performed, for example, in the presence of a polymerization initiator such as dicumyl peroxide, a polymerization inhibitor, a crosslinking agent, or the like, in the presence of an organic solvent or in the absence of a solvent. The temperature conditions suitable for the addition polymerization reaction are preferably 110 ° C. or higher, more preferably 140 ° C. or higher, and preferably 200 ° C. or lower, more preferably 180 ° C. or lower, and further preferably 170 ° C. or lower. .

  When an organic solvent is used in the addition polymerization reaction, xylene, toluene, methyl ethyl ketone, acetone, or the like can be used. The amount of the organic solvent used is preferably 10 parts by mass or more and 50 parts by mass or less based on 100 parts by mass of the raw material monomer of the vinyl resin portion.

The composite resin A is produced, for example, by a method including a polycondensation reaction step (polycondensation step) of a polyester resin portion with a raw material monomer and an addition polymerization reaction step (addition polymerization step) of a vinyl resin portion with a raw material monomer. can do.
The addition polymerization step may be performed after the polycondensation step, the polycondensation step may be performed after the addition polymerization step, or the polycondensation step and the addition polymerization step may be performed simultaneously. Further, the polycondensation step and the addition polymerization step are preferably performed in the same vessel.

  Further, instead of the polycondensation reaction, a polycondensation resin that has been polymerized in advance may be used. When the polycondensation step and the addition polymerization step proceed in parallel, the mixture containing the raw material monomer of the vinyl-based resin part can be dropped and reacted in the mixture containing the raw material monomer of the polyester resin part. .

In the present invention, the composite resin A is
Step A: a step of performing an addition polymerization reaction of a raw material monomer of the vinyl resin portion in the presence of a carboxylic acid component of 5 mol% or more and 50 mol% or less of all carboxylic acid components,
Step B: A step of placing the reaction solution obtained in Step A under a temperature condition of 180 ° C. or more and 250 ° C. or less for 2.5 hours or more and 10 hours or less, and allowing the reaction to occur. Step C performed in the presence of an alcohol component of at least mol%: a method including a step of adding a raw material monomer of the remaining polyester resin portion to the reaction solution obtained in Step B and performing a polycondensation reaction. Is preferred.
In the steps A and C, it is preferable to promote each reaction under a temperature condition suitable for an addition polymerization reaction or a polycondensation reaction. Step B is preferably performed in the presence of an esterification catalyst or in the presence of an esterification catalyst and an esterification cocatalyst, and more preferably performed until the weight average molecular weight of the generated resin reaches 6,000 or more. .
In the step B, a polycondensation reaction of the raw material monomer in the polyester resin portion may occur, but a glass transition of a methyl ethyl ketone insoluble component is caused by a transesterification reaction between the (meth) acrylic compound and the alcohol component in the vinyl resin formed in the step A. It is considered that a binder resin composition for toner having a temperature lower than the glass transition temperature of the composite resin A by 5 ° C. or more and 40 ° C. or less is obtained.

  By performing step A in the presence of a carboxylic acid component, the addition polymerization reaction can be promoted. The amount of the carboxylic acid component used in the step A is preferably at least 5 mol%, more preferably at least 5.5 mol%, and preferably at most 50 mol%, from the viewpoint of glossiness, of all the carboxylic acid components. It is preferably at most 20 mol%, more preferably at most 10 mol%.

  The temperature range of Step B is preferably 180 ° C. or higher, more preferably 200 ° C. or higher, and preferably 245 ° C. or lower, more preferably 240 ° C. or lower, from the viewpoint of promoting the transesterification reaction.

  The time of step B is preferably 3.5 hours or more, more preferably 4.5 hours or more, and is preferably 8 hours or less, more preferably 7 hours or less, from the viewpoint of promoting the transesterification reaction.

  The amount of the alcohol component used in the step B is 98 mol% or more, preferably 100 mol%, of all the alcohol components.

  The alcohol component used in the step B may be added to the reaction system after the step A, but it is preferable that the alcohol component is present in the reaction system together with the carboxylic acid component in the step A from the viewpoint of working efficiency. That is, the addition polymerization reaction in the step A is preferably performed in the presence of 5 mol% to 50 mol% of the total carboxylic acid component and 98 mol% or more of the total alcohol component.

  The mass ratio of the polyester resin portion to the vinyl resin portion in the composite resin A (polyester resin portion / vinyl resin portion) is preferably 85/15 or more, more preferably 88/12 or more, from the viewpoint of glossiness. From the viewpoint of expansion of the non-offset region, it is preferably 95/5 or less, more preferably 92/8 or less. In the above calculation, the mass of the polyester resin portion is the mass obtained by subtracting the amount of reaction water dehydrated by the polycondensation reaction from the mass of the raw material monomer of the polyester resin portion used. Further, the amount of the vinyl-based resin portion is the total amount of the raw material monomers of the vinyl-based resin portion.

  The softening point of the composite resin A is 110 ° C. or higher, preferably 115 ° C. or higher, more preferably 120 ° C. or higher from the viewpoint of expansion of the non-offset region, and 150 ° C. or lower from the viewpoint of low-temperature fixability. And preferably 140 ° C. or lower, more preferably 130 ° C. or lower.

  The glass transition temperature of the composite resin A is 50 ° C. or higher, preferably 52 ° C. or higher, more preferably 54 ° C. or higher, from the viewpoint of adjusting the glass transition temperature of the toner to ensure storage stability. From the viewpoint of glossiness, it is 65 ° C or lower, preferably 60 ° C or lower, more preferably 57 ° C or lower.

  The acid value of the composite resin A is preferably 5 mgKOH / g or more, more preferably 10 mgKOH / g or more, even more preferably 14 mgKOH / g or more from the viewpoint of low-temperature fixability, and the viewpoint of ensuring the charging stability of the toner. Therefore, it is preferably 30 mgKOH / g or less, more preferably 23 mgKOH / g or less, and still more preferably 18 mgKOH / g or less.

  The number average molecular weight of the composite resin A is preferably 1,500 or more, more preferably 2,000 or more, and still more preferably 2,500 or more, and from the viewpoint of low-temperature fixability, preferably 5,000 or less, more preferably 4,000 or less, and still more preferably. Is less than 3,500.

  Further, the weight average molecular weight of the composite resin A is preferably 100,000 or more, more preferably 125,000 or more, further preferably 150,000 or more, and preferably 350,000 or less, more preferably 300,000 or less, and further preferably 250,000 or less. .

  The content of the composite resin A in the binder resin composition is at least 20% by mass, preferably at least 35% by mass, more preferably at least 45% by mass, even more preferably at least 55% by mass, and the non-offset region. From the viewpoint of the expansion of, the content is preferably 85% by mass or less, more preferably 75% by mass or less, and further preferably 65% by mass or less.

  The binder resin composition for a toner of the present invention preferably further contains an amorphous polyester B in which the content of methyl ethyl ketone insoluble matter is smaller than that of the composite resin A. The amorphous polyester B improves the low-temperature fixability.

  The content of the methyl ethyl ketone insoluble content in the amorphous polyester B is preferably 3% by mass or less, more preferably 2% by mass or less, still more preferably 1% by mass or less, and still more preferably 0% by mass from the viewpoint of low-temperature fixability. It is.

  The amorphous polyester B is preferably a polycondensate of an alcohol component containing a propylene oxide adduct of bisphenol A and a carboxylic acid component.

  In the propylene oxide adduct of bisphenol A, the average number of moles of propylene groups added is preferably 1 or more, more preferably 1.5 or more, and preferably 16 or less, more preferably 8 or less, and even more preferably 6 or less. More preferably, it is 4 or less.

  The content of the propylene oxide adduct of bisphenol A in the alcohol component of the amorphous polyester B is preferably at least 80 mol%, more preferably at least 90 mol%, even more preferably at least 95 mol%. Mol% or less, preferably 99.8 mol% or less, more preferably 99.5 mol% or less.

  It is preferable that the alcohol component of the amorphous polyester B further contains an ethylene oxide adduct of bisphenol A from the viewpoint of adjusting the glass transition temperature of the toner in order to ensure storage stability. In the ethylene oxide adduct of bisphenol A, the average number of moles of ethylene groups added is preferably 1 or more, more preferably 1.5 or more, and preferably 16 or less, more preferably 8 or less, and still more preferably 6 or less. More preferably, it is 4 or less.

  The content of the ethylene oxide adduct of bisphenol A in the alcohol component of the amorphous polyester AH is preferably at least 0.2 mol%, more preferably at least 0.5 mol%, and preferably at most 10 mol%, more preferably Is 5 mol% or less. The same applies to the content of the ethylene oxide adduct of bisphenol A in the alcohol component of the amorphous polyester AL.

  Other alcohol components include tri- or higher polyhydric alcohols such as aromatic diols, aliphatic diols, bisphenol A, hydrogenated bisphenol A, and glycerin other than the propylene oxide adduct of bisphenol A and the ethylene oxide adduct of bisphenol A. And the like.

  The carboxylic acid component of the amorphous polyester B and the method of producing the amorphous polyester B are the same as those of the polyester resin portion of the composite resin A.

  The softening point of the amorphous polyester B is preferably 90 ° C. or higher, more preferably 95 ° C. or higher, from the viewpoint of adjusting the glass transition temperature of the toner in order to secure storage stability, and from the viewpoint of low-temperature fixability. Therefore, it is preferably 110 ° C. or lower, more preferably 105 ° C. or lower.

  The glass transition temperature of the amorphous polyester B is preferably 40 ° C. or higher, more preferably 50 ° C. or higher, and still more preferably 55 ° C. or higher, from the viewpoint of adjusting the glass transition temperature of the toner to ensure storage stability. From the viewpoint of low-temperature fixability, the temperature is preferably 80 ° C. or lower, more preferably 70 ° C. or lower, and further preferably 65 ° C. or lower.

  The acid value of the amorphous polyester B is preferably 1 mgKOH / g or more, more preferably 2 mgKOH / g or more, still more preferably 4 mgKOH / g or more, from the viewpoint of low-temperature fixability, and ensuring the charge stability of the toner. In view of the above, it is preferably 15 mgKOH / g or less, more preferably 10 mgKOH / g or less, and still more preferably 7 mgKOH / g or less.

  The number average molecular weight of the amorphous polyester B is preferably 1,500 or more, more preferably 2,000 or more, and still more preferably 2,300 or more, from the viewpoint of adjusting the glass transition temperature of the toner, in order to ensure storage stability. From the viewpoint of low-temperature fixability, it is preferably 3,500 or less, more preferably 3,000 or less, and further preferably 2,700 or less.

  Further, from the same viewpoint, the weight average molecular weight of the amorphous polyester B is preferably 3,000 or more, more preferably 4,000 or more, even more preferably 5,000 or more, and preferably 9,000 or less, more preferably 7,000 or less, More preferably, it is 6,000 or less.

  The crystallinity of the resin is represented by the ratio of the softening point to 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]. A crystalline resin is a resin having a crystallinity index of 0.6 or more, preferably 0.7 or more, more preferably 0.9 or more, and 1.4 or less, preferably 1.2 or less, while an amorphous resin has a crystallinity index of It is a resin of more than 1.4, preferably more than 1.5, more preferably 1.6 or more, or a resin of less than 0.6, preferably 0.5 or less. The crystallinity of the resin can be adjusted by the type and ratio of the raw material monomers, production conditions (eg, reaction temperature, reaction time, cooling rate) and the like. The maximum endothermic peak temperature refers to the temperature of the highest endothermic peak among the observed endothermic peaks. In a crystalline resin, the highest endothermic peak temperature is the melting point. The composite resin A is preferably an amorphous resin.

  In the binder resin composition, the content of the amorphous polyester B is preferably 5% by mass or more, more preferably 10% by mass or more, further preferably 20% by mass or more, and further preferably 30% by mass or more, From the viewpoint of expanding the non-offset region, the content is preferably 60% by mass or less, more preferably 50% by mass or less, and further preferably 40% by mass or less.

  The binder resin composition for a toner of the present invention preferably further contains a crystalline polyester C. The low-temperature fixability is improved by the crystalline polyester C.

  The alcohol component of the crystalline polyester C preferably contains an aliphatic diol having 6 to 12 carbon atoms from the viewpoint of low-temperature fixability.

  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, Examples include 11-undecanediol and 1,12-dodecanediol.

  The carbon number of the aliphatic diol is preferably 6 or more from the viewpoint of lowering the compatibility with the amorphous polyester resin, and from the viewpoint of low-temperature fixability, preferably 12 or less, more preferably 10 or less, More preferably, it is 8 or less.

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

  The alcohol component may contain an alcohol other than an aliphatic diol having 6 to 12 carbon atoms, but the content of the aliphatic diol having 6 to 12 carbon atoms is preferred in terms of low-temperature fixability and storage stability. From the alcohol component, it is preferably at least 70 mol%, more preferably at least 90 mol%, further preferably at least 95 mol%, further preferably at least 100 mol%.

  Examples of the alcohol component other than the aliphatic diol having 6 to 12 carbon atoms include ethylene glycol, 1,2-propanediol, 1,3-propanediol, and α, having 2 to 5 carbon atoms such as 1,4-butanediol. Examples include ω-aliphatic diols, aromatic diols such as alkylene oxide adducts of bisphenol A, and trivalent or higher alcohols such as glycerin.

  The carboxylic acid component of the crystalline polyester resin C preferably contains an aliphatic dicarboxylic acid compound having 4 to 14 carbon atoms from the viewpoint of low-temperature fixability.

  Aliphatic dicarboxylic acid compounds having 4 to 14 carbon atoms include succinic acid (carbon number: 4), suberic acid (carbon number: 8), azelaic acid (carbon number: 9), sebacic acid (carbon number: 10 ), Dodecane diacid (carbon number: 12), tetradecane diacid (carbon number: 14), succinic acid having an alkyl group or an alkenyl group in a side chain, anhydrides of these acids, those having 1 to 3 carbon atoms Alkyl esters and the like. In the present invention, the carboxylic acid compound includes not only a free acid but also an anhydride which is decomposed during the reaction to generate 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 carbon number of the aliphatic dicarboxylic acid compound is preferably 4 or more, more preferably from the viewpoint of durability. It is preferably 6 or more, more preferably 10 or more, and from the viewpoint of low-temperature fixability, preferably 14 or less, more preferably 12 or less.

  The content of the aliphatic dicarboxylic acid compound having 4 to 14 carbon atoms is preferably 70 mol or more, more preferably 80 mol or more, and still more preferably 90 mol, from the viewpoint of heat-resistant storage stability, based on 100 mol of the alcohol component. Mol or more, and from the viewpoint of low-temperature fixability, it is preferably 130 mol or less, more preferably 120 mol or less, and still more preferably 110 mol or less.

  The carboxylic acid component may contain another carboxylic acid compound. Other carboxylic acid compounds include aromatic dicarboxylic acid compounds such as terephthalic acid and isophthalic acid, aliphatic dicarboxylic acid compounds having 2 to 3 carbon atoms, and trivalent or higher trivalent acids such as trimellitic acid and pyromellitic acid. And the like.

  The polycondensation reaction between the carboxylic acid component and the alcohol component is carried out, for example, in an inert gas atmosphere, preferably in the presence of an esterification catalyst, and further, if necessary, in the presence of an esterification cocatalyst or the like at 135 ° C. or higher. It can be performed at a temperature of 250 ° C. or less. Examples of the esterification catalyst include tin compounds such as dibutyltin oxide and tin (II) 2-ethylhexanoate, and titanium compounds such as titanium diisopropylate bistriethanolaminate. Examples of the esterification co-catalyst that can be used together with the esterification catalyst include gallic acid. The amount of the esterification catalyst used is preferably at least 0.01 part by mass, more preferably at least 0.1 part by mass, and preferably at most 1 part by mass, based on 100 parts by mass of the total amount of the alcohol component and the carboxylic acid component. Preferably it is 0.6 parts by mass or less. The amount of the esterification promoter used is preferably at least 0.001 part by mass, more preferably at least 0.01 part by mass, and preferably at most 0.5 part by mass, based on 100 parts by mass of the total amount of the alcohol component and the carboxylic acid component. It is more preferably 0.1 part by mass or less.

  The melting point of the crystalline polyester C is preferably 60 ° C. or higher, more preferably 65 ° C. or higher, and still more preferably 70 ° C. or higher, from the viewpoint of adjusting the glass transition temperature of the toner to ensure storage stability. From the viewpoint of low-temperature fixability, the temperature is preferably 95 ° C. or lower, more preferably 90 ° C. or lower, and further preferably 85 ° C. or lower.

  The acid value of the crystalline polyester C is preferably 1 mgKOH / g or more, more preferably 2 mgKOH / g or more, and still more preferably 3 mgKOH / g or more, from the viewpoint of low-temperature fixability, and From the viewpoint of adjusting the glass transition temperature of the toner, it is preferably 7 mgKOH / g or less, more preferably 6 mgKOH / g or less, and still more preferably 5 mgKOH / g or less.

  The hydroxyl value of the crystalline polyester C is preferably 2 mgKOH / g or more, more preferably 3 mgKOH / g or more, still more preferably 4 mgKOH / g or more, from the viewpoint of low-temperature fixability, and From the viewpoint of adjusting the glass transition temperature of the toner, it is preferably 7 mgKOH / g or less, more preferably 6 mgKOH / g or less, and still more preferably 5 mgKOH / g or less.

  The number average molecular weight of the crystalline polyester C is preferably 5,500 or more, more preferably 6,000 or more, and still more preferably 6,300 or more, from the viewpoint of low-temperature fixability, and the glass transition of the toner for securing the storage stability. From the viewpoint of temperature adjustment, it is preferably 8,000 or less, more preferably 7,500 or less, and further preferably 7,000 or less.

  From the same viewpoint, the weight average molecular weight of the crystalline polyester C is preferably 20,000 or more, more preferably 22,500 or more, further preferably 25,000 or more, and preferably 50,000 or less, more preferably 45,000 or less, furthermore Preferably it is 40,000 or less.

  The content of the crystalline polyester C is preferably 1% by mass or more, more preferably 2% by mass or more, further preferably 3% by mass or more in the resin composition from the viewpoint of low-temperature fixability. From the viewpoint of adjusting the glass transition temperature of the toner in order to ensure the above, the content is preferably 10% by mass or less, more preferably 8% by mass or less, and further preferably 6% by mass or less.

  The resin composition of the present invention may contain a resin other than the above-mentioned composite resin A, amorphous polyester B, and crystalline polyester C. However, composite resin A, amorphous polyester B, and crystal The total content of the conductive polyester C in the binder resin composition is preferably 70% by mass or more, more preferably 80% by mass or more, further preferably 90% by mass or more, further preferably 95% by mass or more, and still more preferably 100% by mass.

  The electrophotographic toner of the present invention is obtained by using the binder resin composition of the present invention as a binder resin. In addition, the binder resin composition of the present invention may use a mixture of the composite resin A, the amorphous polyester B, and the crystalline polyester C as a binder resin. The raw materials may be directly mixed.

  The toner of the present invention includes, in addition to the binder resin (the binder resin composition of the present invention), a colorant, a release agent, a charge control agent, a magnetic powder, a fluidity improver, a conductivity modifier, and a fibrous substance. And other additives such as a reinforcing filler, an antioxidant, and a cleaning improver.

  As the colorant, dyes, pigments and the like used as colorants for toner can be used. For example, carbon black, phthalocyanine blue, permanent brown FG, brilliant fast scarlet, pigment red 122, pigment green B, rhodamine-B base, solvent red 49, solvent red 146, solvent blue 35, quinacridone, carmine 6B, isoindoline, disazo yellow And the like. In the present invention, the toner particles 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, based on 100 parts by mass of the binder resin, from the viewpoint of improving the image density and low-temperature fixability of the toner. Preferably it is 40 parts by mass or less, more preferably 10 parts by mass or less.

  Examples of the release agent include hydrocarbon waxes such as polypropylene wax, polyethylene wax, polypropylene polyethylene copolymer wax, microcrystalline wax, paraffin wax, Fischer-Tropsch wax and Sasol wax and oxides thereof; carnauba wax, montan Waxes and their deoxidizing waxes, ester waxes such as fatty acid ester waxes; fatty acid amides, fatty acids, higher alcohols, fatty acid metal salts, etc., and these can be used alone or in combination of two or more.

  The melting point of the release agent is preferably 60 ° C. or higher, more preferably 70 ° C. or higher, from the viewpoint of transferability of the toner, and preferably 160 ° C. or lower, more preferably 150 ° C., from the viewpoint of low-temperature fixability. It is as follows.

  The content of the release agent is preferably 0.5 parts by mass or more, based on 100 parts by mass of the binder resin, from the viewpoint of the low-temperature fixability and offset resistance of the toner and the dispersibility in the binder resin. It is preferably at least 1.0 part by mass, more preferably at least 1.5 parts by mass, and preferably at most 10 parts by mass, more preferably at most 8 parts by mass, even more preferably at most 7 parts by mass.

  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.

  As positively chargeable charge control agents, 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 "(all manufactured by Orient Chemical Industries, Ltd.); triphenylmethane dyes containing tertiary amines as side chains, quaternary ammonium salt compounds, for example "Bontron P-51" (manufactured by Orient Chemical Industry Co., Ltd.), cetyltrimethylammonium bromide, "COPY CHARGE PX VP435" (manufactured by Clariant), etc .; polyamine resin such as "AFP-B" (Orient Chemical Industry Co., Ltd.) Imidazole derivatives such as "PLZ-2001" and "PLZ-8001" (both manufactured by Shikoku Kasei Kogyo Co., Ltd.); styrene-acrylic resins such as "FCA-701PT" (Fujikura Kasei Co., Ltd.) ), And the like.

  Further, as the 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" (Above, manufactured by Orient Chemical Industry Co., Ltd.), "Eizen Spiron Black TRH", "T-77" (manufactured by Hodogaya Chemical Industry Co., Ltd.); metal compounds of benzylic acid compounds, for example, "LR- 147 "," LR-297 "(all manufactured by Nippon Carlit Co., Ltd.); metal compounds of salicylic acid compounds, such as" Bontron E-81 "," Bontron E-84 "," Bontron E-88 "," Bontron E-304 "(both manufactured by Orient Chemical Industry Co., Ltd.)," TN-105 "(manufactured by Hodogaya Chemical Industry Co., Ltd.), etc .; copper phthalocyanine dye; quaternary ammonium salt, for example," COPY CHARGE NX VP434 " (Manufactured by Clariant), nitroimidazole derivatives, etc .; organic gold Genus compounds and the like.

  The content of the charge control agent is preferably 0.01 parts by mass or more, more preferably 0.2 parts by mass or more, based on 100 parts by mass of the binder resin, from the viewpoint of charging stability of the toner, and preferably 10 parts by mass. Parts by mass, more preferably 5 parts by mass or less, still more preferably 3 parts by mass or less, still more preferably 2 parts by mass or less.

  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, and a polymerization method, but from the viewpoint of productivity and dispersibility of a colorant, Pulverized toner by a melt-kneading method is preferred. In the case of a pulverized toner obtained by a melt-kneading method, for example, raw materials such as a binder resin, a colorant, a release agent, and a charge control agent are uniformly mixed by a mixer such as a Henschel mixer, and then a closed kneader, a single-shaft or two-shaft. It can be manufactured by melt-kneading with a shaft extruder, open roll-type kneader or the like, cooling, pulverizing, and classifying.

  It is preferable to use an external additive in the toner of the present invention in order to improve transferability. Examples of the external additive include inorganic fine particles such as silica, alumina, titania, zirconia, tin oxide, and zinc oxide, and organic fine particles such as resin particles such as melamine resin fine particles and polytetrafluoroethylene resin fine particles. The above may be used in combination. Among these, silica is preferable, and from the viewpoint of transferability of the toner, hydrophobic silica subjected to hydrophobic treatment is more preferable.

  Examples of hydrophobizing agents for hydrophobizing the surface of silica particles include hexamethyldisilazane (HMDS), dimethyldichlorosilane (DMDS), silicone oil, octyltriethoxysilane (OTES), and methyltriethoxysilane. Can be

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

  The content of the external additive is preferably at least 0.05 part by mass, more preferably 0.1 part by mass, based on 100 parts by mass of the toner before being treated with the external additive, from the viewpoint of chargeability, fluidity, and transferability of the toner. Parts by mass, more preferably 0.3 parts by mass or more, and preferably 5 parts by mass or less, more preferably 3 parts by mass or less.

The volume median particle size (D ₅₀ ) of the toner of the present invention is preferably 3 μm or more, more preferably 4 μm or more, and is preferably 15 μm or less, more preferably 10 μm or less. In the present specification, the volume median particle diameter (D ₅₀ ) means a particle diameter at which the cumulative volume frequency calculated by the volume fraction is 50% calculated from the smaller particle diameter. When the toner is treated with an external additive, the volume median particle diameter of the toner particles before the treatment with the external additive is defined as the volume median particle diameter of the toner.

  The toner of the present invention can be used as it is as a one-component developing toner or as a two-component developing toner used by being mixed with a carrier in a one-component developing system or a two-component developing system image forming apparatus.

  Hereinafter, the present invention will be described specifically with reference to Examples, but the present invention is not limited to these Examples. Physical properties of the resin and the like were measured by the following methods.

(Softening point of resin)
Using a flow tester "CFT-500D" (manufactured by Shimadzu Corporation), apply a load of 1.96MPa with a plunger while heating a 1g sample at a heating rate of 6 ° C / min, diameter 1mm, length 1mm Extrude from the nozzle. The plunger descent of the flow tester is plotted against the temperature, and the temperature at which half of the sample has flowed out is taken as the softening point.

[Maximum peak temperature of endothermic resin]
Using a differential scanning calorimeter "Q-100" (manufactured by TA Instruments Japan Co., Ltd.), weigh 0.01 to 0.02 g of a sample into an aluminum pan, and cool down from room temperature (25 ° C.) to 10 ° C. Cool to 0 ° C at / min and maintain at 0 ° C for 1 minute. Thereafter, the measurement is performed at a heating rate of 10 ° C./min. Among the endothermic peaks observed, the temperature of the peak on the highest temperature side is defined as the highest endothermic peak temperature.

[Glass transition temperature (Tg) of resin and MEK insoluble matter]
Using a differential scanning calorimeter "DSC Q20" (manufactured by TA Instruments Japan), a sample of 0.01 to 0.02 g is weighed in an aluminum pan, and the temperature is raised to 200 ° C., and the temperature is reduced at a rate of 10 ° C. Cool to 0 ° C at ° C / min. Next, the sample is heated at a heating rate of 10 ° C./min, and an endothermic peak is measured. The temperature at the intersection of the extension line of the base line below the maximum endothermic peak temperature and the tangent line indicating the maximum slope from the peak rising portion to the peak apex is defined as the glass transition temperature.

(Acid value of resin)
It is measured based on the method of JIS K 0070: 1992. However, only the measurement solvent was a mixed solvent of ethanol and ether specified in JIS K 0070, the amorphous resin was a mixed solvent of acetone and toluene (acetone: toluene = 1: 1 (volume ratio)), and the crystalline resin was chloroform. : Dimethylformamide mixed solvent (chloroform: dimethylformamide = 7: 3 (volume ratio)).

(Resin hydroxyl value)
It is measured based on the method of JIS K 0070: 1992. However, only the measurement solvent is changed from a mixed solvent of ethanol and ether prescribed in JIS K 0070 to tetrahydrofuran.

[Number average molecular weight (Mn) and weight average molecular weight (Mw) of resin]
The number average molecular weight (Mn) and the weight average molecular weight (Mw) are determined by gel permeation chromatography (GPC) according to the following method.
(1) Preparation of sample solution Dissolve the sample in tetrahydrofuran (amorphous resin) or chloroform (crystalline resin) at 40 ° C so that the concentration becomes 0.5 g / 100 mL. Next, this solution is filtered using a PTFE type membrane filter “DISMIC-25JP” (manufactured by Toyo Roshi Kaisha, Ltd.) having a pore size of 0.20 μm to remove insoluble components, thereby obtaining a sample solution.
(2) Measurement of molecular weight Using the following measurement device and analytical column, flow tetrahydrofuran (amorphous resin) or chloroform (crystalline resin) as eluent at a flow rate of 1 mL / min. To stabilize. 100 μL of the sample solution is injected therein and the measurement is performed. The molecular weight of the sample is calculated based on a calibration curve created in advance. The calibration curve at this time includes several types of monodisperse polystyrene (A-500 (5.0 × 10 ² ), A-1000 (1.01 × 10 ³ ), A-2500 (2.63 × 10 ³ ) manufactured by Tosoh Corporation) 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 ), and F-128 (1.09 × 10 ⁶ ) are used as standard samples. The figures in parentheses indicate the molecular weight.
Measuring device: HLC-8220GPC (manufactured by Tosoh Corporation)
Analytical column: TSKgel GMH _XL + TSKgel G3000H _XL (Tosoh Corporation)

[Methyl ethyl ketone (MEK) insolubles in resin]
(1) Sample preparation
Using a JIS Z8801 sieve, a powdery sample that passes through a 22-mesh sieve but does not pass through a 30-mesh sieve is collected. When the sample is a lump or the like, it is pulverized using a commercially available hammer or coffee mill, and sieved as a powder.

(2) Dissolution of sample
2-1. Weigh 2.000 g of the sample in a glass bottle (M-140, manufactured by Kashiyo Glass Co., Ltd.), add 95 g of MEK, and attach the inner and outer lids.
2-2. Stir for 5 hours with a ball mill (peripheral speed: 200 mm / sec).
2-3. Let stand for 10 hours.

(3) Filtration
3-1. Prepare a glass filter (opening standard 11G-3) attached to an eggplant flask (mass A (g)) that has been weighed (in units of 1/1000 g) in advance. A rubber stopper that can be decompressed is used for sealing the glass filter.
3-2. 20 mL of the supernatant of the lysate left undisturbed in 2-3 for 10 hours is sucked with a mesiped and filtered under reduced pressure using the glass filter prepared in 3-1. In addition, the supernatant is used up to 2 cm below the liquid surface. The pressure inside the eggplant flask before the solution is filtered is adjusted to 40 kPa.
3-3. Aspirate 20 mL of unused MEK with a mespiped, and filter the soluble matter adhering to the glass filter under reduced pressure.

(4) drying
4-1. Remove the MEK in the eggplant flask with an evaporator.
Water bath temperature: 70 ° C
Eggplant flask rotation speed: 200r / min
Decompression degree in eggplant flask during MEK removal: adjusted to 40 to 20 kPa Time: 10 minutes
4-2. After drying at 50 ° C. and 1 torr for 12 hours, the mass B (g) of the eggplant flask is weighed.

(5) Calculation of MEK insoluble content
5-1. Calculate MEK soluble X (g) dissolved in 20 mL of MEK.
X = BA
5-2. Calculate MEK-soluble matter Y (g) dissolved in MEK 95g by setting the specific gravity of MEK to 0.805.
Y = X × 95 / (20 × 0.805)
5-3. Calculate the soluble Z (% by mass) per 1 g of the sample.
Z = Y / 2 × 100
5-4. MEK insoluble matter (% by mass) = 100-Z
The MEK insoluble matter (% by mass) is the average of three measurements.

(Melting point of release agent)
Using a differential scanning calorimeter "DSC Q20" (manufactured by TA Instruments Japan Co., Ltd.), weigh 0.01 to 0.02 g of a sample into an aluminum pan, and heat up to 200 ° C at a rate of 10 ° C / min. The temperature is raised and the temperature is lowered to -10 ° C at a rate of 5 ° C / min. Next, the sample is heated to 180 ° C. at a heating rate of 10 ° C./min and measured. The highest endothermic peak temperature observed from the obtained melting endothermic curve is defined as the melting point of the release agent.

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

(Volume median particle size of toner)
Measuring machine: Coulter Multisizer II (manufactured by Beckman Coulter, Inc.)
Aperture diameter: 100μm
Analysis software: Coulter Multisizer AccuComp version 1.19 (Beckman Coulter, Inc.)
Electrolyte: Isoton II (manufactured by Beckman Coulter, Inc.)
Dispersion: Emulgen 109P (manufactured by Kao Corporation, polyoxyethylene lauryl ether, HLB (Griffin): 13.6) dissolved in electrolyte and adjusted to 5% by mass. , And dispersed with an ultrasonic disperser (machine name: US-1 manufactured by SND, Inc., output: 80 W) for 1 minute, and then, 25 mL of the electrolyte solution was added, and the mixture was further dispersed in an ultrasonic disperser. To prepare a sample dispersion.
Measurement conditions: The sample dispersion was added to 100 mL of the electrolyte so that the particle size of 30,000 particles could be measured in 20 seconds, 30,000 particles were measured, and the volume was determined from the particle size distribution. Determine the median particle size (D ₅₀ ).

Resin production example 1
The alcohol component shown in Table 1 was placed in a 10-liter four-necked flask equipped with a dehydrating tube equipped with a nitrogen inlet tube, a stirrer, and a thermocouple, and heated to 100 ° C., followed by terephthalic acid shown in Table 1. Among them, an amount corresponding to 5.9 mol% of the carboxylic acid component (116 g for resin A1) was added, and the temperature was raised to 160 ° C.
The raw material monomer and the polymerization initiator of the vinyl-based resin shown in Table 1 were weighed and stirred in separate containers, and then dropped over 1 hour using a dropping funnel.
After dropping, carry out the addition polymerization reaction for 1 hour while maintaining the temperature at 160 ° C, and after aging for another 1 hour, raise the temperature to 200 ° C, add the esterification catalyst and the esterification promoter, and react at 235 ° C for 5 hours. After cooling, the mixture was cooled to 160 ° C., the remaining terephthalic acid (1975 g-116 g = 1859 g for resin A1, 94 mol% of the carboxylic acid component) was added, and the polycondensation reaction was again performed at 235 ° C. for 5 hours. The mixture was reacted at 8.0 ° C. and 8.0 kPa until the softening point shown in Table 1 was reached to obtain an amorphous composite resin (resins A1 to A6).

Resin production example 2
The alcohol component shown in Table 2 was placed in a 10-liter four-necked flask equipped with a dehydrating tube equipped with a nitrogen inlet tube, a stirrer, and a thermocouple, and heated to 100 ° C., followed by terephthalic acid shown in Table 2. Was added and the temperature was raised to 160 ° C.
The raw material monomer and the polymerization initiator of the vinyl resin shown in Table 2 were weighed and stirred in separate containers, and then added dropwise over 1 hour using a dropping funnel.
After the dropwise addition, an addition polymerization reaction was carried out for 1 hour while maintaining the temperature at 160 ° C., and after aging for 1 hour, the temperature was raised to 200 ° C., and an esterification catalyst and an esterification cocatalyst were added. The mixture was subjected to a condensation reaction and further reacted at 235 ° C. and 8.0 kPa until the softening point shown in Table 2 was reached, to obtain an amorphous composite resin (Resin A7).

Resin production example 3
The alcohol component shown in Table 2 was placed in a 10-liter four-necked flask equipped with a dehydrating tube equipped with a nitrogen inlet tube, a stirrer, and a thermocouple, and heated to 100 ° C., followed by terephthalic acid shown in Table 2. Of these, 116 g (5.9 mol% of the carboxylic acid component in resin A8) was added, and the temperature was raised to 160 ° C.
The raw material monomer and the polymerization initiator of the vinyl resin shown in Table 2 were weighed and stirred in separate containers, and then added dropwise over 1 hour using a dropping funnel.
After dropping, carry out the addition polymerization reaction for 1 hour while maintaining the temperature at 160 ° C, and after aging for another 1 hour, raise the temperature to 200 ° C, add the esterification catalyst and the esterification promoter, and react at 235 ° C for 5 hours. After that, the mixture was cooled to 160 ° C., the remaining terephthalic acid was added, the polycondensation reaction was again performed at 235 ° C. for 5 hours, and the reaction was further performed at 235 ° C. and 8.0 kPa for 2 hours.
After cooling to 180 ° C, trimellitic anhydride shown in Table 2 was added, and the temperature was raised from 180 ° C to 210 ° C at 10 ° C / h until the softening point shown in Table 2 was reached at 210 ° C and 10 kPa. The reaction was performed to obtain an amorphous composite resin (resins A8 to A10).

Resin production example 4
The alcohol component shown in Table 2 was placed in a 10-liter four-necked flask equipped with a dehydrating tube equipped with a nitrogen inlet tube, a stirrer, and a thermocouple, and heated to 100 ° C., followed by terephthalic acid shown in Table 2. Was added and the temperature was raised to 160 ° C.
In the production of the vinyl-based resin raw material monomer and the resin A13 shown in Table 2, the amphoteric monomer and the polymerization initiator were weighed and stirred in separate containers, and then added dropwise over 1 hour using a dropping funnel.
After the dropwise addition, an addition polymerization reaction was carried out for 1 hour while maintaining the temperature at 160 ° C., and after aging for 1 hour, the temperature was raised to 200 ° C., and an esterification catalyst and an esterification cocatalyst were added. A condensation reaction was performed, and the reaction was further performed at 235 ° C. and 8.0 kPa for 2 hours.
After cooling to 180 ° C, trimellitic anhydride shown in Table 2 was added, and the temperature was raised from 180 ° C to 210 ° C at a rate of 10 ° C / hour until the softening point shown in Table 2 was reached at 210 ° C and 10 kPa. The reaction was performed to obtain an amorphous composite resin (resins A11 and A12).

Resin production example 5
The alcohol component shown in Table 3 was placed in a 10-liter four-necked flask equipped with a dehydrating tube equipped with a nitrogen inlet tube, a stirrer, and a thermocouple, and heated to 100 ° C., followed by terephthalic acid shown in Table 3. Among them, 116 g (5.9 mol% of the carboxylic acid component) was added, and the temperature was raised to 160 ° C.
The raw material monomer and the polymerization initiator of the vinyl resin shown in Table 3 were weighed and stirred in separate containers, and then dropped over 1 hour using a dropping funnel.
After dropping, carry out the addition polymerization reaction for 1 hour while maintaining the temperature at 160 ° C, and after aging for another 1 hour, raise the temperature to 200 ° C, add the esterification catalyst and the esterification promoter, and react at 235 ° C for 2 hours (Weight-average molecular weight of the formed resin: 6,670), cooled to 160 ° C., added with the remaining terephthalic acid (1975 g-116 g = 1859 g, 94 mol% of the carboxylic acid component), and weighed again at 235 ° C. for 5 hours. The mixture was subjected to a condensation reaction and further reacted at 235 ° C. and 8.0 kPa until the softening point shown in Table 3 was reached, to obtain an amorphous composite resin (Resin A13).

Resin production example 6
The alcohol component shown in Table 4 was placed in a 10-liter four-necked flask equipped with a dehydrating tube equipped with a nitrogen inlet tube, a stirrer, and a thermocouple, and heated to 100 ° C., and then the terephthalic acid shown in Table 4 was added. Then, 39.3 g of titanium diisopropylate bistriethanol aminate (Orgatics TC-400, manufactured by Matsumoto Fine Chemical Co., Ltd.) as an esterification catalyst and 1.6 g of gallic acid as an esterification co-catalyst were added, and the mixture was added at 235 ° C. for 10 hours. A condensation reaction was performed, and the reaction was further performed at 235 ° C. and 8.0 kPa until the softening point shown in Table 4 was reached, to obtain an amorphous polyester (resin B1).

Resin production example 7
The alcohol component shown in Table 4 was placed in a 10-liter four-necked flask equipped with a dehydrating tube equipped with a nitrogen inlet tube, a stirrer, and a thermocouple, and heated to 100 ° C. After the components were added, the mixture was heated to 140 ° C. and reacted for 6 hours (reaction rate 65%), and then reacted while raising the temperature to 200 ° C. at a rate of 10 ° C./h. After reacting at 200 ° C. to a reaction rate of 80%, 12.0 g of titanium diisopropylate bistriethanolamine (Orgatics TC-400, manufactured by Matsumoto Fine Chemical Co., Ltd.) was used as an esterification catalyst and gallic acid was used as an esterification cocatalyst. 1.2 g was added, and the reaction was further performed at 200 ° C. for 2 hours. The reaction was further performed at 8 kPa for 2 hours to obtain a crystalline polyester (resins C1 and C2). The reaction rate refers to a value of (amount of reaction water produced (mol) / amount of theoretically produced water (mol) × 100).

Examples 1 to 11 and Comparative Examples 1 to 3
100 parts by mass of a binder resin shown in Table 5, 6 parts by mass of a coloring agent "Fastgen Super Magenta R" (CI Pigment Red 122, manufactured by Dainippon Ink and Chemicals, Inc.), and a charge control agent "LR-147" (Japan 1 part by mass of Carlit Co., Ltd.) and 4 parts by mass of a release agent "Carnauba Wax C1" (manufactured by Kato Yoko Co., Ltd., melting point: 80 ° C.) were thoroughly stirred with a Henschel mixer, and then the total length of the kneading portion was 1560 mm, screw diameter Melt kneading was carried out using a co-rotating twin-screw extruder having a diameter of 42 mm and a barrel inner diameter of 43 mm. The rotation speed of the roll was 200 r / min, the heating set temperature in the roll was 100 ° C., the temperature of the kneaded material was 160 ° C., the supply speed of the kneaded material was 10 kg / h, and the average residence time was about 18 seconds. After cooling, toner particles having a volume median particle diameter (D ₅₀ ) of 6.5 μm were obtained by a jet mill.

  To 100 parts by mass of the obtained toner particles, 2 parts by mass of “Aerosil R-972” (hydrophobic silica, manufactured by Nippon Aerosil Co., Ltd., hydrophobizing agent: DMDS, average particle diameter: 16 nm) was added as an external additive. The mixture was mixed with a Henschel mixer at 3600 r / min for 5 minutes to perform an external additive treatment to obtain a toner.

Test Example 1 [Glossiness of image]
The toner was mounted on a copying machine “AR-505” (trade name, manufactured by Sharp Corporation), and an image was formed without fixing (printing area: 2 cm × 12 cm, adhesion amount: 0.5 mg / cm ² ). J paper (trade name, manufactured by Fuji Xerox Co., Ltd.) was used as a print medium. The fixing device of the copying machine was fixed on paper at 160 ° C. and 400 mm / sec off-line. A cardboard was spread under the image, and the glossiness was measured using a gloss meter (manufactured by HORIBA, trade name: “IG-330”) under a light irradiation condition of 60 °. The higher the value obtained, the higher the gloss. The glossiness was evaluated based on the following evaluation criteria. Table 5 shows the results.

〔Evaluation criteria〕
A: The glossiness is 20 or more.
B: The glossiness is 15 or more and less than 20.
C: The glossiness is 10 or more and less than 15.
D: The glossiness is less than 10.

Test example 2 [non-offset area]
The toner was mounted on a copying machine “AR-505” (trade name, manufactured by Sharp Corporation), and an image was formed without fixing (printing area: 2 cm × 12 cm, adhesion amount: 0.5 mg / cm ² ). Ncolor104 (manufactured by Fuji Xerox, 104 g / m ² · 125 μm) was used as a print medium. The fixing machine of the copying machine was fixed on paper at 400 mm / sec off-line. The temperature at which offset occurred was raised from 160 ° C. in increments of 5 ° C., and the non-offset region was determined. Table 5 shows the results.

  From the above results, the toners of Examples 1 to 11 impair the non-offset region in comparison with the toners of Comparative Examples 1 to 3 using a composite resin containing a MEK insoluble matter having a higher glass transition temperature than the resin. And a high-gloss image can be obtained.

  The binder resin composition for a toner according to the present invention is, for example, a binder resin for an electrophotographic toner used for developing a latent image formed in an electrostatic image developing method, an electrostatic recording method, an electrostatic printing method, or the like. It is preferably used as

Claims (9)

  20% by mass or more of a composite resin A having a polyester resin portion which is a reaction product of a raw material monomer containing an alcohol component and a carboxylic acid component and a vinyl resin portion which is a reaction product of a raw material monomer containing a (meth) acrylic compound. A binder resin composition for toner containing, wherein the composite resin A has a softening point of 110 ° C or more and 150 ° C or less, a glass transition temperature of 50 ° C or more and 65 ° C or less, and a methyl ethyl ketone insoluble content of 5% by mass. %, Wherein the glass transition temperature of the methyl ethyl ketone-insoluble component is 5 ° C. to 40 ° C. lower than the glass transition temperature of the composite resin A.   2. The binder resin composition for toner according to claim 1, wherein the proportion of the carboxylic acid compound having a valency of 3 or more in the carboxylic acid component of the polyester resin portion is 5 mol or less based on 100 mol of the alcohol component.   The binder resin composition for a toner according to claim 1, wherein the raw material monomer of the vinyl resin portion further contains a styrene compound.   The binder resin composition for toner according to any one of claims 1 to 3, wherein the mass ratio of the polyester resin portion to the vinyl resin portion in the composite resin A is 85/15 or more and 95/5 or less.   The binder for a toner according to any one of claims 1 to 4, further comprising an amorphous polyester B having a softening point of 90C or more and 110C or less and a content of a methyl ethyl ketone insoluble content of 3% by mass or less. Resin composition.   The binder resin composition for a toner according to claim 1, further comprising a crystalline polyester C.   An electrophotographic toner comprising the binder resin composition for a toner according to claim 1. The method for producing a binder resin composition for toner according to any one of claims 1 to 6, wherein the composite resin A is
Step A: a step of performing an addition polymerization reaction of a raw material monomer of a vinyl-based resin portion in the presence of a carboxylic acid component of 5 mol% to 50 mol% of all carboxylic acid components,
Step B: A step of placing the reaction solution obtained in Step A under a temperature condition of 180 ° C. or more and 250 ° C. or less for 2.5 hours or more and 10 hours or less, and allowing the reaction to occur. Step C performed in the presence of at least mol% of an alcohol component: a toner produced by a method including a step of adding a raw material monomer of the remaining polyester resin portion to the reaction solution obtained in Step B and performing a polycondensation reaction Method for producing a binder resin composition for use.   9. The method according to claim 8, wherein the addition polymerization reaction in the step A is carried out in the presence of at least 5 mol% and at most 50 mol% of the total carboxylic acid component and at least 98 mol% of the total alcohol component. .