JP2017125923A - Electrophotographic toner - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an electrophotographic toner having excellent low-temperature fixability and heat-resistant storage property and excellently suppressing thinning in an image relating to toner supply under high-temperature and high-humidity conditions.SOLUTION: The electrophotographic toner comprises a binder resin and a colorant. The binder resin comprises an amorphous resin A and a crystalline resin C. The amorphous resin A contains an amorphous polyester AP that is a polycondensate of an alcohol component containing an aliphatic diol and a carboxylic acid component containing a succinic acid derivative, in which the proportion of an amorphous polyester having a number average molecular weight of 4,000 or more included in the amorphous resin A is 60 mass% or more. The crystalline resin C contains a crystalline polyester CP that is a polycondensate of an alcohol component containing an aliphatic diol and a carboxylic acid component containing an aliphatic dicarboxylic acid compound, or a composite resin containing the crystalline polyester CP, in which at least one of the aliphatic diol and the aliphatic dicarboxylic acid compound has carbon atoms of 9 or more and 14 or less.SELECTED DRAWING: None

Description

  The present invention relates to an electrophotographic toner used for developing a latent image formed in an electrophotographic method, an electrostatic recording method, an electrostatic printing method or the like.

  In recent years, there has been a strong demand for improved low-temperature fixability of toner from the viewpoint of energy saving, in addition to heat-resistant storage and reduction of energy consumption in the fixing process, in addition to the promotion of miniaturization, higher speed, and higher image quality of electrophotographic devices. It has been.

  For example, Patent Document 1 discloses a specific viscoelasticity containing a dicarboxylic acid selected from aromatic dicarboxylic acids and ester-forming derivatives thereof, trivalent or higher polycarboxylic acids and 1,2-propylene glycol as constituent components. A toner binder containing a polyester resin and a crystalline resin satisfying the behavior is disclosed.

  In addition, as a raw material monomer for a toner binder resin, a plant-derived short chain fat such as 1,2-propanediol is used in place of an aromatic monomer such as an alkylene oxide adduct of bisphenol A which has been widely used conventionally. Attention has been focused on group-based monomers (see Patent Documents 1 to 3).

JP 2013-228724 A Japanese Patent No. 2015-000906 Japanese Patent No. 2014-201634

  However, the polyester resin described in Patent Document 1 does not contain a monomer substituted with an alkyl group having 8 or more and 20 or less carbon atoms or an alkenyl group having 8 or more and 20 or less carbon atoms as a constituent component. Because of the use of group diols, the hygroscopicity becomes high, and the so-called “supply blur” may occur, which is caused by the deterioration of the fluidity in a high-temperature and high-humidity environment. Absent.

  The present invention relates to an electrophotographic toner excellent in low-temperature fixability, heat-resistant storage stability, and suppression of supply blur in a high-temperature and high-humidity environment.

The present invention is an electrophotographic toner containing a binder resin and a colorant,
The binder resin contains an amorphous resin A and a crystalline resin C;
The amorphous resin A is an succinic acid compound substituted with an alcohol component containing an aliphatic diol having 2 to 4 carbon atoms and an alkyl group having 8 to 20 carbon atoms, and an alkenyl group having 8 to 20 carbon atoms. An amorphous polyester AP which is a polycondensation product with a carboxylic acid component containing one or more succinic acid derivatives selected from succinic acid-based compounds substituted with The ratio of amorphous polyester having a number average molecular weight of 4,000 or more is 60% by mass or more,
The crystalline resin C contains a crystalline polyester CP which is a polycondensate of an alcohol component containing an aliphatic diol and a carboxylic acid component containing an aliphatic dicarboxylic acid compound, or a composite resin containing the crystalline polyester CP In addition, the present invention relates to an electrophotographic toner in which at least one carbon number of the aliphatic diol and the aliphatic dicarboxylic acid compound is 9 or more and 14 or less.

  The electrophotographic toner of the present invention exhibits excellent effects in low-temperature fixability, heat-resistant storage stability, and suppression of supply blurring in a high-temperature and high-humidity environment.

Amorphous polyester obtained by polycondensation of an alcohol component containing an aliphatic diol having 2 to 4 carbon atoms and a carboxylic acid component containing an aromatic dicarboxylic acid compound uses an aromatic diol. As compared with, it has a property that it easily absorbs water due to the high ester group concentration and the presence of low molecular weight. When this amorphous polyester is used in combination with the crystalline polyester, the crystallization of the crystalline polyester is hindered due to the low molecular weight, and the crystalline polyester easily absorbs water in a high-temperature and high-humidity environment. .
Therefore, when a monomer substituted with an alkyl group or an alkenyl group having 8 to 20 carbon atoms is introduced as a constituent component of the amorphous polyester, the amorphous polyester is hydrophobized and hardly absorbs water. , The compatibility with the crystalline polyester is increased, the influence of the low molecular weight is combined and the crystallization is inhibited, the crystalline polyester easily absorbs water under high temperature and high humidity, and the supply blur is deteriorated. Conceivable.
On the other hand, as a result of intensive studies by the present inventors, the constituent component includes a monomer substituted with an alkyl group having 8 to 20 carbon atoms or an alkenyl group having 8 to 20 carbon atoms, thereby reducing the low molecular weight. By combining a high molecular weight amorphous polyester and a crystalline polyester, low-temperature fixability, storage stability, especially storage stability at high temperatures (heat resistance storage stability) and without inhibiting the crystallization of the crystalline polyester The present inventors have found that it is possible to achieve both suppression of supply blur in a high-temperature and high-humidity (HH) environment, and have completed the present invention.

  That is, the electrophotographic toner of the present invention contains a binder resin and a colorant, and the binder resin contains an alcohol component containing an aliphatic diol having 2 to 4 carbon atoms and 8 to 20 carbon atoms. Weight of a carboxylic acid component containing one or two or more succinic acid derivatives selected from a succinic acid compound substituted with an alkyl group and a succinic acid compound substituted with an alkenyl group having 8 to 20 carbon atoms An amorphous resin A containing an amorphous polyester AP as a condensate and having a number average molecular weight of 4,000 or more and an amorphous polyester ratio of 60% by mass or more; an alcohol component containing an aliphatic diol; A crystalline polyester CP obtained by polycondensation with a carboxylic acid component containing an aliphatic dicarboxylic acid compound or a composite resin containing a crystalline polyester CP, and an aliphatic diol and an aliphatic dicarboxylic acid. At least one carboxylic acid compound but those containing a crystalline resin C is several 9 to 14 carbon atoms.

  As described above, the amorphous polyester AP includes an alcohol component containing an aliphatic diol having 2 to 4 carbon atoms and a succinic acid compound substituted with an alkyl group having 8 to 20 carbon atoms, and 8 to 20 carbon atoms. It is a polycondensate with a carboxylic acid component containing a carboxylic acid component containing one or more succinic acid derivatives selected from the following succinic acid-based compounds substituted with an alkenyl group.

  In the alcohol component, the aliphatic diol having 2 to 4 carbon atoms includes ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 2, Examples include 3-butanediol and 1,4-butanediol. In this invention, it is preferable to contain the aliphatic diol which has the hydroxyl group couple | bonded with the secondary carbon atom from a viewpoint of improving heat resistant storage stability. As such aliphatic diol, 1,2-propanediol, 1,2-butanediol, 1,3-butanediol, or 2,3-butanediol is preferable, and among these, 1,2-propanediol is more preferable.

  The content of the aliphatic diol having a hydroxyl group bonded to a secondary carbon atom is preferably 50 mol% or more, more preferably from the viewpoint of improving the heat resistant storage stability in the aliphatic diol having 2 to 4 carbon atoms. It is 60 mol% or more, more preferably 70 mol% or more, more preferably 80 mol% or more.

  In addition to aliphatic diols having a hydroxyl group bonded to a secondary carbon atom, aliphatic diols having 2 to 4 carbon atoms have a hydroxyl group at the end of the carbon chain from the viewpoint of low-temperature fixability. It is desirable to contain an α, ω-aliphatic diol, preferably an α, ω-linear alkanediol.

  The content of α, ω-aliphatic diol, preferably α, ω-linear alkanediol is preferably 10 mol% or more from the viewpoint of low-temperature fixability in aliphatic diols having 2 to 4 carbon atoms. Preferably, it is 20 mol% or more, and from the viewpoint of heat resistant storage stability, it is preferably 50 mol% or less, more preferably 40 mol% or less, still more preferably 30 mol% or less, and even more preferably 20 mol% or less. .

  In addition, among aliphatic diols having 2 to 4 carbon atoms, a molar ratio of an aliphatic diol having a hydroxyl group bonded to a secondary carbon atom and an α, ω-aliphatic diol (a hydroxyl group bonded to a secondary carbon atom). The aliphatic diol / α, ω-aliphatic diol) is preferably 0.1 or more, more preferably 0.5 or more, still more preferably 1 or more, more preferably 2 or more, from the viewpoint of heat-resistant storage stability. From the viewpoint of fixability, it is preferably 10 or less, more preferably 8 or less, further preferably 5 or less, and further preferably 3 or less.

  The content of the aliphatic diol having 2 to 4 carbon atoms is preferably 60 mol% or more, more preferably 80 mol%, in the alcohol component of the amorphous polyester AP, from the viewpoint of low-temperature fixability and heat-resistant storage stability. More preferably, it is 90 mol% or more, more preferably 95 mol% or more, more preferably 100 mol%.

  Examples of the other alcohol components include aromatic diols such as alkylene oxide adducts of bisphenol A, aliphatic diols having 5 or more carbon atoms, and trivalent or higher alcohols such as glycerin.

  Specific examples of the succinic acid compound substituted with an alkyl group having 8 to 20 carbon atoms and the succinic acid compound substituted with an alkenyl group having 8 to 20 carbon atoms include dodecyl succinic acid, dodecenyl succinic acid, tetrapropenyl Examples thereof include succinic acid, decenyl succinic acid, acid anhydrides thereof, and alkyl esters having 1 to 3 carbon atoms. Of these, dodecenyl succinic acid, tetrapropenyl succinic acid, or acid anhydrides thereof are preferable, and dodecenyl succinic acid anhydride is more preferable, from the viewpoint of suppressing supply blur in an HH environment.

  The carbon number of the alkyl group or alkenyl group in the succinic acid-based compound is 8 or more, preferably 10 or more, more preferably 12 or more, and 20 or less, preferably from the viewpoint of suppressing supply blurring in an HH environment. Is 18 or less, more preferably 16 or less.

  Accordingly, as a succinic acid derivative, succinic acid substituted with an alkyl group having 10 or more and 20 or less carbon atoms is used from the viewpoint of suppressing supply blurring in an HH environment and from the viewpoint of improving charging stability and suppressing generation of fog. And at least one or more selected from the group consisting of succinic acid substituted with an alkenyl group having 10 to 20 carbon atoms, preferably succinic acid and carbon substituted with an alkyl group having 12 to 16 carbon atoms More preferred is at least one or two or more selected from the group consisting of succinic acid substituted with an alkenyl group having a number of 12 or more and 16 or less.

  The content of the succinic acid derivative is preferably 3 mol% or more in the carboxylic acid component of the amorphous polyester AP from the viewpoint of suppressing supply blurring in an HH environment and from the viewpoint of low-temperature fixability, and more preferably Is 5 mol% or more, more preferably 10 mol% or more, and from the viewpoint of improving the heat-resistant storage stability of the toner, it is preferably 50 mol% or less, more preferably in the carboxylic acid component of the amorphous polyester AP. It is 40 mol% or less, more preferably 30 mol% or less, and still more preferably 25 mol% or less.

  Examples of the divalent carboxylic acid-based compound other than the succinic acid derivative preferably include a dicarboxylic acid having 3 to 30 carbon atoms, more preferably 3 to 20 carbon atoms, and still more preferably 3 to 10 carbon atoms, and These acid anhydrides, derivatives such as alkyl esters having 1 to 3 carbon atoms, and the like. Specifically, an aromatic dicarboxylic acid compound or an aliphatic dicarboxylic acid compound is preferable, and an aromatic dicarboxylic acid compound is more preferable from the viewpoint of improving the charging stability of the toner and suppressing the occurrence of fog. Examples of the aromatic dicarboxylic acid include phthalic acid, isophthalic acid, terephthalic acid and the like. Among these, terephthalic acid is preferable. Examples of the aliphatic dicarboxylic acid include fumaric acid, maleic acid, succinic acid, glutaric acid, adipic acid, sebacic acid and the like. In the present specification, the carboxylic acid compound includes carboxylic acid, ester of carboxylic acid and alcohol having 1 to 3 carbon atoms, and acid anhydride.

  As the trivalent or higher carboxylic acid compound, for example, preferably a carbon number of 4 or more and 30 or less, more preferably a carbon number of 4 or more and 20 or less, further preferably a carbon number of 4 or more and 10 or less, or a trivalent or higher carboxylic acid, These acid anhydrides, derivatives such as alkyl esters having 1 to 3 carbon atoms, and the like. Specifically, 1,2,4-benzenetricarboxylic acid (trimellitic acid), 2,5,7-naphthalenetricarboxylic acid, 1,2,4,5-benzenetetracarboxylic acid (pyromellitic acid) or their 1,2,4-benzenetricarboxylic acid (trimellitic acid) from the viewpoint of suppressing supply blurring in an HH environment and from the viewpoint of improving charging stability and suppressing fogging Alternatively, an acid anhydride thereof is preferable, and 1,2,4-benzenetricarboxylic acid anhydride (trimellitic anhydride) is more preferable.

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

  The equivalent molar ratio (COOH group / OH group) of the carboxylic acid component and the alcohol component is preferably 0.70 or more and 1.15 or less, more preferably 0.75 or more and 1.10 or less, from the viewpoint of improving the molecular weight while reducing the acid value of the polyester. is there.

  The polycondensation reaction between the alcohol component and the carboxylic acid component is not particularly limited. For example, in an inert gas atmosphere, as necessary, an esterification catalyst, an esterification cocatalyst, a polymerization inhibitor, etc. Can be carried out at a temperature of about 180 ° C to 250 ° C. 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. Examples of the catalyst include gallic acid. 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, more preferably 100 parts by mass of the total amount of the alcohol component and the carboxylic acid component. Preferably it is 1.0 mass part or less. The amount of 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 of the total amount of the alcohol component and the carboxylic acid component. More preferably, it is 0.1 parts by mass or less.

Here, the method for obtaining an amorphous polyester having a number average molecular weight of 4,000 or more is not particularly limited.
(1) Step 1A: a step of polycondensing an alcohol component and a carboxylic acid component until the reaction rate reaches 70% or more and 99% or less; and Step 2A: a sulfo group is further added to the polycondensate obtained in Step 1A. A method comprising a step of adding an organic compound having polycondensation, and
(2) Step 1B: Step of polycondensation using alcohol component and carboxylic acid component in a molar ratio of 1.6 to 2.6 (alcohol component / carboxylic acid component) until the reaction rate exceeds 90%, and Step 2B: Fat The method including the step of removing the group diol is exemplified, but the method (1) is preferable from the viewpoint of improving the production yield of the amorphous polyester.

  The polycondensation of the alcohol component and the carboxylic acid component in the steps 1A and 1B is preferably performed in the presence of an esterification catalyst.

  As the esterification catalyst, a tin catalyst or a titanium catalyst is preferable from the viewpoint of reactivity, and a tin catalyst is more preferable from the viewpoint of promptly reaching the target reaction rate and suppressing coloring.

  Examples of the tin catalyst include dibutyltin oxide and tin (II) 2-ethylhexanoate. From the viewpoints of reactivity, molecular weight adjustment, and resin physical property adjustment, tin (II) having no Sn—C bond is used. ) Compounds are preferred.

  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 ¹ COO) ₂ Sn (wherein R ¹ represents an alkyl group or alkenyl group having 5 to 19 carbon atoms), (R ² O) ₂ Sn (where R ² Is C 6-20 alk Alkoxy tin (II) or tin oxide represented by SnO (II) is preferably represented by a group or an alkenyl group), (R ¹ COO) fatty tin represented by ₂ Sn (II) or tin oxide ( II) is more preferable, tin (II) octoate, tin (II) 2-ethylhexanoate, tin (II) stearate or tin (II) oxide is more preferable, tin (II) 2-ethylhexanoate or oxidation Tin (II) is more preferred.

  As the titanium catalyst, a titanium compound having a Ti-O bond is preferable, and a compound having an alkoxy group having 1 to 28 carbon atoms, an alkenyloxy group having 2 to 28 carbon atoms, or an acyloxy group having 1 to 28 carbon atoms in total. More preferred is titanium diisopropylate bistriethanolamate.

  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, further preferably 0.2 parts by mass or more, with respect to 100 parts by mass of the total amount of the alcohol component and the carboxylic acid component. The amount is preferably 2.0 parts by mass or less, more preferably 1.5 parts by mass or less, and still more preferably 1.0 parts by mass or less.

In Steps 1A and 1B, a compound having a benzene ring in which hydrogen atoms bonded to three adjacent carbon atoms are substituted with a hydroxyl group may be used as an esterification co-catalyst together with the esterification catalyst. Examples thereof include gallic acid and the like.
The amount of the esterification cocatalyst 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 with respect to 100 parts by mass of the total amount of the alcohol component and the carboxylic acid component. Below, more preferably 0.1 parts by mass or less.

  In Steps 1A and 1B, a radical polymerization inhibitor may be used from the viewpoint of preventing side reactions other than polycondensation. As the radical polymerization inhibitor, 4-tert-butylcatechol is preferable.

  In Steps 1A and 1B, the polycondensation is preferably performed in an inert gas atmosphere, and the reaction temperature is preferably 160 ° C. or higher, more preferably 180 ° C. or higher, from the viewpoint of reactivity and thermal decomposability of the monomer. And preferably 250 ° C. or lower, more preferably 240 ° C. or lower.

  In step 1A, polycondensation is performed until a predetermined reaction rate is reached. The reaction rate is preferably 70% or more, more preferably 80% or more, from the viewpoint of improving the low-temperature fixability and heat-resistant storage stability of the resulting toner, and promotes the polymerization in Step 2A, under an HH environment. From the viewpoint of improving the suppression of the supply scum in the above, it is preferably 99% or less, more preferably 90% or less, and still more preferably 85% or less. The reaction rate in the present invention refers to a value of product reaction water amount (mol) / theoretical product water amount (mol) × 100.

  In step 2A, an organic compound having a sulfo group is added to the polycondensate obtained in step 1A (reaction system in step 1A) to perform polycondensation.

  The organic compound having a sulfo group in the present invention is preferably an aromatic compound having a sulfo group or an aliphatic compound having a sulfo group. However, from the viewpoint of dispersibility in a resin, compatibility with a polyester, and charging characteristics, An aromatic compound having a group is more preferable.

  Examples of aromatic compounds having a sulfo group include p-toluenesulfonic acid, isotoluenesulfonic acid, metatoluenesulfonic acid, benzenesulfonic acid, p-xylene-2-sulfonic acid, naphthalene-1-sulfonic acid, and naphthalene-2-sulfone. Acid, aminobenzenesulfonic acid, 2-aminotoluene-5-sulfonic acid, 8-amino-2-naphthalenesulfonic acid, 4-biphenylsulfonic acid, benzene-1,3-sulfonic acid, para-toluenesulfonic acid-2 butynyl, P-Toluenesulfonic acid-3butynyl, p-toluenesulfonic acid-2chloroethyl, p-toluenesulfonic acid cyclohexyl, 2,5-dimethylbenzenesulfonic acid, dodecylbenzenesulfonic acid, ethyl benzenesulfonate, ethyl p-toluenesulfonate, bis- ethylene glycol p-toluenesulfonate, isobutyl p-toluenesulfonate, Methyl sulfonate, 1,3,6-naphthalene trisulfonic acid, 1-naphthol-2-sulfonic acid, salts of these compounds (sodium salt, potassium salt, etc.), hydrates, methyl ester compounds, etc. . Among these, alkylbenzenesulfonic acid in which an alkyl group is substituted on the benzene ring is preferable from the viewpoint of improving the reactivity of the polyester monomer and improving the low-temperature fixability, heat-resistant storage stability, and durability of the resulting toner. The number of carbon atoms of the alkyl group substituted on the benzene ring is preferably 1 or more from the viewpoint of improving the reactivity of the polyester monomer and improving the low-temperature fixability of the resulting toner and suppression of supply blurring in an HH environment. And preferably 22 or less, more preferably 14 or less, and still more preferably 6 or less.

  Examples of the aliphatic compound having a sulfo group include ethanesulfonic acid, 1,2-ethanedisulfonic acid, hydroxyamine-O-sulfonic acid, methanesulfonic acid, ethyl methanesulfonate, trifluoromethanesulfonic acid, 1-butanesulfonic acid, 1-decanesulfonic acid, 1-heptanesulfonic acid, 1-hexanesulfonic acid, 3-hydroxypropanesulfonic acid, 1-nonanesulfonic acid, 1-octanesulfonic acid, 1-pentanesulfonic acid, 1,3-propanedisulfonic acid 1-dodecanesulfonic acid, 1-hexadecanesulfonic acid, 1-propanesulfonic acid, vinylsulfonic acid and its salts, hydrates, and the like.

  The use amount of the organic compound having a sulfo group is 100 parts by mass of the total amount of the alcohol component and the carboxylic acid component used in Step 1A from the viewpoint of improving the low-temperature fixability of the toner to be obtained and the suppression of the supply blur in the HH environment. On the other hand, it is preferably 0.01 parts by mass or more, more preferably 0.05 parts by mass or more, and from the viewpoint of improving the heat resistant storage stability of the obtained toner, the total amount of alcohol component and carboxylic acid component used in Step 1A is 100 parts by mass. On the other hand, it is preferably 0.5 parts by mass or less, more preferably 0.2 parts by mass or less.

  When using a tin catalyst or a titanium catalyst in step 1A, the mass ratio of the tin catalyst or titanium catalyst and the organic compound having a sulfo group used in step 2A (tin catalyst or titanium catalyst / an organic compound having a sulfo group) is: From the viewpoint of improving the low-temperature fixability of the obtained toner and suppression of supply blurring in an HH environment, it is preferably 1/2 or more, more preferably 1/1 or more, and preferably 50/1 or less, more Preferably it is 20/1 or less.

  Also in step 2A, the polycondensation is preferably performed in an inert gas atmosphere. From the viewpoint of reactivity and thermal decomposition of the monomer, the reaction temperature is preferably 160 ° C. or higher from the viewpoint of reactivity. The temperature is preferably 200 ° C. or higher, and preferably 240 ° C. or lower, more preferably 230 ° C. or lower, from the viewpoint of the thermal decomposability of the polyester produced in Step 1A.

  Further, the amorphous polyester may be modified to such an extent that the characteristics are not substantially impaired. For example, the modified polyester may be grafted or blocked with phenol, urethane, epoxy or the like by the method described in JP-A-11-133668, JP-A-10-239903, JP-A-8-20636, etc. Polyester.

  The number average molecular weight of the amorphous polyester AP is preferably 4,000 or more, more preferably 4,500 or more, and preferably 10,000 or less, more preferably, from the viewpoint of suppressing low temperature fixability and supply blurring in an HH environment. Is less than 7,000. The number average molecular weight in the case of containing two or more kinds of amorphous polyesters is a value obtained by weighted average.

  The low molecular weight fraction of the amorphous polyester AP in the tetrahydrofuran (THF) soluble component is preferably 6.0% by mass or less, more preferably 5.0% by mass or less, from the viewpoint of suppressing supply blurring in an HH environment. . The low molecular weight fraction is preferably 1.0% by mass or more, more preferably 2.0% by mass or more from the viewpoint of improving the low-temperature fixability.

  The softening point of the amorphous polyester AP is preferably 90 ° C. or more, more preferably 100 ° C. or more from the viewpoint of heat-resistant storage stability, and preferably 160 ° C. or less, more preferably from the viewpoint of low-temperature fixability. 150 ° C. or lower, more preferably 145 ° C. or lower.

  The glass transition temperature of the amorphous polyester AP is preferably 45 ° C. or more, more preferably 50 ° C. or more from the viewpoint of heat-resistant storage stability, and preferably 85 ° C. or less, more preferably from the viewpoint of low-temperature fixability. Is 80 ° C. or lower, more preferably 75 ° C. or lower.

  From the viewpoint of improving productivity, the acid value of the amorphous polyester AP is preferably 1 mgKOH / g or more, more preferably 3 mgKOH / g or more, and further preferably 5 mgKOH / g or more. Therefore, it is preferably 30 mgKOH / g or less, more preferably 25 mgKOH / g or less, further preferably 20 mgKOH / g or less, and further preferably 10 mgKOH / g or less.

  The content of the amorphous polyester AP in the amorphous resin A is preferably 60% by mass or more, more preferably 80% by mass or more, further preferably 90% by mass or more, further preferably 95% by mass or more, and further preferably. Is 100% by mass.

  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 is a resin having a crystallinity index of 0.6 or more and 1.4 or less, preferably 0.7 or more and 1.2 or less, more preferably 0.9 or more and 1.2 or less, and further preferably 0.9 or more and 1.1 or less. Resins having an index greater than 1.4, less than 0.6, preferably greater than 1.5, 0.5 or less, more preferably 1.6 or more, or 0.5 or less. 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. In the crystalline resin, the highest endothermic peak temperature is the melting point.

  In the present invention, the amorphous resin A contains the amorphous polyester AP, and from the viewpoint of improving the suppression of supply blurring in an HH environment, the ratio of the amorphous polyester having a number average molecular weight of 4,000 or more Is 60% by mass or more. The ratio of the amorphous polyester having a number average molecular weight of 4,000 or more contained in the amorphous resin A is preferably 80% by mass or more, more preferably 90% by mass or more, further preferably 95% by mass or more, and further preferably 100%. % By mass. Therefore, the number average molecular weight of the amorphous polyester AP is preferably 4,000 or more.

  Furthermore, in the present invention, the amorphous resin A preferably contains two kinds of amorphous polyesters having different softening points from the viewpoint of high temperature offset resistance and low temperature fixability.

  The softening point of the amorphous polyester H having the higher softening point is preferably 110 ° C. or more, more preferably 130 ° C. or more from the viewpoint of high temperature offset resistance, and preferably from the viewpoint of low temperature fixability. 170 ° C. or lower, more preferably 160 ° C. or lower.

  The softening point of the amorphous polyester L having the lower softening point is preferably 80 ° C. or higher, more preferably 95 ° C. or higher from the viewpoint of durability, and preferably 125 ° C. from the viewpoint of low-temperature fixability. Below, it is 115 degrees C or less more preferably.

  The difference in softening point between the amorphous polyester H and the amorphous polyester L is preferably 10 ° C. or higher, more preferably 20 ° C. or higher, from the viewpoint of high temperature offset resistance and low temperature fixability. From the viewpoint, it is preferably 60 ° C. or lower, more preferably 50 ° C. or lower.

  From the viewpoint of durability and productivity, the mass ratio of the amorphous polyester H to the amorphous polyester L (amorphous polyester H / amorphous polyester L) is preferably 20/80 or more, more preferably 40 / From the viewpoint of low-temperature fixability, it is preferably 80/20 or less, more preferably 60/40 or less.

  Either amorphous polyester H or amorphous polyester L (two kinds of amorphous polyesters having different softening points) is preferably amorphous polyester AP, and amorphous polyester H and amorphous polyester L Any of these is more preferably amorphous polyester AP. Moreover, it is preferable that both the amorphous polyester H and the amorphous polyester L are amorphous polyesters having a number average molecular weight of 4,000 or more.

  As the amorphous resin A, a known amorphous resin other than the amorphous polyester, for example, a vinyl resin such as a styrene-acrylic resin, an epoxy resin, a polycarbonate, and a polyurethane, as long as the effects of the present invention are not impaired. The total content of the amorphous polyester is preferably 60% by mass or more, more preferably 70% by mass in the amorphous resin A from the viewpoint of low-temperature fixability. % Or more, more preferably 80% by mass or more.

  Crystalline resin C contains a crystalline polyester CP or a composite resin containing crystalline polyester CP, which is a polycondensate of an alcohol component containing an aliphatic diol and a carboxylic acid component containing an aliphatic dicarboxylic acid compound. In addition, at least one carbon number of the aliphatic diol and the aliphatic dicarboxylic acid compound is 9 or more and 14 or less.

  The alcohol component of the crystalline polyester CP contains an aliphatic diol from the viewpoint of enhancing the crystallinity of the polyester and improving the low-temperature fixability and heat-resistant storage stability of the toner. The carbon number of the aliphatic diol is preferably 4 or more, more preferably 6 or more, and still more preferably 9 or more, from the viewpoint of increasing the crystallinity of the polyester, and improves the low-temperature fixability and heat-resistant storage stability of the toner. From the viewpoint, it is preferably 14 or less, more preferably 12 or less.

  Examples of the aliphatic diol having 4 to 14 carbon atoms include 1,4-butanediol, 1,4-butenediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, and 1,7-heptane. Diol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,12-dodecanediol, 1,14-tetradecanediol, etc., in particular, from the viewpoint of increasing the crystallinity of the polyester, From the viewpoint of improving the low-temperature fixability and heat-resistant storage stability of the toner, α, ω-linear alkanediol is preferable, and 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, 1,9 -Nonanediol, 1,10-decanediol, or 1,12-dodecanediol is more preferable, and 1,9-nonanediol, 1,10-decanediol, or 1,12-dodecanediol is more preferable.

  The content of the aliphatic diol having 4 to 14 carbon atoms is preferably 70 mol% or more, more preferably 90 mol% or more, and still more preferably 95 mol% or more in the alcohol component from the viewpoint of enhancing the crystallinity of the polyester. More preferably, it is 100 mol%. Further, the content of the aliphatic diol having 9 to 14 carbon atoms is preferably 50 mol% or more, more preferably 70 mol%, further preferably 90 mol% or more, further preferably 100 mol% in the alcohol component. is there.

  The alcohol component may contain a polyhydric alcohol component other than an aliphatic diol having 4 to 14 carbon atoms, and an aliphatic diol such as ethylene glycol, 1,2-propanediol, or 1,3-propanediol. Aromatic diols such as bisphenol A alkylene oxide adducts such as bisphenol A ethylene oxide adduct and bisphenol A propylene oxide adducts; 3 such as glycerin, pentaerythritol, trimethylolpropane, sorbitol, 1,4-sorbitan Alcohols having a value higher than that are listed.

  The carboxylic acid component of the crystalline polyester CP contains an aliphatic dicarboxylic acid compound from the viewpoint of enhancing the crystallinity of the polyester and improving the low-temperature fixability and heat-resistant storage stability of the toner.

  In the present invention, the dicarboxylic acid compound refers to dicarboxylic acid, its anhydride, and its alkyl ester having 1 to 3 carbon atoms. Among these, dicarboxylic acid is preferable. Moreover, a preferable carbon number is the carbon number containing the dicarboxylic acid part of a dicarboxylic acid type compound, and does not include the alkyl ester part.

  The number of carbon atoms of the aliphatic dicarboxylic acid compound is preferably 4 or more, more preferably 6 or more, still more preferably 9 or more, from the viewpoint of improving the crystallinity of the polyester, and the viewpoint of improving the low-temperature fixability of the toner Therefore, it is preferably 14 or less, more preferably 12 or less.

  Examples of the aliphatic dicarboxylic acid compounds having 4 to 14 carbon atoms include maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, succinic acid, adipic acid, azelaic acid, sebacic acid, decanedioic acid, dodecanedioic acid From the viewpoint of improving the durability of the toner, at least one selected from the group consisting of fumaric acid, succinic acid, adipic acid, sebacic acid, decanedioic acid, and dodecanedioic acid is included. preferable.

  From the viewpoint of improving the crystallinity of the polyester, the content of the aliphatic dicarboxylic acid compound having 4 to 14 carbon atoms is preferably 70 mol% or more, more preferably 90 mol% or more, and still more preferably from the viewpoint of increasing the crystallinity of the polyester. It is 95 mol% or more, more preferably 100 mol%.

  The carboxylic acid component may contain a polyvalent carboxylic acid compound other than the aliphatic dicarboxylic acid compound having 4 to 14 carbon atoms. Examples of the polyvalent carboxylic acid compound include phthalic acid and isophthalic acid. , Aromatic dicarboxylic acid compounds such as terephthalic acid; oxalic acid, malonic acid, aliphatic dicarboxylic acids such as succinic acid substituted with an alkyl group having 1 to 30 carbon atoms or an alkenyl group having 2 to 30 carbon atoms Alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid; trivalent or higher aromatic carboxylic acids such as trimellitic acid, 2,5,7-naphthalenetricarboxylic acid, pyromellitic acid, and their anhydrides, having 1 or more carbon atoms Examples include 3 or less alkyl esters.

  In addition, a monovalent alcohol may be appropriately contained in the alcohol component, and a monovalent carboxylic acid compound may be appropriately contained in the carboxylic acid component from the viewpoint of adjusting the molecular weight.

  As described above, at least one carbon number of the aliphatic diol and the aliphatic dicarboxylic acid compound is 9 or more and 14 or less. The content of the compound having 9 to 14 carbon atoms is preferably 30 mol% or more, more preferably 40 mol% or more, from the viewpoint of increasing the crystallinity of the polyester in the total amount of the alcohol component and the carboxylic acid component, And preferably it is 80 mol% or less, More preferably, it is 70 mol%, More preferably, it is 60 mol% or less.

  From the viewpoint of adjusting the softening point of the polyester, the equivalent ratio (COOH group / OH group) of the carboxylic acid component and the alcohol component of the crystalline polyester CP is preferably 0.70 or more, more preferably 0.75 or more, and preferably Is 1.10 or less, more preferably 1.00 or less.

  The polycondensation reaction between the carboxylic acid component and the alcohol component may be performed in an inert gas atmosphere at a temperature of 140 ° C. or higher and 250 ° C. or lower as necessary in the presence of an esterification catalyst, a polymerization inhibitor, or the like. preferable. 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. Examples of the catalyst include gallic acid, and examples of the polymerization inhibitor include tert-butylcatechol. 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, more preferably 100 parts by mass of the total amount of the alcohol component and the carboxylic acid component. Preferably it is 1.0 mass part or less. The amount of 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 of the total amount of the alcohol component and the carboxylic acid component. More preferably, it is 0.1 parts by mass or less. 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, more preferably 100 parts by mass of the total amount of the alcohol component and the carboxylic acid component. Preferably it is 0.1 mass part or less.

  The crystalline polyester includes a polyester modified to such an extent that the characteristics are not substantially impaired. Examples of the modified polyester include urethane-modified polyester in which the polyester is modified with a urethane bond, and epoxy-modified polyester in which the polyester is modified with an epoxy bond.

  In the present invention, the crystalline resin C preferably contains a composite resin containing the crystalline polyester CP from the viewpoint of suppressing supply blurring in an HH environment. A composite resin with a styrene resin is more preferable.

  As a raw material monomer for the styrene resin, at least styrene or styrene derivatives such as α-methylstyrene and vinyltoluene (hereinafter, styrene and styrene derivatives are collectively referred to as “styrene compound”) is used.

  The content of the styrene compound is preferably 70% by mass or more, more preferably 90% by mass or more, and still more preferably 95% by mass in the raw material monomer of the styrene resin from the viewpoint of improving the durability and low-temperature fixability of the toner. More preferably, it is 100% by mass.

  Raw material monomers for styrene resins used in addition to styrene compounds include: (meth) acrylic acid alkyl esters; ethylenically unsaturated monoolefins such as ethylene and propylene; diolefins such as butadiene; dimethylamino (meth) acrylate Examples thereof include ethylenic monocarboxylic acid esters such as ethyl; N-vinyl compounds such as N-vinylpyrrolidone.

  The raw material monomer of the styrene resin used in addition to the styrene compound can be used in combination of two or more. In the present specification, “(meth) acrylic acid” means acrylic acid and / or methacrylic acid.

  The addition polymerization reaction of the raw material monomer of the styrene resin can be performed by a conventional method in the presence of a polymerization initiator such as dicumyl peroxide, a crosslinking agent, or the like, in the presence of an organic solvent, or in the absence of a solvent. The temperature condition for the addition polymerization reaction is appropriately selected depending on the reactivity of the raw material monomer and the polymerization initiator, but is preferably 110 ° C or higher, more preferably 140 ° C or higher, and preferably 200 ° C or lower, more preferably 170 ° C. It is below ℃.

  The composite resin includes (a) a raw material monomer for crystalline polyester CP, which includes an alcohol component and a carboxylic acid component, (b) a raw material monomer for styrene resin, and (c) a raw material monomer for crystalline polyester CP and a styrene resin. A resin obtained by polymerizing a bireactive monomer capable of reacting with any of the raw material monomers is preferred.

  As the both reactive monomers, at least one functional group selected from the group consisting of a hydroxyl group, a carboxy group, an epoxy group, a primary amino group and a secondary amino group in the molecule, preferably a hydroxyl group and / or A compound having a carboxy group, more preferably a carboxy group and an ethylenically unsaturated bond is preferred, and it is at least one selected from the group consisting of acrylic acid, methacrylic acid, fumaric acid, maleic acid and maleic anhydride. Is more preferable, but acrylic acid, methacrylic acid or fumaric acid is more preferable from the viewpoint of the reactivity of the polycondensation reaction and the addition polymerization reaction. However, when used together with a polymerization inhibitor, a polyvalent carboxylic acid compound having an ethylenically unsaturated bond such as fumaric acid functions as a raw material monomer for the crystalline polyester CP. In this case, fumaric acid or the like is not a bireactive monomer but a raw material monomer for the crystalline polyester CP.

  The amount of both reactive monomers used increases the dispersibility of the styrene resin and the crystalline polyester CP, and improves the low-temperature fixability and the suppression of supply blurring in an HH environment. Is preferably 1 mol or more, more preferably 2 mol or more, and preferably 30 mol or less, more preferably 25 mol or less, still more preferably 20 mol or less. Also, it is preferably 2 mol or more, more preferably 5 mol or more, and preferably 30 mol or less, more preferably 100 mol with respect to 100 mol of the total amount of raw material monomers of the styrene resin (excluding the polymerization initiator). It is 20 mol or less, more preferably 15 mol or less.

  The composite resin is, for example, a method in which the step (A) of the polycondensation reaction using the raw material monomer of the crystalline polyester CP and the step (B) of the addition polymerization reaction using the raw material monomer and both reactive monomers of the styrenic resin Can be obtained at

  In this method, step (A) and step (B) are performed under reaction temperature conditions suitable for addition polymerization reaction, the reaction temperature is increased, and crosslinking is performed as necessary under temperature conditions suitable for polycondensation reaction. It is preferable to add a raw material monomer of trivalent or higher crystalline polyester CP as an agent to the polymerization system and further perform the polycondensation reaction in 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.

  When performing the step (A) and the step (B) in parallel, the mixture containing the raw material monomer of the crystalline polyester CP may be dropped and reacted with the mixture containing the raw material monomer of the styrenic resin. it can.

  It is preferable to perform said method in the same container.

  In the composite resin, the mass ratio of the crystalline polyester CP to the styrene resin [crystalline polyester CP / styrene resin] (in the present invention, the mass ratio of the raw material monomer of the crystalline polyester CP to the raw material monomer of the styrene resin) ), That is, [total mass of raw material monomers of crystalline polyester CP / total mass of raw material monomers of styrenic resin] is maintained by maintaining the crystallinity of the polyester, thereby suppressing low-temperature fixability and supply blurring in an HH environment. From the viewpoint of improving the ratio, it is preferably 55/45 to 95/5, more preferably 65/35 to 95/5, and still more preferably 70/30 to 95/5. In the above calculation, the amount of both reactive monomers is included in the raw material monomer amount of the crystalline polyester CP. Further, the amount of the polymerization initiator is not included in the raw material monomer amount of the styrenic resin.

  The softening point of the crystalline polyester CP and the composite resin containing the crystalline polyester CP is preferably 60 ° C. or higher, more preferably 70 ° C. or higher, more preferably 80 ° C. or higher, from the viewpoint of improving the heat resistant storage stability of the toner. From the viewpoint of improving the low-temperature fixability of the toner, it is preferably 120 ° C. or lower, more preferably 115 ° C. or lower, and still more preferably 110 ° C. or lower.

  In addition, the softening point of the crystalline resin CP and the composite resin containing the crystalline polyester CP is preferably lower than the softening point of the amorphous resin A from the viewpoint of improving the low-temperature fixability of the toner. Preferably it is 20 degreeC or more and 60 degrees C or less. Here, the difference from the softening point of the amorphous resin A means the difference from the weighted average softening point when the amorphous resin A is made of a plurality of resins.

  The melting point of the composite resin containing the crystalline polyester CP and the crystalline polyester CP is preferably 55 ° C. or higher, more preferably 65 ° C. or higher, more preferably 70 ° C. or higher, from the viewpoint of improving the heat resistant storage stability of the toner. From the viewpoint of improving the low-temperature fixability of the toner, it is preferably 120 ° C. or lower, more preferably 110 ° C. or lower, and still more preferably 100 ° C. or lower.

  The content of the crystalline polyester CP or the composite resin containing the crystalline polyester CP, or when both are used in combination, the total content of the both in the crystalline resin C is preferably 60% by mass or more, more preferably 80%. It is at least 90% by mass, more preferably at least 90% by mass, even more preferably at least 95% by mass, and even more preferably 100% by mass.

  The mass ratio of the amorphous resin A to the crystalline resin C (amorphous resin A / crystalline resin C) is preferably 70/30 or more, more preferably 80/20 or more, from the viewpoint of heat-resistant storage stability. Preferably, it is 90/10 or more, and from the viewpoint of low-temperature fixability, it is preferably 97/3 or less, more preferably 95/5 or less.

  As the colorant, dyes, pigments and the like used as toner colorants can be used. For example, 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, 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, and preferably 40 parts by mass with respect to 100 parts by mass of the binder resin from the viewpoint of improving the image density of the toner. Part or less, more preferably 10 parts by weight or less.

  The toner further contains additives such as release agents, charge control agents, magnetic powder, fluidity improvers, conductivity modifiers, reinforcing fillers such as fibrous substances, antioxidants, and cleanability improvers. It is preferable that a release agent and a charge control agent are contained.

  Release agents include polypropylene wax, polyethylene wax, polypropylene polyethylene copolymer wax, microcrystalline wax, paraffin wax, Fischer-Tropsch wax, sazol wax and other hydrocarbon waxes and their oxides, carnauba wax, and montan wax. And ester waxes such as deoxidized wax and fatty acid ester wax, fatty acid amides, fatty acids, higher alcohols, fatty acid metal salts and the like, and these can be used alone or in admixture of two or more. . From the viewpoint of improving the heat resistant storage stability of the toner, polypropylene wax is preferred.

  The melting point of the release agent is preferably 60 ° C. or higher, more preferably 70 ° C. or higher from the viewpoint of heat resistant storage stability of the toner, and preferably 150 ° C. or lower from the viewpoint of high temperature offset resistance.

  The content of the release agent is preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, and still more preferably 1.5 parts by mass with respect to 100 parts by mass of the binder resin from the viewpoint of low-temperature fixability and offset resistance of the toner. From the viewpoint of toner durability, it is preferably 10 parts by mass or less, more preferably 6 parts by mass or less, and still more preferably 4 parts by mass or less.

  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, for example “Bontron P-51” (manufactured by Orient Chemical Co., Ltd.), cetyltrimethylammonium bromide, “COPY CHARGE PX VP435” (manufactured by Clariant), etc .; polyamine resins such as “AFP-B” (Orient Chemical Co., Ltd.) Imidazole derivatives such as “PLZ-2001”, “PLZ-8001” (manufactured by Shikoku Kasei Kogyo Co., Ltd.), etc .; styrene-acrylic resins such as “FCA-701PT” (Fujikura Kasei Co., Ltd.) ), And the like.

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

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

  The toner for electrophotography may be a toner obtained by any conventionally known method such as a melt-kneading method, an emulsion phase inversion method, or a polymerization method, but from the viewpoint of productivity and dispersibility of the colorant, A pulverized toner obtained by a melt kneading method is preferred. In the case of pulverized toner by the melt-kneading method, for example, a binder resin and a colorant, and if necessary, raw materials such as a release agent and a charge control agent are uniformly mixed with a mixer such as a Henschel mixer, and then a sealed kneader. It can be produced by melt-kneading with a single-screw or twin-screw extruder, an open roll kneader, etc., cooling, pulverizing and classifying. Therefore, as a more preferable production method of the toner of the present invention, an amorphous polyester is produced by the method including the steps 1A and 1B, the obtained amorphous polyester, a binder resin and a colorant, and a necessary Depending on the method, there may be mentioned a method comprising a step of melt-kneading, pulverizing and classifying raw materials such as a release agent and a charge control agent. On the other hand, from the viewpoint of reducing the particle size of the toner, a toner by a polymerization method is preferable.

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

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

  The average particle diameter of the external additive is preferably 10 nm or more, more preferably 15 nm or more, and preferably 250 nm or less, more preferably 200 nm or less, from the viewpoint of toner chargeability, fluidity, and transferability. Preferably it is 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 with respect to 100 parts by mass of the toner before being processed with the external additive, from the viewpoint of chargeability, fluidity and transferability of the toner. Part or more, more preferably 0.3 part by weight or more, and preferably 5 parts by weight or less, more preferably 3 parts by weight or less.

The volume median particle size (D ₅₀ ) of the toner of the present invention is preferably 3 μm or more, more preferably 4 μm or more, and 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 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 in an image forming apparatus of a one-component development system or a two-component development system as a one-component development toner as it is or as a two-component development toner mixed with a carrier.

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. The physical properties of the resin and the like were measured by the following method.

[Softening point of resin]
Using a flow tester “CFT-500D” (manufactured by Shimadzu Corporation), a 1 g sample was heated at a heating rate of 6 ° C./min, and a 1.96 MPa load was applied by a plunger, and the diameter was 1 mm and the length was 1 mm. Extrude from the nozzle. 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 a sample is weighed into an aluminum pan, and the temperature is reduced from room temperature to 10 ° C./min. Cool to 0 ° C and maintain at 0 ° C for 1 minute. Thereafter, the measurement is performed at a heating rate of 10 ° C./min. Among the observed endothermic peaks, the temperature of the peak on the highest temperature side is defined as the highest endothermic peak temperature.

[Glass transition temperature of resin]
Using a differential scanning calorimeter “Q-20” (manufactured by TA Instruments Japan Co., Ltd.), 0.01 to 0.02 g of sample was weighed into an aluminum pan, heated to 200 ° C., and from that temperature Cool to 0 ° C at a temperature drop rate of 10 ° 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 base line extension below the maximum peak temperature of endotherm and the tangent line indicating the maximum slope from the peak rising portion to the peak apex.

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

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

[Low molecular weight fraction in tetrahydrofuran (THF) solubles]
In the molecular weight distribution obtained by molecular weight measurement, the proportion of components having a molecular weight of 500 or less is defined as the low molecular weight fraction.

[Melting point of release agent]
Using a differential scanning calorimeter “DSC Q20” (manufactured by TA Instruments Japan Co., Ltd.), 0.01 to 0.02 g of sample is weighed into an aluminum pan and heated to 200 ° C. at a heating rate of 10 ° C./min. The temperature is raised and the temperature is cooled to -10 ° C at a rate of 5 ° C / min. Next, the sample is heated to 180 ° C. at a heating rate of 10 ° C./min and measured. The maximum peak temperature of the endotherm observed from the melting endotherm curve thus obtained is taken as the melting point of the release agent.

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

[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 (Beckman Coulter, Inc.)
Electrolyte: Isoton II (Beckman Coulter, Inc.)
Dispersion: Emulgen 109P (manufactured by Kao Corporation, polyoxyethylene lauryl ether, HLB (Griffin): 13.6) dissolved in the electrolyte to adjust to 5% by mass Dispersion condition: 10 mL of measurement sample in 5 mL of the dispersion Is added for 1 minute with an ultrasonic disperser (machine name: US-1 manufactured by SND Co., Ltd., output: 80 W), and then 25 mL of the electrolyte is added. For 1 minute to prepare a sample dispersion.
Measurement conditions: The sample dispersion was added to 100 mL of the electrolyte so that the particle size of 30,000 particles could be measured in 20 seconds, and 30,000 particles were measured. Determine the median particle size (D ₅₀ ).

Resin Production Example 1 [Resin A1 to Resin A8]
The raw material monomer and esterification catalyst shown in Table 1 were placed in a 10 L four-necked flask equipped with a thermometer, a stainless steel stirring rod, a flow-down condenser, and a nitrogen inlet tube, and in a mantle heater in a nitrogen atmosphere, 180 The temperature was raised to 210 ° C. and then raised to 210 ° C. over 5 hours. Thereafter, it was confirmed that the reaction rate reached 70% or higher at 210 ° C., and an organic compound having a sulfo group was added. Then, it heated up to 220 degreeC and it reacted until it reached the softening point shown in Table 1 at 8.0 kPa, and amorphous polyester was obtained. The reaction rate is a value of the amount of generated reaction water / theoretical product water × 100. The reaction rate at the time of adding the organic compound having a sulfo group in the production of each resin and the physical properties of the obtained resin are shown in Table 1. Shown in

Resin Production Example 2 [Resin A9]
Raw material monomers and esterification catalyst other than trimellitic anhydride shown in Table 1 were put into a 10 L four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple. The temperature was raised and reacted for 6 hours. After heating to 210 ° C., trimellitic anhydride was added, reacted at normal pressure (101.3 kPa) for 1 hour, and further reacted at 40 kPa until the desired softening point was reached. Obtained. Table 1 shows the physical properties of the obtained resin.

Resin Production Example 3 [Resin A10]
The raw material monomer and esterification catalyst shown in Table 1 were put into a 10 L four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer and a thermocouple, heated to 200 ° C. in a nitrogen atmosphere, and 6 hours. Reacted. The temperature was further raised to 210 ° C., followed by reaction at normal pressure (101.3 kPa) for 1 hour, and further at 40 kPa until a desired softening point was reached to obtain an amorphous polyester. Table 1 shows the physical properties of the obtained resin.

Resin Production Example 4 [Resin C1, Resin C2]
The raw material monomer of the crystalline polyester shown in Table 2 and the esterification catalyst are put into a 10 L four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer and a thermocouple, heated to 160 ° C., and reacted for 6 hours. I let you.
Then, the raw material monomer of styrene-type resin shown in Table 2 and both reactive monomers were dripped over 1 hour with the dropping funnel. After aging the addition polymerization reaction for 1 hour while maintaining at 160 ° C., the raw material monomer of the styrene resin was removed at 8.3 kPa for 1 hour. Further, the temperature was raised to 200 ° C. over 8 hours and reacted at 8.3 kPa for 2 hours to obtain a composite resin. Table 2 shows the physical properties of the obtained resin.

Resin Production Example 5 [Resin C3]
The raw material monomers shown in Table 2 and the esterification catalyst were placed in a 10-liter four-necked flask equipped with a nitrogen introduction tube, dehydration tube, stirrer and thermocouple, and from nitrogen to 130 ° C for 10 hours under a nitrogen atmosphere. The mixture was heated up and reacted at 200 ° C. and 8 kPa for 1 hour to obtain a crystalline polyester. Table 2 shows the physical properties of the obtained resin.

Examples 1-10 and Comparative Examples 1-4
100 parts by mass of a predetermined amount of binder resin shown in Table 3, colorant “REGAL 330R” (manufactured by Cabot Specialty Chemicals, Inc.) 5.0 parts by mass, mold release agent “NP-055” (Mitsui Chemicals, Inc.) Made of polypropylene wax, melting point: 146 ° C.) and 1.0 part by mass of charge control agent “Bontron E-304” (produced by Orient Chemical Co., Ltd.) for 1 minute using a Henschel mixer, Melt kneading was performed under the conditions shown.

A co-rotating twin screw extruder “PCM-30” (manufactured by Ikegai Co., Ltd., shaft diameter 2.9 cm, shaft cross section 7.06 cm ² ) was used. Operating conditions are: barrel set temperature 100 ° C, shaft rotation speed 200r / min (shaft rotation peripheral speed 0.30m / sec), mixture supply speed 10kg / h (mixture supply rate per unit cross section of shaft 1.42kg / h)・ Cm ² ).

  The obtained resin kneaded product is cooled, coarsely pulverized by a pulverizer “ROTOPLEX” (manufactured by Hosokawa Micron Co., Ltd.), and a coarsely pulverized product having a volume-median particle diameter of 2 mm or less using a sieve having an opening of 2 mm. Obtained. The obtained coarsely pulverized product was finely pulverized by using a DS2 airflow classifier (impact plate type, manufactured by Nippon Pneumatic Co., Ltd.) so that the volume median particle size was adjusted to 8.0 μm. The resulting finely pulverized product is classified by adjusting the static pressure (internal pressure) so that the volume median particle size becomes 8.5 μm using a DSX2 type airflow classifier (manufactured by Nippon Pneumatic Co., Ltd.). Toner particles were obtained.

  100 parts by mass of the toner particles obtained, hydrophobic silica “R972” (manufactured by Nippon Aerosil Co., Ltd., hydrophobic treatment agent: DMDS, average particle size: 16 nm) as an external additive, 0.5 parts by mass, and hydrophobic silica “ RY50 "(manufactured by Nippon Aerosil Co., Ltd., hydrophobizing agent: silicone oil, average particle size: 40 nm) 1.0 part by mass using a Henschel mixer (manufactured by Nihon Coke Industries Co., Ltd.) 2100 r / min (circumferential speed 29 m / sec) for 3 minutes to obtain a toner.

Test Example 1 [low temperature fixability]
The printer “OKI MICROLINE 5400” (made by Oki Data Co., Ltd.), modified to take unfixed images, was filled with toner, and a 2cm square solid image unfixed image was printed. Using an external fixing device modified from "OKI MICROLINE 3010" (Oki Data Co., Ltd.), the fixing roll temperature was increased by 5 ° C from 100 ° C to 230 ° C at a fixing roll rotation speed of 180mm / sec. The unfixed image was fixed at each temperature to obtain a fixed image. The image obtained at each fixing temperature is rubbed 5 times with a sand eraser with a 400 g load (manufactured by Lion Corporation, ER-502R). (Gretag Macbeth Co., Ltd.) was used, and the temperature at which the image density ratio before and after rubbing ([image density after rubbing / image density before rubbing] × 100) first exceeded 85% was defined as the minimum fixing temperature. It was used as an index of fixability. The smaller the value, the better the low-temperature fixability. The results are shown in Table 3.

Test Example 2 [Heat resistant storage stability]
5 g of toner was placed in a 20 ml polypropylene container. The container containing the toner was placed in a constant temperature and humidity chamber at 60 ° C. and a relative humidity of 50%, and stored for 3 hours with the polybin lid open. The degree of aggregation of the toner after standing was measured and used as an index of heat resistant storage stability. The smaller this value, the better the heat resistant storage stability. The results are shown in Table 3.

[Degree of aggregation]
The degree of aggregation is measured using a powder tester (manufactured by Hosokawa Micron Corporation).
Overlay sieves with 150, 75, and 45 μm openings, place 5 g of toner on top, and vibrate for 60 seconds with a vibration width of 1 mm. After the vibration, the amount of toner remaining on the sieve is measured, and the degree of aggregation is calculated using the following formula.

Test Example 3 [Supply Suppression Suppression]
A non-magnetic one-component developing device “MicroLine 5400” (trade name, manufactured by Oki Data Co., Ltd.) was loaded with 50 g of toner, and an A4 size black solid image was printed in an environment of 30 ° C. and 85% humidity. Next, after printing 500 sheets at a printing rate of 1%, a black solid image of A4 size was printed again. Note that J paper (trade name, manufactured by Fuji Xerox Co., Ltd.) was used as a printing medium. Using the “Gretag SPM50” (manufactured by Gretag Macbeth), the image density (ID1) of the central part 5cm from the bottom of the initial black solid image and the image density (ID2) of the central part 5cm from the bottom after printing 500 sheets Measurements were made to confirm the difference in image density between the two. When the difference in image density exceeded 0.4, the number of printed sheets was regarded as the evaluation result for suppressing supply scum, and when not exceeding 0.4, printing was performed 500 sheets at a time and evaluated in the same manner. The greater the number of printed sheets, the better the suppression of supply blur. The results are shown in Table 3.

From the above results, it can be seen that the toners of Examples 1 to 10 are good in all of low-temperature fixability, heat-resistant storage stability, and suppression of supply blur.
In contrast, Comparative Example 1 in which no crystalline polyester is used lacks low-temperature fixability.
In Comparative Example 2 using an amorphous polyester that does not use a succinic acid derivative, the heat-resistant storage stability and the suppression of supply blur are insufficient.
In Comparative Examples 3 and 4 in which the amount of amorphous polyester having a number average molecular weight of 4,000 or more is small, the heat resistant storage stability and the suppression of supply scum are insufficient.

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

Claims (7)

An electrophotographic toner containing a binder resin and a colorant,
The binder resin contains an amorphous resin A and a crystalline resin C;
The amorphous resin A is an succinic acid compound substituted with an alcohol component containing an aliphatic diol having 2 to 4 carbon atoms and an alkyl group having 8 to 20 carbon atoms, and an alkenyl group having 8 to 20 carbon atoms. An amorphous polyester AP which is a polycondensation product with a carboxylic acid component containing one or more succinic acid derivatives selected from succinic acid-based compounds substituted with The ratio of amorphous polyester having a number average molecular weight of 4,000 or more is 60% by mass or more,
The crystalline resin C contains a crystalline polyester CP which is a polycondensate of an alcohol component containing an aliphatic diol and a carboxylic acid component containing an aliphatic dicarboxylic acid compound, or a composite resin containing the crystalline polyester CP An electrophotographic toner in which at least one carbon number of the aliphatic diol and the aliphatic dicarboxylic acid compound is 9 or more and 14 or less.   The electrophotographic toner according to claim 1, wherein the amorphous resin A contains two types of amorphous polyesters having different softening points by 10 ° C. or more.   The toner for electrophotography according to claim 2, wherein both of the two kinds of amorphous polyesters are amorphous polyesters having a number average molecular weight of 4,000 or more. Amorphous polyester AP
Step 1A: Step of polycondensing an alcohol component and a carboxylic acid component until the reaction rate reaches 70% or more and 99% or less, and Step 2A: an organic compound further having a sulfo group on the polycondensate obtained in Step 1A The toner for electrophotography according to any one of claims 1 to 3, which is obtained by a method including a step of adding polycondensation and polycondensation.   The electrophotographic toner according to claim 4, wherein the organic compound having a sulfo group is an aromatic compound having a sulfo group or an aliphatic compound having a sulfo group.   The electrophotographic toner according to claim 5, wherein the aromatic compound having a sulfo group is an alkylbenzene sulfonic acid having an alkyl group having 1 to 22 carbon atoms.   The electrophotographic toner according to claim 1, wherein the composite resin containing the crystalline polyester CP is a composite resin of the crystalline polyester CP and a styrene resin.