JP2015072378A - Binder resin composition for toner - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a binder resin composition for a toner, which can achieve low-temperature fixability and storage property as well as storage property and durability in a high humidity environment of a toner to be obtained, and a toner for electrostatic charge image development comprising the binder resin composition.SOLUTION: The binder resin composition for a toner comprises: an amorphous polyester H; an amorphous composite resin L having a polyester resin moiety and a vinyl resin moiety; and a crystalline polyester C. The polyester H has a softening point of 120 to 170°C; the composite resin L has a softening point of 80 to 110°C; and a mass ratio (polyester resin moiety/vinyl resin moiety) of the polyester resin moiety to the vinyl resin moiety of the composite resin L ranges from 50/50 to 95/5. The toner for electrostatic charge image development comprises the above binder resin composition for a toner.

Description

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

  In the field of electrophotography, with the development of an electrophotographic system, development of toner for electrophotography corresponding to higher image quality and higher speed is required.

  In order to improve image quality and speed, in particular to improve thermal properties, polyester resins that are easy to adjust in composition are widely used as binder resins for toner, and multiple resin components are combined. Attempts have been made to use a mixture of a plurality of resins.

  For example, in Patent Document 1, for the purpose of improving low-temperature fixability, high-temperature offset resistance, and developability, a toner having toner particles containing a binder resin, a wax, and a colorant includes two types of binder resins. The resin A contains the above resin A and resin B, and the resin A is obtained by addition polymerization of a vinyl monomer in the presence of a condensation polymerization monomer, and after completion of the addition polymerization reaction, the condensation polymerization monomer is condensed. Or a resin obtained by condensation polymerization of a condensation polymerization monomer in the presence of a vinyl resin obtained by addition polymerization of a vinyl monomer. The resin B is a resin obtained by condensation of a condensation polymerization monomer. It is a resin obtained by addition polymerization by adding a vinyl monomer to a condensation polymerization resin obtained by polymerization, and the softening point of the resin A is 5 ° C. higher than the softening point of the resin B. There is disclosed a toner characterized in that the resin A and the resin B are contained in a mass ratio of 10:90 to 60:40.

  Patent Document 2 discloses a toner having toner particles containing a binder resin, a colorant, and a crystalline polyester for the purpose of improving fixability, high-temperature offset resistance, and blocking resistance. 3 to 50% by mass of a resin-insoluble tetrahydrofuran-insoluble component, the tetrahydrofuran-insoluble component containing a hybrid resin, hydrolyzing the tetrahydrofuran-insoluble component, and then filtered and filtered. The component has a main peak in the molecular weight range of 10,000 to 100,000 in the molecular weight distribution measured by GPC, and the crystalline polyester has a DSC curve measured by a differential scanning calorimeter (DSC) of 50 ° C. or more and 130 A toner characterized by having a maximum endothermic peak at or below ° C is disclosed.

  Patent Document 3 discloses an alcohol component containing an aliphatic diol having 2 to 10 carbon atoms and a carboxylic acid containing an aromatic dicarboxylic acid for the purpose of improving low-temperature fixability, image glossiness, and filming resistance. A crystalline resin for toner comprising a composite resin containing a condensation polymerization resin component and a styrene resin component obtained by condensation polymerization of components is disclosed.

Patent Document 4 discloses a toner having toner particles containing a binder resin and a colorant for the purpose of improving high gloss and uniformity of gloss and preventing end offset, and the binder resin is DSC. It contains a resin having an endothermic peak at a temperature of 55 ° C. or more and 120 ° C. or less in a curve, and the toner has a softening point Tm of 90 ° C. or more and 140 ° C. or less, and viscoelastic properties measured at a frequency of the toner of 6.28 rad / sec. In a chart where the storage elastic modulus at a temperature of 180 ° C. is 1.0 × 10 ² Pa or more and 1.0 × 10 ⁴ Pa or less, the temperature is the x axis, and tan δ is the y axis, the peak top is in the range of tan δ from 50 ° C. to 70 ° C. And the ratio of tan δ (P) at the peak top temperature to tan δ (Tm) at the Tm temperature (tan δ (P) / tanδ (Tm)) is in the range of 2.5 to 8.0 Donors have been disclosed.

JP 2008-102396 A JP 2008-102390 A JP 2010-139659 A JP 2012-150464 A

  In electrophotography, development of a toner having excellent low-temperature fixability is required. In particular, in a high-speed machine that performs high-speed printing, since the amount of energy conducted to the toner is small with respect to the temperature of the fixing machine, further improvement in low-temperature fixability is required. In order to improve the low-temperature fixability, a method of adjusting the melting behavior by adding crystalline polyester or the like to the toner is used. However, the toner that is easily melted is inferior in durability and storage stability. Polyester resin is suitable as a binder resin for toner because of its ease of structure control, but has a problem that storage stability is further deteriorated in a high humidity environment. Accordingly, there is a need for a toner that achieves both low-temperature fixability and storage stability and durability under high humidity.

  The present invention relates to a binder resin composition for toner that can achieve both low-temperature fixability of the obtained toner, storage stability and durability under high humidity, and toner for developing an electrostatic image containing the binder resin composition. About.

  The present inventors have considered that the factors affecting the low-temperature fixability and storage stability of the toner are due to the state of the resin in the binder resin contained in the toner. As a result, an amorphous polyester having a specific softening point, a composite resin having a specific softening point and structure, and a resin composition containing a crystalline polyester have excellent low-temperature fixability and high humidity in the resulting toner. The present inventors have found that the storage stability and durability are expressed in the present invention, and have completed the present invention.

The present invention
[1] A binder resin composition for toner, comprising amorphous polyester H, amorphous composite resin L having a polyester resin portion and a vinyl resin portion, and crystalline polyester C, The softening point of the composite resin L is 80 to 110 ° C., and the mass ratio of the polyester resin portion to the vinyl resin portion of the composite resin L (polyester resin portion / vinyl resin portion) A binder resin composition for toner, wherein the binder resin composition is 50/50 to 95/5,
[2] A toner for developing an electrostatic image containing the binder resin composition for toner according to [1], and [3] a non-crystalline polyester H, a non-polyester having a polyester resin portion and a vinyl resin portion. An electrostatic charge image developing toner containing a crystalline composite resin L and a crystalline polyester C, wherein the softening point of polyester H is 120 to 170 ° C. and the softening point of composite resin L is 80 to 110 ° C. In addition, the present invention relates to an electrostatic charge image developing toner in which the mass ratio of the polyester resin portion to the vinyl resin portion (polyester resin portion / vinyl resin portion) of the composite resin L is 50/50 to 95/5.

  The binder resin composition for toner according to the present invention has an excellent effect that the low-temperature fixability of the obtained toner can be compatible with storage stability and durability under high humidity.

  Binder resin composition for toner of the present invention is a binder resin for toner containing amorphous polyester H, amorphous composite resin L having a polyester resin portion and a vinyl resin portion, and crystalline polyester C. The composition has a softening point of polyester H of 120 to 170 ° C., a softening point of composite resin L of 80 to 110 ° C., and a mass ratio of the polyester resin portion to the vinyl resin portion of the composite resin L (polyester) (Resin portion / vinyl resin portion) is 50/50 to 95/5.

  The reason why the toner containing the binder resin composition of the present invention can achieve both low-temperature fixability, storage stability under high humidity, and durability is not clear, but is considered as follows.

  The binder resin composition of the present invention includes an amorphous polyester H having a high softening point, an amorphous composite resin L having a low softening point having a polyester resin portion and a vinyl resin portion in a specific ratio, and crystallinity. Polyester C is included. Since amorphous polyester H has a high softening point, it has high elasticity and is considered to be able to impart durability and storage stability to the resulting toner. Furthermore, since the viscosity of the crystalline polyester C rapidly decreases at the melting point, the low temperature fixability is improved. However, since these polyesters have an ester bond, the storage stability in a high humidity environment tends to be lowered.

  In addition to these polyesters, the resin composition of the present invention contains a low softening point amorphous composite resin L having a polyester resin portion and a vinyl resin portion in a specific ratio. The composite resin L has a polyester resin portion, so it is mixed with the amorphous polyester H and the crystalline polyester C appropriately, but has a hydrophobic vinyl resin portion and does not deteriorate the storage stability even under high humidity. it is conceivable that. In this way, by using a resin with a hydrophobic vinyl resin portion as the low softening point that affects storage stability, durability and low-temperature fixability are improved, and storage stability under high humidity is also achieved. Can be improved.

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

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

  The alcohol component of the amorphous polyester H preferably contains an aromatic diol from the viewpoints of toner chargeability, storage stability under high humidity, and durability.

  As the aromatic diol, the formula (I):

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

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

  The molar ratio of ethylene oxide adduct of bisphenol A and propylene oxide adduct of bisphenol A contained in the alcohol component of amorphous polyester H (ethylene oxide adduct / propylene oxide adduct) From the viewpoint of storage stability under humidity, 0/100 to 70/30 is preferable, 3/97 to 65/35 is more preferable, 5/95 to 60/40 is further preferable, and 10/90 to 50/50 is More preferred is 20/80 to 40/60.

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

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

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

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

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

  Examples of the carboxylic acid component other than the aromatic dicarboxylic acid compound include an aliphatic dicarboxylic acid compound, an alicyclic dicarboxylic acid compound, and a trivalent or higher polyvalent carboxylic acid compound. In the present specification, the carboxylic acid compound includes not only a free acid but also an anhydride that decomposes during the reaction to generate an acid, and an alkyl ester having 1 to 3 carbon atoms.

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

  The carboxylic acid component of the amorphous polyester H preferably contains a trivalent or higher polyvalent carboxylic acid compound. Examples of the trivalent or higher polyvalent carboxylic acid compounds include 1,2,4-benzenetricarboxylic acid (trimellitic acid), 2,5,7-naphthalenetricarboxylic acid, pyromellitic acid, anhydrides of these acids, and the like. An alkyl (1 to 3 carbon atoms) ester of the above acid can be used, and among these, trimellitic anhydride is preferable from the viewpoint of hot offset resistance and durability of the toner.

  From the viewpoint of hot offset resistance and durability of the toner, the content of the trivalent or higher polyvalent carboxylic acid compound in the carboxylic acid component of the amorphous polyester H is preferably 3 mol or more with respect to 100 mol of the alcohol component. 5 moles or more is more preferable, and 20 moles or more is more preferable. Further, from the viewpoint of storage stability of the toner under high humidity, it is preferably 40 mol or less, and more preferably 30 mol or less.

  From the viewpoint of molecular weight control, the alcohol component may contain a monovalent alcohol, and the carboxylic acid component may contain a monovalent carboxylic acid compound as appropriate.

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

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

  Examples of esterification catalysts include tin catalysts and titanium catalysts. Examples of tin catalysts include dibutyltin oxide and tin (II) 2-ethylhexanoate. At least one selected from the group consisting of polyester H, polyester M, and polyester L is reactive and molecular weight adjusted. From the viewpoint of adjusting the physical properties of the resin, it is preferably obtained by polycondensation using a tin (II) compound having no Sn—C bond as a catalyst.

  As the tin (II) compound having no Sn-C bond, a tin (II) compound having no Sn-C bond and having a Sn-O bond, Sn-X (X represents a halogen atom) ) A tin (II) compound having a bond is preferable, and a tin (II) compound having a Sn-O bond is more preferable.

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

  Examples of the titanium catalyst include titanium diisopropylate bistriethanolamate.

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

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

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

  The softening point of the amorphous polyester H is 120 ° C. or higher, and preferably 125 ° C. or higher, from the viewpoints of storage stability under high humidity and grindability. Also, from the viewpoint of low-temperature fixability, 170 ° C. or lower is preferable, 160 ° C. or lower is more preferable, and 140 ° C. or lower is further preferable. When the amorphous polyester is composed of two or more kinds of polyesters, the weighted average value thereof is preferably within the above range.

  The glass transition temperature of the amorphous polyester H is preferably 55 ° C. or higher, and more preferably 60 ° C. or higher, from the viewpoint of storage stability under high humidity. Further, from the viewpoint of low-temperature fixability, 75 ° C. or lower is preferable, and 70 ° C. or lower is more preferable.

  The acid value of the amorphous polyester H is preferably 15 mgKOH / g or more, more preferably 20 mgKOH / g or more, from the viewpoint of the chargeability of the toner. Further, from the viewpoint of hygroscopicity of the toner, it is preferably 40 mgKOH / g or less, and more preferably 30 mgKOH / g or less.

  The composite resin L is obtained by performing a polycondensation reaction and an addition polymerization reaction using a raw material monomer for a polyester resin portion and a raw material monomer for a vinyl resin portion.

  As a raw material monomer for the polyester resin portion, an alcohol component and a carboxylic acid component are used.

  The alcohol component of the polyester resin portion preferably contains an aromatic diol from the viewpoints of toner chargeability, durability, and storage stability under high humidity.

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

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

  Examples of alcohols other than aromatic diols include 1,2-propylene glycol, 1,4-butanediol, neopentyl glycol, polyethylene glycol, polypropylene glycol, hydrogenated bisphenol A, and the like; sorbitol, pentaerythritol, glycerin, trimethylol Examples thereof include trihydric or higher polyhydric alcohols such as propane.

  On the other hand, in the carboxylic acid component, divalent carboxylic acid compounds include aromatic dicarboxylic acids such as phthalic acid, isophthalic acid and terephthalic acid; oxalic acid, malonic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutacone An aliphatic dicarboxylic acid such as succinic acid substituted with an alkyl group having 1 to 20 carbon atoms or an alkenyl group having 2 to 20 carbon atoms such as acid, succinic acid, adipic acid, dodecenyl succinic acid, octyl succinic acid; Examples include anhydrides and alkyl (C1-3) esters of these acids. Of these, aromatic dicarboxylic acid compounds are preferred from the viewpoint of chargeability, terephthalic acid and isophthalic acid are more preferred, and terephthalic acid is even more preferred.

  The content of the aromatic dicarboxylic acid compound is preferably 30 mol% or more, more preferably 50 mol% or more, and 60 mol% from the viewpoint of storage stability, particularly long-term storage stability under high temperature and high humidity, in the carboxylic acid component. The above is more preferable. Further, from the viewpoint of low-temperature fixability, it is preferably 95 mol% or less, more preferably 90 mol% or less.

  Examples of the trivalent or higher polyvalent carboxylic acid compound include 1,2,4-benzenetricarboxylic acid (trimellitic acid), 2,5,7-naphthalenetricarboxylic acid, pyromellitic acid and acid anhydrides thereof, lower alkyl (C1-C3) ester etc. are mentioned.

  The content of the trivalent or higher polyvalent carboxylic acid compound is preferably 5 mol% or more, more preferably 8 mol% or more in the carboxylic acid component from the viewpoint of storage stability, durability and grindability of the toner under high humidity. More preferred. Moreover, 20 mol% or less is preferable.

  From the viewpoint of molecular weight control, the alcohol component may contain a monovalent alcohol, and the carboxylic acid component may contain a monovalent carboxylic acid compound as appropriate.

  The temperature during the polycondensation reaction is preferably 200 ° C. or higher, more preferably 225 ° C. or higher, from the viewpoint of reactivity. Further, from the viewpoint of thermal decomposability, 250 ° C. or lower is preferable. The temperature during the polycondensation reaction is preferably 200 to 250 ° C, more preferably 225 to 250 ° C.

  The polycondensation reaction may be performed in the presence of an esterification catalyst, an esterification cocatalyst, a polymerization inhibitor, or the like, if necessary. Examples of esterification catalysts include tin catalysts and titanium catalysts. Examples of the tin catalyst include dibutyltin oxide and tin (II) 2-ethylhexanoate. From the viewpoints of reactivity, molecular weight adjustment and resin physical property adjustment, Sn such as tin (II) 2-ethylhexanoate is used. Tin (II) compounds having no —C bond are preferred. Examples of the titanium catalyst include titanium diisopropylate bistriethanolamate. The amount of the esterification catalyst used is preferably 0.01 to 1.5 parts by mass, more preferably 0.1 to 1.0 part by mass with respect to 100 parts by mass of the total amount of the alcohol component and the carboxylic acid component. Examples of the esterification promoter include gallic acid. The amount of the esterification cocatalyst used is preferably 0.001 to 0.5 parts by mass, more preferably 0.01 to 0.1 parts by mass with respect to 100 parts by mass of the total amount of the alcohol component and the carboxylic acid component. Examples of the polymerization inhibitor include tert-butylcatechol. The amount of the polymerization inhibitor used is preferably 0.001 to 0.5 parts by mass and more preferably 0.01 to 0.1 parts by mass with respect to 100 parts by mass of the total amount of the alcohol component and the carboxylic acid component.

  The vinyl resin part preferably contains styrene as a structural unit. The content of styrene is preferably 50 to 100% by mass, preferably 75 to 95% by mass, from the viewpoint of low temperature fixability of the toner, storage stability under high humidity, and hot offset resistance in the raw material monomer of the vinyl resin part. Is more preferable.

  Raw material monomers other than styrene include styrene derivatives such as α-methylstyrene; ethylenically unsaturated monoolefins such as ethylene and propylene; diolefins such as butadiene; halovinyls such as vinyl chloride; vinyl acetate and vinyl propionate. Vinyl esters such as (meth) acrylic acid alkyl (C 1-18) esters, esters of ethylenic monocarboxylic acids such as dimethylaminoethyl (meth) acrylate; vinyl ethers such as vinyl methyl ether; vinylidene chloride And vinylidene halides such as N-vinyl compounds such as N-vinylpyrrolidone. Of these, alkyl (carbon number 1 to 18) esters of (meth) acrylic acid are preferred from the viewpoints of low-temperature fixability of the toner, storage stability under high humidity, and hot offset resistance. The content of alkyl (1-18) ester of (meth) acrylic acid is from the viewpoint of low-temperature fixability of toner, storage stability under high humidity and hot offset resistance in the raw material monomer of vinyl resin part. 0 to 30% by mass is preferable, and 5 to 25% by mass is more preferable.

  The temperature during the addition polymerization reaction is preferably 140 ° C. or higher, and more preferably 150 ° C. or higher, from the viewpoints of reactivity and molecular weight adjustment. Further, from the viewpoint of reactivity and molecular weight adjustment, 180 ° C. or lower is preferable, and 170 ° C. or lower is more preferable.

  Moreover, you may perform addition polymerization reaction in presence of a polymerization initiator etc. as needed. Examples of the polymerization initiator include peroxides such as dibutyl peroxide and dicumyl peroxide. The amount of the polymerization initiator used is preferably 4 to 12 parts by mass and more preferably 6 to 10 parts by mass with respect to 100 parts by mass of the raw material monomer of the vinyl resin part.

  The composite resin L is obtained by polymerizing a raw material monomer for a polyester resin portion and a raw material monomer for a vinyl resin portion.

  The composite resin L is, for example, (1) a method of polycondensing a raw material monomer of a polyester resin portion in the presence of a vinyl resin having a carboxy group or a hydroxyl group (a carboxy group or a hydroxyl group is a bireactive monomer or chain transfer described later) (2) It can be obtained by a method of addition polymerization of a raw material monomer of a vinyl resin in the presence of a polyester resin.

  The composite resin L preferably includes a structural portion derived from both reactive monomers. Therefore, in the production of the composite resin L, in addition to the raw material monomer for the polyester resin portion and the raw material monomer for the vinyl resin portion, It is preferable that a reactive monomer is used.

  As the bireactive monomer, (meth) acrylic acid, fumaric acid, maleic acid and the like are preferable, and (meth) acrylic acid is more preferable, and acrylic acid is more preferable.

  The content of both reactive monomers is preferably 1.2 mol or more, more preferably 1.5 mol or more, more preferably 2.0 mol or more, from the viewpoint of storage stability and durability under high humidity, with respect to 100 mol of the alcohol component of the polyester resin portion. Is more preferable, and 2.5 mol or more is more preferable. Further, from the viewpoint of low-temperature fixability, 12.0 mol or less is preferable, 11.0 mol or less is more preferable, 10.0 mol or less is more preferable, 8.0 mol or less is further preferable, and 5.0 mol or less is more preferable. The content of the both reactive monomers is preferably 1.2 to 12.0 mol, more preferably 1.5 to 11.0 mol, further preferably 2.0 to 10.0 mol, and further preferably 2.5 to 8.0 mol with respect to 100 mol of the alcohol component of the polyester resin. 2.5 to 5.0 moles is more preferable.

  Both reactive monomers can react with either the raw material monomer of the polyester resin portion or the raw material monomer of the vinyl resin portion. Therefore, when the raw material monomer for the polyester resin portion and the raw material monomer for the vinyl resin portion are polymerized to obtain the composite resin L, the polycondensation reaction and / or the addition polymerization reaction may be performed in the presence of both reactive monomers. preferable. Thereby, the composite resin L becomes a resin (hybrid resin) in which the polyester resin portion and the vinyl resin portion are bonded via the structural unit derived from the both reactive monomers, and the polyester resin portion and the vinyl resin portion are finer. And uniformly dispersed.

  That is, the composite resin L reacts with any of (a) the raw material monomer for the polyester resin portion, (b) the raw material monomer for the vinyl resin portion, and (c) the raw material monomer for the polyester resin portion and the raw material monomer for the vinyl resin portion. It is preferable that the resin be obtained by polymerizing a bifunctional monomer capable of polymerization.

  Specifically, the hybrid resin obtained using the both reactive monomers is preferably produced by the following method. Both reactive monomers are preferably used in the addition polymerization reaction together with the raw material monomer for the vinyl resin portion from the viewpoint of expressing the effects of the present invention by controlling the addition polymerization reaction and the polycondensation reaction.

(i) A method of performing a step (B) of an addition polymerization reaction with a raw material monomer and an amphoteric monomer of a vinyl resin portion after the step (A) of the polycondensation reaction with the raw material monomer of the polyester resin portion. Step (A) is performed under reaction temperature conditions suitable for the condensation reaction, the reaction temperature is lowered, and step (B) is performed under temperature conditions suitable for the addition polymerization reaction. It is preferable that the raw material monomer and the both reactive monomers of the vinyl resin portion are added to the reaction system at a temperature suitable for the addition polymerization reaction. Both reactive monomers undergo an addition polymerization reaction and also react with the polyester resin portion.
After the step (B), the reaction temperature is raised again, and if necessary, a raw material monomer or the like of a trivalent or higher polyester resin part serving as a crosslinking agent is added to the polymerization system, and the polycondensation reaction in the step (A) The reaction with both reactive monomers can be further advanced.

(ii) A method in which the step (A) of the polycondensation reaction with the raw material monomer of the polyester resin portion is performed after the step (B) of the addition polymerization reaction with the raw material monomer and the amphoteric monomer of the vinyl resin portion. Step (B) is carried out under reaction temperature conditions suitable for the polymerization reaction, the reaction temperature is raised, and the polycondensation reaction of step (A) is carried out under temperature conditions suitable for the polycondensation reaction. Both reactive monomers are involved in the polycondensation reaction as well as the addition polymerization reaction.
The raw material monomer for the polyester resin portion may be present in the reaction system during the addition polymerization reaction, or may be added to the reaction system under temperature conditions suitable for the polycondensation reaction. In the former case, the progress of the polycondensation reaction can be controlled by adding an esterification catalyst at a temperature suitable for the polycondensation reaction.

(iii) A method in which the step (A) of the polycondensation reaction with the raw material monomer in the polyester resin portion and the step (B) of the addition polymerization reaction with the raw material monomer and the both reactive monomers in the vinyl resin portion are performed in parallel. The step (A) and the step (B) are carried out under the reaction temperature conditions suitable for the addition polymerization reaction, the reaction temperature is increased, and the esterification catalyst is optionally produced under the temperature conditions suitable for the polycondensation reaction. It is preferable to add an esterification co-catalyst and a raw material monomer of a trivalent or higher polyester resin portion serving as a cross-linking agent to the polymerization system and further perform the polycondensation reaction in the step (A). At that time, under a temperature condition suitable for the polycondensation reaction, a radical polymerization inhibitor can be added to advance only the polycondensation reaction. Both reactive monomers are involved in the polycondensation reaction as well as the addition polymerization reaction.

  In the method (i), a prepolymerized polycondensation resin may be used in place of the step (A) for performing the polycondensation reaction. In the method (iii), when the step (A) and the step (B) are performed in parallel, the mixture containing the raw material monomer for the vinyl resin part in the mixture containing the raw material monomer for the polyester resin part. It can also be made to react by dripping.

  The methods (i) to (iii) are preferably performed in the same container.

  In the present invention, the method (ii) is preferable from the viewpoint of facilitating the adjustment of the molecular weight, facilitating the control of the physical properties of the resin, and exhibiting the effects of the present invention.

  In the present invention, the mass ratio of the polyester resin portion and the vinyl resin portion (polyester resin portion / vinyl resin portion) is 50/50 to 95/5 from the viewpoint of long-term storage under high temperature and high humidity. 50/50 to 90/10 are preferred, 55/45 to 85/15 are more preferred, and 60/40 to 80/20 are even more preferred. In this mass ratio, the mass of both reactive monomers is not included in either the polyester resin portion or the vinyl resin portion.

  The softening point of the composite resin L is 80 ° C. or higher, and preferably 90 ° C. or higher, from the viewpoint of storage stability, particularly long-term storage stability under high temperature and high humidity. Further, from the viewpoint of low-temperature fixability, it is 110 ° C. or less, preferably 100 ° C. or less.

  The glass transition temperature of the composite resin L is preferably 40 ° C. or higher, and more preferably 45 ° C. or higher, from the viewpoint of storage stability, particularly long-term storage stability under high temperature and high humidity. Further, from the viewpoint of low-temperature fixability, it is preferably 60 ° C. or lower, more preferably 55 ° C. or lower, and further preferably 50 ° C. or lower.

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

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

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

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

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

  Examples of alcohol components other than aliphatic diols having 6 to 12 carbon atoms include α and ω having 2 to 7 carbon atoms such as ethylene glycol, 1,2-propanediol, 1,3-propanediol, and 1,4-butanediol. -Aliphatic diols, aromatic diols such as alkylene oxide adducts of bisphenol A, and trihydric or higher polyhydric alcohols such as glycerin.

  The carboxylic acid component of the crystalline polyester C preferably contains an aliphatic dicarboxylic acid compound having 8 to 12 carbon atoms.

  Examples of aliphatic dicarboxylic acid compounds having 8 to 12 carbon atoms include suberic acid (carbon number: 8), azelaic acid (carbon number: 9), sebacic acid (carbon number: 10), 1,10-decanedicarboxylic acid (carbon Number: 12), succinic acid having an alkyl group or alkenyl group in the side chain, anhydrides of these acids, alkyl esters having 1 to 3 carbon atoms thereof, and the like. In the present invention, the carboxylic acid compound includes not only a free acid but also an anhydride that decomposes during the reaction to produce an acid and an alkyl ester having 1 to 3 carbon atoms. However, the carbon number of the alkyl group in the alkyl ester portion is not included in the carbon number of the chain hydrocarbon group.

  The chain hydrocarbon group in the aliphatic dicarboxylic acid compound may be linear or branched, and the aliphatic dicarboxylic acid compound preferably has 10 or more carbon atoms. Also, from the viewpoint of low-temperature fixability, 11 or less is preferable.

  The carboxylic acid component may contain a carboxylic acid compound other than the aliphatic dicarboxylic acid compound having 8 to 12 carbon atoms, but the content of the aliphatic dicarboxylic acid compound having 8 to 12 carbon atoms is Among these, 70 mol% or more is preferable, 80 mol% or more is more preferable, and 90 mol% or more is more preferable. Further, from the viewpoint of storage stability of the toner at high temperature and high humidity, it is preferably 100 mol% or less, more preferably 98 mol% or less, still more preferably 96 mol% or less, and further preferably 95 mol% or less.

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

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

  The content of the aliphatic monocarboxylic acid compound having 8 to 24 carbon atoms is preferably 5 to 30 mol%, more preferably 10 to 20 mol% in the carboxylic acid component.

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

  By using an aliphatic diol having 6 to 12 carbon atoms or an aliphatic dicarboxylic acid compound having 8 to 12 carbon atoms, or an aliphatic diol having 6 to 12 carbon atoms and an aliphatic dicarboxylic acid compound having 8 to 12 carbon atoms, By making the crystalline polyester C hydrophobic, the compatibility with the low-softening point amorphous composite resin L having a hydrophobic vinyl-based resin portion is improved, and a portion that is easily meltable locally is formed in the toner. Since the low-temperature fixability is remarkably improved and these are hydrophobic, it is considered that the storage stability can be maintained even under high humidity.

  The total content of the aliphatic diol having 6 to 12 carbon atoms and the aliphatic dicarboxylic acid compound having 8 to 12 carbon atoms is preferably from 80 to 100 mol%, more preferably from 85 to 100 mol%, in the raw material monomer, from 87 to 87 98 mol% is more preferable.

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

  The softening point of the crystalline polyester C is preferably 65 ° C. or higher, more preferably 70 ° C. or higher, and further preferably 80 ° C. or higher from the viewpoint of storage stability. Further, from the viewpoint of low-temperature fixability, 100 ° C. or lower is preferable, 95 ° C. or lower is more preferable, and 90 ° C. or lower is further preferable.

  The melting point of the crystalline polyester C is preferably 60 ° C. or higher, more preferably 80 ° C. or higher, from the viewpoint of storage stability. Further, from the viewpoint of low-temperature fixability, 100 ° C. or lower is preferable, and 90 ° C. or lower is more preferable.

  The mass ratio of the amorphous polyester H to the composite resin L (amorphous polyester H / composite resin L) is preferably 90/10 to 40/60 from the viewpoint of toner durability and storage stability under high humidity. 85/15 to 45/55 are more preferred, and 80/20 to 60/40 are even more preferred. Further, from the viewpoint of low-temperature fixability of the toner, the mass ratio of the amorphous polyester H to the composite resin L (amorphous polyester H / composite resin L) is preferably 80/20 to 40/60, preferably 60/40 to 45/55 is more preferable, and 40/60 to 60/40 is more preferable.

  The difference between the ratio (% by mass) of the polyester resin part in the amorphous polyester H and the ratio (% by mass) of the polyester resin part in the composite resin L is due to the hot offset resistance of the toner and the storage stability under high humidity. From the viewpoint, 5% by mass or more is preferable, 7% by mass or more is more preferable, and 10% by mass or more is more preferable. Further, from the viewpoint of low-temperature fixability of the toner, it is preferably 50% by mass or less, more preferably 40% by mass or less, and further preferably 30% by mass or less.

  The total amount of the amorphous polyester H and the composite resin L and the mass ratio of the crystalline polyester C ((amorphous polyester H + composite resin L) / crystalline polyester C) is the low-temperature fixability of the toner under high humidity. From the viewpoints of storage stability and durability, 65/35 to 97/3 is preferable, 70/30 to 95/5 is more preferable, and 80/20 to 96/4 is still more preferable.

  The toner for developing an electrostatic charge image containing the binder resin composition of the present invention can achieve both low temperature fixability, storage stability under high humidity and durability. The binder resin composition of the present invention may be obtained by a process of mixing amorphous polyester H, composite resin L and crystalline polyester C. The resin may be directly used for mixing raw materials.

  In the toner of the present invention, a known resin other than the binder resin composition of the present invention may be used in combination as long as the effects of the present invention are not impaired, but amorphous polyester H, composite resin L, and crystal The total content of the conductive polyester C is preferably 90 to 100% by mass, more preferably 93 to 100% by mass, and still more preferably 95 to 100% by mass in the binder resin.

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

  As the colorant, all of dyes and pigments used as toner colorants can be used, such as carbon black, phthalocyanine blue, permanent brown FG, brilliant first scarlet, pigment green B, rhodamine-B base, Solvent Red 49, Solvent Red 146, Solvent Blue 35, Quinacridone, Carmine 6B, Disazo Yellow and the like can be used, and the toner of the present invention may be either a black toner or a color toner. The content of the colorant is preferably 1 part by mass or more and more preferably 2 parts by mass or more with respect to 100 parts by mass of the binder resin from the viewpoint of improving the toner image density and low-temperature fixability. Moreover, 40 mass parts or less are preferable, and 10 mass parts or less are more preferable.

  As the release agent, low molecular weight polypropylene, low molecular weight polyethylene, low molecular weight polypropylene polyethylene copolymer, aliphatic hydrocarbon wax such as microcrystalline wax, paraffin wax, Fischer-Tropsch wax and oxides thereof, carnauba wax, Examples include ester waxes such as montan wax, sazol wax and their deoxidized wax, fatty acid ester wax, fatty acid amides, fatty acids, higher alcohols, fatty acid metal salts, and the like. It can be used by mixing.

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

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

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

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

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

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

  The toner of the present invention may be a toner obtained by any conventionally known method such as a melt-kneading method, an emulsion phase inversion method, or a polymerization method, but from the viewpoint of productivity and dispersibility of the colorant, A pulverized toner obtained by a melt kneading method is preferred. In the case of pulverized toner by the melt-kneading method, for example, the raw materials such as the binder resin including the amorphous polyester H, the composite resin L, and the crystalline polyester C, the colorant, and the charge control agent are uniformly mixed with a mixer such as a Henschel mixer. After mixing, it can be manufactured by melt-kneading with a closed kneader, a single-screw or twin-screw extruder, an open roll kneader, etc., cooling, pulverizing and classifying.

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

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

  Examples of the hydrophobizing agent for hydrophobizing the surface of silica particles include hexamethyldisilazane (HMDS), dimethyldichlorosilane (DMDS), silicone oil, octyltriethoxysilane (OTES), and methyltriethoxysilane. Of these, hexamethyldisilazane is preferred.

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

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

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

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

  In relation to the above-described embodiment, the present invention further discloses the following binder resin composition for toner and toner for developing an electrostatic image containing the binder resin.

<1> A binder resin composition for toner comprising amorphous polyester H, amorphous composite resin L having a polyester resin portion and a vinyl resin portion, and crystalline polyester C, The softening point of the composite resin L is 80 to 110 ° C., and the mass ratio of the polyester resin portion to the vinyl resin portion of the composite resin L (polyester resin portion / vinyl resin portion) Is a binder resin composition for toners having a toner viscosity of 50/50 to 95/5.

<2> The mass ratio of the total amount of amorphous polyester H and composite resin L to crystalline polyester C ((amorphous polyester H + composite resin L) / crystalline polyester C) is 65/35 to 97/3. The binder resin composition for toner according to <1>.
<3> Said <1> or the difference of the ratio (mass%) of the polyester resin part in the amorphous polyester H and the ratio (mass%) of the polyester resin part in the composite resin L is 5 mass% or more. The binder resin composition for toner according to <2>.
<4> The binder resin composition for toner according to any one of <1> to <3>, wherein the alcohol component as a raw material monomer of the polyester resin portion of the composite resin L contains 40 to 100 mol% of an aromatic diol. .
<5> The toner bond according to <4>, wherein the aromatic diol in the alcohol component that is a raw material monomer of the polyester resin portion of the composite resin L is an alkylene oxide adduct of bisphenol A represented by the formula (I). Resin composition.
<6> The binder resin composition for toner according to any one of <1> to <5>, wherein the alcohol component, which is a raw material monomer of the amorphous polyester H, contains 40 to 100 mol% of an aromatic diol.
<7> The binder resin composition for toner according to <6>, wherein the aromatic diol in the alcohol component which is a raw material monomer of the amorphous polyester H is an alkylene oxide adduct of bisphenol A represented by the formula (I) object.
<8> The toner according to any one of <1> to <7>, wherein a mass ratio of the amorphous polyester H to the composite resin L (amorphous polyester H / composite resin L) is 90/10 to 40/60. Binder resin composition.
<9> The binder resin composition for toner according to any one of <1> to <8>, wherein the carboxylic acid component, which is a raw material monomer of amorphous polyester H, contains 30 to 80 mol% of an aromatic dicarboxylic acid compound. object.
<10> The binder resin composition for toner according to any one of <1> to <9>, wherein the vinyl resin portion of the composite resin L contains 50 to 100% by mass of styrene as a structural unit.
<11> The binder resin composition for toner according to any one of <1> to <10>, wherein the crystalline polyester C is obtained using a raw material monomer containing an aliphatic diol having 6 to 12 carbon atoms.
<12> The binder resin composition for toner according to any one of <1> to <11>, wherein the crystalline polyester C has a melting point of 60 to 100 ° C.
<13> The raw material monomer of the crystalline polyester C contains an aliphatic dicarboxylic acid compound having 8 to 12 carbon atoms, and the total content of the aliphatic diol having 6 to 12 carbon atoms and the aliphatic dicarboxylic acid compound having 8 to 12 carbon atoms. The binder resin composition for toner according to any one of <1> to <12>, wherein the amount is 80 to 100 mol% in the raw material monomer.
<14> The binder resin composition for toner according to any one of <1> to <13>, wherein the composite resin L includes a structural portion derived from (meth) acrylic acid.
<15> The toner according to <14>, wherein the content of (meth) acrylic acid in the raw material monomer is 1.2 to 12.0 moles with respect to 100 moles of the alcohol component that is the raw material monomer of the polyester resin portion of the composite resin L. Binder resin composition.
<16> The alkylene oxide adduct of bisphenol A represented by the formula (I) contained in the alcohol component of the amorphous polyester H is selected from a propylene oxide adduct of bisphenol A and an ethylene oxide adduct of bisphenol A. The binder resin composition for toner according to any one of <7> to <15>, comprising at least one kind.
<17> The molar ratio of the ethylene oxide adduct of bisphenol A and the propylene oxide adduct of bisphenol A contained in the alcohol component of the amorphous polyester H is from 0/100 to The binder resin composition for toner according to <16>, wherein the binder resin composition is 70/30.
<18> The binder resin composition for toner according to any one of <1> to <17>, wherein the carboxylic acid component, which is a raw material monomer of the amorphous polyester H, contains a trivalent or higher polyvalent carboxylic acid compound. .
<19> The above <18, wherein the amount of the trivalent or higher polyvalent carboxylic acid compound contained in the carboxylic acid component which is a raw material monomer of the amorphous polyester H is 3 to 40 mol with respect to 100 mol of the alcohol component. > The binder resin composition for toner described.
<20> For toner according to <18> or <19>, wherein the trivalent or higher polyvalent carboxylic acid compound contained in the carboxylic acid component which is a raw material monomer of amorphous polyester H is trimellitic anhydride. Binder resin composition.
<21> The binder resin composition for toner according to any one of <1> to <20>, wherein the crystalline polyester C has a softening point of 65 to 100 ° C.
<22> An electrostatic charge image developing toner containing the binder resin composition for toner according to any one of <1> to <21>.
<23> An electrostatic charge image developing toner comprising amorphous polyester H, amorphous composite resin L having a polyester resin portion and a vinyl resin portion, and crystalline polyester C, The softening point is 120 to 170 ° C, the softening point of the composite resin L is 80 to 110 ° C, and the mass ratio of the polyester resin portion to the vinyl resin portion of the composite resin L (polyester resin portion / vinyl resin portion) is An electrostatic charge image developing toner having a ratio of 50/50 to 95/5.

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

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

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

(Resin acid value (AV))
Measured according to the method of JIS K0070. However, only the measurement solvent is changed from the mixed solvent of ethanol and ether specified in JIS K0070 to the mixed solvent of acetone and toluene (acetone: toluene = 1: 1 (volume ratio)).

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

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

[Volume-median particle diameter of toner (D ₅₀ )]
Measuring machine: Coulter Multisizer II (Beckman Coulter, Inc.)
Aperture diameter: 50μm
Analysis software: Coulter Multisizer AccuComp version 1.19 (Beckman Coulter)
Electrolyte: Isoton II (Beckman Coulter, Inc.)
Dispersion: Emulgen 109P (manufactured by Kao Corporation, polyoxyethylene lauryl ether, HLB: 13.6) 5% electrolyte dispersion condition: 10 mg of measurement sample is added to 5 ml of dispersion, and dispersed for 1 minute with an ultrasonic disperser. Then, 25 ml of the electrolytic solution is added, and further dispersed with an ultrasonic disperser for 1 minute.
Measurement conditions: Add 100 ml of electrolyte and dispersion in a beaker, measure 30,000 particles at a concentration that can measure the particle size of 30,000 particles in 20 seconds, and determine the volume-median particle size ( determine the D _50).

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

Resin Production Example 2 [Resin a-2, a-3]
Raw material monomers other than adipic acid and trimellitic anhydride shown in Table 1, 40 g of tin (II) 2-ethylhexanoate and 2 g of gallic acid were equipped with a dehydration tube equipped with a nitrogen introduction tube, a stirrer and a thermocouple. The mixture was placed in a 10-liter four-necked flask and subjected to a polycondensation reaction at 230 ° C. for 6 hours in a nitrogen atmosphere. After reacting at 230 ° C. and 8.0 kPa for 1 hour, adipic acid and trimellitic anhydride were further reacted at 210 ° C. and reacted at 10 kPa until the softening point shown in Table 1 to obtain an amorphous polyester. .

Resin Production Example 3 [Resin HB-1]
Raw materials other than fumaric acid and trimellitic anhydride shown in Table 2 were put into a 10-liter four-necked flask equipped with a dehydration tube equipped with a nitrogen introduction tube, a stirrer, and a thermocouple, and 160 ° C under a nitrogen atmosphere. The temperature was raised to. Thereafter, a mixture of the both reactive monomers, the raw material monomer of the vinyl resin, and the polymerization initiator was added dropwise over 1 hour using a dropping funnel. After the dropwise addition, the addition polymerization reaction was aged for 1 hour while maintaining the temperature at 160 ° C., and then the temperature was raised to 200 ° C. After adding 40 g of tin (II) 2-ethylhexanoate and 2 g of gallic acid, The polycondensation reaction was continued for 1 hour at 230 ° C. and 8.0 kPa. After cooling to 180 ° C., 5 g of fumaric acid and a polymerization inhibitor (tert-butylcatechol) were added, the temperature was raised from 180 ° C. to 210 ° C. at 10 ° C./hour, and the reaction was performed at 210 ° C. for 1 hour. The reaction was carried out at 10 ° C. to the softening point shown in Table 2 to obtain an amorphous composite resin.

Resin Production Example 4 [Resin HB-2 and HB-3]
Raw materials other than adipic acid and trimellitic anhydride shown in Table 2 were placed in a 10-liter four-necked flask equipped with a dehydration tube equipped with a nitrogen introduction tube, a stirrer, and a thermocouple, and 160 ° C under a nitrogen atmosphere. The temperature was raised to. Thereafter, a mixture of acrylic acid (both reactive monomers), a raw material monomer of vinyl resin, and a polymerization initiator was added dropwise over 1 hour using a dropping funnel. After the dropwise addition, the addition polymerization reaction was aged for 1 hour while maintaining the temperature at 160 ° C., and then the temperature was raised to 200 ° C. After adding 40 g of tin (II) 2-ethylhexanoate and 2 g of gallic acid, The polycondensation reaction was continued for 1 hour at 230 ° C. and 8.0 kPa. After cooling to 180 ° C, adipic acid and trimellitic anhydride were added, the temperature was raised from 180 ° C to 210 ° C at 10 ° C / hour, reacted at 210 ° C for 1 hour, and at 210 ° C and 10kPa. The amorphous composite resin was obtained by performing the reaction up to the softening point shown in FIG.

Resin Production Example 5 [Resin C-1 to C-5 and C-7]
The raw material monomers shown in Table 3 were placed in a 10 L four-necked flask equipped with a nitrogen inlet tube, dehydration tube, stirrer and thermocouple, held at 140 ° C for 6 hours, and further heated to 200 ° C over 6 hours. Then, 20 g of tin (II) 2-ethylhexanoate and 2 g of gallic acid were added, reacted at 200 ° C. for 1 hour, and then reacted at 8.3 kPa for 1 hour to obtain a crystalline polyester.

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

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

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

Test Example 1 [low temperature fixability]
The obtained toner was mounted on a copying machine “AR-505” (manufactured by Sharp Corporation), and an unfixed image (2 cm × 12 cm) having a toner adhesion amount of 0.7 mg / cm ² was obtained. Using a fixing machine (fixing speed 200mm / sec) that is improved so that the fixing machine of the copier “AR-505” (manufactured by Sharp Corporation) can be fixed off-line, the fixing temperature is increased from 90 ° C to 240 ° C. The fixing test was conducted at each fixing temperature while increasing the temperature in steps of ° C. As the fixing paper, “CopyBond SF-70NA” (manufactured by Sharp Corporation, 75 g / m ² ) was used.

  The minimum fixing temperature is a sand eraser with a bottom of 15 mm x 7.5 mm with a load of 500 g. The image fixed through the fixing machine is rubbed 5 times, and the optical reflection density before and after rubbing is measured by the reflection densitometer “RD-915” (Macbeth The temperature of the fixing roller in which the ratio between the two (after rubbing / before rubbing) first exceeds 70% is defined as the minimum fixing temperature. The lower the minimum fixing temperature, the better the low-temperature fixing property. The results are shown in Table 4.

Test example 2 [storability under high humidity]
10 g of toner was put in a cylindrical container having a radius of 12 mm, and a weight of 100 g was placed on the top, and kept in an environment of 50 ° C. and a relative humidity of 80% for 72 hours. In order from the top, a powder tester (manufactured by Hosokawa Micron Co., Ltd.) is installed with three sieves of sieve A (aperture 250 μm), sieve B (aperture 150 μm), and sieve C (aperture 75 μm). A toner (10 g) was placed on A and vibrated for 60 seconds. The toner mass WA (g) remaining on the sieve A, the toner mass WB (g) remaining on the sieve B, and the toner mass WC (g) remaining on the sieve C are measured and calculated according to the following formulas. The storage stability was evaluated based on the value (α). The closer the value (α) is to 100, the better the storage stability. The results are shown in Table 4.
α = 100- (WA + WB × 0.6 + WC × 0.2) / 10 × 100

Test Example 3 [Durability]
The toner was mounted on a non-magnetic one-component developing device “OKI MICROLINE 5400” (Oki Data Co., Ltd.), and a durability test was conducted at a printing rate of 5% under an environment of a temperature of 32 ° C. and a humidity of 85%. In the middle, a black solid image was printed every 500 sheets, and the presence or absence of streaks on the image was confirmed. Printing was stopped when streaks occurred on the image, and printing was performed up to 9000 sheets. The number of prints until the time when the streaks were visually observed on the image was defined as the number of streaks due to the fusion and fixing of the toner on the developing roll, and the durability was evaluated. The greater the number of printed sheets, the better the durability of the toner. The results are shown in Table 4.

  From the above results, it can be seen that the toners of the examples can achieve both low-temperature fixability, storage stability under high humidity, and durability as compared with the toners of the comparative examples.

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

Claims (12)

  A binder resin composition for toner, comprising amorphous polyester H, amorphous composite resin L having a polyester resin portion and a vinyl resin portion, and crystalline polyester C, wherein softening point of polyester H Is 120 to 170 ° C., the softening point of the composite resin L is 80 to 110 ° C., and the mass ratio of the polyester resin portion to the vinyl resin portion (polyester resin portion / vinyl resin portion) of the composite resin L is 50 / A binder resin composition for toner, which is 50 to 95/5.   The total amount of the amorphous polyester H and the composite resin L and the mass ratio of the crystalline polyester C ((amorphous polyester H + composite resin L) / crystalline polyester C) is 65/35 to 97/3. Item 2. A binder resin composition for toner according to Item 1.   The binder resin composition for toner according to claim 1 or 2, wherein the alcohol component as a raw material monomer of the polyester resin portion of the composite resin L contains 40 to 100 mol% of an aromatic diol.   The binder resin composition for toner according to any one of claims 1 to 3, wherein the alcohol component, which is a raw material monomer of amorphous polyester H, contains 40 to 100 mol% of an aromatic diol.   The binder resin composition for toner according to claim 1, wherein a mass ratio of the amorphous polyester H to the composite resin L (amorphous polyester H / composite resin L) is 90/10 to 40/60. .   The binder resin composition for toner according to any one of claims 1 to 5, wherein the vinyl resin portion of the composite resin L contains 50 to 100% by mass of styrene as a structural unit.   The binder resin composition for toner according to claim 1, wherein the crystalline polyester C is obtained using a raw material monomer containing an aliphatic diol having 6 to 12 carbon atoms.   The raw material monomer of the crystalline polyester C contains an aliphatic dicarboxylic acid compound having 8 to 12 carbon atoms, and the total content of the aliphatic diol having 6 to 12 carbon atoms and the aliphatic dicarboxylic acid compound having 8 to 12 carbon atoms is The binder resin composition for toner according to any one of claims 1 to 7, which is 80 to 100 mol% in the raw material monomer.   The binder resin composition for toner according to claim 1, wherein the composite resin L includes a structural portion derived from (meth) acrylic acid.   10. The binder resin composition for toner according to claim 1, wherein the carboxylic acid component, which is a raw material monomer of the amorphous polyester H, contains a trivalent or higher polyvalent carboxylic acid compound.   A toner for developing an electrostatic charge image, comprising the binder resin composition for toner according to claim 1.   An electrostatic charge image developing toner comprising an amorphous polyester H, an amorphous composite resin L having a polyester resin portion and a vinyl resin portion, and a crystalline polyester C, wherein the softening point of the polyester H is 120 to 170 ° C., the softening point of the composite resin L is 80 to 110 ° C., and the mass ratio of the polyester resin portion to the vinyl resin portion of the composite resin L (polyester resin portion / vinyl resin portion) is 50/50. An electrostatic charge image developing toner of ~ 95/5.