JP7019931B2 - Toner for static charge image development - Google Patents

Description

The present invention relates to a toner for developing a static 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, there is a demand for the development of toners for electrophotographics that can achieve high image quality and high speed.

In Patent Document 1, a segment made of a polyester resin (a) 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 in an aqueous medium, and styrene. Obtained in steps (1) and (1) to obtain aggregated particles (1) by aggregating resin particles (X) containing a composite resin containing a vinyl-based resin segment containing a structural unit derived from a system compound. Resin particles (Y) containing polyester resin (b) obtained by polycondensing an alcohol component containing 80 mol% or more of a propylene oxide adduct of bisphenol A with a polyvalent carboxylic acid component on the aggregated particles (1). A method for producing a toner for static charge image development, which comprises a step (2) of obtaining agglomerated particles (2) and a step (3) of fusing the agglomerated particles (2) obtained in the step (2). Is described. According to the manufacturing method, it is described that a toner having excellent low temperature fixing property and heat storage property can be obtained.

In Patent Document 2, an electrophotographic toner containing core-shell particles, wherein the core of the core-shell particles is a segment made of a polyester resin (A1) and a segment made of an addition polymer containing styrene as a constituent unit (A2). The shell contains an amorphous resin (B) obtained by polycondensing an alcohol component containing an aliphatic diol having 2 to 6 carbon atoms and a carboxylic acid component. , Electrophotographic toners containing core-shell particles are described. According to the toner, it is described that a toner having excellent low temperature fixability and hot offset resistance can be obtained.

Japanese Unexamined Patent Publication No. 2016-014872 Japanese Unexamined Patent Publication No. 2014-013384

From the viewpoint of high image quality and high speed, which have been demanded in recent years, even if the image printed with the toner is rubbed while maintaining the low temperature fixing property, stains are less likely to occur and the smear resistance is excellent. Toner is desired. Further, there is a demand for a toner having excellent durability, which is less likely to cause printing defects due to cracking or adhesion of the toner even at a high temperature.
The toners described in Patent Documents 1 and 2 are not always satisfactory in terms of the above characteristics.
The present invention relates to a toner for static charge image development which is excellent in low temperature fixing property, smear resistance, and high temperature durability.

The present invention
An electrostatic charge image developing toner containing an amorphous composite resin (A), an amorphous polyester resin (B), and a wax.
The amorphous 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 aliphatic dicarboxylic acid having 8 or more and 14 or less carbon atoms in the main chain. It contains a vinyl resin segment which is an addition polymer of a raw material monomer containing a styrene compound, and a constituent unit derived from a bireactive monomer bonded to a polyester resin segment and a vinyl resin segment via a covalent bond.
Toner for static charge image development in which the solubility parameter (SP value) of the amorphous polyester resin (B) is 11.0 (cal / cm ³ ) ^1/2 or more and 12.5 (cal / cm ³ ) ^1/2 or less. Regarding.

According to the present invention, it is possible to provide a toner for static charge image development which is excellent in low temperature fixing property, smear resistance, and durability at high temperature.

[Toner for developing static charge image]
The toner for static charge image development of the present invention (hereinafter, also simply referred to as “toner”) is an amorphous composite resin (A) (hereinafter, also simply referred to as “composite resin (A)”) and an amorphous polyester-based toner. It contains a resin (B) (hereinafter, also simply referred to as "polyester resin (B)") and a wax.
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 aliphatic dicarboxylic acid having 8 or more and 14 or less carbon atoms in the main chain, and a styrene compound. It contains a vinyl-based resin segment which is an addition polymer of the raw material monomer, and a structural unit derived from a bireactive monomer bonded to the polyester resin segment and the vinyl-based resin segment via a covalent bond.
The solubility parameter (SP value) of the polyester resin (B) is 11.0 (cal / cm ³ ) ^1/2 or more and 12.5 (cal / cm ³ ) ^1/2 or less.
With the above configuration, an electrostatic charge developing toner having excellent low temperature fixing property, smear resistance, and high temperature durability (hereinafter, also simply referred to as "durability") can be obtained. The reason is not clear, but it can be considered as follows.

The toner of the present invention contains a polyester resin (B) having a high solubility parameter (hereinafter, also simply referred to as “SP value”). Polyester resin (B), which has a high SP value, has a high affinity with paper and is excellent in low-temperature fixability, but because it is hydrophilic, hydrophobic wax is poorly dispersed, and it is durable due to the coarse domain of the wax. Is low.
As a countermeasure, by using a hydrophobic composite resin (A) having a specific aliphatic dicarboxylic acid as a carboxylic acid component in combination, the dispersibility of the wax is improved and the durability is improved. Therefore, by using the composite resin (A) and the polyester resin (B) having a high SP value in combination, it is possible to achieve both low temperature fixability and durability. In addition, since the polyester resin (B) having a high SP value has a relatively low affinity with wax, the wax easily bleeds out at the time of fixing, the wax easily appears on the surface of the printed matter, and the smear resistance is also excellent. it is conceivable that.

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 temperature (softening point (° C.) / maximum endothermic temperature (° C.)) in the measuring 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 anhydrate 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 3). The following) is also included.
In the specification, the main chain of an aliphatic dicarboxylic acid means a carbon chain from one carbonyl group to the other carbonyl group, and the carbon number of the main chain also includes the carbon of the carbonyl group.
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) contains an alcohol component containing an aromatic diol and an aliphatic dicarboxylic acid having 8 or more and 14 or less carbon atoms in the main chain from the viewpoint of obtaining a toner having excellent low temperature fixability, smear resistance, and durability. A polyester resin segment which is a polycondensate with a carboxylic acid component, 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 are bonded via a covalent bond. Includes building blocks derived from bireactive monomers.

[Polyester resin segment]
The polyester resin segment is a carboxylic acid containing an alcohol component containing an aromatic diol and an aliphatic dicarboxylic acid having 8 to 14 carbon atoms in the main chain from the viewpoint of obtaining a toner having excellent low temperature fixability, smear resistance, and durability. It is a polycondensate with the components.

（式中、OR及びROはオキシアルキレン基であり、Rはそれぞれ独立にエチレン基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〕のプロピレンオキサイド付加物、ビスフェノールAのエチレンオキサイド付加物が挙げられる。これらは1種又は2種以上を用いてもよい。
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, OR and RO are oxyalkylene groups, R is an ethylene group or a propylene group, respectively, and x and y indicate the average number of adducts of the alkylene oxide, which are positive numbers, respectively. The sum value of y is 1 or more, preferably 1.5 or more, and 16 or less, preferably 8 or less, more preferably 4 or less), which is an alkylene oxide adduct of bisphenol A.
Examples of the alkylene oxide adduct of bisphenol A include a propylene oxide adduct of bisphenol A [2,2-bis (4-hydroxyphenyl) propane] and an ethylene oxide adduct of bisphenol A. These may be used alone or in combination of two or more.
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, further, in the alcohol component. It is preferably 100 mol%.

In addition to the aromatic diol, the alcohol component may contain a linear or branched aliphatic diol, an alicyclic diol, and a polyhydric alcohol having a valence of 3 or more.
Examples of the linear or branched aliphatic diol include ethylene glycol, propylene glycol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, and 2,3. -Butanediol, neopentyl glycol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,12-dodecanediol can be mentioned.
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 are mentioned.
Examples of the trihydric or higher polyhydric alcohol include glycerin, pentaerythritol, trimethylolpropane, and sorbitol.
One or more of these alcohol components may be used.

By containing an aliphatic dicarboxylic acid having 8 or more carbon atoms and 14 or less carbon atoms in the main chain as the carboxylic acid component, a toner having excellent low temperature fixing property, smear resistance and durability can be obtained.
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 suberic acid, sebacic acid, dodecanedioic acid, and tetradecanedioic acid. Among these, sebacic acid, dodecanedioic acid, and tetradecanedioic acid are preferable from the viewpoint of further improving low temperature fixing property, smear resistance, and durability, and dodecanedioic acid is preferable from the viewpoint of further improving smear resistance. ..
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 fixing property, smear resistance, and durability of the toner. It is more preferably 10 mol% or more, still more preferably 15 mol% or more, still more preferably 20 mol% or more, and preferably 30 mol% or less, more preferably 27 mol% or less, still more preferably 25 mol%. Below, it is more preferably 24 mol% or less.

Examples of the carboxylic acid component other than the aliphatic dicarboxylic acid having 8 or more and 14 or less carbon atoms in the main chain include other dicarboxylic acids and polyvalent carboxylic acids having a trivalent value or more.
Examples of other dicarboxylic acids include aromatic dicarboxylic acids, linear or branched aliphatic dicarboxylic acids having 7 or less carbon atoms, linear or branched aliphatic dicarboxylic acids having 15 or more carbon atoms, and alicyclic dicarboxylic acids. Can be mentioned. Among these, aromatic dicarboxylic acids are preferable.
Examples of the aromatic dicarboxylic acid include phthalic acid, isophthalic acid, and terephthalic acid. Among these, isophthalic acid and terephthalic acid are preferable, and terephthalic acid is more preferable.
The amount of aromatic dicarboxylic acid is preferably 30 mol% or more, more preferably 40 mol% or more, still more preferably 50 mol% or more, and preferably 90 mol% or less, more preferably 90 mol% or more, in the carboxylic acid component. It is 85 mol% or less, more preferably 80 mol% or less.

Examples of the linear or branched aliphatic dicarboxylic acid having 7 or less carbon atoms and the linear or branched aliphatic dicarboxylic acid having 15 or more carbon atoms include glutaconic acid, malonic acid, maleic acid, fumaric acid, citraconic acid, and itaconic acid. Examples thereof include acid, glutaconic acid, succinic acid, adipic acid, and succinic acid substituted with an alkyl group having 1 to 20 carbon atoms or an alkenyl group having 2 to 20 carbon atoms. 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. Among 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 2 mol% or more, and preferably 2 mol% or more in the carboxylic acid component. It is 30 mol% or less, more preferably 20 mol% or less, still more preferably 10 mol% or less, still more preferably 5 mol% or less.
As these carboxylic acid components, one kind or two or more kinds may be used.

The equivalent ratio (COOH group / OH group) of the carboxy group of the carboxylic acid component to the hydroxyl group of the alcohol component 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 obtaining a toner having excellent low-temperature fixability, smear resistance, and durability, and is preferably a styrene-based compound and having 3 or more carbon atoms. It is an addition polymer of a raw material monomer containing a vinyl-based monomer having 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 or more and 5 or less carbon atoms, a halogen atom, an alkoxy group having 1 or more and 5 or less carbon atoms, a sulfonic acid group or a salt thereof and the like.
Examples of the styrene-based compound include styrenes such as styrene, methylstyrene, α-methylstyrene, β-methylstyrene, tert-butylstyrene, chlorostyrene, chloromethylstyrene, methoxystyrene, styrenesulfonic acid or salts thereof. Be done. Among these, styrene is preferable.
The amount of the styrene-based compound is preferably 50% by mass or more, more preferably 65% by mass or more in the raw material monomer of the vinyl-based resin segment from the viewpoint of further improving the low-temperature fixability, smear resistance, and durability of the toner. , More preferably 80% by mass or more, and preferably 98% by mass or less, more preferably 95% by mass or less, still more preferably 90% 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 fixing property, smear resistance, and durability of the toner. It is more preferably 6 or more, and preferably 22 or less, more preferably 20 or less, still more preferably 18 or less, still more preferably 14 or less, still more preferably 10 or less.

Examples of the aliphatic hydrocarbon group include an alkyl group, an alkynyl group and an alkenyl group. Among these, an alkyl group and an alkenyl group are 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 or more and 22 or less 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, smear resistance, and durability of the toner. It is preferably 5% by mass or more, more preferably 10% by mass or more, further preferably 13% by mass or more, and preferably 40% by mass or less, more preferably 30% by mass or less, still more preferably 20% by mass or less. be.

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-based resin segment, the total amount of the styrene-based compound and the vinyl-based monomer having an aliphatic hydrocarbon group having 3 or more and 22 or less carbon atoms determines the low-temperature fixability, smear resistance, and durability of the toner. From the viewpoint of further improvement, 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]
The composite resin (A) has a structural unit derived from a bireactive monomer bonded to the polyester resin segment and the vinyl resin segment via a covalent bond in order to connect the polyester resin segment and the vinyl resin segment.
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 the bireactive monomer is preferably 1 mol part or more, more preferably 5 mol parts or more, still more preferably 8 parts with respect to 100 mol parts of the alcohol component of the polyester resin segment of the composite resin (A). It is more than a molar portion, and is preferably 30 mol parts 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, and further, in the composite resin (A), from the viewpoint of further improving the low temperature fixability, smear resistance, and durability of the toner. It is preferably 60% by mass or more, more preferably 70% by mass or more, further 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. be.
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, smear resistance, and durability of the toner. It is more preferably 15% 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 or less.
The amount of the structural unit derived from the bireactive monomer is preferably 0.1% by mass or more, more preferably 0.5 in the composite resin (A) from the viewpoint of further improving the low temperature fixability, smear resistance, and durability of the toner. It is 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 and the vinyl resin segment in the composite resin (A) and the constituent units derived from the bireactive monomers is from the viewpoint of further improving the low temperature fixability, smear resistance, and durability of the toner. It is 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.

The above amount is calculated based on the ratio of the amounts of the polyester resin segment, the raw material monomer of the vinyl resin segment, the bireactive monomer, and the polymerization initiator, and excludes the amount of dehydration due to polycondensation in the polyester resin segment and the like. 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, from the viewpoint of further improving the low temperature fixability, smear resistance, and durability of the toner. It is g or more, and is preferably 40 mgKOH / g or less, more preferably 30 mgKOH / g or less, still more preferably 20 mgKOH / g or less, still more preferably 17 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, from the viewpoint of further improving the low temperature fixability, smear resistance, and durability of the toner. It is g or more, more preferably 25 mgKOH / g or more, and preferably 60 mgKOH / g or less, more preferably 50 mgKOH / g or less, still more preferably 40 mgKOH / g or less, still more preferably 35 mgKOH / g or less.

The softening point of the composite resin (A) is preferably 70 ° C. or higher, more preferably 90 ° C. or higher, still more 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 130 ° C. or lower, still more preferably 120 ° 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. or higher, from the viewpoint of obtaining a toner having excellent low temperature fixability, smear resistance, and durability. It is more preferably 52 ° C. or higher, and preferably 70 ° C. or lower, more preferably 60 ° C. or lower, still more preferably 55 ° C. or lower.

The acid value, hydroxyl value, softening point, and glass transition temperature of the composite resin (A) can be appropriately adjusted depending on 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 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 using a raw material monomer and a bireactive monomer of a vinyl-based resin segment. The methods (i) to (iii) of (i) to (iii) can be mentioned.
(i) A method of addition polymerization using a raw material monomer and a bireactive monomer of an addition polymerization resin segment after polycondensation with an alcohol component and a carboxylic acid component.
(ii) A method of polycondensation with a raw material monomer of a polyester resin segment after addition polymerization with a raw material monomer and a bireactive monomer of a vinyl resin segment.
(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. Polycondensation and addition of the above methods (i) to (iii). 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, a catalyst such as an esterification catalyst or 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), dibutyl tin oxide, titanium diisopropyrate bistriethanolamineate, etc. 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; Esterification co-catalyst such as galvanic acid (same as 3,4,5-trihydroxybenzoic acid) is added to 100 parts by mass of the total amount of alcohol component and carboxylic acid component. On the other hand, 0.001 part by mass or more and 0.5 part by mass or less; and if necessary, 0.001 part by mass or more and 1 part by mass or less of a radical polymerization inhibitor such as 4-tert-butylcatechol with respect to 100 parts by mass of the total amount of alcohol component and carboxylic acid component. It may be polycondensed using.
The temperature of the polycondensation is preferably 120 ° C. or higher, more preferably 160 ° C. or higher, further preferably 180 ° C. or higher, further preferably 200 ° C. or higher, and preferably 250 ° C. or lower, more preferably 240 ° C. or lower. be.
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 may be subjected to polycondensation, then addition polymerization, and then the rest may be added to the reaction system. preferable.

In addition polymerization, the raw material monomer of the vinyl resin segment and the bireactive monomer 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 220 ° C. or lower, more preferably 200 ° C. or lower, still more preferably 180 ° C. or lower. be. 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 the 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 preferably 0.5% by mass or more, more preferably 1% by mass, from the viewpoint of further improving the low-temperature fixability, smear resistance, and durability of the toner in the binder resin of the toner. The above is more preferably 2% by mass or more, further preferably 5% by mass or more, further preferably 8% by mass or more, still more preferably 10% by mass or more, still more preferably 20% by mass or more, still more preferably 25% by mass or more. Yes, and from the viewpoint of further improving the low temperature fixability, smear resistance, and durability of the toner, it is preferably 60% by mass or less, more preferably 55% by mass or less, still more preferably 50% by mass or less, still more preferably. It is 40% by mass or less, more preferably 35% by mass or less.

<Amorphous polyester resin (B)>
Examples of the polyester resin (B) include a polyester resin and a modified polyester resin. Examples of the modified polyester 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 resin segment. Among these, polyester resin or a urethane modified product thereof is preferable, and polyester resin is more preferable.

The polyester resin is, for example, a polycondensate 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, linear or branched aliphatic diols are preferable, and branched aliphatic diols are more preferable.
As the branched aliphatic diol, an aliphatic diol having a hydroxyl group bonded to a secondary carbon atom is preferable.
The number of carbon atoms of the aliphatic diol having a hydroxyl group bonded to the secondary carbon atom is preferably 3 or more and 6 or less.
Examples of the aliphatic diol having a hydroxyl group bonded to the secondary carbon atom include propylene glycol, 1,2-butanediol, 1,3-butanediol, 2,3-butanediol, and 1,2-pentanediol. 1,3-Pentanediol, 1,4-Pentanediol, 2,3-Pentanediol, 2,4-Pentanediol, 1,2-Hexanediol, 1,5-hexanediol, 2,5-Hexanediol, 3 , 3-Diol-1,2-butanediol. Among these, propylene glycol is preferable from the viewpoint of further improving the low temperature fixability, smear resistance, and durability of the toner.
The amount of the aliphatic diol having a hydroxyl group bonded to the secondary carbon atom is preferably 20 mol% or more, more preferably 20 mol% or more in the alcohol component from the viewpoint of further improving the low temperature fixing property, smear resistance, and durability of the toner. It is preferably 40 mol% or more, more preferably 60 mol% or more, still more preferably 70 mol% or more, still more preferably 75 mol% or more, and preferably 100 mol% or less, more preferably 90 mol% or less. It is more preferably 85 mol% or less, still more preferably 82 mol% or less.
Examples of other linear or branched aliphatic diols other than the aliphatic diol having a hydroxyl group bonded to the secondary carbon atom include ethylene glycol, 1,4-butanediol, and neopentyl glycol. Among these, ethylene glycol or 1,4-butanediol is preferable.
The amount of other linear or branched aliphatic diols other than the aliphatic diol having a hydroxyl group bonded to the secondary carbon atom is preferably 10 mol% or more, more preferably 15 mol% or more, in the alcohol component. It is more preferably 18 mol% or more, and preferably 60 mol% or less, more preferably 40 mol% or less, still more preferably 30 mol% or less, still more preferably 25 mol% or less, still more preferably 23 mol% or less. Is.

Examples of the aromatic 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 polyvalent carboxylic acid having a valence of 3 or more. Examples of the dicarboxylic acid include aromatic dicarboxylic acids, linear or branched aliphatic dicarboxylic acids, and alicyclic dicarboxylic acids. Among these, aromatic dicarboxylic acids are preferable.
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 40 mol% or more, more preferably 50 mol% or more, still more preferably 60 mol% or more, and preferably 95 mol% or less, more preferably 95 mol% or more, in the carboxylic acid component. It is 90 mol% or less, more preferably 85 mol% or less.

Examples of the linear or branched aliphatic dicarboxylic acid include oxalic acid, malonic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, succinic acid, adipic acid, and alkyl groups having 1 to 20 carbon atoms. Alternatively, succinic acid substituted with an alkenyl group having 2 or more and 20 or less carbon atoms can be mentioned. Of these, succinic acid is preferred.
Examples of the substituted succinic acid include dodecyl succinic acid, dodecenyl succinic acid, and octenyl succinic acid. Of these, dodecenyl succinic anhydride is preferred.
The amount of the linear or branched aliphatic dicarboxylic acid is preferably 1 mol% or more, more preferably 3 mol% or more, still more preferably 5 mol% or more, and preferably 50 mol% or more in the carboxylic acid component. Below, it is more preferably 40 mol% or less, still more preferably 30 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 5 mol% or more, more preferably 8 mol% or more, still more 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 the example in the above-mentioned composite resin (A).
Among the above, the polyester resin (B) preferably contains a polycondensate of an alcohol component containing a linear or branched aliphatic diol and a carboxylic acid component containing an aromatic dicarboxylic acid, and is more preferably secondary. It contains a polycondensate of an alcohol component containing an aliphatic diol having a hydroxyl group bonded to a carbon atom and a carboxylic acid component containing an aromatic dicarboxylic acid.
In the polyester resin (B), the content of the polycondensate of the alcohol component containing a linear or branched aliphatic diol and the carboxylic acid component containing an aromatic dicarboxylic acid is preferably 80% by mass or more, more preferably. 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 amorphous polyester resin (B)]
The SP value of the polyester resin (B) by the Fedors method is 11.0 (cal / cm ³ ) ^1/2 or more and 12.5 (cal / cm) from the viewpoint of further improving the low temperature fixability, smear resistance, and durability of the toner. ³ ) It is ^1/2 or less.
The "SP value" in the present specification is the method described in [POLYMER ENGINEERING AND SCIENCE, FEBRUARY, 1974, Vol.14, No.2, ROBERT F. FEDORS. (Pages 147 to 154)] proposed by Fedors et al. It was calculated by.
The SP value of the polyester resin (B) is 11.0 (cal / cm ³ ) ^1/2 or more, preferably 11.2 (cal / cm), from the viewpoint of obtaining excellent low-temperature fixing property, smear resistance, and durability of the toner. ³ ) ^1/2 or more, more preferably 11.4 (cal / cm ³ ) ^1/2 or more, still more preferably 11.5 (cal / cm ³ ) ^1/2 or more, still more preferably 11.6 (cal / cm ³ ) ^1/2 . The above, and 12.5 (cal / cm ³ ) ^1/2 or less, preferably 12.3 (cal / cm ³ ) ^1/2 or less, more preferably 12.1 (cal / cm ³ ) ^1/2 or less, still more preferably. It is 11.9 (cal / cm ³ ) ^1/2 or less, more preferably 11.8 (cal / cm ³ ) ^1/2 or less.

The acid value of the polyester resin (B) is preferably 3 mgKOH / g or more, more preferably 5 mgKOH / g or more, still more preferably 6 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 10 mgKOH / g or more, still more preferably 15 mgKOH / g or more, still more preferably 20 mgKOH / g or more, and preferably 60 mgKOH / g or more. It is g or less, more preferably 50 mgKOH / g or less, still more preferably 45 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 130 ° C. or higher, from the viewpoint of further improving low temperature fixability. The temperature is preferably 150 ° C. or lower, more preferably 145 ° C. or lower, and even more preferably 140 ° C. or lower.

The glass transition temperature of the polyester resin (B) is preferably 40 ° C. or higher, more preferably 45 ° C. or higher, still more preferably 50 ° C. from the viewpoint of further improving the low temperature fixability, smear resistance, and durability of the toner. The above, 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 polyester resin (B) may 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 can be 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 conditions for polycondensation, for example, the conditions shown in polycondensation in the above-mentioned composite resin (A) can be applied.

The mass ratio [(A) / (B)] of the composite resin (A) and the polyester resin (B) is preferably 1 from the viewpoint of further improving the low temperature fixability, smear resistance, and durability of the toner. / 99 or more, more preferably 10/90 or more, still more preferably 20/80 or more, still more preferably 25/75 or more, and preferably 55/45 or less, more preferably 50/50 or less, still more preferably. It is 40/60 or less, more preferably 35/65 or less.

The content of the polyester resin (B) is preferably 40% by mass or more, more preferably 45% by mass, from the viewpoint of further improving the low temperature fixing property, smear resistance, and durability of the toner in the binder resin of the toner. % Or more, more preferably 50% by mass or more, still more preferably 60% by mass or more, still more preferably 65% by mass or more, and preferably 99% by mass or less, more preferably 95% by mass or less, still more preferably 90% by mass. By mass or less, more preferably 85% 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>
Examples of the wax include hydrocarbon wax, ester wax, silicone wax, and fatty acid amide wax.
Examples of the hydrocarbon wax include minerals such as paraffin wax and Fishertropush wax or petroleum-based hydrocarbon wax; 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 may 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 fixing property, smear resistance, and durability of the toner.

The melting point of the wax 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 kinds of waxes are used in combination, it is preferable that the melting point of each wax is within the above range.
The wax content is preferably 0.1 part by mass or more, more preferably 1 part by mass or more, still more preferably 2 parts by mass or more, and preferably 20 parts by mass or less, based on 100 parts by mass of the binder resin. It is more preferably 10 parts by mass or less, still more 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 "niglocin 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 .; Polyamine resin, for example," AFP-B "(manufactured by Orient Chemical Industries Co., Ltd.), 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.) Will be.

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 part by mass or more, more preferably 0.2 part by mass or more, and preferably 10 parts by mass or less, more preferably 5 parts by mass with respect to 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, such as carbon black, phthalocyanine blue, permanent brown FG, brilliant first scarlet, pigment green B, and Rhodamine-B base. Solvent Red 49, Solvent Red 146, Solvent Blue 35, quinacridone, carmine 6B, disazoero 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 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 a magnetic powder, a fluidity improver, a conductivity modifier, a reinforcing filler such as a fibrous substance, an antioxidant, an antioxidant, and a 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, an emulsification aggregation method, etc., 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 crushed toner, the method for producing the toner is, for example, step 1: a step of melting and kneading a toner raw material containing a composite resin (A), a polyester resin (B), and a wax, and step 2: step 1: obtained. It includes a step of crushing and classifying the molten mixture to obtain toner particles.

In step 1, other additives such as a charge control agent and a colorant may be contained in the toner raw material. 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 the melt-kneading is preferably 80 ° C. or higher, more preferably 100 ° C. or higher, still more 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 crystals, 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 coarsely pulverized to 1 mm or more and 5 mm or less, and then further pulverized to a desired particle size.
Examples of the crusher preferably used for coarse crushing include a hammer mill, an atomizer, and a rotoplex. 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 and a collision plate type jet mill, and it is more preferable to use a collision plate type jet mill.

Examples of the classifying machine used for classifying include a rotor type classifying machine, an air flow type classifying machine, an inertial type classifying machine, and a sieve type classifying machine. 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 inorganic fine particles such as hydrophobic silica, titanium oxide, alumina, cerium oxide and carbon black, and polymer fine particles such as polycarbonate, polymethyl methacrylate and silicone resin. Of these, hydrophobic silica is preferred.
When an external additive is used, the amount of the external additive added is preferably 1 part by mass or more, more preferably 1.5 parts by mass or more, still more preferably 2 parts by mass or more, and more preferably 2 parts by mass or more, based on 100 parts by mass of the toner particles. It is preferably 5 parts by mass or less, more preferably 4 parts by mass or less, and further preferably 3 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)).

[Plastic 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 from room temperature (20 ° C) to 0 ° C at a temperature lowering rate of 10 ° C / min using a differential scanning calorimeter "Q-20" (manufactured by TA Instruments Japan Co., Ltd.). Hold the sample as it is for 1 minute, and then measure while raising the temperature to 180 ° C at a heating rate of 10 ° C / min. Of 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 in an aluminum pan, raise the temperature to 200 ° C, and then use the temperature. 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 Corporation, HLB (Hydrophile-Lipophile Balance) = 13.6] was dissolved in the electrolytic solution to obtain a dispersion with a concentration of 5% by mass. rice field.
-Dispersion conditions: Add 10 mg of the dried toner particle measurement sample to 5 mL of the above dispersion, disperse for 1 minute with an ultrasonic disperser, then add 25 mL of electrolyte, and further add to the ultrasonic disperser. The sample 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 A5 (Composite Resins A-1 to A-5)
The raw material monomers of the polyester resin segment other than the 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 a nitrogen atmosphere. A mixture of the raw material monomer of the vinyl resin segment, the bireactive monomer and the polymerization initiator was added dropwise thereto, and the polymerization was carried out. Then, an esterification catalyst was added, and the reaction was carried out at 235 ° C. for 8 hours. Then, trimellitic acid anhydride was added and reacted at 220 ° C. for 3 hours, and the reaction was carried out at 8.0 kPa until the softening point shown in Table 1 was reached to obtain composite resins A-1 to A-5.

Manufacturing Examples B1 to B4 (Resin B-1 to B-4)
The raw material monomers of the polyester resin segment other than the trimellitic acid anhydride shown in Table 2 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. It was put in, heated to 220 ° C. over 5 hours in a mantle heater in a nitrogen atmosphere, and polycondensed at 220 ° C. for 3 hours. After adding trimellitic acid anhydride at 200 ° C, the temperature is raised to 210 ° C, a polycondensation reaction is carried out at 8.0 kPa, and the reaction is carried out until the softening point reaches the softening point shown in the table, and the resin (resin B). -1 to B-4) were obtained.

[Manufacturing of toner]
Examples 1 to 7 and Comparative Examples 1 to 4
Bundling resin, colorant "ECB-301" (manufactured by Dainichiseika Kogyo Co., Ltd.) 5 parts by mass, charge control agent "LR-147" (manufactured by Japan Carlit Co., Ltd.) 1 part by mass, at the ratio shown in Table 3. After thoroughly stirring 5 parts by mass of the wax "Carlitaba Wax C1" (manufactured by Hiroyuki Kato Co., Ltd., melting point: 80 ° C) with a Henshell mixer, the total length of the kneaded part is 1560 mm, the screw diameter is 42 mm, and the barrel inner diameter is 43 mm. It was melt-kneaded using a shaft extruder. 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 ) by a jet mill. ) 5.5 μm toner particles were obtained.

For 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 smear resistance]
Toner was mounted on a device that was improved so that the fixing machine of the copying machine "AR-505" (manufactured by Sharp Corporation) could be fixed outside the device, and an unfixed image was obtained.
After that, with a fixing machine (fixing speed 390 mm / sec) adjusted so that the total fixing pressure becomes 40 kgf, the fixing test of the unfixed image was performed at each temperature while gradually increasing from 100 ° C to 240 ° C by 10 ° C. rice field. "UNICEF cellophane" (manufactured by Mitsubishi Pencil Co., Ltd., width: 18 mm, JIS Z-1522) was attached to the fixing image, passed through a fixing roller set at 30 ° C, and then the tape was peeled off. The optical reflection density before and after the tape is applied is measured using a reflection densitometer "RD-915" (manufactured by Macbeth), and the ratio of the two (after peeling / before applying) first exceeds 90%. The temperature of the roller was set as the minimum fixing temperature, and the low temperature fixing property was evaluated according to the following evaluation criteria. The results are shown in Table 3. The lower the low fixing temperature, the better the low temperature fixing property.
The paper used for the fixing test is "CopyBond SF-70NA" (manufactured by Sharp Corporation, 75 g / m ² ).
A stainless steel weight (contact area: 3 cm x 3 cm) with a length of 3 cm, a width of 3 cm, a height of 6.5 cm, and a weight of 500 g is placed on the printed matter obtained by fixing at the above minimum fixing temperature, and the speed is 0.8 m /. It was reciprocated on the print with s. One round trip was set as one time, and the number of times when black band-shaped toner deposits first appeared on the non-printed part was visually confirmed to evaluate the smearing property. The results are shown in Table 3. The greater the number of times, the better the smear resistance.

[Durability at high temperature]
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 60%. 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 greater the number of streaks, the better the durability of the toner.

As described above, from the examples and comparative examples, it can be seen that according to the present invention, a toner having excellent low temperature fixability, smear resistance, and durability can be obtained.

Claims (5)

An electrostatic charge image developing toner containing an amorphous composite resin (A), an amorphous polyester resin (B), and a wax.
The amorphous composite resin (A) is a polycondensate of an alcohol component containing an aromatic diol and an aliphatic dicarboxylic acid having 8 or more carbon atoms and 14 or less carbon atoms in the main chain and a carboxylic acid component containing an aromatic dicarboxylic acid . 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. Including
The solubility parameter (SP value) of the amorphous polyester resin (B) is 11.0 (cal / cm ³ ) ^1/2 or more and 12.5 (cal / cm ³ ) ^1/2 or less .
The amorphous polyester resin (B) is a polycondensate of an alcohol component containing an aliphatic diol having a hydroxyl group bonded to a secondary carbon atom and a carboxylic acid component.
A toner for developing an electrostatic charge image in which the carboxylic acid component of the amorphous composite resin (A) contains 50 mol% or more of an aromatic dicarboxylic acid . The toner for electrostatic charge development according to claim 1, wherein the amorphous composite resin (A) has a glass transition temperature of 45 ° C. or higher. The invention according to claim 1 or 2 , wherein the mass ratio [(A) / (B)] of the amorphous composite resin (A) and the polyester resin (B) is 1/99 or more and 55/45 or less. Toner for static charge development. According to any one of claims 1 to 3 , the amount of the aliphatic dicarboxylic acid having 8 or more and 14 or less carbon atoms in the main chain in the carboxylic acid component of the composite resin (A) is 2 mol% or more and 30 mol% or less. The described static charge developing toner. According to any one of claims 1 to 4, the amount of the aliphatic diol having a hydroxyl group bonded to the secondary carbon atom in the alcohol component of the polyester resin (B) is 20 mol% or more and 100 mol% or less. The described static charge developing toner.