JP2017116843A - Electrophotographic toner - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an electrophotographic toner having good low temperature fixability and durability.SOLUTION: There is provided an electrophotographic toner which contains an amorphous resin A, an amorphous resin B, a crystalline resin C, wax X, and wax Y, where the amorphous resin A is a resin that has a softening point of 115°C or higher and 150°C or lower and contains a polycondensate-based resin A1 obtained by polycondensation of an alcohol component and a carboxylic acid component in at least a part thereof, the amorphous resin B is a composite resin Bcontaining a polycondensate-based resin B1 obtained by polycondensation of an alcohol component that has a softening point of 80°C or higher and lower than 115°C and contains an aromatic polyol compound and a carboxylic acid component containing an aromatic dicarboxylic acid compound and a styrenic resin component B2, the crystalline resin C is a composite resin Ccontaining a polycondensate-based resin C1 obtained by polycondensation of an alcohol component that contains aliphatic diol having 9 to 14 carbon atoms and a carboxylic acid component containing an aliphatic dicarboxylic acid compound having 9 to 14 carbon atoms and a styrenic resin component C2, the was X is hydrocarbon wax, and the wax Y is carboxylic acid modified hydrocarbon wax having an acid value of 1 mgKOH/g or more and 50 mgKOH/g or less.SELECTED DRAWING: None

Description

  The present invention relates to an electrophotographic toner.

  In recent years, a toner having excellent low-temperature fixability has been demanded from the viewpoint of speeding up printing apparatuses and saving energy. However, if the toner softening point or glass transition temperature is designed to be low in order to improve the low-temperature fixability, there is a problem that the storage stability is lowered. In view of this, development of toner using crystalline polyester has been carried out in order to control the melting state of the toner by including a crystalline resin so as to achieve both low-temperature fixability and storage stability.

  For example, Patent Document 1 discloses a crystalline polyester obtained by using a raw material monomer containing a diol having 8 to 12 carbon atoms and a dicarboxylic acid compound having 10 to 12 carbon atoms and having a total content of 80 mol% or more. A raw material monomer of an amorphous polymerization resin containing a carboxylic acid component containing an alcohol component and an aromatic dicarboxylic acid compound, a raw material monomer of the addition polymerization resin, and 100 parts by weight of the raw material monomer of the addition polymerization resin An amorphous polycondensation resin component obtained by polymerizing a compound capable of reacting with 3 to 15 parts by weight of the raw material monomer of the amorphous polycondensation resin and the raw material monomer of the addition polymerization resin; An electrostatic charge developing toner comprising a binder resin comprising an amorphous hybrid resin containing an addition polymerization resin component is disclosed.

JP2013-109237A

However, a composite resin containing an amorphous polycondensation resin component and an addition polymerization resin component is easier to break than an amorphous resin not containing an addition polymerization resin, and is improved from the viewpoint of toner durability. There was room. In addition, the wax contained in the toner is poorly compatible with the crystalline polyester, and in particular, when an incompatible hydrocarbon wax is used, the dispersibility is further deteriorated, and is improved from the viewpoints of low-temperature fixability and durability. There was room for.
Accordingly, an object of the present invention is to provide an electrophotographic toner having good low-temperature fixability and durability.

That is, the present invention
Containing amorphous resin A, amorphous resin B, crystalline resin C, wax X, and wax Y,
The amorphous resin A is a resin having a softening point of 115 ° C. or more and 150 ° C. or less, and a polycondensation resin A1 obtained by polycondensation of an alcohol component and a carboxylic acid component at least in part.
The amorphous resin B has a softening point of 80 ° C. or higher and lower than 115 ° C., and is obtained by polycondensation of an alcohol component containing an aromatic polyol compound and a carboxylic acid component containing an aromatic dicarboxylic acid compound. A composite resin B _h comprising a polycondensation resin component B1 and a styrene resin component B2,
The crystalline resin C is obtained by polycondensing an alcohol component containing an aliphatic diol having 9 to 14 carbon atoms and a carboxylic acid component containing an aliphatic dicarboxylic acid compound having 9 to 14 carbon atoms. a composite resin C _h containing polycondensation resin component C1 and a styrene resin component C2,
The wax X is a hydrocarbon wax,
The wax Y is an electrophotographic toner which is a carboxylic acid-modified hydrocarbon wax having an acid value of 1 mgKOH / g or more and 50 mgKOH / g or less.

  According to the present invention, it is possible to provide an electrophotographic toner having good low-temperature fixability and durability.

[Electrophotographic toner]
The toner for electrophotography of the present invention contains amorphous resin A, amorphous resin B, crystalline resin C, wax X, and wax Y.
In the electrophotographic toner of the present invention,
The amorphous resin A is a resin having a softening point of 115 ° C. or more and 150 ° C. or less, and a polycondensation resin A1 obtained by polycondensation of an alcohol component and a carboxylic acid component at least in part.
The amorphous resin B has a softening point of 80 ° C. or higher and lower than 115 ° C., and is obtained by polycondensation of an alcohol component containing an aromatic polyol compound and a carboxylic acid component containing an aromatic dicarboxylic acid compound. A composite resin B _h comprising a polycondensation resin component B1 and a styrene resin component B2,
The crystalline resin C is obtained by polycondensing an alcohol component containing an aliphatic diol having 9 to 14 carbon atoms and a carboxylic acid component containing an aliphatic dicarboxylic acid compound having 9 to 14 carbon atoms. a composite resin C _h containing polycondensation resin component C1 and a styrene resin component C2,
The wax X is a hydrocarbon wax,
The wax Y is a carboxylic acid-modified hydrocarbon wax having an acid value of 1 mgKOH / g or more and 50 mgKOH / g or less.
According to the present invention, it is possible to provide an electrophotographic toner having good low-temperature fixability and durability.

The electrophotographic toner of the present invention uses a high softening point amorphous resin A, a low softening point amorphous resin B, a crystalline resin C, a hydrocarbon wax, a carboxylic acid-modified hydrocarbon wax, The crystalline resin C can be finely dispersed, and it is considered that an electrophotographic toner having good low-temperature fixability and durability is obtained.
The reason for such an effect is considered as follows. By making the amorphous resin B a composite resin B _h containing a specific polycondensation resin component and a styrene resin component, the compatibility between the styrene resin component and the crystalline resin C is increased and the dispersibility is good. become. As a result, fixability and storage stability are improved. However, the composite resin _Bh is more easily cracked than the polyester resin, and is less compatible with the wax contained in the toner. Decreases.
In the electrophotographic toner of the present invention, the carboxylic acid modified portion contains the polycondensation resin component of the crystalline resin C and the carboxylic acid modified by containing the carboxylic acid modified hydrocarbon wax Y having an acid value of 1 to 50 mgKOH / g. The hydrocarbon wax Y is easily compatible with the hydrocarbon wax X, and the dispersibility of the hydrocarbon wax X is improved. As a result, it is considered that a toner excellent in fixability and durability can be provided.

In the present invention, the meaning of each term is as follows.
“Crystalline resin” is defined by the ratio of the softening point (° C.) to the maximum endothermic peak temperature (° C.) by a differential scanning calorimeter (DSC), ie, [(softening point) / (maximum endothermic peak temperature)]. A resin having a crystallinity index value of 0.6 or more, preferably 0.8 or more, and less than 1.4, preferably 1.2 or less.
“Amorphous resin” means a resin having a crystallinity index value of 1.4 or more or less than 0.6. The maximum peak temperature of endotherm refers to the temperature of the peak on the highest temperature side among the endothermic peaks observed under the conditions of the measurement methods described in the examples. If the maximum peak temperature is within 20 ° C. from the softening point, the melting point of the crystalline resin is taken, and the peak exceeding 20 ° C. from the softening point is taken as the peak due to the glass transition of the amorphous polyester.
“Binder resin” is a general term for amorphous resin A, amorphous resin B, and crystalline resin C. In terms of content and the like, “to the binder resin” refers to amorphous resin A, The numerical value with respect to the total amount of the amorphous resin B and the crystalline resin C is meant.

<Amorphous resin A>
Amorphous resin A has a softening point of 115 ° C. or higher and 150 ° C. or lower from the viewpoint of low-temperature fixability and durability.
The softening point of the amorphous resin A is preferably 120 ° C. or higher, more preferably 125 ° C. or higher, further preferably 130 ° C. or higher, and preferably 150 ° C. or lower, from the viewpoint of low-temperature fixability and durability. More preferably, it is 145 degrees C or less, More preferably, it is 140 degrees C or less.
The method for measuring the softening point of the present invention is based on the method described in the examples.

The amorphous resin A is preferably a resin containing at least a part of a polycondensation resin A1 obtained by polycondensation of an alcohol component and a carboxylic acid component.
The amorphous resin A, but are not limited to, for example, polyesters, and composite resin A _h and the like having a resin component consisting of polyester.

(Alcohol component)
The alcohol component may be an aromatic polyol compound or an aliphatic polyol compound.
The aromatic polyol compound is preferably an aromatic diol, more preferably an alkylene oxide adduct of bisphenol A, more preferably a formula (I): from the viewpoint of low-temperature fixability and durability.

[Wherein, RO and OR are oxyalkylene groups, R is at least one selected from an ethylene group and a propylene group, and x and y represent the average number of moles of alkylene oxide added, each being a positive number. The value of the sum of x and y is 1 or more, preferably 1.5 or more, and 16 or less, preferably 8 or less, more preferably 4 or less. An alkylene oxide adduct of bisphenol A represented by the formula:

  Examples of the alkylene oxide adduct of bisphenol A represented by the formula (I) include 2,2-bis (4-hydroxyphenyl) propane propylene oxide adduct, 2,2-bis (4-hydroxyphenyl) propane ethylene. And oxide adducts. These can be used alone or in combination of two or more.

  The content of the alkylene oxide adduct of bisphenol A is preferably 70 mol% or more, more preferably 90 mol% or more, still more preferably 95 mol% or more, still more preferably 100 mol% in the alcohol component.

Examples of the aliphatic polyol compound include aliphatic diols having 2 to 20 carbon atoms, and trihydric or higher aliphatic alcohols such as glycerin. Among these, the above aliphatic diols are preferable.
Aliphatic diols include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,4-butenediol 1,3-butanediol, neopentyl glycol, 1,10-decanediol, 1,12-dodecanediol and the like. These can be used alone or in combination of two or more.

  The content of the aliphatic polyol compound is preferably 50 mol% or less, more preferably 30 mol% or less, still more preferably 15 mol% or less, and 0 mol% or more in the alcohol component.

(Carboxylic acid component)
The carboxylic acid component is preferably an aromatic dicarboxylic acid compound from the viewpoint of durability. From the viewpoint of low-temperature fixability, an aliphatic dicarboxylic acid compound is preferable.

  Examples of the aromatic dicarboxylic acid compound include phthalic acid, isophthalic acid, terephthalic acid; anhydrides of these acids or alkyl (C1-3) esters of these acids. These can be used alone or in combination of two or more. In these, a terephthalic acid or isophthalic acid is more preferable, and a terephthalic acid is still more preferable.

  The content of the aromatic dicarboxylic acid compound is preferably 10 mol% or more, more preferably 30 mol% or more, still more preferably 50 mol% or more, and 100 mol% or less in the carboxylic acid component.

  Examples of the aliphatic dicarboxylic acid compound include alkyls 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 or alkyl (C1 to C3) esters of these acids. These can be used alone or in combination of two or more. Of these, fumaric acid is preferred.

  The content of the aliphatic dicarboxylic acid compound is preferably 10 mol% or more, more preferably 20 mol% or more in the carboxylic acid component, and preferably 90 mol% or less, more preferably from the viewpoint of durability. 80 mol% or less.

  The carboxylic acid component preferably contains a trivalent or higher carboxylic acid compound from the viewpoint of productivity.

  Examples of trivalent or higher carboxylic acid compounds include 1,2,4-benzenetricarboxylic acid (trimellitic acid), 2,5,7-naphthalenetricarboxylic acid, pyromellitic acid or acid anhydrides thereof, alkyl (carbon number: 1 -3) Esters, and the like. Among these, trimellitic acid and its anhydride (hereinafter, trimellitic acid and its anhydride are collectively referred to simply as “trimellitic acid and the like”) are preferable.

  The content of the trivalent or higher carboxylic acid compound, preferably the content of trimellitic acid, etc. is preferably 5 mol% or more, more preferably 10 mol% or more, and even more preferably 15 mol% or more in the carboxylic acid component. From the viewpoint of low-temperature fixability, it is preferably 50 mol% or less, more preferably 40 mol% or less, more preferably 35 mol% or less, and still more preferably 30 mol% or less.

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

  The equivalent ratio of the carboxylic acid component and the alcohol component (COOH group / OH group) is preferably 0.7 or more, more preferably 0.8 or more, and preferably 1.3 or less, more preferably from the viewpoint of adjusting the terminal group. 1.2 or less.

  The polycondensation of the alcohol component and the carboxylic acid component should be performed, for example, in an inert gas atmosphere at a temperature of about 180 ° C. to 250 ° C. in the presence of an esterification catalyst, a polymerization inhibitor, etc. Can do. 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 esterification cocatalyst that can be used together with the esterification catalyst include gallic acid and the like. The amount of esterification catalyst used is preferably 0.01 parts by mass or more, more preferably 0.1 parts by mass or more, and preferably 1 part by mass or less, more preferably 100 parts by mass of the total amount of alcohol component and carboxylic acid component. Preferably it is 0.6 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.

[Composite resin A _h ]
The composite resin A _h preferably has a polycondensation resin component A1 and a styrene resin component A2.
A preferable example of the polycondensation resin component A1 is the same as the above-described polycondensation resin A1.

(Styrene resin component A2)
As the styrene-based resin component A2, those obtained by addition polymerization of a raw material monomer containing a styrene compound are preferable.
As the styrene compound, at least styrene or a styrene derivative such as α-methylstyrene or vinyltoluene is used.

  The content of the styrene compound is preferably 50% by mass or more, more preferably 60% by mass or more, still more preferably 70% by mass or more, and further preferably 75% by mass from the viewpoint of durability in the raw material monomer of the styrene resin component. From the viewpoint of low-temperature fixability, it is preferably 95% by mass or less, more preferably 90% by mass or less, and still more preferably 87% by mass or less.

  Raw material monomers for styrene resin components used in addition to styrene compounds include (meth) acrylic acid alkyl esters; ethylenically unsaturated monoolefins such as ethylene and propylene; diolefins such as butadiene; and halovinyls such as vinyl chloride. Vinyl esters such as vinyl acetate and vinyl propionate; ethylenic monocarboxylic acid esters such as dimethylaminoethyl (meth) acrylate; vinyl ethers such as vinyl methyl ether; vinylidene halides such as vinylidene chloride; N-vinyl pyrrolidone; N-vinyl compounds such as

  The raw material monomer of the styrenic resin component used in addition to the styrene compound can be used alone or in combination of two or more. In the present specification, “(meth) acrylic acid” means at least one selected from acrylic acid and methacrylic acid.

  Among the raw material monomers for the styrene resin component used in addition to the styrene compound, (meth) acrylic acid alkyl esters are preferred from the viewpoint of improving the low-temperature fixability of the toner. In view of the above, the carbon number of the alkyl group in the (meth) acrylic acid alkyl ester is preferably 1 or more, more preferably 2 or more, more preferably 3 or more, and preferably 22 or less, more preferably 18 or less. More preferably, it is 12 or less, more preferably 8 or less. In addition, carbon number of this alkyl ester means carbon number derived from the alcohol component which comprises ester.

  Examples of (meth) acrylic acid alkyl esters include methyl (meth) acrylate, ethyl (meth) acrylate, (iso) propyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, (iso or tertiary) butyl (meth) Examples include acrylate, 2-ethylhexyl (meth) acrylate, (iso) octyl (meth) acrylate, (iso) decyl (meth) acrylate, and (iso) stearyl (meth) acrylate. Here, “(iso or tertiary)” and “(iso)” mean that both of these groups are present and not present, and when these groups are not present Indicates normal. Further, “(meth) acrylate” indicates that both acrylate and methacrylate are included.

  The content of the alkyl (meth) acrylate is preferably 5% by mass or more, more preferably 10% by mass or more, and still more preferably 13% by mass in the raw material monomer of the styrene resin component A2 from the viewpoint of low-temperature fixability. From the same viewpoint, it is preferably 50% by mass or less, more preferably 40% by mass or less, still more preferably 30% by mass or less, and further preferably 25% by mass or less.

  A resin obtained by addition polymerization of a raw material monomer containing a styrene compound and a (meth) acrylic acid alkyl ester is also referred to as a styrene- (meth) acrylic resin.

  The addition polymerization reaction of the raw material monomer of the styrene-based resin component A2 can be performed by a conventional method, for example, in the presence of a polymerization initiator such as dicumyl peroxide, a crosslinking agent, or the like, in the presence or absence of an organic solvent. However, the temperature condition is preferably 110 ° C or higher, more preferably 120 ° C or higher, more preferably 130 ° C or higher, and preferably 250 ° C or lower, more preferably 235 ° C or lower, more preferably 220 ° C or lower. It is.

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

(Amotropic monomer)
From the viewpoints of low-temperature fixability and durability, the composite resin A _h is composed of, in addition to the raw material monomer of the polycondensation resin component A1 and the raw material monomer of the styrene resin component A2, further the raw material monomer of the polycondensation resin component A1 and styrene. A composite resin obtained by using both reactive monomers capable of reacting with any of the raw material monomers of the resin component A2 is preferable. Therefore, in obtaining the raw material monomer and styrenic starting monomer is polymerized with the composite resin A _h of the resin component A2 polycondensation resin component A1, the polycondensation reaction and / or addition polymerization reaction, the presence of both the reactive monomer It is preferable to carry out below. Thus, the composite resin A _h is dually reactive monomer derived from the composite resin A _h next configuration through the unit and polycondensation resin component A1 and a styrene resin component A2 is bond, styrene and polycondensation resin component A1 The resin component A2 is more finely and uniformly dispersed.

That is, from the viewpoint of improving the durability and low-temperature fixability of the toner, the composite resin A _h includes (i) an alcohol component containing an alkylene oxide adduct of bisphenol A represented by the formula (I) and an aromatic dicarboxylic acid. A raw material monomer of the polycondensation resin component A1 including a carboxylic acid component containing an acid compound, (ii) a raw material monomer of the styrene resin component A2, and (iii) a raw material monomer of the polycondensation resin component A1 and a styrene system A resin obtained by polymerizing a bireactive monomer capable of reacting with any of the raw material monomers of the resin component A2 is preferable.

  As the both reactive monomers, at least one functional group selected from a hydroxyl group, a carboxy group, an epoxy group, a primary amino group and a secondary amino group in the molecule, preferably at least selected from a hydroxyl group and a carboxy group. A compound having one kind of functional group, more preferably a carboxy group and an ethylenically unsaturated bond is preferred, and by using such a bireactive monomer, the dispersibility of the resin as the dispersed phase can be further improved. it can. The both reactive monomers are preferably at least one selected from acrylic acid, methacrylic acid, fumaric acid, maleic acid and maleic anhydride. From the viewpoint of the reactivity of polycondensation reaction and addition polymerization reaction, acrylic acid is preferred. More preferred is methacrylic acid or fumaric acid. However, when used with a polymerization inhibitor, a polyvalent carboxylic acid having an ethylenically unsaturated bond such as fumaric acid functions as a raw material monomer for the polycondensation resin component. In this case, fumaric acid or the like is not a bireactive monomer but a raw material monomer for a polymerization resin component.

  The amount of both reactive monomers used is preferably 1 mol or more, more preferably 2 mol or more, and still more preferably 3 with respect to a total of 100 mol of the alcohol component of the polycondensation resin component A1 from the viewpoint of low-temperature fixability. From the viewpoint of durability, it is preferably 20 moles or less, more preferably 10 moles or less, and even more preferably 7 moles or less.

The mass ratio of the polycondensation resin component A1 and the styrene resin component A2 (polycondensation resin component A1 / styrene resin component A2) in the composite resin A _h is preferably 60/40 or more from the viewpoint of low-temperature fixability. More preferably 70/30 or more, still more preferably 75/25 or more, and from the viewpoint of durability, it is preferably 95/5 or less, more preferably 90/10 or less, still more preferably 85/15 or less. is there. In the above calculation, the mass of the polycondensation resin component A1 is the amount obtained by subtracting the amount (calculated value) of reaction water dehydrated by the polycondensation reaction from the mass of the raw material monomer of the polycondensation resin component used. The amount of both reactive monomers is included in the amount of raw material monomers of the polycondensation resin component A1. The amount of the styrene resin component A2 is the amount of the raw material monomer of the styrene resin component A2, but the amount of the polymerization initiator is included in the amount of the raw material monomer of the styrene resin component A2.

[Physical properties of amorphous resin A]
The glass transition temperature of the amorphous resin A is preferably 45 ° C. or higher, more preferably 50 ° C. or higher, further preferably 55 ° C. or higher, from the viewpoint of improving durability, and the viewpoint of improving low-temperature fixability. Therefore, it is preferably 80 ° C. or lower, more preferably 75 ° C. or lower, more preferably 70 ° C. or lower, and further preferably 65 ° C. or lower.

  The acid value of the amorphous resin A is preferably 40 mgKOH / g or less, more preferably 30 mgKOH / g or less, still more preferably 20 mgKOH / g or less, and preferably 1 mgKOH / g from the viewpoint of improving low-temperature fixability. g or more, more preferably 2 mgKOH / g or more.

[Content of Amorphous Resin A]
The content of the amorphous resin A is preferably 10% by mass or more, more preferably 20% by mass or more, still more preferably 30% by mass or more, and preferably 80% by mass with respect to the total amount of the binder resin. It is at most 70% by mass, more preferably at most 70% by mass, even more preferably at most 50% by mass.

<Amorphous resin B>
Amorphous resin B has a softening point of 80 ° C. or higher and lower than 115 ° C. from the viewpoint of low-temperature fixability and durability.
The softening point of the amorphous resin B is preferably 90 ° C. or higher, more preferably 95 ° C. or higher, still more preferably 100 ° C. or higher, and preferably 113 ° C. or lower, from the viewpoint of low-temperature fixability and durability. More preferably, it is 110 degrees C or less.
The method for measuring the softening point of the present invention is based on the method described in the examples.

Amorphous resin B is a polycondensation system obtained by polycondensation of an alcohol component containing an aromatic polyol compound and a carboxylic acid component containing an aromatic dicarboxylic acid compound from the viewpoint of low-temperature fixability and durability. a composite resin B _h containing resin component B1 and the styrenic resin component B2.

[Polymerized resin component B1]
As an aromatic polyol compound, the thing similar to the aromatic polyol compound illustrated by the amorphous resin A is mentioned as a suitable example, The content is the same range as the case of the amorphous resin A, too.
As the alcohol component, in addition to the aromatic polyol compound, an aliphatic polyol compound may be contained, and the aliphatic polyol compound is preferably exemplified by the amorphous resin A and the content range.

As an aromatic dicarboxylic acid compound, the thing similar to the aromatic dicarboxylic acid compound illustrated by the amorphous resin A is mentioned as a suitable example, The content is also the same range as the case of the amorphous resin A. .
As the carboxylic acid component, in addition to the aromatic dicarboxylic acid compound, an aliphatic dicarboxylic acid compound, a trivalent or higher carboxylic acid compound, or the like may be contained. The aliphatic dicarboxylic acid compound, the trivalent or higher carboxylic acid compound is Preferred are those exemplified for the amorphous resin A and the content range.

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

  The equivalent ratio of the carboxylic acid component and the alcohol component (COOH group / OH group) is preferably 0.7 or more, more preferably 0.8 or more, and preferably 1.3 or less, more preferably from the viewpoint of adjusting the terminal group. 1.0 or less, more preferably 0.9 or less.

  Suitable conditions for the polycondensation of the alcohol component and the carboxylic acid component are the same as those exemplified for the amorphous resin A.

[Styrene resin component B2]
As the styrene-based resin component B2, those obtained by addition polymerization of a raw material monomer containing a styrene compound are preferable.
Styrene compound and its content, raw material monomer of styrene resin component used in addition to styrene compound and its content, addition polymerization reaction condition of raw material monomer of styrene resin component, both reactive monomers and their use amount, in composite resin Suitable examples of the mass ratio of the polycondensation resin component and the styrene resin component are the same as those exemplified for the amorphous resin A.

[Physical properties of amorphous resin B]
From the viewpoint of improving durability, the glass transition temperature of the amorphous resin B is preferably 45 ° C. or higher, more preferably 50 ° C. or higher, and further preferably 55 ° C. or higher, and the viewpoint of improving low-temperature fixability. Therefore, it is preferably 80 ° C. or lower, more preferably 75 ° C. or lower, more preferably 70 ° C. or lower, and further preferably 65 ° C. or lower.

  From the viewpoint of improving low-temperature fixability, the acid value of the amorphous resin B is preferably 40 mgKOH / g or less, more preferably 30 mgKOH / g or less, still more preferably 20 mgKOH / g or less, and preferably 1 mgKOH / g. g or more, more preferably 2 mgKOH / g or more.

[Content of amorphous resin B]
The content of the amorphous resin B is preferably 10% by mass or more, more preferably 25% by mass or more, still more preferably 40% by mass or more, and preferably 80% by mass or more with respect to the total amount of the binder resin. It is at most 70% by mass, more preferably at most 70% by mass, even more preferably at most 70% by mass.

<Crystalline resin C>
The crystalline resin C is a carboxylic acid containing an alcohol component containing an aliphatic diol having 9 to 14 carbon atoms and an aliphatic dicarboxylic acid compound having 9 to 14 carbon atoms from the viewpoint of low-temperature fixability and durability. it is a resin containing at least a portion of the composite resin C _h containing polycondensation resin component C1 and the styrenic resin component C2 obtained the components by polycondensation.

[Polycondensation resin component C1]
(Alcohol component)
The alcohol component contains an aliphatic diol having 9 to 14 carbon atoms.
Aliphatic diols having 9 to 14 carbon atoms include 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, and 1,12-dodecanediol from the viewpoint of low-temperature fixability and durability. Etc. Among these, at least one selected from 1,10-decanediol and 1,12-dodecanediol is preferable, and 1,12-dodecanediol is more preferable.
The content of the aliphatic diol having 9 to 14 carbon atoms is preferably 70 mol% or more, more preferably 80 mol% or more, and still more preferably 90 mol% in the alcohol component from the viewpoint of low-temperature fixability and durability. Above, still more preferably 95 mol% or more, and preferably 100 mol% or less, more preferably 100 mol%.

The alcohol component may contain other alcohols other than aliphatic diols having 9 to 14 carbon atoms.
Other alcohol components include aliphatic diols other than aliphatic diols having 9 to 14 carbon atoms, aromatic diols, alicyclic diols, trivalent or more polyhydric alcohols, or those having 2 to 4 carbon atoms. Examples include adducts of alkylene oxide (average added mole number of 1 to 16).
Examples of alcohol components other than aliphatic diols having 9 to 14 carbon atoms include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1, 4-butanediol, 1,2-pentanediol, 1,3-pentanediol, 1,4-pentanediol, 1,5-pentanediol, 1,2-hexanediol, 1,3-hexanediol, 1,4 -Hexanediol, 1,5-hexanediol, 1,6-hexanediol, 1,8-octanediol, 1,4-butenediol, neopentyl glycol, 2,3-butanediol, 2,3-pentanediol, Examples include 2,4-pentanediol, 2,3-hexanediol, 3,4-hexanediol, 2,4-hexanediol, 2,5-hexanediol, and the like.

(Carboxylic acid component)
The carboxylic acid component contains an aliphatic dicarboxylic acid compound having 9 to 14 carbon atoms.
Examples of the aliphatic dicarboxylic acid compound having 9 to 14 carbon atoms include azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, an alkyl group having 5 to 10 carbon atoms, or carbon. And succinic acid substituted with an alkenyl group having a number of 5 or more and 10 or less. These can be used alone or in combination of two or more. Among these, at least one selected from sebacic acid and dodecanedioic acid is preferable from the viewpoint of low-temperature fixability and durability, and sebacic acid is more preferable.
In addition, the carbon number of the aliphatic dicarboxylic acid compound includes the carbon number of the carboxy group in the carbon number of the linear or branched hydrocarbon group, and does not include the carbon number of the alkyl ester.

  The content of the aliphatic dicarboxylic acid compound having 9 to 14 carbon atoms in the carboxylic acid component is preferably at least 70 mol%, more preferably at least 80 mol%, still more preferably from the viewpoint of low-temperature fixability and durability. Is 90 mol% or more, more preferably 95 mol% or more, and preferably 100 mol% or less, more preferably 100 mol%.

The carboxylic acid component may contain a carboxylic acid component other than the aliphatic dicarboxylic acid compound having 9 to 14 carbon atoms.
Other carboxylic acid components include dicarboxylic acids other than aliphatic dicarboxylic acid compounds having 9 to 14 carbon atoms, aromatic dicarboxylic acids, alicyclic dicarboxylic acids, trivalent or higher polyvalent carboxylic acids, and anhydrides thereof. And alkyl esters having 1 to 3 carbon atoms thereof.
The carboxylic acid component includes not only a free acid but also an anhydride that decomposes to generate an acid during the reaction, and an alkyl ester having 1 to 3 carbon atoms of each carboxylic acid.
Examples of the aromatic dicarboxylic acid include phthalic acid, isophthalic acid, terephthalic acid and the like.
Examples of the aliphatic dicarboxylic acid compound other than the aliphatic dicarboxylic acid compound having 9 to 14 carbon atoms include malonic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, succinic acid, adipic acid, and suberic acid. , Pentadecanedioic acid, hexadecanedioic acid, succinic acid substituted with an alkyl group having 1 to 4 carbon atoms or an alkenyl group having 2 to 4 carbon atoms, an alkyl group having 11 to 20 carbon atoms, or 11 to 20 carbon atoms Examples include succinic acid substituted with the following alkenyl groups.
Examples of the trivalent or higher polyvalent carboxylic acid include trimellitic acid, 2,5,7-naphthalene tricarboxylic acid, and pyromellitic acid.
These can be used alone or in combination of two or more.

The alcohol component may contain a monovalent alcohol, and the carboxylic acid component may contain a monovalent carboxylic acid from the viewpoint of molecular weight adjustment, but the carboxylic acid component contains a monovalent carboxylic acid. It is preferable to do.
The monovalent carboxylic acid is preferably an aliphatic monocarboxylic acid having 8 to 25 carbon atoms.
The number of carbon atoms of the aliphatic monocarboxylic acid is preferably 10 or more, more preferably 12 or more, still more preferably 14 or more, and is preferably 23 or less, more preferably 20 or less, more preferably 18 or less.
Examples of the aliphatic monocarboxylic acid include octanoic acid, decanoic acid, dodecanoic acid, tetradecanoic acid, and octadecanoic acid. These can be used alone or in combination of two or more.

  The content of the monovalent carboxylic acid is preferably 1 mol% or more, more preferably 3 mol% or more, still more preferably 5 mass% or more with respect to the carboxylic acid component, from the viewpoint of molecular weight control. Preferably it is 20 mass% or less, More preferably, it is 15 mass% or less, More preferably, it is 10 mass% or less.

[Styrene resin component C2]
As the styrene resin component C2, those obtained by addition polymerization of a raw material monomer containing a styrene compound are preferable.
As the styrene compound, at least styrene or a styrene derivative such as α-methylstyrene or vinyltoluene is used.

The content of the styrene compound is preferably 50% by mass or more, more preferably 60% by mass or more, still more preferably 70% by mass or more, from the viewpoint of low-temperature fixability and durability in the raw material monomer of the styrene resin component C2. More preferably, it is 75% by mass or more, and 100% by mass or less, and more preferably 100% by mass.
Among these, styrene is preferable from the viewpoint of low-temperature fixability and durability.
The content of styrene is preferably 70% by mass or more, more preferably 80% by mass or more, still more preferably 90% by mass or more, and still more preferably 95% by mass or more, from the viewpoint of low-temperature fixability and durability. And it is 100 mass% or less, More preferably, it is 100 mass%.

(Amotropic monomer)
Examples of the bireactive monomer include the same ones as the bireactive monomers mentioned in the above-mentioned amorphous resin A, and the types and amounts used of preferred compounds are also the same.

The mass ratio of the composite resin C polycondensation resin component C1 in the _h and the styrenic resin component C2 (polycondensation resin component C1 / styrenic resin component C2), from the viewpoint of low-temperature fixing property, preferably 60/40 or more More preferably 70/30 or more, still more preferably 75/25 or more, and from the viewpoint of durability, it is preferably 95/5 or less, more preferably 90/10 or less, still more preferably 85/15 or less. is there. In the above calculation, the mass of the polycondensation resin component C1 is the mass of the raw material monomer of the polycondensation resin component C1 used, excluding the amount of reaction water dehydrated by the polycondensation reaction (calculated value). The amount of both reactive monomers is included in the raw material monomer amount of the polycondensation resin component C1. The amount of the styrene resin component C2 is the amount of the raw material monomer of the styrene resin component C2, but the amount of the polymerization initiator is included in the amount of the raw material monomer of the styrene resin component C2.

  The addition polymerization reaction conditions of the raw material monomer of the styrene-based resin component C2, the both reactive monomers and the amount used thereof are the same as those exemplified for the amorphous resin A.

[Physical properties of crystalline resin C]
The softening point of the crystalline resin C is preferably 55 ° C. or higher, more preferably 65 ° C. or higher, more preferably 78 ° C. or higher, and preferably 120 ° C. or lower, from the viewpoint of low-temperature fixability and durability. Preferably it is 105 degrees C or less, More preferably, it is 95 degrees C or less.
The acid value of the crystalline resin C is preferably 40 mgKOH / g or less, more preferably 30 mgKOH / g or less, still more preferably 20 mgKOH / g or less, and preferably 1 mgKOH / g from the viewpoint of low-temperature fixability and durability. g or more, more preferably 2 mgKOH / g or more.
The softening point and acid value of the crystalline resin C can be appropriately adjusted depending on the type and ratio of the raw material monomers and the production conditions such as reaction temperature, reaction time, and cooling rate.
The softening point and acid value of the crystalline resin C can be measured by the methods described in the examples.

  The content of the crystalline resin C is preferably 1% by mass or more, more preferably 3% by mass or more, and further preferably 5% by mass with respect to the total amount of the binder resin from the viewpoint of low-temperature fixability and durability. The amount is preferably 40% by mass or less, more preferably 30% by mass or less, more preferably 20% by mass or less, and still more preferably 15% by mass or less.

<Wax X>
The electrophotographic toner contains wax X which is a hydrocarbon wax (hereinafter also simply referred to as “wax X”). The wax X does not include the wax Y, and is preferably a hydrocarbon wax having an acid value of less than 1 mgKOH / g, more preferably an acid value of 0 mgKOH / g.
The melting point of the wax X is preferably 50 ° C. or higher, more preferably 60 ° C. or higher, more preferably 70 ° C. or higher, further preferably 75 ° C. or higher, more preferably 80 ° C. or higher, from the viewpoint of low-temperature fixability and durability. Further, it is preferably 90 ° C. or higher, and preferably 120 ° C. or lower, more preferably 110 ° C. or lower, from the viewpoint of improving low-temperature fixability.
The details of the measurement method will be described in the examples described later.

The wax X is preferably an unmodified hydrocarbon wax, specifically, polypropylene wax, polyethylene wax, polypropylene polyethylene copolymer wax; microcrystalline wax, paraffin wax, Fischer-Tropsch wax, sazol wax, etc. Aliphatic hydrocarbon waxes may be mentioned. These can be used alone or in combination of two or more.
Among these, at least one selected from paraffin wax and Fischer-Tropsch wax is preferable. Commercially available paraffin wax and Fischer-Tropsch wax include “HNP-11”, “HNP-9”, “HNP-10”, “FT-0070”, “HNP-51”, “ FNP-0090 ”,“ SX-105 ”and the like.

  The content of the wax X is preferably 0.5 parts by mass or more, more preferably 1.0 parts by mass or more, and further preferably 3 parts by mass or more from the viewpoint of low temperature fixability and durability with respect to 100 parts by mass of the binder resin. From the same viewpoint, it is preferably 20 parts by mass or less, more preferably 15 parts by mass or less, and still more preferably 10 parts by mass or less.

<Wax Y>
The electrophotographic toner contains wax Y (hereinafter, also simply referred to as “wax Y”), which is a carboxylic acid-modified hydrocarbon wax having an acid value of 1 mgKOH / g or more and 50 mgKOH / g or less.
The acid value of the wax Y is preferably 1 mgKOH / g or more, more preferably 5 mgKOH / g or more, still more preferably 10 mgKOH / g or more from the viewpoint of low-temperature fixability and durability, and from the same viewpoint, Is 50 mgKOH / g or less, more preferably 40 mgKOH / g or less, and still more preferably 30 mgKOH / g or less.
The melting point of the wax Y is preferably 50 ° C. or higher, more preferably 60 ° C. or higher, more preferably 70 ° C. or higher, more preferably 80 ° C. or higher, from the viewpoint of low-temperature fixability and durability. From the viewpoint of increasing the temperature, it is preferably 130 ° C. or lower, more preferably 120 ° C. or lower, more preferably 110 ° C. or lower, more preferably 100 ° C. or lower.
The details of the measurement method will be described in the examples described later.

The carboxylic acid-modified hydrocarbon wax used as the wax Y can be obtained by introducing a carboxy group into the hydrocarbon wax.
Examples of the carboxylic acid modification method include a method in which a hydrocarbon wax is brought into contact with a gas containing oxygen such as air and heated. In this case, the heating temperature is preferably 80 ° C. or higher, more preferably 100 ° C. or higher, more preferably 150 ° C. or higher, and preferably 250 ° C. or lower, more preferably 200 ° C. or lower, more preferably 180 ° C. or lower. It is.
Examples of other carboxylic acid modification methods include the methods described in JP 2006-328388 A, JP 2007-84787 A, and the like. Specifically, a carboxy group can be introduced by adding an organic peroxide compound (reaction initiator) such as dicumyl peroxide and a carboxylic acid compound to a melt of hydrocarbon wax and reacting them. As the raw material hydrocarbon wax, the examples given in the above-mentioned wax X are preferable.
Examples of commercially available wax Y include “High Wax 1105A” (maleic anhydride-modified ethylene / propylene copolymer, manufactured by Mitsui Chemicals, Inc.).

  The content of the wax Y is preferably 0.01 parts by mass or more, more preferably 0.1 parts by mass or more, and further preferably 0.5 parts by mass or more, from the viewpoint of low temperature fixability and durability with respect to 100 parts by mass of the binder resin. From the same viewpoint, it is preferably 10 parts by mass or less, more preferably 5 parts by mass or less, and still more preferably 3 parts by mass or less.

  The mass ratio of wax X to wax Y (wax X / wax Y) is preferably 1 or more, more preferably 2 or more, still more preferably 3 or more, and preferably from the viewpoint of low-temperature fixability and durability. 15 or less, more preferably 10 or less, and still more preferably 8 or less.

<Charge control agent>
The electrophotographic toner of the present invention contains a charge control agent.
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.) and the like; triphenylmethane dyes containing tertiary amines as side chains, quaternary ammonium salt compounds such as“ Bontron P-51 "(manufactured by Orient Chemical Industry Co., Ltd.), cetyltrimethylammonium bromide," COPY CHARGE PX VP435 "(manufactured by Clariant), etc .; polyamine resin such as" AFP-B "(manufactured by Orient Chemical Industry Co., Ltd.) Imidazole derivatives such as “PLZ-2001” and “PLZ-8001” (manufactured by Shikoku Kasei Kogyo Co., Ltd.); styrene-acrylic resins such as “FCA-701PT” (Fujikura Chemical) Etc., Ltd.) 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, made by Orient Chemical Co., Ltd.), “Eisenspiron Black TRH”, “T-77” (made by Hodogaya Chemical Co., Ltd.), etc .; metal compounds of benzylic acid compounds, such as “LR-147” , “LR-297” (manufactured by Nippon Carlit Co., Ltd.), etc .; metal compounds of salicylic acid compounds such as “Bontron E-81”, “Bontron E-84”, “Bontron E-88”, “Bontron E-” "304" (made by Orient Chemical Co., Ltd.), "TN-105" (made by Hodogaya Chemical Co., Ltd.), etc .; copper phthalocyanine dyes; quaternary ammonium salts such as "COPY CHARGE NX VP434" (made by Clariant) Nitroimidazole derivatives ; Organometallic compounds, and the like.
Among charge control agents, negatively chargeable charge control agents are preferable, and metal compounds of salicylic acid compounds are more preferable.

  The content of the charge control agent is preferably 0.01 parts by mass or more, more preferably 0.05 parts by mass or more, still more preferably 0.1 parts by mass or more, with respect to 100 parts by mass of the binder resin from the viewpoint of low-temperature fixability and durability. From the same viewpoint, it is preferably 10 parts by mass or less, more preferably 5 parts by mass or less, and still more preferably 3 parts by mass or less.

<Colorant>
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, 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 low-temperature fixability and durability. Part or less, more preferably 20 parts by weight or less, still more preferably 10 parts by weight or less.

  Further, additives such as magnetic powder, fluidity improver, conductivity modifier, fibrous filler and other reinforcing fillers, antioxidants, anti-aging agents, and cleaning improvers are appropriately used as raw materials. Also good.

The volume median particle size (D ₅₀ ) of the electrophotographic toner of the present invention is preferably 2 μm or more, more preferably from the viewpoints of low-temperature fixability and offset resistance of the toner and dispersibility in the binder resin. Is 3 μm or more, more preferably 4 μm or more, and preferably 20 μm or less, more preferably 15 μm or less, more preferably 10 μm or less.
The volume median particle size (D ₅₀ ) is measured by the method described in the examples.

[Method for producing toner for electrophotography]
As a method for producing the electrophotographic toner of the present invention,
(1) A method for producing a toner by melt-kneading a toner raw material mixture containing a binder resin, wax X and wax Y, and pulverizing the obtained melt-kneaded product,
(2) Toner by obtaining toner particles by aggregating and fusing binder resin particles in a toner raw material mixture containing a dispersion in which binder resin, wax X and wax Y are dispersed in an aqueous medium How to manufacture,
(3) A method for producing toner by, for example, obtaining toner particles by stirring a dispersion liquid in which a binder resin, wax X and wax Y are dispersed in an aqueous medium and a toner raw material at high speed.

  In the case of producing the toner by any of the above methods, the amount of the binder resin used is preferably 70% by mass or more, more preferably 80% by mass or more, from the viewpoint of low temperature fixability and durability in the toner. More preferably, it is 90 mass% or more, and is 100 mass% or less, More preferably, it is 99 mass% or less.

(1) A method for producing a toner by melt kneading a toner raw material mixture containing a binder resin, wax X and wax Y, and pulverizing the obtained melt kneaded product (melt kneading method)
The method (1) preferably includes the following step 1 and step 2.
Step 1: Melting and kneading the toner raw material mixture containing the binder resin, wax X and wax Y Step 2: Grinding and classifying the melt-kneaded product obtained in Step 1

In Step 1, it is preferable to melt and knead additives such as a colorant and a charge control agent together.
The melt-kneading can be carried out using a known kneader such as a hermetic kneader, a single or biaxial extruder, and an open roll kneader. It is possible to use an open roll type kneader from the viewpoint of efficiently and highly dispersing additives such as a colorant, a charge control agent, and a release agent in the toner without repeating kneading and using a dispersion aid. Preferably, the open roll kneader is provided with a supply port and a kneaded product discharge port along the axial direction of the roll.

  It is preferable that toner raw materials such as a binder resin, a wax, a colorant, and a charge control agent are mixed in advance with a mixer such as a Henschel mixer or a ball mill and then supplied to the kneader.

  The open roll type kneader refers to a kneading section that is not sealed and released, and can easily dissipate the kneading heat generated during kneading. The continuous open roll type kneader is preferably a kneader equipped with at least two rolls, and the continuous open roll type kneader used in the present invention comprises two rolls having different peripheral speeds, That is, it is a kneader equipped with two rolls, a high rotation side roll with a high peripheral speed and a low rotation side roll with a low peripheral speed. In the present invention, the viewpoint of improving the dispersibility in the toner of additives such as a colorant, a charge control agent, and a release agent, a viewpoint of reducing mechanical force during melt-kneading and suppressing heat generation, and melt-kneading. From the viewpoint of reducing the temperature at the time, the high rotation side roll is preferably a heating roll, and the low rotation side roll is preferably a cooling roll.

The temperature of the roll can be adjusted by, for example, the temperature of the heat medium passed through the roll.
The heating temperature in the roll is preferably 20 ° C. or higher, more preferably 30 ° C. or higher, and preferably 200 ° C. or lower, more preferably 150 ° C. or lower, from the viewpoint of the dispersibility of the additive.

The roll rotation peripheral speed of the high rotation side roll is the viewpoint of improving the dispersibility in the toner of additives such as wax, colorant, charge control agent, etc., the viewpoint of reducing the mechanical force during melt kneading and suppressing heat generation From the above, preferably 20 m / min or more, more preferably 25 m / min or more, more preferably 30 m / min or more, and preferably 50 m / min or less, more preferably 45 m / min or less, more preferably 40 m / min. It is as follows.
From the same viewpoint, the roll rotation peripheral speed of the low rotation side roll is preferably 10 m / min or more, more preferably 15 m / min or more, more preferably 20 m / min or more, and preferably 40 m / min or less, More preferably, it is 35 m / min or less, and more preferably 30 m / min or less.

  The structure, size, material, etc. of the roll are not particularly limited, and the roll surface may be any of smooth, corrugated, uneven, etc., but the kneading share is increased, and the colorant, charge control agent, mold release From the viewpoint of improving the dispersibility of additives such as additives in the toner, reducing the mechanical force during melt-kneading, and suppressing heat generation, each roll surface may have a plurality of spiral grooves. preferable.

  The melt-kneaded product obtained in step 1 is cooled to such an extent that it can be crushed, and then subjected to subsequent step 2.

  In step 2, the melt-kneaded product obtained in step 1 is pulverized and classified.

  The pulverization process may be performed in multiple stages. For example, the resin kneaded material obtained by curing the melt-kneaded material may be coarsely pulverized to about 1 to 5 mm and further pulverized to a desired particle size.

  The pulverizer used in the pulverization step is not particularly limited, and examples of the pulverizer suitably used for coarse pulverization include a hammer mill, an atomizer, and a rotplex. Further, examples of the pulverizer suitably used for fine pulverization include a fluidized bed jet mill, a collision plate jet mill, and a rotary mechanical mill. From the viewpoint of pulverization efficiency, it is preferable to use a fluidized bed jet mill and a collision plate jet mill, and more preferably a fluidized bed jet mill.

  Examples of the classifier used in the classification process include a rotor classifier, an airflow classifier, an inertia classifier, and a sieve classifier. In the classification step, the pulverized product that has been removed due to insufficient pulverization may be subjected to the pulverization step again, and the pulverization step and the classification step may be repeated as necessary.

In the case of the method (1), the following step 3 may be further included.
Step 3: Step of mixing powder obtained by classification and external additive As external additive, hydrophobic silica, titanium oxide fine particles, alumina fine particles, cerium oxide fine particles, inorganic fine particles such as carbon black, polycarbonate, polymethacryl Examples thereof include polymer fine particles such as methyl acid and silicone resin, and among these, hydrophobic silica is preferable.
When the toner particles are subjected to surface treatment using an external additive, the amount of the external additive added is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, and still more preferably 100 parts by mass of the toner particles. 1 part by mass or more, and preferably 5 parts by mass or less, more preferably 4 parts by mass or less, and further preferably 3 parts by mass or less.

  About each physical-property value of resin etc., it measured and evaluated by the following method.

[Measuring method]
[Melting point of hydrocarbon wax (Mp)]
Using a differential scanning calorimeter (Seiko Instruments Co., Ltd., DSC210), the temperature was raised to 200 ° C, and the sample cooled to 0 ° C at a temperature drop rate of 10 ° C / min was raised at a temperature rise rate of 10 ° C / min. The maximum peak temperature of heat of fusion was taken as the melting point.

[Acid value of hydrocarbon wax]
Measurement was performed based on the method of JIS K0070. However, only the measurement solvent was changed from the mixed solvent of ethanol and ether specified in JIS K0070 to chloroform.

[Acid value of the resin]
The acid value of the resin was measured based on the method of JIS K0070. However, only the measurement solvent was changed from the mixed solvent of ethanol and ether specified in JIS K0070 to a mixed solvent of acetone and toluene (acetone: toluene = 1: 1 (volume ratio)).

[Softening point of resin, maximum peak temperature of endotherm, and glass transition temperature]
(1) Softening point Using a flow tester “CFT-500D” (manufactured by Shimadzu Corporation), a 1 g sample was heated at a heating rate of 6 ° C./min. Extruded from a 1 mm long nozzle. The amount of plunger drop of the flow tester was plotted against the temperature, and the temperature at which half of the sample flowed out was taken as the softening point.
(2) Maximum peak temperature of endotherm Using a differential scanning calorimeter “Q-100” (manufactured by TA Instruments Japan Co., Ltd.), it was cooled from room temperature (20 ° C.) to 0 ° C. at a rate of temperature decrease of 10 ° C./min. The sample was maintained at the same temperature for 1 minute, and then measured while raising the temperature to 180 ° C. at a rate of temperature increase of 10 ° C./min. Of the endothermic peaks observed, the peak temperature on the highest temperature side was defined as the maximum endothermic peak temperature.
(3) Glass transition temperature 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 heated to 200 ° C. The temperature was cooled to 0 ° C. at a rate of temperature decrease of 10 ° C./min. Next, the measurement was performed while increasing the temperature to 150 ° C. at a temperature increase rate of 10 ° C./min. The glass transition temperature was defined as the temperature at the intersection of the base line extension below the maximum peak temperature of endotherm and the tangent indicating the maximum slope from the peak rising portion to the peak apex.

[Volume-median particle size (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 ( D ₅₀ ) was determined.

[Evaluation method]
(Low temperature fixability)
The printer “OKI MICROLINE 5400” (made by Oki Data Co., Ltd.), modified to take unfixed images, was filled with toner, and an unfixed image of 3 × 4 cm square was printed. Using an external fixing device modified from "OKI MICROLINE 3010" (manufactured by Oki Data Co., Ltd.), increasing the fixing roll temperature in increments of 5 ° C from 100 ° C to 200 ° C at a rotating speed of 120mm / sec. However, this unfixed image was fixed at each temperature to obtain a fixed image. The image obtained at each fixing temperature was applied with a weight so that a load of 500 g was applied thereto, and then the tape was peeled off. The image density before and after rubbing was measured. The image density before and after rubbing is measured using an image density measuring device “GREGSPM50” (Gretag), and the image density ratio before and after rubbing ([image density after rubbing / image density before rubbing] × 100) is the first. In addition, a temperature exceeding 90% was defined as the minimum fixing temperature, and was used as an index of low-temperature fixing property. The smaller the value, the better the low-temperature fixability.

〔durability〕
Toner is mounted on ID cartridge “ML-5400, Image Drum” manufactured by Oki Data Co., Ltd., modified so that the developing roller can be seen visually. 70r / min under conditions of 30 ° C and 50% humidity (Equivalent to 36 ppm (number of sheets / minute)) was run, and filming of the developing roller was visually observed. The time until filming occurred was used as an index of durability. The durability indicates that the longer the time until the developing roller filming occurs, the better the durability.

[Examples of resin production]
Production Examples A1, B2: Resins A-1 and B-2
Raw material monomer of polyester other than fumaric acid and trimellitic anhydride shown in the table, 40 g of tin (II) 2-ethylhexanoate and 1 g of gallic acid, 10 liter capacity equipped with nitrogen introduction tube, dehydration tube, stirrer and thermocouple The reaction was carried out at 230 ° C. for 8 hours. After the reaction, the mixture was reacted at 8.3 kPa for 1 hour.
Further, the temperature was lowered to 210 ° C., trimellitic anhydride and fumaric acid were added to obtain resins A-1 and B-2 (amorphous polyester resin).

Production Examples A2 and B1: Resins A-2 and B-1
Put raw material monomers of polycondensation resin components other than trimellitic anhydride shown in the table, esterification catalyst into a 10-liter four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple. The reaction was carried out for 12 hours at 8.3 kPa and then for 1 hour at 8.3 kPa.
The temperature was lowered to 160 ° C., and the raw material monomer of the styrene resin component, the bireactive monomer, and dicumyl peroxide were added dropwise over 1 hour with a dropping funnel. After aging the addition polymerization reaction for 1 hour while maintaining the temperature at 160 ° C., the temperature was raised to 210 ° C., and the raw material monomer of the styrene resin component was removed at 8.3 kPa for 1 hour.
Further, trimellitic anhydride was added at 210 ° C. and reacted until the desired softening point was reached to obtain resins A-2 and B-1 (amorphous composite resin).

Production Examples C1, C2: Resins C-1 and C-2
Polyester raw material monomers other than sebacic acid shown in the table were placed in a 10-liter four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer and a thermocouple, and heated to 120 ° C. At 120 ° C., 1.5 kg of sebacic acid shown in Table 2 was added, further heated to 160 ° C., and reacted for 6 hours. Thereafter, the raw material monomers of the styrenic resin component shown in Table 2 and the both reactive monomers were added dropwise over 1 hour using a dropping funnel. After aging the addition polymerization reaction for 1 hour while maintaining at 160 ° C., the raw material monomer of the styrene resin component was removed at 8.3 kPa for 1 hour. Further, the remaining sebacic acid was added, the temperature was raised to 200 ° C. over 8 hours, and the mixture was reacted at 8.3 kPa for 30 minutes. Further, 20 g of tin (II) 2-ethylhexanoate and 2 g of gallic acid were added and reacted at 200 ° C. for 1 hour, and then reacted at 8.3 kPa for 1 hour to obtain resins C-1 and C-2 ( Crystalline hybrid resin) was obtained.

[Production of modified wax]
Production Example Y1: Method for Producing Carboxylic Acid Modified Wax 1200 g of paraffin wax “SX-105” (manufactured by Nippon Seiwa Co., Ltd.) was placed in a glass cylindrical reactor and heated to 170 ° C. while blowing a small amount of air. The reaction was carried out for 120 minutes with no catalyst while blowing air (22 liters / minute) at ℃ to obtain a carboxylic acid-modified wax. The acid value of the carboxylic acid-modified wax was 21 mgKOH / g. The melting point was 100 ° C.

[Manufacture of toner for electrophotography]
Examples 1-6
The specified amount of binder resin shown in the table, 4 parts by weight of coloring agent “ECB-301” (manufactured by Dainichi Seika Kogyo Co., Ltd., phthalocyanine blue (PB15: 3)), charge control agent “Bontron E-304” (Orient) (Made by Chemical Industry Co., Ltd.) 0.5 parts by mass, 5 parts by mass of wax X and 1 part by mass of wax Y were mixed with a Henschel mixer, and then melt-kneaded under the conditions shown below. The wax X used in the table has an acid value of 0 mgKOH / g.
The obtained raw material mixture was supplied to a continuous open roll kneader “NIDEX” (manufactured by Mitsui Mining Co., Ltd.) with a table feeder and kneaded to obtain a kneaded product. The continuous open roll type kneader used at this time had a roll outer diameter of 0.14 m and an effective roll length of 0.8 m, and the operating conditions were that the rotation speed of the high rotation side roll (front roll) was 75 r / min (peripheral speed 33m / min), low speed side roll (rear roll) rotation speed 50r / min (peripheral speed 22m / min), ratio of peripheral speed of two rolls (low speed side roll / high speed side) Roll) was 0.67, and the roll gap was 0.1 mm. The heating and cooling medium temperature in the roll is 150 ° C on the raw material input side of the high-rotation roll, 100 ° C on the kneaded material discharge side, 75 ° C on the raw material input side of the low-rotation roll, and the kneaded material discharge side The temperature of was set to 30 ° C. The feed rate of the raw material mixture was 10 kg / h, and the average residence time was about 5 minutes.
The obtained kneaded product was cooled and coarsely pulverized by a pulverizer “Rotoplex” (manufactured by Toa Machine Industry Co., Ltd.) to obtain a coarsely pulverized product having a particle size of 2 mm or less using a sieve having an opening of 2 mm. Fine grinding and upper limit classification (removal of coarse powder) were performed with a turbo mill “RS400” (Freund Turbo Co., Ltd.). Furthermore, lower limit classification (fine powder removal) was performed with a classifier “TTSP” (manufactured by Hosokawa Alpine Co., Ltd.) to obtain toner particles having a volume median particle size of 7.0 μm. The toner circularity was adjusted by changing the raw material supply amount at the time of fine pulverization by the turbo mill and the number of times of fine pulverization by the turbo mill.
100 parts by mass of the obtained toner particles, 1.0 part by mass of hydrophobic silica “R972” (manufactured by Nippon Aerosil Co., Ltd., hydrophobizing agent: DMDS, average particle size: 16 nm), and hydrophobic silica “ RY-50 "(manufactured by Nippon Aerosil Co., Ltd., hydrophobizing agent: silicone oil, average particle size: 40 nm) 1.0 part by mass with a Henschel mixer (manufactured by Mitsui Mining Co., Ltd.) 3000 r / min (circumferential speed 32 m / sec) Was mixed for 3 minutes to obtain a toner. Table 3 shows the results of the evaluation.

Comparative Examples 1-7
The specified amount of binder resin shown in the table, 4 parts by weight of coloring agent “ECB-301” (manufactured by Dainichi Seika Kogyo Co., Ltd., phthalocyanine blue (PB15: 3)), charge control agent “Bontron E-304” (Orient) (Made by Chemical Industry Co., Ltd.) 0.5 parts by mass, 5 parts by mass of wax X, and 1 part by mass of wax Y were mixed with a Henschel mixer and then melt-kneaded under the conditions shown below.
After the melt kneading, a toner was obtained in the same manner as in Example 1. Table 3 shows the results of the evaluation.

In the table, the materials used are as follows.
Wax X
X-1: Paraffin wax “SX-105” (manufactured by Nippon Seiwa Co., Ltd., melting point: 102 ° C.)
X-2: Paraffin wax “HNP-9” (manufactured by Nippon Seiwa Co., Ltd., melting point: 78 ° C.)
Comparison wax
C-1: Carnauba wax “C2” (manufactured by Hiroyuki Kato, melting point: 85 ° C.)
Wax Y
Y-1: Carboxylic acid-modified wax obtained in Production Example Y1

  By comparing the electrophotographic toners of Examples 1 to 6 and the toners of Comparative Examples 1 to 7, according to the electrophotographic toner of the present invention, excellent low temperature fixability and excellent durability It can be understood that an electrophotographic toner capable of satisfying both of the above can be obtained.

Claims (5)

Containing amorphous resin A, amorphous resin B, crystalline resin C, wax X, and wax Y,
The amorphous resin A is a resin having a softening point of 115 ° C. or more and 150 ° C. or less, and a polycondensation resin A1 obtained by polycondensation of an alcohol component and a carboxylic acid component at least in part.
The amorphous resin B has a softening point of 80 ° C. or higher and lower than 115 ° C., and is obtained by polycondensation of an alcohol component containing an aromatic polyol compound and a carboxylic acid component containing an aromatic dicarboxylic acid compound. A composite resin B _h comprising a polycondensation resin component B1 and a styrene resin component B2,
The crystalline resin C is obtained by polycondensing an alcohol component containing an aliphatic diol having 9 to 14 carbon atoms and a carboxylic acid component containing an aliphatic dicarboxylic acid compound having 9 to 14 carbon atoms. a composite resin C _h containing polycondensation resin component C1 and a styrene resin component C2,
The wax X is a hydrocarbon wax,
The wax Y is a carboxylic acid-modified hydrocarbon wax having an acid value of 1 mgKOH / g or more and 50 mgKOH / g or less.
Toner for electrophotography.   The toner for electrophotography according to claim 1, wherein the crystalline resin C has a softening point of 70 ° C. or higher and 120 ° C. or lower.   The toner for electrophotography according to claim 1 or 2, wherein the alcohol component of the amorphous resin A contains an alkylene oxide adduct of bisphenol A.   The toner for electrophotography according to any one of claims 1 to 3, wherein the alcohol component of the amorphous resin B contains an alkylene oxide adduct of bisphenol A.   The toner for electrophotography according to claim 1, wherein the carboxylic acid component of the crystalline resin C contains a monovalent carboxylic acid.