JP6940062B2 - Toner for static charge image development - Google Patents

Description

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

In the field of electrophotographic, with the development of electrophotographic systems, the development of toners for electrophotographics corresponding to high image quality and high speed is required.

In Patent Document 1, an amorphous resin for an electrophotographic toner containing core-shell particles, wherein the core is obtained by shrink-polymerizing an alcohol component containing an aliphatic diol having 2 to 6 carbon atoms and a carboxylic acid component. Core-shell particles containing (A) and the shell comprising an amorphous composite resin (B) having a segment (B1) made of a polyester resin and a segment (B2) made of an addition polymer containing styrene as a constituent unit. Toners for electrophotographics including. According to the toner, it is described that a toner having excellent low-temperature fixability and heat-resistant storage property, and also excellent charge stability and smear property (rubbing fixability) under high temperature and high humidity can be obtained.

In Patent Document 2, a toner for static charge image development having a core-shell structure, which contains a binder resin containing a composite resin (A) and a crystalline polyester (B) and a wax in a core portion, and is a polyester resin (C). ) Is contained in the shell portion, and the composite resin (A) is obtained by polycondensing an alcohol component containing 80 mol% or more of a propylene oxide adduct of bisphenol A and a polyvalent carboxylic acid component. It is a composite resin containing a segment made of polyester resin (a1) and a vinyl resin segment (a2) containing a structural unit derived from a styrene compound, and the crystalline polyester (B) has 8 or more and 16 or less carbon atoms. It is obtained by polycondensing an alcohol component containing 80 mol% or more of α, ω-aliphatic diol and a polyvalent carboxylic acid component containing 80 mol% or more of an aliphatic saturated dicarboxylic acid having 8 or more and 16 or less carbon atoms. It is a crystalline polyester, and the polyester resin (C) is a polyester resin obtained by polycondensing an alcohol component containing 80 mol% or more of an ethylene oxide adduct of bisphenol A and a polyvalent carboxylic acid component. The image development toner is described. It is described that the toner has both excellent low-temperature fixability and heat-resistant storage property, and is also excellent in chargeability.

Patent Document 3 is a method for producing an aqueous dispersion of binder resin composition particles for an electrophotographic toner containing an amorphous composite resin (A) and a crystalline polyester resin (C). A) is a polycondensation resin component (A-1) obtained by polycondensing an alcohol component and a carboxylic acid component containing an aliphatic dicarboxylic acid compound having 8 or more and 14 or less carbon atoms, and a styrene resin component (A). A resin containing A-2), and the crystalline polyester resin (C) contains an alcohol component containing 80 mol% or more and 100 mol% or less of an aliphatic diol having 8 or more and 14 or less carbon atoms, and 8 or more and 14 carbon atoms. A resin obtained by polycondensing with a carboxylic acid component containing 80 mol% or more and 100 mol% or less of the following aliphatic dicarboxylic acid compounds. Step 1: Amorphous composite resin (A), crystalline polyester resin ( C) is mixed to obtain a mixture, Step 2: A step of mixing a neutralizing agent with the mixture obtained in Step 1, and Step 3: An aqueous medium is added to the mixture obtained in Step 2. A method for producing an aqueous dispersion of binder resin composition particles for an electrophotographic toner, which includes a step of phase inversion emulsification, is described. According to the production method, an aqueous dispersion of binder resin composition particles for an electrophotographic toner capable of obtaining an electrophotographic toner having excellent low-temperature fixability, heat-resistant storage under high humidity, and durability can be obtained. It is stated that it will be done.

Japanese Unexamined Patent Publication No. 2014-13385 Japanese Unexamined Patent Publication No. 2016-114934 Japanese Unexamined Patent Publication No. 2016-133769

According to the techniques of Patent Documents 1 to 3, there are problems from the viewpoints of low temperature fixing property, high temperature offset resistance, and durability. That is, according to the techniques of Patent Documents 1 to 3, further improvement is required from the viewpoints of low temperature fixing property, high temperature offset resistance, and durability.
The present invention relates to an electrostatic charge developing toner having excellent low temperature fixability, high temperature offset resistance, and durability.

The present invention is a toner for static charge image development containing a binder resin containing an amorphous composite resin (A) and a wax (W).
The amorphous composite resin (A) is an addition polymerization of a polyester resin segment which is a polycondensate of an alcohol component containing an aromatic diol and a carboxylic acid component containing an aromatic dicarboxylic acid, and a raw material monomer containing a styrene compound. The amorphous composite resin (A) containing a vinyl-based resin segment, which is a product, and a constituent unit derived from a bireactive monomer bonded to a polyester resin segment and a vinyl-based resin segment via a covalent bond, and which comprises the above-mentioned amorphous composite resin (A). The content is 0.5% by mass or more and 15% by mass or less with respect to the total amount of the binder resin.
The present invention relates to a toner for developing an electrostatic charge image, wherein the mass ratio [(A) / (W)] of the amorphous composite resin (A) and the wax (W) is 0.2 or more and 3.5 or less.

According to the present invention, it is possible to provide a toner for electrostatic charge development which is excellent in all of low temperature fixability, high temperature offset resistance, and durability.

[Toner for static charge image development]
The toner for static charge image development of the present invention (hereinafter, also simply referred to as “toner”) is a binder resin containing an amorphous composite resin (A) (hereinafter, also simply referred to as “composite resin (A)”). Contains wax (W).
The composite resin (A) is a polyester resin segment which is a polycondensate of an alcohol component containing an aromatic diol and a carboxylic acid component containing an aromatic dicarboxylic acid, and vinyl which is an addition polymer of a raw material monomer containing a styrene compound. It contains a based resin segment and a structural unit derived from a bireactive monomer bonded to a polyester resin segment and a vinyl resin segment via a covalent bond.
The content of the composite resin (A) is 0.5% by mass or more and 15% by mass or less with respect to the total amount of the binder resin.
Further, the mass ratio [(A) / (W)] of the composite resin (A) and the wax (W) is 0.2 or more and 3.5 or less.
With the above configuration, a toner for electrostatic charge development having excellent low temperature fixability, high temperature offset resistance, and durability can be obtained. The reason is not clear, but it can be considered as follows.

Wax is used to prevent offset during fixing at high temperature, but in this case, the dispersed state of wax is the key. If the dispersibility of the wax is poor, the durability of the toner deteriorates, while if it is excessively dispersed, the effect as a wax is not exhibited and a high temperature offset occurs.
Since the toner of the present invention contains the composite resin (A), it has high hydrophobicity and a very high affinity with wax, so that the dispersibility of wax can be improved by using a small amount. Further, it is considered that the durability and the high temperature offset resistance can be improved by setting the ratio of the wax and the composite resin (A) in a specific range. Furthermore, since the composite resin (A) can improve the dispersibility of the wax by adding a small amount, the content of the composite resin (A), which has a reduced affinity with paper, is reduced, and the low temperature fixability is also improved. It is thought that it became possible to make it.

Definitions of various terms in the present specification are shown below.
Whether the resin is crystalline or amorphous is determined by the crystallinity index. The crystallinity index is defined by the ratio of the softening point of the resin to the maximum endothermic peak temperature (softening point (° C.) / maximum endothermic peak temperature (° C.)) in the measurement method described in Examples described later. The crystalline resin is a resin having a crystallinity index of 0.6 or more and less than 1.4, preferably 0.7 or more, more preferably 0.9 or more, and preferably 1.2 or less. The amorphous resin is a resin having a crystallinity index of 1.4 or more or less than 0.6, preferably 1.5 or more or 0.5 or less, more preferably 1.6 or more or 0.5 or less. The crystallinity index 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 maximum endothermic temperature refers to the temperature of the peak on the highest temperature side among the observed endothermic peaks. The crystallinity index can be calculated from the values obtained by the method for measuring the softening point of the resin and the maximum endothermic temperature described in the examples.
In the specification, the carboxylic acid component of the polyester resin includes not only the exemplified compound, but also an anhydride that decomposes during the reaction to generate an acid, and an alkyl ester of each carboxylic acid (alkyl group having 1 or more carbon atoms and 3 carbon atoms). The following) is also included.
In the specification, the "binding resin" means a resin component contained in a toner containing a composite resin (A) and a polyester-based resin (B).

<Amorphous composite resin (A)>
The composite resin (A) is a polycondensate of an alcohol component containing an aromatic diol and a carboxylic acid component containing an aromatic dicarboxylic acid from the viewpoint of obtaining a toner having excellent low temperature fixability, high temperature offset resistance, and durability. A certain polyester resin segment, a vinyl resin segment which is an addition polymer of a raw material monomer containing a styrene compound, and a structural unit derived from a bireactive monomer bonded to the polyester resin segment and the vinyl resin segment via a covalent bond. ,including.

[Polyester resin segment]
The polyester resin segment is a polycondensate of an alcohol component containing an aromatic diol and a carboxylic acid component containing an aromatic dicarboxylic acid from the viewpoint of obtaining a toner having excellent low temperature fixability, high temperature offset resistance, and durability.

（式中、R¹O及びOR²はオキシアルキレン基であり、R¹及びR²はそれぞれ独立にエチレン又はプロピレン基であり、x及びｙはアルキレンオキサイドの平均付加モル数を示し、それぞれ正の数であり、xとｙの和の値は、１以上、好ましくは1.5以上であり、そして、16以下、好ましくは8以下、より好ましくは4以下である）で表されるビスフェノールAのアルキレンオキサイド付加物である。
ビスフェノールAのアルキレンオキサイド付加物としては、例えば、ビスフェノールA〔2,2-ビス(4-ヒドロキシフェニル)プロパン〕のポリオキシプロピレン付加物、ビスフェノールAのポリオキシエチレン付加物が挙げられる。これらの1種又は2種以上を用いることが好ましい。
ビスフェノールAのアルキレンオキサイド付加物の量は、アルコール成分中、好ましくは70モル％以上、より好ましくは90モル％以上、更に好ましくは95モル％以上であり、そして、100モル％以下であり、更に好ましくは100モル％である。 The aromatic diol is preferably an alkylene oxide adduct of bisphenol A, more preferably of the formula (I) :.

(In the formula, R ¹ O and OR ² are oxyalkylene groups, R ¹ and R ² are independently ethylene or propylene groups, and x and y indicate the average number of adducts of the alkylene oxide, which are positive. An alkylene oxide of bisphenol A represented by a number, the sum of x and y being 1 or greater, preferably 1.5 or greater, and 16 or less, preferably 8 or less, more preferably 4 or less). It is an adduct.
Examples of the alkylene oxide adduct of bisphenol A include a polyoxypropylene adduct of bisphenol A [2,2-bis (4-hydroxyphenyl) propane] and a polyoxyethylene adduct of bisphenol A. It is preferable to use one or more of these.
The amount 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, and 100 mol% or less, and further, in the alcohol component. It is preferably 100 mol%.

In addition to aromatic diols, linear or branched aliphatic diols, alicyclic diols, and trihydric or higher polyhydric alcohols may be contained as alcohol components.
Examples of the linear or branched aliphatic diol include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, and 1,4-butanediol. , 2,3-Butanediol, 2,2-dimethyl-1,3-propanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1 , 12-Dodecanediol.
Examples of the alicyclic diol include hydrogenated bisphenol A [2,2-bis (4-hydroxycyclohexyl) propane] and alkylene oxide having 2 or more and 4 or less carbon atoms of hydrogenated bisphenol A (average number of added moles 2 or more and 12). The following) Additives can be mentioned.
Examples of the trihydric or higher polyhydric alcohol include glycerin, pentaerythritol, trimethylolpropane, and sorbitol.
These alcohol components can be used alone or in combination of two or more.

By containing an aromatic dicarboxylic acid as a carboxylic acid component, a toner having excellent low-temperature fixability, high-temperature offset resistance, and durability can be obtained.
Examples of the aromatic dicarboxylic acid include phthalic acid, isophthalic acid, and terephthalic acid. Among these, isophthalic acid or terephthalic acid is preferable, and terephthalic acid is more preferable, from the viewpoint of further improving the low temperature fixability, high temperature offset resistance, and durability of the toner.
The amount of the aromatic dicarboxylic acid is preferably 50 mol% or more, more preferably 60 mol% or more, and further, from the viewpoint of further improving the low temperature fixability, high temperature offset resistance, and durability of the toner. It is preferably 70 mol% or more, and 100 mol% or less, preferably 95 mol% or less, more preferably 90 mol% or less, still more preferably 85 mol% or less.

Examples of the carboxylic acid component other than the aromatic dicarboxylic acid include other dicarboxylic acids and polyvalent carboxylic acids having a trivalent or higher valence.
Examples of other dicarboxylic acids include aliphatic dicarboxylic acids and alicyclic dicarboxylic acids. Of these, aliphatic dicarboxylic acids are preferable.
As the aliphatic dicarboxylic acid, an aliphatic dicarboxylic acid having 8 to 14 carbon atoms in the main chain is preferable.
The aliphatic dicarboxylic acid is preferably a linear aliphatic dicarboxylic acid.
The carbon number of the main chain of the aliphatic dicarboxylic acid is preferably 10 or more and 14 or less.
Examples of the aliphatic dicarboxylic acid having 8 or more and 14 or less carbon atoms in the main chain include sebacic acid, dodecanedioic acid, and tetradecanedioic acid. Among these, sebacic acid, dodecanedioic acid, and tetradecanedioic acid are preferable from the viewpoint of further improving the low temperature fixability, high temperature offset resistance, and durability of the toner.
The amount of the aliphatic dicarboxylic acid having 8 or more and 14 or less carbon atoms in the main chain is preferably 2 mol% or more in the carboxylic acid component from the viewpoint of further improving the low temperature fixability, high temperature offset resistance, and durability of the toner. , More preferably 3 mol% or more, still more preferably 5 mol% or more, and preferably 30 mol% or less, more preferably 20 mol% or less, still more preferably 15 mol% or less, still more preferably 10 mol%. It is as follows.

Examples of the aliphatic dicarboxylic acid other than the aliphatic dicarboxylic acid having 8 or more and 14 or less carbon atoms in the main chain include an aliphatic dicarboxylic acid having 7 or less carbon atoms and an aliphatic dicarboxylic acid having 15 or more carbon atoms. Examples of these are oxalic acid, malonic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, succinic acid, adipic acid, alkyl groups with 1 to 20 carbon atoms or 2 to 20 carbon atoms. Examples include succinic acid substituted with an alkenyl group. Examples of the succinic acid substituted with an alkyl group having 1 to 20 carbon atoms or an alkenyl group having 2 to 20 carbon atoms include dodecyl succinic acid, dodecenyl succinic acid, and octenyl succinic acid.

The trivalent or higher valent carboxylic acid is preferably a trivalent carboxylic acid, and examples thereof include trimellitic acid. Of these, trimellitic acid or its anhydride is preferable.
When a trivalent or higher polyvalent carboxylic acid is contained, the amount of the trivalent or higher polyvalent carboxylic acid is preferably 1 mol% or more, more preferably 5 mol% or more, still more preferably 10 mol% in the carboxylic acid component. And more, preferably 30 mol% or less, more preferably 20 mol% or less, still more preferably 15 mol% or less.
These carboxylic acid components can be used alone or in combination of two or more.

The ratio of the carboxy group of the carboxylic acid component to the hydroxyl group of 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 1.2 or less.

[Vinyl resin segment]
The vinyl-based resin segment is an addition polymer of a raw material monomer containing a styrene-based compound from the viewpoint of further improving the low-temperature fixability, high-temperature offset resistance, and durability of the toner, and the styrene-based compound and the number of carbon atoms are preferable. It is an addition polymer of a raw material monomer containing a vinyl-based monomer having 3 or more and 22 or less aliphatic hydrocarbon groups.

Examples of the styrene-based compound include substituted or unsubstituted styrene. Examples of the substituent include an alkyl group having 1 to 5 carbon atoms, a halogen atom, an alkoxy group having 1 to 5 carbon atoms, a sulfonic acid group or a salt thereof and the like.
Examples of styrene-based compounds include styrenes such as styrene, methylstyrene, α-methylstyrene, β-methylstyrene, tert-butylstyrene, chlorostyrene, chloromethylstyrene, methoxystyrene, styrenesulfonic acid or salts thereof. Be done. Of these, styrene is preferable.
The amount of the styrene-based compound is preferably 50% by mass or more, more preferably 65% by mass, in the raw material monomer of the vinyl-based resin segment from the viewpoint of further improving the low-temperature fixability, high-temperature offset resistance, and durability of the toner. As mentioned above, it is more preferably 70% by mass or more, and 100% by mass or less, preferably 95% by mass or less, more preferably 90% by mass or less, still more preferably 85% by mass or less.

The number of carbon atoms of the hydrocarbon group of the vinyl-based monomer having an aliphatic hydrocarbon group is preferably 3 or more, more preferably 4 or more from the viewpoint of further improving the low-temperature fixability, high-temperature offset resistance, and durability of the toner. , More preferably 6 or more, and preferably 22 or less, more preferably 20 or less, still more preferably 18 or less.

Examples of the aliphatic hydrocarbon group include an alkyl group, an alkynyl group, and an alkenyl group. Among these, an alkyl group or an alkenyl group is preferable, and an alkyl group is preferable. The aliphatic hydrocarbon group may be either branched or linear.
The vinyl-based monomer having an aliphatic hydrocarbon group is preferably an alkyl ester of (meth) acrylic acid. In the case of alkyl esters of (meth) acrylic acid, the hydrocarbon group is the alcohol-side residue of the ester.
Examples of the alkyl ester of (meth) acrylic acid include (meth) acrylic acid (iso) propyl, (meth) acrylic acid (iso) butyl, (meth) acrylic acid (iso) hexyl, and (meth) acrylic acid cyclohexyl. (Meta) Acrylic Acid (Iso) Octyl (hereinafter, also referred to as (Meta) Acrylic Acid 2-Ethylhexyl), (Meta) Acrylic Acid (Iso) Decyl, (Meta) Acrylic Acid (Iso) Dodecyl (hereinafter, (Meta) Acrylic) Examples thereof include acid (iso) lauryl), (meth) acrylic acid (iso) palmityl, (meth) acrylic acid (iso) stearyl, and (meth) acrylic acid (iso) behenyl. Among these, 2-ethylhexyl (meth) acrylate is preferable.
Here, "alkyl (meth) acrylate" means alkyl acrylate or alkyl methacrylate. Further, with respect to the alkyl moiety, "(iso)" means normal alkyl or isoalkyl.

The amount of the vinyl-based monomer having an aliphatic hydrocarbon group having 3 to 22 carbon atoms is included in the raw material monomer of the vinyl-based resin segment from the viewpoint of further improving the low-temperature fixability, high-temperature offset resistance, and durability of the toner. It is preferably 5% by mass or more, more preferably 10% by mass or more, further preferably 15% by mass or more, and preferably 50% by mass or less, more preferably 35% by mass or less, still more preferably 25% by mass or less. Is.

Examples of other raw material monomers include ethylenically unsaturated monoolefins such as ethylene and propylene; conjugated dienes such as butadiene; halovinyls such as vinyl chloride; vinyl esters such as vinyl acetate and vinyl propionate; (meth). ) (Meta) acrylic acid aminoalkyl esters such as dimethylaminoethyl acrylate; vinyl ethers such as methyl vinyl ether; vinylidene halides such as vinylidene chloride; N-vinyl compounds such as N-vinylpyrrolidone.

Among the raw material monomers in the vinyl resin segment, the total amount of the styrene compound and the vinyl monomer having an aliphatic hydrocarbon group having 3 to 22 carbon atoms is the low temperature fixability, high temperature offset resistance, and durability of the toner. From the viewpoint of further improving, it is preferably 80% by mass or more, more preferably 90% by mass or more, further preferably 95% by mass or more, and 100% by mass or less, preferably 100% by mass.

[Constituent units derived from bireactive monomers]
Since the composite resin (A) connects the polyester resin segment and the vinyl resin segment, the composite resin (A) has a structural unit derived from both reactive monomers bonded to the polyester resin segment and the vinyl resin segment via a covalent bond.
The “structural unit derived from a bireactive monomer” means a unit in which the functional group and the vinyl moiety of the bireactive monomer have reacted.
Examples of the bireactive monomer include vinyl-based monomers having 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. Among these, from the viewpoint of reactivity, a vinyl-based monomer having a hydroxyl group or a carboxy group is preferable, and a vinyl-based monomer having a carboxy group is more preferable.
Examples of the bireactive monomer include acrylic acid, methacrylic acid, fumaric acid, maleic acid and the like. Among these, acrylic acid or methacrylic acid is preferable, and acrylic acid is more preferable, from the viewpoint of reactivity of both the polycondensation reaction and the addition polymerization reaction.
The amount of the structural unit derived from both reactive monomers is preferably 1 mol part or more, more preferably 5 mol parts or more, still more preferably 8 parts, based on 100 mol parts of the alcohol component of the polyester resin segment of the composite resin (A). It is more than a molar part, and preferably 30 parts by mole or less, more preferably 25 mol parts or less, still more preferably 20 mol parts or less.

The amount of the polyester resin segment is preferably 40% by mass or more, more preferably 50% by mass or more in the composite resin (A) from the viewpoint of further improving the low temperature fixability, high temperature offset resistance, and durability of the toner. More preferably 60% by mass or more, further preferably 70% by mass or more, still more preferably 75% by mass or more, and preferably 95% by mass or less, more preferably 85% by mass or less, still more preferably 80% by mass or less. Is.
The amount of the vinyl-based resin segment is preferably 5% by mass or more, more preferably 10% by mass or more in the composite resin (A) from the viewpoint of further improving the low-temperature fixability, high-temperature offset resistance, and durability of the toner. , More preferably 15% by mass or more, still more preferably 18% by mass or more, and preferably 60% by mass or less, more preferably 50% by mass or less, still more preferably 40% by mass or less, still more preferably 30% by mass. Hereinafter, it is more preferably 25% by mass or less.
The amount of the structural unit derived from both reactive monomers is preferably 0.1% by mass or more, more preferably 0.1% by mass or more in the composite resin (A) from the viewpoint of further improving the low temperature fixability, high temperature offset resistance, and durability of the toner. It is 0.5% by mass or more, more preferably 0.8% by mass or more, and preferably 10% by mass or less, more preferably 5% by mass or less, still more preferably 3% by mass or less.
The total amount of the polyester resin segment, the vinyl resin segment, and the structural unit derived from the bireactive monomer in the composite resin (A) is from the viewpoint of further improving the low temperature fixability, high temperature offset resistance, and durability of the toner. , Preferably 80% by mass or more, more preferably 90% by mass or more, still more preferably 93% by mass or more, still more preferably 95% by mass or more, and 100% by mass or less, preferably 99% by mass or less. Is.

The above amount is calculated based on the ratio of the amounts of the raw material monomer, the bireactive monomer, and the polymerization initiator of the polyester resin segment and the vinyl resin segment, and the amount of dehydration due to polycondensation in the polyester resin segment and the like is not taken into consideration. When a polymerization initiator is used, the mass of the polymerization initiator is included in the vinyl resin segment for calculation.

[Physical characteristics of amorphous composite resin (A)]
The acid value of the composite resin (A) is preferably 5 mgKOH / g or more, more preferably 8 mgKOH / g or more, still more preferably 10 mgKOH / g or more, and the toner has low temperature fixability, high temperature offset resistance, and durability. From the viewpoint of further improving the properties, it is preferably 40 mgKOH / g or less, more preferably 35 mgKOH / g or less, still more preferably 20 mgKOH / g or less, still more preferably 17 mgKOH / g or less, still more preferably 15 mgKOH / g or less, still more preferably. It is 12 mgKOH / g or less.

The hydroxyl value of the composite resin (A) is preferably 5 mgKOH / g or more, more preferably 15 mgKOH / g or more, still more preferably 20 mgKOH / g or more, still more preferably 25 mgKOH / g or more, and preferably 60 mgKOH / g or more. Hereinafter, it is more preferably 50 mgKOH / g or less, still more preferably 40 mgKOH / g or less.

The softening point of the composite resin (A) is preferably 70 ° C. or higher, more preferably 90 ° C. or higher, further preferably 100 ° C. or higher, still more preferably 110 ° C. or higher, and more preferably 110 ° C. or higher, from the viewpoint of further improving the low temperature fixability. It is preferably 140 ° C. or lower, more preferably 135 ° C. or lower, and even more preferably 130 ° C. or lower.

The glass transition temperature of the composite resin (A) is preferably 45 ° C. or higher, more preferably 48 ° C. or higher, still more preferably 50 ° C., from the viewpoint of further improving the low temperature fixability, high temperature offset resistance, and durability of the toner. Above, it is more preferably 52 ° C. or higher, and preferably 80 ° C. or lower, more preferably 70 ° C. or lower, still more preferably 65 ° C. or lower.

The acid value, hydroxyl value, softening point, and glass transition temperature of the composite resin (A) can be appropriately adjusted according to the type and amount of the raw material monomer used, and the production conditions such as reaction temperature, reaction time, and cooling rate. , And those values are determined by the method described in the examples.
When two or more types of the composite resin (A) are used in combination, it is preferable that the acid value, hydroxyl value, softening point, and glass transition temperature of any of the resins are within the above ranges.

[Manufacturing method of amorphous composite resin (A)]
The method for producing the composite resin (A) includes, for example, polycondensation of an alcohol component and a carboxylic acid component, and addition polymerization with a raw material monomer and a bireactive monomer of a vinyl resin segment, for example. The following methods (i) to (iii) can be mentioned.
(i) Method of polycondensation with alcohol component and carboxylic acid component, followed by addition polymerization with raw material monomer and bireactive monomer of addition polymerization resin segment
(ii) A method of polycondensation with a raw material monomer of a polyester resin segment after addition polymerization with a raw material monomer of a vinyl resin segment and a bireactive monomer.
(iii) Method of performing polycondensation by alcohol component and carboxylic acid component and addition polymerization by addition polymerization resin segment raw material monomer and bireactive monomer in parallel The polycondensation and addition of the methods (i) to (iii) above. It is preferable that the polymerization is carried out in the same container.
The composite resin is preferably produced by the method (i) or (ii) above because of the high degree of freedom in the reaction temperature of the polycondensation reaction, and the above (i) is more preferable.
From the viewpoint of reactivity, catalysts such as an esterification catalyst and an esterification co-catalyst may be used, and a polymerization initiator and a polymerization inhibitor may be used.

In polycondensation, if necessary, an esterification catalyst such as di (2-ethylhexanoic acid) tin (II), dibutyltin oxide, and titanium diisopropylate bistriethanolaminate is used as the total amount of alcohol component and carboxylic acid component. 0.01 part by mass or more and 5 parts by mass or less with respect to 100 parts by mass; 100 parts by mass of total amount of alcohol component and carboxylic acid component of esterification co-catalyst such as gallic acid (same as 3,4,5-trihydroxybenzoic acid) 0.001 part by mass or more and 0.5 part by mass or less; and if necessary, add a radical polymerization inhibitor such as 4-tert-butylcatechol to 0.001 part by mass or more and 0.5 part by mass with respect to 100 parts by mass of the total amount of alcohol component and carboxylic acid component. It may be polycondensed using the following.
The polycondensation temperature is preferably 120 ° C. or higher, more preferably 160 ° C. or higher, further preferably 180 ° C. or higher, and preferably 250 ° C. or lower, more preferably 230 ° C. or lower.
The polycondensation may be carried out in an inert gas atmosphere.
From the viewpoint of further advancing the reaction with the polycondensation and, if necessary, the bireactive monomer, a part of the carboxylic acid component is subjected to polycondensation, then addition polymerization is carried out, and then the reaction temperature is raised again, and the rest is reacted. It is preferable to add it to the system.

In the addition polymerization, the raw material monomer and the bireactive monomer of the vinyl resin segment are addition-polymerized.
The temperature of the addition polymerization is preferably 110 ° C. or higher, more preferably 130 ° C. or higher, further preferably 150 ° C. or higher, and preferably 230 ° C. or lower, more preferably 220 ° C. or lower. Further, it is preferable to accelerate the reaction by reducing the pressure of the reaction system in the latter half of the polymerization.

Examples of the polymerization initiator for addition polymerization include peroxides such as di-tert-butyl peroxide, persulfates such as sodium persulfate, and 2,2'-azobis (2,4-dimethylvaleronitrile). A known polymerization initiator such as an azo compound can be used.
The amount of the polymerization initiator used is preferably 1 part by mass or more, more preferably 3 parts by mass or more, still more preferably 5 parts by mass or more, and preferably 5 parts by mass or more, based on 100 parts by mass of the raw material monomer of the vinyl resin segment. Is 20 parts by mass or less, more preferably 15 parts by mass or less, still more preferably 10 parts by mass or less.

The content of the composite resin (A) is 0.5% by mass or more, preferably 1% by mass, from the viewpoint of obtaining excellent low-temperature fixability, high-temperature offset resistance, and durability with respect to the total amount of the binder resin. % Or more, more preferably 2% by mass or more, further preferably 3% by mass or more, still more preferably 5% by mass or more, and from the viewpoint of obtaining excellent low-temperature fixability, high-temperature offset resistance, and durability. It is 15% by mass or less, preferably 13% by mass or less, more preferably 10% by mass or less, still more preferably 8% by mass or less, still more preferably 7% by mass or less.

<Amorphous polyester resin (B)>
From the viewpoint of further improving the low temperature fixability, high temperature offset resistance, and durability of the toner, the toner is preferably an amorphous polyester resin (B) as a binder resin (hereinafter, "polyester resin (B)". )")including.
Examples of the polyester resin (B) include a polyester resin and a modified polyester resin. Examples of the modified polyester-based resin include a urethane-modified product of a polyester resin, an epoxy-modified product of a polyester resin, and a composite resin containing a polyester resin segment and a vinyl-based resin segment. Among these, a polyester resin or a urethane modified product thereof is preferable, and a polyester resin is more preferable.

The polyester resin is, for example, a condensate of an alcohol component and a carboxylic acid component.
Examples of the alcohol component include aromatic diols, linear or branched aliphatic diols, alicyclic diols, and trihydric or higher polyhydric alcohols. Among these, aromatic diols are preferable.
The aromatic diol is preferably an alkylene oxide adduct of bisphenol A, and more preferably an alkylene oxide adduct of bisphenol A represented by the above formula (I).
The amount 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, and 100 mol% or less, and further, in the alcohol component. It is preferably 100 mol%.

Examples of the alkylene oxide adduct of bisphenol A, the linear or branched aliphatic diol, the alicyclic diol, and the trihydric or higher polyhydric alcohol are the same as those in the above-mentioned composite resin (A).

Examples of the carboxylic acid component include a dicarboxylic acid and a trivalent or higher valent carboxylic acid. Examples of the dicarboxylic acid include aromatic dicarboxylic acids, linear or branched aliphatic dicarboxylic acids, and alicyclic dicarboxylic acids. Of these, aromatic dicarboxylic acids are preferred.
As the aromatic dicarboxylic acid, isophthalic acid or terephthalic acid is preferable, and terephthalic acid is more preferable.
The amount of aromatic dicarboxylic acid is preferably 20 mol% or more, more preferably 40 mol% or more, still more preferably 60 mol% or more, and preferably 98 mol% or less, more preferably 98 mol% or more, in the carboxylic acid component. It is 95 mol% or less, more preferably 90 mol% or less.

The carboxylic acid component preferably contains a trivalent or higher valent carboxylic acid, and preferably contains trimellitic acid or an anhydride thereof.
The amount of the trivalent or higher polyvalent carboxylic acid is preferably 3 mol% or more, more preferably 5 mol% or more, further preferably 10 mol% or more, and preferably 40 mol% or less in the carboxylic acid component. , More preferably 30 mol% or less, still more preferably 20 mol% or less.

Examples of the aromatic dicarboxylic acid, the linear or branched aliphatic dicarboxylic acid, and the trivalent or higher valent polyvalent carboxylic acid are the same as those in the above-mentioned composite resin (A).
The ratio of the carboxy group of the carboxylic acid component to the hydroxyl group of the alcohol component is the same as in the above-mentioned example of the composite resin (A).
Among the above, the polyester resin (B) preferably contains a polycondensate of an alcohol component containing an aromatic diol and a carboxylic acid component containing an aromatic dicarboxylic acid or a urethane modified product thereof, and preferably contains an aromatic diol. It contains a polycondensate of an alcohol component containing an alcohol component and a carboxylic acid component containing an aromatic dicarboxylic acid.
The content of the polycondensate of the alcohol component containing an aromatic diol and the carboxylic acid component containing an aromatic dicarboxylic acid or the urethane modified product thereof in the polyester resin (B) is preferably 80% by mass or more, more preferably 80% by mass or more. It is 90% by mass or more, more preferably 95% by mass or more, and 100% by mass or less, preferably 100% by mass.

[Physical characteristics of polyester resin (B)]
The acid value of the polyester resin (B) is preferably 5 mgKOH / g or more, more preferably 8 mgKOH / g or more, still more preferably 10 mgKOH / g or more, and preferably 40 mgKOH / g or less, more preferably 30 mgKOH / g. It is g or less, more preferably 20 mgKOH / g or less.

The hydroxyl value of the polyester resin (B) is preferably 5 mgKOH / g or more, more preferably 15 mgKOH / g or more, still more preferably 20 mgKOH / g or more, and preferably 60 mgKOH / g or less, more preferably 50 mgKOH / g. It is g or less, more preferably 40 mgKOH / g or less.

The softening point of the polyester resin (B) is preferably 70 ° C. or higher, more preferably 90 ° C. or higher, still more preferably 110 ° C. or higher, still more preferably 120 ° C. or higher, from the viewpoint of further improving low-temperature fixability. Then, it is preferably 150 ° C. or lower, more preferably 140 ° C. or lower, and further preferably 135 ° C. or lower.

The glass transition temperature of the polyester resin (B) is preferably 50 ° C. or higher, more preferably 55 ° C. or higher, still more preferably 55 ° C. or higher, from the viewpoint of further improving the low temperature fixability, high temperature offset resistance, and durability of the toner. Is 60 ° C. or higher, and preferably 80 ° C. or lower, more preferably 75 ° C. or lower, still more preferably 70 ° C. or lower.

The acid value, hydroxyl value, softening point, and glass transition temperature of the polyester resin (B) can be appropriately adjusted according to the type and amount of the raw material monomer used, and the production conditions such as reaction temperature, reaction time, and cooling rate. Yes, and their values are determined by the method described in the examples.
When two or more types of polyester resin (B) are used in combination, the acid value, hydroxyl value, softening point, and glass transition temperature obtained as a mixture thereof must be within the above ranges. preferable.

The polyester resin (B) is obtained, for example, by polycondensation of an alcohol component and a carboxylic acid component. As the polycondensation condition, for example, the condition shown in the polycondensation in the composite resin (A) described above can be applied.

The mass ratio [(A) / (B)] of the composite resin (A) and the polyester resin (B) is preferable from the viewpoint of further improving the low temperature fixability, high temperature offset resistance, and durability of the toner. 1/99 or more, more preferably 3/97 or more, still more preferably 5/95 or more, and from the viewpoint of further improving low temperature fixability, preferably 60/40 or less, more preferably 45/55 or less, It is more preferably 30/70 or less, still more preferably 20/80 or less, still more preferably 10/90 or less, still more preferably 7/93 or less.

The content of the polyester resin (B) is preferably 40% by mass or more, more preferably 55, from the viewpoint of further improving the low-temperature fixability, high-temperature offset resistance, and durability of the toner in the binder resin of the toner. Mass% or more, more preferably 70% by mass or more, still more preferably 80% by mass or more, still more preferably 90% by mass or more, still more preferably 93% by mass or more, and preferably 99% by mass or less, more preferably. It is 97% by mass or less.

The content of the composite resin (A) and the polyester-based resin (B) in the binder resin of the toner is preferably 80% by mass or more, more preferably 90% by mass or more, still more preferably 95% by mass or more, and , 100% by weight or less, and preferably 100% by weight.

<Wax (W)>
Examples of the wax (W) include hydrocarbon wax, ester wax, silicone wax, and fatty acid amide wax.
Examples of the hydrocarbon wax include mineral or petroleum hydrocarbon wax such as paraffin wax and Fishertroph wax; and synthetic hydrocarbon wax such as polyolefin wax such as polyethylene wax, polypropylene wax and polybutene wax.
Examples of the ester wax include mineral or petroleum ester wax such as Montan wax; plant-based ester wax such as carnauba wax, rice wax and candelilla wax; and animal-based ester wax such as honey wax.
Examples of the fatty acid amide wax include oleic acid amide and stearic acid amide. These can be used alone or in combination of two or more.
Among these, fatty acid amide wax or ester wax is preferable, and ester wax is more preferable, from the viewpoint of further improving the low temperature fixability, gloss, and carrier stain resistance of the toner.

The melting point of the wax (W) is preferably 60 ° C. or higher, more preferably 70 ° C. or higher, and preferably 160 ° C. or lower, more preferably 150 ° C. or lower, still more preferably 140 ° C. or lower.
When two or more types of wax (W) are used in combination, the melting point of each wax is preferably within the above range.

The mass ratio [(A) / (W)] of the composite resin (A) and the wax (W) is 0.2 or more, preferably 0.3 or more, more preferably 0.5 or more, from the viewpoint of obtaining excellent durability. It is more preferably 0.8 or more, and from the viewpoint of obtaining excellent high temperature offset resistance, it is 3.5 or less, more preferably 2.5 or less, still more preferably 2 or less, still more preferably 1.5 or less.
The content of wax (W) is preferably 0.1 part by mass or more, more preferably 1 part by mass or more, and further preferably 2 parts by mass with respect to 100 parts by mass of the binder resin from the viewpoint of improving high temperature offset resistance. From the viewpoint of further improving durability, it is preferably 20 parts by mass or less, more preferably 10 parts by mass or less, and further preferably 7 parts by mass or less.

<Charge control agent>
The toner may contain a charge control agent.
The charge control agent may contain either a positive charge control agent or a negative charge control agent.
Positive charge control agents include niglosin dyes such as "niglosin base EX", "oil black BS", "oil black SO", "bontron N-01", "bontron N-04", and "bontron N-07". , "Bontron N-09", "Bontron N-11" (all manufactured by Orient Chemical Industries Co., Ltd.), etc .; Triphenylmethane dyes containing tertiary amines as side chains, quaternary ammonium salt compounds, for example, " Bontron P-51 "(manufactured by Orient Chemical Industries Co., Ltd.), cetyltrimethylammonium bromide," COPY CHARGE PX VP435 "(manufactured by Clariant), etc .; Imidazole derivatives such as "PLZ-2001" and "PLZ-8001" (manufactured by Shikoku Kasei Kogyo Co., Ltd.); styrene-acrylic resins such as "FCA-701PT" (manufactured by Fujikura Kasei Co., Ltd.) Be done.

Negative charge control agents include metal-containing azo dyes such as "Varifast Black 3804", "Bontron S-31", "Bontron S-32", "Bontron S-34", and "Bontron S-36" ( (Manufactured by Orient Chemical Industry Co., Ltd.), "Eisenspiron Black TRH", "T-77" (manufactured by Hodoya Chemical Industry Co., Ltd.), etc .; Metal compounds of benzylic acid compounds, for example, "LR-147", " LR-297 "(above, manufactured by Nippon Carlit Co., Ltd.), etc .; Metal compounds of salicylic acid compounds, for example," Bontron E-81 "," Bontron E-84 "," Bontron E-88 "," Bontron E-304 " (The above is manufactured by Orient Chemical Industry Co., Ltd.), "TN-105" (manufactured by Hodoya Chemical Industry Co., Ltd.), etc .; Copper phthalocyanine dye; Quadruple ammonium salt, for example, "COPY CHARGE NX VP434" (manufactured by Clariant), Nitro Imidazole derivatives and the like; organic metal compounds and the like can be mentioned.
Among the charge control agents, a negative charge control agent is preferable, and a metal compound of a benzylic acid compound is more preferable.

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 or less, more preferably 5 parts by mass, based on 100 parts by mass of the binder resin. Hereinafter, it is more preferably 3 parts by mass or less, still more preferably 2 parts by mass or less.

<Colorant>
The toner may contain a colorant.
As the colorant, all dyes, pigments, etc. used as colorants for toner can be used, and 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, disazoero, etc. 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 improving the image density of the toner. Parts or less, more preferably 20 parts by mass or less, still more preferably 10 parts by mass or less.

The toner may also contain additives such as magnetic powder, fluidity improver, conductivity modifier, reinforcing filler such as fibrous substance, antioxidant, antiaging agent, and cleaning property improver.

[Toner manufacturing method]
The toner may be a toner obtained by any known method such as a melt-kneading method, an emulsification phase inversion method, a polymerization method, or an emulsion aggregation method, but from the viewpoint of productivity and dispersibility of the colorant, the toner is melted. Grinded toner by the kneading method is preferable.

In the case of pulverized toner, the method for producing the toner is, for example, step 1: a step of melt-kneading a toner raw material containing a composite resin (A) and a wax (W), and step 2: a melt mixture obtained in step 1. Includes steps of crushing and classifying to obtain toner particles.
The mass ratio [(A) / (W)] of the composite resin (A) and wax (W) is 0.2 or more and 3.5 or less from the viewpoint of obtaining toner with excellent low-temperature fixability, high-temperature offset resistance, and durability. be.

In step 1, the toner raw material may contain other additives such as a polyester resin (B), a charge control agent, and a colorant. It is preferable that these toner raw materials are mixed in advance with a mixer such as a Henschel mixer or a ball mill and then supplied to the kneader.
The temperature of melt-kneading is preferably 80 ° C. or higher, more preferably 100 ° C. or higher, further preferably 120 ° C. or higher, and preferably 160 ° C. or lower, preferably 150 ° C. or lower.
The melt kneading in step 1 can be carried out using a known kneader such as a closed kneader, a single-screw extruder, a twin-screw extruder, or an open roll type kneader. From the viewpoint of melting and mixing the toner raw materials, a twin-screw extruder that can be set to high temperature conditions is preferable.
The molten mixture obtained in step 1 is cooled to the extent that it can be pulverized, and then subjected to the subsequent step 2.

The pulverization in step 2 may be performed in multiple stages. For example, the resin kneaded product obtained by curing the melt mixture may be roughly pulverized to 1 mm or more and 5 mm or less, and then finely pulverized to a desired particle size.
Examples of the crusher preferably used for coarse crushing include a hammer mill, an atomizer, and a Rohtoplex. Examples of the pulverizer preferably used for fine pulverization include a fluidized bed type jet mill, a collision plate type jet mill, and a rotary mechanical type mill. From the viewpoint of pulverization efficiency, it is preferable to use a fluidized bed type jet mill or a collision plate type jet mill, and it is more preferable to use a collision plate type jet mill.

Examples of the classifier used for classification include a rotor type classifier, an air flow type classifier, an inertial type classifier, and a sieve type classifier. In the classification step, the pulverized product removed due to insufficient pulverization may be subjected to the pulverization step again, or the pulverization step and the classification step may be repeated as necessary.

The volume median particle size (D ₅₀ ) of the toner particles is preferably 2 μm or more, more preferably 3 μm or more, still more preferably 4 μm or more, and preferably 10 μm or less, from the viewpoint of obtaining a high-quality image. It is preferably 8 μm or less, more preferably 6 μm or less.

The toner is preferably treated by adding a fluidizing agent or the like as an external additive to the surface of the toner particles.
Examples of the external additive include hydrophobic fine particles, titanium oxide fine particles, alumina fine particles, cerium oxide fine particles, inorganic fine particles such as carbon black, and polymer fine particles such as polycarbonate, polymethyl methacrylate, and silicone resin. Among these, hydrophobic silica is preferable.
When an external additive is used, the amount of the external additive added is preferably 1 part by mass or more, more preferably 2 parts by mass or more, and preferably 5 parts by mass or less, based on 100 parts by mass of the toner particles. It is more preferably 4.5 parts by mass or less, still more preferably 4 parts by mass or less.

The toner is used for developing a latent image formed by an electrophotographic method, an electrostatic recording method, an electrostatic printing method, or the like. The toner can be used as a one-component developer or mixed with a carrier as a two-component developer.

Hereinafter, the present invention will be specifically described 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 methods.

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

[Resin softening point, maximum endothermic temperature, glass transition temperature]
(1) Softening point Using a flow tester "CFT-500D" (manufactured by Shimadzu Corporation), a 1 g sample is heated at a heating rate of 6 ° C / min, and a load of 1.96 MPa is applied by a plunger to a diameter of 1 mm. , Extrude from a 1 mm long 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 used as the softening point.
(2) Temperature of the highest peak of endothermic cooling using a differential scanning calorimeter "Q-20" (manufactured by TA Instruments Japan Co., Ltd.) from room temperature (20 ° C) to 0 ° C at a temperature lowering rate of 10 ° C / min. The sample is held as it is for 1 minute, and then the measurement is performed while raising the temperature to 180 ° C 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 maximum endothermic temperature.
(3) Glass transition temperature Using a differential scanning calorimeter "Q-20" (manufactured by TA Instruments Japan Co., Ltd.), weigh 0.01 to 0.02 g of the sample into an aluminum pan, raise the temperature to 200 ° C, and then raise the temperature to 200 ° C. Cool from temperature 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 temperature at the intersection of the extension of the baseline below the maximum peak temperature of heat absorption and the tangent line indicating the maximum slope from the rising portion of the peak to the peak of the peak is defined as the glass transition temperature.

[Melting point of wax]
Using the differential scanning calorimeter "Q100" (manufactured by TA Instruments Japan Co., Ltd.), weigh 0.02 g of the sample into an aluminum pan, raise the temperature to 200 ° C, and then lower the temperature from 200 ° C to 10 ° C / min. Cool to 0 ° C. Next, the sample is heated at a heating rate of 10 ° C./min, the amount of heat is measured, and the maximum peak temperature of endotherm is taken as the melting point.

[Volume medium particle size of toner particles (D ₅₀ )]
The volume median particle size (D ₅₀ ) of the toner particles is measured as follows.
-Measuring machine: "Coulter Multisizer (registered trademark) III" (manufactured by Beckman Coulter Co., Ltd.)
・ Aperture diameter: 50 μm
-Analysis software: "Multisizer (registered trademark) III version 3.51" (manufactured by Beckman Coulter Co., Ltd.)
-Electrolytic solution: "Isoton (registered trademark) II" (manufactured by Beckman Coulter Co., Ltd.)
-Dispersion: Polyoxyethylene lauryl ether "Emargen (registered trademark) 109P" [manufactured by Kao Co., Ltd., HLB (Hydrophile-Lipophile Balance) = 13.6] was dissolved in the electrolyte to obtain a dispersion with a concentration of 5% by mass. rice field.
-Dispersion conditions: To 5 mL of the above dispersion, add 10 mg of the measurement sample of the dried toner particles, disperse for 1 minute with an ultrasonic disperser, then add 25 mL of electrolyte, and further add to the ultrasonic disperser. The mixture was dispersed for 1 minute to prepare a sample dispersion.
-Measurement conditions: By adding the sample dispersion to 100 mL of the electrolytic solution, the particle size of 30,000 particles is adjusted to a concentration that can be measured in 20 seconds, and then 30,000 particles are measured and the particle size is measured. The volume median particle size (D ₅₀ ) was determined from the distribution.

[Manufacturing of resin]
Manufacturing Examples A1 to A3 (Composite Resins A-1 to A-3)
Raw polyester monomers other than trimellitic acid anhydride shown in Table 1 are placed in a 10-liter four-necked flask equipped with a thermometer, a stainless stir bar, a flow-down condenser equipped with a dehydration tube, and a nitrogen introduction tube. The temperature was raised to 160 ° C in a mantle heater in the atmosphere. A mixture of the raw material monomer of the vinyl resin segment, the bireactive monomer and the polymerization initiator was added dropwise thereto to carry out the polymerization. Then, an esterification catalyst was added, and the temperature was raised to 210 ° C. over 5 hours. Then, trimellitic acid anhydride was added, the temperature was raised to 220 ° C., and the reaction was carried out at 8.0 kPa until the softening point shown in the table was reached to obtain composite resins A-1 to A-3.

Production example B1 (resin B-1)
Raw polyester monomers other than trimellitic acid anhydride shown in Table 2 are placed in a 10 L four-necked flask equipped with a thermometer, a stainless stir bar, a flow-down condenser equipped with a dehydration tube, and a nitrogen introduction tube, and a nitrogen atmosphere is provided. In a mantle heater, polycondensation was carried out at 210 ° C. for 7 hours. After adding trimellitic acid anhydride at 200 ° C, the temperature is raised to 210 ° C, a polycondensation reaction is carried out, and the reaction is carried out until the softening point reaches the softening point shown in the table to obtain the resin (resin B-1). Obtained.

[Manufacturing of toner]
Examples 1 to 8 and Comparative Examples 1 to 3
Bundling resin, colorant "ECB-301" (manufactured by Dainichi Seika Kogyo Co., Ltd.) 5 parts by mass, charge control agent "LR-147" (manufactured by Nippon Carlit Co., Ltd.) 1 part by mass, in the ratio shown in Table 3. Wax "Carnauba Wax C1" (manufactured by Hiroyuki Kato Co., Ltd., melting point: 80 ° C) or "paraffin wax HNP-9" (manufactured by Nippon Seiwa Co., Ltd., melting point 80 ° C) at the ratio shown in Table 3 with a Henschel mixer. After stirring well, melt-kneading was performed using a co-rotating twin-screw extruder having a total length of the kneaded portion of 1560 mm, a screw diameter of 42 mm, and a barrel inner diameter of 43 mm. The rotation speed of the roll was 200 r / min, the set heating temperature in the roll was 90 ° C., the temperature of the kneaded product was 140 ° C., the supply speed of the kneaded product was 10 kg / hour, and the average residence time was about 18 seconds. The obtained kneaded product is cooled from 140 ° C. to 50 ° C. for 1.5 hours, rolled and cooled at 50 ° C. with a cooling roller, allowed to stand at 45 ° C. for 4 hours, and then subjected to a medium volume particle size (D _{50) with a jet mill.} ) 5.5 μm toner particles were obtained.

With respect to 100 parts by mass of the obtained toner particles, 1.5 parts by mass of the external additive "Aerosil R-972" (hydrophobic silica, manufactured by Nippon Aerosil Co., Ltd., number average particle diameter: 16 nm) and "SI-Y" (hydrophobicity) Silica, manufactured by Nippon Aerosil Co., Ltd., number average particle size: 40 nm) 1.0 part by mass was added and mixed with a Henshell mixer at 3600 r / min for 5 minutes to perform an external additive treatment to obtain toner.

[evaluation]
[Low temperature fixability and high temperature offset resistance]
Toner was mounted on a device that was an improvement of the fixing machine of the copying machine "AR-505" (manufactured by Sharp Corporation) so that it could be fixed outside the device, and printed matter was obtained in an unfixed state (printed area: 2 cm). × 12 cm, adhesion amount: 0.5 mg / cm ² ). After that, using a fixing machine (fixing speed 300 mm / sec) adjusted so that the total fixing pressure becomes 40 kgf, the temperature of the fixing roll is gradually increased from 100 ° C to 240 ° C by 5 ° C, and unfixed at each temperature. A fixing test was performed on the printed matter in the state. A cellophane adhesive tape "UNICEF cellophane" (manufactured by Mitsubishi Pencil Co., Ltd., width: 18 mm, JIS Z 1522) is attached to the image part of the obtained printed matter, passed through a fixing roller set at 30 ° C, and then the tape is peeled off. rice field. "CopyBond SF-70NA" (manufactured by Sharp Corporation, 75g / m ² ) was used as the fixing paper.
The optical reflection density before and after the tape was applied was measured using a reflection densitometer "RD-915" (manufactured by Gretag Macbeth), and the ratio of the two (after peeling / before applying x 100) was initially 90%. The temperature of the fixing roller exceeding the above was set as the minimum fixing temperature. The lower the minimum fixing temperature, the better the low temperature fixing property.
Further, the fixing image obtained above was visually judged, and the lowest temperature of the fixing roll in which the high temperature offset was observed was defined as the high temperature offset temperature. The higher the high temperature offset temperature, the better the high temperature offset resistance. The high temperature offset temperature is preferably 170 ° C. or higher.

〔durability〕
Toner is mounted on the laser printer "Page Presto N-4" (manufactured by Casio Computer Co., Ltd., fixing: contact fixing method, development: non-magnetic one-component development method, development roll diameter: 2.3 cm), temperature 40 ° C, relative humidity. Printing was performed with a diagonal stripe pattern with a blackening rate of 5.5% under the condition of 85%. On the way, a solid black image was printed every 500 sheets, and streaks on the image were confirmed. Durability was evaluated according to the following evaluation criteria, with the number of printed sheets up to the time when streaks were visually observed on the image as the number of sheets in which streaks were generated due to the fusion and adhesion of toner to the developing roll. The results are shown in Table 3. The larger the number of streaks, the better the durability of the toner. The number of sheets is preferably 3,000 or more, more preferably 4,000 or more, and even more preferably 5,000 or more.

As described above, from Examples and Comparative Examples, it can be seen that according to the present invention, a toner having excellent low-temperature fixability, high-temperature offset resistance, and durability can be obtained.

Claims (3)

A toner for static charge image development containing a binder resin containing an amorphous composite resin (A) and an amorphous polyester resin (B) and a wax (W).
The amorphous composite resin (A) is a polycondensate of an alcohol component containing an aromatic diol and a polyvalent carboxylic acid component containing an aromatic dicarboxylic acid (however, it does not have an ester group in the molecule). A constituent unit derived from a bireactive monomer bonded to a polyester resin segment, a vinyl resin segment which is an addition polymer of a raw material monomer containing a styrene compound, and a polyester resin segment and a vinyl resin segment via a covalent bond. And the content of the amorphous composite resin (A) is 0.5% by mass or more and 15% by mass or less with respect to the total amount of the binder resin.
The mass ratio of the amorphous composite resin (A) and the wax (W) [(A) / (W)] is Ri der 0.2 to 3.5,
The polyvalent carboxylic acid component of the amorphous composite resin (A) contains an aliphatic dicarboxylic acid having 8 or more and 14 or less carbon atoms in the main chain, and is contained in the polyvalent carboxylic acid component of the amorphous composite resin (A). , The amount of aliphatic dicarboxylic acid having 8 or more and 14 or less carbon atoms in the main chain is 2 mol% or more and 30 mol% or less.
The amorphous polyester resin (B) is a polycondensate of an alcohol component containing an aromatic diol and a polyvalent carboxylic acid component containing an aromatic dicarboxylic acid (however, it does not have an ester group in the molecule). Including the urethane modified product
Polycarboxylic acid component, the amount of the aromatic dicarboxylic acids, Ru der 60 mol% 98 mol% or more or less, the toner for developing electrostatic images of the amorphous polyester resin (B). The toner for developing an electrostatic charge image according to claim 1, wherein the glass transition temperature of the amorphous composite resin (A) is 45 ° C. or higher. The toner for developing an electrostatic charge image according to claim 1 or 2 , wherein the amorphous composite resin (A) has an acid value of 17 mgKOH / g or less.