JP7153581B2 - Binder resin composition for toner - Google Patents

Description

The present invention provides, for example, a binder resin composition for toner used for developing latent images formed by electrophotography, electrostatic recording, electrostatic printing and the like, and electrophotography containing the binder resin composition. for toner.

Patent Document 1 discloses a binder resin composition for electrophotographic toner which is excellent in all of low-temperature fixability, hot-offset resistance, and long-term storage stability. Amorphous composite resin of resin P and vinyl resin, containing amorphous composite resin AC having a softening point of 107°C or higher and 140°C or lower, and 95 mol% or more of aliphatic diol having 2 or more and 16 or less carbon atoms. and a crystalline polyester resin CP which is a polycondensation product 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 mol or more and 18 mol or less of an aromatic carboxylic acid compound having a valence of 3 or higher with respect to 100 mol of the alcohol component, and the vinyl resin contains carbon in the alkyl group; A binder resin composition for toner is disclosed which is an addition polymer of raw material monomers containing 25% by mass or more and 50% by mass or less of a (meth)acrylic acid alkyl ester having a number of 2 or more and 6 or less.

Patent Document 2 discloses an alcohol component containing 10 mol % or more and 100 mol % or less of an ethylene oxide adduct of bisphenol A as a binder resin composition for electrophotographic toner excellent in low-temperature fixability, gloss, and roller peelability. A raw material containing 10% to 60% by mass of 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. An addition polymerization resin component obtained by addition polymerization of a monomer, and an amorphous composite resin having a softening point of 100 ° C or higher and 130 ° C or lower and a methyl ethyl ketone insoluble content of 5 mass% or more and 50 mass% or less. A binder resin composition for toner is disclosed.

JP 2017-203831 A JP 2016-130797 A

The applications of office copiers are not limited to conventional office documents, but are expanding to commercial applications such as flyers and pamphlets. In commercial applications, images with a high print rate such as photographs are often used, and the image portion is often folded. In printing using toner, since the toner layer is fragile, there is a problem that the toner layer is broken when folded, resulting in the generation of white streaks in the image. To solve this problem, it is conceivable to increase the strength of the resin by increasing the molecular weight of the resin.

TECHNICAL FIELD The present invention relates to a binder resin composition for toner and an electrophotographic toner containing the binder resin composition, which can achieve both pulverization property and image bending resistance.

In order to solve the above problem, the present inventors have found that in a composite resin having a polyester resin portion and a vinyl resin portion, by giving a polyacrylic acid skeleton to the polyester, it is possible to achieve both crushability and image bending resistance. I found out.

The present invention
[1] Containing a composite resin A having a polyester resin portion that is a reaction product of a raw material monomer containing an alcohol component and a carboxylic acid component, and a vinyl resin portion that is a reaction product of a raw material monomer containing a (meth)acrylic compound. wherein the (meth)acrylic compound comprises a (meth)acrylic acid alkyl ester S having an alkyl group having 1 to 5 carbon atoms and an alkyl group having 6 to 20 carbon atoms. The following (meth)acrylic acid alkyl ester L is included, and the total content of the (meth)acrylic acid alkyl ester S and the (meth)acrylic acid alkyl ester L is 90% by mass in the raw material monomer of the vinyl resin portion above, wherein the mass ratio of the polyester resin portion to the vinyl resin portion is 80/20 or more and 96/4 or less,
[2] An electrophotographic toner containing the binder resin composition for toner described in [1]; and [3] A method for producing the binder resin composition for toner described in [1], comprising: resin A,
Step A: a step of performing an addition polymerization reaction of raw material monomers of the vinyl-based resin portion in the presence of 5 mol% or more and 50 mol% or less of the total carboxylic acid component;
Step B: The reaction solution obtained in Step A is placed under temperature conditions of 180°C or higher and 250°C or lower for 2.5 hours or more and 10 hours or less to react, provided that the reaction in Step B is 98% of all alcohol components. Step C carried out in the presence of mol % or more of an alcohol component: A toner produced by a method including a step of adding raw material monomers for the remaining polyester resin portion to the reaction solution obtained in Step B and conducting 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 exhibits an excellent effect that it is possible to achieve both pulverizability and image bending resistance.

The binder resin composition for toner of the present invention contains a composite resin A having a polyester resin portion and a vinyl resin portion, and raw material monomers of the vinyl resin portion are short-chain (meth)acrylic acid alkyl esters. One characteristic is that it contains a long-chain (meth)acrylic acid alkyl ester. This is because the (meth)acrylic acid alkyl ester having a short-chain alkyl group binds to the polyester resin portion by transesterification with the end of the alcohol component of the polyester resin portion, but the (meth)acrylic acid having a long-chain alkyl group Due to the effect of steric hindrance, alkyl esters are much less likely to undergo transesterification than short-chain alkyl groups, and remain as side chains, so the flexibility (bending resistance of the image) provided by the side chains and the composite with the polyester resin portion It is presumed that this is because of the reduction in the molecular weight of the polyester skeleton and the resulting suppression of molecular entanglement between the polyester skeletons and the pulverizability.

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

The alcohol component of the polyester resin portion has the formula (I):

(Wherein, OR and RO are oxyalkylene groups, R is an ethylene group and/or propylene group, x and y represent the average number of added moles of alkylene oxide, each being a positive number, and 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 preferably contains an alkylene oxide adduct of bisphenol A represented by. Examples of the alkylene oxide adduct of bisphenol A represented by formula (I) include a polyoxypropylene adduct of 2,2-bis(4-hydroxyphenyl)propane and a polyoxypropylene adduct of 2,2-bis(4-hydroxyphenyl)propane. polyoxyethylene adducts, and the like. It is preferable to use one or more of these.

The content of the alkylene oxide adduct of bisphenol A represented by formula (I) is preferably 70 mol% or more, more preferably 80 mol% or more, still more preferably 90 mol% or more, still more preferably It is 95 mol % or more, 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 Aliphatic diols such as diols, 1,3-butanediol and neopentyl glycol, trivalent or higher alcohols such as glycerin, and the like.

The carboxylic acid component of the polyester resin portion preferably contains an aromatic dicarboxylic acid compound from the viewpoint of adjusting the glass transition temperature of the toner to ensure storage stability. Examples of aromatic dicarboxylic acid compounds include phthalic acid, isophthalic acid, terephthalic acid, anhydrides of these acids, and alkyl esters of these acids having 1 to 3 carbon atoms. Terephthalic acid is preferred. In the present invention, the carboxylic acid compounds include not only free acids but also anhydrides that decompose during the reaction to produce acids, and alkyl esters 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, still more preferably 90 mol% or more, still more preferably 95 mol% or more, 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 bending resistance, it is preferable that the carboxylic acid component does not contain a carboxylic acid compound having a valence of 3 or more, or, if it does contain it, the amount thereof is small. Therefore, the content of the trivalent or higher carboxylic acid compound is preferably 20 mol or less, more preferably 10 mol or less, more preferably 5 mol or less, and further preferably 5 mol or less, with respect to 100 mol of the alcohol component. It is preferably 3 mol or less, more preferably 1 mol or less, still more preferably 0.5 mol or less, still more preferably 0 mol.

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

From the viewpoint of adjusting the softening point of the polyester resin, the equivalent ratio (COOH group/OH group) of the carboxylic acid component and the alcohol component is preferably 0.6 or more, more preferably 0.7 or more, still more preferably 0.75 or more, and still more preferably It is 0.8 or more, and preferably 1.1 or less, more preferably 1.05 or less, still more preferably 1.0 or less, still more preferably 0.9 or less.

For the polyester resin portion, for example, an alcohol component and a carboxylic acid component are mixed in an inert gas atmosphere, preferably in the presence of an esterification catalyst, and if necessary, in the presence of an esterification co-catalyst, a polymerization inhibitor, etc. 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 bistriethanolamine, and titanium compounds are preferred. The amount of the esterification catalyst used is preferably 0.01 parts by mass or more, more preferably 0.1 parts by mass or more, and preferably 1.5 parts by mass or less, or more, relative to 100 parts by mass of the total amount of the alcohol component and the carboxylic acid component. It is preferably 1 part by mass or less. Gallic acid etc. are mentioned as an esterification co-catalyst. The amount of the esterification promoter used is preferably 0.001 parts by mass or more, more preferably 0.01 parts by mass or more, and preferably 0.5 parts by mass or less, with respect to 100 parts by mass as the total amount of the alcohol component and the carboxylic acid component. More preferably, it is 0.1 part by mass or less. Polymerization inhibitors include t-butylcatechol and the like. The amount of the polymerization inhibitor used is preferably 0.001 parts by mass or more, more preferably 0.01 parts by mass or more, and preferably 0.5 parts by mass or less, or more, relative to 100 parts by mass of the total amount of the alcohol component and the carboxylic acid component It is preferably 0.1 part by mass or less.

In addition, in the present invention, the polyester resin may be a polyester resin that has been modified to such an extent that its properties are not substantially impaired. Modified polyester resins include, for example, grafting or blocking with phenol, urethane, epoxy, etc. by the methods described in JP-A-11-133668, JP-A-10-239903, JP-A-8-20636, etc. Among the modified polyester resins, urethane-modified polyester resins obtained by urethane-extending a polyester resin with a polyisocyanate compound are preferred.

The vinyl-based resin portion is a reaction product of a raw material monomer containing a (meth)acrylic compound, and the (meth)acrylic compound is a (meth)acrylic acid alkyl ester S having at least a short-chain alkyl group and a long-chain alkyl group. A (meth)acrylic acid alkyl ester L having a group is included.

The number of carbon atoms in the alkyl group of the (meth)acrylic acid alkyl ester S is 1 or more, preferably 3 or more, more preferably 4 or more, and 5 or less, preferably 4 or less.

Examples of the (meth)acrylic acid alkyl ester S include methyl (meth)acrylate, ethyl (meth)acrylate, (iso)propyl (meth)acrylate, (iso)butyl (meth)acrylate, and (meth)acrylic acid. (iso)pentyl and the like. It is preferable to use one or more of these. In the present specification, "(iso)" means including both cases where this group exists and cases where it does not exist, and when these groups do not exist, normal indicates that Moreover, "(meth)acrylic acid" indicates acrylic acid, methacrylic acid, or both.

The number of carbon atoms in the alkyl group of the (meth)acrylic acid alkyl ester L is 6 or more, preferably 8 or more, and 20 or less, preferably 18 or less, more preferably 14 or less, still more preferably 10 or less.

(Meth)acrylate alkyl esters L include (iso)hexyl (meth)acrylate, (iso)heptyl (meth)acrylate, (iso)octyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate. , stearyl (meth)acrylate, and the like. It is preferable to use one or more of these.

The molar ratio of the (meth)acrylic acid alkyl ester S having an alkyl group having 1 to 5 carbon atoms to the (meth)acrylic acid alkyl ester L having an alkyl group having 6 to 20 carbon atoms ((meth)acrylic acid alkyl ester S/(meth)acrylic acid alkyl ester L)) is preferably 20/80 or more, more preferably 40/60 or more, from the viewpoint of enhancing the combination of the polyester resin portion and the vinyl resin portion. From the viewpoint of increasing the mobility of the resin due to the acrylic skeleton, the ratio is preferably 90/10 or less, more preferably 80/20 or less, even more preferably 70/30, still more preferably 60/40.

The total content of (meth)acrylic acid alkyl ester S and (meth)acrylic acid alkyl ester L is 90% by mass or more, preferably 95% by mass or more, more preferably 100% by mass in the raw material monomer of the vinyl resin portion. % by mass.

Raw material monomers for the vinyl resin portion other than (meth)acrylic compounds include styrene compounds such as styrene, α-methylstyrene, and vinyltoluene; ethylenically unsaturated monoolefins such as ethylene and propylene; diolefins such as butadiene. vinyl esters such as vinyl acetate and vinyl propionate; ethylenic monocarboxylic acid esters such as dimethylaminoethyl (meth)acrylate; vinyl ethers such as methyl vinyl ether; vinylidenes such as vinylidene chloride Halide; N-vinyl compounds such as N-vinylpyrrolidone.

The addition polymerization reaction of the raw material monomers of the vinyl resin portion can be carried out, for example, in the presence of a polymerization initiator such as dicumyl peroxide, a polymerization inhibitor, a cross-linking 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 still more preferably 170°C or lower. .

When using an organic solvent for the addition polymerization reaction, xylene, toluene, methyl ethyl ketone, acetone, etc. 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 with respect to 100 parts by mass of the raw material monomer for the vinyl resin portion.

Composite resin A is produced by a method including, for example, a polycondensation reaction step (polycondensation step) using raw material monomers for the polyester resin portion and an addition polymerization reaction step (addition polymerization step) using raw material monomers for the vinyl resin portion. 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. Moreover, the polycondensation step and the addition polymerization step are preferably carried out in the same vessel.

Further, instead of the polycondensation step, prepolymerized polycondensation resin may be used. When the polycondensation step and the addition polymerization step are carried out in parallel, the mixture containing the raw material monomers for the vinyl resin portion can be added dropwise to the mixture containing the raw material monomers for the polyester resin portion to cause the reaction. .

In the present invention, the composite resin A is
Step A: a step of performing an addition polymerization reaction of raw material monomers of the vinyl-based resin portion in the presence of 5 mol% or more and 50 mol% or less of the total carboxylic acid component;
Step B: The reaction solution obtained in Step A is placed under temperature conditions of 180°C or higher and 250°C or lower for 2.5 hours or more and 10 hours or less to react, provided that the reaction in Step B is 98% of all alcohol components. Step C carried out in the presence of mol% or more of an alcohol component: production by a method including a step of adding raw material monomers for the remaining polyester resin portion to the reaction solution obtained in step B and conducting a polycondensation reaction is preferred.
In steps A and C, it is preferable to promote the respective reactions under temperature conditions suitable for addition polymerization reaction or polycondensation reaction. Moreover, step B is preferably carried out in the presence of an esterification catalyst, or in the presence of an esterification catalyst and an esterification co-catalyst.
In step B, a polycondensation reaction of the raw material monomers of the polyester resin portion may also occur. It is presumed that the transesterification reaction with the hydroxyl group is promoted, and the composite of the polyester resin portion and the vinyl resin portion is enhanced.

The addition polymerization reaction can be promoted by carrying out the step A in the presence of a carboxylic acid component. The amount of the carboxylic acid component used in step A is preferably 5 mol% or more, more preferably 5 mol% or more, and still more preferably 6 mol% or more of the total carboxylic acid component, and from the viewpoint of bending resistance , preferably 50 mol % or less, more preferably 20 mol % or less, still more preferably 10 mol % or less.

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 for step B is preferably 3.5 hours or more, more preferably 4.5 hours or more, and 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 step B is 98 mol% or more, preferably 100 mol%, of the total alcohol component.

The alcohol component used in step B may be added to the reaction system after step A, but from the viewpoint of work efficiency, it is preferably present in the reaction system together with the carboxylic acid component in step A. That is, the addition polymerization reaction of step A is preferably carried out in the presence of 5 mol % or more and 50 mol % or less of the total carboxylic acid component and 98 mol % or more of the total alcohol component of the 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 80/20 or more from the viewpoint of adjusting the glass transition temperature of the toner to ensure storage stability. preferably 86/14 or more, more preferably 88/12 or more, and from the viewpoint of bending resistance, 96/4 or less, preferably 92/8 or less, more preferably 90/10 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. Also, the amount of the vinyl resin portion is the total amount of raw material monomers of the vinyl resin portion.

The softening point of composite resin A is preferably 110° C. or higher, more preferably 120° C. or higher, from the viewpoint of ensuring a fixable temperature range, and preferably 150° C. or lower, more preferably, from the viewpoint of pulverization It is 140°C or less, more preferably 130°C or less.

The glass transition temperature of composite resin A is preferably 48° C. or higher, more preferably 50° C. or higher, from the viewpoint of adjusting the glass transition temperature of the toner to ensure storage stability, and from the viewpoint of low-temperature fixability. , preferably 56°C or lower, more preferably 54°C or lower, still more preferably 52°C or lower.

The acid value of the composite resin A is preferably 10 mgKOH/g or more, more preferably 12 mgKOH/g or more, from the viewpoint of low-temperature fixability, and preferably 40 mgKOH/g or less from the viewpoint of ensuring charging stability of the toner. , more preferably 26 mgKOH/g or less, still more preferably 21 mgKOH/g or less, still more preferably 16 mgKOH/g or less.

The content of the methyl ethyl ketone-insoluble matter in the composite resin A is preferably 14% by mass or more, more preferably 20% by mass or more, and still more preferably 26% by mass or more, from the viewpoint of ensuring a fixing temperature range. From the viewpoint of properties, it is preferably 40% by mass or less, more preferably 35% by mass or less, and even more preferably 30% by mass or less.

The content of composite resin A in the binder resin composition is preferably 20% by mass or more, more preferably 40% by mass or more, still more preferably 50% by mass or more, further preferably 60% by mass or more, From the viewpoint of adjusting the glass transition temperature of the toner to ensure storage stability, the content is preferably 85% by mass or less, more preferably 80% by mass or less, and even more preferably 75% by mass or less.

The binder resin composition for toner of the present invention preferably further contains a polyester B having a glass transition temperature higher than that of the composite resin A. The polyester B makes it possible to keep the molecular weight of the toner lower than when the composite resin A is used alone, so that the pulverizability is further improved.

The difference in glass transition temperature between polyester B and composite resin A is preferably 1° C. or higher, more preferably 2° C. or higher, and still more preferably 3° C. or higher. °C or less, more preferably 15°C or less, and even more preferably 10°C or less.

The glass transition temperature of the polyester B is preferably 55° C. or higher, more preferably 60° C. or higher from the viewpoint of adjusting the glass transition temperature of the toner to ensure storage stability, and is preferably 60° C. or higher from the viewpoint of pulverization. is 70°C or lower, more preferably 66°C or lower, and even more preferably 62°C or lower.

The softening point of the polyester B is preferably 90° C. or higher, more preferably 94° C. or higher, and still more preferably 98° C. or higher from the viewpoint of adjusting the glass transition temperature of the toner to ensure storage stability. From the viewpoint of quality, the temperature is preferably 115° C. or lower, more preferably 110° C. or lower, and even more preferably 105° C. or lower.

The softening point of the polyester B is preferably lower than that of the composite resin A from the viewpoint of low-temperature fixability, and the difference therebetween is preferably 15° C. or higher, more preferably 20° C. or higher, and still more preferably 25° C. or higher. The temperature is preferably 35°C or lower, more preferably 30°C or lower.

The acid value of polyester B is preferably 6 mgKOH/g or more, more preferably 6.5 mgKOH/g or more, still more preferably 7 mgKOH/g or more, from the viewpoint of low-temperature fixability, and from the viewpoint of securing toner charging stability. Therefore, it is preferably 10.5 mgKOH/g or less, more preferably 9 mgKOH/g or less, still more preferably 7.5 mgKOH/g or less.

The number average molecular weight of the polyester B is preferably 1,700 or more, more preferably 2,000 or more, still more preferably 2,300 or more, from the viewpoint of adjusting the glass transition temperature of the toner to ensure storage stability. from the viewpoint of, it is preferably 3,200 or less, more preferably 3,000 or less, and even more preferably 2,700 or less.

From the same point of view, the weight average molecular weight of polyester B is preferably 4,000 or more, more preferably 5,000 or more, still more preferably 6,000 or more, and preferably 12,000 or less, more preferably 10,000 or less, further preferably 8,000 or less.

The alcohol component, the carboxylic acid component, and the production method of Polyester B are the same as those of the polyester resin portion of Composite Resin A.

The content of the polyester B in the binder resin composition is preferably 80% by mass or less, more preferably 60% by mass or less, and even more preferably 40% by mass or less. From the viewpoint of adjusting the transition temperature, the content is preferably 10% by mass or more, more preferably 20% by mass or more, and still more preferably 25% by mass or more.

Both composite resin A and polyester B are preferably amorphous resins.
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]. The 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, more preferably 1.1 or less. is a resin with a crystallinity index greater than 1.4, preferably greater than 1.5, more preferably 1.6 or higher, or less than 0.6, preferably 0.5 or lower. The crystallinity of the resin can be adjusted by the type and ratio of 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 maximum endothermic peak temperature is taken as the melting point.

The resin composition of the present invention may contain a resin other than the composite resin A and the polyester B, but the total content of the composite resin A and the polyester B in the binder resin composition is preferably It is 70% by mass or more, more preferably 80% by mass or more, still more preferably 90% by mass or more, still more 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, in the binder resin composition of the present invention, a mixture of the composite resin A and the polyester B may be used as the binder resin, and these resins may be directly mixed with raw materials when producing the toner. .

In the toner of the present invention, in addition to the binder resin (the binder resin composition of the present invention), a coloring agent, a release agent, a charge control agent, a magnetic powder, a fluidity improver, a conductivity modifier, and a fibrous substance may be added. Additives such as reinforcing fillers, antioxidants, and cleanability improvers may also be contained.

As the colorant, dyes, pigments and the like used as colorants for toners can be used. Examples include carbon black, phthalocyanine blue, permanent brown FG, brilliant first scarlet, pigment green B, rhodamine-B base, solvent red 49, solvent red 146, solvent blue 35, quinacridone, carmine 6B, isoindoline, and disazo yellow. . In the present invention, the toner particles may be either black toner or color toner.

The content of the colorant is preferably 1 part by mass or more, 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 image density and low-temperature fixability of the toner, and It is preferably 40 parts by mass or less, more preferably 10 parts by mass or less.

Release agents include hydrocarbon waxes such as polypropylene wax, polyethylene wax, polypropylene polyethylene copolymer wax, microcrystalline wax, paraffin wax, Fischer-Tropsch wax, Sasol wax, and oxides thereof; carnauba wax, montan Waxes and their deacidified waxes, ester waxes such as fatty acid ester waxes; fatty acid amides, fatty acids, higher alcohols, fatty acid metal salts and the like;

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

The content of the release agent is preferably 0.5 parts by mass or more, or more, with respect to 100 parts by mass of the binder resin, from the viewpoints of low-temperature fixability and anti-offset properties of the toner and dispersibility in the binder resin. It is preferably 1.0 parts by mass or more, more preferably 1.5 parts by mass or more, and preferably 10 parts by mass or less, more preferably 8 parts by mass or less, and even more preferably 7 parts by mass or less.

The charge control agent is not particularly limited, and may contain either a positive charge control agent or a negative charge control agent.

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

In addition, as a negative charge control agent, a metal-containing azo dye such as "Barifast Black 3804", "Bontron S-31", "Bontron S-32", "Bontron S-34", "Bontron S-36" ” (manufactured by Orient Chemical Industry Co., Ltd.), “Eizenspiron Black TRH”, “T-77” (manufactured by Hodogaya Chemical Industry Co., Ltd.), etc.; metal compounds of benzilic 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", " Bontron E-304" (manufactured by Orient Chemical Industry Co., Ltd.), "TN-105" (manufactured by Hodogaya Chemical Industry Co., Ltd.), etc.; copper phthalocyanine dye; quaternary ammonium salt, such as "COPY CHARGE NX VP434" (manufactured by Clariant), nitroimidazole derivatives and the like; organometallic compounds and the like.

From the viewpoint of the charging stability of the toner, 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, and preferably 10 parts by mass with respect to 100 parts by mass of the binder resin. parts or less, more preferably 5 parts by mass or less, still more preferably 3 parts by mass or less, and even more preferably 2 parts by mass or less.

The toner of the present invention is preferably a pulverized toner obtained by a melt-kneading method from the viewpoint of productivity and dispersibility of a colorant. In the case of the pulverized toner by the melt-kneading method, raw materials such as binder resin, colorant, release agent, charge control agent, etc. are uniformly mixed with a mixer such as a Henschel mixer, and then mixed with a closed kneader, single screw or double screw. It can be produced by melt-kneading with a shaft extruder, an open-roll type kneader, or the like, followed by cooling, pulverization, and classification.

An external additive is preferably used in the toner of the present invention in order to improve transferability. External additives 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 toner transferability, hydrophobic silica subjected to hydrophobic treatment is more preferable.

Hexamethyldisilazane (HMDS), dimethyldichlorosilane (DMDS), silicone oil, octyltriethoxysilane (OTES), methyltriethoxysilane and the like are examples of hydrophobizing agents for hydrophobizing the surface of silica particles. be done.

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

The content of the external additive is preferably 0.05 parts by mass or more, more preferably 0.1 part by mass, with respect to 100 parts by mass of the toner before being treated with the external additive, from the viewpoint of charging property, fluidity, and transferability of the toner. parts or more, 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 ( _D50 ) of the toner of the present invention is preferably 3 μm or more, more preferably 4 μm or more, and preferably 15 μm or less, more preferably 10 μm or less. In the present specification, the volume-median particle size (D ₅₀ ) means a particle size at which the cumulative volume frequency calculated as a volume fraction is 50% 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 taken as the volume median particle size of the toner.

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

EXAMPLES The present invention will be specifically described below with reference to Examples, but the present invention is not limited to these Examples. Physical properties such as resins were measured by the following methods.

[Resin softening point]
Using a flow tester "CFT-500D" (manufactured by Shimadzu Corporation), while heating a 1 g sample at a temperature increase rate of 6 ° C / min, a load of 1.96 MPa was applied with a plunger, and the diameter was 1 mm and the length was 1 mm. extruded from the nozzle of Plot the amount of plunger descent of the flow tester against the temperature, and let the softening point be the temperature at which half of the sample flows out.

[Maximum peak temperature of resin endotherm]
Using a differential scanning calorimeter "Q-100" (manufactured by TA Instruments Japan Co., Ltd.), weigh 0.01 to 0.02 g of the sample in an aluminum pan and cool it from room temperature (25 ° C) to a cooling rate of 10 ° C. /min to 0°C and hold at 0°C for 1 minute. After that, measure at a heating rate of 10°C/min. Among the observed endothermic peaks, the temperature of the highest endothermic peak is defined as the maximum endothermic peak temperature.

[Glass transition temperature of resin]
Using a differential scanning calorimeter "DSC Q20" (manufactured by TA Instruments Japan), weigh 0.01 to 0.02 g of the sample in an aluminum pan, heat it up to 200 ° C, and then cool it down at a rate of 10 from that temperature. Cool to 0°C at °C/min. Next, the sample is heated at a heating rate of 10°C/min, and the endothermic peak is measured. The glass transition temperature is defined as the temperature at the intersection of the extended line of the baseline below the maximum endothermic peak temperature and the tangential line showing the maximum slope from the rising portion of the peak to the apex of the peak.

[Acid value of resin]
Measured based on the method of JIS K 0070:1992. However, only the measurement solvent is changed from the mixed solvent of ethanol and ether specified in JIS K 0070 to a mixed solvent of acetone and toluene (acetone:toluene = 1:1 (volume ratio)).

[Number average molecular weight (Mn) and weight average molecular weight (Mw) of resin]
A number average molecular weight (Mn) and a weight average molecular weight (Mw) are determined by gel permeation chromatography (GPC) by the following method.
(1) Preparation of sample solution Dissolve the sample in tetrahydrofuran at 40°C so that the concentration becomes 0.5g/100mL. Next, this solution is filtered using a PTFE type membrane filter "DISMIC-25JP" (manufactured by Toyo Roshi Kaisha, Ltd.) with a pore size of 0.20 µm to remove insoluble components, and the sample solution is obtained.
(2) Molecular weight measurement Using the following measuring apparatus and analytical column, tetrahydrofuran is passed as an eluent at a flow rate of 1 mL per minute, and the column is stabilized in a constant temperature bath at 40°C. Inject 100 μL of the sample solution into it and perform the measurement. The molecular weight of the sample is calculated based on a previously prepared calibration curve. In the calibration curve at this time, several types of monodisperse polystyrene (Tosoh Corporation A-500 (5.0 × 10 ² ), A-1000 (1.01 × 10 ³ ), A-2500 (2.63 × 10 ³ ), A-5000 (5.97×10 ³ ), F-1 (1.02×10 ⁴ ), F-2 (1.81×10 ⁴ ), F-4 (3.97×10 ⁴ ), F-10 (9.64×10 ⁴ ), F-20 (1.90×10 ⁵ ), F-40 (4.27×10 ⁵ ), F-80 (7.06×10 ⁵ ), F-128 (1.09×10 ⁶ )) are used as standard samples. Molecular weights are shown in parentheses.
Measuring device: HLC-8220GPC (manufactured by Tosoh Corporation)
Analysis column: TSKgel GMH _XL + TSKgel G3000H _XL (manufactured by Tosoh Corporation)

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

(2) Sample dissolution
2-1. After weighing 2.000 g of the sample into a glass bottle (M-140, manufactured by Kashiwayo Glass Co., Ltd.), add 95 g of MEK and attach the inner and outer lids.
2-2. Stir in a ball mill for 5 hours (peripheral speed: 200 mm/sec).
2-3. Allow to stand for 10 hours.

(3) Filtration
3-1. Prepare a glass filter (opening standard 11G-3) attached to an eggplant flask (mass A (g)) weighed in advance (in units of 1/1000 g). A rubber stopper that can be depressurized is used to seal the glass filter.
3-2. Aspirate 20 mL of the supernatant of the dissolution solution left at rest for 10 hours in 2-3 with a graduated pipette, and filter under reduced pressure using the glass filter prepared in 3-1. The supernatant is defined as 2 cm below the liquid surface. Adjust the degree of vacuum in the eggplant flask to 40 kPa before filtering the solution.
3-3. Take up 20 mL of unused MEK with a graduated pipette, and filter the soluble matter adhering to the glass filter under reduced pressure.

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

(5) Calculation of MEK insoluble matter
5-1. Calculate the MEK soluble matter X (g) dissolved in 20 mL of MEK.
X=BA
5-2. Calculate the MEK soluble matter Y (g) dissolved in 95 g of MEK assuming the specific gravity of MEK to be 0.805.
Y = X x 95/(20 x 0.805)
5-3. Calculate the soluble content Z (% by mass) per 1 g of sample.
Z=Y/2×100
5-4. MEK insoluble content (% by mass) = 100 - Z
The MEK insoluble matter (% by mass) is the average value 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 the sample in an aluminum pan and heat it up to 200 ° C at a heating rate of 10 ° C / min. The temperature is raised and then cooled to -10°C at a cooling rate of 5°C/min. Next, the sample is heated up to 180°C at a heating rate of 10°C/min and measured. The maximum endothermic peak temperature observed from the melting endothermic curve thus obtained is taken as the melting point of the release agent.

[Average particle size of external additive]
The average particle size refers to the number average particle size, and the particle size (average value of major and minor axes) of 500 particles is measured from a scanning electron microscope (SEM) photograph, and the number average value thereof is taken.

[Volume Median Particle Size of Toner]
Measuring machine: Coulter Multisizer II (manufactured by Beckman Coulter, Inc.)
Aperture diameter: 100 μm
Analysis software: Coulter Multisizer AccuComp version 1.19 (manufactured by 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) was dissolved in the electrolytic solution to adjust it to 5% by mass Dispersion conditions: 10 mg of measurement sample in 5 mL of the dispersion and dispersed for 1 minute with an ultrasonic dispersion machine (machine name: US-1 manufactured by SND Co., Ltd., output: 80 W), then 25 mL of the electrolytic solution is added, and furthermore, the ultrasonic dispersion machine Disperse for 1 minute to prepare a sample dispersion.
Measurement conditions: Add the sample dispersion to 100 mL of the electrolytic solution so that the particle size of 30,000 particles can be measured in 20 seconds, measure 30,000 particles, and determine the volume from the particle size distribution. Determine the median particle size ( _D50 ).

Resin production example 1
The alcohol components shown in Table 1 are placed in a 10-liter four-necked flask equipped with a dehydration tube equipped with a nitrogen inlet tube, a stirrer and a thermocouple, heated to 100 ° C., and then the terephthalic acid shown in Table 1 is added. Of this, 116 g (5.9 mol % of the carboxylic acid component) was added, and the temperature was raised to 160°C.
Raw material monomers for the vinyl-based resin portion and the polymerization initiator shown in Table 1 were weighed and stirred in a separate container, 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. After aging for another 1 hour, the temperature was raised to 200°C, an esterification catalyst and an esterification co-catalyst were added, and a reaction was carried out at 235°C for 5 hours. After cooling to 160 ° C, the remaining terephthalic acid (1975 g - 116 g = 1859 g, 94 mol% of the carboxylic acid component) is added, polycondensation reaction is performed again at 235 ° C for 5 hours, and further 235 ° C, The mixture was allowed to react at 8.0 kPa until it reached the softening point shown in Table 1 to obtain amorphous composite resins (resins A1 to A5).

Resin production example 2
The alcohol components shown in Table 2 are placed in a 10-liter four-necked flask equipped with a dehydration tube equipped with a nitrogen inlet tube, a stirrer and a thermocouple, heated to 100 ° C., and then terephthalic acid shown in Table 2. was added and the temperature was raised to 160°C.
Raw material monomers and a polymerization initiator for the vinyl resin portion shown in Table 2 were weighed and stirred in a separate container, and then added dropwise over 1 hour using a dropping funnel.
After the dropping, an addition polymerization reaction was carried out for 1 hour while maintaining the temperature at 160°C. After aging for another hour, the temperature was raised to 200°C, an esterification catalyst and an esterification co-catalyst were added, and polymerization was carried out at 235°C for 10 hours. Condensation reaction and addition polymerization reaction were carried out, 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 A6).

Resin production example 3
The alcohol components shown in Table 2 are placed in a 10-liter four-necked flask equipped with a dehydration tube equipped with a nitrogen inlet tube, a stirrer and a thermocouple, heated to 100 ° C., and then terephthalic acid shown in Table 2. Of this, 116 g (5.9 mol % of the carboxylic acid component for resin A7) was added, and the temperature was raised to 160°C.
Raw material monomers and a polymerization initiator for the vinyl resin portion shown in Table 2 were weighed and stirred in a separate container, 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. After aging for another 1 hour, the temperature was raised to 200°C, an esterification catalyst and an esterification co-catalyst were added, and a reaction was carried out at 235°C for 5 hours. After cooling to 160°C, the remaining terephthalic acid was added, polycondensation reaction was carried out again at 235°C for 5 hours, and further reaction was carried out at 235°C and 8.0 kPa for 2 hours.
After cooling to 180°C, trimellitic anhydride shown in Table 2 is added, the temperature is raised from 180°C to 210°C at a rate of 10°C/h, and the softening point shown in Table 2 is reached at 210°C and 10 kPa. Amorphous composite resins (resins A7 to A9) were obtained by reacting.

Resin production example 4
The alcohol components shown in Table 2 are placed in a 10-liter four-necked flask equipped with a dehydration tube equipped with a nitrogen inlet tube, a stirrer and a thermocouple, heated to 100 ° C., and then terephthalic acid shown in Table 2. was added and the temperature was raised to 160°C.
Raw material monomers and a polymerization initiator for the vinyl resin portion shown in Table 2 were weighed and stirred in a separate container, and then added dropwise over 1 hour using a dropping funnel.
After the dropping, an addition polymerization reaction was carried out for 1 hour while maintaining the temperature at 160°C. After aging for another hour, the temperature was raised to 200°C, an esterification catalyst and an esterification co-catalyst were added, and polymerization was carried out at 235°C for 10 hours. Condensation reaction and addition polymerization reaction were carried out, and further reaction was carried out at 235° C. and 8.0 kPa for 2 hours.
After cooling to 180°C, trimellitic anhydride shown in Table 2 is added, the temperature is raised from 180°C to 210°C at a rate of 10°C/h, and the softening point shown in Table 2 is reached at 210°C and 10 kPa. A reaction was performed to obtain an amorphous composite resin (resin A10).

Resin production example 5
The alcohol components shown in Table 3 are placed in a 10-liter four-necked flask equipped with a dehydration tube equipped with a nitrogen inlet tube, a stirrer and a thermocouple, heated to 100 ° C., and then terephthalic acid shown in Table 3. , 48.0 g of titanium diisopropylate bistriethanolamine (Orgatics TC-400, manufactured by Matsumoto Fine Chemicals Co., Ltd.) as an esterification catalyst and 1.9 g of gallic acid as an esterification co-catalyst were added, and the mixture was heated at 235°C for 10 hours. A polycondensation reaction was carried out, and the reaction was further carried out at 235° C. and 8.0 kPa until the softening point shown in Table 3 was reached to obtain amorphous polyesters (resins B1 to B3).

Examples 1 to 11 and Comparative Example 1
100 parts by mass of the binder resin shown in Table 4, 6 parts by mass of the coloring agent "Fastgen Super Magenta R" (CI Pigment Red 122, manufactured by Dainippon Ink and Chemicals), and the charge control agent "LR-147" (Japan). Carlit Co.) 1 part by mass and 4 parts by mass of release agent "Sasol Wax H105" (Sasol Co., melting point: 110°C) were thoroughly stirred with a Henschel mixer. The mixture was melt-kneaded using a co-rotating twin-screw extruder with a barrel inner diameter of 43 mm (part of the resulting melt-kneaded product was used in Test Example 1). The rotation speed of the rolls was 200 r/min, the heating temperature inside the rolls was 100°C, the temperature of the kneaded product was 160°C, the kneaded product was supplied at a rate of 10 kg/h, and the average residence time was about 18 seconds. After cooling, toner particles with a volume median particle size (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 size: 16 nm) was added as an external additive. , and a Henschel mixer at 3600 r/min for 5 minutes to carry out external additive treatment and obtain a toner.

Test Example 1 [Grindability]
In the toner manufacturing process, 1 kg of the melt-kneaded product (about 3 cm square plate) was put into a Rotoplex (model R20/10) manufactured by Hosokawa Micron Co. with a 3 mm mesh screen and pulverized. After about 20 minutes, all the pulverized material passed through the screen and was discharged, and the volume median particle diameter (D ₅₀ ) of the obtained particles was measured using a Japanese laser (HELOS) (model number QICPIC/R), Furthermore, pulverizability was evaluated according to the following evaluation criteria. Table 4 shows the results.

〔Evaluation criteria〕
A: The pulverizability of the resin does not pose a problem during toner production.
B: If the production conditions are finely adjusted, no problem will occur during toner production.
C: If the manufacturing conditions are changed, there will be no problem during toner manufacturing.
D: Toner production is possible, but production efficiency is slightly reduced.
E: Toner production is possible, but production efficiency is greatly reduced.

Test Example 2 [Folding resistance of image]
Toner is mounted on the color printer "C612dnw" (product name, manufactured by Oki Data Co., Ltd.), and two types of images are printed without fixation (printing area: length 4 cm x width 12 cm (common), adhesion amount: 1.5 mg / cm ² and 0.7 mg/cm ² ).
The unfixed image was fixed at 150° C. and 200 mm/sec using the fixing machine of the printer offline. J paper (manufactured by Fuji Xerox, basis weight: 82 g/m ² , paper thickness: 97 µm) was used as the fixing paper.
Fold the 2cm vertical line of the printed image, fold it in half with the printed image facing inward, and pass a 1kg cylindrical weight "M1CSB-1KA" (manufactured by Ikeda Rika, bottom diameter 5cm) back and forth twice on the fold. , and the creases were observed, and the bending resistance was evaluated according to the following evaluation criteria. Table 4 shows the results.

〔Evaluation criteria〕
A: No white spots are observed in both the 1.5 mg/cm ² and 0.7 mg/cm ² images.
B: White spots are observed in several places on the 1.5 mg/cm ² image, but not observed on the 0.7 mg/cm ² image.
C: Several white spots are observed in the 0.7 mg/cm ² image.
D: A white line of 5 mm or more and less than 1 cm is observed in an image of 0.7 mg/cm ² .
E: A white line of 1 cm or more and less than 5 cm is observed in an image of 0.7 mg/cm ² .
F: A white line of 5 cm or more is observed in an image of 0.7 mg/cm ² .

From the above results, it can be seen that the toners of Examples 1 to 11 are excellent in both pulverization property and image folding resistance. On the other hand, in Comparative Example 1 containing the composite resin in which the main component of the raw material monomer of the vinyl-based resin portion is styrene, the pulverizability and bending resistance are lacking.

The binder resin composition for toners of the present invention is a binder resin for electrophotographic toners used for developing latent images formed by, for example, electrostatic charge image development methods, electrostatic recording methods, electrostatic printing methods, and the like. It is preferably used as.

Claims (8)

For a toner containing a composite resin A having a polyester resin portion that is a reaction product of a raw material monomer containing an alcohol component and a carboxylic acid component, and a vinyl resin portion that is a reaction product of a raw material monomer containing a (meth)acrylic compound. In the binder resin composition, the (meth)acrylic compound comprises a (meth)acrylic acid alkyl ester S having an alkyl group having 1 to 5 carbon atoms and a (meth)acrylic acid alkyl ester S having an alkyl group having 6 to 20 carbon atoms ( It contains a meth)acrylic acid alkyl ester L, and the total content of the (meth)acrylic acid alkyl ester S and the (meth)acrylic acid alkyl ester L is 90% by mass or more in the raw material monomers of the vinyl resin portion. A binder resin composition for toner, wherein the mass ratio of the polyester resin portion to the vinyl resin portion is 80/20 or more and 96/4 or less. The molar ratio of the (meth)acrylic acid alkyl ester S having 1 to 5 carbon atoms in the alkyl group to the (meth)acrylic acid alkyl ester L having 6 to 20 carbon atoms in the alkyl group is 20/80 to 90/ 2. The binder resin composition for toner according to claim 1, which is 10 or less. 3. The binder resin composition for toner according to claim 1, wherein the content of the carboxylic acid compound having a valence of 3 or higher in the polyester resin portion is 20 mol or less per 100 mol of the alcohol component. 4. The binder resin composition for toner according to any one of claims 1 to 3, wherein the softening point of the composite resin A is 110°C or higher and 150°C or lower. Furthermore, a polyester resin B having a softening point of 90° C. or higher and 115° C. or lower and a glass transition temperature of 55° C. or higher and 70° C. or lower is contained, and the glass transition temperature of the polyester resin B is 1 higher than that of the composite resin A. 5. The binder resin composition for toner according to any one of claims 1 to 4, which has a temperature higher than 20°C. An electrophotographic toner comprising the binder resin composition for toner according to any one of claims 1 to 5. A method for producing a binder resin composition for toner according to any one of claims 1 to 5, wherein the composite resin A is
Step A: a step of performing an addition polymerization reaction of raw material monomers of the vinyl-based resin portion in the presence of 5 mol% or more and 50 mol% or less of the total carboxylic acid component;
Step B: The reaction solution obtained in Step A is placed under temperature conditions of 180°C or higher and 250°C or lower for 2.5 hours or more and 10 hours or less to react, provided that the reaction in Step B is 98% of all alcohol components. Step C carried out in the presence of mol % or more of an alcohol component: A toner produced by a method including a step of adding raw material monomers for the remaining polyester resin portion to the reaction solution obtained in Step B and conducting a polycondensation reaction. a method for producing a binder resin composition for 8. The production method according to claim 7, wherein the addition polymerization reaction in step A is carried out in the presence of a carboxylic acid component of 5 mol% or more and 50 mol% or less of all carboxylic acid components and an alcohol component of 98 mol% or more of all alcohol components. .